EPA/530-SW-88-031A
FINAL
BEST DEMONSTRATED AVAILABLE TECHNOLOGY (BOAT)
BACKGROUND DOCUMENT FOR
K015
James R. Berlow, Chief
Treatment Technology Section
Lisa Jones
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 Group 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 BOAT 1-32
1.2.7 BOAT Treatment Standards for "Derived-From"
and "Mixed" Wastes 1-36
1.2.8 Transfer of Treatment Standards 1-40
1.3 Variance from the BOAT Treatment Standard 1-41
2. INDUSTRY AFFECTED AND WASTE CHARACTERIZATION 2-1
2.1 Industry Affected and Process Description 2-1
2.2 Waste Characterization 2-3
3. APPLICABLE/DEMONSTRATED TREATMENT TECHNOLOGIES 3-1
3.1 Applicable Treatment Technologies 3-1
3.2 Demonstrated Treatment Technologies 3-2
3.2.1 Incineration 3-4
3.2.2 Fuel Substitution 3-23
3.2.3 Chromium Reduction 3-38
3.2.4 Chemical Precipitation 3-43
4. PERFORMANCE DATA BASE 4-1
4.1 BOAT List Organics Treatment Data 4-1
4.2 BOAT List Metals Treatment Data 4-2
5. IDENTIFICATION OF BEST DEMONSTRATED AVAILABLE
TECHNOLOGY (BOAT) 5-1
5.1 BOAT for Treatment of Organics 5-1
5.2 BOAT for Treatment of Metals 5-3
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TABLE OF CONTENTS (Continued)
Section Page
6. SELECTION OF REGULATED CONSTITUENTS 6-1
6.1 Identification of BOAT Constituents in K015 6-1
6.2 Determination of Significant Treatment from BOAT 6-3
6.3 Selection of Regulated Constituents 6-5
7. CALCULATION OF THE BOAT TREATMENT STANDARDS 7-1
8. ACKNOWLEDGMENTS 8-1
9. REFERENCES 9-1
APPENDIX A STATISTICAL METHODS A-1
APPENDIX B ANALYTICAL QA/QC B-l
APPENDIX C METHOD OF MEASUREMENT FOR THERMAL CONDUCTIVITY C-l
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LIST OF TABLES
Table Page
1-1 BOAT Constituent List 1-18
2-1 Major Constituent Composition for K015 Waste 2-4
2-2 BOAT Constituent Composition and Other Data 2-5
4-1 Performance Data Collected by EPA for Liquid
Injection Incineration of K015 Waste 4-4
4-2 Performance Data for Chromium Reduction and
Chemical Precipitation on Mixed Waste Sampled
by EPA at Envirite Co 4-7
6-1 Status of BOAT List Constituent Presence in
Untreated K015 Waste 6-6
6-2 K015 Waste Constituents with Treatable
Concentrations 6-13
6-3 Major Constituent Concentration Data 6-14
7-1 Calculation of BOAT Treatment Standards for
Regulated Organc Constituents in K015
Wastewaters 7-3
7-2 Treatment Standards for K015 Wastewater Regulated
Metal Constituents Treated by Chromium Reduction
and Chemical Precipitation 7-4
A-l 95th Percentile Values for the
F Distribution A-2
B-l Analytical Methods B-3
B-2 Base Neutral Matrix Spike Data for K015
Wastewater B-4
B-3 Metal Matrix Spike Data for K015 Wastewater ....... B-5
IV
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LIST OF FIGURES
Figure Page
2-1 Benzyl Chloride Production by the
Chlorination of Toluene 2-2
3-1 Liquid Injection Incinerator 3-8
3-2 Rotary Kiln Incinerator 3-9
3-3 Fluidized Bed Incinerator 3-10
3-4 Fixed Hearth Incinerator 3-12
3-5 Continuous Hexavalent Chromium Reduction System 3-41
3-6 Continuous Chemical Precipitation 3-46
3-7 Circular Clarifiers 3-49
3-8 Inclined Plate Settler 3-50
C-l Schematic Diagram of the Comparative Method C-2
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EXECUTIVE SUMMARY
BOAT Treatment Standards for K015
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 (BOAT) treatment standards for the
listed waste identified in 40 CFR 261.32 as K015. Compliance with these
BOAT treatment standards is a prerequisite for placement of the waste in
units designated as land disposal units according to 40 CFR Part 268.
These treatment standards become effective as of August 8, 1988.
This background document provides the Agency's rationale and
technical support for selecting the constituents to be regulated in K015
waste and for developing treatment standards for those regulated
constituents. The document also provides waste characterization
information that serves as a basis for determining whether treatment
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 treatment standards have been
established.
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
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discusses the petition process necessary for requesting a variance from
the treatment standards. The remainder of the document presents waste-
specific informationthe number and locations of facilities'affected by
land disposal restrictions for K015 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.
According to 40 CFR 261.32, waste code K015 is generated by the
organic chemicals industry and is listed as "still bottoms from the
distillation of benzyl chloride." EPA has estimated that two facilities
are potential generators of K015 waste.
The Agency is regulating five organic and two inorganic constituents
in wastewater forms of K015. (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). Waste not meeting this definition must comply with the treatment
*The term "total suspended solids" (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, 16th Edition.
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standards for nonwastewaters.) The BOAT treatment standard of "no land
disposal" for K015 nonwastewater is based on the performance of liquid
injection incineration and the fact that the waste contained no
measurable ash (the solid residue from incineration). The treatment
standards for the BOAT list organic constituents in wastewater forms of
K001 are based on performance data from liquid injection incineration.
For the BOAT list metal constituents, the treatment standards for
wastewater are based on performance data from chromium reduction and
chemical precipitation.
The following table presents the treatment standards for K015
nonwastewater and wastewater. The BOAT treatment standard for K015
nonwastewater is "no land disposal" based on no measurable ash (solid
residue) generated from liquid injection incineration. For BOAT list
organic constituents in K015 wastewater, treatment standards reflect the
total constituent concentration in the scrubber water from liquid'
injection incineration. For BOAT list metal constituents, the treatment
standards in the v/astewater reflect the total constituent concentration.
The units for the total constituent concentration are mg/1 (parts per
million on a weight-by-volume basis) for the wastewater. Note that if
the concentrations of the regulated constituents in the waste, as
generated, are lower than or equal to the treatment standards, then
treatment is not required prior to land disposal.
Testing procedures for all sample analyses performed for the
regulated constituents are specifically identified in Appendix B of this
background document.
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BOAT Treatment Standards for K015
Maximum for any single grab sample
Constituent
Nonwastewater'
Total
concentration
(nig/kg)
TCLP leachate
concentration
(mg/1)
Wastewater
Total
concentration
(mg/1)
Volatile Orqanics
Toluene
Semivolatile Orqanics
Anthracene
Benzal chloride
Benzo(b and/or k)fluoranthene
Phenanthrene
Metals
Chromium
Nickel
No Land Disposal
0.15
1.0
0.28
0.29
0.27
0.32
0.44
aThe Agency is establishing a treatment standard of "No Land Disposal"
for K015 nonwastewater based on no ash.
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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 (BOAT) 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 BOAT treatment standards.
1.1 Legal 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)(l), (e)(l), (g)(5),
42 U.S.C. 6924 (d)(l), (e)(l), (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)(l)). 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 thac 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 (51 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
"[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 well-operated systems.
