E PA/530-SW-88-03IL
FINAL
BEST DEMONSTRATED AVAILABLE TECHNOLOGY (BDAT)
BACKGROUND DOCUMENT FOR
F006
James R. Berlow, Chief
Treatment Technology Section
John Keenan
Project Manager
U.S. Environmental Protection Agency
Office of Solid Waste
401 M Street, S.W.
Washington, D.C. 20460
August 1988
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TABLE OF CONTENTS
Section Page
EXECUTIVE SUMMARY vi
1. INTRODUCTION 1-1
1.1 Legal Background 1-1
1.1.1 Requirements Under HSWA 1-1
1.1.2 Schedule for Developing Restrictions 1-4
1.2 Summary of Promulgated BOAT Methodology 1-5
1.2.1 Waste Treatability Groups 1-7
1.2.2 Demonstrated and Available Treatment Technologies ... 1-7
1.2.3 Collection of Performance Data 1-11
1.2.4 Hazardous Constituents Considered and Selected for
Regulation 1-17
1.2.5 Compliance with Performance Standards 1-30
1.2.6 Identification of BDAT 1-32
1.2.7 BDAT Treatment Standards for "Derived From" and
"Mixed" Wastes 1-36
1.2.8 Transfer of Treatment Standards 1-40
1.3 Variance from the BDAT Treatment Standard 1-41
2. INDUSTRIES AFFECTED AND WASTE CHARACTERIZATION 2-1
2.1 Industries Affected 2-1
2.2 Process Description 2-5
2.2.1 Electroplating 2-6
2.2.2 Anodizing 2-8
2.2.3 Chemical Etching and Milling 2-10
2.2.4 Metal Cleaning and Stripping 2-11
2.3 Waste Characterization 2-11
3. APPLICABLE/DEMONSTRATED TREATMENT TECHNOLOGIES 3-1
3.1 Applicable Treatment Technologies 3-1
3.2 Other Treatment Technologies to Reduce the
Generation of F006 3-2
3.3 Demonstrated Treatment Technologies 3-2
3.3.1 Stabilization of Metals 3-3
3.3.2 High Temperature Metals Recovery 3-12
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TABLE OF CONTENTS (Continued)
Section Page
4. PERFORMANCE DATA BASE 4-1
4.1 Stabilization Data 4-1
4.2 High Temperature Metals Recovery 4-2
4.3 Vitrification 4-3
5. IDENTIFICATION OF BEST DEMONSTRATED AVAILABLE TECHNOLOGY 5-1
6. SELECTION OF REGULATED CONSTITUENTS 6-1
6.1 Identification of BDAT List Constituents in F006 Waste 6-1
6.2 Selection of Constituents 6-2
7. CALCULATION OF BDAT TREATMENT STANDARDS 7-1
8. ACKNOWLEDGMENTS 8-1
9. REFERENCES 9-1
APPENDIX A STATISTICAL ANALYSIS A-l
APPENDIX B ANALYTICAL QA/QC B-l
APPENDIX C METHOD OF MEASUREMENT FOR THERMAL CONDUCTIVITY C-l
APPENDIX D DELETION OF PERFORMANCE DATA FOR F006 WASTES D-l
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LIST OF TABLES
Table Page
1-1 BDAT Constituent List 1-18
2-1 Facilities Producing F006 Waste by State and Region 2-3
2-2 Typical Electroplating Baths and Their .Chemical
Composition 2-9
2-3 Major Constituents in F006 Waste 2-13
2-4 BDAT Constituent Composition for Untreated F006 Waste 2-14
3-1 Cement Kiln Dust Composition Data 3-6
4-1 Performance Data for Untreated and Treated F006 Waste 4-4
4-2 Untreated Wastes for Recovery in Rotary Hearth Furnace ... 4-7
4-3 High Temperature Metals Recovery - Treated Samples 4-12
4-4 Vitrification of F006 4-13
5-1 Accuracy-Corrected Performance Data for Untreated and
Treated F006 Wastes by Stabilization 5-5
6-1 Status of BDAT List Constituent Presence in Untreated
F006 Waste 6-4
7-1 Regulated Constituents and Calculated Treatment
Standards for F006 — 7-2
A-l 96th Percentile Values for the F Distribution A-2
B-l Matrix Spike Recoveries for Treated Waste B-3
B-2 Analytical Methods for Regulated Constituents B-4
D-l Deletion of Stabilization Performance Data for F006 Wastes D-2
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LIST OF FIGURES
Figure Page
2-1 Geographic Distribution of Electroplating Facilities
Generating F006 Waste 2-2
2-2 General Schematic of a Wastewater Treatment System 2-7
3-1 Example of High Temperature Metals Recovery System 3-15
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EXECUTIVE SUMMARY
BDAT Treatment Standards for F006
Pursuant to section 3004(m) of the Resource Conservation and Recovery
Act as enacted by the Hazardous and Solid Waste Amendments on November 8,
1984, the Environmental Protection Agency (EPA) is establishing best
demonstrated available technology (BDAT) treatment standards for the
listed waste identified in 40 CFR 261.31 as F006. Compliance with these
BDAT treatment standards is a prerequisite for placement of the waste in
units designated as land disposal units according to 40 CFR Part 268.
The effective date of these treatment standards is August 8, 1988.
This background document provides the Agency's rationale and
technical support for selecting the constituents to be regulated in F006
waste and for developing treatment standards for those regulated
constituents. The document also provides waste characterization and
treatment information that serves as a basis for determining whether
variances may be warranted. EPA may grant a treatment variance in cases
where the Agency determines that the waste in question is more difficult
to treat than the waste upon which the BDAT treatment standards are based.
The introductory section, which appears verbatim in all the First
Third background documents, summarizes the Agency's legal authority and
promulgated methodology for establishing treatment standards and
discusses the petition process necessary for requesting a variance from
the treatment standards. The remainder of the document presents
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waste-specific information: the number and locations of facilities
affected by the land disposal restrictions for F006 waste, the
waste-generating process, characterization data, the technologies used to
treat the waste (or similar wastes), and available performance data,
including data on which the treatment standards are based. The document
also explains EPA's determination of BOAT, selection of constituents to
be regulated, and calculation of treatment standards.
F006 waste is listed in 40 CFR 261.31 as "wastewater treatment
sludges from electroplating operations except from the following
processes: (1) sulfuric acid anodizing of aluminum; (2) tin plating on
carbon steel; (3) zinc plating (segregated basis) on carbon steel;
(4) aluminum or zinc-aluminum plating on carbon steel;
(5) cleaning/stripping associated with tin, zinc, and aluminum plating on
carbon steel; and (6) chemical etching and milling of aluminum."
This listing includes wastewater treatment sludges from the following
processes: (1) common and precious metals electroplating, except tin,
*
zinc (segregated basis), aluminum, and zinc-aluminum plating on
"Zinc plating (segregated basis)" refers to noncyanidic zinc plating
processes. For example, wastewater treatment sludges from zinc plating
using baths formulated from zinc oxide and/or sodium hydroxide would be
excluded from the listing, while sludges from baths formulated from zinc
cyanide and/or sodium cyanide would not be excluded. Where both cyanidic
and noncyanidic baths are used, the exclusion applies to sludges from the
noncyanidic processes as long as they are segregated from sludges that
result from cyanidic plating processes.
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carbon steel; (2) anodizing, except sulfuric acid anodizing of aluminum;
(3) chemical etching and milling, except when performed on aluminum; and
(4) cleaning and stripping, except when associated with tin, zinc, and
aluminum plating on carbon steel (See 51 FR 43350). EPA has established
a separate group of waste codes for spent cyanide electroplating baths
and residues (F007, F008, and F009) and a separate waste code for the
wastewater treatment sludges from the electroplating operation referred
to as chemical conversion coating of aluminum (F019). EPA is currently
studying these codes and will develop treatment standards for them based
on these studies.
EPA has estimated that 4,500 facilities are potential generators of
F006 waste. Generators of F006 usually fall under Standard Industrial
Classification (SIC) Code series 3000.
At this time treatment standards are only being established for F006
nonwastewaters; EPA intends to propose and promulgate treatment standards
for F006 wastewaters by May 8, 1990. (For the purpose of determining the
applicability of the treatment standards, wastewaters are defined as
wastes containing less than 1 percent (weight basis) total suspended
solids* and less than 1 percent (weight basis) total organic carbon
(TOC). Wastes not meeting this definition must comply with the treatment
~The term "total suspended sol Ids" (TSS) clarifies EPA's previously used
terminology of "total solids" and "filterable solids." Specifically,
total suspended solids is measured by method 209C (Total Suspended Solids
Dried at 103-105'C) in Standard Methods for the Examination of Water
and Wastewater. Sixteenth Edition.
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standards for nonwastewaters.) Regarding the status of F006 wastewaters
prior to May 8, 1990, facilities are referred to Section III.C.3 of the
preamble for the final First Third rule.
For F006 nonwastewaters, the Agency is establishing treatment
standards for cadmium, chromium, lead, nickel, and silver, which were
found to leach at treatable levels from the untreated waste. The
treatment standards are based on performance data from stabilization.
The Agency is not regulating cyanide in F006 wastes at this time;
however, EPA is presently collecting data on treatment of cyanide and
expects to propose standards in the near future. EPA may also in the
future develop regulations for other BOAT metals and organics depending
on data and information that become known to the Agency regarding their
presence in the untreated waste.
The following table presents the treatment standards for F006
nonwastewaters. These treatment standards reflect the concentration of
constituents in the leachate from the Toxicity Characteristic Leaching
Procedure (TCLP). The units for the leachate concentration are mg/1
(parts per million on a weight-by-volume basis). If the concentrations
of the regulated constituents in F006 waste, as generated, are lower than
or equal to the proposed BOAT treatment standards, then treatment is not
necessary as a prerequisite to land disposal.
Testing procedures are specifically identified in Appendix B of this
background document.
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BOAT Treatment Standards for F006
Maximum for any single grab sample
Nonwastewater Wastewater3
Constituent
Total
TCLP leachate
Total
concentration
concentration
concentration
(mg/kg)
(mg/1)
(mg/1)
Cadmium
NA
0.066
Chromium
NA
5.2
Lead
NA
0.51
Nickel
NA
0.32
Silver
NA
0.072
Cyanide
Reserved
Reserved
NA ¦ Not applicable.
aEPA intends to propose and promulgate F006 wastewater treatment
standards prior to May 8, 1990.
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1. INTRODUCTION
This section of the background document presents a summary of the
legal authority pursuant to which the best demonstrated available
technology (BDAT) treatment standards were developed, a summary of EPA's
promulgated methodology for developing the BOAT treatment standards, and,
finally, a discussion of the petition process that should be followed to
request a variance from the BDAT treatment standards.
i-1 Leoal Background
1.1.1 Requirements Under HSWA
The Hazardous and Solid Waste Amendments of 1984 (HSWA), which were
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
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constituents from the disposal unit or injection zone for as long as the
wastes remain hazardous" (RCRA section 3004(d)(1), (e)(1), (g)(5),
42 U.S.C. 6924 (d)(1), (e)(1), (g)(5)).
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)(1)). Wastes that satisfy such levels or methods of
treatment established by EPA, i.e., treatment standards, are not
prohibited from being 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
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characteristic is the physical form of the waste. This frequently leads
to different standards for wastewaters and nonwastewaters.
Alternatively, EPA can establish a treatment standard that is applicable
to more than one waste code when, in EPA's judgment, a particular
constituent present in the wastes can be treated to the same
concentration in all the wastes.
In those instances where a generator can demonstrate that the
standard promulgated for the generator's waste cannot be achieved, the
amendments allow the Agency to 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 treatment standards by the statutory deadline for
any hazardous waste in the First Third or Second Third waste groups (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
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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
landfills and surface impoundments applies until EPA sets treatment
standards for the waste or until May 8, 1990, whichever is sooner. If
the Agency fails to set treatment standards 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:
1. Solvent and dioxin wastes by November 8, 1986;
2. The "California List" wastes by July 8, 1987;
3. At least one-third of all listed hazardous wastes by
August 8, 1988 (First Third);
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4. At least two-thirds of all listed hazardous wastes by
June 8, 1989 (Second Third); and
5. 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 by May 8, 1990 (Third
Third).
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 treatment
standards for metals. Therefore, the statutory limits became effective.
On May 28, 1986, EPA published a final rule (SI FR 19300) that
delineated the specific waste codes that would be addressed by the First
Third, Second Third, and Third Third land disposal restriction rules.
This schedule is incorporated Into 40 CFR 268.10, 268.11, and 268.12.
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).
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Congress Indicated in the legislative history accompanying the HSWA that
M[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 section 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 wel1-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 to require the use of specific
treatment "methods." EPA believes that concentration-based treatment
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levels offer the regulated community greater 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 hazardous constituents in wastes represented by different
waste codes could be treated to similar concentrations using identical
technologies, the Agency combines the wastes 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 of the
wastes in the group, the waste from which treatment standards are to be
developed, is expected to be most difficult to treat.
Once the treatability groups have beerf 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 currently used on a full-scale basis to
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treat the waste of interest or a waste judged to be similar (see 51 FR
40588, November 7, 1986). EPA also will consider as demonstrated
treatment those technologies used to separate or otherwise process
chemicals and other materials on a full-scale basis. 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 to be a demonstrated
technology for many waste codes containing hazardous organic
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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.
If no full-scale 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. 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
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toxicity of the waste or substantially reduce the likelihood of migration.
of hazardous constituents from the waste. These criteria are discussed
below.
1. Commercially available treatment. 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 a 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 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 (provided the nondetectable
levels are low relative to the concentrations in the untreated
waste). 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:
• Number and types of constituents treated;
• Performance (concentration of the constituents in the
treatment residuals); and
• Percent of constituents removed.
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EPA will only set treatment standards based on a technology that
meets both availability criteria. Thus, the decision to classify a
technology as "unavailable" will have a direct impact on the treatment
standard. If the best demonstrated technology is unavailable, the
treatment standards will be based on the next best demonstrated 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.
1.2.3 Collection of Performance Data
Performance data on the demonstrated available technologies are
evaluated by the Agency to determine whether the data are representative
of well-designed and well-operated treatment systems. Only data from
well-designed and well-operated systems are considered in determining
BOAT. The data evaluation includes data already collected directly by
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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: (1) the
identification of facilities for site visits, (2) the engineering site
visit, (3) the sampling and analysis plan, (4) the sampling visit, and
(5) the 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 their 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: (1J generators treating
single wastes on site; (2) generators treating multiple wastes together
on site; (3) commercial treatment, storage, and disposal facilities
(TSDFs); and (4) EPA in-house treatment. This hierarchy is based on two
concepts: (1) to the extent possible, EPA should develop treatment
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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
full-scale treatment systems. If performance data from properly designed
and operated full-scale systems treating a particular waste or a waste
judged to be similar are not available, EPA may use data from research
facility operations. Whenever research facility data are used, EPA will
explain in the preamble and background document why such data were used
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.
(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
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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 wel1-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 olan. 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 Restrictions
Program f"BDAT"). EPA/530-SW-87-011. In brief, the SAP discusses where
the Agency plans to sample, how the samples will be taken, the frequency
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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 SAP
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 BOAT treatment
standards. 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.
1-15
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(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 Restrictions Program ("BDAT"). 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) Samolina 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.
1-16
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(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 that appear in Test Methods for Evaluating Solid Waste. SW-846,
Third Edition, November 1986.
After the OER is completed, the report is submitted to the waste
generator and/or treater for review. This review provides a final
opportunity for claiming 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.
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,
Appendices VII and VIII, as well as several ignitable constituents used
as the basis of listing wastes as F003 and F005. These sources provide a
1-17
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lSZlg
Table 1-1 BOAT Constituent List
BOAT
reference Constituent CAS no.
no
Volatile oraanics
22?.
Acetone
67-64-I
1.
Acetonitri le
75-05-8
2.
Acrolein
107-02-8
3.
Acrylonitri le
107-13-1
4.
Benzene
71-43-2
5.
Bramod ich lorcmcthdne
75-27-4
6.
Bramomethdne
74-83-9
223.
n-Butyl alcohol
71-36-3
/.
Carbon tetrachloride
56-23-5
8.
Carbon dtsuIfide
75-15-0
9.
Ch lorobenzene
108-90-7
10.
2-Chloro-1,3-butadtene
126-99-8
11.
Ch lorod i bramoNethane
124-48-1
12.
Chloroethane
75-00-3
13.
2 Chloroethyl vinyl ether
110 75 8
14.
Chlorofonii
67-66-3
15.
Chloronethane
74-87-3
16.
3-Ch loropropene
107-05-1
17.
1.2-0 i brono-3 - ch loropropane
96-12-8
18.
1,2-Dibroaoethane
106-93-4
19.
Oibroaonethane
74-95-3
20.
trans-1,4-0ich loro-2-butene
110-57-6
21.
0 ich lorod t f1uoroM*thane
75-71-8
22.
1.1-Oichloroethane
75-34-3
?3.
1.2-0ich loroethane
107-06-2
24.
1.1-Otch loroethylenc
75-35-4
25.
trans-l.2-0ichloroethene
156-60-5
26.
1.2-Oichloropropane
78-87-5
27.
tran>-l,3-0ichloropropene
10061-02-6
28.
cis-l,3-0ich loropropene
10061-01-5
23.
1,4-Oioxana
123-91-1
224.
2-Ethoxyethanol
110-80-5
225.
Ethyl acetate
141-78-6
226.
Ethyl banians
100-41-4
30.
Ethyl cyanide
107-12-0
227.
Ethyl ether
60-29-7
31.
Ethyl aethacrylate
97-63-2
214.
Ethylene oxide
75-21-8
32.
lodoMthene
74-88 4
33.
Isobutyl alcohol
78-83-1
??a.
Methanol
67-56-1
34.
