&EPA
United States
Environmental Protection
Agency
Office of
Solid Waste
Washington, D C 20460
EPA/530-SW-88-0009-d
April 1988
Solid Waste
Best
Demonstrated
Available Technology
(BOAT) Background
Document for
K061
Proposed
Volume 4
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EPA/530-SW-88-009D
Volume IV
BEST DEMONSTRATED AVAILABLE TECHNOLOGY (BOAT)
BACKGROUND DOCUMENT FOR
K061
(IRON AND STEEL INDUSTRY)
U.S. Environmental Protection Agency
Office of Solid Waste
401 M Street, S.W.
Washington, D.C. 20460
James R. Berlow, Chief
Treatment Technology Section
John Keenan
Project Manager
April 1988
U.S. Environmental Protection Agency
Region 5, Library (PL-12J)
77 West Jackson Boulevard, 12th Floor
Cmcago, 11 60604^3590
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Table of Contents
Volume IV
Executive Summary
1. INTRODUCTION .
1.1 Legal Background 1
1.1.1 Requirements Under HSWA 1
1.1.2 Schedule for Developing Restrictions 4
1.2 Summary of Promulgated BOAT Methodology 5
1.2.1 Waste Treatability Groups 7
1.2.2 Demonstrated and Available Treatment
Technologies 7
(1) Proprietary or Patented Processes 10
(2) Substantial Treatment 10
1.2.3 Collection of Performance Data 11
(1) Identification of Facilities for
Site Visits 12
(2) Engineering Site Visit 14
(3) Sampling and Analysis Plan 14
(4) Sampling Visit 16
(5) Onsite Engineering Report 17
1.2.4 Hazardous Constituents Considered and
Selected for Regulation 17
(1) Development of BOAT List 17
(2) Constituent Selection Analysis 27
(3) Calculation of Standards 29
1.2.5 Compliance with Performance Standards 30
1.2.6 Identification of BOAT 32
(1) Screening of Treatment Data 32
(2) Comparison of Treatment Data 33
(3) Quality Assurance/Quality Control 34
1.2.7 BOAT Treatment Standards for "Derived From"
and "Mixed" Wastes 36
(1) Wastes from Treatment Trains
Generating Multiple Residues 36
(2) Mixtures and Other Derived From
Residues 37
(3) Residues from Managing Listed Wastes
or that Contain Listed Wastes 38
1.2.8 Transfer of Treatment Standards 40
1.3 Variance from the BOAT Treatment Standard 41
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Table of Contents (continued)
2. INDUSTRY AFFECTED AND WASTE CHARACTERIZATION 46
2.1 Industry Affected and Process Description 46
2.2 Waste Characterization 50
3. APPLICABLE TREATMENT TECHNOLOGIES 57
3.1 Applicable Treatment Technologies 57
3.2 Demonstrated Treatment Technologies 59
3.2.1 High Temperature Metals Recovery (HTMR) 61
(1) Applicability and Use of HTMR 61
(2) Underlying Principles of Operation 62
(3) Description of HTMR Processes 64
(4) Waste Characteristics Affecting Performance 69
(5) Design and Operating Parameters 71
3.2.2 Performance Data for High Temperature Metals
Recovery 73
3.2.3 Stabilization of Metals 93
(1) Applicability and Use of Stabilization 93
(2) Underlying Principles of Operation 93
(3) Description of Stabilization Processes 95
(4) Waste Characteristics Affecting Performance 96
(5) Design and Operating Parameters 97
3.2.4 Performance Data for Stabilization 100
3.3 other Applicable Treatment Technologies 112
4. IDENTIFICATION OF BEST DEMONSTRATED AVAILABLE TECHNOLOGY
(BOAT) FOR K061 114
4.1 Introduction 114
4.2 Data Screening 114
4.3 Data Accuracy 117
4.4 Analysis of Variance 117
5. SELECTION OF REGULATED CONSTITUENTS 121
6. CALCULATION OF BOAT TREATMENT STANDARDS 132
6.1 Screening of Data 133
6.2 Correction of Analytical Data 134
6.3 Calculation of Variability Factors and Treatment
Standards 139
7. CONCLUSIONS 142
REFERENCES 149
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Table of Contents (continued)
Page
APPENDICES
Appendix A - Analysis of Variance Test and
Variability Factor Calculation 153
Appendix B - Analytical Methods and QA/QC 165
Appendix C - Kiln Temperature Strip Charts (CBI) 177
Appendix D - Statistical Analysis - ANOVA for High
Temperature Metals Recovery and Stabilization 178
Appendix E - Analytical Method for Determining
Thermal Conductivity of a Waste 182
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LIST OF TABLES
Page
1-1 BOAT List of Constituents 18
2-1 Number of Producers of Steel in Electric Furnaces by State. 47
2-2 Number of Producers of Steel in Electric Furnaces by
EPA Region 48
2-3 Major Constituent Composition - Untreated K061 Waste 52
2-4 BOAT List Constituent Composition and Other Data 54
3-1 Summary of Treatment Performance Data for High Temperature
Metals Recovery (Rotary Kiln) 76
3-2 High Temperature Metals Recovery (Rotary Kiln) -
Sampl e Set #1 77
3-3 High Temperature Metals Recovery (Rotary Kiln) -
Sample Set #2 78
3-4 High Temperature Metals Recovery (Rotary Kiln) -
Sampl e Set #3 79
3-5 High Temperature Metals Recovery (Rotary Kiln) -
Sampl e Set #4 80
3-6 High Temperature Metals Recovery (Rotary Kiln) -
Sample Set #5 81
3-7 High Temperature Metals Recovery (Rotary Kiln) -
Sampl e Set #6 82
3-8 High Temperature Metals Recovery (Rotary Kiln) -
Sampl e Set #7 83
3-9 High Temperature Metals Recovery (Rotary Kiln)
Design and Operating Data and Waste Characteristics
Affecting Performance 84
3-10 High Temperature Metals Recovery (Plasma Arc Reactor)
Sample Set #1 85
3-11 High Temperature Metals Recovery (Plasma Arc Reactor)
Sampl e Set #2 86
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List of Tables (continued)
Page
3-12 High Temperature Metals Recovery (Rotary Hearth/Electric
Furnace) Sample Set #1 87
3-13 High Temperature Metals Recovery (Rotary Hearth/Electric
Furnace) Sample Set #2 88
3-14 High Temperature Metals Recovery (Rotary Hearth/Electric
Furnace) Sample Set #3 89
3-15 High Temperature Metals Recovery (Molten Slag System)
Sampl e Set #1 90
3-16 High Temperature Metals Recovery (Molten Slag System)
Sample Set #2 91
3-17 High Temperature Metals Recovery (Flame Reactor) 92
3-18 Summary of Treatment Performance Data for Stabilization ... 102
3-19 Stabilization Testing - Set #1 - Binder: Cement 103
3-20 Stabilization Testing - Set #2 - Binder: Kiln Dust ... 104
3-21 Stabilization Testing - Set #3 - Binder: Lime/Fly Ash 105
3-22 Stabilization Testing - Design and Operating Data and
Waste Characteristics Affecting Performance 106
3-23 Stabilization Testing - Chemically Stabilized Electric Arc
Furnace Dust (CSEAFD) 107
3-24 Stabilization Testing - Sample Set #1 108
3-25 Stabilization Testing - Sample Set #2 109
3-26 Stabilization Testing - Sample Set #3 110
3-27 Stabilization Testing - Sample Set #4 Ill
4-1 Data for ANOVA Between High Temperature Metals Recovery
and Stabilization 119
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List of Tables (continued)
Page
5-1 BOAT List Constituents Detection Limits for K061 123
5-2 Regulated Constituent Reduction by High Temperature
Metals Recovery (Rotary Kiln Process) 131
6-1 Matrix Spike Recoveries for Treated Waste and Accuracy
Correction Factors for High Temperature Metals Recovery ... 136
6-2 Matrix Spike Recoveries for Treated Waste (TCLP) for
High Temperature Metals Recovery 137
6-3 Matrix Spike Recoveries and Accuracy Correction Factors
for TCLP Extracts from Stabilization 138
6-4 Variability Factors and Calculated Treatment Standards
for K061 141
7-1 BOAT Treatment Standards for K061 143
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List of Figures
Figure 2-1 Facilities Producing Steel in Electric Furnaces by
State and EPA Region 49
Figure 2-2 Steel Production in Electric Furnaces 51
Figure 3-1 Example High Temperature Metals Recovery 65
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Executive Summary
BOAT Treatment Standards for K061
Pursuant to the Hazardous and Solid Waste Amendments (HSWA) enacted
on November 8, 1984, and in accordance with the procedures for
establishing treatment standards under Section 3004(m) of the Resource,
Conservation and Recovery Act (RCRA), the Environmental Protection Agency
(EPA) is proposing treatment standards for the listed waste, K061, based
on the performance of a recovery technology determined by the Agency to
represent Best Demonstrated Available Technology (BOAT). This background
document provides the detailed analyses that support this determination.
These BOAT treatment standards represent maximum acceptable
concentration levels for selected hazardous constituents in the wastes or
residuals from recovery. The levels are established as a prerequisite
for disposal of these wastes in units designated as land disposal units
according to 40 CFR Part 268 (Code of Federal Regulations). Wastes that,
as generated, contain the regulated constituents at concentrations which
do not exceed the treatment standards are not restricted from land
disposal units. The Agency has chosen to set levels for these wastes
rather than to designate the use of a specific technology.
These proposed standards have an effective date of August 8, 1990.
This date reflects a 2 year nationwide variance to the promulgation date
due to a lack of nationwide capacity for high temperature metals recovery.
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According to 40 CFR Part 261.32 (hazardous wastes from specific
sources), waste code K061 is listed as "emission control dust/sludge from
the primary production of steel in electric furnaces." Descriptions of
the industry and specific processes generating these wastes, as well as,
descriptions of the physical and chemical waste characteristics, are
provided in Section 2.0 of this document. The four-digit Standard
Industrial Classification (SIC) code most often reported for the industry
generating this waste code is 3312 (iron and steel production). The
Agency estimates that approximately 85 facilities have the potential to
generate wastes identified as K061.
The Agency has determined that K061 represents a single treatability
group based on its physical and chemical composition, and consists of
only one subgroup--nonwastewaters. For the purpose of the land disposal
restrictions rule, wastewaters are defined as wastes containing less than
1 percent (weight basis) filterable solids and less than 1 percent
(weight basis) total organic carbon (TOC). Wastes not meeting this
definition are classified as nonwastewaters. While the Agency has not,
at this time, specifically identified additional wastes that would fall
into this treatability group or subgroup, this does not preclude the
Agency from extrapolating these standards to other wastes in the future.
K061 wastes, as generated, are metallic dusts or sludges with low to
moderate water content and low organic content: they are classified as
nonwastewaters. Solid residues from the treatment or recycling of K061
wastes also fall into this classification. K061 wastewaters may
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potentially be generated primarily as a result of the "derived-from rule"
and the "mixture-rule" as outlined in 40 CFR Part 261.3 (definition of
hazardous waste). Aqueous residues from inadvertent mixtures of the
waste with other wastewaters or aqueous wastes could be classified as
K061 wastewaters. Since the Agency has not identified any K061
wastewaters, EPA is proposing "No Land Disposal" as the treatment
standard.
The Agency has proposed BOAT treatment standards for the treatability
subgroup of K061 wastes identified as nonwastewaters. These treatment
standards have been proposed for a total of five metals that the Agency
has identified as being present in K061 wastes. These metals include
cadmium, chromium, lead, mercury, and zinc. A detailed discussion of the
selection of constituents to be regulated is presented in Section 5 of
this document.
BOAT treatment standards for nonwastewater K061 have been proposed
based on performance data using a high temperature metals recovery
process designed to recover zinc oxide from K061 and other scrap
materials containing zinc. The Agency has examined additional
performance data for treatment of K061 using high temperature metals
recovery and stabilization. Analyses of these data indicate that high
temperature metals recovery provides more effective treatment than
stabilization. In addition, the Agency believes that establishing
recovery as the Best Demonstrated Available Technology is consistent with
the national policy identified in HSWA by which Congress set up a
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hierarchy of waste management alternatives. This hierarchy places source
reduction as the first priority of waste management, with recycling as
the second priority, treatment as the next, and land disposal as the last.
The following table lists the specific BOAT treatment standards for
K061 wastes. The Agency is setting standards based on both the analysis
of total concentration and a leachate of the waste for K061
nonwastewaters, but it is not setting standards for K061 wastewaters.
The leachate is obtained by use of the Toxicity Characteristic Leaching
Procedure (TCLP). The units for total concentration analysis are in
parts per million (mg/kg) on a weight by weight basis. The units for
leachate analysis are in parts per million (mg/1) on a weight by volume
basis. Testing procedures are specifically identified in the quality
assurance sections of this document.
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BOAT TREATMENT STANDARDS FOR K061*
(As Concentration in Nonwastewater Treatment Residual)
Total TCLP
Constituent Concentration (mq/kq) Concentration (mq/1)
Cadmium 44 0.19
Chromium 1,730 0.33
Lead 20,300 0.09
Mercury 0.28 0.02
Zinc 24,100 0.50
*Both total concentration and TCLP concentration values must be complied
with prior to land disposal.
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1. INTRODUCTION
This section of the background document presents a summary of the
legal authority pursuant to which the BOAT treatment standards were
developed, a summary of EPA's promulgated methodology for developing
BOAT, and finally a discussion of the petition process that should be
followed to request a variance from the BOAT treatment standards.
1.1 Legal Background
1.1.1 Reauirements Under HSWA
The Hazardous and Solid Waste Amendments of 1984 (HSWA), enacted on
November 8, 1984, and which amended the Resource Conservation and
Recovery Act of 1976 (RCRA), impose substantial new responsibilities on
those who handle hazardous waste. In particular, the amendments require
the Agency to promulgate regulations that restrict the land disposal of
untreated hazardous wastes. In its enactment of HSWA, Congress stated
explicitly that "reliance on land disposal should be minimized or
eliminated, and land disposal, particularly landfill and surface
impoundment, should be the least favored method for managing hazardous
wastes" (RCRA section 1002(b)(7), 42 U.S.C. 6901(b)(7)).
One part of the amendments specifies dates on which particular groups
of untreated hazardous wastes will be prohibited from land disposal
unless "it has been demonstrated to the Administrator, to a reasonable
degree of certainty, that there will be no migration of hazardous
constituents from the disposal unit or injection zone for as long as the
wastes remain hazardous" (RCRA section 3004(d)(l), (e)(l), (g)(5), 42
U.S.C. 6924 (d)(l), (e)(l), (g)(5)).
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For the purpose of the restrictions, HSWA defines land disposal "to
include, but not be limited to, any placement of ... hazardous waste in
a landfill, surface impoundment, waste pile, injection well, land
treatment facility, salt dome formation, salt bed formation, or
underground mine or cave" (RCRA section 3004(k), 42 U.S.C. 6924(k)).
Although HSWA defines land disposal to include injection wells, such
disposal of solvents, dioxins, and certain other wastes, known as the
California List wastes, is covered on a separate schedule (RCRA section
3004(f)(2), 42 U.S.C. 6924 (f)(2)). This schedule requires that EPA
develop land disposal restrictions for deep well injection by
August 8, 1988.
The amendments also require the Agency to set "levels or methods of
treatment, if any, which substantially diminish the toxicity of the waste
or substantially reduce the likelihood of migration of hazardous
constituents from the waste so that short-term and long-term threats to
human health and the environment are minimized" (RCRA section 3004(m)(l),
42 U.S.C. 6924 (m)(l)). Wastes that meet treatment standards established
by EPA are not prohibited and may be land disposed. In setting treatment
standards for listed or characteristic wastes, EPA may establish
different standards for particular wastes within a single waste code with
differing treatability characteristics. One such characteristic is the
physical form of the waste. This frequently leads to different standards
for wastewaters and nonwastewaters.
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alternatively, EPA can establish a treatment standard that is applicable
to more than one waste code when, in EPA's judgment, all the waste can be
treated to the same concentration. In those instances where a generator
can demonstrate that the standard promulgated for the generator's waste
cannot be achieved, the Agency also can grant a variance from a treatment
standard by revising the treatment standard for that particular waste
through rulemaking procedures. (A further discussion of treatment
variances is provided in Section 1.3.)
The land disposal restrictions are effective when promulgated unless
the Administrator grants a national variance and establishes a different
date (not to exceed 2 years beyond the statutory deadline) based on "the
earliest date on which adequate alternative treatment, recovery, or
disposal capacity which protects human health and the environment will be
available" (RCRA section 3004(h)(2), 42 U.S.C. 6924 (h)(2)).
If EPA fails to set a treatment standard by the statutory deadline
for any hazardous waste in the First Third or Second Third of the
schedule (see section 1.1.2), the waste may not be disposed in a landfill
or surface impoundment unless the facility is in compliance with the
minimum technological requirements specified in section 3004(o) of RCRA.
In addition, prior to disposal, the generator must certify to the
Administrator that the availability of treatment capacity has been
investigated and it has been determined that disposal in a landfill or
surface impoundment is the only practical alternative to treatment
currently available to the generator. This restriction on the use of
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landfills and surface impoundments applies until EPA sets a treatment
standard for the waste or until May 8, 1990, whichever is sooner. If the
Agency fails to set a treatment standard for any ranked hazardous waste
by May 8, 1990, the waste is automatically prohibited from land disposal
unless the waste is placed in a land disposal unit that is the subject of
a successful "no migration" demonstration (RCRA section 3004(g), 42
U.S.C. 6924(g)). "No migration" demonstrations are based on case-
specific petitions that show there will be no migration of hazardous
constituents from the unit for as long as the waste remains hazardous.
1.1.2 Schedule for Developing Restrictions
Under Section 3004(g) of RCRA, EPA was required to establish a
schedule for developing treatment standards for all wastes that the
Agency had listed as hazardous by November 8, 1984. Section 3004(g)
required that this schedule consider the intrinsic hazards and volumes
associated with each of these wastes. The statute required EPA to set
treatment standards according to the following schedule:
(a) Solvents and dioxins standards must be promulgated by
November 8, 1986;
(b) The "California List" must be promulgated by July 8, 1987;
(c) At least one-third of all listed hazardous wastes must be
promulgated by August 8, 1988 (First Third);
(d) At least two-thirds of all listed hazardous wastes must be
promulgated by June 8, 1989 (Second Third); and
(e) All remaining listed hazardous wastes and all hazardous wastes
identified as of November 8, 1984, by one or more of the
characteristics defined in 40 CFR Part 261 must be promulgated
by May 8, 1990 (Third Third).
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The statute specifically identified the solvent wastes as those
covered under waste codes F001, F002, F003, F004, and F005; it identified
the dioxin-containing hazardous wastes as those covered under waste codes
F020, F021, F022, and F023.
Wastes collectively known as the California List wastes, defined
under Section 3004(d) of HSWA, are liquid hazardous wastes containing
metals, free cyanides, PCBs, corrosives (i.e., a pH less than or equal to
2.0), and any liquid or nonliquid hazardous waste containing halogenated
organic compounds (HOCs) above 0.1 percent by weight. Rules for the
California List were proposed on December 11, 1986, and final rules for
PCBs, corrosives, and HOC-containing wastes were established
August 12, 1987. In that rule, EPA elected not to establish standards
for metals. Therefore, the statutory limits became effective.
On May 28, 1986, EPA published a final rule (51 FR 19300) that
delineated the specific waste codes that would be addressed by the First
Third, Second Third, and Third Third. This schedule is incorporated into
40 CFR 268.10, .11, and .12.
1.2 Summary of Promulgated BOAT Methodology
In a November 7, 1986, rulemaking, EPA promulgated a technology-based
approach to establishing treatment standards under section 3004(m).
Section 3004(m) also specifies that treatment standards must "minimize"
long- and short-term threats to human health and the environment arising
from land disposal of hazardous wastes.
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Congress indicated in the legislative history accompanying the HSWA
that "[t]he requisite levels of [sic] methods of treatment established by
the Agency should be the best that has been demonstrated to be
achievable," noting that the intent is "to require utilization of
available technology" and not a "process which contemplates
technology-forcing standards" (Vol. 130 Cong. Rec. S9178 (daily ed.,
July 25, 1984)). EPA has interpreted this legislative history as
suggesting that Congress considered the requirement under 3004(m) to be
met by application of the best demonstrated and achievable (i.e.,
available) technology prior to land disposal of wastes or treatment
residuals. Accordingly, EPA's treatment standards are generally based on
the performance of the best demonstrated available technology (BOAT)
identified for treatment of the hazardous constituents. This approach
involves the identification of potential treatment systems, the
determination of whether they are demonstrated and available, and the
collection of treatment data from well-designed and well-operated systems.
The treatment standards, according to the statute, can represent
levels or methods of treatment, if any, that substantially diminish the
toxicity of the waste or substantially reduce the likelihood of migration
of hazardous constituents. Wherever possible, the Agency prefers to
establish BOAT treatment standards as "levels" of treatment
(i.e., performance standards) rather than adopting an approach that would
require the use of specific treatment "methods." EPA believes that
concentration-based treatment levels offer the regulated community greater
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flexibility to develop and implement compliance strategies as well as an
incentive to develop innovative technologies.
1.2.1 Waste Treatability Group
In developing the treatment standards, EPA first characterizes the
waste(s). As necessary, EPA may establish treatability groups for wastes
having similar physical and chemical properties. That is, if EPA
believes that wastes represented by different waste codes could be
treated to similar concentrations using identical technologies, the
Agency combines the codes into one treatability group. EPA generally
considers wastes to be similar when they are both generated from the same
industry and from similar processing stages. In addition, EPA may
combine two or more separate wastes into the same treatability group when
data are available showing that the waste characteristics affecting
performance are similar or that one waste would be expected to be less
difficult to treat.
Once the treatability groups have been established, EPA collects and
analyzes data on identified technologies used to treat the wastes in each
treatability group. The technologies evaluated must be demonstrated on
the waste or a similar waste and must be available for use.
1.2.2 Demonstrated and Available Treatment Technologies
Consistent with legislative history, EPA considers demonstrated
technologies to be those that are used to treat the waste of interest or
a similar waste with regard to parameters that affect treatment selection
(see November 7, 1986, 51 FR 40588). EPA also will consider as treatment
those technologies used to separate or otherwise process chemicals and
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other materials. Some of these technologies clearly are applicable to
waste treatment, since the wastes are similar to raw materials processed
in industrial applications.
For most of the waste treatability groups for which EPA will
promulgate treatment standards, EPA will identify demonstrated
technologies either through review of literature related to current waste
treatment practices or on the basis of information provided by specific
facilities currently treating the waste or similar wastes.
In cases where the Agency does not identify any facilities treating
wastes represented by a particular waste treatability group, EPA may
transfer a finding of demonstrated treatment. To do this, EPA will
compare the parameters affecting treatment selection for the waste
treatability group of interest to other wastes for which demonstrated
technologies already have been determined. The parameters affecting
treatment selection and their use for this waste are described in
Section 3.2 of this document. If the parameters affecting treatment
selection are similar, then the Agency will consider the treatment
technology also to be demonstrated for the waste of interest. For
example, EPA considers rotary kiln incineration a demonstrated technology
for many waste codes containing hazardous organic constituents, high
total organic content, and high filterable solids content, regardless of
whether any facility is currently treating these wastes. The basis for
this determination is data found in literature and data generated by EPA
confirming the use of rotary kiln incineration on wastes having the above
characteristics.
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If no commercial treatment or recovery operations are identified for
a waste or wastes with similar physical or chemical characteristics that
affect treatment selection, the Agency will be unable to identify any
demonstrated treatment technologies for the waste, and, accordingly, the
waste will be prohibited from land disposal (unless handled in accordance
with the exemption and variance provisions of the rule). The Agency is,
however, committed to establishing treatment standards as soon as new or
improved treatment processes are demonstrated (and available).
Operations only available at research facilities, pilot- and bench-
scale operations will not be considered in identifying demonstrated
treatment technologies for a waste because these technologies would not
necessarily be "demonstrated." Nevertheless, EPA may use data generated
at research facilities in assessing the performance of demonstrated
technologies.
As discussed earlier, Congress intended that technologies used to
establish treatment standards under Section 3004(m) be not only
"demonstrated," but also available. To decide whether demonstrated
technologies may be considered "available," the Agency determines whether
they (1) are commercially available and (2) substantially diminish the
toxicity of the waste or substantially reduce the likelihood of migration
of hazardous constituents from the waste.
EPA will only set treatment standards based on a technology that
meets the above criteria. Thus, the decision to classify a technology as
"unavailable" will have a direct impact on the treatment standard. If
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the best technology is unavailable, the treatment standard will be based
on the next best treatment technology determined to be available. To the
extent that the resulting treatment standards are less stringent, greater
concentrations of hazardous constituents in the treatment residuals could
be placed in land disposal units.
There also may be circumstances in which EPA concludes that for a
given waste none of the demonstrated treatment technologies are
"available" for purposes of establishing the 3004(m) treatment
performance standards. Subsequently, these wastes will be prohibited
from continued placement in or on the land unless managed in accordance
with applicable exemptions and variance provisions. The Agency is,
however, committed to establishing new treatment standards as soon as new
or improved treatment processes become "available."
(1) Proprietary or Patented Processes. If the demonstrated
treatment technology is a proprietary or patented process that is not
generally available, EPA will not consider the technology in its
determination of the treatment standards. EPA will consider proprietary
or patented processes available if it determines that the treatment
method can be purchased or licensed from the proprietor or is
commercially available treatment. The services of the commercial
facility offering this technology often can be purchased even if the
technology itself cannot be purchased.
(2) Substantial Treatment. To be considered "available," a
demonstrated treatment technology must "substantially diminish the
10
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toxicity" of the waste or "substantially reduce the likelihood of
migration of hazardous constituents" from the waste in accordance with
section 3004(m). By requiring that substantial treatment be achieved in
order to set a treatment standard, the statute ensures that all wastes
are adequately treated before being placed in or on the land and ensures
that the Agency does not require a treatment method that provides little
or no environmental benefit. Treatment will always be deemed substantial
if it results in nondetectable levels of the hazardous constituents of
concern. If nondetectable levels are not achieved, then a determination
of substantial treatment will be made on a case-by-case basis. This
approach is necessary because of the difficulty of establishing a
meaningful guideline that can be applied broadly to the many wastes and
technologies to be considered. EPA will consider the following factors
in an effort to evaluate whether a technology provides substantial
treatment on a case-by-case basis:
(a) Number and types of constituents treated;
(b) Performance (concentration of the constituents in the
treatment residuals); and
(c) Percent of constituents removed.
If none of the demonstrated treatment technologies achieve
substantial treatment of a waste, the Agency cannot establish treatment
standards for the constituents of concern in that waste.
1.2.3 Collection of Performance Data
Performance data on the demonstrated available technologies are
evaluated by the Agency to determine whether the data are representative
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of well-designed and well-operated treatment systems. Only data from
well-designed and well-operated systems are included in determining
BOAT. The data evaluation includes data already collected directly by
EPA and/or data provided by industry. In those instances where
additional data are needed to supplement existing information, EPA
collects additional data through a sampling and analysis program. The
principal elements of this data collection program are: (a) identifi-
cation of facilities for site visits, (b) engineering site visit,
(c) Sampling and Analysis Plan, (d) sampling visit, and (e) Onsite
Engineering Report.
(1) Identification of Facilities for Site Visits. To identify
facilities that generate and/or treat the waste of concern, EPA uses a
number of information sources. These include Stanford Research
Institute's Directory of Chemical Producers, EPA's Hazardous Waste Data
Management System (HWDMS), the 1986 Treatment, Storage, Disposal Facility
(TSDF) National Screening Survey, and EPA's Industry Studies Data Base.
In addition, EPA contacts trade associations to inform them that the
Agency is considering visits to facilities in their industry and to
solicit assistance in identifying facilities for EPA to consider in its
treatment sampling program.