The treatment standards, according to the statute, can represent
levels or methods of treatment, if any, that substantially diminish the
toxicity of the waste or substantially reduce the likelihood of migration
of hazardous constituents. Wherever possible, the Agency prefers to
establish BOAT treatment standards as "levels" of treatment
(i.e., performance standards), rather than 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 been established, EPA collects and
analyzes data on identified technologies used to treat the wastes in each
treatability group. The technologies evaluated must be demonstrated on
the waste or a similar waste and must be available for use.
1.2.2 Demonstrated and Available Treatment Technologies
Consistent with legislative history, EPA considers demonstrated
technologies to be those that are 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 wa^ste
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: (1) 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
stngle 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 well-designed facility to be one that
contains the unit operations necessary to treat the various hazardous
constituents of the waste, as well as to control other nonhazardous
materials in the waste that may affect treatment performance.
In addition to ensuring that a system is reasonably well designed,
the engineering visit examines whether the facility has a way to measure
the operating parameters that affect performance of the treatment system
during the waste treatment period. For example, EPA may choose not to
sample a treatment system that operates in a continuous mode, for which
an important operating parameter cannot be continuously recorded. In
such systems, instrumentation is important in determining whether the
treatment system is operating at design values during the waste treatment
period.
(3) Sampling and analysis plan. If after the engineering site visit
the Agency decides to sample a particular plant, the Agency will then
develop a site-specific sampling and analysis plan (SAP) according to the
Generic Quality Assurance Pro.iect Plan for the Land Disposal Restrictions
Program ("BOAT"). EPA/530-SW-87-011. In brief, the SAP discusses where
the Agency plans to sample, how the samples will be taken, the frequency
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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 vis-it.
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.
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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 ("BOAT"), which delineates all of the
quality control and quality assurance measures associated with sampling
and analysis. Quality assurance and quality control procedures are
summarized in Section 1.2.6 of this document.)
(4) Sampling visit. The purpose of the sampling visit is to collect
samples that characterize the performance of the treatment system and to
document the operating conditions that existed during the waste treatment
period. At a minimum, the Agency attempts to collect sufficient samples
of the untreated waste and solid and liquid treatment residuals so that
variability in the treatment process can be accounted for in the
development of the treatment standards. To the extent practicable, and
within safety constraints, EPA or its contractors collect all samples and
ensure that chain-of-custody procedures are conducted so that the
integrity of the data is maintained.
In general, the samples collected during the sampling visit will have
already been specified in the SAP. In some instances, however, EPA will
not be able to collect all planned samples because of changes in the
facility operation or plant upsets; EPA will explain any such deviations
from the SAP in its follow-up onsite engineering report.
1-16
-------
(5) Onsite engineering report. EPA summarizes all its data
collection activities and associated analytical results for testing at a
facility in a report referred to as the onsite engineering report (OER).
This report characterizes the waste(s) treated, the treated residual
concentrations, the design and operating data, and all analytical results
including methods used and accuracy results. This report also describes
any deviations from EPA's suggested analytical methods for hazardous
wastes 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
-------
1521g
Table 1-1 BOAT Constituent List
BOAT
reference
no.
222.
1.
2.
3.
4.
5.
6.
223.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
25.
26.
27.
28.
29.
224.
225.
226.
30.
227.
31.
214.
32.
33.
228.
34.
Constituent
Volatile orqanics
Acetone
Acetonitri le
Acrolein
Aery Ion i tr i le
Benzene
Bromod ich lorome thane
Bromomethane
n-Butyl alcohol
Carbon tetrachlor ide
Carbon disulfide
Chlorobenzene
2-Chloro-l,3-butadiene
Ch lorod i bromome thane
Chloroethane
2-Chloroethyl vinyl ether
Chloroform
Chloromethane
3-Chloropropene
1.2-Dibromo-3-chloropropane
1.2-Oibromoethane
Di bromome thane
trans-1.4-Dichloro-2-butene
Oichlorodif luoromethane
1.1-Oichloroethane
1,2-0 ich loroethane
1 . 1 -0 ich loroethy lene
trans-1.2-0ichloroethene
1 ,2-Oichloropropane
trans- 1 , 3-0 ich loropropene
cis-l,3-0ichloropropene
1.4-Oioxane
2-Ethoxyethanol
Ethyl acetate
Ethyl benzene
Ethyl cyanide
Ethyl ether
Ethyl methacrylate
E thy lene oxide
lodomethane
Isobutyl alcohol
Hethano 1
Methyl ethyl ketone
CAS no.
67-64-1
75-05-8
107-02-8
107-13-1
71-43-2
75-27-4
74-83-9
71-36-3
56-23-5
75-15-0
108-90-7
126-99-8
124-48-1
75-00-3 '
110-75-8
67-66-3
74-87-3
107-05-1
96-12-8
106-93-4
74-95-3
110-57-6
75-71-8
75-34-3
107-06-2
75-35-4
156-60-5
78-87-5
10061-02-6
10061-01-5
123-91-1
110-80-5
141-78-6
100-41-4
107-12-0
60-29-7
97-63-2
75-21-8
74-88-4
78-83-1
67-56-1
78-93-3
1-18
-------
1521g
Table 1-1 (Continued)
BOAT
reference
no.
229.
35.
37.
38.
230.
39.
40.
41.
42.
43.
44.
45.
46.
47.
48.
49.
231.
50.
215.
216.
217.
51.
52.
53.
54.
55.
56.
57.
58.
59.
218.
60.
61.
62.
63.
64.
65.
66.
Constituent
Volatile organ ics (continued)
Methyl isobutyl ketone
Methyl methacrylate
Methacrylonitri le
Methylene chloride
2-Nitropropane
Pyridine
1.1,1. 2-Tetrachloroethane
1.1.2. 2-Tet rach loroethane
Tetrachloroethene
Toluene
T r i bromomethane
1 , 1 , 1-Trich loroethane
1 , 1,2-T rich loroethane
Trichloroethene
Trichloromonof luoromethane
1 , 2 . 3-Tr ich loropropane
1. 1.2-Trichloro- 1.2,2- tr if luoro-
ethane
Vinyl chloride
1.2-Xylene
1.3-Xylene
l.4-Xylene
Semi volatile organ ics
Acenaphthalene
Acenaphthene
Acetophenone
2-Acetylaminof luorene
4-Aminobiphenyl
Aniline
Anthracene
Aramite
Benz ( a (anthracene
Benzal chloride
Benzenethiol
Deleted
Benzo( a Ipyrene
Benzo ( b ) f luoranthene
Benzo(ghi)perylene
Benzo(k ) f luoranthene
p-Benzoquinone
CAS no.
108-10-1
80-62-6
126-98-7
75-09-2
79-46-9
110-86-1
630-20-6
79-34-6
127-18-4
108-88-3
75-25-2
71-55-6
79-00-5
79-01-6
75-69-4
96-18-4
76-13-1
75-01-4
97-47-6
108-38-3
106-44-5
208-96-8
83-32-9
96-86-2
53-96-3
92-67-1
62-53-3
120-12-7
140-57-8
56-55-3
98-87-3
108-98-5
50-32-8
205-99-2
191-24-2
207-08-9
106-51-4
1-19
-------
1521g
Table 1-1 (Continued)
BOA I
reference
no.
67.
68.
69.
70.
71.
72.
73.
74.
75.
76.
77.
78.
79. "
80.
81.
82.
232.
83.
84.
85.
86.
87.
88.
89.
90.
91.
92.
93.
94.
95.
96.
97.
98.
99.
100.
101.
102.
103.
104.
105.
106.
219.