Methyl ethyl ketone
78-93-3
1-18
-------
l«lg
I able 1-1 (Continued)
UOAt
reference Constituent CAS no.
no
Volatile oroanics (continued)
??9 Methyl isobutyl ketone 108-10-1
35. Methyl methacry late 80-62-6
3/. Methacry Ionitri le 126-98-7
3tJ. Methylene chloride* 75-09-2
?3Q ?-N itropropone 79-46-9
39. Pyridine 110-86 1
40. 1,1,1.2-letrachloroethane 630-20-6
41. 1,1,2.2-letrachloroethane 79-34-6
4?, Tetrachloroethenc 127-18-4
43. Toluene 108-B8-3
44. TribromoMthane 75-25-2
45. 1.1,1-Irichloroethane /1-55-6
46. 1.1,2-Trichloroethane 79-00-5
47. Irichloroethene 79-01-6
48. Irichloromonofluoronethane 75-69-4
49. 1,2,3-frichloropropane 96-18-4
231. 1,1,2-Trichloro 1,2,2-tr if luoro- 76-13-1
ethane
50. Vinyl chloride 75-01-4
215. 1.2-Xylene 97-47-6
716 1,3-Xylene 108-38 3
217, 1.4 Xylene 106-44-5
Shwivq lit i le oroan ics
51. Acenaphthalene 208-96-8
52. AcaMpfcthww 83-32-9
53. Acatophanom 96-86-2
54. 2-Acaty iMinof luorenc 53-96-3
55. 4-Aaiinobiptwnyl 92-67-1
56. Anilirw 62-53-3
5/. Anthracene 120-12-7
58. Arwite 140-57-8
59. Beni(a)«nthracene 56 55 3
218. Bciual chloride 98-87-3
60. BonztnothioI 108-98-5
61. Deleted
62. 6«uo(«)pyrena 50-32-8
63. 8o»uo(b)f luoranthene 205-99-2
64. Bon2o(gtii)pory lene 191-24-2
65. B«uo(k)f luoranthene 207-08-9
66. p-Banzoquinora 106-51-4
1-19
-------
I S? 1 y
Idblc 1-1 (Cont inueti)
UIMI
reference Constituent CAS no.
no
SanivoUt i le oroanics (continued)
67
Bis(2-chloroethoxy)methane
111 -91 -1
68.
Bis(2-chloroethyl)ether
111-44-4
09.
bis(2-chloro isopropy1(ether
39638-32-9
/Q.
Bis(?-othyIhoxy 1 )phthd Idle
117-81 - 7
71 .
4 Bromophenyl phenyl ether
101 55-3
n.
Butyl benzyl phthalate
85-68 7
/3.
2-sec-Buty 1-4,b-dinitrophenol
88-85-7
74
p-Ch lorodn11ine
106-47-8
75.
Chloroben/iIdle
510-15 6
76.
p-Chloro-m-cresol
59-50-7
//.
2-Ch loronaphthd lene
91-58-7
/8.
2-Chlorophenol
95-57-8
79
3-Chloropropionitrile
542-76 7
80.
Chrysene
218-01-9
81.
ortho-Crasol
95-48-/
8?
para-Crcso1
106-44-5
?3?
Cyclohexanone
108 94 1
83
Dib«ni(a.h)anthracene
53-70-3
84.
0iben/oU.e)pyrene
192-65-4
8b.
l)iben/o(d. i )pyrene
189-55-9
86.
m Dichloroben/ene
541 73 1
87.
o-Dichlorobenzene
95-50-1
88.
p-0 ich lorobenzene
106-46-7
89.
3,3'-0ich loroben/idine
91-94-1
90.
2.4-0 ich loropheno1
120-83 2
91.
2,6-Dictilorophenol
87-65-0
92.
Diethyl phthalate
84-66-2
93.
3,3'-0iMthoiytocfi/ id ine
119-90-4
94.
p Oiaathylaannoaioten/ene
60 11-7
95.
3.3'-0iMethyIbenzidine
119-93-7
96.
2,4-DiMthy 1 phenol
105-67-9
9/.
0 iMtthy 1 phtha Ute
131-11-3
98.
Di-n-butyl phthalate
84 74-2
99.
1.4-0initroto#niene
100-25-4
100.
4,6-Dinitro-o-crcsol
534-S2-1
101.
2,4-0initrophanol
51-28-5
102.
2,4-0initrotoluene
121 14 2
103.
2,6-Dimtrotoluene
606-20-2
104.
Oi-n-octyl phthalate
11/-B4-0
105.
0 i-n-propyInitrosamine
621-64-7
106.
Oipheny laaine
122-39-4
219.
DiphenyInitrosaMine
86-30-6
1-20
-------
15?lg
Table 1-1 (Continued)
UOAI
reference Constituent CAS no.
no.
Sanivoldt i le oruanms (continued)
107. 1.2-0iphenylhydraztne 122-66-7
108. f luoranthene 206-44-0
109. Fluorene 86-73-/
110. Hexachloroben/ene 118-74-1
111. Hexach lorobutadiene 87-68-3
112. Hexachlorocyc lopentadiene 77-47-4
113. Hexach loroethanu 67-/2-1
U4. Hexach lorophenc 70-30-4
115. Hexachloropropene 1888-71-7
116. lndeno(1.2.3-cd)pyrene 193-39-5
11/ Isosafrole 120-58-1
118. Hethapyri lene 91-80-5
119. 3 WethyIcholanthrene 56 49-5
120. 4.4'-Methylenebts
(2-chloroani line) 101-14-4
36. Methyl methancsuIfonate 66-27-3
121. Naphthalene 91-20 3
122. 1.4-Naphthoquinone 130-15-4
123. 1-Naphthylaaine 134-32-/
124. 2-Naphthylaaine 91-59-8
125. p-Nitroam 1 ine 100-01 6
126. Nitrobenzene 98-95-3
12/. 4-Nitrophenol 100-02-7
178. N-Nitro«odi-n-boty lamne 924-16-3
129. N-Nitrosodiethylaanne 55-18-5
130. N-NitrosodiMthylaaine 62-75-9
131. N-NitrottMthylethylaaiint 10595-95-6
132. N-NitroM»rptoline 59-89 2
133. N-Nttrosopip«ridine 100-75-4
134. N-Nitrosopyrrolidine 930-55-2
135. S-Wltro-o-toluidine 99-65-8
136. Pontachlorotoenjone 608 93 5
137. Pentachloroethane 76-01-7
138. Pentachloron11 robenzene 8Z-68-8
139. PentachloroptenoI 87-86-5
140. PhwMcetin 62-44-?
141. Phenanthrene 85-01-8
142. Phenol 106-95-2
220. Phthalic anhydride 8S-44-9
143. 2-Picoline 109-06-8
144. PrwiMide 23950-56 5
145. Pyrent 129-00-0
146. ResorcinoI 108-46-3
1-21
-------
1521 q
Table 11 (Continued)
BOAT
reference Constituent CAS no.
no.
SamvoUtile organics (continued)
147. Safrole 94-59-7
14a. l,Z,4,b-tetr
-------
lS21g
Table 1-1 (Continued)
BOAT
reference Constituent CAS no.
no
Orqanochlorine pesticides (continued)
176. udimu-BHC 58-89-9
177 Inlordane 57-74-9
178. 000 72-54-8
179. OOt 72-55-9
180. 001 '50-29-3
181. Oieldrin 60-57-1
182. Endosulfan I 939-98 8
183. Endosulfan II 33213-6-5
184. Endrm 72-20-8
185. Endrm aldehyde 7421-93-4
186. Heptachlor 76-44-8
187. Heptachlor epoxide 1024-57-3
188. isodrin 465-73-6
189. Kepone 143-50-0
190. Hethoxyclor 72-43-5
191. Toxaphene 8001-35-2
Ph»no»wjcetic acid herbicides
192. 2.4-Oichlorophenoxyacetic acid 94-75-7
193. S11 vex 93-72-1
194. 2.4.5-T 93-76-5
Qraannoliosnhorous insect ictdw
195. Oisulfoton 298-04-4
196. Faiephur 52 85-7
197. Methyl parathion 298-00-0
198. Parathion 56-38-2
199. Phorate 298-02-2
PCBs
200. Aroclor 1016 12674-11-2
201. Aroclor 1221 11104 28 2
202. Aroclor 1232 11141-16-5
203. Aroclor 1242 53469-21-9
204. Aroclor 1248 12672-29-6
205. Aroclor 1254 11097-69-1
206. Aroclor 1260 11096-82-5
1-23
-------
1521 g
I able 1-1 (Continued)
BOAT
reference Constituent CAS no.
no.
Dloxins and furans
? 07. Hexachlorodibcnzo-p-dioxins
?0S. exachlorodtbenzofurans
209. Pentachlorodibenzo-p-dtoxins
210. Pentach lorodibenzofurans
211. Tetrachlorodibcn/o-p-dioxins
212. Tetrach lorod ibenzofurans
213. 2,3.7,8-fetrachlorodibenzo-p-dioxin 1746-01-6
1-24
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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.
The initial BDAT constituent list was published in EPA's Generic
Quality Assurance Project Plan for Land Disposal Restrictions Program
("BDAT") in March 1987. Additional constituents are added to the BDAT
constituent list as more 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,
18 additional constituents (hexavalent chromium, xylenes (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 1ist.
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. A waste can be listed as a toxic waste on the basis that
it contains a constituent in Appendix VIII.
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
1-25
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waste matrix. Therefore, constituents that could not be readily analyzed
in an unknown waste matrix were not included on the initial BOAT
constituent list. As mentioned above, however, the BDAT constituent list
is a continuously growing list that does not preclude the addition of new
constituents when analytical methods are developed.
There are five major reasons that constituents were not included on
the BOAT constituent list:
1. 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.
2. 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.
3. The constituent is a member of a chemical group designated in
Appendix VIII as not otherwise specified (N.O.S.). Constituents
listed as N.Q.S., such as chlorinated phenols, are a generic
group of some types of chemicals for which a single analytical
procedure is not available. Th6 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
constituent list.
4. 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
performance liquid chromatography (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
usually not an appropriate analytical procedure for complex
samples containing unknown constituents.
1-26
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5. 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.
Two constituents (fluoride and sulfide) are not specifically included
in Appendices VII and VIII; however, these compounds are included on the
BDAT list as indicator constituents for compounds' from Appendices VII and
VIII such as hydrogen fluoride and hydrogen sulfide, which ionize in
water.
The BDAT 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; and
• Dioxins and furans.
The constituents were placed in these categories based on their chemical
properties. The constituents in each group are expected to behave
similarly during treatment and are also analyzed, with the exception of
the metals and the other Inorganics, by using the same analytical methods.
(2) Constituent selection analysis. The constituents that the
Agency selects for regulation in each waste are, in general, those found
in the untreated wastes at treatable concentrations. For certain waste
1-27
-------
codes, the target list -"or the untreated waste may have been shortened
(relative to analyses performed to test treatment technologies) because
of the extreme unlikelihood that the constituent will be present.
In selecting constituents for regulation, the first step is to
develop of list of potentially regulated constituents by summarizing all
the constituents that are present or are likely to be present in the
untreated waste at treatable concentrations. A constituent is considered
present in a waste if the constituent (1) is detected in the untreated
waste above the detection limit, (2) is detected in any of the treated
residuals above the detection limit, or (3) is likely to be present based
on the Agency's analyses of the waste-generating process. In case (2),
the presence of other constituents in the untreated waste may interfere
with the quantification of the constituent of concern, making the
detection limit relatively high and resulting in a finding of "not
detected" when, in fact, the constituent is present in the waste. Thus,
the Agency reserves the right to regulate such constituents.
After developing a list of potential constituents for regulation.
EPA 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 on the list. This indicator analysis is done 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 cr-nituents for
this waste code is presented in Section 6 of this background document.
1-28
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(3) Calculation of standards. The final step in the calculation of
the BDAT treatment standard is the multiplication of the average'
accuracy-corrected 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 wel1-designed and
well-operated treatment facilities. Therefore, setting treatment
standards utilizing a variability factor should be viewed not as a
relaxing of section 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.
1-29
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There is an additional step in the calculation of the treatment
standards in those instances where the ANOVA analysis shows that more
than one technology achieves a level of performance that represents
BOAT. In such instances, the BOAT treatment standard for each
constituent of concern is calculated by first averaging the mean
performance value for each technology and then multiplying that value by
the highest variability factor among the technologies considered. This
procedure ensures that all the technologies used as the basis for the
BOAT treatment standards will achieve full compliance.
1.2.5 Compliance with Performance Standards
Usually the treatment standards reflect performance achieved by the
best demonstrated available technology (BDAT). As such, compliance with
these numerical standards requires only 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 standards is prohibited, wastes that are generated in
such a way as to naturally meet the standards can be land disposed
without treatment. With the exception of treatment standards that
prohibit land disposal or that specify use of certain treatment methods,
all established treatment standards are expressed as concentration levels.
EPA is using both the total constituent concentration and the
concentration of the constituent in the TCLP extract of the treated waste
as a measure of technology performance.
1-30
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For all organic constituents, EPA is basing the treatment standards
on the total constituent concentration found in the treated waste. EPA
is using this measurement because most technologies for treatment of
organics destroy or remove organics compounds. Accordingly, the best
measure of performance would be the total amount of constituent remaining
after treatment. (NOTE: EPA's land disposal restrictions for solvent
waste codes F001-F005 (51 FR 40572) use the TCLP extract 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 extract concentration 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 that it reduces the amount of
metal in a waste by separating the metal for recovery; total constituent
concentration in the treated residual, therefore, 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 leachable; accordingly, EPA is also using
the TCLP extract concentration as a measure of performance. It is
important to note that for wastes for which treatment standards are based
1-31
-------
on a metal recovery process, the facility has to comply with both the
total and the TCLP extract constituent concentrations prior to land
disposing the waste.
In cases where treatment standards for metals are not based on
recovery techniques but rather on stabilization, EPA is using only the
TCLP value 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
BDAT for a waste must be the "best" of the demonstrated available
technologies. EPA determines which technology constitutes "best" after
screening the available data from each demonstrated technology, adjusting
these data for accuracy, and comparing the performance of each
demonstrated technology to that of the others. If only one technology is
identified as demonstrated, it is considered "best"; if it is available,
the technology is BDAT.
(1) Screening of treatment data. The first activity in
determining which of the treatment technologies represent treatment by
BOAT is to screen the treatment performance data from each of the
demonstrated and available technologies according to the following
criteria:
1. 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 the waste
code(s) of interest are discussed in Section 3.2 of this
document.)
1-32
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2. 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 true 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.
3. 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 extract concentration for metals from the residual).
In the absence of data needed to perform the screening analysis, EPA
will make decisions on a case-by-case basis as to whether to use the data
as a basis for the treatment standards. The factors included in this
case-by-case analysis will be the 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.
(2) Comparison of treatment data. In cases in which EPA has
treatment data from more than one demonstrated available technology
following the screening activity, EPA uses the statistical method known
as analysis of variance (ANOVA) to determine if one technology performs
significantly better than the others. This statistical method
(summarized in Appendix A) provides a measure of the differences between
two data sets. 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 EPA finds that one technology
performs significantly better (i.e., is "best"), BOAT treatment standards
1-33
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are the level of performance achieved by that best technology multiplied
by the corresponding variability factor for each regulated constituent.
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
technologies.
(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-87-011.
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, all divided by the spike amount added) for
each spiked sample of the treated residual. Once the recovery values are
determined, the following procedures are used to select the appropriate
percent recovery value to adjust the analytical data:
1-34
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1. 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.
2. 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 (1) above.
3. 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 spike 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 using the lowest average value.
4. 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 similar (e.g., if the data represent 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 (1),
(2), and (3) 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 methods, the
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specific procedures and equipment used are documented. 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 standards presented in Section 7 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 oeneratino 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:
1. 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 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.
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2. 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 derived-from wastes meeting the Agency definition of
wastewater (less than 1 percent total organic carbon (TOC) and
less than 1 percent total suspended solids) would have to meet
the treatment standard for wastewaters. All residuals not
meeting this definition would have to meet the treatment
standard for nonwastewaters. EPA wishes to make clear that this
approach is not meant to allow partial treatment in order to
comply with the applicable standard.
3. 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 BDAT 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 261.3(c)(2)(i)) or the mixture rule (40 CFR
261.3(a)(2)(iii) and (iv)) or because the listed waste is contained in
the matrix (see, for example, 40 CFR 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
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separate treatability subcategorization). For the most part, these
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.
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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 listed hazardous waste as originally
generated. Residues 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 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 that
address 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 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 original listed waste. Consequently, these residues are treated
as the original 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
1-39
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covered by the existing prohibitions and treatment standards for the
listed hazardous waste that these residues contain or from which they are
derived.
1.2.8 Transfer of Treatment Standards
EPA is proposing some treatment standards that are not based on
testing of the treatment technology on the specific waste subject to the
treatment standard. The Agency has determined that the constituents
present in the untested 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 data for use in establishing treatment standards for untested
wastes is technically valid in cases where the untested wastes are
generated from similar industries or 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 a case
where only the industry is similar, EPA more closely examines the waste
characteristics prior to deciding whether the untested waste constituents
can be treated to levels associated with tested wastes.
EPA undertakes a two-step analysis when determining whether
constituents in the untested wastes can be treated to the same level of
performance as in the tested waste. First, EPA reviews the available
waste characterization data to identify those parameters that are
1-40
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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 the given waste(s) in Section 3.
Second, when 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
characteristies 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 can be treated as well or better than the tested waste,
the treatment standards can be transferred.
1.3 Variance from the BDAT 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 on which
the treatment standards are based because the subject 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.
1-41
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Variance petitions must demonstrate that the treatment standard
established for a given waste cannot be met. This demonstration can be
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
orrly the inner envelope marked "Treatability Variance" and "Confidential
Business Information" and with the contents marked in accordance with the
1-42
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requirements of 40 CFR Part 2 (41 FR 36902, September 1, 1976, amended by
43 FR 4000).
The petition should contain the following information:
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 1n the treatment
residual or extract of the treatment residual (i.e., using the
TCIP, 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 for a discussion of
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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.
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 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 BDAT, 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 BDAT 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
1-44
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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.
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.
1-45
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2. INDUSTRIES AFFECTED AND WASTE CHARACTERIZATION
The purpose of this section is to describe the industry affected by
the land disposal restrictions for F006, the electroplating processes
generating the waste, and the available waste characterization data.