After identifying facilities that treat the waste, EPA uses this
hierarchy to select sites for engineering visits: (1) generators treating
single wastes on site; (2) generators treating multiple wastes together
on site; (3) commercial treatment, storage, and disposal facilities
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(TSDFs); and (4) EPA in-house treatment. This hierarchy is based on two
concepts: (1) to the extent possible, EPA should develop treatment
standards from data produced by treatment facilities handling only a
single waste, and (2) facilities that routinely treat a specific waste
have had the best opportunity to optimize design parameters. Although
excellent treatment can occur at many facilities that are not high in
this hierarchy, EPA has adopted this approach to avoid, when possible,
ambiguities related to the mixing of wastes before and during treatment.
When possible, the Agency will evaluate treatment technologies using
commercially operated systems. If performance data from properly
designed and operated commercial treatment methods for a particular waste
or a waste judged to be similar are not available, EPA may use data from
research facilities operations. Whenever research facility data are
used, EPA will explain why such data were used in the preamble and
background document and will request comments on the use of such data.
Although EPA's data bases provide information on treatment for
individual wastes, the data bases rarely provide data that support the
selection of one facility for sampling over another. In cases where
several treatment sites appear to fall into the same level of the
hierarchy, EPA selects sites for visits strictly on the basis of which
facility could most expeditiously be visited and later sampled if
justified by the engineering visit.
13
-------
(2) Engineering Site Visit. Once a treatment facility has been
selected, an engineering site visit is made to confirm that a candidate
for sampling meets EPA's criteria for a well-designed facility and to
ensure that the necessary sampling points can be accessed to determine
operating parameters and treatment effectiveness. During the visit, EPA
also confirms that the facility appears to be well operated, although the
actual operation of the treatment system during sampling is the basis for
EPA's decisions regarding proper operation of the treatment unit. In
general, the Agency considers a well-designed facility to be one that
contains the unit operations necessary to treat the various hazardous
constituents of the waste as well as to control other nonhazardous
materials in the waste that may affect treatment performance.
In addition to ensuring that a system is reasonably well designed,
the engineering visit examines whether the facility has a way to measure
the operating parameters that affect performance of the treatment system
during the waste treatment period. For example, EPA may choose not to
sample a treatment system that operates in a continuous mode, for which
an important operating parameter cannot be continuously recorded. In
such systems, instrumentation is important in determining whether the
treatment system is operating at design values during the waste treatment
period.
(3) Sampling and Analysis Plan. If after the engineering site visit
the Agency decides to sample a particular plant, the Agency will then
develop a site-specific Sampling and Analysis Plan (SAP) according to the
Generic Quality Assurance Project Plan for the Land Disposal Restriction
14
-------
Program ("BOAT"), EPA/530-SW-87-011. In brief, the SAP discusses where
the Agency plans to sample, how the samples will be taken, the frequency
of sampling, the constituents to be analyzed and the method of analysis,
operational parameters to be obtained, and specific laboratory quality
control checks on the analytical results.
The Agency will generally produce a draft of the site-specific
Sampling and Analysis Plan within 2 to 3 weeks of the engineering visit.
The draft of the SAP is then sent to the plant for review and comment.
With few exceptions, the draft SAP should be a confirmation of data
collection activities discussed with the plant personnel during the
engineering site visit. EPA encourages plant personnel to recommend any
modifications to the SAP that they believe will improve the quality of
the data.
It is important to note that sampling of a plant by EPA does not mean
that the data will be used in the development of treatment standards for
BOAT. EPA's final decision on whether to use data from a sampled plant
depends on the actual analysis of the waste being treated and on the
operating conditions at the time of sampling. Although EPA would not
plan to sample a facility that was not ostensibly well-designed and
well-operated, there is no way to ensure that at the time of the sampling
the facility will not experience operating problems. Additionally, EPA
statistically compares its test data to suitable industry-provided data,
where available, in its determination of what data to use in developing
treatment standards. The methodology for comparing data is presented
later in this section.
15
-------
(Note: Facilities wishing to submit data for consideration in the
development of BOAT standards should, to the extent possible, provide
sampling information similar to that acquired by EPA. Such facilities
should review the Generic Quality Assurance Project Plan for the Land
Disposal Restriction Program ("BOAT"), which delineates all of the
quality control and quality assurance measures associated with sampling
and analysis. Quality assurance and quality control procedures are
summarized in Section 1.2.6 of this document.)
(4) Sampling Visit. The purpose of the sampling visit is to collect
samples that characterize the performance of the treatment system and to
document the operating conditions that existed during the waste treatment
period. At a minimum, the Agency attempts to collect sufficient samples
of the untreated waste and solid and liquid treatment residuals so that
variability in the treatment process can be accounted for in the
development of the treatment standards. To the extent practicable, and
within safety constraints, EPA or its contractors collect all samples and
ensure that chain-of-custody procedures are conducted so that the
integrity of the data is maintained.
In general, the samples collected during the sampling visit will have
already been specified in the SAP. In some instances, however, EPA will
not be able to collect all planned samples because of changes in the
facility operation or plant upsets; EPA will explain any such deviations
from the SAP in its follow-up Onsite Engineering Report.
16
-------
(5) Onsite Engineering Report. EPA summarizes all its data
collection activities and associated analytical results for testing at a
facility in a report referred to as the Onsite Engineering Report (OER).
This report characterizes the waste(s) treated, the treated residual
concentrations, the design and operating data, and all analytical results
including methods used and accuracy results. This report also describes
any deviations from EPA's suggested analytical methods for hazardous
wastes (Test Methods for Evaluating Solid Waste, SW-846, Third Edition,
November 1986).
After the Onsite Engineering Report is completed, the report is
submitted to the plant for review. This review provides the plant with a
final opportunity to claim any information contained in the report as
confidential. Following the review and incorporation of comments, as
appropriate, the report is made available to the public with the
exception of any material claimed as confidential by the plant.
1.2.4 Hazardous Constituents Considered and Selected for Regulation
(1) Development of BOAT List. The list of hazardous constituents
within the waste codes that are targeted for treatment is referred to by
the Agency as the BOAT constituent list. This list, provided as Table
1-1, is derived from the constituents presented in 40 CFR Part 261,
Appendix VII and Appendix VIII, as well as several ignitable constituents
used as the basis of listing wastes as F003 and F005. These sources
provide a comprehensive list of hazardous constituents specifically
regulated under RCRA. The BOAT list consists of those constituents that
can be analyzed using methods published in SW-846, Third Edition.
17
-------
1521g
Table 1-1 BOAT Constituent List
BOAT
reference
no
222
1
2
3
4.
5
6
223.
7.
8
9
10.
11.
12.
13.
14.
15
16
17.
la.
19
20
21
22
23.
24.
25.
26
27.
28.
29
224
225
226
30
227
31
214
32.
Parameter
Volat i les
Acetone
Acetomtri le
Acrolein
Acrylonitn le
Benzene
Bromodichloromethane
Bromomethane
n-Butyl alcohol
Carbon tetrachloride
Carbon disulfide
Chlorobenzene
2-Chloro-l ,3-butadiene
Chlorodibromomethane
Chloroethane
2-Chloroethyl vinyl ether
Chloroform
Chloromethane
3-Chloropropene
l,2-Dibromo-3-chloropropane
1,2-Dibromoethane
Dibromomethane
Trans-1 ,4-Dichloro-2-butene
Dichlorodif luoromethane
1,1-Dichloroethane
1 ,2-Dichloroethane
1 , 1-Dichloroethylene
Trans-1 ,2-Dichloroethene
1 ,2-Dichloropropane
Trans-1 ,3-Dichloropropene
cis-1 ,3-Dichloropropene
1 ,4-Dioxane
2-Ethoxyethanol
Ethyl acetate
Ethyl benzene
Ethyl cyanide
Ethyl ether
Ethyl methacrylate
Ethylene oxide
lodomethane
CAS no.
67-64-1
75-05-8
107-02-8
107-13-1
71-43-2
75-27-4
74-83-9
71-36-3
56-23-5
75-15-0
108-90-7
126-99-8
124-48-1
75-00-3
110-75-8
67-66-3
74-87-3
107-05-1
96-12-8
106-93-4
74-95-3
110-57-6
75-71-8
75-34-3
107-06-2
75-35-4
156-60-5
78-87-5
10061-02-6
10061-01-5
123-91-1
110-80-5
141-78-6
100-41-4
107-12-0
60-29-7
97-63-2
75-21-8
74-88-4
18
-------
1521g
Table 1-1 (continued)
BOAT
reference
no
33
228.
34
229
35
37
38
230.
39
40
41
42.
43
44
45.
46
47.
48.
49
231.
50
215
216.
217.
51
52.
53
54
55
56
57.
58
59.
218
60
61
62.
Parameter
Volati les (continued)
Isobutyl alcohol
Methanol
Methyl ethyl ketone
Methyl isobutyl ketone
Methyl methacrylate
Methacrylomtnle
Methylene chloride
2-Nitropropane
Pyndine
1,1, 1 ,2-Tetrachloroethane
1,1,2,2-Tetrachloroethane
Tetrachloroethene
Toluene
Tribromomethane
1,1, 1-Trichloroethane
1,1,2-Tricnloroethane
Trichloroethene
Tnchloromonof luoromethane
1 ,2, 3 -Trich loropropane
l,l,2-Trichloro-l,2,2-tnfluoro-
ethane
Vinyl chloride
1,2-Xylene
1,3-Xylene
1,4-Xylene
Semivolat i les
Acenaphthalene
Acenaphthene
Acetophenone
2-Acetylaminof luorene
4-Aminobipheny 1
An 1 1 me
Anthracene
Aramite
Benz(a)anthracene
Benzal chloride
Benzenethiol
Deleted
Benzo(a)pyrene
CAS no.
78-83-1
67-56-1
78-93-3
108-10-1
80-62-6
126-98-7
75-09-2
79-46-9
110-86-1
630-20-6
79-34-6
127-18-4
108-88-3
75-25-2
71-55-6
79-00-5
79-01-6
75-69-4
96-18-4
76-13-1
75-01-4
97-47-6
108-38-3
106-44-5
208-96-8
83-32-9
96-86-2
53-96-3
92-67-1
62-53-3
120-12-7
140-57-8
56-55-3
98-87-3
108-98-5
50-32-8
19
-------
Table 1-1 (continued)
BOAT
reference
no
63
64.
65.
66.
67.
68.
69.
70.
71
72.
73
74.
75.
76
77.
78.
79.
80.
81
82
232
83.
84.
85.
86.
87
88
89
90.
91
92.
93
94
95.
96
97.
98
99.
100.
101
Parameter
Semwolat i les (continued)
Benzo( b)f luoranthene
Benzo(ghi)perylene
Benzo(k)f luoranthene
p-Benzoquinone
Bis(2-chloroethoxy)methane
Bis(2-chloroethyl)ether
Bis(2-chloroisopropyl)ether
Bis(2-ethylhexyl)phthalate
4-Bromophenyl phenyl ether
Butyl benzyl phthalate
2-sec-Butyl-4,6-dinitrophenol
p-Chloroani 1 me
Chlorobenzi late
p-Chloro-m-cresol
2-Chloronaphtha lene
2-Chlorophenol
3-Chloropropionitri le
Chrysene
ortho-Cresol
para-Cresol
Cyclohexanone
D i benz( a, h) anthracene
Dibenzo(a,e)pyrene
Dibenzo(a, i)pyrene
m-Dichlorobenzene
o-Dichlorobenzene
p-Dichlorobenzene
3,3'-Dichlorobenzidine
2,4-Dichlorophenol
2,6-Oichlorophenol
Diethyl phthalate
3,3'-Dimethoxybenzidme
p-OimethylaminoazQbenzene
3,3'-Dimethylbenzidine
2,4-Dimethylphenol
Dimethyl phthalate
Di-n-butyl phthalate
1,4-Dinitrobenzene
4,6-Dimtro-o-cresol
2,4-Dmitrophenol
CAS no.
205-99-2
191-24-2
207-08-9
106-51-4
111-91-1
111-44-4
39638-32-9
117-81-7
101-55-3
85-68-7
88-85-7
106-47-8
510-15-6
59-50-7
91-58-7
95-57-8
542-76-7
218-01-9
95-48-7
106-44-5
108-94-1
53-70-3
192-65-4
189-55-9
541-73-1
95-50-1
106-46-7
91-94-1
120-83-2
87-65-0
84-66-2
119-90-4
60-11-7
119-93-7
105-67-9
131-11-3
84-74-2
100-25-4
534-52-1
51-28-5
20
-------
1521g
Table 1-1 (continued)
BOAT
reference
no
102
103
104
105
106
219
107
106
109.
110
111
112.
113
114.
115
116
117.
118.
119.
120
36
121.
122
123
124.
125.
126.
127.
128.
129.
130.
131
132.
133.
134.
135
136.
137
138
Parameter
Semivolat i les (continued)
2,4-Dinitrotoluene
2,6-Dmitrotoluene
Di-n-octyl phthalate
Di-n-propylmtrosamine
Diphenylamine
Diphenylnitrosamme
1,2-Diphenylhydrazine
Fluoranthene
Fluorene
Hexachlorobenzene
Hexachlorobutadiene
Hexachlorocyclopentadlene
Hexachloroethane
Hexachlorophene
Hexach loropropene
I ndeno (1,2 , 3-cd) pyrene
Isosaf role
Methapyri lene
3-Methylcholanthrene
4,4'-Methylenebis
(2-chloroani 1 me)
Methyl methanesulfonate
Naphthalene
1 ,4-Naphthoqumone
1-Naphthylamine
2-Naphthylamme
p-Nitroani 1 me
Nitrobenzene
4-Nitrophenol
N-Nitrosodi-n-butylamme
N-Nitrosodiethy lamme
N-Nitrosodimethylamme
N-Nitrosomethylethylamme
N-Nitrosomorphol me
N-Nitrosopipendme
n-Nitrosopyrrol idine
5-Nitro-o-toluidme
Pentachlorobenzene
Pentach loroethane
Pentachloron Itrobenzene
CAS no.
121-14-2
606-20-2
117-84-0
621-64-7
122-39-4
86-30-6
122-66-7
206-44-0
86-73-7
118-74-1
87-68-3
77-47-4
67-72-1
70-30-4
1888-71-7
193-39-5
120-58-1
91-80-5
56-49-5
101-14-4
66-27-3
91-20-3
130-15-4
134-32-7
91-59-8
100-01-6
98-95-3
100-02-7
924-16-3
55-18-5
62-75-9
10595-95-6
59-89-2
100-75-4
930-55-2
99-65-8
608-93-5
76-01-7
82-68-8
21
-------
1521g
Table 1-1 (continued)
BOAT
reference
no
139.
140
141.
142
220.
143
144.
145
146
147.
148
149.
150.
151.
152.
153.
154.
155.
156.
157.
158.
159.
221.
160
161.
162
163.
164
165.
166
167
168
169
170
171.
Parameter
Semivolat i les (continued)
Pentach loropheno 1
Phenacet in
Phenanthrene
Phenol
Phthalic anhydride
2-Picoline
Pronamide
Pyrene
Resorcinol
Saf role
1,2,4, 5-Tetrachlorobenzene
2,3,4,6-Tetrachlorophenol
1,2,4-Trichlorobenzene
2, 4, 5-T rich loropheno 1
2, 4, 6-Trich loropheno 1
Tris(2,3-dibromopropyl)
phosphate
Metals
Antimony
Arsenic
Barium
Beryllium
Cadmium
Chromium (total)
Chromium (hexavalent)
Copper
Lead
Mercury
Nickel
Selenium
Silver
Thai 1 lum
Vanadium
Zinc
Inorganics
Cyanide
Fluoride
Sulf ide
CAS no.
87-86-5
62-44-2
85-01-8
108-95-2
85-44-9
109-06-8
23950-58-5
129-00-0
108-46-3
94-59-7
95-94-3
58-90-2
120-82-1
95-95-4
88-06-2
126-72-7
7440-36-0
7440-38-2
7440-39-3
7440-41-7
7440-43-9
7440-47-32
-
7440-50-8
7439-92-1
7439-97-6
7440-02-0
7782-49-2
7440-22-4
7440-28-0
7440-62-2
7440-66-6
57-12-5
16964-48-8
8496-25-8
22
-------
1521g
Table 1-1 (continued)
BOAT
reference
no
172
173
174
175
176
177
178.
179.
180.
181
182
183.
184
185
186.
187.
188.
189.
190.
191.
192
193.
194.
195
196
197
198.
199.
200
201
202
Parameter
Orqanochlorine pesticides
Aldrin
alpha-BHC
beta-BHC
delta-BHC
gamma-BHC
Chlordane
ODD
DDE
DDT
Dieldrin
Endosulfan I
Endosulfan II
Endrin
Endrin aldehyde
Heptachlor
Heptachlor epoxide
Isodrin
Kepone
Methoxyclor
Toxaphene
Phenoxyacet ic acid herbicides
2,4-Dichlorophenoxyacet ic acid
Si Ivex
2,4,5-T
Orqanophosphorous insecticides
Disulfoton
Famphur
Methyl parathion
Parathion
Phorate
PCBs
Aroclor 1016
Aroclor 1221
Aroclor 1232
CAS no.
309-00-2
319-84-6
319-85-7
319-86-8
58-89-9
57-74-9
72-54-8
72-55-9
50-29-3
60-57-1
939-98-8
33213-6-5
72-20-8
7421-93-4
76-44-8
1024-57-3
465-73-6
143-50-0
72-43-5
8001-35-2
94-75-7
93-72-1
93-76-5
298-04-4
52-85-7
298-00-0
56-38-2
298-02-2
12674-11-2
11104-28-2
11141-16-5
23
-------
1521g
Table 1-1 (continued)
BOAT
reference Parameter CAS no.
PCBs (continued)
203 Aroclor 1242 53469-21-9
204 Aroclor 1248 12672-29-6
205. Aroclor 1254 11097-69-1
206. Aroclor 1260 11096-82-5
Dioxins and furans
207. Hexachlorodibenzo-p-dioxins
208. Hexachlorodibenzofurans
209 Pentachlorodibenzo-p-dioxins
210 Pentachlorodibenzofurans
211. Tetrachlorodibenzo-p-dioxins
212 Tetrachlorodibenzofurans
213. 2,3,7,8-Tetrachlorodibenzo-p-dioxin 1746-01-6
24
-------
The initial BOAT constituent list was published in EPA's Generic
Quality Assurance Project Plan, March 1987 (EPA/530-SW-87-011).
Additional constituents will be added to the BOAT constituent list as
additional key constituents are identified for specific waste codes or as
new analytical methods are developed for hazardous constituents. For
example, since the list was published in March 1987, eighteen additional
constituents (hexavalent chromium, xylene (all three isomers), benzal
chloride, phthalic anhydride, ethylene oxide, acetone, n-butyl alcohol,
2-ethoxyethanol, ethyl acetate, ethyl benzene, ethyl ether, methanol,
methyl isobutyl ketone, 2-nitropropane, l,l,2-trichloro-l,2,2-
trifluoroethane, and cyclohexanone) have been added to the list.
Chemicals are listed in Appendix VIII if they are shown in scientific
studies to have toxic, carcinogenic, mutagenic, or teratogenic effects on
humans or other life-forms, and they include such substances as those
identified by the Agency's Carcinogen Assessment Group as being
carcinogenic. Including a constituent in Appendix VIII means that the
constituent can be cited as a basis for listing toxic wastes.
Although Appendix VII, Appendix VIII, and the F003 and F005
ignitables provide a comprehensive list of RCRA-regulated hazardous
constituents, not all of the constituents can be analyzed in a complex
waste matrix. Therefore, constituents that could not be readily analyzed
in an unknown waste matrix were not included on the initial BOAT list.
As mentioned above, however, the BOAT constituent list is a continuously
growing list that does not preclude the addition of new constituents when
analytical methods are developed.
25
-------
There are 5 major reasons that constituents were not included on the
BOAT constituent list:
(a) Constituents are unstable. Based on their chemical structure,
some constituents will either decompose in water or will
ionize. For example, maleic anhydride will form maleic acid
when it comes in contact with water and copper cyanide will
ionize to form copper and cyanide ions. However, EPA may choose
to regulate the decomposition or ionization products.
(b) EPA-approved or verified analytical methods are not available.
Many constituents, such as 1,3,5-trinitrobenzene, are not
measured adequately or even detected using any of EPA's
analytical methods published in SW-846 Third Edition.
(c) The constituent is a member of a chemical group designated in
Appendix VIII as not otherwise specified (N.O.S.). Constituents
listed as N.O.S., such as chlorinated phenols, are a generic
group of some types of chemicals for which a single analytical
procedure is not available. The individual members of each such
group need to be listed to determine whether the constituents
can be analyzed. For each N.O.S. group, all those constituents
that can be readily analyzed are included in the BOAT
constituents list.
(d) Available analytical procedures are not appropriate for a
complex waste matrix. Some compounds, such as auramine, can be
analyzed as a pure constituent. However, in the presence of
other constituents, the recommended analytical method does not
positively identify the constituent. The use of high pressure
liquid chromotography (HPLC) presupposes a high expectation of
finding the specific constituents of interest. In using this
procedure to screen samples, protocols would have to be
developed on a case-specific basis to verify the identity of
constituents present in the samples. Therefore, HPLC is not an
appropriate analytical procedure for complex samples containing
unkown constituents.
(e) Standards for analytical instrument calibration are not
commercially available. For several constituents, such as
benz(c)acridine, commercially available standards of a
"reasonably" pure grade are not available. The unavailability
of a standard was determined by a review of catalogs from
specialty chemical manufacturers.
26
-------
Two constituents (fluoride and sulfide) are not specifically included
in Appendices VII and VIII; however, these compounds are included on the
BOAT list as indicator constituents for compounds from Appendices VII and
VIII such as hydrogen fluoride and hydrogen sulfide, which ionize in
water.
The BOAT constituent list presented in Table 1-1 is divided into the
following nine groups:
Volatile organics
Semivolatile organics
Metals
Other inorganics
Organochlorine pesticides
Phenoxyacetic acid herbicides
Organophosphorous insecticides
PCBs
Dioxins and furans
The constituents were placed in these categories based on their chemical
properties. The constituents in each group are expected to behave
similarily during treatment and are also analyzed, with the exception of
the metals and inorganics, by using the same analytical methods.
(2) Constituent Selection Analysis. The constituents that the
Agency selects for regulation in each treatability group are, in general,
those found in the untreated wastes at treatable concentrations. For
certain waste codes, the target list for the untreated waste may have
been shortened (relative to analyses performed to test treatment
technologies) because of the extreme unlikelihood of the constituent
being present.
27
-------
In selecting constituents for regulation, the first step is to
summarize all the constituents that were found in the untreated waste at
treatable concentrations. This process involves the use of the
statistical analysis of variance (ANOVA) test, described in Section
1.2.6, to determine if constituent reductions were significant. The
Agency interprets a significant reduction in concentration as evidence
that the technology actually "treats" the waste.
There are some instances where EPA may regulate constituents that are
not found in the untreated waste but are detected in the treated
residual. This is generally the case where presence of the constituents
in the untreated waste interferes with the quantification of the
constituent of concern. In such instances, the detection levels of the
constituent are relatively high, resulting in a finding of "not detected"
when, in fact, the constituent is present in the waste.
After determining which of the constituents in the untreated waste
are present at treatable concentrations, EPA develops a list of potential
constituents for regulation. The Agency then reviews this list to
determine if any of these constituents can be excluded from regulation
because they would be controlled by regulation of other constituents in
the list.
EPA performs this indicator analysis for two reasons: (1) it reduces
the analytical cost burdens on the treater and (2) it facilitates
implementation of the compliance and enforcement program. EPA's
rationale for selection of regulated constituents for this waste code is
presented in Section 5 of this background document.
28
-------
(3) Calculation of Standards. The final step in the calculation of
the BOAT treatment standard is the multiplication of the average
treatment value by a factor referred to by the Agency as the variability
factor. This calculation takes into account that even well-designed and
well-operated treatment systems will experience some fluctuations in
performance. EPA expects that fluctuations will result from inherent
mechanical limitations in treatment control systems, collection of
treated samples, and analysis of these samples. All of the above
fluctuations can be expected to occur at well-designed and well-operated
treatment facilities. Therefore, setting treatment standards utilizing a
variability factor should be viewed not as a relaxing of 3004(m)
requirements, but rather as a function of the normal variability of the
treatment processes. A treatment facility will have to be designed to
meet the mean achievable treatment performance level to ensure that the
performance levels remain within the limits of the treatment standard.
The Agency calculates a variability factor for each constituent of
concern within a waste treatability group using the statistical
calculation presented in Appendix A. The equation for calculating the
variability factor is the same as that used by EPA for the development of
numerous regulations in the Effluent Guidelines Program under the Clean
Water Act. The variability factor establishes the instantaneous maximum
based on the 99th percentile value.
There is an additional step in the calculation of the treatment
standards in those instances where the ANOVA analysis shows that more
29
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than one technology achieves a level of performance that represents
BOAT. In such instances, the BOAT treatment standard is calculated by
first averaging the mean performance value for each technology for each
constituent of concern and then multiplying that value by the highest
variability factor among the technologies considered. This procedure
ensures that all the BOAT technologies used as the basis for the
standards will achieve full compliance.
1.2.5 Compliance with Performance Standards
All the treatment standards reflect performance achieved by the Best
Demonstrated Available Technology (BOAT). As such, compliance with these
standards only requires that the treatment level be achieved prior to
land disposal. It does not require the use of any particular treatment
technology. While dilution of the waste as a means to comply with the
standard is prohibited, wastes that are generated in such a way as to
naturally meet the standard can be land disposed without treatment. With
the exception of treatment standards that prohibit land disposal, all
treatment standards proposed are expressed as a concentration level.
EPA has used both total constituent concentration and TCLP analyses
of the treated waste as a measure of technology performance. EPA's
rationale for when each of these analytical tests is used is explained in
the following discussion.
For all organic constituents, EPA is basing the treatment standards
on the total constituent concentration found in the treated waste. EPA
based its decision on the fact that technologies exist to destroy the
30
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various organics compounds. Accordingly, the best measure of performance
would be the extent to which the various organic compounds have been
destroyed or the total amount of constituent remaining after treatment.
(NOTE: EPA's land disposal restrictions for solvent waste codes
F001-F005 (51 FR 40572) uses the TCLP value as a measure of performance.
At the time that EPA promulgated the treatment standards for F001-F005,
useful data were not available on total constituent concentrations in
treated residuals and, as a result, the TCLP data were considered to be
the best measure of performance.)
For all metal constituents, EPA is using both total constituent
concentration and/or the TCLP as the basis for treatment standards. The
total constituent concentration is being used when the technology basis
includes a metal recovery operation. The underlying principle of metal
recovery is the reduction of the amount of metal in a waste by separating
the metal for recovery; therefore, total constituent concentration in the
treated residual is an important measure of performance for this
technology. Additionally, EPA also believes that it is important that
any remaining metal in a treated residual waste not be in a state that is
easily Teachable; accordingly, EPA is also using the TCLP as a measure of
performance. It is important to note that for wastes for which treatment
standards are based on a metal recovery process, the facility has to
comply with both the total constituent concentration and the TCLP prior
to land disposal.
31
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In cases where treatment standards for metals are not based on
recovery techniques but rather on stabilization, EPA is using only the
TCLP as a measure of performance. The Agency's rationale is that
stabilization is not meant to reduce the concentration of metal in a
waste but only to chemically minimize the ability of the metal to leach.
1.2.6 Identification of BOAT
(1) Screening of Treatment Data. This section explains how the
Agency determines which of the treatment technologies represent treatment
by BOAT. The first activity is to screen the treatment performance data
from each of the demonstrated and available technologies according to the
following criteria:
(a) Design and operating data associated with the treatment data
must reflect a well-designed, well-operated system for each
treatment data point. (The specific design and operating
parameters for each demonstrated technology for this waste code
are discussed in Section 3.2 of this document.)