Constituent
Semivolatile organ ics (continued)
Bis(2-chloroethoxy)methane
Bis(2-chloroethyl)ether
B i s ( 2-ch loro i sopropy 1 ) ether
Bis(2-ethylhexyl)phthalate
4-Bromophenyl phenyl ether
Butyl benzyl phthalate
2-sec-Buty 1-4 . 6-d in i t ropheno 1
p-Chloroani 1 ine
Chlorobenzi late
p-Chloro-m-cresol
2-Ch loronaphtha lene
2-Chlorophenol
3-Chloropropionitri le
Chrysene
ortho-Cresol
para-Cresol
Cyc lohexanone
Dibenz(a.h)anthracene
D i benzo( a, elpyrene
Dibenzofa, ijpyrene
m-Dichlorobenzene
o-Oichlorobenzene
p-Dichlorobenzene
3,3'-Dichlorobenzidine
2,4-0 ich loropheno 1
2.6-Dichlorophenol
Diethyl phthalate
3,3'-Diniethoxybenzidine
p - D imethy lam i noazobenzene
3.3'-Dimethylbenz1dine
2.4-Oimethylphenol
Dimethyl phthalate
Di-n-butyl phthalate
1 ,4-Oinitrobenzene
4.6-Dinitro-o-cresol
2,4-Dinitrophenol
2.4-Oinitrotoluene
2.6-Dinitrotoluene
Di-n-octyl phthalate
Di-n-propylnitrosamine
Oi phenyl am ine
0 i pheny 1 n i t rosami ne
CAS no.
111-91-1
111-44-4
39638-32-9
117-81-7
101-55-3
85-68-7
88-85-7
106-47-8
510-15-6
59-50-7
91-58-7
95-57-8
542-76-7
218-01-9
95-48-7
106-44-5
108-94-1
53-70-3
192-65-4
189-55-9
541-73-1
95-50-1
106-46-7
91-94-1
120-83-2
87-65-0
84-66-2
119-90-4
60-11-7
119-93-7
105-67-9
131-11-3
84-74-2
100-25-4
534-52-1
51-28-5
121-14-2
606-20-2
117-84-0
621-64-7
122-39-4
86-30-6
1-20
-------
1521g
Table 1-1 (Continued)
BOAT
reference
no.
107.
108.
109.
110.
111.
112.
113.
114.
115.
116.
117.
118.
119.
120.
36.
121.
122.
123.
124.
125.
126.
127.
128.
129.
130.
131.
132.
133.
134.
135.
136.
137.
138.
139.
140.
141.
142.
220.
143.
144.
145.
146.
Constituent
Semivolat i le organ ics (continued)
1 ,2-Diphenylhydrazine
Fluoranthene
F luorene
Hexach lorobenzene
Hexach lorobu tad i ene
Hexach lorocyclopentadiene
Hexach loroethane
Hexach lorophene
Hexach loropropene
Indeno(1.2.3-cd)pyrene
Isosafrole
Methapyri lene
3-Methylcholanthrene
4.4'-Methylenebis
(2-chloroani line)
Methyl methanesu Ifonate
Naphthalene
1 , 4 -Napht hoqu i none
1-Naphthy lamine
2-Naphthy lamine
p-Nitroani 1 ine
N i trobenzene
4-Nitrophenol
N-Nitrosodi-n-buty lamine
N-Nitrosodiethy lamine
N-Nitrosodimethy lamine
N-Nitrosomethylethy lamine
N-Nitrosomorphol ine
N-Nitrosopiperidine
N-Nitrosopyrrol idine
5-Nitro-o-toluidine
Pentach lorobenzene
Pentach loroethane
Pentach loron i t robenzene
Pentach loropheno 1
Phenacetin
Phenanthrene
Pheno 1
Phthalic anhydride
2-Picoline
Pronamide
Pyrene
Resorcinol
CAS no.
122-66-7
206-44-0
86-73-7
118-74-1
87-68-3
77-47-4
67-72-1
70-30-4
1888-71-7
193-39-5
120-58-1
91-80-5
56-49-5
101-14-4
66-27-3
91-20-3
130-15-4
134-32-7
91-59-8
100-01-6
98-95-3
100-02-7
924-16-3
55-18-5
62-75-9
10595-95-6
59-89-2
100-75-4
930-55-2
99-65-8
608-93-5
76-01-7
82-68-8
87-86-5
62-44-2
85-01-8
108-95-2
85-44-9
109-06-8
23950-58-5
129-00-0
108-46-3
1-21
-------
1521g
Table 1-1 (Continued)
BOAT
reference
no.
147.
148.
149.
150.
151.
152.
153.
154.
155.
156.
157.
158.
159.
221.
160.
161.
162.
163.
164.
165.
166.
167.
168.
169.
170.
171.
17Z.
173.
174.
175.
Constituent
Semivolati 1e organ ics (continued)
Safrole
1,2.4, 5-Tetrach lorobenzene
2,3,4, 6-Tet rach loropheno 1
1 . 2 , 4-Tr ich lorobenzene
2, 4, 5-Trich loropheno 1
2 , 4 , 6-Tr ich loropheno 1
Tris(2,3-dibromopropyl)
phosphate
Metals
Antimony
Arsenic
Barium
Beryllium
Cadmium
Chromium (total)
Chromium (hexavalent)
Copper
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Inorganics other than metals
Cyanide
Fluoride
Sulfide
Orqanochlorine pesticides
Aldrin
alpha-BHC
beta-BHC
delta-8HC
CAS no.
94-59-7
95-94-3
58-90-2
120-82-1
95-95-4
88-06-2
126-72-7
7440-36-0
7440-38-2
7440-39-3
7440-41-7
7440-43-9
7440-47-3
-
7440-50-8
7439-92-1
7439-97-6
7440-02-0
7782-49-2
7440-22-4
7440-28-0
7440-62-2
7440-66-6
57-12-5
16964-48-8
8496-25-8
309-00-2
319-84-6
319-85-7
319-86-8
1-22
-------
1521g
Table 1-1 (Continued)
BOAT
reference
no.
176.
177.
178.
179.
180.
181.
182.
183.
184.
185.
186.
187.
188.
189.
190.
191.
192.
193.
194.
195.
196.
197.
198.
199.
200.
201.
202.
203.
204.
205.
206.
Constituent
Orqanochlorine pesticides (continued)
ganroa-BHC
Chlordane
000
ODE
DOT
Dieldrin
Endosulfan I
Endosulfan 11
Endrin
Endrin aldehyde
Heptachlor
Heptachlor epoxide
Isodrin
Kepone
Methoxyclor
Toxaphene
Phenoxyacet ic acid herbicides
2,4-Oichlorophenoxyacet ic acid
Si Ivex
2.4.5-T
Orqanoohosohorous insecticides
Oisulfoton
Famphur
Methyl parathion
Pa rath ion
Phorate
PCBs
Aroclor 1016
Aroclor 1221
Aroclor 1232
Aroclor 1242
Aroclor 1248
Aroclor 1254
Aroclor 1260
CAS no.
58-89-9
57-74-9
72-54-8
72-55-9
50-29-3
60-57-1
939-98-8
33213-6-5
72-20-8
7421-93-4
76-44-8
1024-57-3
465-73-6
143-50-0
72-43-5
8001-35-2
94-75-7
93-72-1
93-76-5
298-04-4
52-85-7
298-00-0
56-38-2
298-02-2
12674-11-2
11104-28-2
11141-16-5
53469-21-9
12672-29-6
11097-69-1
11096-82-5
1-23
-------
1521g
Table 1-1 (Continued)
BOAT
reference Constituent CAS no.
no.