2.1 Industries Affected
The listed waste F006 is generated as the wastewater treatment
sludges from the following processes: (1) common and precious metals
*
electroplating, except tin, zinc (segregated basis), aluminum, and
zinc-aluminum plating on carbon steel; (2) anodizing, except sulfuric
acid anodizing of aluminum; (3) chemical etching and milling, except when
performed on aluminum; and (4) cleaning and stripping, except when
associated with tin, zinc, and aluminum plating on carbon steel. Using
the 1985 Biennial Report Data Base, EPA identified approximately 4,500
facilities as generators of F006 wastes. Figure 2-1 depicts the number
of f006 generators by State, while Table 2-1 identifies the number
"Zinc plating (segregated basis)" refers to noncyanidic zinc plating
processes. For example, wastewater treatment sludges from zinc plating
using baths formulated from zinc oxide and/or sodium hydroxide would be
excluded from the listing while sludges from baths formulated from zinc
cyanide and/or sodium cyanide would not be excluded. Where both cyanidic
and noncyanidic baths are used, the exclusion applies to sludges from the
noncyanidic processes as long as they are segregated from sludges that
result from cyanidic plating processes.
2-1
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(7
WASHMOTON
NORTH
DAKOTA
MAINE
MONTANA
VERMONT
PUERTO RICO
VIRGIN ISLANDS
NEW
IAMPSHIRE
DAMO
SOUTH
DAKOTA
J 314
NEW YORK
WISCONSIN
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I 237 ;
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it I 2W
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N
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47
KANSAS
DC.
N
MISSOURI
MARYLANO
39
KENTUCKY
NORTH CAROLINA
TENNESSEE
OKLAHOMA
SOUTH
CAROLINA
ARKANSAS
NEW MEXICO
ALABAMA \ GEORGIA
TEXAS
HAWAN
LOUISIANA
.ORIOi
114
FIGURE 2-1 GEOGRAPHICAL DISTRIBUTION OF ELECTROPLATING FACILITIES GENERATING F006 WASTE
-------
i670g/d 25
Table 2-1 Facilities Producing r006 Waste
by State and Region
EPA Region State Number of facilities
I Connecticut 252
Maine 18
Massachusetts 264
New Hampshire 29
Rhode Island 69
Vermont 10
II New York. 314
New Jersey 160
Puerto Rico 27
Virgin Islands 0
III Delaware 5
Pennsylvania 223
Maryland 39
Virginia 47
West Virginia 7
Washington, DC. 1
IV Alabama 54
Georgia 40
Florida 114
Kentucky 40
North Carolina 92
Mississippi 18
South Carolina 62
Tennessee 72
V Illino i s 259
Indiana 131
Michigan 237
Minnesota 59
Ohio 276
Wisconsin 88
VI Arkansas 35
Louisiana 22
New Mexico 10
Oklahoma 39
Texas 169
2-3
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167Oa/d 26
Table 2-1 (Continued)
EPA Region State Number of facilities
VII Iowa 43
kansas 20
Missouri 73
Nebraska IS
VIII Colorado 51
Montana 2
North Dakota 3
South Dakota 4
Utah 26
Wyoming 0
IX California 854
Arizona 68
Nevada 18
X Oregon 34
Washington 38
Hawaii 4
Idaho 9
Alaska
4544
Source: USEPA 1986. F006 generators data extracted from 1965 Biennial
Report date base computer run dated March 12, 1988.
2-4
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of F006 generators by State and by Region. In the preamble for the
Effluent Limitation Guidelines for the Metal Finishing Industry (40 CFR
Part 413), the Agency identified 13,500 facilities in the
electroplating/metal finishing industry that use 46 electroplating and
metal finishing unit operations listed in 48 FR 32482. The 4,500
facilities generating F006 are a subset of the 13.,500 facilities in the
metal finishing industry.
Generators of F006 usually fall under Standard Industrial
Classification (SIC) code series 3000 described as the fabricated metal
products except machinery and transportation equipment; machinery except
electrical; electrical and electronic machinery, equipment, and supplies;
transportation equipment; measuring, analyzing, and controlling
instruments; and miscellaneous manufacturing industries. EPA is
currently compiling data and information on the amount of F006 generated
and the quantities of F006 wastes land disposed. One source of
information estimates that 1.4 million tons of F006 waste are generated
in this country each year. The Agency estimates, on the basis of the
recently compiled EPA Treatment, Storage, Disposal and Recovery Survey,
that approximately 5 million tons of F006 waste are land disposed every
year.
2.2 Process Description
The following subsections describe each of the four operations that
EPA has determined generate F006. These operations are electroplating,
anodizing, chemical etching and milling, and metal cleaning and
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stripping. Figure 2-2 presents a general schematic of an electroplating
wastewater system and shows where F006 is generated.
2.2.1 Electroplating
Electroplating is the application of a thin surface coating of one
metal upon another by electrodeposition. This surface coating is applied
to provide corrosion protection, wear or erosion resistance, or
antifrictional characteristics, or for decorative purposes. The
electroplating of common metals includes the processes in which ferrous
or nonferrous base material is electroplated with the following metals or
metal alloys: copper, nickel, chromium, brass, bronze, zinc, tin, lead,
cadmium, iron, aluminum, or combinations thereof. The alloy brass
consists of copper and zinc; the alloy bronze consists of copper and
tin. Precious metals electroplating include the processes in which a
ferrous or nonferrous base material is plated with gold, silver,
palladium, platinum, rhodium, indium, ruthenium, iridium, osmium, or
combinations thereof.
In electroplating, metal ions in acid, alkaline, or neutral solutions
are reduced on cathodic surfaces. The cathodic surfaces are the
workpieces being plated. The metal ions in solution are usually
replenished by the dissolution of metal from anodes or small pieces
contained 1n inert wire or metal baskets. Replenishment with metal salts
is also practiced, especially for chromium plating. In this case, an
inert material must be selected for the anodes. Hundreds of different
electroplating solutions have been adopted commercially, but only two or
2-6
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Reducing
Agent Acid
Cr*®
Rinse Waters
Collection
Tank
Chromium
Reduction
Tank
Hexavalent
Chromium •
Wastewaters
Polymer
Filtrate to Sewer
or Surface Water
or Recycled to
Collection Tank
Precipitation
Reaction or
Neutralization
Tank
Acld/Alkalt
Wastewaters
F006
(Sludge)
Filter
Collection
Tank
Clarlller
Figure 2-2 General Schematic of a Wastewater Treatment System
-------
three types are used widely for a particular metal or alloy. For
example, cyanide solutions are popular for copper, zinc, brass, cadmium,
silver, and gold. However, noncyanide alkaline solutions containing
pyrophosphate have come into use recently for zinc and copper. Acid
sulfate solutions are used for plating zinc, copper, tin, and nickel,
especially, relatively simple shapes. Cadmium and zinc are sometimes
electroplated from neutral or slightly acidic chloride solutions.
Electroplating baths contain metals, metal salts, acids, alkalies,
and various bath control compounds. All of these material contribute to
the wastewater streams either through part dragout, batch dump, or floor
spill. The sludge from spent plating baths also contains metals.
Table 2-2 outlines some typical electroplating bath chemical compositions.
2.2.2 Anodizing
Anodizing is an electrolytic oxidation process that converts the
surface of the metal to an oxide. These oxide coatings provide corrosion
protection, decorative surfaces, a base for painting and other coating
processes, and special electrical and mechanical properties. Aluminum is
the most frequently anodlzed material, while some magnesium, stainless
steel (electropolish), and limited amounts of zinc and titanium are also
treated.
Although most of anodizing is carried out by the immersion of racked
parts in tanks, continuous anodizing is done on large coils of aluminum
performed in a manner similar to continuous electroplating. For aluminum
parts, the formation of the oxide occurs when the parts are made anodic
2-8
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J670g/p 1
Table 2-2 Typical Electroplating Baths and Their Chenical Composition
Plating compound Constituents Concentration (g/1)
Cadmium cyanide CadniiiR oxide 22.5
Cadmus 19.5
Sod it* cyanide 77.9
Sodium hydroxide 14.?
Cadmium fluoroborate Cadnium fluoroborate 251.2.
Cad# tun (as metal) 94.4
Aumoniun fluoroborate 59.9
Boric acid 27.0
Chromium electroplate Chromic acid 172.3
Sulfate 1.3
Fluoride 0.7
Copper cyanide Copper cyanide 26-2
Free sodiu* cyanide 5.6
Sodiup carbonate 37.4
Roche lie salt 44.9
Gold cyanide Gold (as potassiiw 8
gold cyanide)
Potassium cyanide 30
Potassium carbonate 30
Depotassiue phosphate 30
Acid nickel Nickel sulfate 330
Nickel chloride- 45
Boric acid 37
SiIwr cyanide Silver cyanide 35.9 .
Potassiw cyanide 59.9
Potasstia carbonate (atn.) 15.0
Metallic silver 23.8
Free cyanide 41.2
Zinc cyanids Ztnc sulfate 374.5
Sodiua sulfate 71.5
Magnesium sulfate 59.9
Reference: USCPA 1980b.
2-9
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in dilute sulfuric acid or dilute chromic acid solutions. The oxide
layer begins formation at the extreme outer surface, and as the reaction
proceeds, the oxide grows into the metal. The oxide formed last, known
as the boundary layer, is located at the interface between the base metal
and oxide. The boundary is extremely thin and nonporous. Chromic acid
anodic coatings are more protective than sulfuric acid coatings and have
a relatively thick boundary layer. For these reasons, a chromic acid
bath is used if a complete rinsing of the part cannot be achieved.
2.2.3 Chemical Etching and Milling
These processes are used to produce specific design configurations
and tolerances or surface appearances on parts by controlled dissolution
with chemical reagents or etchants. Included in this classification are
the processes of chemical milling, chemical etching, and bright dipping.
Chemical etching is the same process as chemical milling, but the rates
and depths of metal removal are usually much greater in chemical
milling. Typical solutions for chemical milling and etching include
ferric chloride, nitric acid, ammonium persulfate, chromic acid, cupric
chloride, hydrochloric acid, and combinations of these reagents. Bright
dipping is a specialized form of etching that is used to remove oxide and
tarnish from ferrous and nonferrous materials and is frequently performed
just prior to plating. Bright dipping can produce a range of surface
appearances from bright clean to brilliant depending on the surface
smoothness desired for the finished part. Bright dipping solutions
usually involve mixtures of two or more of these acids: sulfuric,
chromic, phosphoric, nitric, and hydrochloric.
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2.2.4 Metal Cleaning and Stripping
Metal cleaning and stripping operations are designed to prepare metal
surfaces for electroplating. Cleaning activities involve a preliminary
bath which may include solvent degreasing, emulsion cleaners, and/or
alkali or acid cleaners. Following precleaning, metal parts are usually
electrocleaned. This step typically employs an alkaline solution and
cement to provide either anodic or cathodic cleaning. A third type of
electrocleaning referred to as periodic reversal (PR) employs an
alternating anodic/cathodic current to remove smut, oxide, and scale from
ferrous metal parts. Cleaning baths eventually become contaminated with
metals derived from the cleaned parts and result in generation of sludges
that may be hazardous.
Metal stripping is the chemical removal of metal plating coatings
from base metal products by immersion of the plated part in an aqueous
bath of appropriate chemical composition. When a plated coating on a
part does not meet product quality specifications, it may be more
economical to remove the metal plating and replace the part rather than
scrap the entire plated part. Stripping baths can contain strong
alkaline solutions of cyanide salts (for instance to strip copper plating
from steel parts) or strong acids. The stripping solution dissolves the
plated coating, leaving the base metal essentially untouched.
2.3' Waste Characterization
All waste characterization data available to the Agency for the F006
waste are summarized below. The major constituents in the waste and
2-11
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their approximate concentrations are presented in Table 2-3. Table 2-4
presents the concentration of each BDAT list metal constituent and
cyanide in the waste. The concentration of individual metals is
dependent on the type of electroplating solutions used in the
electroplating process.
The waste characterization data presented in this background document
are solely for the F006 sludge generated following the treatment of
electroplating wastewaters. The Agency wishes to emphasize that sludges
generated from treatment of spent cyanide plating baths are also
classified as F007, F008, or F009 under EPA's "derived from" rule (40 CFR
261.3(c)(2)(i)). An example is a spent nickel sludge generated from
nickel cyanide plating solution (an F007 wastewater). This bath solution
may be sent through cyanide destruction and metal hydroxide precipitation
for nickel removal separate from other wastewaters. The precipitated
residual would be F007.
2-12
-------
16/Qg/p 4
lable 2-3 Major Constituents in F006 Waste
Constituent Concentrations (X)
Solids 2-/3
(Consisting of metal precipitates,
including the BOAT metals
associated with a particular
electroplating process, (usually
hydroxides) and urireacted
treatment chemicals (usually lime))
Water 24-98
Cyanide 0-.05
lota I organic carbon 0.04-3.0
100
2-13
-------
I able 2-4 BM1 Const ituent Conpos it ion for Untrpated I 006 Waste
Concent rat ion (tn—1
Constituent Source 1 Source 2 Source 3 Source 4 Source b Source 6 Source 1
HetaIs
154.
Antiaony
MA
MA
<10
22 4
HA
155.
Arsenic
HA
2 S
<0 4
<6.24
156.
Bar iua
0.74 - OS.5
MA
20 4S
28.8
9 57
IS/.
Berylliua
HA
MA
<2
<0.1
<97.6
ISS.
Cadniua
1.3 - 720
1.280 - 4.070
10 20
0.37-1.75
<11 1.320
HO 22.000 0 003 1.180
159.
lota 1 chraaiun
2 - 49.000
147 - 8.610
3.200 - 75.000
1,650 2.625
35 730
700 137,000 <0.00? 290.000
160.
Capper
1.4 - 27.400
345 - 28.100
90 - 775
1.87 135
<6 760
161.
Lead
1.69 - 24,500
MA
85 134
184 305
<6 408
<0.001 13.900
16?.
Mercury
MA
<1
<0.2
<0.32
163.
Nickel
234 23.700
1.330 - 26.000
7.300 -49.000
11.8 17
0.06-170.000
164.
SeleniuB
MA
<10
<0.03
<19 <23
I6S.
Silver
0.51 - 38.9
MA
<2
<0.6-
-------
16/0g/p 6
table 2 4 (Coot inucd)
_____ Concentrat ion (i>pm)
Constituent Source 1 Source 2 Source 3 Source 4 Source 5 Source 6 Source 7
Organic (continued)
Z Butanone
<25 <26
Carbon disulf ide
<4 9 <5 .2
Carbon tetrachloride
<4.9 <5.2
Chlorobenzene
<4.9 <5.2
Chloroethane
<1? <13
2-Chloroethy1 vinyl ether
<4.9 <5.2
Chlorof om
<4.9 <5 2
Ch lorwethane
<1? <13
C is -1,3-d ich loropropene
<4.9 <5 2
0 ibronochloroaethane
<4.9 <5 2
1. I D ich loroethane
<4 9 <5 2
1 .2-Dich loroethane
<4.9 <5 2
1.1 -Dichloroethy lene
<4.9 <5.2
1 ,2Dichlorapropane
A
*
ID
A
&
f\3
f thylbeiurene
<4.9 <5.2
?Hexanone
<25 <26
Methylene chloride
<12 <13
4 -Methy1pentanone
<25 <26
Styrene
<4.9 <5 2
1,1.2.2-letrachloroethane
<12 <13
let rachlorethylene
<4.9 <5 2
loluene
<4 9 <5 2
lrans-I,2-dichloroethylene
<4.9 <5 2
1rans-1.3-dichloropropene
<4 9 <5.2
1 r ich loroethy lene
<4 ? <5,2
Vinyl acetate
MA
Vinyl chloride
<12 <13
Xylenes (total)
<4 9 <5.2
-------
lable ? 4 (Continued)
Concentration (diwiI
Constituent Source I Source ? Source 3 Source 4 Source S Source 6 Source /
Other Parameters
Iluoride
Oil and grease (ag/g)
Moisture X
SP gravity (g/ml)
Acidity as CaCo^ (mg/l)
Alkalinity as CaCO^ (aj/l)
Sulf ide
lota I organic carbon
. HA = Not analyzed.
o>
Source 1 - Table I fro* CheaicaI Waste Management Report lechnical Hole 8/11/.
September 22. 198/. Ihe complete data set for this facility can be found in Appendix B.
Source 2 - Mil draft memo to Id Abrams. tPVOSW. dated November 5. 1987.
Source 3 - Onsite engineering Analysis Report for Envirite Corp., December 19. 1986. lable 613.
Source 4 - Nam to Ron lurner from R.O. Grotelueschem, John Deere Company, dated January IS. 1988.
Source S - f006 Waste description from Inviron Report. 1984.
Source 6 - Listing Qociment lable 2 data provided on a dry-weight basis.
Source 7 - Data extracted for fable 3 of Oraft Report. Review of Delisting Petitions for California list wastes subject to land Disposal Restrictions.
Versar Inc...March 1986.
0.03 - 37.7
?9.I - 91.2
4/4 48 94
1.38 1.493
1.41?
?68
-------
3. APPLICABLE/DEMONSTRATED TREATMENT TECHNOLOGIES
In the previous section, a discussion of the industry and process
generating F006 waste and a major constituent analysis of this waste were
presented. This section describes the applicable and demonstrated
treatment technologies and performance data for treatment of F006 waste.
The technologies that are considered applicable to the treatment of F006
waste are those that treat BOAT list metals by reducing their
concentration and/or their leachability in the waste. Included in this
section are discussions of those applicable treatment technologies that
have been demonstrated (i.e., are used on a full-scale basis for
treatment of F006 waste). As shown in the previous section, F006 waste
is principally composed of water, precipitated metals including BOAT list
metals, other solids, cyanides, and low concentrations of volatile and
semivolatile organics. The individual organic constituents present in
F006 waste are measured at parts per billion levels. These
concentrations are not believed to be treatable.
3.1 Applicable Treatment Technologies
EPA has identified three technologies as potentially applicable for
treatment of F006--stabilIzation, vitrification, and metals recovery.
The first two technologies are designed to reduce the leachability of the
metals; the third reduces both the total concentration and the
leachability of the metals.