(b) Sufficient QA/QC data must be available to determine the true
values of the data from the treated waste. This screening
criterion involves adjustment of treated data to take into
account that the type value may be different from the measured
value. This discrepancy generally is caused by other
constituents in the waste that can mask results or otherwise
interfere with the analysis of the constituent of concern.
(c) The measure of performance must be consistent with EPA's
approach to evaluating treatment by type of constituents (e.g.,
total concentration data for organics, and total concentration
and TCLP for metals in the leachate from the residual).
In the absence of data needed to perform the screening analysis, EPA
will make decisions on a case-by-case basis of whether to include the
data. The factors included in this case-by-case analysis will be the
32
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actual treatment levels achieved, the availability of the treatment data
and their completeness (with respect to the above criteria), and EPA's
assessment of whether the untreated waste represents the waste code of
concern. EPA's application of these screening criteria for this waste
code are provided in Section 4 of this background document.
(2) Comparison of Treatment Data. In cases in which EPA has
treatment data from more than one technology following the screening
activity, EPA uses the statistical method known as analysis of variance
(ANOVA) to determine if one technology performs significantly better.
This statistical method (summarized in Appendix A) provides a measure of
the differences between two data sets. If EPA finds that one technology
performs significantly better (i.e., the data sets are not homogeneous),
BOAT treatment standards are the level of performance achieved by the
best technology multiplied by the corresponding variability factor for
each regulated constituent.
If the differences in the data sets are not statistically
significant, the data sets are said to be homogeneous. Specifically, EPA
uses the analysis of variance to determine whether BOAT represents a
level of performance achieved by only one technology or represents a
level of performance achieved by more than one (or all) of the
technologies. If the Agency finds that the levels of performance for one
or more technologies are not statistically different, EPA averages the
performance values achieved by each technology and then multiplies this
value by the largest variability factor associated with any of the
33
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acceptable technologies. A detailed discussion of the treatment
selection method and an example of how EPA chooses BOAT from multiple
treatment systems is provided in Section A-l.
(3) Quality Assurance/Quality Control. This section presents the
principal quality assurance/quality control (QA/QC) procedures employed
in screening and adjusting the data to be used in the calculation of
treatment standards. Additional QA/QC procedures used in collecting and
screening data for the BOAT program are presented in EPA's Generic
Quality Assurance Project Plan for Land Disposal Restrictions Program
("BOAT") (EPA/530-SW-87-001, March 1987).
To calculate the treatment standards for the Land Disposal
Restriction Rules, it is first necessary to determine the recovery value
for each constituent (the amount of constituent recovered after spiking,
which is the addition of a known amount of the constituent, minus the
initial concentration in the samples divided by the amount added) for a
spike of the treated residual. Once the recovery value is determined,
the following procedures are used to select the appropriate percent
recovery value to adjust the analytical data:
(a) If duplicate spike recovery values are available for the
constituent of interest, the data are adjusted by the lowest
available percent recovery value (i.e., the value that will
yield the most conservative estimate of treatment achieved).
However, if a spike recovery value of less than 20 percent is
reported for a specific constituent, the data are not used to
set treatment standards because the Agency does not have
sufficient confidence in the reported value to set a national
standard.
34
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(b) If data are not available for a specific constituent but are
available for an isomer, then the spike recovery data are
transferred from the isomer and the data are adjusted using the
percent recovery selected according to the procedure described
in (a) above.
(c) If data are not available for a specific constituent but are
available for a similar class of constituents (e.g., volatile
organics, acid-extractable semivolatiles), then spike recovery
data available for this class of constituents are transferred.
All spike recovery values greater than or equal to 20 percent
for a spiked sample are averaged and the constituent
concentration is adjusted by the average recovery value. If
spiked recovery data are available for more than one sample, the
average is calculated for each sample and the data are adjusted
by the lowest average value.
(d) If matrix spike recovery data are not available for a set of
data to be used to calculate treatment standards, then matrix
spike recovery data are transferred from a waste that the Agency
believes is a similar matrix (e.g., if the data are for an ash
from incineration, then data from other incinerator ashes could
be used). While EPA recognizes that transfer of matrix spike
recovery data from a similar waste is not an exact analysis,
this is considered the best approach for adjusting the data to
account for the fact that most analyses do not result in
extraction of 100 percent of the constituent. In assessing the
recovery data to be transferred, the procedures outlined in (a),
(b), and (c) above are followed.
The analytical procedures employed to generate the data used to
calculate the treatment standards are listed in Appendix B of this
document. In cases where alternatives or equivalent procedures and/or
equipment are allowed in EPA's SW-846, Third Edition (November 1986)
methods, the specific procedures and equipment used are also documented
in this Appendix. In addition, any deviations from the SW-846, Third
Edition, methods used to analyze the specific waste matrices are
documented. It is important to note that the Agency will use the methods
and procedures delineated in Appendix B to enforce the treatment
35
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standards presented in Section 6 of this document. Accordingly,
facilities should use these procedures in assessing the performance of
their treatment systems.
1.2.7 BOAT Treatment Standards for "Derived-From" and "Mixed" Wastes
(1) Wastes from Treatment Trains Generating Multiple Residues. In a
number of instances, the proposed BOAT consists of a series of operations
each of which generates a waste residue. For example, the proposed BOAT
for a certain waste code is based on solvent extraction, steam stripping,
and activated carbon adsorption. Each of these treatment steps generates
a waste requiring treatment -- a solvent-containing stream from solvent
extraction, a stripper overhead, and spent activated carbon. Treatment
of these wastes may generate further residues; for instance, spent
activated carbon (if not regenerated) could be incinerated, generating an
ash and possibly a scrubber water waste. Ultimately, additional wastes
are generated that may require land disposal. With respect to these
wastes, the Agency wishes to emphasize the following points:
(a) All of the residues from treating the original listed wastes are
likewise considered to be the listed waste by virtue of the
derived-from rule contained in 40 CFR Part 261.3(c)(2). (This
point is discussed more fully in (2) below.) Consequently, all
of the wastes generated in the course of treatment would be
prohibited from land disposal unless they satisfy the treatment
standard or meet one of the exceptions to the prohibition.
(b) The Agency's proposed treatment standards generally contain a
concentration level for wastewaters and a concentration level
for nonwastewaters. The treatment standards apply to all of the
wastes generated in treating the original prohibited waste.
Thus, all solids generated from treating these wastes would have
36
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to meet the treatment standard for nonwastewaters. All
derived-from wastes meeting the Agency definition of wastewater
(less than 1 percent TOC and less than 1 percent total
filterable solids) would have to meet the treatment standard for
wastewaters. EPA wishes to make clear that this approach is not
meant to allow partial treatment in order to comply with the
applicable standard.
(c) The Agency has not performed tests, in all cases, on every waste
that can result from every part of the treatment train.
However, the Agency's treatment standards are based on treatment
of the most concentrated form of the waste. Consequently, the
Agency believes that the less concentrated wastes generated in
the course of treatment will also be able to be treated to meet
this value.
(2) Mixtures and Other Derived-From Residues. There is a further
question as to the applicability of the BOAT treatment standards to
residues generated not from treating the waste (as discussed above), but
from other types of management. Examples are contaminated soil or
leachate that is derived from managing the waste. In these cases, the
mixture is still deemed to be the listed waste, either because of the
derived-from rule (40 CFR Part 261.3(c)(2)(i)) or the mixture rule
(40 CFR Part 261.3(a)(2)(iii) and (iv) or because the listed waste is
contained in the matrix (see, for example, 40 CFR Part 261.33(d)). The
prohibition for the particular listed waste consequently applies to this
type of waste.
The Agency believes that the majority of these types of residues can
meet the treatment standards for the underlying listed wastes (with the
possible exception of contaminated soil and debris for which the Agency
is currently investigating whether it is appropriate to establish a
separate treatability subcategorization). For the most part, these
37
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residues will be less concentrated than the original listed waste. The
Agency's treatment standards also make a generous allowance for process
variability by assuming that all treatability values used to establish
the standard are lognormally distributed. The waste also might be
amenable to a relatively nonvariable form of treatment technology such as
incineration. Finally, and perhaps most important, the rules contain a
treatability variance that allows a petitioner to demonstrate that its
waste cannot be treated to the level specified in the rule (40 CFR Part
268.44(a). This provision provides a safety valve that allows persons
with unusual waste matrices to demonstrate the appropriateness of a
different standard. The Agency, to date, has not received any petitions
under this provision (for example, for residues contaminated with a
prohibited solvent waste), indicating, in the Agency's view, that the
existing standards are generally achievable.
(3) Residues from Managing Listed Wastes or that Contain Listed
Wastes. The Agency has been asked if and when residues from
managing hazardous wastes, such as leachate and contaminated ground
water, become subject to the land disposal prohibitions. Although the
Agency believes this question to be settled by existing rules and
interpretative statements, to avoid any possible confusion the Agency
will address the question again.
Residues from managing First Third wastes, listed California List
wastes, and spent solvent and dioxin wastes are all considered to be
subject to the prohibitions for the underlying hazardous waste. Residues
38
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from managing California List wastes likewise are subject to the
California List prohibitions when the residues themselves exhibit a
characteristic of hazardous waste. This determination stems directly
from the derived-from rule in 40 CFR Part 261.3(c)(2) or in some cases
from the fact that the waste is mixed with or otherwise contains the
listed waste. The underlying principle stated in all of these provisions
is that listed wastes remain listed until delisted.
The Agency's historic practice in processing delisting petitions
addressing mixing residuals has been to consider them to be the listed
waste and to require that delisting petitioners address all constituents
for which the derived-from waste (or other mixed waste) was listed. The
language in 40 CFR Part 260.22(b) states that mixtures or derived-from
residues can be delisted provided a delisting petitioner makes a
demonstration identical to that which a delisting petitioner would make
for the underlying waste. These residues consequently are treated as the
underlying listed waste for delisting purposes. The statute likewise
takes this position, indicating that soil and debris that are
contaminated with listed spent solvents or dioxin wastes are subject to
the prohibition for these wastes even though these wastes are not the
originally generated waste, but rather are a residual from management
(RCRA section 3004(e)(3)). It is EPA's view that all such residues are
covered by the existing prohibitions and treatment standards for the
listed hazardous waste that these residues contain and from which they
are derived.
39
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1.2.8 Transfer of Treatment Standards
EPA is proposing some treatment standards that are not based on
testing of the treatment technology of the specific waste subject to the
treatment standard. Instead, the Agency has determined that the
constituents present in the subject waste can be treated to the same
performance levels as those observed in other wastes for which EPA has
previously developed treatment data. EPA believes that transferring
treatment performance for use in establishing treatment standards for
untested wastes is valid technically in cases where the untested wastes
are generated from similar industries, similar processing steps, or have
similar waste characteristics affecting performance and treatment
selection. Transfer of treatment standards to similar wastes or wastes
from similar processing steps requires little formal analysis. However,
in the case where only the industry is similar, EPA more closely examines
the waste characteristics prior to concluding that the untested waste
constituents can be treated to levels associated with tested wastes.
EPA undertakes a two-step analysis when determining whether wastes
generated by different processes within a single industry can be treated
to the same level of performance. First, EPA reviews the available waste
characteristic data to identify those parameters that are expected to
affect treatment selection. EPA has identified some of the most
important constituents and other parameters needed to select the
treatment technology appropriate for a given waste. A detailed
discussion of each analysis, including how each parameter was selected
for each waste, can be found in the background document for each waste.
40
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Second, when an individual analysis suggests that an untested waste
can be treated with the same technology as a waste for which treatment
performance data are already available, EPA analyzes a more detailed list
of constituents that represent some of the most important waste
characteristics that the Agency believes will affect the performance of
the technology. By examining and comparing these characteristics, the
Agency determines whether the untested wastes will achieve the same level
of treatment as the tested waste. Where the Agency determines that the
untested waste is easier to treat than the tested waste, the treatment
standards can be transferred. A detailed discussion of this transfer
process for each waste can be found in later sections of this document.
1.3 Variance from the BOAT Treatment Standard
The Agency recognizes that there may exist unique wastes that cannot
be treated to the level specified as the treatment standard. In such a
case, a generator or owner/operator may submit a petition to the
Administrator requesting a variance from the treatment standard. A
particular waste may be significantly different from the wastes
considered in establishing treatability groups because the waste contains
a more complex matrix that makes it more difficult to treat. For
example, complex mixtures may be formed when a restricted waste is mixed
with other waste streams by spills or other forms of inadvertent mixing.
As a result, the treatability of the restricted waste may be altered such
that it cannot meet the applicable treatment standard.
Variance petitions must demonstrate that the treatment standard
established for a given waste cannot be met. This demonstration can be
41
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made by showing that attempts to treat the waste by available
technologies were not successful or by performing appropriate analyses of
the waste, including waste characteristics affecting performance, which
demonstrate that the waste cannot be treated to the specified levels.
Variances will not be granted based solely on a showing that adequate
BOAT treatment capacity is unavailable. (Such demonstrations can be made
according to the provisions in Part 268.5 of RCRA for.case-by-case
extensions of the effective date.) The Agency will consider granting
generic petitions provided that representative data are submitted to
support a variance for each facility covered by the petition.
Petitioners should submit at least one copy to:
The Administrator
U.S. Environmental Protection Agency
401 M Street, S.W.
Washington, DC 20460
An additional copy marked "Treatability Variance" should be submitted
to:
Chief, Waste Treatment Branch
Office of Solid Waste (WH-565)
U.S. Environmental Protection Agency
401 M Street, S.W.
Washington, DC 20460
Petitions containing confidential information should be sent with
only the inner envelope marked "Treatability Variance" and "Confidential
Business Information" and with the contents marked in accordance with the
requirements of 40 CFR Part 2 (41 FR 36902, September 1, 1976, amended by
43 FR 4000).
The petition should contain the following information:
42
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(1) The petitioner's name and address.
(2) A statement of the petitioner's interest in the proposed action.
(3) The name, address, and EPA identification number of the facility
generating the waste, and the name and telephone number of the
plant contact.
(4) The process(es) and feed materials generating the waste and an
assessment of whether such process(es) or feed materials may
produce a waste that is not covered by the demonstration.
(5) A description of the waste sufficient for comparison with the
waste considered by the Agency in developing BOAT, and an
estimate of the average and maximum monthly and annual
quantities of waste covered by the demonstration. (Note: The
petitioner should consult the appropriate BOAT background
document for determining the characteristics of the wastes
considered in developing treatment standards.)
(6) If the waste has been treated, a description of the system used
for treating the waste, including the process design and
operating conditions. The petition should include the reasons
the treatment standards are not achievable and/or why the
petitioner believes the standards are based on inappropriate
technology for treating the waste. (Note: The petitioner should
refer to the BOAT background document as guidance for
determining the design and operating parameters that the Agency
used in developing treatment standards.)
(7) A description of the alternative treatment systems examined by
the petitioner (if any); a description of the treatment system
deemed appropriate by the petitioner for the waste in question;
and, as appropriate, the concentrations in the treatment
residual or extract of the treatment residual (i.e., using the
TCLP where appropriate for stabilized metals) that can be
achieved by applying such treatment to the waste.
(8) A description of those parameters affecting treatment selection
and waste characteristics that affect performance, including
results of all analyses. (See Section 3.0 for a discussion of
waste characteristics affecting performance that the Agency has
identified for the technology representing BOAT.)
(9) The dates of the sampling and testing.
(10) A description of the methodologies and equipment used to obtain
representative samples.
43
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(11) A description of the sample handling and preparation techniques,
including techniques used for extraction, containerization, and
preservation of the samples.
(12) A description of analytical procedures used including QA/QC
methods.
After receiving a petition for a variance, the Administrator may
request any additional information or waste samples that may be required
to evaluate and process the petition. Additionally, all petitioners must
certify that the information provided to the Agency is accurate under
40 CFR Part 268.4(b).
In determining whether a variance will be granted, the Agency will
first look at the design and operation of the treatment system being
used. If EPA determines that the technology and operation are consistent
with BOAT, the Agency will evaluate the waste to determine if the waste
matrix and/or physical parameters are such that the BOAT treatment
standards reflect treatment of this waste. Essentially, this latter
analysis will concern the parameters affecting treatment selection and
waste characteristics affecting performance parameters.
In cases where BOAT is based on more than one technology, the
petitioner will need to demonstrate that the treatment standard cannot be
met using any of the technologies, or that none of the technologies are
appropriate for treatment of the waste. After the Agency has made a
determination on the petition, the Agency's findings will be published in
the Federal Register, followed by a 30-day period for public comment.
44
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After review of the public comments, EPA will publish its final
determination in the Federal Register as an amendment to the treatment
standards in 40 CFR Part 268, Subpart D.
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2. INDUSTRY AFFECTED AND WASTE CHARACTERIZATION
The previous section discussed the BOAT program and the methodology
used by the Agency to develop treatment standards. The purpose of this
section is to describe the industry affected by the land disposal
restrictions for K061, the process generating the waste, and the
available waste characterization data.
According to 40 CFR Part 261.32 (hazardous wastes from specific
sources), the waste identified as K061 is specifically generated by the
iron and steel industry and is defined as: emission control dust/sludge
from the primary production of steel in electric furnaces. The waste is
listed for lead, chromium, and cadmium.
2.1 Industry Affected and Process Description
The four digit Standard Industrial Classification (SIC) code most
often reported for the iron and steel industry is 3312. Information
compiled from trade associations provide a geographic distribution of the
number of electric furnace steel producers across the United States.
Table 2-1 lists the number of facilities by State. Table 2-2 summarizes
the number of facilities for each EPA Region. Figure 2-1 illustrates
these data geographically on a map of the United States.
K061 is generated during the primary production of steel in electric
furnaces. The primary production of steel in electric furnaces generates
particulate emissions which contain hazardous constituents present in the
raw materials. The particulates, which are primarily comprised of iron,
BOAT list metals, and other inorganics, are removed from off gases by
46
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81199g
Table 2-1 Number of Producers of Steel in Electric Furnaces
by State
EPA Region
State
Producers*
I
II
II
III
III
III
IV
IV
IV
IV
IV
IV
IV
IV
V
V
V
V
V
VI
VI
VII
Vlf
VIII
VIII
IX
IX
X
Connecticut
New Jersey
New York
Delaware
Maryland
Pennsylvania
Alabama
Florida
Georgia
Kentucky
Mississippi
North Carolina
South Carolina
Tennessee
1 1 1 inois
Indiana
Michigan
Minnesota
Ohio
Louisiana
Texas
Montana
Nebraska
Colorado
Utah
Arizona
Cal ifornia
Washington
1
2
4
1
2
24
2
3
2
3
1
1
2
1
11
3
4
1
6
1
8
1
1
1
1
1
3
3
Reference: Directory of Iron and Steel Works of the U.S. and Canada,
American Iron and Steel Institute, 1984.
*These data are based on 1984 survey by the American Iron and Steel
Institute Of the above listed 94 plants, it has been estimated that
10%, or 9, have closed. The estimate of 85 plants reflects this
information.
47
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81199g
Table 2-2 Number of Producers of Steel in E ectric Furnaces
by EPA Region
EPA Region
Producers*
I
11
III
IV
V
VI
VII
VIII
IX
X
1
6
27
15
25
9
2
2
4
3
Reference- Directory of Iron and Steel Works of the U.S. and Canada.
American Iron and Steel Institute, 1984
*These data are based on 1984 survey by the American Iron and Steel
Institute. Of the above listed 94 plants, it has been estimated that
10%, or 9, have closed. The estimate of 85 plants reflects this
information.
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FIGURE 2-1. FACIUTIES PRODUCING STEEL IN ELECTRIC FURNACES BY STATE AND EPA REGION*
* These data based on 1984 survey by the American Iron and Steel Institute. Of the above listed 94 plants, it has been estimated that
10%, or 9, have closed. The estimate of 85 plants reflect this information.
-------
baghouses,venturi scrubbers, or electrostatic precipitators. The process
that generates K061 is illustrated in Figure 2-2.
The raw materials used in primary steel production in electric
furnaces include steel scrap, alloying elements, cold iron, and fluxes
such as limestone and/or fluorspar. The feed materials are charged into
a refractory-lined furnace and melted by the electric current surging
through the steel between electrodes. The high temperature arc-zone
(about 3,000°F) melts the scrap in an oxidizing atmosphere.
Particulate emissions containing iron, zinc, lead, cadmium, chromium, and
other components are liberated in the fume from the furnace during the
melting of scrap material, injection of additives, refining periods, and
tapping of furnaces.
The formation of particulates occurs as a result of the oxidation,
condensation, and deposition of material from the vapor phase onto
fugitive dust. Therefore, the particulates formed consist of numerous
constituents. The dust collected by baghouses, venturi scrubbers, or
electrostatic precipitators is the listed waste K061.
2.2 Waste Characterization
This section includes all waste characterization data available to
the Agency for K061. An estimate of the major constituents which
comprise the waste and their approximate concentrations is presented in
Table 2-3. The percent concentration of each major constituent in the
waste was determined by best estimates based on chemical analyses.
(Analytical results upon which the estimate is based are reported in
50
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STEEL SCRAP
FLUXES
OXYGEN
FERRO ALLOYS
ELECTRIC
FURNACE
OFF-GASES
AND PARTICULATES
-»>SLAG
STEEL PRODUCTS
VENT GASES
EMISSION
CONTROL
DEVICE
K061
FIGURE 2-2: STEEL PRODUCTION IN ELECTRIC FURNACES
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1507g
Table 2-3 Major Constituent Composition*
Untreated K061 Waste
Ma.ior Constituents Concentration {%)
Iron 26
Oxygen (in metal oxides) 18
Zinc 16
Water 12
Calcium 7
Other elements (C,N,H) 4
Fluorides 3
Manganese 3
Lead 2
Magnesium 2
Alkali Metals (Na, K) 2
Silica 2
Chlorides 2
Other BOAT metals (Cd,Cr,Cu,Ni,Ba,Hg,As,etc.) <0.5
TOTAL 100%
Approximate percent concentrations presented here were developed based
on EPA's review of chemical analyses.
52
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reference numbers 20 and 21.) The Agency has obtained waste composition
data from its own testing programs and from numerous industry sources.
The ranges of BOAT list constituents present in these wastes and other
available data are presented in Table 2-4.
Table 2-4 represents waste characterization data for K061 wastes
collected from 21 sources. The data presented display the wide variation
in concentrations of BOAT list metals found in K061 wastes from different
generators. The BOAT list metals present in the greatest concentrations
include zinc, lead, cadmium, and chromium, however, their concentrations
vary widely from sample to sample. In some cases, the concentrations of
some metals may vary by greater than a factor of 10, as is the case for
chromium and nickel. The wide variations for chromium and nickel in K061
may be attributed to wastes generated from stainless steel production,
which contains higher concentrations of these metals than carbon steels.
Overall, the composition of the emission control dust varies depending on
the grade of steel produced and the scrap material used.
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Table 2-4 BOAT Constituent Composition and Other Data
Untreated K061 Waste Total Concentration (ppm)
BOAT Constituent Source of Data
(a)
(b)
(c)
(d)
(e)
(f)
(9)
Ant imony
Arsenic
Barium
Beryl 1 lum
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selen lum
Si Iver
Thai 1 lum
Vanadium
Zinc
52-89
42-127
164-204
<0.5-1.5
290-857
803-1,190
1,460-2,640
14,900-21,900
1.0-2.0
184-449
5 2-20
23-44
0.75-2.7
24-37
129,000-155,000
294
36
238
0.15
481
1,370
2,240
20,300
3.8
243
<5 0
59
<1.0
25
244,000
.
-
280 -
3,800 1,380 2,690
1,200
15,000 24,220 7,900 1,400
-
700 - - 5,900
.
-
-
-
154,000 - - 3,900
-
-
1,600
102,000
-
11,000
-
21,000
-
-
-
-
10.000
Water (•/=)
Total Organic Carbon
12%
- = No data
(a) Reference 20 - Onsite Engineering Report for Horsehead Resource Development Co. for K061
(b) Reference 21 - Onsite Engineering Report for Waterways Experiment Station for K061
(c) Reference 6 - U.S Department of Commerce, Characterization, Recovery and Recycling of EAF Dust
(d) Reference 18 - USEPA - RCRA Background Listing Document
(e) Reference 18 - USEPA - RCRA Background Listing Document
(f) Reference 16 - USEPA - RCRA Background Listing Document
(g) Reference 6 - U.S. Department of Commerce, Charatenzation, Recovery and Recycling of EAF Dust
54
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IWg
Table 2-4 BOAT Constituent Composition and Other Data
Untreated K061 Waste Total Concentration (ppm)
BOAT Constituent Source of Data: (h) (i) (j) (k) (1) (m)
Antimony
Arsenic
Barium
Beryl 1 lum
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Si Iver
Thai 1 lum
Vanadium
2 me
470
-
1,000
25,900 1,380
-
14,600 24,200
-
246
600
-
-
-
95.710
10.2
61.4
-
1.35 293
<0.05 848
742
1.29 8,967
0.059
137
1.03
14.5
-
-
71,333
5.03
58.7
205
8.08
1,053 682
1,053 1,029
-
40,275 15,875
15.1
152.3
590
39.5
<10
46.5
~
41.9
-
13.1
354
-
1,495
0.038
-
0.068
-
-
-
-
- = No data
(h) Reference 4 - U.S Bureau of Mines, Characterization of Steelmaking Dusts from Electric Furnaces
(i) Reference 5 - Calspan Corporation, Metal and Refining Industry
(j) Reference 9 - Harrison Steel Casting, Delisting Petition
(k) Reference 10 - U.S. Steel, Delisting Petition
(1) Reference 11 - Stablex Corp, Delisting Petition
(m) Reference 12 - Marathon Steel, Delisting Petition
(n) Reference 13 - McLouth Steel, Delisting Petition
55
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1507g
Table 2-4 BOAT Constituent Composition and Other Data
Untreated K061 Waste Total Concentration (ppm)
BOAT Constituent
Antimony
Arsenic
Barium
Beryllium
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
- = No data
Source of data: (o) (p) (q)
46.7 40
400
-
370 600 100-600
426.6 1,100 60,000-100,000
600-3,000
11,133 38,000 6,000-14,000
2 0.7-16
200 15,000-22,000
<10
<50
-
_
186,000 167,000 22,000-53,000
(r) (s) (t) (u)
50-150 - BDL
<100-400 - 140-260
20-37
BDL
200-900 600 60-1,100 1,000
400-5,000 3,900 80-15,000 8,000
1,500-2,000 - 490-6,400
24,000-50,000 4,500 7,300-25,000 30,000
7-41 - BDL
1,000-3,000 - 30-16,000
BDL
BDL-70
-
320-4,800
150,000-320,000 188,000 33,000-257,000 220,000
BDL = Below the Detection Limit.
(o) Reference 14
(p) Reference 15
(q) Reference 31
(r) Reference 31
(s) Reference 33
(t) Reference 19
(u) Reference 32
- Raritan River Steel, Delisting Petition
- Bethlehem Steel, Delisting Petition
- SKF Plasmadust
- SKF Plasmadust
- Sumitomo Molten Slag
- EPA/OSW Relisting Analyses of EAF Steel
- St. Joe Flame Reactor
-------
3. APPLICABLE/DEMONSTRATED TREATMENT TECHNOLOGIES
This section describes the applicable treatment technologies and
performance data for K061. The Agency identified applicable treatment
technologies based on available waste composition data, contacts with
industry, and from technical publications. The technologies considered
to be applicable are those that treat toxic metals by reducing their
concentration and/or their Teachability. Included in this section are
discussions of those applicable treatment technologies that have been
demonstrated on a commercial basis. Treatment performance data collected
by the Agency for these technologies also are presented.