Dioxins and furans
207. Hexachlorodibenzo-p-dioxins
208. Hexachlorodibenzofurans
209. Pentachlorodibenzo-p-dioxins
210. Pentachlorodibenzofurans
211. Tetrachlorodibenzo-p-dioxins
212. Tetrachlorodibenzofurans
213. 2.3.7.8-Tetrachlorodibenzo-p-dioxin 1746-01-6
1-24
-------
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 BOAT constituent list was published in EPA's Generic
Quality Assurance Pro.iect Plan for Land Disposal Restrictions Program
("BOAT") in March 1987. Additional constituents are added to the BOAT
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,
1,l,2-trichloro-l,2,2-trifluoroethane, and cyclohexanone) have been added
to the list.
Chemicals are listed in Appendix VIII if they are shown in scientific
studies to have toxic, carcinogenic, mutagenic, or teratogenic effects on
humans or other life-forms, and they include such substances as those
identified by the Agency's Carcinogen Assessment Group as being
carcinogenic. 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
-------
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 BOAT 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.O.S., such as chlorinated phenols, are'a generic
group of some types of chemicals for which a single analytical
procedure is not available. The individual members of each such
group need to be listed to determine whether the constituents
can be analyzed. For each N.O.S. group, all those constituents
that can be readily analyzed are included in the BOAT
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
-------
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
BOAT list as indicator constituents for compounds from Appendices VII and
VIII such as hydrogen fluoride and hydrogen sulfide, which ionize in
water.
The BOAT constituent list presented in Table 1-1 is divided into the
following nine groups:
Volatile organics;
Semivolatile organics;
Metals;
Other inorganics;'
Organochlorine pesticides;
Phenoxyacetic acid herbicides;
Organophosphorous insecticides;
PCBs; 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 for 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 constituents for
this waste code is presented in Section 6 of this background document.
1-28
-------
(3) Calculation of standards. The final step in the calculation of
the BOAT 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 well-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
-------
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 (BOAT). 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
-------
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 Teachable; 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
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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
BOAT 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 BOAT.
(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.)
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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
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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 Pro.iect 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 constituentminus 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:
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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 generating multiple residues. In a
number of instances, the proposed BOAT consists of a series of
operations, each of which generates a waste residue. For example, the
proposed BOAT for a certain waste code is based on solvent extraction,
steam stripping, and activated carbon adsorption. Each of these
treatment steps generates a waste requiring treatment a
solvent-containing stream from solvent extraction, a stripper overhead,
and spent activated carbon. Treatment of these wastes may generate
further residues; for instance, spent activated carbon (if not
regenerated) could be incinerated, generating an ash and possibly a
scrubber water waste. Ultimately, additional wastes are generated that
may require land disposal. With respect to these wastes, the Agency .
wishes to emphasize the following points:
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 BOAT treatment standards to
residues generated not from treating the waste (as discussed above), but
from other types of management. Examples are contaminated soil or
leachate that is derived from managing the waste. In these cases, the
mixture is still deemed to be the listed waste, either because of the
derived-from rule (40 CFR 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
characteristics that the Agency believes will affect the performance of
the technology. By examining and comparing these characteristics, the
Agency determines whether the untested wastes will achieve the same level
of*treatment as the tested waste. Where the Agency determines that the
untested waste can be treated as well or better than the tested waste,
the treatment standards can be transferred.
1.3 Variance from the BOAT Treatment Standard
The Agency recognizes that there may exist unique wastes that cannot
be treated to the level specified as the treatment standard. In such a
case, a generator or owner/operator may submit a petition to the
Administrator requesting a variance from the treatment standard. A
particular waste may be significantly different from the wastes 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.
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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
only 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 p.etition 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.
usea in developing treainieni. standards.;
A description of the alternative treatment systems examined by
the petitioner (if any); a description of the treatment system
deemed appropriate by the petitioner for the waste in question;
and, as appropriate, the concentrations in the treatment
residual or extract of the treatment residual (i.e., using iL~
TCLP, where appropriate, for stabilized metals) that can be
achieved by applying such treatment to the waste.
the
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 wil.l
first look at the design and operation of the treatment system being
used. If EPA determines that the technology and operation are consistent
with BOAT, the Agency will evaluate the waste to determine if the waste
matrix and/or physical parameters are such that the BOAT treatment
standards reflect treatment of this waste. Essentially, this latter
analysis will concern the parameters affecting treatment selection and
waste characteristics- affecting performance parameters.
In cases where BOAT is based on more than one technology, the
petitioner will need to demonstrate that the treatment standard cannot be
met using any of the technologies, or that none of the technologies are
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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.
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2. INDUSTRY AFFECTED AND WASTE CHARACTERIZATION
This section discusses the industry affected by the land disposal
restrictions for K015 waste, describes the process that generates the
waste, and presents available waste characterization data.
2.1 Industry Affected and Process Description
According to 40 CFR Part 261.32, waste identified as K015 is
specifically generated by the organic chemicals industry and is listed as
"still bottoms from the distillation of benzyl chloride." The Agency
estimates that two facilities in the United States currently generate
K015 waste. These facilities are located in New Jersey and Tennessee
(EPA Regions II and IV, respectively). Benzyl chloride is used as a raw
material or chemical intermediate in the production of benzyl phthalates,
Pharmaceuticals, quaternary ammonium salts, benzyl alcohol, and other
compounds including esters, dyes, and solvents.
In the United States, benzyl chloride is currently produced by
photochemical chlorination of toluene. A flow diagram of the production
process is presented in Figure 2-1. Chlorine is fed into a heated
reactor or series of reactors containing boiling toluene. The toluene
and chlorine react to form benzyl chloride and hydrogen chloride gas.
The hydrogen chloride gas is purged from the reactor(s), while the
unreacted toluene and the remaining reaction products are sent to a
distillation column where toluene is recovered. The product stream is
further distilled, producing purified benzyl chloride. The still bottoms
from this step are the listed waste K015.
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HYDROGEN CHLORIDE GAS UNREACTED TOLUENE
I
1
CHLORINE
TOLUENE
rv>
i
ro
w
^
REACTOR
^
TOLUENE
RECOVERY
^-
BENZYL
CHLORIDE
RECOVERY
1
^BENZYL CHLORIDE
K015 WASTE
FIGURE 2-1. BENZYL CHLORIDE PRODUCTION BY THE CHLORINATION OF TOLUENE
-------
2.2 Waste Characterization
K015 waste generally contains greater than 88 percent benzal
chloride, less than 12 percent benzotrichloride and other chlorinated
benzenes, less than 5 percent benzyl chloride, less than 1 percent
toluene, less than 1 percent other BOAT constituents, and less than
1 percent water. Other industry-submitted information 'indicates the
following approximations: 80 to 90 percent benzal chloride, 3 to
10 percent benzyl chloride, 8 to 12 percent other chlorinated
hydrocarbons (usually toluene), and less than 1 percent water. These
approximations are listed in Table 2-1. The constituent concentrations
are estimates based on chemical analyses and information generated by
earlier EPA studies. Results of the chemical analyses used in estimating
the composition of K015 waste from tests conducted by the Agency are
presented in Table 2-2. These tests determined that the heating value
was 10,000 Btu/lb, the carbon content and sulfur content were
approximately 51 and 0.22 percent, respectively, and the waste had a low
(0.09 percent) ash content.