Stabilization chemically reduces the mobility of hazardous metal
constituents in a waste. Stabilizing agents, binders, and chejnicals are
3-1
-------
added to a waste to minimize the quantities of metals that leach when the
waste is in contact with water. Commonly used stabilization agents
include portland cement, 1ime/pozzolan-based material, and cement kiln
dust. Stabilization is described in Section 3.3.
Vitrification has also been identified by the Agency as an applicable
technology. A vitrification process is used to immobilize hazardous
constituents in the F006 waste to produce a vitrous or glass-like mass.
Available performance data for this technology can be found in Section 4.
EPA has also identified high temperature metal recovery technologies
as applicable. All high temperature metal recovery technologies act to
reduce the concentration of metal in the waste through volatilization and
recovery.
3-2 Other Treatment Technologies to Reduce the Generation of FQ06
A number of treatment technologies are available to reduce the amount
of F006 that is initially generated or to generate F006 in such a manner
that the leachability of constituents in1 it is reduced. EPA will be
examining such technologies as part of its work in developing treatment
standards for "0" wastes in the Final Third waste group. A brief
discussion of many of these discussions can be found in EPA's Development
Document for Effluent Limitations Guidelines and Standards for the Metal
Finishing Point Source Category.
3.3 Demonstrated Treatment Technologies
Available information shows that all of the applicable technologies
are demonstrated. Stabilization is used by at least ten facilities to
3-2
-------
treat F006 wastes. EPA knows of two full-scale facilities that use
metals recovery for F006 wastes and one full-scale facility that treats
F006 waste by vitrification. Below are detailed discussions of
stabilization and high temperature metal recovery.
3.3.1 Stabilization of Metals
Stabilization refers to a broad class of treatment processes that
chemically reduce the mobility of hazardous constituents in a waste.
Solidification and fixation are other terms that are sometimes used
synonymously with stabilization or to describe specific variations within
the broader class of stabilization. Related technologies are
encapsulation and thermoplastic binding; however, EPA considers these
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 BDAT list metals and having a high filterable solids content,
low total organic carbon content, and low oil and grease content. This
technology is commonly used to treat residuals generated from treatment
of electroplating wastewaters. For some wastes, an alternative to
stabilization is metal recovery.
(2) Underlying principles of operation. The basic principle
underlying this technology is that stabilizing agents and other chemicals
are added to a waste to minimize the amount of metal that leaches. The
3-3
-------
reduced "teachability is accomplished by the formation of a lattice,
structure and/or chemical bonds that bind the metals to the solid matrix
and thereby limit the amount of metal constituents that can be leached
when water or a mild acid solution comes into contact with the waste
materi al.
There are two principal stabilization processes used--cement-based
and lime-based. A brief discussion of each is provided below. In both
cement-based or 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*C/25506F to 1500'C/2730eF). 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
3-4
-------
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 may also be incorporated
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.
(c) Cement kiln dust process. A standard cement kiln dust (CKD)
method is used for liquid wastes that do not pass the paint filter test
(PFT) as received. Table 3-1 gives cement kiln dust composition data for
the type of dust used for the stabilization of F006 waste. When cement
kiln dust is used with liquid wastes, the mix ratio of 1 is common; for
solid wastes, the mix ratio is typically 0.2 to 0.5. If the water
content is. high, then the higher mix ratio of 1.5 appears to be
adequate. Typically, the mixture is cured at 38°C/100°F to
stimulate the temperature rise for 24 hours. No additional additives or
/
fixative agents are necessary; at times, water may be added to the
mixture to aid in mixing the waste and stabilizing agent (in this case,
cement kiln dust) and to maximize utilization of the reagent.
-------
]6/Og/pj 8
Idblc 3-1 Cement Kiln Oust Composition Odta
Constituent
Concentration (my/I)
Total composition TCLP
Other characteristics
BDAT Wt;td Is
Arsen ic
Bar lum
Cd&nium
Chromium (total)
Copper
Lead
Hercury
Nickel
Selenium
SiIver
Z inc
38
92./
3.14
31.9
44.8
1!>6
<0.033
12.6
8.67
4.13
65.6
<0.01
2./ 4
<0.01
0.05
0.16
0.29
<0.001
0.02
0.03
0.02
0.04
"mi?
Altasinun
Iron (total)
Magnes iim
31,000
15.200
3,790
NA
NA
NA
Other Non-BOAT Constituents
Sodium
Potass i t
Calcine
2300
33,100
41,900
NA
NA
NA
Total sulfide (pp»)
Ash content (X)
Total residua (0 105*c)X
Alkalinity (as CaO X)
pH (10X solution)
<8
99.8
100
56.16
12.55
NA » Not available
Reference:: Special waste analysis report dated June 15, 1987.
Provided by Cheenca 1 Waste Ha nag—¦ nt (Technical Center).
Actiinistrative Record for F006).
(See
3-6
-------
(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 location of the waste in relation
to the disposal site, the particular stabilization formulation to be
used, and the curing rate. After curing, the solid formed is recovered
from the processing equipment and shipped 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
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 generally can be
used with wastes. Weighing conveyors, metering cement hoppers, and
mixers similar to concrete batching plants have been adapted in some
operations. 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
3-7
-------
on an untested waste as on a previously tested waste, 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
(1) other metals and their concentrations, (2) fine particulates,
(3) oil and grease, (4) organic compounds, and (5) sulfates and chloride
concentrations.
(a) Other metals and their concentrations. When a waste contains
a mixture of metals, it may not be possible to chemically stabilize the
waste in a manner that optimizes the reduction in leachability for all
constituents. The extent to which synergistic effects impact performance
will depend on the type and concentration of other metals in the waste.
The individual metals present and their concentrations can be measured by
EPA Method 6010.
(b) Fine particulates. For both cement-based and
1ime/pozzolan-based processes, the literature states that very fine solid
materials (i.e., those that pass through a No. 200 mesh sieve, 74-um
particle size) can weaken the bonding between waste particles and cement
by coating the particles. This coating can inhibit chemical bond
formation and decrease the resistance of the material to leaching.
(c) 011 and grease. The presence of oil and grease in both
cement-based and 11me/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 chemical bond formation,
thereby decreasing the resistance of the material to leaching.
3-8
-------
(d) Organic compounds. The presence of organic compounds in the
waste interferes with the chemical reactions and bond formation, which
inhibits curing of the stabilized material. This results in a stabilized
waste having decreased resistance to leaching.
(e) Sulfate 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 dimensional stability of the cured matrix,
thereby increasing leachability potential.
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 should be optimized so that the
amount of leachable metal constituents is minimized are (1) selection of
stabilizing agents and other additives, (2) ratio of waste to stabilizing
agents and other additives, (3) degree of mixing, and (4) curing
conditions.
(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, therefore, will affect the
leachability 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
3-9
-------
of sulfates in a waste must be considered when a choice is being made
between a 1ime/pozzolan-based system and a Portland cement-based system.
To select the type of 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 other additives. The
amount of stabilizing agents and other 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 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.
(c) Mixing. 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 undermixing
and overmixing are undesirable. The first condition results in a
nonhomogeneous mixture; therefore, areas will exist within the waste
where waste particles are neither chemically bonded to the stabilizing
3-10
-------
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 generally are determined through laboratory tests. 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. The 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,
resulting in too little water being available for completion of the
stabilization reaction. The duration of the curing process, which should
also be determined during the design stage, typically will be between 7
and 28 days.
3-11
-------
3.3.2 High Temperature Metals Recovery
High temperature metals recovery (HTMR) provides for recovery of
metals from wastes primarily by volatilization and collection. The
process yields a metal product or products for reuse and reduces the
concentration of metals in the residual. This process also significantly
reduces, the amount of treated waste that needs to be land disposed.
There are a number of different types of high temperature metal
recovery systems; these systems generally differ from one another
relative to the source of energy and the method of recovery. Such HTMR
systems include the rotary kiln process, plasma arc reactor, rotary
hearth/electric furnace system, molten slag reactor, and flame reactor.
This technology is different from retorting in that HTMR is conducted in
a carbon-reducing atmosphere while the retorting process simply vaporizes
the untreated metal.
(1) Applicability and use of high temperature metals recovery. This
process is applicable to wastes containing BOAT list metals with low
water content (or a water content that can either be blended to the
required level or lowered by dewatering) and low concentration of
organics. The technology is applicable to a wide range of metal salts
including cadmium, chromium, lead, mercury, nickel, and zinc.
This process is usually not used for mercury-containing wastes even
though mercury will volatilize readily at the process temperatures
present in high temperature units. The rotary kiln recovery process is
3-12
-------
one example of the technology, and it has been applied to zinc-bearing
wastes as an upgrading step that yields a zinc oxide product for further
refinement and subsequent reuse. Although this technology was originally
developed in the 1920s for upgrading zinc from ores, it has recently been
applied to electric furnace dust from the steel-making industry.
(2) Underlying principles of operation. The basic principle of
operation for this technology is that metals are separated from a waste
through volatilization in a reducing atmosphere where carbon is the
reducing compound. An example chemical reaction would be:
2ZnO + C - 2Zn + CO,
2
In some cases, the waste contains not only BOAT list metal
constituents that can be volatilized but also nonvolatile BOAT list
metals. In such cases, the HTMR process can yield two recoverable
product streams. Whether such recovery can be accomplished, however,
depends on the type and concentration of metals in the original
wastestream. Below is a discussion of the recovery techniques for the
volatile stream, as well as for the waste material that is not
volatilized.
(a) Recovery of volatilized metals. The volatilized metals can
be recovered in the metallic form or as an oxide. Recovery is
accomplished in the case of the metallic form by condensation alone and
in the case of the oxide by reoxidation, condensation, and subsequent
collection of the metal oxide particulates in a baghouse. There is no
difference between these two types of metal product recovery systems
3-13
-------
relative to the kinds of waste that can be treated; the difference is 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.
(b) Less volatile treatment residuals. The fraction of the
waste that is not 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 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 process. The
process essentially consists of four operations: (1) a blending operation
to control feed parameters, (2) high temperature processing, (3) a
product collection system, and (4) handling of the less volatile treated
residuals. A generic schematic diagram for high temperature metals
recovery is shown in Figure 3-2.
(a) Blending operation. For the system shown, variations in
feeds are minimized by blending wastes from different sources. Prior to
3-14
-------
K061
CARBON
REUSE
FLUXES
(ADDITIVES)
in
FEED
BLENDING
RESIDUAL
COLLECTION
HIGH
TEMPERATURE
PROCESSING
PRODUCT
COLLECTION
RECOVERY OR
LAND DISPOSAL
FIGURE 3-1 EXAMPLE HIGH TEMPERATURE METALS RECOVERY SYSTEM
-------
feeding the kiln, fluxing agents are added to the waste. Carbon is also
added to the waste as required. The fluxes (limestone or sand) are added
to react with certain waste components, preventing their volatilization,
thus improving the purity of the desired metals recovered. In addition,
the moisture content is adjusted by either adding water or blending
various wastes.
(b) High temperature processing. These materials are fed to
the furnace, where they are heated and the chemical reactions take
place. The combination of residence time and turbulence helps ensure
maximum volatilization of metal constituents.
(c) Product collection. As discussed previously, the product
collection system can consist of either a condenser or a combination
condenser and baghouse. As noted earlier, the particular system depends
on whether the metal is to be collected in the metallic form or as an
oxide.
(d) Handling of less volatile treatment residuals. The
equipment needed to handle the less volatile metal treated residuals
depends on the final disposition of the material. If further recovery
were performed, then the waste would be treated in another furnace. If
the material were to be land disposed, the final process step would
generally consist of quenching.
(4) Waste characteristics affecting performance In determining
whether high temperature metals recovery technologies are likely to
achieve the same level of performance on an untested waste as on a
3-16
-------
previously tested waste, EPA will examine the following three waste
characteristics that have an impact on treatability: (1) type and
concentrations of metals in the waste, (2) relative volatility of the
metals, and (3) heat transfer characteristics of the waste.
(a) Type and concentrations of metals in the waste. Because
this is a metals recovery process, the product must meet certain
requirements for recovery. If the waste contains other volatile metals
that are difficult to separate and whose presence may affect the ability
to refine the product for subsequent reuse, high temperature metals
recovery may provide less effective treatment. Analytical methods for
metals can be found in SW-846.
(b) Relative volatility. The relative volatilities of the
metals in the waste also affect the ability to separate various metals.
There is no conventional measurement technique for determining the
relative volatility of a particular constituent in a given waste. EPA
believes that the best measure of volatility of a specific metal
constituent is the boiling point. EPA recognizes that the boiling point
has certain shortcomings, primarily the fact that although boiling points
are given for pure components, the other constituents in the waste will
affe.ct partial pressures and, thus, will affect the boiling point of the
mixture. EPA has not identified a parameter that can better assess
relative volatility. Boiling points of metals can be determined from the
literature.
3-17
-------
(c) Heat transfer characteristics. The ability to heat
constituents within a waste matrix is a function of the heat transfer
characteristics of a heterogeneous waste material. To be volatilized and
recovered, the constituents being recovered from the waste must be heated
near or above their boiling points. Whether sufficient heat will be
transferred to the particular constituent to cause the metal to
volatilize will depend on the heat transfer characteristics of a 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
conductivity is named "Guarded, Comparative, Longitudinal Heat Flow
Technique"; it is described in Appendix D.
(5) Design and operating parameters The parameters that EPA will
evaluate when determining whether a high temperature metals recovery
system is well designed and well operated* are (1) the furnace
temperature, (2) the furnace residence time, (3) the amount and ratio of
the feed blending materials, and (4) 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. For sufficient heat to be transferred
to the waste for volatilization, high temperatures must be provided. The
higher the temperature in the furnace, the more likely the constituents
are to react with carbon to form free metals and volatilize. The
3-18
-------
temperature must be approximately equal to or greater than the boiling
point of the metals being volatilized. Excessive temperatures could
volatilize unwanted metals into the product, possibly inhibiting the
potential for reuse of the volatilized product. In assessing performance
during the treatment period, EPA would want continuous temperature data.
(b) Furnace residence time. Furnaces must be designed to
ensure that the waste has sufficient time to be heated to the boiling
point of the metals to be volatilized. The time necessary for complete
volatilization of these constituents is dependent on the furnace
temperature and the heat transfer characteristics of the waste. The
residence time is a function of the physical dimensions of the furnace
(length, diameter, and slope (for rotary kilns)), the rate of rotation
(if applicable), and the feed rate.
(c) Amount and ratio of feed blending materials. For the
maximum volatilization of the metals being recovered, the following feed
parameters must be controlled by the addition of carbon, fluxes, and
other agents if necessary; blending of these feed components is also
needed to adjust the following feed parameters to the required volume:
carbon content, moisture content, calcium-to-silica ratio, and initial
concentration of the metals to be recovered. These parameters all affect
the rate of the reduction reaction and volatilization. EPA will examine
blending ratios during treatment to ensure that they comply with design
conditions.
3-19
-------
(d) Mixing. Effective mixing of the total components is
necessary to ensure that a uniform waste is being treated. Turbulence in
the furnace also ensures that no "pockets" of waste go untreated.
Accordingly, EPA will examine the type and degree of mixing involved when
assessing treatment design and performance.
3-20
-------
4. PERFORMANCE DATA BASE
This section discusses all available performance data that EPA has on
the demonstrated technologies discussed in Section 3 (stabilization, high
temperature metals recovery, and vitrification). Performance data
include the untreated and treated waste concentrations for a given
constituent, the operating values that existed at the time the waste was
being treated, the design values for the treatment technology, and data
on waste characteristics that affect treatment performance. EPA has
provided all such data to the extent that they are available in tables
found at the end of this section.
EPA's use of these data in determining the technology that represents
BOAT, and in the development of treatment standards, is discussed in
Sections 5 and 7, respectively.
4.1 Stabilization Data
The stabilization data that the Agency has evaluated in the
development of treatment standards for F006 are discussed below. EPA is
presenting some of these data in this document; other data on
stabilization of F006, evaluated but not used in the development of the
treatment standards, can be found in the Administrative Record for this
rulemaking.
The stabilization data that the Agency evaluated, but did not use in
the development of the treatment standards for F006 were for the most
part insufficient to assess treatment effectiveness. Specifically, the
Agency did not have sufficient data on the binder-to-waste ratios to
4-1
-------
assess dilution effects, or data on the untreated leachate values were
insufficient to determine whether treatment had occurred. These data
consist primarily of EPA delisting petition data and data submitted in
response to the California List "Notice of Availability" and the First
Third rule. As noted above, all these data can be found in the
Administrative Record for this rulemaking.
The data that EPA is using for the development of treatment standards
for F006 are shown in Table 4-1. These data consist of a total of 209
treated data points for 11 metals. Nine of the 10 separate wastes are
stabilized using two distinct binder-to-waste ratios; the other waste is
stabilized using one binder-to-waste ratio. These data were submitted to
EPA by a member of the waste management industry. The data represent
wastes from a range of electroplating industries including automotive
part manufacturing, aircraft overhauling, zinc plating, small engine
manufacturing, circuit board manufacturing, and four wastes identified as
F006 but not specifically characterized.' A discussion of how EPA used
these data in the development of the BOAT treatment standards can be
found in Sections 5, 6, and 7.
4.2 Hioh Temperature Metals Recovery
For high temperature metals recovery, EPA has untreated and treated
waste data that include F006 wastes; however, the available data cannot
be used to determine the level of performance achieved specifically for
F006 wastes. The available high temperature metals recovery data that
include treatment of F006 waste are shown in Table 4-2. As can be seen,
the untreated waste data represent a range of wastes including D007,
-------
F006, K061, K062, carbon fines, unspecified grindings, slag, and other
wastes. The data were taken over a 5-month period (January through May
of 1988), and analyses were performed for 12 different metals including
chromium, lead, and nickel.
The treated waste data, shown in Table 4-3, do not correspond to the
untreated waste data shown in Table 4-2; however, these data represent
treatment of the same type of wastes described above. The available data
do not provide any information as to the percentage of F006 in the
untreated wastes from which the treated waste data were generated.