3.1 Applicable Treatment Technologies
In the previous section there was a discussion of the industries
generating K061 and the untreated waste composition. The chemical
composition of K061 most directly affects the technology applicable to
the waste. As shown in Section 2, K061 waste primarily contains high
concentrations of BOAT list metals and other inorganic constituents.
There are BOAT list organic compounds present, but these compounds are
not found at concentrations for which there is a demonstrated technology
capable of providing significant changes in the toxicity or mobility of
the waste. Other waste characteristics that may affect the treatment
technologies applicable to K061 are filterable solids concentration.
Therefore, the treatment technologies that the Agency has identified
as being applicable to K061 are designed to treat BOAT list metal
constituents in high filterable solids matrices. These technologies
57
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reduce the concentration of BOAT list metals present in the treated
residual and/or result in a treated residual with low Teachability of
BOAT list metals. The selection of the treatment technologies applicable
for treating BOAT list metals in K061 waste is based on current technical
publications, available waste composition data, and information submitted
by industry.
Initial data gathering on the generation/treatment of K061 waste
consisted of: telephone contacts to the American Iron and Steel
Institute (AISI), identification of generators from EPA's Hazardous Waste
Data Management System (HWDMS), contacts with EPA's Office of Solid Waste
Relisting Program, and compilation of available technical publications on
electric furnace steel production and K061 waste generation/treatment.
The Agency identified several variations on the following treatment
technologies as being applicable for K061 waste: direct and indirect
recycle, high temperature metals recovery, hydrometallurgical extraction
(leaching), and stabilization. These technologies provide varying
degrees of treatment to BOAT list metal constituents. Recycling of K061
directly back into the electric furnace where it was originally produced
facilitates the recovery of the metals for steel making while reducing or
eliminating the material to be land disposed. High temperature metals
recovery is used to recover metals from wastes for reuse and reduces the
concentration, Teachability, and volume of hazardous waste to be land
disposed. Leaching is also used to remove certain metals from wastes
based on relative solubilities of the metal compounds. Stabilization is
58
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used to reduce the Teachability of metals from the material to be land
disposed.
3.2 Demonstrated Treatment Technologies
This section describes the Agency's methodology for identifying the
demonstrated treatment technologies for K061. In addition, performance
data collected for these technologies that demonstrate their relative
effectiveness in treating BOAT list metal constituents are presented.
In order to determine the demonstrated technologies for K061, a list
of facilities that may utilize these technologies onsite as an
alternative to land disposal was compiled. This list was compiled from
the information sources listed previously, and included telephone
contacts to several K061 generators and commerical treatment facilities.
The available information indicate that there is no onsite treatment of
K061 and that most companies land dispose the waste. Of the applicable
technologies, recycle (direct/indirect), high temperature metals
recovery, hydrometallurgical extraction (leaching), and stabilization,
EPA has identified only two of these as being demonstrated on K061
waste: high temperature metals recovery and stabilization. EPA has not
been able to identify any instances where leaching and recycling have
been successfully applied to K061 or a similar waste on a commercial
scale. Additional descriptions of recycling technologies that have been
attempted and other potentially applicable technologies is provided in
Section 3.3.
59
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The Agency is aware of at least four facilities in the United States
and ten in foreign countries that use high temperature metals recovery to
treat emission control dust/sludge from primary steel production in
electric furnaces. As a result, five different systems of high
temperature metals recovery have been identified as being demonstrated
for K061: the rotary kiln process, rotary hearth/electric furnace, the
plasma arc reactor, molten slag reactor, and flame reactor systems. In
addition, stabilization using several different binding agents has been
demonstrated for reducing the Teachability of metals in K061.
High temperature metals recovery is currently used to recover metals
from hazardous waste for reuse; this technology also results in the
formation of a treated residual (i.e., slag) with reduced concentrations
of hazardous metals. The Agency collected treatment performance data for
the five demonstrated high temperature metals recovery processes. The
rotary kiln process, rotary hearth/electric furnace, plasma arc reactor,
molten slag reactor, and flame reactor systems are based on similar
principles; however, their design and operation are different. A more
detailed discussion of the principles of high temperature metals recovery
and descriptions of these systems is provided in Section 3.2.1.
Performance data collected by EPA for high temperature metals recovery
are also presented in Tables 3-1 to 3-17.
Stabilization is used to reduce the Teachability of metals in K061
waste. It does not result in any recovery of metals or reduction in the
60
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composition of the BOAT list metal constituents. The stabilization of
K061 is a demonstrated technology for reducing the Teachability of BOAT
list metals from the residual to be land disposed, and therefore, also
was selected by the Agency for testing. The Agency collected treatment
performance data for several stabilization processes demonstrated on K061
waste. Performance data collected by EPA for stabilization are presented
in Tables 3-18 to 3-27. A detailed description of stabilization
processes is presented in Section 3.2.3.
3.2.1 High Temperature Metals Recovery
High temperature metals recovery provides for recovery of metals from
wastes primarily by volatilization of the metals to be recovered,
subsequent condensation from the gas phase, and product collection
steps. The process yields metal products for reuse and substantially
reduces the concentration of metals in the residual. This process also
reduces the volume of treated waste that requires land disposal.
(1) Applicability and use of high temperature metals recovery. This
process is applicable to the treatment of wastes containing BOAT list
metals, low to moderate water content (or a water content that can either
be blended to the required level or lowered by dewatering), and low
concentration of organics. This technology is applicable to a wide
variety of metals including cadmium, chromium, lead, mercury, nickel, and
zinc. The five high temperature metals recovery processes that have been
demonstrated for K061 are: the rotary kiln process, rotary
hearth/electric furnace, the plasma arc reactor, the molten slag reactor,
61
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and flame reactor systems. These technologies are designed to recover
metals from K061 wastes through high temperature reduction,
volatilization, and product collection steps. Also generated are
treatment residuals that have reduced hazardous metals concentration and
low Teachability, however, in some cases, the treatment residual
(sometimes referred to as slag) can be drastically reduced in volume or
even eliminated. This can occur if the iron content is converted to the
metallic form rather than the oxide form and can be recycled to steel
production as feed material. High temperature metals recovery is
particularly applicable because it is a reuse/waste minimization
technology, which is consistent with EPA's desire to reduce the land
disposal of hazardous waste.
(2) Underlying principles of operation. The theory of operation of
high temperature metals recovery is that sufficient heat is transferred
to the waste to separate metal constituents through volatilization in a
reducing atmosphere. The volatile metals can then be recovered for
reuse. An example of the chemical reduction reaction would be:
2ZnO + C - 2Zn + CO
In some cases, multiple products may be collected from high temperature
metals recovery if the waste contains not only BOAT list metal
constituents that can be volatilized but also nonvolatile BOAT list
metals as well.
In the first processing step, the metal oxides are reduced to their
metallic form in the presence of carbon, which is provided in the form of
62
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coal or coke. Heat transfer is externally supplied by burning fossil
fuels (natural gas, coal, coke, etc.), electricity, or molten slag from
other steel production operations. In some cases, the reaction can be
exothermic and may only need enough energy to initiate the reaction.
Once reduced to their metallic form, the volatile metals, primarily
cadmium, zinc, and lead, escape from the other feed materials. The
gaseous metals may be reoxidized and collected in a baghouse or wet
scrubber, or they may be condensed and recovered in the metallic form.
There is no difference between these two types of metal product recovery
systems relative to the kinds of waste that can be treated; the
difference is simply reflected in a facility's preference relative to
product purity. In the former case, the direct condensation of metals,
while more costly, allows for the separation and collection of metals in
a relatively uncontaminated form; in the latter case the metals are
collected as a combination of several metal oxides. If necessary, this
combination of metal oxides could be further processed to produce
individual metal products of increased purity.
The fraction of the waste that isn't originally volatilized has three
possible dispositions: 1) the material is such that it can be used
directly as a product (e.g., a waste residual containing mostly metallic
iron can be reused directly in steelmaking), 2) the material can be
reused after further processing (e.g., a waste residual containing oxides
of iron, chromium, and nickel can be reduced to the metallic form and
63
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then recovered for use in the manufacture of stainless steel), and 3) the
material has no recoverable value and is land disposed as a slag.
(3) Description of high temperature metals recovery processes.
These processes essentially consist of four operations: (1) a blending
operation to control feed parameters, (2) high temperature processing,
(3) volatile product collection systems, and (4) handling of the less
volatile treated residual. As stated previously, the five high
temperature metals recovery systems operate on similar principles. Many
steps and operations are present in all of these systems and will be
described generally. Areas that differ in their design, operation, or
equipment used, will be discussed separately. A generic schematic
diagram for high temperature metals recovery is shown in Figure 3-1.
K061 in the form of a baghouses dust or a sludge from a wet scrubber
can be treated by high temperature metals recovery. In some cases, it
may be necessary to reduce the water content of the waste prior to
treatment. This can be accomplished mechanically or by blending wastes.
Variations in feeds can be minimized by blending various wastes from
different sources or from different batches of steel production over
time. Prior to feeding the kiln, fluxing agents and carbon are added to
the waste as required. Carbon is supplied to reduce metal oxides to
their metallic states as the reducing agent. The fluxes (limestone or
sand) and other additives may be blended with the waste to improve the
recovery of volatile metals. In some cases, these feeds are pelletized
prior to processing, while in others they may be input directly to the
64
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K061
CARBON
FLUXES
(ADDITIVES)
FEED
BLENDING
HIGH
TEMPERATURE
PROCESSING
PRODUCT
COLLECTION
REUSE
RESIDUAL
COLLECTION
REUSE OR
LAND DISPOSAL
FIGURE 3-1 EXAMPLE HIGH TEMPERATURE METALS RECOVERY SYSTEM
-------
process. Below are descriptions of the five demonstrated high
temperature metals recovery process: (a) rotary kiln process, (b) plasma
arc reactor, (c) rotary hearth/electric furnace, (d) molten slag reactor
system, and (e) flame reactor.
(a) Rotary kiln process. The rotary kiln process was designed
to treat zinc bearing ores and has been adapted to recover zinc from
electric furnace dust (K061). The feed materials (K.061, coal, fluxes)
are blended and input to the kiln where they are heated and the reduction
reactions begin. Volatile metals including zinc, cadmium, and lead are
removed from the waste and concentrated in a zinc rich product. These
volatile metals can be collected as oxidized particulates or can be
condensed and collected in the metallic form. In some rotary kiln
processes, an air stream is fed into the kiln countercurrent with the
waste. The air stream flowing through the kiln provides the means to
physically separate the product from the slag. As the volatile metals
escape from the kiln, they are reoxidized and condensed in the air stream
as particles. The enriched metal oxide particles are swept out of the
kiln in the air stream and are collected in a baghouse, as a product.
This material is sent for further refining to produce a final zinc
product.
The residual slag exits the kiln, is quenched by water, and is
collected. High evaporation rates of quench water result in a net loss
of water and eliminate the need for wastewater discharge. The slag, now
being reduced in both volume and concentration of metals is sometimes
66
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land disposed, although it can be recycled back to steel production if
the iron is sufficiently metallized. This can be beneficial when
treating K061 from specialty steel production which may contain high
concentrations of chromium and nickel, which are concentrated with the
iron in the slag.
(b) Plasma arc reactor. The plasma arc process is designed to
recover zinc, lead, cadmium, chromium, and iron from electric furnace
dust. The system can be used to treat emission control dust from carbon
steel production or specialty steel production. The feed (K061, coal,
and fluxes) is fed into the lower section of a shaft furnace where the
metals are reduced in the presence of coal. The high temperatures
generated by the plasma arc vaporize the more volatile metals such as
zinc, lead, and cadmium, which are condensed and collected as products.
In addition, an iron product is generated by the process and is recycled
to steel producers. The process also generates a slag and sludge.
(c) Rotary hearth/electric furnace process. The rotary
hearth/electric furnace process is designed to recover a product
containing iron, chromium, and nickel for reuse in specialty steel
making, along with a zinc dust. This process is especially applicable
for high chromium and nickel dusts from specialty steel production
because the iron is metallized and also contains chromium and nickel for
recycle to specialty steel making. The waste is pelletized along with
coal or coke prior to treatment. The treatment process primarily
consists of two treatment steps: (1) reducing metallic oxides and
67
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volatilizing zinc and lead in a rotary hearth and (2) producing the final
iron product in an electric furnace. The function of the rotary hearth
is similar to that of the rotary kiln. Metallic oxides are reduced and a
volatile product containing zinc and lead is recovered in a wet scrubber
for reuse. The remaining metal is then resmelted in an electric
furnace. During this second step, the metals volatilized from the waste
are collected in a baghouse, and the zinc and lead are recovered for
reuse. The iron product (containing chromium and nickel) is cast into
ingots and recycled to specialty steel producers. A slag is generated
from the process which requires land disposal.
(d) Molten slag reactor system. The molten slag reactor system
is designed to recover zinc from electric furnace dust through high
temperature reduction and volatilization. The K061 is pelletized with
coal and injected into a molten slag, which supplies the heat for
reduction and volatilization. The coal serves as the reducing agent and
special additives are included to improve product recovery. Auxiliary
heat can be supplied if necessary by an oil burner. A zinc oxide product
is collected in a baghouse for reuse and the remaining slag is land
disposed.
(e) Flame reactor. The flame reactor is carbon-fueled flash
smelting process designed to recover zinc and lead from electric furnace
dust/sludge. In the reactor, coke is mixed with oxygen at high
temperatures. The K061 is directly injected into the reactor where the
metals are reduced. The volatile metals (zinc, lead, cadmium) are
68
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collected with a baghouse and a residual slag is also generated.
Generally, this slag is land disposed.
(4) Waste characteristics affecting performance. Consistent with
the theory of its design, the waste characteristics that affect high
temperature metals recovery are those that inhibit volatilization of
metals from the waste and the recovery of metallic products. In
determining whether high temperature metals recovery technologies are
likely to achieve the same level of performance on an untested waste as
on a previously tested waste, EPA will examine the following three waste
characteristics that have an impact on treatability: (a) type of metals
in the waste, (b) relative volatility of the metals, and (c) heat
transfer characteristics of the waste.
(a) Type of metals in the waste. Because this is a metals
recovery process, the products must meet certain requirements for reuse.
The purity of the product is a direct function of the constituents in the
waste and their relative volatilities. If the waste contains other
metals that are difficult to separate and whose presence may affect the
ability to refine the products for reuse, high temperature metals
recovery may provide less effective treatment. The metal constituents
that compose K061 waste can be analyzed by EPA Method 6010 from SW-846.
(b) Volatility. The relative volatilities of the metals in the
waste also affect the ability to separate various metals. Depending on
the composition of the waste, the high temperature metals recovery system
used, and the metal constituents being recovered, different metals will
69
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be concentrated in the volatile products and the residual slag. As a
result, undesirable metals may be present in products if their
volatilities are similar. There is no conventional measurement technique
for determining the relative volatility of metal constituents in a given
waste. EPA believes that the best measure of volatility of a given
constituent is the boiling point. EPA recognizes that boiling point has
certain shortcomings, primarily the fact that boiling points are given
for pure components, while clearly the other constituents in the waste
will affect partial pressures and, thus, the boiling point of the •
mixture. EPA has not identified a parameter that can better assess
relative volatility. Boiling points of metals can be found in a variety
of scientific handbooks.
(c) Heat transfer characteristics. The ability to heat and
volatilize constituents within a waste matrix is a function of the heat
transfer characteristics of a heterogeneous waste material. The
constituents being volatilized from the waste must be heated near or
above their boiling points in order for them to be volatilized and
recovered. Within a given treatment unit, whether sufficient heat will
be transferred to the particular constituent to cause the metal to
volatilize will depend on the heat transfer characteristics of the
waste. There is no conventional direct measurement of the heat transfer
characteristics of a waste. EPA believes that the best measure of heat
transfer characteristics of the waste is thermal conductivity. The
analytical method that EPA has identified for measurement of thermal
70
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conductivity is named "Guarded, Comparative, Lungitudinal Heat Flow
Technique," it is described in Appendix E.
(5) Design and Operating Parameters
Consistent with the theory of operation, these processes are designed
so that sufficient heat is transferred to the waste in order to assure
that the volatile metal constituents can be removed from the waste. The
parameters that EPA will evaluate when determining whether a high
temperature metals recovery system is well designed and well operated are
(a) the furnace temperature, (b) the furnace residence time, (c) the
amount and ratio of the feed blending materials, and (d) mixing. Below
is an explanation of why EPA believes these parameters are important to
an analysis of the design and operation of the system.
(a) Furnace Temperature. In order for volatilization to occur,
sufficient heat must be transferred to the waste. The treatment system
must be designed to provide high temperatures for reduction and
volatilization. The higher the temperature, the more likely the
constituents are to react with carbon to form free metals and
volatilize. The volatility of the metals in the waste and the metals to
be recovered thus determine the specific temperature for the system.
Excessive temperatures may volatilize less volatile, undesirable metals
into the product, inhibiting its potential for reuse. If the temperature
is low, incomplete vaporization of volatile metals may occur, resulting
in poor recoveries of metals from the waste. In assessing treatment
performance, EPA would want continuous temperature data.
71
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(b) Furnace Residence Time. The system must be designed to
ensure that the waste has sufficient time to be heated to a temperature
where the metals will be volatilized. The residence time necessary for
complete volatilization of these constituents is dependent on the system
temperature and the heat transfer characteristics of the waste. In
practice, the residence time is a function of the physical dimensions of
the system (length, diameter) and the feed rate. For the rotary kiln and
rotary hearth/electric furnace systems, the rate of rotation also impacts
residence time. The molten slag reactor system is a batch process and
residence time is controlled by the system operator.
(c) Amount and Ratio of Feed Blending Materials. High
temperature metals recovery systems must be designed with respect to the
waste being treated so that metals recovery is successfully
accomplished. Uniform feed conditions with regard to metals content,
water content, carbon content, and calcium to silica ratio must be
provided for most effective treatment. Then parameters affect the rate
of reduction and volatilization of metals. The system can be designed
for the treatment of a particular waste, or various wastes may be blended
together to minimize variations in feed composition. Different wastes
may be blended from several sources or over time from steel production at
one facility. Additionally, coal, fluxes, and other additives must be
blended with the waste to attain the proper feed conditions. EPA will
examine blending ratios during treatment to ensure that they comply with
the design values.
72
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(d) Mixing. The system must mix the waste sufficiently enough
so that the material is uniformly heated and is exposed to the surface so
that the metal constituents can volatilize. Accordingly, EPA will
examine the type and degree of mixing involved when assessing treatment
design and performance. In the case of the rotary kiln process and the
rotary kiln/electric furnace system, this turbulence is provided by the
rotary motion and depends on the rate of rotation. Mixing in the plasma
arc process is provided by the injection system, which delivers a fine,
granular feed material into the furnace by pressurized air. Oxygen
injected into the molten slag bath provides turbulence in the molten slag
reactor.
3.2.2 Performance Data for High Temperature Metals Recovery
The Agency collected 15 data sets for treatment of K061 by high
temperature metals recovery. A data set constitutes a paired set of
untreated and treated total composition analyses and the associated
design and operating values for the treatment process. For high
temperature metals recovery, treatment performance is based on the
reduction of metal constituents and the Teachability of the metals in the
residual. Tables 3-1 to 3-17 summarize the treatment performance data
collected for high temperature metals recovery.
Specifically, Tables 3-1 to 3-9 present the treatment performance
data for high temperature metals recovery by the rotary kiln process.
73
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Table 3-1 summarizes the ranges of composition of BOAT list metals for
three data sets collected by the Agency representing a well operated
rotary kiln system (Sample Sets #3, #4, and #7). Additionally, the data
show the reduction in concentration of the BOAT list metal constituents
that are present in the untreated waste in the highest concentrations:
zinc, lead, cadmium, and chromium. The table also presents the low
Teachability of the treated residual as determined by the TCLP. Tables
3-2 to 3-8 present the seven analytical data sets (untreated total
composition, treated total composition, treated-TCLP) collected by EPA
for this treatment system. The waste characteristics affecting
performance and the design and operating data collected during sampling
of this rotary kiln process are presented in Table 3-9.
The waste characteristics affecting performance for the rotary kiln
system are those characteristics which impact the volatility of metals
and the recovery of reusable products. Both the boiling point of the
metals and their concentrations affect volatility. The purity of the
volatilized product is impacted by the presence of other metals with
similiar volatilities. For example, if mercury were present in very high
concentrations in the waste, it would be concentrated in the product.
The result may be the generation of a volatilized product with little or
no potential for reuse.
Performance data for the plasma arc reactor system are presented in
Tables 3-10 and 3-11. These data show the variability in performance and
the composition of the various treatment residuals including slags, and
sludges. Additionally, the ranges of untreated waste compositions vary
74
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considerably. These variations may be attributed to different steel
grades being produced and the source of scrap used. Table 3-10
represents treatment of K061 from stainless steel production while Table
3-11 presents data for K061 from carbon steel production.
Tables 3-12 to 3-14 present TCLP data for untreated and treated
wastes from the rotary hearth/electric furnace system. These data show
the reduction in Teachability of chromium, lead, zinc, and cadmium in the
treated waste following reduction and volatilization in the rotary hearth.
Tables 3-15 and 3-16 present the performance data for the molten slag
reactor system. Table 3-15 shows the treatment provided based on total
composition for cadmium, chromium, lead, and zinc, while Table 3-16
provides EP Toxicity procedure leachate data for cadmium, chromium, and
lead. Table 3-17 presents one data set collected for the flame reactor
system. These data display the treatment provided for cadmium, chromium,
lead, and zinc based on total concentration.
For all of the data and information submitted by industry on high
temperature metals recovery, see the Administrative Record for K061.
75
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1469g
Table 3-1 Summary of Treatment Performance Data for High
Temperature Metals Recovery (Rotary Kiln)*
EPA Collected Data
Untreated
Concentra ion
BOAT Constituent
Ant imony
Arsenic
Barium
Beryl 1 lum
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Silver
Thai 1 lum
Vanadium
Zinc
Range
(ppm)
73 -
56 -
184 -
<0.5 -
394 -
903 -
1,590 -
15,500 -
1 0 -
261 -
5.2 -
23 -
<1.0 -
25 -
135,000 -
80
127
204
1.5
808
1,190
2,640
20,800
1 6
449
20
44
1.5
37
155,000
Treated
Concentration
Range
(ppm)
155 -
75 -
345 -
1.7 -
<15
476 -
3,190 -
365 -
<0 1
579 -
4.2 -
39 -
<0 1
31 -
4,550 -
Treated
TCLP
Range
(mg/1)
405
113
467
4.0
978
5,470
2,370
952
8.8
59
44
11,200
0.344
<0.010
2 93
<0 001
<0.
<0.
<0.
<0,
<0 0002
0.024
<0.
<0
<0
<0
0.080
- 0.
- 0.
- 4
- 0
060
080
.080
.025
- 0
- 0
.005
.080
.010
.060
- 0
.853
.013
.32
.002
.0027
.153
.241
*These data represent three test runs that represent treatment by a well
operated rotary kiln system (Sample Set #3. #4, and #,').
Reference 20 - Onsite Engineering Report for Horsehead Resource Development Co.
76
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146yg
Table 3-2 High Temperature Metals Recovery (Rotary Kiln)
EPA Col lected Data
Sample Set #1
Ant imony
Arsenic
Barium
Beryl 1 lum
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Si Tver
Thai 1 lum
Vanadium
Zinc
Untreated
Concentraion
(ppm)
89
59
169
0.55
737
905
2,080
19.400
1.4
184
13
30
2.7
24
129,000
BOAT Constituents
Treated
Concentration
(ppm)
196
77
348
1 9
<15
662
3,180
1,720
<0 1
434
2 5
32
<1.0
8.6
24,300
Detected
Treated
TCLP
(mg/D
<0.021
<0.010
1.42
0.001
<0.060
<0.080
<0.004
<0.025
<0.0002
0.203
<0.025
<0.004
<0 010
<0.060
2.64
Reference 20 - Onsite Engineering Report for Horsehead Resource Development Co.
77
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Table 3-3 High Temperature Metals Recovery (Rotary Kiln)
EPA Collected Data
Sample Set »2
Ant imony
Arsenic
Barium
Beryl 1 lum
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
S i Iver
Tha 1 1 lum
Vanadium
Zinc
Untreated
Concentra ion
(ppm)
65
55
164
<0.5
345
959
1,620
14,900
1.4
285
18
23
1 5
26
145,000
BOAT Constituents
Treated
Concentration
(ppm)
187
77
363
1.9
<15
741
3,370
2,080
<0 1
422
5.7
35
<1 0
20
23,600
Detected
Treated
TCLP
(rng/1)
0.795
0.068
2.66
0.017
<0.060
0.103
0.100
<0.025
<0.0002
1.40
<0.025
0.099
<0.010
<0.060
65.7
Reference 20 - Onsite Engineering Report for Horsehead Resource Development Co.
78
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1469g
Table 3-4 High Temperature Metals Recovery (Rotary Kiln)
EPA Collected Data
Sample Set #3
Ant imony
Arsenic
Barium
Beryl 1 lum
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Si Iver
Thai 1 lum
Vanadium
Zinc
Untreated
Concentraion
(ppm)
73
56
184
0 81
394
1,190
1,980
15,500
1 0
449
5.2
23
1.5
37
145,000
BOAT Constituents
Treated
Concentration
(ppm)
162
75
346
1.9
<15
748
3,290
1,940
<0 1
579
4.2
42
<1.0
32
11,200
Detected
Treated
TCLP
(mg/1)
0.769
0.013
4.32
<0.001
<0.060
<0.080
<0.080
<0.025
<0.0002
0.097
<0.005
<0.080
<0.010
<0.060
0.241
Reference 20 - Onsite Engineering Report for Horsehead Resource Development Co.
79
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1469g
Table 3-5 High Temperature Metals Recovery (Rotary Kiln)
EPA Collected Data
Sample Set #4
Ant imony
Arsenic
Barium
Beryl 1 lum
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Si Iver
Thai 1 lum
Vanadium
Zinc
Untreated
Concentraion
(ppm)
80
65
190
1 5
808
903
2,640
20,800
1.6
261
8.2
29
1.3
25
135,000
BOAT Constituents
Treated
Concentration
(ppm)
405
113
467
4.0
<15
978
5,470
365
<0.1
952
5.2
39
<0.5
44
4,680
Detected
Treated
TCLP
(mg/1)
0.853
<0.010
2.93
0.002
<0.060
' <0.080
<0.004
<0 025
0.0027
0.153
<0.005
<0.004
<0.010
<0.060
0.128
Reference 20 - Onsite Engineering Report for Horsehead Resource Development Co.
80
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14b9g
Table 3-6 High Temperature Metals Recovery (Rotary Kiln)
EPA Collected Data
Sample Set #5
Ant imony
Arsenic
Barium
Beryl 1 lum
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Si Iver
Thai 1 lum
Vanadium
Z me
Untreated
Concentraion
(ppm)
52
56
168
0 83
857
803
2,610
21,900
2 0
202
4.2
25
0.75
27
145,000
BOAT Constituents
Treated
Concentrat ion
(ppm)
146
105
383
3.3
<15
205
4,560
738
<0.1
588
3 6
33
<1.0
<1.5
6,710
Detected
Treated
TCLP
(mg/1)
0.700
<0.010
2.64
0.022
<0.060
<0.080
<0.080
<0.025
<0.0002
0.445
<0.025
<0.080
<0.010
<0.060
26.7
Reference 20 - Onsite Engineering Report for Horsehead Resource Development Co.
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1469g
Table 3-7 High Temperature Metals Recovery (Rotary Kiln)
EPA Collected Data
Sample Set #6
Ant imony
Arsenic
Barium
Beryl 1 lum
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Si Iver
Thai 1 lum
Vanadium
Zinc
Untreated
Concentraion
(pptn)
58
42
193
<0.5
298
909
1,460
15,400
1.1
234
8.0
37
<1.0
34
148,000
BOAT Constituents Detected
Treated
Concentration
(ppm)
111
76
331
2.6
<15
477
3,610
4,270
-0.1
460
4.4
32
<1.0
16
27,400
Treated
TCLP
(mg/1)
0.532
<0.010
2.35
<0.001
<0.060
<0.080
<0.080
0.046
<0.0002
0.579
<0.025
<0.080
<0.010
<0.060
61.1
Reference 20 - Onsite Engineering Report for Horsehead Resource Development Co.