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1541g
Table 2-1 Major Constituent Composition for K015 Waste
Constituent
Range of concentrations (percent)
(1) , (2)
Benzal chloride
Benzotrichloride and other
chlorinated benzenes
Benzyl chloride
Toluene
Other BOAT constituents
Water
>88
<12
<5
<1
<1
<1
80-90
8-12
3-10
8-12
Source References: (1) USEPA 1987a, p.2-2.
(2) USEPA 1967b.
2-4
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1541g
Table 2-2 BOAT Constituent Composition and Other Data
Parameter
Untreated waste concentration (ing/kg)
BOAT volatile orqanics (mq/kq)
Toluene
BOAT seinivolati 1e orqanics (mq/kq)
Anthracene
Benzal chloride
Benzo(b and/or k)f luoranthene
Phenanthrene
Other parameters
Ash content (%)
Heating value (Btu/lb)
Carbon content (%)
Dry loss (X)
Sulfur content (%)
Water content (%)
<5,000
880,000
<5,000
<5,000
0.01 - 0.29 (0.09 average)
10.000
51.0 - 51.3 (51.1 average)
96.0 - 99.0 (97.2 average)
0.03 - 0.32 (0.22 average)
Reference: USEPA 1987a, p. 6-3.
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3. APPLICABLE/DEMONSTRATED TREATMENT TECHNOLOGIES
This section describes the applicable and demonstrated treatment
technologies for K015 waste. Detailed discussions are provided for those
technologies that have been demonstrated on a commercial basis.
3.1 Applicable Treatment Technologies
The Agency identified applicable treatment technologies based on
available waste composition data, literature sources, engineering site
visits, and industry-submitted data. As shown in Section 2, K015 waste
primarily contains high concentrations of organic compounds and has a low
suspended solids concentration and a low water content. The technologies
considered to be applicable for K015 waste are those that destroy or
reduce the concentration of organic constituents in the waste. The
Agency has identified two treatment technologies as applicable for K015
waste--incineration and fuel substitution and has identified chromium .
reduction and chemical precipitation as applicable technologies for
metals reduction in incineration scrubber water.
Incineration destroys the organic constituents in the waste; the
technology also results in the formation of residuals (i.e., ash and
scrubber water) with reduced concentrations of organic constituents. As
shown in Section 2, K015 waste has a very low (0.09 percent) ash content,
so no ash is expected to be generated from incineration. The wastewater
(scrubber water) residual generated from incineration may contain
treatable concentrations of BOAT list metals if they are present in the
untreated waste. Fuel substitution, similar to incineration, destroys
3-1
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the organic constituents in the waste; however, fuel substitution,also
derives fuel value from the waste.
The Agency believes that solvent extraction may be applicable to K015.
waste; however, EPA has not identified any facilities using solvent
extraction on K015 or a similar-waste. The Agency does not currently
have sufficient information on waste parameters that affect treatment
selection for solvent extraction to suggest that this technology is
applicable for wastes similar to K015. Accordingly, EPA does not
consider solvent extraction to be an applicable technology.
For treatment of BOAT list metals in the wastewater from incineration
of K015, EPA has identified chromium reduction followed by chemical
precipitation as applicable technologies. These technologies are
commonly practiced for metal-containing wastewaters. Chromium reduction
reduces hexavalent chromium to the less soluble trivalent form; chemical
precipitation removes dissolved metals from solution.
3.2 Demonstrated Treatment Technologies
EPA has identified incineration and fuel substitution as the
demonstrated treatment technologies for K015 waste, as well as chromium
reduction and chemical precipitation for removal of metals from
incineration scrubber water. The Agency has identified three facilities
using incineration for treatment of BOAT list organics in K015.
Incineration is a widely used full-scale treatment technology for wastes
containing high concentrations of BOAT list organic constituents. The
goal of incineration is to thermally destroy (oxidize) the organic
3-2
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constituents of a waste. Typically, the types of incineration systems
that are demonstrated on wastes include fluidized bed, rotary kiln, fixed
hearth, and liquid injection. Liquid injection incineration systems are
specifically designed to handle liquids with low concentrations of
suspended solids such as K015. However, while rotary kilns and fluidized
bed incinerators are generally designed to handle sludges and solids,
these units often are used to incinerate liquids. The Agency believes
that the performance of liquid injection incineration adequately
represents the performance achievable by other incineration technologies
(including fuel substitution) that are well designed and well operated.
Section 3.2.1 describes incineration technologies in more detail.
The Agency considers fuel substitution to be demonstrated on K015
waste because it is demonstrated on other wastes having similar
parameters affecting treatment selection. Fuel substitution is described
in greater detail in Section 3.2.2.
For K015 wastewaters containing treatable concentrations of BOAT list
metals resulting from incineration, the Agency has not identified any
facilities using chromium reduction followed by chemical precipitation on
the scrubber water generated by incineration of K015. However, the
Agency believes that chromium reduction and chemical precipitation are
demonstrated for K015 wastewaters because they are demonstrated on other
wastewater streams containing BOAT list metals. Sections 3.2.3 and 3.2.4
describe chromium reduction and chemical precipitation.
3-3
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3.2.1 Incineration
This section addresses the commonly used incineration
technologies: liquid injection, rotary kiln, fluidized bed, and fixed
hearth. A discussion is provided regarding the applicability of these
technologies, the underlying principles of operation, a technology
description, waste characteristics that affect performance, and, finally,
important design and operating parameters. As appropriate, the
subsections are divided by type of incineration unit.
(1) Applicability and use of incineration.
(a) Liquid injection. Liquid injection is applicable to wastes
that have viscosity values low enough that the waste can be atomized in
the combustion chamber. A range of literature maximum viscosity values
are reported, with the low being 100 SSU and the high being 10,000 SSU.
It is important to note that viscosity is temperature dependent so that
while liquid injection may not be applicable to a waste at ambient
conditions, it may be applicable when the waste is heated. Other factors
that affect the use of liquid injection are particle size and the
presence of suspended solids. Both of these waste parameters can cause
plugging of the burner nozzle.
(b) Rotary kiln/fluidized bed/fixed hearth. These incineration
technologies are applicable to a wide range of hazardous wastes. They
can be used on wastes that contain high or low total organic content,
high or low filterable solids, various viscosity ranges, and a range of
other waste parameters. EPA has not found these technologies to be
3-4
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demonstrated on wastes that are composed essentially of metals with low
organic concentrations. In addition, the Agency expects that air
emissions from incinerating some of the high metal content wastes may not
be compatible with existing and future air emission limits without
emission controls far more extensive than those currently used.
(2) Underlying principles of operation.
(a) Liquid injection. The basic operating principle of this
incineration technology is that incoming liquid wastes are volatilized
and then additional heat is supplied to the waste to destabilize the
chemical bonds. Once the chemical bonds are broken, these constituents
react with oxygen to form carbon dioxide and water vapor. The energy
needed to destabilize the bonds is referred to as the energy of
activation.
(b) Rotary kiln and fixed hearth. There are two distinct
principles of operation for these incineration technologies, one for each
of the chambers involved. In the primary chamber, energy, in the form of
heat, is transferred to the waste to achieve volatilization of the
various organic waste constituents. During this volatilization process
some of the organic constituents will oxidize to carbon dioxide and water
vapor. In the secondary chamber, additional heat is supplied to overcome
the energy requirements needed to destabilize the chemical bonds and
allow the constituents to react with excess oxygen to form carbon dioxide
and water vapor. The principle of operation for the secondary chamber is
similar to that of liquid injection.