4.3 Vitrification
For vitrification, EPA has performance data from one facility. The
data consists of one data set showing the total concentration in the
untreated waste and the TCLP leachate concentrations in the treated
waste. EPA does not have data showing the concentrations of TCLP
leachate of the untreated waste, nor does the Agency have data on the
specific types or amounts of additives used in the vitrification
process. The data on this process are shown in Table 4-4.
4-3
-------
I9S5g
faille 4-1 Performance Data for Untreated and frealed 1006 Wastes
Source
Oil and
grease
Ja&aL-
IOC
Nix
rat ioArsen ic Bar in
Metal concentrations Iwl
CadaiuM Chroaiias
Copper
lead
Mercury Nickel Seleniua Silver
I inc
Unstabilued
As received
IQP
Stabilized
iar
1.520 14.600
<0.01
0.2 <0.01
36.4
0.00
0.12
1.3 12/0
0.01 0.34
0.01
0.51
40.2
0.15
0.20
35 5
0.26
0 30
435
<0.001 0.71
<0.001
0.04
<0.01
0.06
2.3 1560
0.01 0.16
0 03
0.03
Auto part
¦anufacturing
Unstatn li/ed
As received
lap
Stabilized
TttP
TUP
GO
1.500
0.2
0.5
<0.01
<0.01
<0.01
21.6
0.32
0.50
0.42
31.3
2.21
0.50
0.01
755
0.76
0.40
0.39
7030
368
5.4
0.25
409
10.7
0.40
0.36
989
<0.001 22.7
<0.001
<0.001
1.5
0.03
<0.01
0 06
0.11
6.62
0.14
0.03
0.05
4020
219
36 9
0.01
Aircraft overhauling
Unstabili?ed
As received 37.000
TUP
Stabilized
TOP
TUP
13/,000
0.2
0.5
0.01
<0.01
<0.01
85.5
1.41
0.33
0.31
67.3
1.13
0.06
0.02
716
0.43
0.08
0.20
693
1.33
1.64
1.84
25.7
0.26
0.30
0.41
<0.001
<0.001
<0.001
259
i.l
0.23
0.15
<0.01
0.07
0.11
39
0.02
0.20
0.05
631
5 41
0 05
0 03
Aerospace Manufacturing
(aixture of F006 ft F007)
Unstabili/ed
As received 3.870
TUP
Stabi I ized
lap
lttP
8.280
10
1.5
<0.01
<0.01
<0.01
0.74
0.83
0 5?
1 18
1.69
0.66
<0.01
0 01
12.9
7.58
0 40
0 34
18.6
4 12
0.23
0.19
114
6.86
0.20
0 36
0.003
<0.001
<0 001
234
158
4 35
2 4/
<0.01
0.1/
0.20
6 26
1.64
0.09
0.15
8.86
2.2 8
0 05
0 03
-------
1975g
table 4 1 (Continued)
Source
Oil and Mix
grease IOC ratioaArsenic
(n/fcq)
Hi'lal concentrations (pawl
Bariuai Cadaiun Chraaiuai Copper
Lead
Mercury Nickel Selenm
S i Iver
Z inc
Zinc plating
Unstabi lized
As received
TttP
Stabilized
lap
IttP
I.ISO 21.200
0.2
0.5
<0.01
<0.01
17.2
0.84
0.?0
0.23
1 30
0 22
0.01
0 01
110
0. IB
0.23
0.30
IS10
4.6
0 30
0.21
88.5
0 45
0.30
0.34
<0.001
<0 001
<0.001
3/
0.52
0 10
0 02
0 08
0.14
9.OS 90200
0.16 2030
0.03
0.04
32
0 04
U1
Unknown
Uhstabilized
As received
iap
Stabilized
iap
iap
¦ill engine
Manufacturing
Unstabilized
As received
iap
Stabilized
iap
iap
20.300 28.600
2.770
6.5S0
0 2
OS
0 2
OS
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
14.3
0.38
0.31
0.19
24.5
0.07
0.30
0.33
720
23.6
3.23
0.01
7.28
0.3
0.02
0.01
12200
25.3
0.25
0.38
3100
38.7
0 21
0.76
160
1.14
0.20
0.29
1220
31.7
0 21
0 20
52
0.45
0.24
0.36
113
3.37
0.30
0.36
<0.001
<0.001
<0 001
0.003
<0.001
<0.001
701
9.78
0 53
0.04
19400
730
16 5
0.05
<0.01
0 04
0.09
<0.01
0 05
Oil
5.28
0.08
0.04
0.06
4 08
0.12
0.03
0.05
35900
867
3 4
0 03
27800
1?00
36 3
0 04
Circuit board
Manufacturing'1
Unstabilized
As received
ICtP
Stabilized
ICIP
iap
130
550
0 2
0.5
<0.01
<0.01
<0.01
12.6
0.04
0.04
0 14
5 39
0 06
0.01
0 01
42900
360
3 0
I 21
10600
8 69
0 40
0.42
156
1.0
0 30
0.38
<0.001
<0.001
<0.001
13000
152
0.40
0.10
<0 01
0 04
0.0/
1?. 5
0 05
0.03
0 05
120
0.6?
0 0?
0 0?
-------
I able 4 I (Cant invert)
Source
Oil and
grease IOC
t—ftg) Ino/ka)
Metal concentrations JeesL
Hi*
ratio*Arsenic Bar iub Catkiwi Chrcniu* Copper lead Mercury Nickel Seleniu* Silver
I inc
Unknown
Itastabilized
As received
lap
St alii tiled
ICtP
far
30 10,700
0.2
0.5
<0.01
<0.01
<0.01
IS.3
0.53
0.32
0.27
5 81
0.18
0.01
0.01
47.9
0.04
0.10
0.2
17600
483
0.50
0 32
169
4.22
0 31
0.37
<0.001
<0.001
<0.001
23700
644
IS.7
0 04
<0 01
0.07
0.07
8.11
0.31
0.03
0.05
15700
650
4 54
0 0?
-f*
I
a*
UW tab lined
As received
iar
Stabilized
iar
iar
1.430 5,960
0.2
0.5
0.08
<0.02
<0.02
19.2
0.28
0.19
0.00
5.04
0.01
<0.01
<0.01
644
0.01
0.03
0.21
27400
16.9
3.18
0.46
24500
50.2
2.39
0.27
<0.001
<0 001
<0 001
5730
16.1
109
0.02
<0.45
<0.01
<0.01
19.1
<0.01
<0.01
<0.01
32?
1.29
0.07
<0 01
*Hix rat io = weight of reagent
Height of waste
^Circuit hoard Manufacturing waste is not in its entirety defined as f006; however, an integral part of the Manufacturing operation is electroplating.
Ireataent residuals generated fro* treataent of these electroplating wastes are f006.
Source: OM 1987.
-------
*'?°3
0.31
0 37
0.15
2.80
84.00
89.00
14 10
0.20
0 87
0 91
0.90
0 63
2 00
I 20
I 31
1 50
0 57
3 40
0.66
3.80
table 4 2 Untreated Wastes lor Recovery in Rotary llearth I urnace
January 1988
0 40
0.?6
1.20
1.50
2 60
? .40
0 66
0 88
0 75
0 91
0 1?
1.90
4.80
10.60
7.88
8.70
8.10
29 96
4 40
8.38
13 30
0 50
5.00
0.00
2 50
1.50
2.30
1.61
2.50
2.?0
3 40
0.01
9 30
7.80
1 50
1 60
4.18
0 50
-------
A!,03
3 40
0.?0
0.3?
0 4?
1.99
0 IB
0 ?l
0 38
0.13
0 ?3
0 08
0.88
0 89
0.99
0.10
0.50
l.?8
I 29
2 00
i 20
?.36
0 94
I SO
0 21
lable 4 ? (Continued)
lehruary 1988
Fe Cr Hi Mn Cu Co Ho
Values in percent
Pb SiO? CaO
42.10
7.30
5.SO
1.00
0 14
0.01
0 12
0.066
4.20
0 44
7.90
2 30
9 30
/ 80
37.40
7.20
5.00
0.?4
0.23
0.06
0 05
0.016
1.30
?.?0
0 16
0 ?4
4.80
10 60
3/30
9.90
4.40
1.33
0.48
0.19
0.?9
0.015
0 50
0.48
0.03
0 16
1 10
0 34
20.30
3.20
13.30
0.36
0.15
0.25
0.94
0 01?
0.1?
0 08
0 05
0 10
0 58
0 4/
24.40
f .20
10.00
0.29
4.10
0.10
0.05
0.040
0.80
0.?0
0.0/
0.07
3 00
3 04
7.40
6.60
36.SO
0.44
0.06
0.07
0.05
0.020
0.81
0.16
0.01
0 0/
1 40
10/
9 40
0.00
32.30
0.43
0.06
0 08
0.05
0.028
0.10
0.30
0.09
0.11
3 80
?.?9
22.50
3.20
17.00
0.34
0.17
0.72
0.71
0.010
0.0?
0 01
0.10
0 14
0 90
0.?4
24 90
9 30
3.50
0.10
0 05
0 06
0.0!
0.044
0.24
0 15
0.05
0.05
4.80
1.90
3S.50
13.30
3.70
1.50
0.43
0.17
0 ?8
0.0?
0.00
0.00
0 0?
0.16
? 30
0 35
39 10
7.70
5.10
0.96
0.39
0.21
0.22
0.0?
0.00
0.00
0.0?
o.?o
0/6
0.28
27.10
0.34
2.42
4.44
0.49
0.13
0 55
0.0?6
0.50
0.40
5.??
1.10
8.00
8 14
34.10
9.16
3.18
2.36
0 53
0.27
0.40
0.052
0.30
0.30
1 49
0.51
4.68
9 04
36. SO
6 60
S.60
0.67
0.24.
0.25
0.17
0.072
0.30
0.25
0.0?
0.14
16.03
0.34
47.40
14.SO
1.00
0.01
0.09
0.10
0.11
0.0.6
0.0?
0.01
0.10
0.10
0.75
0 SO
21.00
29.10
1.30
0.10
0.10
0.05
0.11
0.010
0.00
4.60
0.19
0.01
0.50
0 01
?8 50
4.20
6 00
0.40
0.25
0.22
0.16
0.06
0.00
0.00
0.03
0.15
?9.00
0.34
30.20
4.SO
6.30
0.44
0.26
0.22
0.14
0.05
0 00
0.00
0.03
0.23
?6.10
0 37
2.00
0.00
0.00
0.00
0.00
0.00
0.00
0.019
85.00
0.50
0.00
0 00
S.00
0 00
S6./0
10.30
5 80
0.85
0 80
0.15
0 44
0.023
1.50
1.30
0.1?
0.1?
?.50
1.50
SI .50
9.30
11.60
0.7S
0 69
1.33
1.03
0.0?6
1.51
l.?9
0.5?
0 ?3
6.?0
1.61
54.00
B.70
11.30
0.10
0.78
0.76
0 SI
0.035
0.10
0.10
0.10
0 10
1.35
0 10
S3.SO
a io
2.65
1.00
0 47
0.18
0 3?
0.018
0.50
0.?0
0.10
0 10
?.S0
? ?0
59 80
9.6?
5.7?
I.I?
0.39
0.23
0 21
0.043
1.10
0.30
0 04
0 20
0.88
0 26
-------
?190g
Iable 4 2 (Continued)
March 19(18
Va lues in percent
Materia 1
Fe
Cr
Hi
Nn
Cu
Co
Mo
P
C
S
In
Pb
SiO?
CaO
MgO
A12°3
0007
33.SO
15.60
4.70
1.75
0.31
0 18
0.40
0.016
4 20
0.44
0 70
0 3?
1 00
0/6
0 40
0 36
0007
37.3S
7.57
4.97
1.50
0.31
0.70
0.?8
0.0.5
1 30
2.20
0 02
0.20
1 00
0 55
0 25
0.10
0007
26.70
7.30
4.40
1.43
0.38
0.70
0 36
0.018
0.50
0 48
0 05
0 22
1 00
0 39
0 21
0 14
0007
73.00
3.60
70.10
0.30
0.15
0.18
0.7?
0.015
0.12
0.08
0 10
0 05
0 90
0.50
0.33
0.50
0007
7.3S
6.SO
35.00
0.64
0.06
0.1?
0.02
0.044
0 80
0.20
0.01
0 08
1 5?
1 70
0 1?
0 19
0007
6.90
6.30
35 00
0.6?
0.07
0.10
0 05
0.047
0 81
0.16
0 02
0 0/
1 50
1 66
0 1?
0 ?3
0007
76.70
8.10
17.70
0.7?
7.40
0.10
0.05
0.036
0.10
0.30
0 05
0 0/
2 30
2.20
0 1?
3 40
0007
37.00
9.70
4.79
t.4?
0.48
0.18
0.27
0.014
0 00
0.00
0 06
0 24
0.75
0.29
0 22
0 16
0007
40.10
7.10
5.74
1.09
0.47
0.7?
0 25
0.019
^ 0 .00
0.00
0 02
0.2?
0 91
0 63
0 18
0 23
0007
40.00
8.30
5.59
1.34
0.51
0 71
0.27
0 018
0.00
0.00
0 04
0 21
1 20
1 12
0 56
0 24
0007
30.70
4.50
6.69
0.44
0.76
0.7?
0.14
0 049
0.00
0 00
0 03
0 23
26 10
0.3/
0 46
1.29
0007
39.50
9.90
4.89
1.00
0.34
0.70
0.19
0.017
0 00
0.00
0 03
0 1/
1 10
O./O
0 40
0 30
0007
6.70
6.60
37.50
0.55
0.06
0 40
0.05
0.700
0.00
0 00
00?
0 0/
2 10
1 55
0.40
0.20
0007
6.90
5.90
35.70
0.50
0.06.
0.09
0.05
0.035
0 00
0.00
0 05
0 08
1 90
4.20
0.17
0 20
KOSi
76. St
8.39
7.57
4.51
0.54
0.13
0.7?
0.073
0.50
0.40
4 55
0 99
7 55
9 00
6 1?
0 84
K06?
34.58
10.10
4.04
7.10
0.5S
0.35
0.37
0.041
0 30
0.30
1.44
0 SO
5.10
/ 45
2.20
0 81
K06?
36.00
5.30
5 89
0.48
0.75
0.76
0.14
0.055
0 30
0.25
0.02
0.15
25 60
0 31
0 39
1 14
K0G7
30.70
4.70
4.69
0.46
0.74
0.18
0.15
0.057
0 50
0.30
0.0 2
0 20
22 30
0 40
0 60
1.0/
K06?
31.70
4.60
5.69
0.41
0.7?
0.73
0.18
0.055
0 0?
0.01
0 05
0.16
18 20
0.34
0 58
1 02
IC06?
58.10
19.90
7.00
0.10
0.13
0.70
0.1/
0.016
0.0?
0.0!
0.10
0.10
0 24
0 50
0 0?
0 12
K06?
3S.70
6.80
5 89
0 54
025
0 74
0 14
0 053
0 24
0 IS
0.04
0 22
18 90
0 3/
0 41
0 91
K06?
3.00
0 01
0 01
0 01
0 01
0 01
0.01
0 030
72 40
1 00
0 01
0 01
9 80
I/O
0 50
4.60
K06?
78.50
4 60
6.19
0 44
0 23
0 70
0 16
0 063
0 30
0 30
0.0?
0 ?0
0 50
2 80
0 80
2 00
Carbon Tines
7.00
0.00
0.00
0 00
0 00
0 00
0 00
0 019
85 00
0 50
0 00
0 00
5 00
0 00
0 00
2 00
lerro Silicon
66.50
0 00
0 00
0 00
0 00
0 00
0 00
0 000
0 00
0 00
0 00
0 00
33 50
0 00
0 00
0 00
Or indings
58.70
10.30
5 98
0.85
0 80
0 15
0 44
0073
1 50
1 30
0 12
0.12
2 SO
I 50
0 40
1 20
Mi II Scile
53.87
8.85
7.93
0/7
0 5/
0 13
0 30
0 0? 4
0 50
0 20
0 10
0.10
3 ?0
1 84
0 15
1.07
hnhu Waste
80.40
5.00
4.10
0 68
0 14
0 01
0 35
0 024
0 10
0 10
0 10
0 10
0 BO
0 01
0 01
0 01
Pellets
58.00
0.15
0 15
0.40
0 10
0 10
0 10
0 0??
0 30
0.30
0 0?
o.?o
0 50
2 80
0 80
2 00
Swarf
60 71
10 85
5.55
7.1?
0 45
0 10
0 59
0.038
1 10
0 30
0 04
0 ?0
6 43
1.39
0 10
/ 60
Swarf
46.50
12.00
6 50
1 00
0 ?/
0 25
0 30
0 034
0 00
0 00
0 00
0 00
5 10
2.10
0 35
2 50
-------
Idble 4 ? (Continued)
April I9H8
Materia)
Te
Cr
Ni
Cu
Va lues in percent
Co
No
P
In
Pb
S iO,
CaO
NgO
ai?o3
o
000/
000/
000/
000/
F006
K061
*062
UK?
K062
Carbon Fines
lerro Silicon
Gr Hidings
Hill Scale
Pellets
Swarf
SMirf
36.00
20.9/
14.76
0.56
12.80
27.88
33.10
3/. 16
31.19
2.00
66.50
63.57
53.60
58.00
59 60
46.50
11.30
4 99
/.3I
9.20
6.20
10.10
9.71
6.00
25.30
0.00
0 00
8.57
9.50
0.15
10./0
12.00
4.10
17.55
25.05
0.00
32.30
2.29
3.04
4.84
0.87
0.00
0.00
10.77
3.40
0.15
5.00
6.50
0.98
0.31
0.81
0.00
0.00
4.58
2.91
0.57
0.10
0.00
0.00
0.85
0.77
0.40
2.12
1.00
0.39
0.15
0.61
0.00
0.65
0.56
0.64
0.24
0 10
0.00
0.00
0.93
0.65
0.10
0.51
0.27
0 26
1 48
0.15
0.00
0.00
0 14
0.23
0.25
0 20
0.00
0.00
0.36
0.15
0.10
0.57
0.25
0 30
0.82
0.04
0.00
0.06
0.73
0.46
0.13
0)9
0.00
0.00
0.59
0.30
0.10
0.33
0.30
0 073
0.012
0 039
0.010
0.150
0.072
0.032
0.061
0 010
0.109
0.000
0.035
0.023
0.022
0.039
0.034
I 30
0 1?