S2
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Table 3-8 High Temperature Metals Recovery (Rotary Kiln)
EPA Collected Data
Sample Set #7
Antimony
Arsenic
Barium
Beryl 1 lum
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
S i Iver
Thai 1 lum
Vanadium
Zinc
Untreated
Concentraion
(ppm)
78
127
204
<0.5
290
1,080
1,590
16,400
1 1
295
20
44
<1.0
33
155,000
BOAT Constituents
Treated
Concentration
(ppm)
155
79
381
1.7
<15
476
3,190
2,370
<0 1
683
8.8
59
<1 0
31
4,550
Detected
Treated
TCLP
(mg/T)
0.344
<0.010
3.690
<0.001
<0.060
<0.080
<0.040
<0.025
<0.0002
0.024
<0.005
<0.040
<0.010
<0.030
0.080
Reference 20 - Onsite Engineering Report for Horsehead Resource Development Co.
83
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1469g
Table 3-9 High Temperature Metals Recovery (Rotary Kiln)
Design and Operating Data and Waste Characteristics Affecting Performance
EPA Collected Data
Waste Characteristics Affecting Performance*
Boi 1 ing Point (in increasing order)
Mercury
Cadmium
Zinc
Lead
356"C
765°C
907"C
1760"C
Chromium 2672"C
Type of metal - No low boiling point metals are present in concentrations that could impact product purity
and use.
Thermal Conductivity** - The thermal conductivity of K061 has been estimated to be approximately
28 Btu/hr-ffF.
* The waste charaterict ics affecting performance for high temperature metals recovery are volatility and
heat transfer characteristics of the waste. EPA is using, as the best approximate measure of the
parameters, boiling point and thermal conductivity.
** Calculated based on major constituents present in waste and their respective thermal conductivities
This calculation can be found in the Administrative Record for K061
DESIGN AND OPERATING DATA
Parameter
Kiln Temperature (°C)
Feed Rate (tons/hr)
Rate of Rotation (mm/rev)
Zinc Content (%)
Moisture Content (%)
Carbon Content (%)
Calcium/Silica Ratio
Design Value
Operating Value
SS #1
SS
SS #3
SS »4
SS »5
SS *6
SS #7
The information in this table has been
claimed confidential business information (CBI)
by the company providing it.
Reference 20 - Onsite Engineering Report for Horsehead Resource Development Co.
84
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1469y
Table 3-10 High Temperature Metals Recovery (Plasma Arc Reactor)
Sample Set #1
(Stainless Steel)
Ant imony
Arsenic
Barium
Beryl 1 ium
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Si Iver
Thai 1 lum
Vanadium
Zinc
BOAT Constituents
Untreated Treated
Waste Waste
(ppm) slag
(ppm)
20
2.1
<200
-
100-600 <2
60,000-100,000 40,000-170,000
600-3,000 10
6,000-14,000 <5
0 7-16 <1
15,000-22,000 300-2,200
-
-
-
-
22,000-53,000 50-98
Detected
Treated
Water
(mg/1)
0.100
<0.04
<0.250
0.0014
<0. 002-0. 004
0.05-0 10
0.10-0.14
<0.01
0.0001-0 0011
<0.01-0 02
0.450
-
-
-
0.05-0.10
- = No data
Reference 32 - SKF Plasmadust Data
85
-------
1469q
Table 3-11 High Temperature Metals Recovery (Plasma Arc Reactor)
Sample Set #2
(Carbon Steel)
Ant imony
Arsen ic
Bar i urn
Beryl 1 lum
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Si Iver
Tha 1 1 lum
Vanadium
Zinc
BOAT
Untreated
Waste
(ppm)
50-150
<100-400
-
-
200-900
400-5,000
1,500-2,800
24,000-50.000
7-41
1,000-3,000
-
-
-
-
150,000-320,000
Constituents Detected
Treated
Waste
(slag)
(ppm)
<20
<4-13
<3,000
-
<10-500
2,000-12,000
10-1,500
50-1,500
<5
200-1,000
-
-
-
-
50-2,000
Treated
Waste
(slag)
TCLP (ppm)
_
•=0.005
2.5
-
<0.005
0.013
-
<0 05
<0 0002
0.22
<0 05
0.014
-
<0.02
Treated
Sludge
(ppm)
<20
1.6
<200
-
550
23
-
900
0.59
-
-
-
-
<1,000
3,500
Treated
Water
(mg/1)
0.020-0.100
<0.040
0.02-0.140
0.00016-0.00021
0.005-0 018
0.03-0.08
0.05-0.30 •
<0.01-0 01
0.0013-0.006
<0. 01-0. 03
<0.040
-
-
-
0.05-0 08
- = No data
Reference 32 - SKF Plasmadust Data
86
-------
I469g
Table 3-12 High Temperature Metals Re:overy
(Rotary Hearth/Electric Furnace)
Sample Set #1
Constituent
Chromium(+6)
Chromium
Untreated
Waste
TCLP
(ppm)
213
256
Treated
Waste
TCLP
(ppm)
0.62
0 65
Reference 23 - INMETCO Data for Rotary Hearth/Electric Furnace
87
-------
1469g
Table 3-13 High Temperature Metals Recovery
(Rotary Hearth/Electric Furnace)
Sample Set #2
Const ituent
Lead
Chromium
Chromium(+6)
Untreated
Waste
TCLP
(ppm)
0.39
6.8
5.4
Treated
Waste
TCLP
(ppm)
0.35
0.40
0.28
Reference 23 - INMETCO Data for Rotary Hearth/Electric Furnace
88
-------
1469g
Table 3-14 High Temperature Metals Recovery
(Rotary Hearth/Electric Furnace)
Sample Set #3
Const i tuent
Lead
Z me
Cadmium
Chromium
Untreated Treated
Waste Waste
TCLP TCLP
(ppm) (ppm)
365 0 38
4973 0.94
56 0.05
<0.1 <0.10
Reference 23 - 1NMETCO Data for Rotary Hearth/Electric Furnace
89
-------
146'Jq
Table 3-15 High Temperature Metals Recovery
(Molten Slag System)
Sample Set 1
BDAT Constituents Detected
Untreated Treated
Waste Slag
(ppm) (ppm)
Ant imony
Arsen ic
barium
Beryl 1 lum
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Si Iver
Thall lum
Vanadium
Zinc
_
trace trace
-
-
600 trace
3,900 6,500
-
4,500 200
-
-
-
-
-
-
188,200 12,200
- = No data.
Reference 33 - Sumitomo Molten Slag Data
90
-------
1469g
Table 3-16 High Temperature Metals Recovery
(Molten Slag System)
Sample Set #2
BOAT Constituents Detected
Untreated
Waste
EP Tox (ppm)
Treated
Slag
EP Tox (ppm)
Ant imony
Arsenic
Barium
Beryl 1 lum
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Si Iver
Thai 1 lum
Vanadium
I me
_
-
-
-
20.2-30 0 0.01-0.07
0 7-1.4 0.04-0.3
-
348-556 0.05-0.80
-
-
-
-
-
-
- = No data.
Reference 33 - Sumitomo Molten Slag Data
91
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Table 3-17 High Temperature Metals Recovery (Flame Reactor)
BOAT Constituenrs Detected
Untreated
Waste
(ppm)
Treated
Waste
(ppm)
Antimony
Arsenic
Barium
Bery11lum
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenlum
S i Iver
Thai 1lum
Vanadium
Z me
1,000
8,000
30,000
50
13,000
2,000
220,000
40,000
- - No Data
Reference 32 - St Joe Flame Reactor Data
92
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3.2.3 Stabilization of Metals
Stabilization refers to a broad class of treatment processes that
chemically reduce the mobility of hazardous metal constituents in a
waste. Solidification and fixation are other terms that are sometimes
used synonymously for stabilization or to describe specific variations
within the broader class of stabilization. Related technologies are
encapsulation and thermoplastic binding; however, EPA considers the
technologies to be distinct from stabilization in that the operational
principles are significantly different.
(1) Applicability and use of stabilization. Stabilization is used
when a waste contains metals that will leach from the waste when it is
contacted by water. In general, this technology is applicable to wastes
containing BOAT list metals having a high filterable solids content, low
TOC content, and low oil and grease content. Stabilization has been
applied to electric furnace dust (K061) to reduce the Teachability of
hazardous metal constituents. This technology does not destroy, recover,
or otherwise change the waste constituents, but is used to prevent metals
from leaching.
(2) Underlying principles of operation. The basic principle
underlying this technology is that stabilizing agents and other chemicals
are added to a waste in order to minimize the amount of metal that
leaches. The reduced Teachability is accomplished by the formation of a
lattice structure and/or chemical bonds that bind the metals to a solid
93
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matrix and, thereby, limit the amount of constituents which can be
leached when water or a mild acid solution comes into contact with the
materi al.
The two principal stabilization processes used are the cement based
process and the 1ime/pozzolan-based process. A brief discussion of each
is provided below. In both cement-based and 1ime/pozzolan-based
techniques, the stabilizing process can be modified through the use of
additives, such as silicates, that control curing rates or enhance the
properties of the solid material.
(a) Portland cement-based process. Portland cement is a
mixture of powdered oxides of calcium, silica, aluminum, and iron,
produced by kiln burning of materials rich in calcium and silica at high
temperatures (i.e., 1400 to 1500°C). When the anhydrous cement
powder is mixed with water, hydration occurs and the cement begins to
set. The chemistry involved is complex because many different reactions
occur, depending on the composition of the cement mixture.
As the cement begins to set, a colloidal gel of indefinite
composition and structure is formed. Over a period of time, the gel
swells and forms a matrix composed of interlacing, thin, densely-packed
silicate fibrils. Constituents present in the waste slurry, e.g.,
hydroxides and carbonates of various heavy metals, are incorporated into
the interstices of the cement matrix. The high pH of the cement mixture
tends to keep metals in the form of insoluble hydroxide and carbonate
salts. It has been hypothesized that metal ions also may be incorporated
94
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into the crystal structure of the cement matrix, but this hypothesis has
not been verified.
(b) Lime/pozzolan-based process
Pozzolan, which contains finely divided, noncrystalline silica (e.g.,
fly ash or components of cement kiln dust), is a material that is not
cementitious in itself, but becomes so upon the addition of lime. Metals
in the waste are converted to silicates or hydroxides which inhibit
leaching. Additives, again, can be used to reduce permeability and
thereby further decrease leaching potential.
(3) Description of stabilization processes. In most stabilization
processes, the waste, stabilizing agent, and other additives, if used,
are mixed and then pumped to a curing vessel or area and allowed to
cure. The actual operation (equipment requirements and process
sequencing) will depend on several factors such as the nature of the
waste, the quantity of the waste, the locations of the waste, the curing
rate, the disposal site location, the physical characteristics of the
site, the particular stabilization formulation to be used, and the curing
rate. After curing, the solid formed is recovered from the processing
equipment and stripped for final disposal.
In instances where waste contained in a lagoon is to be treated, the
material should be first transferred to mixing vessels where stabilizing
agents are added. The mixed material is then fed to a curing pad or
vessel. After curing, the solid formed is removed for disposal.
Equipment commonly used also includes facilities to store waste and
chemical additives. Pumps can be used to transfer liquid or light sludge
95
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wastes to the mixing pits and pumpable uncured wastes to the curing
site. Stabilized wastes are then removed to a final disposal site.
Commercial concrete mixing and handling equipment can generally be
used with wastes. Weighing conveyors, metering cement hoppers, and
mixers similar to concrete batching plants have been adapted in some
operations. Unless severe corrosion occurs, no adaptation of equipment
is required. Where extremely dangerous materials are being treated,
remote control and in-drum mixing equipment, such as that used with
nuclear waste, can be employed.
(4) Waste characteristics affecting performance. In determining
whether stabilization is likely to achieve the same level of performance
on an untested waste as on a waste previously tested, the Agency will
focus on the characteristics that inhibit the formation of either the
chemical bonds or the lattice structure. The four characteristics EPA
has identified as affecting treatment performance are the presence of:
(a) fine particulates, (b) oil and grease, (c) organic compounds, and
(d) inorganic compounds (including sulfates and chlorides).
(a) Fine particulates. For both cement-based and
1ime/pozzolan-based processes, the literature states that very fine,
insoluble materials (i.e., those that pass through a No. 200 mesh sieve,
74 urn particle size) can weaken the bonding between waste particles and
cement by coating the particles. This coating can inhibit chemical bond
formation and thereby decrease the resistance of the material to
leaching. Particle size can be measured by ASTM Method D422.
96
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(b) Oil and grease. The presence of oil and grease in both
cement-based and 1ime/pozzolan-based systems results in the coating of
waste particles and the weakening of the bonding between the particle and
the stabilizing agent. This coating can inhibit bond formation, thereby
decreasing the resistance of the material to leaching. Oil and grease
content can be measured by EPA Method 9070.
(c) Organic compounds. The presence of organic compounds in
the waste interferes with the chemical reactions. This interference
inhibits setting and decreases the resistance of the material to
leaching. Total organic carbon can be measured by EPA Method 9060.
(d) Sulfates and chlorides. The presence of certain inorganic
compounds will interfere with the chemical reactions, weakening bond
strength, and prolonging setting and curing time. Sulfate and chloride
compounds may reduce the diversional stability of the cured matrix,
thereby increasing leaching potential. Chlorides can be measured by EPA
Method 9252, and sulfates can be measured by EPA Method 9038.
Accordingly, EPA will examine these constituents when making decisions
regarding transfer of treatment standards based on stabilization.
(5) Design and operating parameters
In designing a stabilization system, the principal parameters
that are important to optimize so that the amount of Teachable metal
constituents is minimized are: (a) the selection of stabilizing agents
and other additives, (b) the ratio of waste to stabilizing agents and
other additives, (c) the degree of mixing, and (d) curing conditions.
97
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(a) Selection of stabilizing agents and other additives. The
stabilizing agent and additives used will determine the chemistry and
structure of the stabilized material and thus will affect the
Teachability of the solid material. Stabilizing agents and additives
must be carefully selected based on the chemical and physical
characteristics of the waste to be stabilized. For example, the amount
of sulfates in a waste should be considered when a choice is being made
between a 1ime/pozzolan-based system and a Portland cement-based system.
In order to select the stabilizing agents and additives, the waste should
be tested in the laboratory with a variety of materials to determine the
best combination.
(b) Amount of stabilizing agents and additives. The amount of
stabilizing agents and additives is a critical parameter in that
sufficient stabilizing materials are necessary in the mixture to bind the
waste constituents of concern properly, thereby making them less
susceptible to leaching. The appropriate weight ratios of amounts of
waste to stabilizing agent and other additives are established
empirically by setting up a series of laboratory tests that allow
separate leachate testing of different mix ratios. The ratio of water to
stabilizing agent (including water in waste) will also impact the
strength and leaching characteristics of the stabilized material. Too
much water will cause low strength; too little will make mixing difficult
and, more importantly, may not allow the chemical reactions that bind the
hazardous constituents to be fully completed.
98
-------
(cl Mixinq. The conditions of mixing include the type and
duration of mixing. Mixing is necessary to ensure homogeneous
distribution of the waste and the stabilizing agents. Both under-mixing
and over-mixing are undesirable. The first condition results in a
nonhomogeneous mixture; therefore, areas can exist within the waste where
waste particles are neither chemically bonded to the stabilizing agent
nor physically held within the lattice structure. Overmixing, on the
other hand, may inhibit gel formation and ion adsorption in some
stabilization systems. As with the relative amounts of waste,
stabilizing agent, and additives within the system, optimal mixing
conditions can be determined through laboratory experiments. During
treatment it is important to monitor the degree (i.e., type and duration)
of mixing to ensure that it reflects design conditions.
(d) Curing conditions. Curing conditions include the duration
of curing and the ambient curing conditions (temperature and humidity).
The duration of curing is a critical parameter to ensure that the waste
particles have had sufficient time in which to form stable chemical bonds
and/or lattice structures. The time necessary for complete stabilization
depends upon the waste type and the stabilization used. The performance
of the stabilized waste (i.e., the levels of constituents in the
leachate) will be highly dependent upon whether complete stabilization
has occurred. Higher temperatures and lower humidity increase the rate
of curing by increasing the rate of evaporation of water from the
solidification mixtures. However, if temperatures are too high, the
evaporation rate can be excessive and result in too little water being
99
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available for completion of the stabilization reaction. The duration of
the curing process should also be determined during the design stage and
typically will be between 7 and 28 days.
3.2.4 Performance Data for Stabilization
The Agency collected 40 data sets for treatment of K061 by
stabilization. Because stabilization is not used to reduce the
concentration of metals in the waste but only to reduce the ability of
metals to leach, treatment performance is measured by analysis of the
leachate from the TCLP. A data set for stabilization consists of a
paired set of untreated TCLP and treated TCLP values and the associated
design and operating parameters. Tables 3-18 to 3-27 summarize the data
collected for stabilization of K061.
Specifically, Table 3-18 summarizes the performance of stabilization
of K061 as tested by the Agency. The data presented include the
untreated waste composition and TCLP values and the TCLP extract of the
treated waste. These data are the results of 9 test runs performed using
three different binding agents: cement, kiln dust, and lime/fly ash.
These data display a tremendous variability in the treatment provided for
the BOAT metals using the different stabilizing agents. Generally, lead,
and zinc achieve the greatest reduction in Teachability. In several
cases, however, the performance of stabilization for certain constituents
(e.g., cadmium, zinc) varies by greater than one order of magnitude. In
some instances, the Teachability is increased by stabilization as is
displayed for vanadium and chromium. Tables 3-19 to 3-21 display the
particular performance results for the Agency's testing of the three
100
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binding agents: cement, kiln dust, and lime/fly ash. It can be noted
that there is not one binding agent that is most effective for all of the
BOAT metals, because treatment performance varies for each metal with
each binding agent. Table 3-22 presents the design and operating data
including binder to waste ratios and water to waste ratios collected
during the stabilization tests. Also presented are the waste
characteristics that impact performance of stabilization and the values
measured for the K061 waste tested by the Agency. Table 3-22 shows that
the waste characteristics affecting performance for K061 are not
favorable for stabilization (i.e., fine particles, sulfates, chlorides,
and oil and grease).
Tables 3-23 through 3-27 are stabilization data for K061 submitted by
industry. Table 3-23 represents 21 data points for the EP Toxicity
extraction procedure from stabilized K061. The data include untreated
waste concentration, untreated EP Toxicity extraction results and treated
waste EP Toxicity extraction results for a few of the BOAT metals. Table
3-24 through 3-27 represent 10 data sets for stabilization of K061
submitted by industry. These data include EP Toxicity extraction results
for both the untreated and treated waste for several BOAT metals. The
treatment performance provided by these stabilization processes varies
considerably for the metals analyzed. In some cases, the Teachability of
certain metals in the stabilized wastes increases based on the EP
Toxicity extraction procedure. In other cases, little or no treatment is
provided by stabilization.
For all of the data submitted by industry for stabilization, see the
Administrative Record for K061.
101
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1469g
Table 3-18 Summary of Treatment Performance Data
for Stabilization* - EPA Collected Data
BOAT Constituents
Ant imony
Arsen ic
Barium
Beryl 1 lum
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
S i Iver
Thai 1 lum
Vandium
Zinc
Untreated
Total
(ppm)
294
36
238
0.15
481
1,370
2,240
20,300
3.8
243
<5 0
59
<1.0
25
244,000
Waste
TCLP
(mg/1)
0.040
<0 010
0 733
<0.001
12.8
<0 007
0 066
45.1
0.0026
0.027
<0 050
0.021
0.038
<0.006
445
Treated Waste
TCLP
(mg/1)
<0.050
<0 010
0.431 -
<0.001
0.033 -
0.027 -
<0.004 -
0.350 -
0.0005 -
<0.012 -
<0.025
<0.003
<0.007 -
0.080 -
0.179 -
0.670
3.64
0.093
0.058
1.30
0.0018
0.024
0.015
0.290
23.5
'These data summarizes 9 data sets for stabilization of K061 using three
binding agents: cement, kiln dust, and lime/fly ash.
Reference 21 - Onsite Engineering Report for Waterways Experiment Station
for K061
102
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1469q
Table 3-19 Stabilization Testing' - EPA Collected Data
Test #1 - Binder Cement
BDAI
Const ituents
Ant imony
Arsenic
Barium
Bery 1 1 lum
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Si Iver
Thai 1 lum
Vanadium
Zinc
Untreated
lotal
(ppm)
294
36
238
0.15
481
1,370
2,240
20,300
3.8
243
<5.0
59
<1 0
25
244,000
Waste
TCLP
(mg/1)
0.040
<0.010
0.733
<0.001
12 8
<0 007
0 066
45.1
0.0026
0.027
<0.050
0.021
0.038
<0.006
445
Treated
Run
#1
^0.050
<0 010
0 670
<0.001
2 86
0 049
0.058
1.03
0.0013
0 024
<0.010
<0.003
<0.007
0.084
21.0
Waste - TCLP
Run
n
<0.050
<0.010
0.550
<0.001
3.64
0 039
0.009
1.20
0.0014
0.014
<0.010
<0.003
0.013
0.091
23.5
(mq/1)
Run
#3
<0 050
<0.010
0 516
<0.001
3.38
0 040
0.005
1.24
0.0012
0.018
<0.010
<0.003
0.015
0.290
23.4
*See Table 3-22 for the design and operating data collected for these stabilization tests.
Reference 21 - Onsite Engineering Report for Waterways Experiment Station
for K061
103
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Table 3-20 Stabilization Testing - EPA Collected Data
Test #2 - Binder Ki In Dust
BOAT
Const ituentb
Ant imony
Arsenic
Barium
Bery 1 1 lum
Cadmi um
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Si Iver
Tha 1 1 lum
Vanadium
Zinc
Untreated
Total
(ppm)
294
36
238
0.15
481
1,370
2,240
20.300
3 8
243
-=5 0
59
<1 0
25
244,000
Waste
TCLP
(mg/1)
0.040
<0.010
0.733
<0 001
12 8
<0.007
0 066
45.1
0.0026
0.027
<0.05
0.021
0 038
<0.006
445
Treated
Run
»4
<0.050
<0.010
0 516
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1469g
Table 3-21 Stabilization Testing - EPA Col ected Data
Test #3 - Binder Lime/Fly Ash
BOAT
Const ituents
Ant imony
Arsen ic
Bar luin
Beryl 1 luin
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Se len lum
Si Iver
Tha 1 1 lum
Vanadium
Zinc
Untreated
Total
(ppm)
294
36
23«
0 15
481
1,370
2,240
20,300
3 8
243
<5 0
59
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Table 3-22 Stabilization Testing - EPA Collected Data
Parameter
Binder to Waste Rat 10
Lime to Waste Rat 10
Fly Ash to Waste Rat 10
Water to Waste Ratio
Mixture pH
Cure Time (Days)
Unconfinect Compress ive
Strength ( lb/in2)
Design and Operating Data
Stabilization Process/Binder
Cement Kiln Dust Lime and Fly Ash
Run »1 Run f2 Run #3 Run *4 Run #5 Run #6 Run #7 Run #8 Run #9
0 05 0.05 0.05 0.05 0 05 0.05
0.05 0.05 0.05
0.05 0.05 0.05
0 5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5
10 9 11.5 10.5 11.5 11.6 11.1 12.1 12.0 12.0
28 28 28 28 28 28 28 28 28
59.7 88.8 95.7 133.0 167.2 141.2 54.6 58.0 50.7
Waste Characteristics Affecting Performance
Fine Participates - 90'/c of the waste composed of particles <63 urn or less than 230 mesh sieve size
Oi1 and Grease - 282 ppm
Sulfates - 8,440 ppm
Chlorides - 19,300 ppm
Total Organic Carbon - 4,430 ppm
Reference 21 - Onsite Engineering Report for Waterways Experiment Station for K061
1U6
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1469g
Table c-23 Stabilization Testing - Chemically Stabilized
Electric Arc Furnace Oust (CSEAFD)
Ant imony
Arsenic
Barium
Beryl 1 lum
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Si Iver
Thai lium
Vanadium
Zinc
BOAT Constituents Detected
Untreated Untreated Treated
Waste Waste Waste
(ppm) EP Tox (ppm) EP Tox {ppm)
.
40
400
-
600 1.7 0.02
1,100 0.9 0.07
-
38,000 139 0.02
2
200
<10
<50
-
-
167,000
1
- Based on average of six samples
- Mean of 12 values.
0 - Mean value of 21 data points for EP Tox extract analyses.
- = No data.
Reference 15 - Bethlehem Steel (CSEAFD) Stabilization Data
107
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- = No Data.
Table 3-24 Stabilization Testing
Sample Set #1
BOAT Constituents Detected
Ant imony
Arsenic
Barium
Beryl 1 lum
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
S i Iver
Thallium
Vanadium
Zinc
Untreated
Waste
EP TOX (ppm)
.
<0.01
<1
-
<0.01
1.38
-
<0 2
<0.01
<0 04
0.021
<0.005
-
-
-
Run
0
<1
-
0
0
-
0
<0
<0
0.
<0
-
-
-
Treated
Waste
EP TOX (ppm)
fl Run #2
.07 0.05
<1
-
.27 <0.01
.06 0.05
-
.049 0.011
.01 <0.01
.1 <0.1
.051 0.045
.05 <0.05
-
-
-
Reference 26 - Lopat Enterprises Stabilization Data
1U8
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1469g
Table 3-25 Stabilization Testing
Sample Set #2
BDAT Constituents Detected
Ant imony
Arsenic
Barium
Beryl 1 lum
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Si Tver
Thai! lum
Vanadium
Zinc
Untreated
Waste
EP TOX (ppm)
.
3.0
110
-
4.44
0.08
-
40.0
<0.01
NA
1.81
0.06
-
-
-
Treated
Waste
EP TOX (ppm)
Run #1 Run #2
_
0.01 0.01
<1 <1
-
<0.01 <0.01
0.23 0.10
-
0.006 0.027
<0.01 <0.01
<0.1 <0.1
0.033 0 010
<0 05 <0.05
-
-
-
Run #3
_
<0.01
<1
-
<0.01
0.84
-
0.18
<0.01
<0.1
0.061
<0.05
-
-
-
- = No Data.
Reference 26 - Lopat Enterprises Stabilization Data
1U9
-------
1469C]
Table 3-26 Stabilization Testing
Sample Set #3
BOAT Constituents Detected
Ant imony
Arsenic
Barium
Beryl 1 lum
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Si Iver
Thai 1 lum
Vanadium
Zinc
Untreated
Waste
EP TOX (ppm)
_
0.02
3.0
-
<0.01
0.07
-
100
<0.01
<0.1
0.009
<0.05
-
-
-
Treated
Waste
EP TOX (ppm)
Run #1 Run #2
.
0 02 0.14
^1.0 3
-
<0.01 <0.0
0.56 0.16
-
0 078 0 39
<0.01 <0.01
<0.1 <0.1
0.024 0.034
<0 05 <0.05
-
-
-
Run #3
0.11
<1
-
<0.01
0.39
-
0.054
<0.01
<0.1
0.063
<0.05
-
-
-
- - No Data
Reference 26 - Lopat Enterprises Stabilization Data
110
-------
- = No Data.