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(c) Fluidized bed. The principle of operation for this
incineration technology is somewhat different from that for rotary kiln
and fixed hearth incineration relative to the functions of the primary
and secondary chambers. In fluidized bed incineration, the purpose of
the primary chamber is not only to volatilize the wastes but also to
essentially combust the waste. Destruction of the waste organics can be
accomplished to a better degree in the primary chamber of a fluidized bed
incinerator than in that of a rotary kiln or fixed hearth incinerator
because of (1) improved heat transfer from fluidization of the waste
using forced air and (2) the fact that the fluidization process provides
sufficient oxygen and turbulence to convert the organics to carbon
dioxide and water vapor. The secondary chamber (referred to as. the
freeboard) generally does not have an afterburner; however, additional
time is provided for conversion of the organic constituents to carbon
dioxide, water vapor, and hydrochloric acid if chlorine.is present in the
waste.
(3) Description of the incineration process.
(a) Liquid injection. The liquid injection system is capable
of incinerating a wide range of gases and liquids. The combustion system
has a simple design with virtually no moving parts. A burner or nozzle
atomizes the liquid waste and injects it into the combustion chamber,
where it burns in the presence of air or oxygen. A forced draft system
supplies the combustion chamber with air to provide oxygen for combustion
and turbulence for mixing. The combustion chamber is usually a cylinder
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lined with refractory (i.e., heat-resistant) brick and can be fired
horizontally, vertically upward, or vertically downward. Figure 3-1
illustrates a liquid injection incineration system.
(b) Rotary kiln. A rotary kiln is a slowly rotating,
refractory-lined cylinder that is mounted at a slight incline from the
horizontal (see Figure 3-2). Solid wastes enter at the high end of the
kiln, and liquid or gaseous wastes enter through atomizing nozzles in the
kiln or afterburner section. Rotation of the kiln exposes the solids to
the heat, vaporizes them, and allows them to combust by mixing with air.
The rotation also causes the ash to move to the lower end of the kiln,
where it can be removed. Rotary kiln systems usually have a secondary
combustion chamber or afterburner following the kiln for further
combustion of the volatilized components of solid wastes.
(c) Fluidized bed. A fluidized bed incinerator consists of a
column containing inert particles such as sand, which is referred to as
the bed. Air, driven by a blower, enters the bottom of the bed to
fluidize the sand. Air passage through the bed promotes rapid and
uniform mixing of the injected waste material within the fluidized bed.
The fluidized bed has an extremely high heat capacity (approximately
three times that of flue gas at the same temperature), thereby providing
a large heat reservoir. The injected waste reaches ignition temperature
quickly and transfers the heat of combustion back to the bed. Continued
bed agitation by the fluidizing air allows larger particles to remain
suspended in the combustion zone (see Figure 3-3).
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WATER
AUXILIARY FUEL
HBURNER
AIR-
LIQUID OR GASEOUS.
WASTE INJECTION
BURNER
PRIMARY
COMBUSTION
CHAMBER
AFTERBURNER
(SECONDARY
COMBUSTION
CHAMBER)
SPRAY
CHAMBER
GAS TO AIR
POLLUTION
CONTROL
HORIZONTALLY FIRED
LIQUID INJECTION
INCINERATOR
ASH
WATER
FIGURE 3-1
LIQUID INJECTION INCINERATOR
-------
GAS TO
AIR POLLUTION
CONTROL
AUXILIARY
FUEL
AFTERBURNER
SOLID
WASTE
INFLUENT
FEED
MECHANISM
COMBUSTION
GASES
LIQUID OR
GASEOUS
WASTE
INJECTION
ASH
FIGURE 3-2
ROTARY KILN INCINERATOR
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WASTE
INJECTION
BURNER
FREEBOARD
SAND BED
GAS TO
AIR POLLUTION
CONTROL
MAKE-UP
SAND
AIR
ASH
FIGURE 3-3
FLUIDIZED BED INCINERATOR
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(d) Fixed hearth. Fixed hearth incineration, also called
controlled air or starved air incineration, is another major technology
used for hazardous waste incineration. Fixed hearth incineration is a
two-stage combustion process (see Figure 3-4). Waste is ram-fed into the
first stage, or primary chamber, and burned at less than stoichiometric
conditions. The resultant smoke and pyrolysis products, consisting
primarily of volatile hydrocarbons and carbon monoxide, along with the
normal products of combustion, pass to the secondary chamber. Here,
additional air is injected to complete the combustion. This two-stage
process generally yields low stack particulate and carbon monoxide (CO)
emissions. The primary chamber combustion reactions and combustion gas
are maintained at low levels by the starved air conditions so that
particulate entrainment and carryover are minimized.
(e) Air pollution controls. Following incineration of
hazardous wastes, combustion gases are generally further treated in an
air pollution control system. The presence of chlorine or other halogens
in the waste requires a scrubbing or absorption step to remove
hydrochloric acid and other halo-acids from the combustion gases. Ash in
the waste is not destroyed in the combustion process. Depending on its
composition, ash will exit either as bottom ash, at the discharge end of
a kiln or hearth for example, or as particulate matter (fly ash)
suspended in the combustion gas stream. Particulate emissions from most
hazardous waste combustion systems generally have particle diameters of
less than 1 micron and require high-efficiency collection devices to
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AIR
to
I1
ro
WASTE
INJECTION
AIR
GAS TO AIR
POLLUTION
CONTROL
PRIMARY
COMBUSTION
CHAMBER
GRATE
SECONDARY
COMBUSTION
CHAMBER
AUXILIARY
FUEL
2-STAGE FIXED HEARTH
INCINERATOR
ASH
FIGURE 3-4
FIXED HEARTH INCINERATOR
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minimize air emissions. In addition, scrubber systems provide an
additional buffer against accidental releases of incompletely destroyed
waste products, which result from poor combustion efficiency or
combustion upsets, such as flameouts.
(4) Waste characteristics affecting performance.
(a) Liquid injection. In determining whether liquid injection
is likely to achieve the same level of performance on an untested waste
as on a previously tested waste, the Agency will compare dissociation
bond energies of the constituents in the untested and tested wastes.
This parameter is being used as a surrogate indicator of activation
energy which, as discussed previously, destabilizes molecular bonds. In
theory, the bond dissociation energy would be equal to the activation
energy; in practice, however, this is not always the case. Other energy
effects (e.g., vibrational effects, the formation of intermediates, and
interactions between different molecular bonds) may have a significant
influence on activation energy.
Because of the shortcomings of bond energies in estimating activation
energy, EPA analyzed other waste characteristic parameters to determine
whether these parameters would provide a better basis for transferring
treatment standards from an untested waste to a tested waste. These
parameters include heat of combustion, heat of formation, use of
available kinetic data to predict activation energies, and general
structural class. All of these parameters were rejected for the reasons
provided below.
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The heat of combustion measures only the difference in energy of the
products and reactants; it does not provide information on the transition
state. Heat of formation is used as a tool to predict whether reactions
are likely to proceed; however, there are a significant number of
hazardous constituents for which these data are not available. Use of
kinetic data was rejected because these data are limited and could not be
used to calculate free energy values (AG) for the wide range of
hazardous constituents to be addressed by this rule. Finally, EPA
decided not to use structural classes because the Agency believes that
evaluation of bond dissociation energies allows for a more direct
determination of whether a constituent will be destabilized.
(b) Rotary kiln/fluidized bed/fixed hearth. Unlike liquid
injection, these incineration technologies also generate a residual ash.