0 80
0 00
0.10
0.50
0.30
0.30
0 0?
85.00
0.00
1.50
0.50
0.30
1.10
0.00
2.20
0.08
0.20
0.00
0.30
0.40
0.30
0.25
0 01
0.50
0.00
1.30
0.20
0.30
0.30
0.00
0 03
0.04
0 05
0.00
0.00
4.01
?.60
0.1?
0.10
0.00
0.00
0.12
0.10
0 02
0.04
0.00
0 19
0 10
0.07
0 00
0.00
0 99
0.70
0.14
0.10
0.00
0 00
0.1?
0.10
0.20
0.?0
0.00
I 04
0.60
1.9?
0.64
6.00
7.25
5 44
18.??
0 ?4
5 00
33.50
1.63
3.?0
0.50
6 87
5.10
0.43
0.21
2 59
6.40
0.00
8.16
6.48
0 65
0 50
0.00
0 00
1 50
1.84
2.80
1.39
2.10
0 ?3
0.25
0 36
0.66
0.00
5.22
? 81
0.68
0 0?
0 00
0 00
0.40
0 15
0.80
0.10
0.35
0 18
0 55
1 45
0 96
0.00
0 75
0 90
1.0?
0.12
? 00
0.00
1 53
1.07
2.00
5.25
2.50
-------
A.?°3
0.33
0 39
6 46
0 96
0.13
0 00
0.7/
8.30
0 71
0 50
0 1?
ZOO
0.00
I?.04
1.07
1 07
0.00
4 13
lable 4 ? (Continued)
ttiy 1988
Values in percent
fe
Cr
Ni
Nn
Cu
Co
No
P
t
s
Zn
Pb
Si0?
CaO
34 89
9 89
4.55
0.72
0.47
0.18
0.27
0.019
1.30
2 20
0 09
0 17
1.28
0.4?
lb.60
13.66
12.70
0.43
0.14
0.47
1.23
0 009
0 50
0 30
0.15
0 13
1.04
0.46
27.98
6.68
5.57
0.65
1.28
0.11
0 07
0.028
0 80
0.20
0 05
0.1?
6.74
10.93
0.56
9.20
0.00
0.00
0.00
0.00
0.00
0.010
0 00
0.00
0 00
0.00
0.64
8 40
62.20
5.90
0 09
0.50
0.02
0.08
0.05
0.075
2.30
0.03
0 00
0.00
0.75
0.50
12.80
6.20
32.30
0.00
0.65
0.00
0 06
0.1.50
0 10
0.30
0 00
0 00
6.00
0 00
27.60
10.00
2.46
4.49
0.57
0.13
0.59
0.020
0.50
0.40
4 68
1 ?4
6 65
8 76
45.00
10.10
0.85
0.00
0.55
0.10
0.05
0.025
3.60
0.26
0.00
0.00
50 70
1 80
37.26
9.67
3.21
146
0.53
0.32
0 31
0.044
0 30
0 30
0.88
0 31
4 37
8.36
40.91
7.20
5 06
0.62
0.24
0.28
0.13
0 048
0 30
0.25
0 0?
0 1?
9 17
0.??
37.70
25.30
0.87
0.10
0.10
0.20
0.19
0.010
0 0?
0.01
0 10
0 10
0.?4
0.50
2.00
0.00
0.00
0.00
0 00
0.00
0.00
0.019
85.00
0.50
0 00
0 00
S.00
0.00
66.50
0.00
0.00
0 00
0.00
0.00
0.00
0.000
0.00
0.00
0.00
0 00
32.50
0 00
26.00
10.00
22.40
0.31
0.22
0.6?
2.10
0.044
0.12
0.08
0.04
0 10
6.89
0.21
51.95
9.70
12.94
0.85
1.08
0.33
0.66
0.027
1.50
1.30
0.1?
0.1?
1.76
1.50
58.50
9.90
3.90
0.77
0.50
0.13
0.25
0.020
0.50
0.20
0 10
0 10
3 ?0
1.84
0.01
0.01
5.88
0.00
0.01
0.15
0.00
0.005
0.00
0.00
O.OO
0.00
0.00
0 00
53.40
11.74
7.00
2.12
0.57
0.44
0.38
0.034
1 10
0.30
0.04
0 20
6.26
1 39
-------
720? g
table 4-
¦3 High Temperature Metals Recovery-Ireated Samples
Cr
Kg C a
Si
MgO
CaO
Si0?
A1?03
(X)
(X) (X)
(X)
(X)
(X)
(X)
(X)
Ave X
3.32
8.86 20.27
10.60
14.37
28.38
22.68
Max X
7.64
10.20 23.80
12.45
16.93
33.32
26.64
Low X
0.83
6.73 16.80
8.55
11.27
22.40
18.30
March t of samples
186
186 186
186
186
186
186
Ave X
3.03
15.71
26.10
22.51
15.55
Max X
5.75
32.54
30.04
27.26
16.25
Low X
0.73
12.19
16.80
19.26
14.99
April # of Saeples
159
159
159
159
3
Ave X
3.61
14.33
27.09
21.98
Md< X
6. SO
17.41
31.15
26.10
Low X
0.8S
11.66
23.23
18.93
May I of Samples
146
146
146
146
TOTAL #
491
491
491
491
3
Not*: The treated data represent 491 slag assays covering the period March through Nay 1988. For each metal
for which data Mm provided, the table than the reported mater of data points for that metal, the
average value, the aaxiaua value, and the ainiase value*. Value* are reported as percentages. Slag
assay* include residues resulting froa the rotary hearth furnace treataant of the following wastes:
K061. K062. F008. 0007, Mill scale, swarf, slag, carbon fines, (unhazardous waste. Miscellaneous. and
grinding*. In addition, the slag also includes residue resulting fras electric arc saalting furnace
treatment of cold reduced pellets. EF carbon, doloaite, and dill scale.
4-12
-------
)97Sg
lable 4-4 Vitrification of F006
Constituent Untreated (mg/kg) Treated TCLP values (mg/1)
Ant imony
-
<0.06
Arsenic
-
<0.01
Barium
-
<0.2
Beryllium
-
<0.005
Cadnium
4.5
<0.005
Chromium
30,600
0.089
Copper
1/
6.0
Lead
1,760
<0.005
Mercury
-
<0.0002
Nickel
CI.040
11.0
Selen turn
-
<0.005
S ilwer
-
<0.01
Thallium
-
<0.01
Zinc
13.700
0.10
4-13
-------
5. IDENTIFICATION OF BEST DEMONSTRATED AVAILABLE TECHNOLOGY
In this section, EPA explains its determination of which technology
represents the "best" level of performance in addition to being
demonstrated and available. As discussed in Section 3, the demonstrated
treatment technologies are stabilization, metals recovery, and
vitrification.
As shown in Section 4, some performance data is available for all of
the demonstrated technologies. The data on high temperature metals
recovery and vitrification, however, are insufficient to assess the level
of treatment achieved by these technologies on F006 wastes. EPA finds,
therefore, that available data support stabilization as the technology
that provides the "best" level of performance for F006 wastes. Note:
Both high temperature metals recovery and vitrification can be used to
treat F006 wastes provided these technologies achieve the
performance-based treatment standards. Additionally, EPA may reevaluate
these technologies as candidates for BDAT if more data become available.
In addition to being "best," stabilization is also "available" in
that it is commercially available and provides substantial treatment. In
determining whether stabilization provides "substantial" treatment, EPA
first evaluated the data base (shown in Section 4) to determine whether
any data should be deleted because the data are generated from treatment
of wastes determined to be less representative of F006 than other wastes
for which EPA has treatment data. EPA's review of the data showed that
waste from the aerospace manufacturing industry contained both F006 and
5-1
-------
F007 wastes. EPA deleted these data from consideration because the
Agency had other data on treatment of F006 wastes alone and because EPA
had no information as to the percentage of F006 and F007 in the aerospace
industry waste.
EPA's assessment of substantial treatment also included review of the
data to determine whether any data should be deleted because they could
be shown to not represent a wel1-designed and/or well-operated system.
EPA reviewed the treatment data associated with each binder-to-waste
ratio and deleted data from the less effective binder-to-waste ratio;
this process resulted in deletion of 99 treated data points (see Table
D-l in Appendix D for specific constituents deleted). Other data were
deleted for individual constituents for one of the following reasons:
(1) the treated leachate concentration was higher than the untreated
waste leachate concentration; (2) insufficient information was present on
the untreated constituent to determine treatment effectiveness (i.e.,
without the untreated leachate value, it is not possible to determine
whether the treated leachate value represents a significant reduction);
(3) the untreated leachate concentration was already at a low level (at
or below 0.02 ppm), and therefore the treated value is not meaningful in
determining treatment performance; and (4) the treated level of
performance could be attributed solely to dilution from the binder. The
specific constituents deleted for each rationale are shown in Table D-l
in Appendix 0.
5-2
-------
In general, although a specific leachable concentration of
constituent may not be reduced or, in some cases, may increase after
stabilization, EPA does not believe that this is the basis for
eliminating consideration of the sample where substantial treatment
occurs. We believe this approach is reasonable in that the data not used
are the anomalous results that will occur when constituents are at or
below the treatable concentrations. (When operating near minimum
solubilities, small changes in pH, for example, can cause increases in
leachable concentrations.) We believe that this in no way affects the
results where substantial treatment of other constituents occurs. By
only using the data where treatment occurred, EPA has essentially assumed
that each waste has the highest observed concentrations from any waste in
every waste. This approach obviously is conservative with respect to the
ability of any specific generator to comply with the standard. This is
clearly supported by the fact that no measurement in any of EPA's TCLP
data base exceeded the promulgated standard when the proper chemical
binders and mix ratio were used.
Further, it has been alleged that EPA's data base for F006 has been
somehow tainted by the fact that additional testing by the same data
source using different k11n dusts did not achieve the same zinc and
copper performances. The data source has denied that this is the case,
and EPA sees no technical basis for such an assumption. If, in fact,
zinc and copper performance was not attained with other kiln dusts, it
was more likely the result of the zinc and copper content of the specific
5-3
-------
kiln dusts than of any specific matrix impact on the pozzolanic capture
of the metals. However, EPA will consider any data supporting other
conclusions.
The performance data that EPA used in assessing substantial treatment
are shown in Table 5-1. As shown, stabilization achieved reductions in
the leachate value for all of the metals selected for regulation.
(Section 6 presents a detailed discussion of constituents selected for
regulation.) Specifically, leachate reductions were as high as 2.2 mg/1
for cadmium, 358 mg/1 for chromium, 49 mg/1 for lead, 729 mg/1 for
nickel, and 0.25 mg/1 for silver.
The Agency believes the reduction in the range and magnitude of the
various hazardous constituents to be substantial. Stabilization has been
determined to be demonstrated and best, has provided substantial
treatment, and is commercially available; therefore, stabilization
represents BOAT for F006 nonwastewaters.
5-4
-------
Iable S-l Accuracy-Corrected Performance Data for Untreated and treated (006 Wastes by Stabilization
Hi* Hetal concentrations tPf)
Source ratio' Bariiaa Cadaiiaa Chraaiua Copper Lead Nickel Silver Zinc
Unknown
Unstabilized
As received
lap
Stabilized .
iap
0.2
435
0 71
0 05
1560
0.16
0.03
Auto part aanufactur ing
Unstabi lized
As received
lap
Stabilized
lap
0 5
31.3
2.21
0.01
755
0.76
0.45
7030
638
0.27
409
10 7
0.39
989
22.7
0.03
6.6?
0.14
0.06
40?0
219
0.01
in
i
(71
Aircraft overhauling
Unstabilized
As received
lap
Stabilized
lap
0.2
85.5
1.41
0.34
61.3
1.13
0.06
716
0.43
0.09
259
1.1
0.27
631
5.41
0.03
Zinc plating
Unstabilized
As received
lUP
Stabilized
lap
0.5
17.2
0.84
0.25
1.30
0.22
0 01
1510
4.6
0 21
37
0.52
0.02
9.05 90.200
0.16 2050
0 05
0.04
Unknown
Unstabilized
As received
iap
Stabilized
ICtP
0.5
14.3
0.38
0.21
720
23.6
0.01
12,200
25.3
0.44
160
1.14
0.31
701
9 78
0.04
25.900
86/
0.03
-------
2?00g
lable b ) (Coi)linued)
Source
Mix
rat ioa
BariiM
Caikiw
Metal concentrations (pom)
ChroMiuM
Copper
lead
* icke 1
Si Ner
I inc
Small engine Manufacturing
Unstabilized
As received
ICIP
Stabilized
iar 0.5
7 28
0.3
0.01
3.100
38.7
0.89
1220
31.7
0.31
113
3 37
0.39
19.400
730
4.08 27.800
0.1? 1200
0 06
0.06
0 040
Circuit board unufacturinq
Unstabi lized
As received
icip
Stabilized
TUP OS
5 39 42.900
0.06 360
0.01
1.4!
10.600
8.69
0.4S
IS6
1.0
0 41
13.000
152
0.11
120
0 62
0.020
Unknown
Unstabilized
As received
ICIP
Stabilized
ICtf
0.5
IS.3
0.53
0.294
5.81
0.18
0.01
17.600
483
0 35
169
4 22
0 40
23.700
644
0.04
8.11
0.31
0.06
15.700
650
0.020
Unknown
Uistabilized
As received
IQP
Stabilized
tap
0 5
19.2
0.28
0.087
27.400
16 9
0 50
24.500
50.2
0.29
5.730
16.1
<0.0?
322
1 ?9
<0 01
*M»* ratio = weight of reagent
weight of waste
Source: CUM 1987
-------
6. 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, EPA may revise this list as additional data and
information become available. The list is divided into the following
categories: volatile orgartics, semivolatile organics, metals, inorganics
other than metals, organochlorine pesticides, phenoxyacetic acid
herbicides, organophosphorous insecticides, PCBs, and dioxins and furans.
This section describes the selection of the constituents to be
regulated for KQ61. In general, EPA regulates all constituents that are
found in the untreated waste at treatable concentrations and are not
likely to be reduced by regulation of other constituents. As noted in
the Executive Summary, EPA is regulating only specific constituents for
K06J where the treatment technology represents stabilization.
6.1 Identification of BDAT list Constituents in F006 Maste
As discussed in Sections 2 and 4, the Agency has characterization
data as well as performance data from treatment of F006. All these data,
as well as information on the waste generating process, have been used to
determine which BDAT list constituents may be present in the waste and
therefore are potential candidates for regulation in F006 nonwastewater.
Table 6-1, a standard table for the First Third wastes background
documents, shows which constituents were analyzed, which constituents
were detected, and which constituents the Agency believes to be present
even though not detected in the untreated waste. For constituents that
were detected, the concentration range is shown.
6-1
-------
Under the column "Believed to be present," constituents other than
those detected in the untreated waste are marked with an X or Y if EPA
believes they are likely to be present in the untreated waste. For those
constituents marked with X, an engineering analysis of the waste
generating process indicates that they are likely to be present
(e.g., the engineering analysis shows that a particular constituent is a
major raw material). Those constituents marked with Y have been detected
in the treated residual(s), and thus EPA believes that they are present
in the untreated waste. Constituents may not have been detected in the
untreated waste for one of several reasons: (1) none of the untreated
waste* samples were analyzed for these constituents, (2) masking or
interference by other constituents prevented detection, and/or (3) the
constituent is indeed not present (such a case can occur when the waste
of concern is defined as being generated by a process and the process can
involve a number of different constituents, only some of which would be
present in any given sample).
6.2 Selection of Constituents
As shown in Table 6-1, 15 constituents have been detected and no
additional constituents have been identified as believed to be present.
Of these constituents, EPA has selected cadmium, chromium, lead, nickel,
and silver for regulation. Of the remaining constituents not being
regulated, 7 are believed to be treatable. EPA 1s not regulating copper
and zinc because these constituents are not in Appendix VIII as elemental
constituents but rather are listed in Appendix VIII as specific metal
compounds (i.e., copper cyanide, zinc phosphate, and zinc cyanide).
6-2
-------
Regulation of the other BOAT metals will reduce leachate concentrations
of both these metals. EPA is not regulating any of the other treatable
constituents because the untreated leachate concentrations of these
metals are far below the regulated constituents.
6-3
-------
2166g
Table 6-1 Status of BOAT List Constituent Presence
in Untreated F00(i Waste
BOAT
reference Constituent
no.
Detection Believed to
status* be present
Volatile organics
727
Acetone
NO
1.
Acetonitri le
NA
2.
Acrolein
NA
3.
Acrylonitri le
NA
4.
Benzene
NA
5.
Bromodichloromethane
NO
6.
Bromomethane
NO
223.
n-Buty 1 a Icoho 1
NA
7.
Carbon tetrachloride
NO
8.
Carbon disulfide
NO
9.
Chlorobenzene
NO
10.
2-Chloro-1.3-butadtene
NA
11.
Chlorod ibramoNethanc
NO
12.
Ch loroethane
NO
13.
2-Chloroethyl vinyl ether
NO
14.
Chlorofom
NO
15.
Ch loromethane
NO
16.
3-Ch loropropene
NA
17.
1,2-0ibraiio-3-chloropropane
NA
18.
1.2-0ibranoethane
NA
19.
Oibromowethane
NA
20.
trans-1.4 Dichloro 2 butene
NA
21.
0 ichlorodi fluoromethane
NO
22.
1,1-0 ich loroethane
NO
23.
1,2-0ich loroethane
NO
24.
1,1 -Oichloroethylene
NO
25.
t rans-1.2-Dichloroethene
NO
26.
1,2-0ichloropropane
NO
27.
trans-1,3-0 ichloropropene
NO
28.
cis-1,3-0ichloropropene
NO
29.
1,4-Oioxane
NA
224.
2-Ethoxyethano1
NA
225.
Ethyl acetate
NA
226.
Ethyl benzene
NO
30.
Ethyl cyenide
NA
227.