Table 3-27 Stabilization Testing
Sample Set #4
BOAT Constituents Detected
Ant imony
Arsenic
Barium
Beryl 1 lum
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Si Tver
Thai 1 lum
Vanadium
Zinc
Untreated
Waste
EP TOX (ppm)
_
<0.1
2.2
-
0.023
<0.03
-
500
0.0064
NA
<0.1
<0.02
-
-
-
Treated
Waste
EP TOX (ppm)
Run #1 Run #2
_
<0 01 <0.01
<1 <1
-
0.03 0.02
0.21 <0.05
-
0.17 0.36
<0.01 <0.01
<0.1 <0.1
0.065 0.038
<0.05 <0.05
-
-
-
Reference 26 - Lopat Enterprises Stabilization Data
111
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3.3 Other Applicable Treatment Technologies
The Agency is aware that other existing treatment technologies may be
applicable to K061. Generally, these technologies have not been
demonstrated on a commercial scale and therefore were not selected for
testing. Based on technical publications, it is evident that recycling
the waste back into the electric furnace has been attempted on a limited
basis, and is a waste minimization technique that reduces the amount of
waste requiring land disposal. The Agency encourages recycling and waste
minimization practices, however, they cannot be required because process
changes may be necessary. Several different strategies for direct
recycle of K061 to steel production have been studied. Additionally,
some recycle technologies utilize high temperature processing to prepare
the material to be reintroduced to the electric furnace for reuse.
The dust may be directly injected back into the furnace or it may be
pelletized or briquetted to improve handling. This step may involve the
addition of water and binders to improve the strength of the pellets or
briquettes. The resulting aggregate may be directly inserted into the
electric furnace, or processed by high temperature roasting or sintering
to improve the strength and composition of the pellets/briquettes.
Recycling the waste facilitates recovery of the iron and calcium for
reuse in steel making, while the volatile metals (zinc) are enriched in
the dust to the air pollution control systems. The enriched zinc dust
may be periodically purged from the system and sold as K061 to zinc
smelters.
112
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A process related to both direct recycle of pelletized dust and high
temperature metals recovery involves high temperature reduction of
pelletized dust to yield metallized iron pellets for use in cupola,
blast, or electric furnaces and a zinc dust for zinc smelters. This
process has not been demonstrated on a commercial scale for K061.
Another process which has not been demonstrated involves the recycle of
K061 as an additive to fluxes in steel production.
Hydrometallurgical extraction techniques may be applicable to K061.
These techniques involve leaching metals from the dust using acidic,
caustic, or special solutions, and then recovering metals from solution
by precipitation and/or electrolysis. The volume of residual to be land
disposed is also reduced. Hydrometallurgical technologies have limited
applicability because of their lack of selectivity for leaching specific
metals, however, and therefore, have not been developed on a commercial
scale.
The Agency does not believe that other technologies are applicable
because various physical and chemical characteristics of the waste would
not allow treatment. For example, chemical precipitation cannot be used
for this waste because the metals are already in solid form and therefore
are not amenable to precipitation. Similarly, physical separation of
metal constituents by centrifugation or magnetic separation does not
appear to be applicable because of the size, weight, and composition of
the various metal particles.
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4. IDENTIFICATION OF BEST DEMONSTRATED AVAILABLE TECHNOLOGY (BOAT)
FOR K061
4.1 Introduction
In this section, EPA explains its analyses for determining which of
the demonstrated technologies provides the best level of treatment and
also complies with the Agency's criteria for "available". As explained
in Section 1, a determination of "best" will generally involve a
statistical comparison of performance data from each of the demonstrated
treatment technologies; the statistical method used is the analysis of
variance (ANOVA) and is described in Appendix A of this document.
As discussed in Section 3, the demonstrated treatment technologies
for K061 are high temperature metals recovery and stabilization. The
Agency collected performance data for these treatment technologies from
field testing, review of literature sources, and data submitted by
industry. Performance data consists of 55 data sets for the treatment of
K061 by high temperature metals recovery and stabilization. (A data set
consists of paired untreated and treated waste analytical data).
Specifically, the Agency has collected 15 data sets for high temperature
metals recovery (7 for rotary kiln, 2 for plasma arc reactor, 3 for
rotary kiln/electric furnace, 2 for molten slag reactor and 1 for flame
reactor). 40 data sets for stabilization of K061 were also collected.
4.2 Data Screening
As discussed in Section 1, in cases where EPA has data from more than
one technology, the Agency first screens the data to ensure performance
114
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comparisons are made on data of comparable quality. Screening criteria
include the design and operating parameters associated with the treated
data, the type of analytical testing (i.e., total waste concentration,
EP, or TCLP), and finally, quality control/quality assurance analyses.
Below is a discussion of the results of applying the above screening
criteria to the 15 data sets for high temperature metal recovery and the
40 data sets for stabilization.
Fifteen data sets were considered in the development of BOAT for high
temperature metals recovery. Twelve of these data sets were deleted
because they did not meet the requirements of the BOAT program. For the
rotary kiln process, 4 of the 7 data sets were deleted due to poor
operation of the treatment system during the time data were being
collected.
The two data sets from the plasma arc reactor system were deleted for
several reasons. The first set was deleted because the data did not
include TCLP analysis for the treated residual, and analytical quality
assurance/quality control data were incomplete. For the second data set,
the analytical testing was also incomplete as were the quality assurance
quality control data. Additionally, insufficient design and operating
data were submitted. Therefore, these data could not be used to assess
the treatment performance of the plasma arc reactor sytem.
The three data sets for the rotary hearth/electric furnace system
included incomplete analytical results, and did not contain design and
operating data or quality assurance/quality control analyses.
115
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Specifically, only TCLP analyses for the untreated and treated waste were
performed. In addition, analyses were only provided for a limited number
of BOAT list metal constituents. These data were not sufficient for the
Agency to assess treatment performance.
The two data sets for the molten slag reactor were not used to
determine BOAT because the data collected did not include complete
analytical testing and analytical quality assurance/quality control
analyses. These data only included total waste concentration and EP
Toxicity analysis for the untreated and treated waste. Additionally, no
design and operating data were included.
One data set for the flame reactor system was collected. These data
included limited analytical testing (total concentration for only four
constituents and no TCLP analyses). Additionally, the design and
operating data collected were inadequate to evaluate treatment
performance so these data were deleted from consideration.
For stabilization of K061, 40 data sets were collected. Thirty-one
of these data sets were deleted for the following reasons. For twenty
one data sets collected from one facility, only EP Toxicity analyses were
performed on the stabilized waste and was only performed for cadmium,
chromium, and lead. Additionally, no design and operating data and
quality assurance/quality control data were submitted. Ten data sets
collected from another facility were also deleted because they only
contained EP Toxicity data for the untreated and treated wastes and
contained no quality assurance/quality control or design and operating
data.
116
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Nine data sets for stabilization using three different binding
agents: cement, kiln dust, and lime/fly ash, met the requirements of the
program. The design and operating data collected during testing did not
indicate that the system was poorly designed or poorly operated.
Therefore, these data sets were used to determine the best demonstrated
available technology for K061.
4.3 Data Accuracy
After the screening tests, EPA adjusted the remaining analytical data
based on the analytical recovery values in order to take into account
analytical interferences associated with the chemical makeup of the
treated sample. In developing recovery data (also referred to as
accuracy data), EPA first analyzed a waste for a constituent and then
added a known amount of the same constituent (i.e., spike) to the waste
material. The total amount recovered after spiking minus the initial
concentration in the sample divided by the amount added is the recovery
value. The analytical data used to identify BOAT were adjusted for
accuracy using the lowest recovery value for each constituent. This
adjustment ensures that treatment data from high temperature metals
recovery and stabilization can be compared on an equal basis.
4.4 Analysis of Variance
Following accuracy adjustments of the performance data remaining
after the screening process, EPA then compared the performance data using
the ANOVA to determine which, if any, of the two demonstrated technologies
provides the best treatment. As mentioned, these technologies are high
temperature metal recovery and stabilization. For K061, performance was
117
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compared from two standpoints: 1) the total composition of the BOAT list
metals remaining after treatment and 2) the amount of metal found in the
leachate from the TCLP.
Relative to the first criteria, high temperature metal recovery was
clearly better in that stabilization is not meant to reduce the amount of
a constituent present but rather minimize the amount that can be
leached. Accordingly, the Agency did not perform any statistical
analysis comparing the performance of these technologies on a total
constituent basis.
Relative to the TCLP, the Agency compared the leachate concentrations
of the following BOAT list metals following high temperature metals
recovery and stabilization. Prior to this comparison, EPA examined the 3
types of stabilization that use different binding agents: cement, kiln
dust, and lime/fly ash to determine which type provides the "best"
stabilization treatment. The best stabilization was determined to be
lime/fly ash. A comparison of lime/fly ash stabilization to high
temperature metals recovery was made based on the TCLP values of the
following BOAT list metals: cadmium, chromium, lead, mercury, and zinc.
The treated values for these metals achieved by high temperature metals
recovery and stabilization are shown in Table 4-1.
The results of the ANOVA test are presented in Appendix D. They
indicate that high temperature metals recovery provides significantly
better treatment for lead and zinc and equivalent (i.e., no significant
difference in treatment performance) treatment for cadmium, chromium, and
118
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lS34g
Table 4-1 Data for ANOVA Between High Temperature Metals Recovery and Stabilization
(Accuracy Corrected Values)
1
High Temperature Metals Recovery |
Treated Waste (mg/1) |
Const ituent
Cd (TCLP)
Cr (TCLP)
Pb (TCLP)
Hg (TCLP)
Zn (TCLP)
SS #5
<0.069
<0 lib
<0 033
<0 0002
0 246
SS #4
<0.069
<0.118
<0.033
0 0030
0.131
SS #7 |
1
<0.069 |
<0 118 |
<0.033 |
<0 0002 |
0.0820 |
1
Const ituent
Cd (TCLP)
Cr (TCLP)
Pb (TCLP)
Hg (TCLP)
Zn (TCLP)
Stabilization (Lime/Fly Ash)
Treated Waste (mg/1)
SS #7
0.036
0.113
0.140
0.0015
0.681
SS #8
0.053
0.087
0.064
0.0015
0.206
SS #9
0.080
0.065
0.061
0.0016
0.458
Reference 20 - Onsite Engineering Report for Horsehead Resource Development Co., Inc.
Reference 21 - Onsite Engineering Report for Waterways Experiment Station for K061
119
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mercury; accordingly, high temperature metal recovery is also "best"
relative to the amount of BOAT list metals found in the leachate from the
TCLP value.
In addition to being "best" and "demonstrated", high temperature
metals recovery also complies with the criteria for "available". High
temperature metals recovery is commercially available or can be purchased
from a proprietor, and high temperature metals recovery provides
substantial reduction of the concentration of BOAT list metal
constituents. Because EPA has determined that this technology is "best",
"demonstrated", and "available", high temperature metal recovery is the
technology basis for treatment standards for K061.
In addition to being the best technology, high temperature metals
recovery provides for resource recovery and reduction in volume of the
residual to be land disposed. The Agency believes that establishing
recovery as the best demonstrated available technology is consistent with
the national policy identified in HSWA by which Congress set up a
hierarchy of waste management alternatives. The hierarchy places source
reduction as the first priority of waste management, with recycling as
the second, treatment as the next, and land disposal as the last.
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5. SELECTION OF REGULATED CONSTITUENTS
As discussed in Section 1, the Agency has developed a list of
hazardous constituents (Table 1-1) from which the constituents to be
regulated are selected. The list is a "growing list" that does not
preclude the addition of new constituents as additional key data and
information become available. The list is divided into the following
nine categories: volatile organics, semivolatile organics, metals,
inorganics other than metals, organochlorine pesticides, phenoxyacetic
acid herbicides, organophosphorous pesticides, PCBs, and dioxins and
furans. Also discussed in Section 1 is EPA's process for selecting
constituents to regulate. In general, this process consists of
identifying constituents in the untreated waste that are present at
treatable concentrations and then regulating the constituents in that
group necessary to ensure effective treatment. Below is a discussion
that details how EPA arrived at the list of constituents to be regulated
for K061.
Of the 232 constituents on the BOAT list, EPA analyzed for
153 organics, 15 metals, and 3 inorganic compounds. Forty-two
constituents, including organochlorine pesticides, phenoxyacetic acid
herbicides, organophosphorus insecticides, PCBs, and dioxins and furans,
were not analyzed because they have a very low probability of being found
in the waste. In addition, eighteen constituents have been added to the
BOAT list since the time of sampling and therefore, were not analyzed,
such as hexavalent chromium and xylenes. EPA's analysis showed that five
121
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organics and fifteen BOAT list metals were present. (Table 5-1 shows the
specific constituents that were analyzed and detected in the K061
waste.) Of the one volatile and four semivolatile BOAT list organics
detected in the untreated waste, none were present at treatable
concentrations. Of the 15 BOAT list metals, only five were determined to
be present at levels that could be treated using the rotary kiln process
for high temperature metals recovery. These metals are cadmium,
chromium, lead, mercury, and zinc.
Table 5-2 presents the three data sets representing a well-operated
rotary kiln high temperature metals recovery system for these five
constituents. EPA is regulating all of these metals both with regard to
the total concentration and the concentration of the metals in the
leachate from the TCLP. The total constituent concentration is being
used because the underlying principle of metals recovery is the reduction
of the amount of metals in the waste by separating the metals for
recovery; therefore, total constituent concentration in the treated
residual is an important measure of performance for high temperature
metals recovery. Additionally, EPA believes it is important that any
remaining metal in a treated residual not be in a state that is easily
Teachable; accordingly, EPA is using the TCLP as the measure of
performance.
122
-------
170-lg
TaMe 5-1 BOAT list of Constituents-Detection
Limits for Untreated K061
BOAT Constituents
Volatile Organic Compounds
Acetorntr i le
Acrolein
Acrylon itri le
Benzene
Bromodichloromethane
Bromomethane
Carbon Tetrachlor ide
Carbon disulfide
Chlorobenzene
2 Chloro- 1 , 3-butadiene
Chlorodibromomethane
Chloroethane
2-Chloroethyl vinyl ether
Ch loroform
Chloromethane
3-Chloropropene
1 , 2-Dibromo-3-chloropropane
1 , 2-Dibromoethane
Dibromomethane
Trans -1 ,4-Dich loro-2-butene
Dichlorodif luoromethane
1, 1-Dichloroethane
1 ,2-Dichloroethane
1 , 1-Dichloroethy lene
Trans -1 , 2-Dichloroethene
1 ,2-Dichloropropane
Trans- 1 , 3-Dichloropropene
cis-l,3-Dichloropropene
1 ,4-Dioxane
Ethyl cyanide
Ethyl methacry late
lodomethane
Isobutyl alcohol
Methyl ethyl ketone
Methyl methacrylate
Methyl methanesu Ifonate
Units
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
D = Detected
ND = Not Detected
NA = Not Analyzed
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Detection
Limit
100
100
100
5
5
10
5
5
5
100
5
10
10
5
10
100
10
5
5
100
10
5
5
5
5
5
5
5
200
100
100
50
200
10
100
200
123
-------
1704q
Table 5-1 (Continued)
BOAT Const ituents
Volatile Organic Compounds
i cont inued)
Methylacrylonitn le
Methylene chloride
Pyr idine
i , 1 , 1 , 2-Tetrachloroethane
1,1,2, 2-Tetrachloroethane
Tetrachloroethene
Toluene
Tr ibromomethane
1,1,1 -Trichloroethane
1 , 1 , 2-Tnchloroethane
Tr ichloroethene
Trichloromonof luoromethane
1,2 ,3- Inch loropropane
Vinyl chloride
Semivolat i le Organic Compounds
Acenaphtha lene
Acenaphthene
Acetophenone
2-Acetylaminof luorene
4-Aminobiphenyl
An i 1 me
Anthracene
Aramite
Units
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
D = Detected
ND = Not Detected
NA - Not Analyzed
ND
ND
ND
ND
ND
D
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Detection
Limit*
100
5
400
5
5
5
5
5
5
5
5
5
5
10
400
400
800
800
800
400
400
NA
*NA = No detection limit available
124
-------
l/04g
Table 5-1 (Continued)
bDAl Constituents
Semivolatile Orqanic Compounds
Benz (a) anthracene
Benzenethiol
Benz idine
Benzo(a)pyrene
Benzo(b)f luoranthene
Benzo(ghi jperylene
Benzo(k)f luoranthene
p-Benzoqu inone
Bis( 2- chloroethoxy) ethane
Bis(2-chloroethyl ) ether
Bis(2-chloroisopropy 1) ether
Bis(2-ethylhexyl)phthalate
4-Bromophenyl phenyl ether
Butyl benzyl phthalate
2-sec-Buty 1-4,6-dinitrophenol
p-Chloroani 1 me
Chlorobenzi late
p-Chloro-m-cresol
2-Chloronaphthalene
2-Chlorophenol
3-Chloropropiomtri le
Chrysene
ortho-Cresol
para-Cresol
D i benz ( a, h) anthracene
Dibenzo(a,e)pyrene
Dibenzofa, i jpyrene
m-Dichlorobenzene
o-Dichlorobenzene
p-Dichlorobenzene
D
Units ND
NA
(cont mued)
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
= Detected
= Not Detected
= Not Analyzed
ND
ND
ND
ND
D
ND
ND
ND
ND
ND
ND
D
ND
ND
ND
ND
ND
ND
ND
ND
ND
D
ND
ND
ND
ND
ND
ND
ND
ND
Detection
Limit
400
-
2,000
400
400
400
400
-
400
400
400
400
400
400
200
400
NA
400
400
400
NA
400
400
400
400
NS
NA
400
400
400
NA = No detection limit available
NS = No standards available.
- = Not detected, estimated detection liaison has not been established.
125
-------
1704g
Table 5-1 (Continued)
BOAT Constituents
D = Detected Detection
Units ND = Not Detected Limit*
NA = Not Analyzed
Semivolat i le Organic Compounds
(cont inued)
3,3 ' -Dichlorobenz idine
2,4-Dichlorophenol
2,6-Dichlorophenol
Diethyl phthalate
3,3 ' -Dimethoxybenzidine
p- Dimethyl am inoazobenzene
3,3'-Dimethylbenzidine
2,4-Dimethylphenol
Dimethyl phthalate
Di-n-butyl phthalate
1 ,4-Dinitrobenzene
4,6-Dinitro-o-cresol
2,4-Dimtrophenol
2,4-Dinitrotoluene
2,6-Dimtrotoluene
Di-n-octyl phthalate
Di-n-propylnitrosamine
1 ,2-Diphenylhydrazine
Fluoranthene
Fluorene
Hexachlorobenzene
Hexachlorobutadiene
Hexachlorocyclopentadlene
Hexachloroethane
Hexachlorophene
Hexach loropropene
Indenofl ,2,3-cd)pyrene
Isosaf role
Methapyri lene
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
Ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ND
ND
ND
NO
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
D
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
800
400
400
400
400
800
NA
400
400
400
2,000
1,980
1,980
400
400
400
400
2,000
400
400
400
400
400
400
NA
ND
400
800
NS
*NA = No detection limit available.
NS = No standard available.
126
-------
1704g
Table 5-1 (Continued)
BOAT Constituents
Semivolatile Orqanic Compounds
(cont inued)
3-Methylcholanthrene
4,4 ' -Methylenebis
(2-chloroam 1 me)
Naphtha lene
1 ,4-Naphthoqumone
1-Naphthylamine
2-Naphthylamme
p-Nitroam 1 me
Nitrobenzene
4-Nitrophenol
N-Nitrosodi-n-butylamme
N-Nitrosodiethylamine
N-Nitrosodimethylamme
N Nltrosomethylethy lam me
N-Nitrosomorphol me
N-Nitrosopiper idine
n-Nitrosopyrrolidme
5-Nitro-o-toluidme
Pentachlorobenzene
Pentachloroethane
Pentachloronltrobenzene
Pentachlorophenol
Phenacet in
Phenanthrene
Phenol
2-Picoline
Pronamide
Pyrene
Resorcmol
Saf role
Units
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
PPb
ppb
ppb
ppb
ppb
PPb
ppb
PPb
PPb
ppb
PPb
ppb
PPb
ppb
ppb
PPb
ppb
PPb
PPb
D = Detected
ND = Not Detected
NA = Not Analyzed
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Detect ion
Limit*
800
800
400
NA
2,000
2,000
1,980
400
1,980
-
400
400
400
800
400
2,000
800
-
NA
4,000
1,980
800
400
400
400
-
400
NA
2,000
'NA = No detection limit available
- = Not detected, estimated detection limit has not been established
127
-------
1704g
Table 5-1 (Continued)
BOAT Constituents Units
Semwolat i le Organic Compounds
(continued)
] ,2,4, 5-Tetrachlorobenzene ppb
2,3,4,6-Tetrachlorophenol ppb
1 ,2,4-Trichlorobenzene ppb
2,4, 5-Tnchlorophenol ppb
2,4,6-Trichlorophenol ppb
T r i s ( 2 , 3-d i bromopropy 1 )
phosphate ppb
Metals1
Ant imony
Arsenic
Barium
Beryl 1 lum
Cadmium
Chromium (total)
Copper
Lead
Mercury
Nickel
Selenium
Si Iver
Tha 1 1 lum
Vanadium
Zinc
Inorganics
Cyanide
F luor ide
Sulf ide
Orqanochlonne Pesticides
Aldrin
alpha-BHC
beta-BHC
delta-BHC
D = Detected
ND = Not Detected
NA = Not Analyzed
ND
ND
ND
ND
ND
ND
D
D
D
D
D
D
D
D
D
D
D
D
D
D
D
D
D
D
NA
NA
NA
NA
Detection
Limit
800
-
400
1,980
400
-
1
70.4
5.6
All BOAT list metals were detected at concentrations above the detection
1 units
128
-------
1704g
Table 5-1 (Continued)
D = Detected Detection
BOAT Constituents Units ND = Not Detecte-i Limit
NA = Not Analyzed
Orqanochlorlne Pesticides (continued)
gamma-BHC NA
Chlordane NA
ODD NA
DDE NA
DDT NA
Dieldrin NA
Endosulfan I NA
Endosulfan II NA
Endrin NA
Endrin aldehyde NA
Heptachlor NA
Heptachlor epoxide NA
Isodrin NA
Kepone NA
Methoxychlor NA
Toxaphene NA
Phenoxyacetic Acid Herbicides
2,4-Dichlorophenoxyacetic acid NA
Silvex NA
2.4.5-T NA
Orqanophosphorous Insecticides
Disulfoton NA
Famphur NA
Methyl parathion NA
Parathion NA
Phorate NA
PCBs
Aroclor 1016 NA
Aroclor 1221 NA
Aroclor 1232 NA
Aroclor 1242 NA
Aroclor 1248 NA
Aroclor 1254 NA
Aroclor 1260 NA
129
-------
1704y
Table 5-1 (Continued)
EDAT Constituents
D - Detected Detection
Units NO = Not Detected Limit*
NA = Not Analyzed
Dioxins and Furans
Hexachlorodibenzo-p-diox ins
Hexachlorodibenzofurans
Pentachlorodibenzo-p-dioxins
Pentachlorodibenzofurans
Tetrachlorodibenzo-p-dioxins
Tetrachlorodibenzofurans
2,3,7,8-Tetrachlorodibenzo-p-dioxin
NA
NA
NA
NA
NA
NA
NA
130
-------
Table 5-2 Regulated Constituent Reduction by High Temperature
Metals Recovery (Rotary Kiln) - Range of 3 Data Sets
EPA Collected Data (Treated Values are Accuracy Corrected Values)
Untreated Treated TCLP Treated
Waste Waste Waste
Constituent (ppm) (ppm) (mg/1)
Cadmium 394 - 800 <15.6 <0.069
Chromium 903 - 1,190 500 - 1,027 <0.1i8
Lead 15,500 - 20,800 569 - 3,697 <0.33
Mercury 1.0 - 1.6 <0.1 <0.0002 - 0.0030
Zinc 135,000 - 155,000 5,369 - 13,216 0.0820 - 0.246
Reference 20 - Onsite Engineering Report for Horsehead Resource and Development Co., Inc.
131
-------
6. CALCULATION OF BOAT TREATMENT STANDARDS
This Section presents the calculation of treatment standards for
K061. Details of the methodology are provided in Section 1 and in the
"Generic Quality Assurance Project Plan (QAPP) for the Land Disposal
Restriction Program (BOAT)," March, 1987. As discussed in Section 5, the
BOAT treatment standards are proposed for the regulated constituents
cadmium, chromium, lead, mercury, and zinc. These standands are based on
treatment performance data collected by the Agency for the rotary kiln
process for high temperature metals recovery. As presented in Section 4,
several data sets submitted by industry could not be used because they
did not contain sufficient analytical data to evaluate the system. In
addition, many of these data sets also lacked design and operating data
and quality assurance/quality control data. Also presented in Section 4
was the Agency's methodology for determining that the rotary kiln process
for high temprature metals recovery provides better treatment than
stabilization. Treatment standards for K061 are being proposed for both
total concentration and the TCLP leachate from the nonwastewater
residuals.
The BOAT treatment standards (1) are reflective of treatment data
from a well designed and well operated treatment system, (2) account for
analytical uncertainty, and (3) account for variability resulting from
treatment, sampling, and analytical techniques and procedures.
The BOAT treatment standards for K061 were developed following the
following methodology.
132
-------
6.1 Screening of Data
As the first step in the development of BOAT treatment standards, EPA
screened the available treatment performance data with regard to three
criteria: (1) design and operation, (2) quality assurance/quality
control analyses and (3) the analytical tests used to assess performance.
The performance data collected for treatment of K061 were screened
for completeness with regard to design and operating data, quality
assurance/quality control analyses, and analytical testing used. A
complete data set consists of paired untreated and treated waste analyses
for BOAT metals, including total concentration and TCLP extract analyses
for the treated residual, design and operating data, and quality
assurance/quality analyses. For high temperature metals recovery,
treatment performance is judged on both total constituent reduction and
the Teachability of the treated residuals, as measured by TCLP. For
stabilization, which is used to reduce the leachability of metals, the
Agency is using the TCLP as the measure of performance. Several data
sets collected did not contain the required data to evaluate the
treatment performance, and threfore were not used to determine BOAT.
As described in Section 4, four of the seven data sets for high
temperature metals recovery (rotary kiln process) were deleted due to
poor operation of the treatment system during the time data were being
collected. Nine data sets for stabilization using three different
133
-------
binding agents: cement, kiln dust, and lime/fly ash, contained all of
the required data elements. The design and operating data collected
during stabilization testing did not indicate that the system was poorly
designed or operated.
Following these data screening procedures, the performance data for
high temperature metals recovery were compared to stabilization using the
analysis of variance test (ANOVA) to determine which technology provides
the best treatment for the regulated constituents cadmium, chromium,
lead, mercury, and zinc.
As presented in Section 4, the ANOVA was performed on 3 data sets for
high temperature metals recovery (rotary kiln process) and 3 data sets
from lime/fly ash stabilization. The comparison was performed on
accuracy corrected values for the regulated constituents to account for
analytical variability. High temperature metals recovery was identified
as the "best" treatment technology for K061 based on the ANOVA using
these accuracy corrected performance data.
6.2 Correction of Analytical Data
The analytical data used to select BOAT and calculate treatment
standards are adjusted in order to take into account analytical
interferences associated with the chemical composition of the sample.
Because of the concentration of the various constituents of the residual
slag, the detection limits attainable for lead, cadmium, and chromium for
134
-------
both total treated concentration and TCLP, varied due to interferences.
Generally, where this occurred, we selected the highest detection limit
measured to develop treatment standards because the low detection limits
may not be consistently achievable.
The treated analytical data are corrected for accuracy by multiplying
the raw data by a correction factor. The correction factors are
calculated based on the matrix spike recoveries performed for each
regulated constituent (total concentration and TCLP). Additionally, two
matrix spike recoveries are performed for each constituent, and the
lowest value is used to calculate the correction factor. As a result,
the correction factor used to develop treatment standards is conservative
to account for analytical variability and uncertainty. The correction
factors are calculated by dividing the lowest recovery into 100 to
provide the most conservative correction factor. The matrix spike
recoveries and accuracy correction factors for total concentration for
high temperature metals recovery are presented in Table 6-1. The matrix
spike recoveries and accuracy correction factors for TCLP extracts for
high temperature metals recovery are presented in Table 6-2. Table 6-3
presents the percent recoveries and correction factors for the TCLP
extracts for stabilization.