Accordingly, in determining whether these technologies are likely to
achieve the same level of performance on an untested waste as on a
previously tested waste, EPA would need to examine the waste
characteristics that affect volatilization of organics from the waste, as
well as destruction of the organics once volatilized. Relative to
volatilization, EPA will examine thermal conductivity of the entire waste
and boiling point of the various constituents. As with liquid injection,
EPA will examine bond energies in determining whether treatment standards
for scrubber water residuals can be transferred from a tested waste to an
untested waste. Below is a discussion of how EPA arrived at thermal
conductivity and boiling point as the best method to assess
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volatilization of organics from the waste; the discussion relative to
bond energies is the same for these technologies as for liquid injection
and will not be repeated here.
(i) Thermal conductivity. Consistent with the underlying
principles of incineration, a major factor with regard to whether a
particular constituent will volatilize is the transfer of heat through
the waste. In the case of rotary kiln, fluidized bed, and fixed hearth
incineration, heat is transferred through the waste by three mechanisms:
radiation, convection, and conduction. For a given incinerator, heat
transferred through various wastes by radiation is more a function of the
design and type of incinerator than of the waste being treated.
Accordingly, the type of waste treated will have a minimal impact on the
amount of heat transferred by radiation. With regard to convection, EPA
also believes that the type of heat transfer will generally be more a
function of the type and design of the incinerator than of the waste
itself. However, EPA is examining particle size as a waste
characteristic that may significantly impact the amount of heat
transferred to a waste by convection and thus impact volatilization of
the various organic compounds. The final type of heat transfer,
conduction, is the one that EPA believes will have the greatest impact on
volatilization of organic constituents. To measure this characteristic,
EPA will use thermal conductivity; an explanation of this parameter, as
well as how it can be measured, is provided below.
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Heat flow by conduction is proportional to the temperature gradient
across the material. The proportionality constant is a property of the
material and is referred to as the thermal conductivity. (Note: 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 C.) In theory, thermal
conductivity would always provide a good indication of whether a
constituent in an untested waste would be treated to the same extent in
the primary incinerator chamber as the same constituent in a previously
tested .waste.
In practice, thermal conductivity has some limitations in assessing
the transferability of treatment standards; however, EPA has not
identified a parameter that can provide a better indication of the heat
transfer characteristics of a waste. Below is a discussion of both the
limitations associated with thermal conductivity and the other parameters
considered.
Thermal conductivity measurements, as part of a treatability
comparison for two different wastes through a single incinerator, are
most meaningful when applied to wastes that are homogeneous (i.e., major
constituents are essentially the same). As wastes exhibit greater
degrees of nonhomogeneity (e.g., significant concentration of metals in
soil), then thermal conductivity becomes less accurate in predicting
treatability because the measurement essentially reflects heat flow
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through regions having the greatest conductivity (i.e., the path of least
resistance) and not heat flow through all parts of the waste.
Btu value, specific heat, and ash content were also considered for
predicting heat transfer characteristics. These parameters can no better
account for nonhomogeneity than can thermal conductivity; additionally,
they are not directly related to heat transfer characteristics.
Therefore, these parameters do not provide a better indication of the
heat transfer that will occur in any specific waste.
(ii) Boiling point. Once heat is transferred to a constituent
within a waste, removal of this constituent from the waste will depend on
its volatility. EPA is using boiling point as a surrogate of volatility
of the constituent. Compounds with lower boiling points have higher
vapor pressures and therefore would be more likely to vaporize. The
Agency recognizes that this parameter does not take into consideration
the impact of other compounds in the waste on'the boiling point of a
constituent in a mixture; however, the Agency is not aware of a better
measure of volatility that can easily be determined.
(5) Design and operating parameters.
(a) Liquid injection. For a liquid injection unit, EPA's
analysis of whether the unit is well designed will focus on (1) the
likelihood that sufficient energy is provided to the waste to overcome
the activation level for breaking molecular bonds and (2) whether
sufficient oxygen is present to convert the waste constituents to carbon
dioxide and water vapor. The specific design parameters that the Agency
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will evaluate to assess whether these conditions are met are temperature,
excess oxygen, and residence time. Below is a discussion of why EPA
believes these parameters to be important, as well as a discussion of how
these parameters will be monitored during operation.
It is important to point out that, relative to the development of
land disposal restriction standards, EPA is concerned with these design
parameters only when a quench water or scrubber water residual is
generated from treatment of a particular waste. If treatment of a
particular waste in a liquid injection unit would not generate a
wastewater stream, then the Agency, for purposes of land disposal
treatment standards, would be concerned only with the waste
characteristics that affect selection of the unit, not with the
above-mentioned design parameters.
(i) Temperature. Temperature is important in that it provides
an indirect measure of the energy available (i.e., Btu/hr) to overcome
the activation energy of waste constituents. As the design temperature
increases, it is more likely that the molecular bonds will be
destabilized and the reaction completed.
The temperature is normally controlled automatically through the use
of instrumentation that senses the temperature and automatically adjusts
the amount of fuel and/or waste being fed. The temperature signal
transmitted to the controller can be simultaneously transmitted to a
recording device, referred to as a strip chart, and thereby continuously
recorded. To fully assess the operation of the unit, it is important to
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know not only the exact location in the incinerator at which the
temperature is being monitored but also the location of the design
temperature.
(ii) Excess oxygen. "It is important that the incinerator
contain oxygen in excess of the stoichiometric amount necessary to .
convert the organic compounds to carbon dioxide and water vapor. If
insufficient oxygen is present, then destabilized waste constituents
could recombine to the same or other BOAT list organic .compounds and
potentially cause the scrubber water to contain higher concentrations of
BOAT list constituents than would be the case for a well-operated unit.
In practice, the amount of oxygen fed to the incinerator is
controlled by continuous sampling and analysis of the stack gas. If the
amount of oxygen drops below the design value,.then the analyzer
transmits a signal to the valve controlling the air supply and thereby
increases the flow of oxygen to the afterburner.' The analyzer
simultaneously transmits a signal to a recording device so that the
amount of excess oxygen can be continuously recorded. Again, as with
temperature, it is important to know the location at which the combustion
gas is being sampled.
(iii) Carbon monoxide. Carbon monoxide is an important
operating parameter because it provides an indication of the extent to
which the waste organic constituents are being converted to carbon
dioxide and water vapor. An increase in the carbon monoxide level
indicates that greater amounts of organic waste constituents are
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unreacted or partially reacted. Increased carbon monoxide levels can
result from insufficient excess oxygen, insufficient turbulence in the
combustion zone, or insufficient residence time.
(iv) Waste feed rate. The waste feed rate is important to
monitor because it is correlated to the residence time. The residence
time is associated with a specific Btu energy value of the feed and a
specific volume of combustion gas generated. Prior to incineration, the
Btu value of the waste is determined through the use of a laboratory
device known as a bomb calorimeter. The volume of combustion gas
generated from the waste to be incinerated is determined from an analysis
referred to as an ultimate analysis. This analysis determines the amount
of elemental constituents present, which include carbon, hydrogen,
sulfur, oxygen, nitrogen, and halogens. Using this analysis plus the
total amount of air added, one can calculate the volume of combustion
gas. After both the Btu content and the expected combustion gas volume
have been determined, the feed rate can be fixed at the desired residence
time. Continuous monitoring of the feed rate will determine whether the
unit is being operated at a rate corresponding to the designed residence
time.