Ethyl ether
NA
31.
Ethyl aethacrylate
NA
214.
Ethylene oxide
NA
32.
lodot thane
NA
33.
lsobutyl alcohol
NA
2?8.
Methanol
NA
34.
Methyl ethyl ketone
NO
6-4
-------
21G6q
Table 6 1 (Continued)
BOAT Detection Believed to
reference Constituent status* be present
no.
Volat1 le organics (continued)
?29. Methyl isobutyl ketone NO
36. Methyl mcthacrylate NA
37. Methacrylonitrile NA
3B. Methylene chloride ND
230. 2-N itropropane NA
39. Pyridine NA
40. 1,1,1.2-Tetrachloroethane NA
41. 1,1,2,2-Tetrachloroethane ND
4?. letrachlorocthene ND
43. Toluene ND
44. TribromMthane NO
4b. l.l.l-lrichloroethane NA
46. 1,1,2-Trichlorocthane NA
47. Trichloroethene NO
48. TrichloroMonofluoronethane NA
49. 1.2,3-TrichloropropaiM NA
231. 1,1,2-Trichloro-1,2.2-
trif luoroethane NO
50. Vinyl chloride NO
215. 1,2-Xylene NO
216. 1,3-Xy lene NO
217. I,4-Xylene NO
Sawivalat i le oraamcs
51. Acenaphthalene NA
52. Acenaphthene NA
53. AcataphMOM NA
54. 2-Acety laainof luorene NA
55. 4-Aninotoiptwnyl NA
56. Aniline NA
57. Anthracene NA
58. Araait* NA
SS. Bew(a)anthracen» NA
218. Berual chloride NA
GO. Bwuwwthtol NA
61. Oeleled
62. 6«uo(a)pyr«ne NA
63. Bcnzo(b)f luoranthMW NA
64. Befuo(ghi) per y lene NA
65. B«uo(k)f luoranthene NA
66. p-Beruoquinone NA
6-5
-------
2166q
Table 6 1 (Continued)
BOAT
reference Constituent
no.
Detection Believed to
status3 be present
Semivolat i le oraamcs (continued)
6/.
Bis(2-chloroethoxy)methane
NA
68
Bis(2-chloroethy1)ether
NA
69.
Bis(2-chloroisopropyl)ether
NA
70.
B is(2-ethylhexy1)phthalate
NA
/1.
4-Bramopheny 1 phenyl ether
NA
72.
Butyl benzyl phthalate
NA
73.
2-sec-Butyl 4,6-dinitrophenol
NA
74.
p-Chloroani1ine
NA
/!).
Ch lorobenz i late
NA
76.
p-Chloro-w-creso1
NA
77.
2-Chloronaphthalene
NA
78.
2-Chlorophenol
NA
79.
3-Ch loroprop ionitr i le
NA
80.
Chryseno
NA
81.
ortho-Cresol
NA
82.
para-Cresol
NA
232.
Cyclohexanone
NA
83.
0 i benz(a,h)anthracene
NA
84.
0 i benzo(a,e)pyrene
NA
as.
Dibenzo(a.i)pyrene
NA
86.
m-0ichlorobenzene
NA
87.
o-Dichlorobenzcne
NA
88.
p- 0ich lorobenzene
NA
89.
3,3'-Dich lorobenzidine
NA
90.
2,4-0ichlorophenol
NA
91.
2.6-0ichlorophenol
NA
92.
Diethyl phthalate
NA
93.
3.3' -DiMthoxytwiu idine
NA
94.
p-D iwthy lam i noazofcenzene
NA
95.
3,3'-D inathy lbeiw id ine
NA
96.
2,4-DlMthy lpheno 1
NA
97.
OiMthyl phthalate
NA
98.
Di-n-butyl phthalate
NA
99.
1.4-Dtnitrobenzene
NA
100.
4,6-0initro-o-cresol
NA
101.
2,4-Dimtrophenol
NA
102.
2.4-Dinitrotoluene
NA
103.
2,6-Oinltrotoluene
NA
104.
Di-n-octyl phthalate
NA
105.
Di-n-propylnitrosa«nne
NA
106.
OiphonyIa*ine
NA
219.
Oiphenylnitrosaanne
NA
6-6
-------
2166<|
Table 6 1 (Continued)
BOAT Detection Believed to
reference Constituent status* be present
2SL
Semi volatile oroanics (continued)
1,2-Diphenythydraz me MA
10B. F luoranthene NA
109. Fluorene NA
110. Hexachlorobenzene NA
111. Hexach lorobutadiene NA
112. Hexach lorocyclopentadienc NA
113. Hexachloroet hane NA
114. Hexachlorophene NA
115. Hexachloropropene NA
116. Inderal 1,2.3-cd)pyreno NA
117. Isosafrole NA
118. Methapyrilene NA
119. 3-Nethy Icholanthrene NA
1?0. 4,4'-Nethylenebis
(2-chloroani1ine) NA
36. Methyl Mthanesulfonate NA
121. Naphthalene NA
122. 1,4-Naphthoquinone NA
123. 1-Naphthylamine NA
124. 2-Naphthylanine NA
12!). p-Nitroani line NA
126. Nitrobenzene NA
127. 4-Nitrophenol NA
128. N-Nitrosodi-n-tHitylMifM NA
129. N-Nitrosodiethylaaiirw NA
130. N*Nitrosodiaethylaaine NA
131. N-NttroMMthylethylaaiine NA
132. N-Nttroscaorpholine NA
133. N-Nitrosopiperidine NA
134. n«*ttro»apyrrohdine NA
135. S-Nltro-o-toluidine NA
136. Pentachlorobenzene NA
137. Pentachloroethane NA
138. Pentachloronitroben/ene NA
139. Pentachloropheno 1 NA
140. PtafMCttin NA
141. Phananthrene NA
14?. Phenol NA
220. Phthaltc anhydride NA
143. 2-PicoHne NA
144. Pronaaide NA
145. Pyrene NA
146. Resorcinol NA
6-7
-------
2166q
Table 6 1 (Continued)
BOAT Detection Believed to
reference Constituent status8 be present
no.
Setnivol.it i le organ ics (continued)
14/. Sdfrole NA
148. 1.?,4,5-Tctrach lorobcn/ene NA
149. 2.3,4.6 Tetrachlorophenol NA
lliO. 1,2,4-Irichlorobenzene NA
151. 2,4,5-Triuhlorophenol NA
15?. 2,4,6-Trichlorophenol NA
153. Tris(2.3 dibromopropyl)
phosphate NA
Metals
154. Antimony <10-22.4
155. Arsenic <04.-5
156. Bariu* 0.74-5?
157. Beryl liua NO
IStt. CaitanuM 0.003-4.0/0
159. ChroMiiw (total) <0.002-290.000
??1. Chraniun (hcxavalent) <0.001-910
160. Copper 1.4-28.100
161. Lead <0.001-24,500
162. Mercury NO
163. Nickel 0.06-170,000
164. Seleniu* NO
165. Silver <0.6-38.9
166. Thallium NO
167. Vanadium 1-26
168. Zinc 8.86-90.200
Inorganic^ other than metals
169. Cyanide <0.025-1,970
170. Fluoride 268
1/1. Sulfide 21
Oroanochlorine pesticides
172. Aldrin NA
173. atpha-BHC NA
174. beta-BHC NA
1/5. delta-BHC NA
6-8
-------
2166g
Table 6-1 (Continued)
BOA I
reference Constituent
no.
Detection Believed to
status* be present
Oraanochlorine pesticides (continued)
176. ganma-BHC NA
177. Chlordane NA
178. ODD NA
1/9. DOE NA
180. DOT NA
181. Oieldrin NA
1B2. Cndosulfan I NA
183. Endosultan 11 NA
184. Endrin NA
185. Endrin aldehyde NA
1B6. Heptachlor NA
IB/. Heptachlor epoxide NA
188. Isodrin NA
189. Kepone NA
190. Methoxyclor NA
191. Toxaphene NA
Phenoxvacetic acid herbicides
192. 2,4-Oichlorophenoxyacetic acid NA
193. Silvex NA
194. 2.4.5-T NA
OroanoBhoanhoraus inaecticidaa
195. Oisulfoton NA
196. Taaphur NA
197. Methyl parathion NA
198. Parathion NA
199. Phorate NA
PCBs
200. Aroclor 1016 NA
201. Aroclor 1221 NA
202. Araclor 1232 NA
?03. Aroclor 1242 NA
204. Aroclor 1248 NA
205. Aroclor 1254 NA
206. Aroclor 1260 NA
6-9
-------
2 lbtig
ldble 6-1 (Continued)
UOAI
reference Const i tuent
no.
Detection believed to
stdLusd be present
Oioxins and furans
207.
Hexach lorodibenzo p dioxins
NA
208.
Hexach lorodibenzofurans
NA
209.
Pentach lorodibenzo-p-dioxins
NA
210.
Pentach lorod ibcn/ofur
-------
7. CALCULATION OF BOAT TREATMENT STANDARDS
In this section, EPA presents its determination of treatment
standards using the performance data shown in Section 4 and again
presented in Section 5 as part of the Agency's determination of
substantial treatment.
As discussed in Section 1, EPA's methodology requires the Agency to
first delete any performance data that do not represent a well-designed
and well-operated treatment system. Additionally, all data must be
adjusted for analytical recoveries. EPA previously performed this
analysis in Section 5; as shown, EPA found 30 treated data points that
represent treatment of F006 wastes using a well-designed and
well-operated treatment system. (See Appendix 0, Table 0-1, for EPA's
rationale for deleting data on F006.) These 30 treated data points are
shown in Table 7-1.
Using the accuracy-corrected data, EPA developed treatment standards
by averaging the performance data for each constituent and then
multiplying the average value by a variability factor that accounts for
variations in technology performance, waste characteristics, and
laboratory analysis. This procedure is consistent with the Agency's
methodology as detailed in Section 1.
Table 7-1 shows the calculations for the five metals regulated for
F006 nonwastewaters. These standards represent instantaneous maximum
concentrations that must be achieved as a prerequisite for land
disposal. The concentrations ar« in mg/1 (parts per million on a
weight-per-volume basis) and represent values for the TCLP leachate.
7-1
-------
1670g/p 25
Table 1 1 Regulated Constituents and Calculated Treatment Standards for F00
-------
8. ACKNOWLEDGMENTS
This document was prepared for the U.S. Environmental Protection
Agency, Office of Solid Waste, by Versar Inc. under Contract
No. 68-01-7053. Mr. James Berlow, Chief, Treatment Technology Section,
Waste Treatment Branch, served as the EPA Program Manager during the
preparation of this document and the development of treatment standards
for the F006 electroplating waste. The technical project officer for
K099 waste was Mr. John Keenan. Mr. Steven Silverman served as legal
advisor.
Versar personnel involved in the preparation of this document
included Mr. Jerome Strauss, Program Manager; Ms. Rajani Joglekar,
Engineering Team Leader; Mr. David Pepson, Senior Technical Reviewer;
Ms. Justine Alchowiak, Quality Assurance Officer; Mr. James Morgan and
Ms. Olenna Truskett, Technical Reviewers; Ms. Juliet Crumrine, Technical
Editor; and the Versar secretarial staff, Ms. Linda Gardiner and Ms. Mary
Burton.
We greatly appreciate the cooperation of the National Association of
Metal Finishers and the Individual companies that permitted their plants
to be sampled and that submitted additional data and information to the
U.S. EPA.
8-1
-------
9. REFERENCES
Ajax Floor Products Corp. n.d. Product literature: technical data
sheets on hazardous waste disposal system. Ajax Floor Products Corp.,
P.O. Box 161, Great Meadow's, N.J. 07838.
Austin, G.T. 1984. Shreve's chemical process industries. 5th ed.
New York: McGraw-Hi11.
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. May 10-12, 1983,
at Purdue University, West Lafayette, Indiana.
Center for Metals Production. 1985. Electric arc furnace dust-disposal.
recycle and recovery. Pittsburgh, Pa.: Center for Metals Production.
Conner, J.R. 1986. Fixation and solidification of wastes. Chem. Eng.
Nov. 10, 1986.
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.
CWM. 1987. Chemical Waste Management. Technical report no. 87-117,
Stabilization treatment of metal-containing wastes. September 22,
1987. Chemical Waste Management, 150 West 137th Street, Riverdale,
111inois.
Duby, Paul. 1980. Extractive metallurgy. In Kirk-Othmer encyclopedia of
chemical technology. Vol. 9, p. 741.
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.
Lloyd, T. 1980. Zinc compounds. Kirk-Othmer encyclopedia of chemical
technology. 3rd ed. Vol. 24, p. 856.
Lloyd, T., and Showak, W. 1980. Zinc and zinc alloys. In Kirk-Othmer
encyclopedia of chemical technology. 3rd ed. Vol. 24, p. 824.
Maczek, H. and Kola, R. 1980. Recovery of zinc and lead from electric
furnace steelmaking dust at Berzelius. Journal of Metals 32:53-58.
9-1
-------
Malone, P.G., Jones, L.W., and Burkes, J.P. Add!ication of
solidification/stabilization technology to electroplating wastes.
SW-872. Office of Water and Waste Management. Washington, D.C.: U.S.
Environmental Protection Agency.
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.
Pojasek, R.B. 1979. Sol id-waste disposal: solidification. Chem. Eno.
86(17): 141-145.
Price, L. Tensions mount in EAF dust bowl. Metal Producing.
February 1986.
USEPA. 1980a. 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/ORO under
Interagency Agreement No. EPA-IAG-D4-0569. PB81-181505. Cincinnati,
Ohio: U.S. Environmental Protection Agency.
USEPA. 1980b. U.S. Environmental Protection Agency, Office of Solid
Waste. RCRA listing background document for F006. Washington, O.C.:
U.S. Environmental Protection Agency.
USEPA. 1986a. U.S. Environmental Protection Agency, Office of Solid
Waste and Emergency Response. Test methods for evaluating solid waste.
SW-846. 3rd ed. Washington, D.C.: U.S. Environmental Protection
Agency.
USEPA. 1986b. U.S. Environmental Protection Agency, Office of Solid
Waste. Hazardous waste management systems; land disposal restrictions
final rule; Appendix I to Part 268--Tox1c1ty Characteristic Leaching
Procedure (TCLP). 51 FR 40643-40654. November 7, 1986.
9-2
-------
APPENDIX A
STATISTICAL METHODS
A.1 F Value Determination for ANOVA Test
As noted in Section 1.2, EPA is using the statistical method known as
analysis of variance (ANOVA) to determine 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 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), the "best" technology would be the
technology that achieves the best level of performance, i.e., the
technology with the lowest mean valye.
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).
A-l
-------
Table A-l
9Sth PSRCENTIll VALUES FOR
TH! F DISTRIBUTION
fit * degrees of freedom for numerator
»t * deffrMS of freedom for denomiaator
(shaded am * 46)
I 2 8 4 6 6 1 12 16 20 30 40 50 100 •
1
*>
*
*
4
4
5
161.4 199.5 215.7 224.6 230.2 234.0 2314 2434 2404 248.0 250.1 251.1 2512 253.0 234.3
18.51 19.00 19.16 19.25 1940 1943 1947 19.41 19.43 19.45 19.46 19.46 19.47 19.4. 19.50
10.13 9.35 9.28 9.12 9.01 144 145 8.74 8.69 8.66 8.62 8.00 8.58 8.36 S.5o
7.71 6,94 6.59 649 646 6.16 6.04 5.91 544 5.10 5.75 5.71 5.70 5.66 5.6*
6.61 5.79 5.41 5.19 5.05 4.95 4J2 4.68 4.60 4.56 440 4.46 4.44 4.40
C
«¦
4
8
9
10
5.99 5.14 4.76 4*3 4.39 441 405 4.00 34S 347 ?41 3.77 3.75 3.71 347
5.59 4.74 4.35 4.12 347 347 3.73 347 3.49 3.44 4.38 3.34 3.32 3 8 3-j
5.32 4.46 4.07 3J4 3.69 131 3.44 341 120 3.15 3.01 3.05 3.03 -98 -.93
5.12 4.26 SJ6 3.03 341 347 343 3.07 248 2.93 188 ~«0 1,6 -..1
4.96 4.10 3.71 3.48 343 342 3.07 191 2.81 2.77 2.70 2.67 2.64 -59 ^
11
12
IS
14
15
4.84 3.91 3.51 IM U9 J.M Ul 171 1*0 1« 153 ISO 145 140
4.75 349 3.49 126 3.11 3.00 111 161 180 2.54 2.41 2.42 1« 245 W0
4.67 341 3.41 111 3.03 2.93 177 160 151 146 131 134 -» -J ^
4.60 3.74 344 3.11 246 245 170 153 144 249 131 12?
4.54 3.68 3.29 3.06 240 171 164 141 139 243 125 121 1H H- 1°'
16
IT
18
19
20
4.49 3.63 344 3.01 241 174 159 141 133 121 120 116 111 107 2.01
4.45 3.39 340 196 241 170 135 241 129 123 115 111 101 lj«
4.41 345 3.11 193 177 166 241 134 123 lit 111 107 104 141 14.
4.31 3.52 3.11 240 174 163 141 241 121 HI 107 102 1JJ ^ JjJ
4.35 3.49 3.10 147 171 1C0 145 131 111 111 104 149 146 140 144
«M»
24
26
21
30
4.30 3.44 3.01 242 161 135 140 123 113 247 141 141 141 IjJ MS
446 3.40 3.01 171 ICS 151 246 111 10« 103 144 149 lJ« 140 LTC
443 347 241 174 tM 147 242 US 101 I4f 140 141 Lit JJJ
440 144 195 171 241 141 121 111 101 146 147 141 1.71 1.72 *•«
4.17 34* 241 249 133 141 147 109 14! 141 144 1.71 1.78 1.61 1.62
40
80
60
70
BO
4.01 US 146 143 141 H4 241 100 140 144 174 1.6J J-JJ
4.03 Ul 179 246 140 249 113 145 141 L» |JJ -J }J J*JJ £J{
4.00 111 176 243 147 12S 110 141 Lll ITS « «• JjJ « JjJ
341 303 174 150 241 243 107 149 L7S L7t 14S U« J-JJ JJJ
346 301 171 141 131 241 101 141 LTT 1.70 1.10 144 141 1.42 142
100
150
200
400
•
344 101 170 141 84® lit 101 143 US 1M 147 Ul Ul U» ^
341 3.01 2.67 143 1S7 116 100 142 L71 144 144 UT 144 1.34 1—
Pi \l iS £ £ iS IS tS V£ S $ S ill
A-2
-------
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
necessary co 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 (SS6) is computed:
ssb ¦
where:
k
i«l
Ti
rT"
(i" r
k * number of treatment technologies
n^ - number of data points for technology i
N » number of data points for all technologies
Ti » sum of natural logtransformed data points for each technology.