The accuracy corrected data were calculated by multiplying the
analytical value by the correction factor. If a regulated constituent
135
-------
1351g
Table 6-1 Matrix Spike Recoveries for Treated Waste Total Concentrations and Accuracy Correction Factors
for High Temperature Metals Recovery
BOAT constituent
Cadmium
Chromium
Lead
Mercury
Zinc
Original amount Spike added
found (mg/kg) (mg/kg)
<1.5 2 5
978 2.000
365 500
<0.1 0.5
4,680 6.000
Sample
Spike result
(mg/kg)
<1 5
2.970
683
0.5
9,770
Sample ciupl icate
Percent
recovery*
NC
100
64
100
85
Spike added
(mg/kg)
2 5
2.000
500
0.5
6,000
Spike result
(mg/kg)
2 4
2,870
705
0 5
9,950
Percent
recovery*
96
95
68
100
88
Correct ion
Factor
1 04
1 05
1.56
1.00
1 18
NC = Not Calculatable.
to *Percent Recovery = [(Spike Result - Original Amount)/Spike Added] x 100.
Reference 20 - Onsite Engineering Report for Horsehead Resource Development Co., Inc.
-------
1351 g
Table 6-2 Matrix Spike Recovery for TCLP Extract for Treated Waste and Accuracy Correction Factors
for High Temperature Metals Recovery
BOAT constituent
Cadmium
Chromium
Lead
Mercury
Z me
*Percent Recovery =
GO
Original sample
(ug/1)
4 2
<4 0
<5 0
<0 2
2,640
[(Spike Result - Original
Sample
Spike added Spike result
(ug/1) (ug/1)
25 26
50 35
25 22
1.0 0.9
10,000 12,600
Amount) /Spike Added]* 100
Sample dupl icate
Percent
recovery*
87
70
88
90
100
Spike result
(ug/1)
27
34
19
1 1
12,400
Percent
recovery*
91
68
76
110
98
CoTect ion
Factor
1 15
1 47
1 32
1 11
1 02
-------
Table 6-3 Matrix bpike Recoveries and Accuracy Correction Factors for the TCLP Extracts from Stabilization
BOAT Regulated
Const i tuent
Cadmium
Cnromium
Lead
Mercury
Z me
Or ig ina 1
amount
found
(ug/1)
34
71
71
1 4
226
L ime/F lyash
Amount
spiked
(ug/1)
100
100
50
3
500
Amount
recovered
(ug/1)
123
140
131
5.3
690
Percent
recovery*
92
82
108
120
95
Lime/Flyash
Amount
recovered
(ug/1)
122
142
138
4.8
632
Percent
recovery*
91
83
114
110
87
Correction
Factor
1.09
1.22
0.93
0.91
1.15
^Percent Recovery = [(Spike Result - Original Amount)/Spike]* 100.
Reference 21 - Onsite Engineering Report for Waterways Experiment Station for K061
138
-------
was not detected in the treated waste, the corrected value was calculated
by multiplying the detection limit of that constituent by the correction
factor. These accuracy corrected data are then used to evaluate the
treatment standard by multiplying the average treated concentration by a
variability factor.
6.3 Calculation of Variability Factors and Treatment Standards
The treatment standards for each regulated constituent (total
concentration and TCLP) are calculated by multiplying the average treated
concentration by the appropriate variability factor. For each regulated
constituent, average treated concentrations and variability factors were
calculated for both total concentration and TCLP extract. Because the
treatment standards are based on high temperature metals recovery and the
performance is evaluated by both constituent reduction and Teachability
of the residual as measured by TCLP, the variability factors are
calculated for both parameters.
The variability factor represents a variability inherant in the
treatment process and the sampling and analytical methods. Variability
factors are determined by statistically calculating the variability seen
for a number of data points for each regulated constituent (total
concentration and TCLP).
The variability factors were calculated for both total concentration
and TCLP extract for the five regulated constituents. These variability
139
-------
factors were calculated based on the logarithmic concentration values of
the regulated constituents in the treated residual (total concentration
and TCLP), their logarithmic mean and their logarithmic standard
deviation. A detailed description of the variability factor calculation
is presented in Appendix A. For regulated constituents not detected in
the treated waste in all data sets used for regulation, a variability
factor of 2.8 was used. The rationale and methodology used to calculate
this variability factor is presented in Section 1, as well as in
Appendix A.
The treatment standards were calculated by multiplying the average
treated concentration (total concentration and TCLP) by the corresponding
variability factor. This calculation is presented in Table 6-4.
The BOAT treatment standards for K061 are proposed for both total
concentration and the Teachability of the residual as measured by the
TCLP and are as follows:
Total TCLP
Constituent Concentration (mq/kq) Concentration (mq/1)
Cadmium 44 0.19
Chromium 1,730 0.33
Lead 20,300 0.09
Mercury 0.28 0.02
Zinc 24,100 0.50
140
-------
1199g
Table 6-4 Variability Factors and Calculated Treatment Standards for KOG!
Untreated Total Accuracy Adjusted
Concentration Treated Concentration
Regulated
Const ituent
Cadmium
Residual
Residual TCLP
Chromium
Residual
Residual-TCLP
Lead
Residual
Residual-TCLP
Mercury
Residual
Residual-TCLP
Zinc
Residual
Residual-TCLP
Range for Sample
SS #3,/M,#7 Set #3
(ppm)
290 to b08 <15.6
<0 069
903 to 1,190 785
<0 118
15,500 to 20,600 3,026
<0 033
1.0 to 1 6 <0 1
<0 0002
135,000 to 155,000 13,216
0.246
Sample Sample
Set #4 Set #7
<15 6 <15 6
<0 069 <0.069
1,027 500
<0 118 <0.118
569 3,697
<0 033 <0.033
<0 1 <0.1
0.0030 <0.0002
5,522 5,369
0 131 0.082
Average Treated
Concentrat ion
(mg/kg)/ (mg/1)
15 6
0 069
771
0 118
2,431
0 033
0 10
0 0011
8,036
0 153
Var lability"*
Factor
2.8
2 8
2.24
2.8
8.35
2.8
2 8
17 13
3.00
3.28
Average
xVF
43 7
0 193
1.727
0 330
20,296
0 092
0 28
0 019
24,107
0 502
Treatment
Standard
(mg/kg)/ (mg/ 1 )
44
0 19
1,730
0 33
20,300
0.09
0 28
0 02
24,100
0.50
*For constituents having values at the detection limit, a variability factor of 2.8 was used.
See Appendix 0 for the rationale
-------
7. CONCLUSIONS
The Agency has proposed treatment standards for the listed waste K061
from the iron and steel industry. The treatment standards presented in
Table 7-1 are established for total concentration and TCLP leachate of
non-wastewater residuals. The treatment standards proposed for K061 have
been developed consistent with EPA's promulgated methodology for BOAT
(November 7, 1986, 51 FR 40572).
The waste K061 is generated in the primary production of steel in
electric furnaces. This waste is primarily comprised of metals,
inorganics, and water. Although the concentrations of specific
constituents will vary from facility to facility, all of the wastes are
expected to contain concentrations of BOAT list metals, high filterable
solids contents, and low to moderate water content, and are expected to
be treatable to the same levels using the same technology.
All BOAT list metal constituents are generally present in the waste,
but in varying concentrations. As a result, to reduce the monitoring
burden on treaters, the Agency has developed the treatment standard based
on five BOAT list metals that are generally found in the highest
concentrations in K061 wastes.
Through available data bases, EPA's technology testing program, and
data submitted by industry, the Agency has identified two demonstrated
treatment technologies for treatment of BOAT list metals present in the
waste. The demonstrated treatment technologies for K061 are high
142
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1199g
Table 7-1 BOAT Treatment Standards for K061*
(As Concentration in Nonwastewater Treatment Residual)
Total TCLP
Constituent Concentration (mq/kq) Concentration (mq/1)
Cadmium 44 0.19
Chromium 1,730 0.33
Lead 20,300 0.09
Mercury 0.28 0.02
Zinc 24,100 0.50
*Both total concentration and TCLP concentration values must be complied with
prior to land disposal.
143
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temperature metals recovery and stabilization. As discussed in
Section 3, several high temperature metals recovery systems have been
demonstrated for K061: rotary kiln process, rotary hearth/electric
furnace, plasma arc reactor, molten slag reactor, and flame reactor.
Stabilization is demonstrated for treatment of K061 by the reduction of
the leachability of BOAT list metals in the treated waste. Other
technologies are potentially applicable for treatment of K061 including
hydrometallurgical extraction (acid leaching) and recycle.
In the development of treatment standards for K061, the Agency
examined all available treatment data. The Agency collected treatment
data from literature sources and received industry submitted data. The
Agency also conducted tests using high temperature metals recovery and
stabilization of K061 waste. The Agency collected 15 data sets for high
temperature metals recovery. The 15 data sets consist of seven data sets
for the rotary kiln process, two for plasma arc reactor, three for rotary
kiln/electric furnace, two for molten slag reactor system and 1 for the
flame reactor. The Agency also collected 40 data sets for stabilization
of K061. The data consists of 21 data sets from one facility, 10 data
sets from another facility and nine data sets collected by Agency testing
for three different binders: cement, kiln dust, and lime/fly ash.
Many of the data sets collected did not contain all of the required
information needed by the Agency to assess treatment performance (i.e.,
total concentration and TCLP leachate results), quality assurance/quality
control analyses data, design and operating information, and thus they
144
-------
were deleted from consideration. In addition to the analytical data for
the untreated waste and treated residual, design and operating data were
collected during the testing of each technology. For high temperature
metals recovery, the data collected by the Agency indicated that four of
the seven data sets were collected during periods of poor operation of
the treatment system. As a result, only three of the data sets from the
Agency's testing for high temperature metals recovery met the
requirements of the BOAT program.
For stabilization data, the Agency was able to analyze results from
the use of three different binders (i.e., cement, kiln dust, and lime/fly
ash) on K061 wastes. Data sets for stabilization by lime/fly ash were
considered in the development of BOAT based on an analysis of variance
(ANOVA) comparison of the three binders.
A statistical comparison of performance data for the two technologies
(high temperature metals recovery and stabilization) was performed to
identify the "best demonstrated" technology for K061. The analyses of
variance test was used to compare the TCLP extract analysis for cadmium,
chromium, lead, mercury, and zinc for the two technologies. The results
of the test indicated that high temperature metals recovery provides
superior performance for lead and zinc and that the two technologies are
equivalent (i.e., no significant difference in treatment performance) for
cadmium, chromium, and mercury. Additionally, the selection of high
temperature metals recovery as BOAT over stabilization is consistent with
the Agency's policy to promote reuse/recycling technologies that reduce
145
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the amount of hazardous waste to be land disposed. EPA also determined
that high temperature metals recovery is an available technology.
The treatment standards for K061 are based on the treatment data
collected by the Agency for high temperature metals recovery by the
rotary kiln process.
The regulated constituents were selected based on an evaluation of
the BOAT list constituents found in the untreated wastes at treatable
concentrations and were reduced in concentration in the treated
residual. All available waste characterization data and applicable
treatment data consistent with the type and quality of data needed by the
Agency for this program were used to make this determination. Five
constituents were selected for regulation: cadmium, chromium, lead,
mercury, and zinc. The treatment standards for the five regulated
constituents were derived after adjustment of laboratory data to account
for recoveries of these constituents in the analytical process.
Subsequently, the mean of the adjusted data points was multiplied by the
appropriate variability factor to derive the standard. The variability
factor represents the variability inherent in the treatment process and
sampling and analytical methods. Variability factors were determined by
statistically calculating the variability observed in a given constituent
(total concentration and TCLP) for all data sets used in developing the
standand. For constituents for which specific variability factors could
not be calculated, a variability factor of 2.8 was used (e.g., when the
146
-------
treated residua] concentration for a particular constituent is below
detectable levels for all data sets). The rationale for using this
variability factor of 2.8 is presented in Section 1 and Appendix D.
Wastes determined to be K061 may be land disposed if they meet both
of the treatment standards at the point of disposal. For K061, the
treatment standards are based on both total concentration and TCLP
extract. The total constituent concentration is being used because the
underlying principle of metals recovery is the reduction of the amount of
metals in the waste by separating the metals for recovery; therefore,
total constituent concentration in the treated residual is an important
measure of performance for high temperature metals recovery.
Additionally, EPA believes it is important that any remaining metal in a
treated residual not be in a state that is easily Teachable; accordingly,
we are using the TCLP as the measure of performance.
The BOAT technology upon which the treatment standards are based
(high temperature metals recovery) need not be specifically utilized
prior to land disposal, provided an alternate technology utilized
achieves both standards.
These proposed standards have an effective date of August 8, 1990.
This date reflects a two-year nationwide variance to the promulgation
date due to the lack of nationwide high temperature metals recovery
capacity. A detailed discussion of the Agency's determination that a
lack of capacity exists is presented in the Capacity Background Document
147
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which is available in the Administrative Record for the First Sixths'
rule.
Consistent with Executive Order 12291, EPA prepared a regulatory
impact analysis (RIA) to assess the economic effect of compliance with
this proposed rule. The RIA prepared for this proposal rule is available
in the Administrative Record for the First Sixth's Rule.
148
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REFERENCES
1. Ajax Floor Products Corp. n.d. Product literature: technical data
sheets, Hazardous Waste Disposal System. P.O. Box 161, Great
Meadows, N.J. 07838.
2. Austin, G.T. 1984. Shreve's chemical process industries, 5th ed.
New York: McGraw-Hill.
3. Bishop, P.L., Ransom, S.B., and Grass, D.L. 1983. Fixation
Mechanisms in Solidification/Stabilization of Inorganic Hazardous
Wastes. In Proceedings of the 38th Industrial Waste Conference,
10-12 May 1983, at Purdue University, West Lafayette, Indiana.
4. U.S. Bureau of Mines, 1983. Characterization of Steel Making Dusts
from Electric Furnaces. (As cited by Summary of Available Waste
Composition Data from Review of Literature and Data Bases for Use in
Treatment Technology Application and Evaluation for "California
List" Waste Streams. Prepared for EPA Office of Solid Waste by
Versar, Inc. under Contract No. 68-01-7053, Work Assignment No. 38,
April 1986.).
5. Calspan Corporation, 1977. Assessment of Industrial Hazardous Waste
Practices in the Metal and Refining Industry. (As cited by Summary
of Available Waste Composition Data from Review of Literature and
Data Bases for Use in Treatment Technology Application and
Evaluation for "California List" Waste Streams. Prepared for EPA
Office of Solid Waste by Versar, Inc. under Contract No. 68-01-7053,
Work Assignment No. 38, April 1986.).
6. U.S. Department of Commerce. Characterization, Recovery and
Recycling of EAF Dust, (by Lehigh University), 1982.
7. Conner, J.R. 1986. Fixation and Solidification of Wastes.
Chemical Engineering. Nov. 10, 1986.
8. Cullinane, M.J., Jr., Jones, L.W., and Malone, P.G. 1986. Handbook
for stabilization/solidification of hazardous waste. U.S. Army
Engineer Waterways Experiment Station. EPA report No.
540/2-86/001. Cincinnati, Ohio: U.S. Environmental Protection
Agency.
9. Delisting Petition #0535, Harrison Steel Castings Co., Attica, IN
(As cites by Summary of Available Waste Composition Data from Review
of Literature and Data Bases for Use in Treatment Technology
Application and Evaluation for "California List" Waste Streams.
Prepared for EPA Office of Solid Waste by Versar, Inc. under
Contract No. 68-01-7053, Work Assignment No. 38, April 1986.).
149
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REFERENCES (continued)
10. Delisting Petition #0555, U.S. Steel Corp., Chicago, IL. (As cited
by Summary of Available Waste Composition Data from Review of
Literature and Data Bases for Use in Treatment Technology
Application and Evaluation for "California List" Waste Streams.
Prepared for EPA Office of Solid Waste by Versar, Inc. under
Contract No. 68-01-7053, Work Assignment No. 38, April 1986.).
11. Delisting Petition #0601, Stablex Corp., Rock Hill, SC. (As cited
by Summary of Available Waste Composition Data from Review of
Literature and Data Bases for Use in Treatment Technology
Application and Evaluation for "California List" Waste Streams.
Prepared for EPA Office of Solid Waste by Versar, Inc. under
Contract No. 68-01-7053, Work Assignment No. 38, April 1986.)
12. Delisting Petition #0210, Marathon Steel Co., Longview, TX. (As
cited by Summary of Available Waste Composition Data from Review of
Literature and Data Bases for Use in Treatment Technology
Application and Evaluation for "California List" Waste Streams.
Prepared for EPA Office of Solid Waste by Versar, Inc. under
Contract No. 68-01-7053, Work Assignment No. 38, April 1986.).
13. Delisting Petition #0250, McClouth Steel Products Co., Trenton, MI.
(As cited by Summary of Available Waste Composition Data from Review
of Literature and Data Bases for Use in Treatment Technology
Application and Evaluation for "California List" Waste Streams.
Prepared for EPA Office of Solid Waste by Versar, Inc. under
Contract No. 68-01-7053, Work Assignment No. 38, April 1986.).
14. Delisting Petition #0443, Raritan River Steel, Perth Amboy, NJ. (As
cited by Summary of Available Waste Composition Data from Review of
Literature and Data Bases for Use in Treatment Technology
Application and Evaluation for "California List" Waste Streams.
Prepared for EPA Office of Solid Waste by Versar, Inc. under
Contract No. 68-01-7053, Work Assignment No. 38, April 1986.).
15. Delisting Petition #0617, Bethlehem Steel, Steelton, PA. (Industry
Submitted Data)
16. Duby, Paul. 1980. Extractive metallurgy, In Kirk-Othmer
encyclopedia of chemical technology. Vol. 9, p. 741.
17. Electric Power Research Institute. 1980. FGD sludge disposal manual,
2nd ed. Prepared by Michael Baker Jr., Inc. EPRI CS-1515
Project 1685-1 Palo Alto, California: Electric Power Research
Institute.
150
-------
REFERENCES (continued)
18. U.S. Environmental Protection Agency. Background Listing Document,
November 14, 1980.
19. U.S. Environmental Protection Agency. Engineering Analysis of the
Production of Electric Arc Furnace Steel, Draft Report, 1987.
20. U.S. Environmental Protection Agency. Onsite Engineering Report for
Horsehead Resource Development Company for K061, Draft Report, 1987.
21. U.S. Environmental Protection Agency. Onsite Engineering Report for
Waterways Experiment Station for K061, Draft Report, 1988.
22. U.S. Environmental Protection Agency. U.S. Army Engineer Waterways
Experiment Station. Guide to the disposal of chemically stabilized
and solidified waste. Prepared for MERL/ORD under Interagency
Agreement No. EPA-IAG-D4-0569. PB81-181505. Cincinnati, Ohio.
23. Description of INMETCO's Operations and Identification of the
Materials that it Processes (Industry Submitted Data).
24. Lloyd, Thomas. 1980. Zinc compounds. Kirk-Othmer Encyclopedia of
Chemical Technology, 3rd. ed. Vol. 24, p. 856.
25. Lloyd, Thomas, and Showak, Walter, 1980. Zinc and zinc alloys. In
Kirk-Othmer encyclopedia of Chemical Technology, 3rd. ed. Vol. 24,
p. 824.
26. Lopat Enterprises, 1987. A Representative Selection of Laboratory
Experiments and Reports of Full-Scale Commercial Use Which
Demonstrate the Effectiveness of K-20 Lead-in-Soil Control System in
Physical Chemical Solidification, Fixation, Encapsulation and
Stabilization of Certain Contaminated Soil, Ash, Debris, and Similar
Wastes.
27. Maczek, Helnut and Kola, Rolf, 1980. Recovery of zinc and lead from
electric furnace steelmaking dust at Berzelius. Journal of Metals.
32:53-58.
28. Mishuck, E. Taylor, D.R., Telles, R. and Lubowitz, H. 1984.
Encapsulation/ Fixation (E/F) mechanisms. Report No.
DRXTH-TE-CR-84298. Prepared by S-Cubed under Contract No.
DAAK11-81-C-0164.
29. Pojasek RB. 1979. "Sol id-Waste Disposal: Solidification" Chemical
Engineering 86(17): 141-145.
151
-------
REFERENCES (continued)
30. Price, Laurence. Tensions Mount in EAF Dust Bowl. Metal
Producing. February 1986.
31. SKF Plasmadust, Key Data for the Scandust Plant for Treating EAF
Flue Dust (K061), August, 1987. (Industry Submitted Data)
32. St. Joe Flame Reactor Process for EAF Dust (Industry Submitted Data)
33. Sumitomo Corporation of America, On-site Treatment of EAF Dust Via
the NMD System Using Sensible Heat From Molten Slag, 1987.
(Industry submitted data)
152
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APPENDICES
-------
APPENDIX A
A.1 F Value Determination for ANOVA Test
As noted earlier in Section 1.0, EPA is using the statistical method
known as analysis of variance in the determination of the level of
performance that represents "best" treatment where more than one
technology is demonstrated. This method provides a measure of the
differences between data sets. If the differences are not statistically
significant, the data sets are said to be homogeneous.
If the Agency found that the levels of performance for one or more
technologies are not statistically different (i.e., the data sets are
homogeneous), EPA would average the long term performance values achieved
by each technology and then multiply this value by the largest
variability factor associated with any of the acceptable technologies.
If EPA found that one technology performs significantly better (i.e., the
data sets are not homogeneous), BOAT would be the level of performance
achieved by the best technology multiplied by its variability factor.
To determine whether any or all of the treatment performance data
sets are homogeneous using the analysis of variance method, it is
necessary to compare a calculated "F value" to what is known as a
"critical value." (See Table A-l.) These critical values are available
in most statistics texts (see, for example, Statistical Concepts and
Methods by Bhattacharyya and Johnson, 1977, John Wiley Publications, New
York).
Where the F value is less than the critical value, all treatment data
sets are homogeneous. If the F value exceeds the critical value, it is
153
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necessary to perform a "pair wise F" test to determine if any of the sets
are homogeneous. The "pair wise F" test must be done for all of the
various combinations of data sets using the same method and equation as
the general F test.
The F value is calculated as follows:
(i) All data are natural logtransformed.
(ii) The sum of the data points for each data set is computed (T.).
(iii) The statistical parameter known as the sum of the squares
between data sets (SSB) is computed:
SSB =
where:
k = number of treatment technologies
n-j = number of data points for technology i
N = number of data points for all technologies
T.J = sum of natural logtransformed data points for each technology.
(iv) The sum of the squares within data sets (SSW) is computed:
k
I
i-1
I11']
ni
-
" k
&T'
N
d <
SSW =
where:
XH •;
1=1 j=l
k
- I
= the natural logtransformed observations (j) for treatment
technology (i).
(v) The degrees of freedom corresponding to SSB and SSW are
calculated. For SSB, the degree of freedom is given by k-1. For SSW,
the degree of freedom is given by N-k.
154
-------
(vi) Using the above parameters, the F value is calculated as
follows:
MSB
F = MSW
where:
MSB = SSB/(k-l) and
MSW = SSW/(N-k).
A computational table summarizing the above parameters is shown below.
Computational Table for the F Value
Source
Between
Within
Degrees of
freedom
K-l
N-k
Sum of
squares
SSB
SSW
Mean square
MSB = SSB/k-1
MSW = SSW/N-k
F
MSB/MSW
Below are three examples of the ANOVA calculation. The first two
represent treatment by different technologies that achieve statistically
similar treatment; the last example represents a case where one
technology achieves significantly better treatment than the other
technology.
155
-------
179Lg
Example 1
Methylene Chloride
MCJIT st r ipj) rvl
Irit luent
(/'(] 1)
15L,0 00
U'90 00
1T40 00
MOO 00
1-150 00
4t.OO 00
i/CO 00
.'•100 00
4hOO 00
IL'100 00
df f luur.l
i/iQ' i;
10 00
10 00
10 00
12 00
10 00
10 00
10 00
10 00
10 00
10 00
Bioloqical treatment
i;i(cff l^ent) [ln(eff luent)] Influent Effluent In(effluent)
2 50
2 oO
? 30
2 48
2 30
2 30
2 30
2 oO
? 30
2 30
Ug/1) Ug/1)
5.29 1960 00 10 00 2.30
5.29 2568 00 10.00 2.30
5 29 1B17 00 10.00 2 30
6 15 1640.00 26 00 3.26
5.29 3907 00 10.00 2.30
5.29
5.29
5.29
5 29
5 29
[ln(eff luent)]2
5 29
5 29
5 29
10 63
5.29
23 18
53 76
12.46
31.79
'"ample Size
10 10
Mean
3669 10 2
Standard Devlation.
3328 67 63
Vanabi 1 ity Factor
1 15
10
2 32
06
2378
923 04
13.2
7.15
2 48
2.49
.43
ANOVA Calculations.
SSB =
SSW =
>
k
MSB = SSB/(k
T,2
n i
?' x2
ii
i)
MSW - SbW/(N-k)
T,2
156
-------
Example 1 (continued)
r = MSB/MSW
wnere
h, = number of treatment technologies
n = number of data points for technology i
i
N = number of natural log transformed data points for all technologies
T = sum of log transformed data points for each technology
i
X = the nat log transformed observations (j) for treatment technology
n - 10, n = 5, N = 15, k = 2, T = 23 18, T - 12.46, T = 35 64, T = 1270 21
12 1 2
T = 5o7 31 T = 155.25
537 31 155 25
10
1270.21
15
= 0.10
MSB = 0 10/1 = 0 10
MSW = 0 77/13 = 0 06
0 10
F
= 1 67
0.06
10
= 0.77
ANOVA Table
Degrees of
Source freedom
Between (B) 1
Within(W) 13
SS MS F
0.10 0 10 1.67
0.77 0.06
The critical value of the F test at the 0 05 significance level is 4.67 Since
the F value is less than the critical value, the means are not significantly
different (i e., they are homogeneous)
Note All calculations were rounded to two decimal places. Results may differ
depending upon the number of decimal places used in each step of the calculations
157
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Example 2
Tr icbloroethylene
Meam str ippmq
I nf luent
Ua/l)
1650 00
WOO 00
SOOO 00
1720 00
1560 00
10300 00
210 00
1600 00
204 00
160 00
Effluent
Ug'l)
10 00
10 QO
10 00
10 00
10 00
10 00
10 00
27 00
85 00
10 00
ln(eff luent)
2 30
2 30
2 30
2 30
2 30
2.30
2 30
3.30
4 44
2 30
[In(effluent)]2
5.29
5 29
5 29
5 29
5.29
5 29
5.29
10.89
19.71
5.29
Influent
Ug/D
200 00
224 . 00
134 00
150 00
484 00
163 00
182 00
Biological treatment
Effluent
(ug/l)
10.00
10.00
10.00
10.00
16.25
10.00
10.00
ln(eff luent)
2.30
2.30
2.30
2.30
2.79
2.30
2.30
[In(effluent)]2
5.29
5.29
5.29
5.29
7.78
5 29
5.29
bample Size
10 10
Mean
27CO
19.2
Standard Deviation
3209 6 23 7
Var idbi1ity Factor.