(iv) The sum of the squares within data sets (SSW) is computed:
k
SSW
where
x
r r1 2
X. X x i,j
i»l j»l
k
'Ii!'
- 1
i-1
. ni ^
ij • the natural logtransformed observations (j) for treatment
technology (i).
A-3
-------
(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.
(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
Degrees of
Sum of
Source
freedom
squares
Mean square
F value
Between
k-1
SSB
MSB - SSB/k-1
MSB/MSW
Within
N-k
SSW
MSW - SSW/N-k
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 in which one
technology achieves significantly better treatment than the other
technology.
A-4
-------
i/aug
Example 1
Methylene Chloride
Inf luent
I)
Steam stripping
t f fluent
(*g/D
Biological treatment
ln(eff luent) [Infeff luent)]2 Influent tff luent ln(eff luent)
[ ln(ef f luent)]
1550.00
10.00
2.30
5.29
1960.00
10.00
2.30
5.29
1290.00
10.00
2.30
5.29
2568.00
10.00
2.30
5.29
1640.00
10.00
2.30
5 29
1817.00
10.00
2.30
5.29
5100.00
12.00
2.48
6.15
1640.00
26.00
3.26
10.63
1450.00
10.00
2.30
5.29
3907.00
10.00
2.30
5.29
4600.00
10.00
2.30
5.29
1760.00
10 00
2.30
5.29
2400.00
10.00
2.30
5.29
4800.00
10.00
2.30
5.29
12100.00
10.00
2.30
5 29
Sum:
23.18
53 76
12 46
31.79
Sample Si/e:
10 10
10
Mean:
3669
10 2
2.32
2378
13.2
2 49
Standard Deviation:
3328.6/ .63
06
923.04
7.15
43
Variabi1lty factor:
1.15
2.48
ANOVA Calculations:
SSB
* 2 1
It
Tl
S
l-l
n. J
SSW *
MSB * SSB/(k-l)
* nl O
s, 1 . j
i»l j'l J
(A")!
ih
k
r. i —
l«l {
MSW = SSW/(N-k)
-------
I /90q
Example 1 (Continued)
F = MSB/NSW
where:
k - number of treatment techno log les
» manber of data points for technology
N - number of natural log trans formed data points for all technologies
T - sin of logtransformed data points for each technology
X - the nat. loqtransformed observations (j) for treatment technology (t)
= 10, n2 = 5. N * 15. k - 2, ^ « 23.18, T? * 12.46. T * 35.64. I * 1270.21
T? * 537.31 T? ; 155.25
1 2
SSB -
537.31 155.25
¦¥
5
10
1270.21
15
- 0.10
SSW - (53.76 ~ 31.79) -
537.31 155.25'
~
10
0.77
MSB * 0.10/1 • 0.10
MSW - 0.77/13 - 0.06
0.10
F »
1.67
0.06
ANOVA Table
Degrees of
Source
freedom
SS
MS
F value
Bet«een(B)
I
0.10
0.10
1.67
Within(W)
13
0.//
0.06
The critical value of the F test at the 0.0S significance level is 4.67. Since
the F value is less than the critical value, the wank are not sign if icant ly
different (i.e., they are homogeneous).
Note-. All calculations Mr* rounded to two decimal places. Results my differ
depending upon the number of decimal places used in each step of the calculations.
A-6
-------
1 /auq
Example 2
Irichloroethylene
Influent
U J I -.1 f — 1
-I j-1 -J J 1*1 I nt J
-------
l/90q
Example 2 (Continued)
r - MSB/MSW
•here:
k. • ntMbcr of treatment technologies
* nutter of data points for technology i
N * number of data points for all technologies
T - sum of natural logtransformed data points for each technology
X - the natural logtransformed observations (j) for treatment technology (i)
N - 10. N-/.M-1/, k- 2. T, - 26.14, f - 1C.S9, I - 42.73, f2* 1825.85, I? = 683.30,
T2 - 27 3
f683.30 275.23
SSft • ~
10
1825.85
17
0.25
SSW -- (72.92 ~ 39.52) -
083.30 2/5.23
~
10
- 4.79
MSB ¦* 0.25/1 * 0.25
NSW * 4.79/15 * 0.32
r 0.25
F » _____
0.32
0.78
AtiOVA Table
Degrees of
Source
freedom
SS
MS
F value
8etwen(8)
1
0.25
0.2S
0.78
Vithin(V)
IS
4.79
0.3?
rhe critical value of the F test at the 0.05 significance level is 4.54. Since
the F value is lass than the critical value, the means are not significantly
different (i.e.. they are homogeneousI.
Note: AH calculations were rounded to two decimal places. Results may differ
depending upon the number of decimal places used in each step of the calculations.
A-8
-------
Fxamp Ic 3
Ch lorobenzene
Activated slurioc followed bv carbon adsorption
Bio logical treatment
Influent
Effluent
In(effluent)
[ln(eff luent)]?
Influent
Eff luent
ln(effluent)
1 n[(eff luent
(rt/D
(m9/D
Ug/1)
Ufl/1)
7200.00
80.00
4 38
19.18
9206.00
1083 00
6.99
48 86
6500.00
70.00
4.25
18.06
16646.00
709.50
6.56
43.03
6075.00
35.00
3.56
12.67
49775.00
460.00
6.13
37.58
3040.00
10.00
2.30
5.29
14731.00
142.00
4,96
24.60
3159.00
603.00
6.40
40.96
6756.00
153.00
5.03
25.30
3040.00
17.00
2.83
8.01
Sum:
Sample Size:
4 4
14 49
55.20
38.90
228.34
Mean-
5703
49
Standard Dev iat ion:
1835.4 32.24
Var labi 111y Factor:
3.62
.95
14759
16311.86
7.00
452.5
379.04
15.79
5.56
1.42
ANOVA Calculations
„ 2
SS8 -
SSV
k
¦5l i n
MSB = SSB/(k-l)
MSW « SSU/(M k)
F - MSB/HSU
(I, «)!
II
k n, , 1 k f T1
£, *Z|.i S, |
l-l j»l ,J J i«l ( nj J
-------
txample 3 (Continued)
whopc,
k - nuntoer of treatment technologies
n - nuntoer of data points for technology 1
N - number of data points far all technologies
T = sua of natural logtransformed data points for each technology
ij
the natural logtransformed observations (j) for treatment technology (i)
Hj 1 <• 7. N • 11. k » 2. Tt « 14.49. T? « 38.90. T • 53.39. T?» 2850.49. T* • 209.96
\\ -
?
SSB -
209.96
4
1513.21
2850.49
11
9.52
SSU = (55.20 ~ 228.34)
209.96 1513.21
* 14.88
MSB ¦ 9.52/1 * 9.52
HSU - 14.88/9 * 1.6S
- 9.52/1.65 - 5.77
ANOVA Table
Degrees of
Source freedom
SS
MS f value
Bct«ccn(B)
yuhin(W)
9.53
14.89
9.S3
165
5.77
The critical value of the F test at the O.OS significance level is 5.12. Since
the T value is larger than the critical value, the wans are sign if icantly
different (i.e.. they are heterogeneous). Activated sludge followed by carbon
adsorption is "best" in this example because the Man of the long-ten* performance
value, i.e., the effluent concentration, is lowr.
Note: All calculations wire rounded to Ino decimal places. Results may liifTer depending
upon the mater of dec ism 1 places used in each step of the calculations.
A-10
-------
A.2 Variability Factor
C99
VF - Mean
where:
VF = estimate of daily maximum variability factor determined
from a sample population of daily data;
C99 ¦ estimate of performance values for which 99 percent of the
daily observations will be below. Cgg is calculated
using the following equation: C90 ¦ Exp(y + 2.33 Sy)
where y and Sy are the mean and standard deviation,
respectively, of the logtransformed data; and
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, al1 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 show that the treatment residual concentrations are
A-U
-------
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 BDAT program.
The variability factor (VF) was defined as the ratio of the 99th
percentile (C) of the lognormal distribution to its arithmetic mean
(Mean), as follows:
VF » _^99.
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 (m) and standard deviation {a) of the normal distribution as
follows:
C99 - Exp U + 2.33a) (2)
Mean » Exp U + 0.5a*). (3)
By substituting (2) and (3) in (1), the variability factor can then
be expressed in terms of a as follows:
VF - Exp (2.33 a - 0.5
-------
that are below the detection limit, the above equations can be used in
conjunction with the following assumptions to develop a variability
factor.
• Assumption 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 wel1-operated treatment systems
generally fall within one order of magnitude.
• Assumption 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).
• Assumption 3: The standard deviation (a) of the normal
distribution is approximated by:
a - [In(UL) - ln(LL)] / [(2)(2.33)]
« [In(UL/LL)] / 4.66. (5)
(Note that when LL « (0.1)(UL) as in Assumption 1, then
- (lnlO) / 4.66 - 0.494.)
Substitution of the a value from equation (5) into equation (4)
yields the variability factor, VF, as shown:
VF ¦ 2.8. (6)
A-13
-------
APPENDIX B
ANALYTICAL QA/QC
This appendix presents quality assurance/quality control (QA/QC)
information for the available performance data presented in Section 4 and
identifies the methods and procedures used for analyzing the constituents
to be regulated. The QA/QC information includes matrix spike recovery
data that are used for adjusting the analytical results for accuracy.
The adjusted analytical results (referred to as accuracy-corrected
concentrations), in general, are used for comparing the performance of
one technology to that of another and for calculating treatment standards
for those constituents to be regulated.
B.l Accuracy Correction
The accuracy-corrected concentration for a constituent in a matrix is
the analytical result multiplied by the correction factor (the reciprocal
*
of the recovery fraction, i.e., the correction factor is 100 divided
by the percent recovery). For example, if Compound A is measured at
2.55 mg/1 and the percent recovery is 85 percent, the accuracy-corrected
concentration is 3.00 mg/1:
2.55 mg/1 x 1/0.85 • 3.00 mg/1
(analytical result) (correction factor) (accuracy-corrected
concentration)
The recovery fraction is the ratio of (1) the measured amount of
constituent in a spiked aliquot minus the measured amount of constituent
in the original unspiked aliquot to (2) the known amount of constituent
added to spike the original aliquot (refer to the Generic Quality
Assurance Project Plan for Land Disposal Restriction Program ("BOAT")).
B-l
-------
The appropriate recovery values are selected according to the procedures
specified in Section 1.2.6.
Table B-l presents matrix spike recovery data for the stabilized F006
waste residuals. Using these analytical recovery values, all the data
points were corrected for accuracy.
B.2 Methods and Procedures Employed to Generate the Data Used in
Calculating Treatment Standards
Table 8-2 lists the methods used for analyzing the constituents to be
regulated in F006 waste. Most of these methods are specified in SW-846
(USEPA 1986a). For some analyses, SW-846 methods allow alternatives or
equivalent procedures and/or equipment to be used. The Agency plans to
use these methods and procedures to enforce the treatment standards for
F006 waste.
B-2
-------
1670g/p 25
Table B-l Matrix Spike Recoveries for Treated Waste
Const ituent
Original
Mount
found
(pp«)
Duplicate
(PP«)
X Error
Actual
spike
X Recovery
Accuracy-
correel ion
factor
Arsenic
0.101*
0.01
0.0
0.086
94.5
1.06
0.01b
0.01
0.0
0.068
104
0.96
Banian
0.3737a
0.3326
5.82
4.9474
91.9
1.09
0.276Sb
0.222
10.9
5.1462
97.9
1.02
Cadniun
0.0075a
0.0069
4.17
4.9010
97.9
1.02
2.9034b
0.7555
58.7
6.5448
94.3
1.06
Chromium
0.3494*
0.4226
9.48
4.6780
85.8
1.17
0.2213**
0.2653
9.0
4.5709
86.6
1.15
Copper
0.2247*
0.2211
0.81
4.8494
92.5
1.08
0.1526b
0.1462
2.14
4.9981
97.0
1.03
Lead
0.3226*
0.3091
2.14
4.9619
92.9
1.08
0.2142b
0.2287
3.27
4.6930
89.4
1.12
Mercury
0.001*
0.001
0.0
0.0034
92
1.09
0.001b
0.001
0.0
0.0045
110
0.91
Nicke 1
0.028*
0.0264
6.87
4.5400
90.3
1.11
0.4742b
0.0859
69.3
4.6093
86.6
1.15
Selenium0
0.101*
0.12
8.6
0.175
86
1.16
0.043b
0.053
10.4
0.095
66d
0.96
Silver0
0.0437*
0.0399
4.55
4.2837
84.8
1.18
0.0344b
0.0411
8.87
0.081
0.87d
114.9
Zinc
0.0133*
0.0238
28.3
5.0910
101.4
0.99
27.202*
3.65
76.3
19.818
87.8
1.14
aAt a *ix ratio of 0.5.
bAt a mix ratio of 0.2.
cFor a mix ratio of 0.2, correction factors of 1.16 and 1.18 «n used «hen cor roc ting for seleniiM «nd silver
concentrations, respectively.
dThis value is not considered in the calculation for the accuracy-correction factor.
Reference: tao to R. Turner, USEPA/HUERL from Jesse R. Conner, Chwical Waste Managwant, dated January 20. 1988.
B-3
-------
ltJ4/g
Table B-2 Analytical Methods for Regulated Constituents
Analysis/methods
Method
Reference
Vo Ul i lo Oru<»i ics
Purqe-and trap
Gas chromatography/mass spectrometry for
volatt le organ ics
S030
8240
Sown volatile Organ ics
Continuous liquid liquid extraction (treated waste) 3520
Soxhlet extraction (untreated waste) 3640
Gds chromatagraphy/mdss spectrometry for semi-
volatile organics: Capillary Colum Technique 8270
Meta Is
Ac id digest ion
• Aqueous samples and extracts to be analyzed by
inductively coupled plasma (1CP) atomic mission
spectroscopy
• Aqueous samples and standards to be ana lyied by
furnace atomic absorption (AA) spectroscopy
• Sediments, sludges, and soils
Lead (AA. furnace technique)
Zinc (1CP)
Toxicity Characteristic Leaching Procedure (TCLP)
3010
30?0
3050
7421
6010
SI FR 40643
References:
1. USEPA 1986a.
2. (JSC PA 1986b.
B-4
-------
APPENDIX C
METHOD OF MEASUREMENT FOR THERMAL CONDUCTIVITY
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
that 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 C-l.
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 inches in diameter and 0.5 inch thick. Thermocouples are not placed
into the sample; 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.
C-l
-------
GUARD
GRADIENT
STACK
GRADIENT
THERMOCOUPLE
CLAMP
UPPER
GUARD
HEATER
i
UPPER STACK
HEATER
¦T'
TOP
REFERENCE
SAMPLE
(•
SAMPLE
-«r
HEAT PLOW
DIRECTION
BOTTOM
REFERENCE
SAMPLE
-.r
LOWER STACK
HEATER
On
LOWER
GUARS
HEATER
I
LIQUID COOLED
HEAT SINK
i
FIGURE C-l SCHEMATIC DIAGRAM OF THE COMPARATIVE METHOD
C-2
-------
The stack is clamped with a reproducible load to ensure intimate
contact between the components. 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
Q - a (dT/dx)
out 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 were confined to flow down the stack, then Q
in
and Q „ would be equal. If Q. and Q are in reasonable
out 'h out
agreement, the average heat flow is calculated from
Q - (Q + Q )/2.
in out
The sample thermal conductivity Is then found from
a - Q/(dT/dx)
sample sample.
C-3
-------
APPENDIX 0
DELETION OF PERFORMANCE DATA FOR F006 WASTES
Table D-l shows the deletion of data points from F006 stabilization
performance data.
D-l
-------
table 0-1 Deletion of Stabilization Performance Data for (006 Wastes
Nik Hctal concentrations lPP")
Source ratio* Arsenic Bariui Cadniiai ChroMiun topper Lead Mercury Nickel Seleniua Silver Zinc
UnknoMi
Unstabilized
As received 36 4 1.3 1270 40 ? 35.S 435 2.3 1560
iar t«re)f
Uhstabilized
As received 0.74 1.69 12.9 18 6 11.4 ?34 6 26 8 86
iaP <0.01 0.83 0.66 7.S8 4.12 6.86 0.003 158 <0.01 1.64 ? ?8
Stabilized
lap 1.0 <0.01 0.530 <0.01 0.46 0.237 0.274 <0.001 5.00 0.16 0 106 0 0b/
lap I S <0.01 1.29 0.010 0 398 0.205 0.389 <0 001 ? 74 0 23? 0.1/7 0 0.10
-------
2?0/g
lablc D 1 (Continued)
Mix Metal concentrations (mm)
Source ratio* Arsenic Bariu* Caitmua Chraaiua Copper lead Mercury Nickel Selenium Silver Zinc
Zinc plating
llnslab i I ized
As received
ICIP
Stabilized
iap
ICIP
0 2
O.S
<0.01*
<0.01fc
17.2
0.84
0.204s
0.251
1 30
0.??
0.01le
0.010
110
0.18
0 263*
0.35lc
1510
4 6
0 309e
0.206
88.5
0 45
0 336e
0.36/9
<0 001
-------
table 0 1 (Continued)
Source
Nix
nt io*
Arsenic
Hetal concentrations 1m—)
Bariun
tadiiui
OirmiuM
Copper
lead
Mercury Nickel
Seleniu
S iIwer
1 inc
Unknown
Unstabilized
As received
lap
Stabilized
iar
iar
0.2
0.5
<0.01
------- |