?6 14
10
2 61
.71
72 92
16 59
39 52
220
120.5
3 70
10 89
2.36
1 53
2.37
19
ANOVA Calculations
SSB . f I lJjl
1=1 m
k ni -
SSW - 2 2, x2
MSB = SSB/(k-l)
MSW = SSW/(N-k)
1?1T'
158
-------
1790g
F
Example 2 (continued)
where
k = number of treatment technologies
n = number of data points for technology i
i
N = number of data points for all technologies
T = sum of natural log transformed data points for each technology
X = the natural log transformed observations (j) for treatment technology
2 2
N = 10, N = 1, N = 17, k = 2, T = 26 14, T = 16.59, T = 42.73, T = 1825.85, T = 683.30,
275 23
10
1825 85
SSW = (72 92 + 39 52) -
MSB = 0 25/1 - 0 25
MSW = 4 79/15 = 0 32
0 25
F = = 0 7«
0 32
7 I 17
6«3 30 275.23'
10
7
= 0 25
= 4 79
ANOVA Table
Degrees of
Source freedom
Between) B) 1
Within(W) 15
SS MS
0 25 0.25
4 79 0 32
F
0 78
The critical value of the F test at the 0 05 significance level is 4.54. Since
the F value is less than the critical value, the means are not significantly
different (i e , they are homogeneous)
Note All calculations were rounded to two decimal places Results may differ
depending upon the number of decimal places used in each step of the calculations
159
-------
Example 3
Chlorohenzene
Inf luent
Effluent
Ug.'D
in(effluent) [ln(ef fluent )] 2
Influent Effluent
(ng/D (ng/1)
ln(eff luent )
ln[(effluent)]2
SO 00
70 00
;b 00
10 00
4 38
4 25
j 56
2 30
19 18
18.06
12 67
5 29
9206 00
16646.00
49775 00
14731 00
3159 00
6756.00
3040 00
1083 00
709 50
460.00
142 00
603.00
153.00
17.00
6.99
6.56
6.13
4.96
6.40
5 03
2.83
48 86
43 03
37.58
24 60
40.96
25 30
8.01
bU/I!
14 49
55 20
38 90
228 34
Mean
5703 49
Standard Deviation
1S35 4 32 24
Vanabi 1 ity Factor.
3.62
95
14759
16311.86
7 00
452.5
379.04
15.79
5.56
1 42
ANOVA Calculations-
i = l
If
"i
MSB - SSB/(k-l)
MSW = SSW/(N-k)
f = MbB/MSW
k
,ii
160
-------
Table A-l
95fh PERCENTILE VALUES FOR
THE F DISTRIBUTION
ni — degrees of freedom for numerator
«2 = degrees of freedom for denominator
(shaded area — .so)
/-^
^95
V1
"A
1
o
3
4
1
5
G
(
8
9
10
11
12
13
14
15
16
17
18
19
20
22
24
26
28
30
40
50
60
70
80
100
150
200
400
00
1
1C1.4
18.51
10.13
7.71
6.61
5.99
5.59
5.32
5.12
4.96
4.84
4.75
4.67
4.60
4.54
4.49
4.45
4.41
4.38
4.35
4.30
4.26
4.23
4.20
4.17
4.08
4.03
4.00
3.98
3.96
3.94
3.91
3.89
3.86
3.84
2
199.5
19.00
9.55
6.94
5.79
5.14
4.74
4.4G
4.2G
4.10
3.98
3.89
3.S1
3.74
3.68
3.63
3.59
3.55
3.52
3.49
3.44
3.40
3.37
3.34
3.32
3.23
3.18
3.15
3.13
3.11
3.09
3.06
3.04
3.02
2.99
3
215.7
19.16
9.28
6.59
5.41
4.76
4.35
4.07
S.86
3.71
3.59
3.49
3.41
3.34
3.29
3.24
3.20
3.16
3.13
3.10
3.05
3.01
2.98
2.95
2.92
2.84
2.79
2.76
2.74
2.72
2.70
2.67
2.65
2.62
2.60
4
224.6
19.25
9.12
6.39
5.19
4.53
4.12
3.84
3.G3
3.48
3.36
3.26
3.18
3.11
3.06
3.01
2.96
2.93
2.90
2.87
2.82
2.78 '
2.74
2.71
2.69
2.61
2.56
2.53
2.50
2.48
2.46
2.43
2.41
2.39
2.37
5
230.2
19.30
9.01
6.26
5.05
4.39
3.97
3.69
3.48
3.33
3.20
3.11
3.03
2.96
2.90
2.85
2.81
2.77
2.74
2.71
2.66
2.62
2.59
2.56
2.53
2.45
2.40
2.37
2.35
2.33
2.30
2.27
2.26
2.23
2.21
6
234.0
19.33
8.94
6.16
4.95
4.28
3.87
3.58
3.37
3.22
3.09
3.00
2.92
2.85
2.79
2.74
2.70
2.66
2.63
2.60
2.55
2.51
2.47
2.45
2.42
2.34
2 29
2.25
2.23
2.21
2.19
2.16
2.14
2.12
2.09
8
238.9
19.37
8.85
6.04
4.82
4.15
3.73
3.44
3.23
3.07
2.95
2.85
2.77
2.70
2.64
2.59
2.55
2.51
2.48
2.45
2.40
2.36
2.32
2.29
2.27
2.18
2.13
2.10
2.07
2.05
2.03
2.00
1.98
1.96
1.94
12
243.9
19.41
8.74
5.91
4.68
4.00
3.57
3.28
3.07
2.91
2.79
2.69
2.60
2.53
2.48
2.42
2.38
2.34
2.31
2.28
2.23
2.18
2.15
2.12
2.09
2.00
1.95
1.92
1.89
1.88
1.85
1.82
1.80
1.78
1.75
16
246.3
19.43
8.69
5.84
4.60
3.92
3.49
3.20
2.98
2.82
2.70
2.60
2.51
2.44
2.39
2.33
0 OQ
A..M.7
2.25
2 21
2.18
2.13
2.09
2.05
2.02
1.99
1.90
1.85
1.81
1.79
1.77
1.75
1.71
1.69
1.67
1.64
20
248.0
19.45
8.66
5.80
4.56
3.87
3.44
3.15
2.93
2.77
2.65
2.54
2.46
2.39
2.33
2.28
2.23
2.19
2.15
2.12
2.07
2.03
1.99
1.96
1.93
1.84
1.78
1.75
1.72
1.70
1.68
1.64
1.62
1.60
1.57
30
250.1
19.46
8.62
5.75
4.50
3.81
3.38
3.08
2.86
2.70
2.57
2.46
2.38
2.31
2.25
2.20
2.15
2.11
2.07
2.04
1.98
1.94
1.90
1.S7
1.84
1.74
1.69
1.65
1.62
1.60
1.57
1.54
1.52
1.49
1.46
40
251.1
19.46
8.GO
5.71
4.46
3.77
3.34
3.05
2.82
2.67
2.53
2.42
2.34
O O*7
2 °1
2.16
2.11
2.07
2.02
1.99
1.93
1.89
1.85
1.81
1.79
1.69
1.63
1.59
1.56
1.54
1.51
1.47
1.45
1.42
1.40
50
252.2
19.47
8.58
5.70
4.44
3.75
3.32
3.03
2.80
2.64
2.50
2.40
2.32
2.24
2.18
2.13
2.08
2.04
2.00
1.96
1.91
1.86
1.82
1.78
1.76
1.66
1.60
1.56
1.53
1.51
1.48
1.44
1.42
1.38
1.32
100
253.0
19.49
8.56
5.66
4.40
3.71
3.28
2.98
2.76
2.59
2.45
2.35
2.26
2.19
2.12
2.07
2.02
1.98
1.94
1.90
1.84
1.80
1.76
1.72
1.69
1.59
1.52
1.48
1.45
1.42
1.39
1.34
1.32
1.28
1.24
ec
254.3
19.50
S.5S
5.63
4.36
3.67
3.23
2.93
2.71
2.54
2.40
2.30
2.21
2.13
2.07
2.01
1.96
1.92
1.88
1.84
1.78
1.73
1.69
1.65
1.62
1.51
1.44
1.39
1.35
1.32
1.28
1.22
1.19
1.13
1.00
-------
Example 3 (continued)
k - number ot treatment technologies
p = ru. T.ner ot clcttd points for technology i
i
N = number of datd points for all technologies
1 - sum ot natural log transformed data points for each technology
X = the natural log transformed observations (j) for treatment technology (i)
i i
M - 4, N -- /, N = 11, k = 2, T = 14 49, T = 3b 90, 1 = 53.39, T"= 2850 49, T = 209 9b
1 2 12 1
SSB =
'209 96
4
(55 20
1513.21 ) 2850 49
+ 1 -
7 j 11
+ 22H 34) -
209 96
4
1513 21
7
9.52
- 14.
MSB = 9.52/1 - 9.52
MSW - 14 fab/9 = 1 65
F = 9 52/1 65 = 5 77
Degrees of
bource freedom
ANOVA Table
SS
MS
Between(B)
Within(W)
1
9
9 53
14 89
9.53
1 65
5.77
The critical value of the F test at the 0 05 significance level is 5.12. Since
the F value is larger than the critical value, the means are significantly
different (i e , they are heterogeneous)
Note. All calculations were rounded to two decimal places Results may differ depending
upon the number of decimal places used in each step of the calculations.
161
-------
A.2. Variability Factor
-£•99-
VF = Mean
where:
VF = estimate of daily maximum variability factor determined from
a sample population of daily data.
Cgg = Estimate of performance values for which 99 percent of the
daily observations will be below. Cgg is calculated using
the following equation': Cgg = Exp(y + 2.33 Sy) where y and
Sy are the mean and standard deviation, respectively, of the
logtransformed data.
Mean = average of the individual performance values.
EPA is establishing this figure as an instantaneous maximum because
the Agency believes that on a day-to-day basis the waste should meet the
applicable treatment standards. In addition, establishing this
requirement makes it easier to check compliance on a single day. The
99th percentile is appropriate because it accounts for almost all process
variability.
In several cases, all the results from analysis of the residuals from
BOAT treatment are found at concentrations less than the detection
limit. In such cases, all the actual concentration values are considered
unknown and hence, cannot be used to estimate the variability factor of
the analytical results. Below is a description of EPA's approach for
calculating the variability factor for such cases with all concentrations
below the detection limit.
It has been postulated as a general rule that a lognormal
distribution adequately describes the variation among concentrations.
Agency data shows that the treatment residual concentrations are
162
-------
distributed approximately lognormally. Therefore, the lognormal model
has been used routinely in the EPA development of numerous regulations in
the Effluent Guidelines program and is being used in the BOAT program.
The variability factor (VF) was defined as the ratio of the 99th
percentile (C ) of the lognormal distribution to its arithmetic mean
(Mean).
VF = C99 (1)
Mean
The relationship between the parameters of the lognormal distribution
and the parameters of the normal distribution created by taking the
natural logarithms of the lognormally-distributed concentrations can be
found in most mathematical statistics texts (see for example:
Distribution in Statistics-Volume 1 by Johnson and Kotz, 1970). The mean
of the lognormal distribution can be expressed in terms of the
mean (^) and standard deviation (a) of the normal distribution as
follows:
Cgg = Exp (? + 2.33a) (2)1
Mean = Exp (M + .5o2) (3)
Substituting (2) and (3) in (1) the variability factor can then be
expressed in terms of a as follows:
VF = Exp (2.33 a - .5a2) (4)
For residuals with concentrations that are not all below the
detection limit, the 99 percentile and the mean can be estimated from
the actual analytical data and accordingly, the variability factor (VF)
can be estimated using equation (1). For residuals with concentrations
163
-------
that are below the detection limit, the above equations can be used in
conjunction with the assumptions below to develop a variability factor.
Step 1: The actual concentrations follow a lognormal distribution. The
upper limit (UL) is equal to the detection limit. The lower limit (LL)
is assumed to be equal to one tenth of the detection limit. This
assumption is based on the fact that data from well-designed and
well-operated treatment systems generally falls within one order of
magnitude.
Step 2: The natural logarithms of the concentrations have a normal
distribution with an upper limit equal to In (UL) and a lower limit equal
to In (LL).
Step 3: The standard deviation (a) of the normal distribution is
approximated by
a = [(In (UL) - In (LL)] / [(2)(2.33)] = [ln(UL/LL)] / 4.66
when LL = (0.1)(UL) then a = (InlO) / 4.66 = 0.494
Step 4: Substitution of the value from Step 3 in equation (4) yields the
variability factor, VF.
VF = 2.8
164
-------
APPENDIX B - ANALYTICAL QA/QC
From Onsite Engineering Report
for Horsehead Resource Development Co., Inc.
165
-------
1809g
APPENDIX
Analytical Methods
Analytical Method Method Number Reference
Metals
Acid Digestion of Aqueous Samples and 3010
Extracts for Total Metals for Analysis
by Flame Atomic Absorption Spectroscopy (AA)
or Inductivily Coupled Plasma Spectroscopy (ICP)
Acid Digestion of Aqueous Samples and Extracts 3020
for Total Metals for Analysis by Furnace
Atomic Absorption Spectroscopy (AA)
Acid Digestion of Sediments, Sludges, and 3050
soi Is
Inductively Coupled Plasma Atomic Emission 6010
Spectroscopy
(Cadmium, Chromium, Lead, Zinc)
Mercury in Liquid Waste (Manual Cold-Vapor ' 7471
Technique)
Toxicity Characteristic Leaching Procedure 51 FR 40643
(TCLP)
References
1 Environmental Protection Agency. 1986. Test Methods for Evaluating Solid
Waste. Third Edition. U S. EPA Office of Solid Waste and Emergency
Response November 1986.
2 Federal Register. 1986. Hazardous Waste Management Systems, Land Disposal
Restrictions, Final Rule; Appendix I to Part 268 - Toxicity Leaching
Procedure (TCLP). Vol. 51, No. 216 November 7, 1986 pp 40643-40654.
166
-------
Specific Procedures or Equipment Used in Analysis of Metals
When Alternative or Equivalents Allowed in the SW-846 Methods
Analys is
SW-846
Method
Equipment
Alternative or Equivalent
Allowed by SW-846 Methods
Specific Procedures or
Equipment Used
Inductively coupled
plasma atomic
emission
spectroscopy
6010 Jarrell Ash 1140
Operate equipment following
instructions provided by
instument's manufacturer
For operation with organic
solvents, auxilliary argon gas
inlet is recommended.
Equipment operated using
procedures specified in the
Jarrell Ash (JA) 1140
Operator's Manual.
Auxiliary argon gas was not
required for sample matrix
analyzed
cn
—i
Mercury
7471 Perkin Elmer 50A
Operate equipment following
instructions by instrument's
manufacturer
Equipment operated using
procedures specified in Perkin
Elmer 50A Instructions Manual
Cold vapor apparatus is
described in SW-846 or an
equivalent apparatus may be
used
Sample may be prepared using
the water bath method or the
autoclave method described in
SW-846
Mercury was analyzed by cold
vapor method using the
apparatus as specified in
SW-846 except, there was no
scrubber.
Samples were prepared using
the water bath method
-------
1122g
Specific Procedures or Equipment Used in Analysis of Metals
When Alternative or Equivalents Allowed in the SW-846 Methods
(continued)
Analysis
SW-846
Method
Equipment
Alternative or Equivalent
Allowed by SW-846 Methods
Specific Procedures or
Equipment Used
Acid Digestion for
metals analyzed
3010
Digest 100 ml of sample in
a conical beaker
Initial sample volume of
50 ml is digested in Griffin
straight-side beakers. All
acids and peroxides are
halved.
cr\
CO
-------
1123g
Duplicate Analysis for the Total Composition
Sample from S6:Residual Slag Material^
BOAT Metals
Chromium
Lead
Zinc
Sample Set 1
(n>g/kg)
662
1,720
24,300
Sample Set 1 Relative percent
(mg/kg)
752
1,780
25,800
difference (RPD)*
13
3
6
*RPD = [(Sl-S2)/((Sl+S2)/2)] x 100%, where SI is the larger of the two observed values.
1 - Duplicates not run constitutes not detected in any of the treated samples (cadmium, mercury).
169
-------
1123g
Duplicate Analysis for Matrix Spikes for TCLP Extract
for Sample Point 6: Residual Slag Material
BOAT Metals**
Cadmium
Chromium
Lead
Mercury
Zinc
Sample Set 4
(ug/1)
26
35
22
0.9
12,600
Sample Set 4
(ug/1)
27
34
19
1.1
12,400
Relative percent
difference (RPD)*
4
3
15
20
2
NC = Not Calculatable
*RPD = [(Sl-S2)/((Sl+S2)/2)] x 100%, where SI is the larger of the two observed values.
170
-------
1158g
BOAT Constituents for Spiking Mixture for Total
Composition Sample and for TCLP Extract Sample
Total Composition TCLP Extract
Spike Concentration Spike Concentration
Constituent (mg/Kg) (ug/1)
Metals
Cadmium 2.5 25
Chromium 2,000 50
Lead 500 25
Mercury 0.5 1
Zinc 6,000 1.000
171
-------
1351g
Matrix Spike Recoveries for Treated Waste Total Concentrations and Accuracy Correction Factors
for High Temperature Metals Recovery
BOAT constituent
Cadmium
Chromium
Lead
Mercury
Zinc
Original amount Spike added
found (mg/kg) (mg/kg)
<1.5 2.5
978 2.000
365 500
<0.1 0.5
4.680 6.000
Sample
Spike result
(mg/kg)
<1.5
2,970
683
0.5
9.770
Sample dupl icate
Percent
recovery*
NC
100
64
100
85
Spike added
(mg/kg)
2.5
2,000
500
0.5
6.000
Spike result
(mg/kg)
2.4
2.870
705
0.5
9.950
Percent
recovery*
96
95
68
100
88
Correction
Factor
1.04
1.05
1.56
1.00
1.18
ro
NC = Not Calculatable.
*Percent Recovery = [(Spike Result - Original Amount)/Spike Added] x 100.
-------
1351g
Matrix Spike Recovery for TCLP Extract for Treated Waste and Accuracy Correction Factors
for High Temperature Metals Recovery
BOAT constituent
Cadmium
Chromium
Lead
Mercury
Zinc
Original sample
(ug/1)
4.2
<4.0
<5.0
<0.2
2,640
Spike added
(ug/1)
25
50
25
1.0
10.000
Sample
Spike result
(ug/1)
26
35
22
0.9
12,600
Sample duplicate
Percent
recovery*
87
70
88
90
100
Spike result
(ug/1)
27
34
19
1.1
12,400
Percent
recovery*
91
68
76
110
98
Correct ion
Factor
1.15
1.47
1.32
1.11
1.02
*Percent Recovery = [(Spike Result - Original Amount)/Spike Added]* 100.
-------
112bg
Calibration Procedures Used to Analyze Organic and
Inorganic BOAT Constituents
Analysis
SW-846
method
Standards
Calibration Procedures
Inductively Coupled
Plasma Atomic
Emission spectroscopy
6010
Calibration Standards for ICP -
calibration blank; antimony, barium,
beryllium, cadmium, chromium,
copper, lead, nickel, selenium,
silver, thallium, zinc, aluminum,
arsenic, boron, calcium, cobalt,
iron, magnesium, manganese,
silicon, tin, and vanadium at
1 ppm; sodium at 10 ppm;
potassium and iron at 50 ppm;
Initial calibration veri-
fication was run at begin-
ning of each batch. The
concentrations are barium
at 1,980 ppb, beryllium at
4B1 ppb, cadmium at 489
ppb, chromium at 506 ppb,
copper at 542 ppb, lead at
4,510 ppb, nickel at 496
ppb, silver at 509 ppb,
vanadium at 511 ppb, zinc at
3,100 ppb, aluminum at 1,980
ppb, calcium at 49,800 ppb,
cobalt at 542 ppb, iron at
1,990 ppb, magnesium at
25,000 ppb, manganese at 513
ppb, potassium at 50,200 ppb,
and sodium at 50,700 ppb..
This meets the requirements
in SW-646.
Instrument check samples
contained all the elements to be
analyzed by method 6010.
Instrument check samples
were used at a frequency
of 10 percent. The
concentration is at 500 ppb
for antimony, barium,
beryllium, cadmium, chromium,
copper, nickel, silver,
vanadium, and zinc, aluminum,
arsenic, boron, calcium,
cobalt, iron, magnesium,
manganese, and silicon; lead
at 1000 ppb; selenium,
thallium, and tin at 2,000
ppb; potassium and sodium at
20,000 ppb. This meets the
require- ments specified in
SW-846.
Mercury in
Liquid Waste
(Manual Co Id-Vapor
Technique)
7470
Calibration standards for mercury
were a blank, 0.5 ppb, 2 ppb, 5 ppb
and 10 ppb.
The calibration curve
was run once per day. This
meets the requirements in
SW-846.
The concentration of the
check standard was 5.0 ug/1
and it was run at a 10
percent frequency. This
meets the requirements in
SW-846.
174
-------
1174g
Source and Purity of Calibration Standards
Source for Purity or Grade or
Constituents Standards Concentration
BOAT Metals
158 Cadmium Aesar 1000 ppm
159 Chromium (total) Aesar 1000 ppm
162 Lead Aesar 1000 ppm
163 Mercury Aesar 1000 ppm
169 Zinc Aesar 1000 ppm
175
-------
1162g
Source and/or Purity of System Performance
Check Compounds and Calibration Check Standards
Compound EPA Check Standard Purity/Grade
Method 6010: Inductively Coupled Plasma Atomic Emission
Spectroscopy
Cal ibration
Check Compounds
ICP metals1 UNLV 1CV1 *
Mercury - 1CV5 UNLV 1CV5 *
Check standard contains cadmium, chromium, lead, and zinc.
* EPA check standard with certified high purity level.
UNLV - University of Nevada at Las Vegas
1CV - Initial calibration verification.
176
-------
APPENDIX C
Kiln Temperature Strip Charts
This information has been claimed CBI by
the facility pursuant to 40 CFR Part 2
177
-------
APPENDIX D
Statistical Analysis
ANOVA - High Temperature Metals Recovery/Stabilization
178
-------
i396g
APPENDIX D
Statistical Analysis of High Temperature Metals Recovery
EPA Collected Data - Accuracy Corrected Values
Treated Waste (ppm) _ _
Pollutant
Cd (TOT)
Cd (TCLP)
Cr (TOT)
Cr (TCLP)
Pb (TOT)
Pb (TCLP)
Hg (TOT)
Hg (TCLP)
Zn (TOT)
Zn (TCLP)
SS *3
<15 6
^0.069
785
-------
-fog
Statistical Analysis of Stabilization (Lime/Fly Ash)
EPA Collected Data - Accuracy Corrected Values
Treated Waste (ppm) _ _
Pollutant SS *7 C,S »8 SS #9 X Y
Cd (TCLP) 0 036 0.053 0.080 0.056 -2.919
Cr (TCLP) 0 113 0.087 0.065 0.088 -2 452
Pb (TCLP) 0.140 0.064 0.061 0.088 -2.504
Hg (TCLP) 0 001S 0 0015 0.0016 0 002 -6.481
Zn (TCLP) 0 681 0.206 0 458 0.448 -0.915
Mean of x, X = 2x
n
Mean of y, Y = Sy
n
/> ,\7
Sy VF
0.399 2.42
0.277 1 86
0.4664 2.74
0.037 1.11
0.609 3.69
Standard Deviation Sy =/ zly-y)
A
I
/
VF = Exp (Y + 2.33 A Sy)/X
180
-------
Variable LNiONC (LN(CONCENTRATION))
Variable TREAT
ANALYSIS OF VARIANCE RESULTS
D F
bum of Squares
Between Groups 1
Within Groups 4
lotal 5
0 0979
0 3189
0 416b
Mean Squares Computed F Tabulated F
0 0979 1.228 7.22
0.0797
Decision
No statistical difference
Cr
Variable LNCONC (LN(CONCENTRATION))
by Variable TREAT
ANALYSIS OF VARIANCE RESULTS
Source
Between Groups
Within Groups
Total
D F
1
4
Sum of Squares
0 1486
0 1531
0.3017
Mean Squares Computed F Tabulated F
0 1486 3.885 7.22
0.0383
Decision
No statistical difference
PD
Variable LNCONC (LN(CONCENTRATION))
By Variable TREAT
ANALYSIS OF VARIANCE RESULTS
Source
Between Groups
Within Groups
Total
D F.
1
4
5
Sum of Squares
1 2348
0 4351
1.6698
Mean Squares
1.2348
0.1088
Computed F
11.3525
Tabulated F
7.22
Decision
There is a significant
difference between
the two High
Variable LNCONC (LN(CONCENTRATION)]
Variable TREAT
ANALYSIS OF VARIANCE RESULTS
temperature metals
recovery is better.
Source
Between Groups
Within Groups
Total
D F.
1
4
5
Sum of Squares
2 0493
4 5188
6 5681
Mean Squares
2 0493
1.1297
Computed F
1.8141
Tabulated F
7.22
Decision
No statistical difference
Variable LNCONC (LN(CONCENTRATION))
By Variable TREAT
Source
D F Sum of Squares
Between Groups 1
Within Groups 4
Total 5
2 6877
1 3474
4 0351
ANALYSIS OF VARIANCE RESULTS
Mean Squares Computed F
2.6877 7 9689
0 3368
181
Tabulated F
7.22
Decision
There is a significant
difference between the
two High temperature
metals recovery is better
-------
APPENDIX E
Analytical Method for Determining the
Thermal Conductivity of a Waste
182
-------
APPENDIX £
The comparative method of measuring thermal conductivity has been
proposed as an ASTM test method under the name "Guarded, Comparative,
Longitudinal Heat Flow Technique." A thermal heat flow circuit is used
which is the analog of an electrical circuit with resistances in series.
A reference material is chosen to have a thermal conductivity close to
that estimated for the sample. Reference standards (also known as heat
meters) having the same cross-sectional dimensions as the sample are
placed above and below the sample. An upper heater, a lower heater, and
a heat sink are added to the "stack" to complete the heat flow circuit.
See Figure 1.
The temperature gradients (analogous to potential differences) along
the stack are measured with type K (chromel/alumel) thermocouples placed
at known separations. The thermocouples are placed into holes or grooves
in the references and also in the sample whenever the sample is thick
enough to accommodate them.
For molten samples, pastes, greases, and other materials that must be
contained, the material is placed into a cell consisting of a top and
bottom of Pyrex 7740 and a containment ring of marinite. The sample is 2
inch in diameter and .5 inch thick. Thermocouples are not placed into
the sample but rather the temperatures measured in the Pyrex are
extrapolated to give the temperature at the top and bottom surfaces of
the sample material. The Pyrex disks also serve as the thermal
conductivity reference material.
183
-------
GUARD
GRADIENT
STACK
GRADIENT
THERMOCOUPLE
CLAMP
1
UPPER STACK
HEATER
I
TOP REFERENCE
SAMPLE
I
7
TEST/SAMPLE
7
7TI
BOTTOM
REFERENCE
SAMPLE
I
LOWER STACK
HEATER
1
LIQUID 'COOLED
HEAT SINK
I
HEAT FLOW
DIRECTION
]• :
UPPER
GUARD
HEATER
LOWER
GUARD
HEATER
SCHEMATIC DIAGRAM OF THE COMPARATIVE METHOD
184
-------
The stack is clamped with a reproducible load to insure intimate
contact between the components. In order to produce a linear flow of
heat down the stack and reduce the amount of heat that flows radially, a
guard tube is placed around the stack and the intervening space is filled
with insulating grains or powder. The temperature gradient in the guard
is matched to that in the stack to further reduce radial heat flow.
The comparative method is a steady state method of measuring thermal
conductivity. When equilibrium is reached the heat flux (analogous to
current flow) down the stack can be determined from the references. The
heat into the sample is given by
Q. = A (dT/dx).
in top top
and the heat out of the sample is given by
Qout = A (dT/dx),
bottom bottom
where
A = thermal conductivity
dT/dx = temperature gradient
and top refers to the upper reference while bottom refers to the lower
reference. If the heat was confined to flow just down the stack, then
Q. and Q would be equal. If Q and Q are in reasonable
in out in out
agreement, the average heat flow is calculated from
The sample thermal conductivity is then found from
A = Q/(dT/dx)
sample sample
185
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