(b) Rotary kiln. For this incineration, EPA will examine both
the primary and secondary chamber in evaluating the design of a
particular incinerator. Relative to the primary chamber, EPA's
assessment of design will focus on whether sufficient energy is likely to
be provided to the waste to volatilize the waste constituents. For the
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secondary chamber, analogous to the sole liquid injection incineration
chamber, EPA will examine the same parameters discussed previously under
liquid injection incineration. These parameters will not be discussed
again here.
The particular design parameters to be evaluated for the primary
chamber are kiln temperature, residence time, and revolutions per
minute. Below is a discussion of why EPA believes these parameters to be
important, as well as a discussion of how these parameters will be
monitored during operation.
(i) Temperature. The primary chamber temperature is important,
in that it provides an indirect measure of the energy input (i.e.,
Btu/hr) available for heating the waste. The higher the temperature is
designed to be in a given kiln, the more likely it is that the
constituents will volatilize. As discussed earlier under "Liquid
injection," temperature should be continuously monitored and recorded.
Additionally, it is important to know the location of the temperature
sensing device in the kiln.
(ii) Residence time. This parameter is important in that it
affects whether sufficient heat is transferred to a particular
constituent in order for volatilization to occur. As the time that the
waste is in the kiln is increased, a greater quantity of heat is
transferred to the hazardous waste constituents. The residence time will
be a function of the specific configuration of the rotary kiln, including
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the length and diameter of the kiln, the waste feed rate, and the rate of
rotation.
(iii) Revolutions- per minute (RPM). This parameter provides an
indication of the turbulence that occurs in the primary chamber of a
rotary kiln. As the turbulence increases, the quantity of heat
transferred to the waste would also be expected to increase. However, as
the RPM value increases, the residence time decreases, resulting in a
reduction of the quantity of heat transferred to the waste. This
parameter needs to be carefully evaluated because it provides a balance
between turbulence and residence time.
(c) Fluidized bed. As discussed previously in the section
"Underlying principles of operation," the primary chamber accounts for
almost all of the conversion of organic wastes to carbon dioxide, water
vapor, and acid gas (if halogens are present). The secondary chamber
will generally provide additional residence time for thermal oxidation of
the waste constituents. Relative to the primary chamber, the parameters
that the Agency will examine in assessing the effectiveness of the design
are temperature, residence time, and bed pressure differential. The
first two were included in the discussion of the rotary kiln and will not
be discussed here. The last, bed pressure differential, is important in
that it provides an indication of the amount of turbulence and therefore
indirectly the amount of heat supplied to the waste. In general, as the
pressure drop increases, both the turbulence and heat supplied increase.
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The pressure drop through the bed should be continuously monitored and
recorded to ensure that the designed value is achieved.
(d) Fixed hearth. The design considerations for this
incineration unit are similar to those for a rotary kiln with the
exception that rate of rotation (i.e., RPM) is not an applicable design
parameter. For the primary chamber of this unit, the parameters that the
Agency will examine in assessing how well the unit is designed are the
same as those discussed under "Rotary kiln"; for the secondary chamber
(i.e., afterburner), the design and operating parameters of concern are
the same as those previously di-scussed under "Liquid injection,."
3.2.2 Fuel Substitution
Fuel substitution involves using hazardous waste as a fuel in
industrial furnaces or in boilers for generation of steam. The hazardous
waste may be blended with other nonhazardous wastes (e.g., municipal
sludge) and/or fossil fuels.
(1) Applicability and use of fuel substitution. Fuel substitution
has been used with industrial waste solvents, refinery wastes, synthetic
fibers/petrochemical wastes, and waste oils. It can also be used when
combusting other waste types produced during the manufacture of
Pharmaceuticals, pulp and paper, and pesticides. These wastes can be
handled in a solid, liquid, or gaseous form.
The most common types of units in which waste fuels are burned are
industrial furnaces and industrial boilers. Industrial furnaces include
a diverse variety of industrial processes that produce heat and/or
3-23
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products by burning fuels. They include blast furnaces, smelters, and
coke ovens. Industrial boilers are units wherein fuel is used to produce
steam for process and plant use. Industrial boilers typically use coal,
oil, or gas as the primary fuel source.
A number of parameters affect the selection of fuel substitution.
These parameters are as follows:
Halogen content of the waste;
Inorganic solids content (ash content) of the waste,
particularly heavy metals;
Heating value of the waste;
Viscosity of the waste (for liquids);
Filterable solids concentration (for liquids); and
Sulfur content.
If halogenated organics are burned, halogenated acids and free
halogen are among the products of combustion. These released corrosive
gases may require subsequent treatment prior to venting to the
atmosphere. Also, halogens and halogenated acids formed during
combustion are likely to severely corrode boiler tubes and other process
equipment. For this reason, halogenated wastes are blended into fuels
only at very low concentrations to minimize such problems. High chlorine
content can also lead to the incidental production (at very low
concentrations) of other hazardous compounds such as polychlorinated
biphenyls (PCBs), polychlorinated dibenzo-p-dioxins (PCDDs),
polychlorinated dibenzofurans (PCDFs), and chlorinated phenols.
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High inorganic solids content (i.e., ash content) of wastes may cause
two problems: (1) scaling in the boiler and (2) participate air
emissions. Scaling results from deposition of inorganic solids on the
walls of the boiler. Particulate emissions are produced by
noncombustible inorganic constituents that flow out of the boiler with
the gaseous combustion products. Because of these problems, wastes with
significant concentrations of inorganic materials are not usually handled
in boilers unless the boilers have an air pollution control system.
Industrial furnaces vary in their tolerance to inorganic
constituents. Heavy metal concentrations, found in both halogenated and
nonhalogenated wastes used as fuel, can cause environmental concern
because they may be emitted in the gaseous emissions from the combustion
process, in the ash residues, or in any produced solids. The
partitioning of the heavy metals to these residual streams primarily
depends on the volatility of the metal, waste matrix, and furnace design.
The heating value of the waste must be sufficiently high (either
alone or in combination with other fuels) to maintain combustion
temperatures consistent with efficient waste destruction and operation of
the boiler or furnace. For many applications, only supplemental fuels
having minimum heating values of 4,400 to 5,600 kcal/kg (8,000 to 10,000
Btu/lb) are considered to be feasible. Below this value, the unblended
fuel would not be likely to maintain a stable flame, and its combustion
would release insufficient energy to provide needed steam generation
potential in the boiler or the necessary heat for an industrial furnace.
Some wastes with heating values of less than 4,400 kcal/kg (8,000 Btu/lb)
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can be used if sufficient auxiliary fuel is employed to support
combustion or if special designs are incorporated into the combustion
device. Occasionally, for wastes with heating values higher than virgin
fuels, blending with auxiliary fuel may be required to prevent
overheating or overcharging the combustion device.
In combustion devices designed to burn liquid fuels, the viscosity of
liquid waste must be low enough that the liquid can be atomized in the
combustion chamber. If the viscosity is too high, heating of storage
tanks may be required prior to combustion. For atomization of liquids, a
viscosity of 165 centistokes (750 Saybolt Seconds Universal (SSU)) or
less is typically required.
Filterable material suspended in the liquid fuel may prevent or
hinder pumping or atomization.
Sulfur content in the waste may prevent burning of the waste because
of potential atmospheric emissions of sulfur oxides. For instance, there
are proposed Federal sulfur oxide emission regulations for certain new
source industrial boilers (51 FR 22385). Air pollution control devices
are available to remove sulfur oxides from the stack gases.
(2) Underlying principles of operation. For a boiler and most
industrial furnaces, there are two distinct principles of operation.
Initially, energy in the form of heat is transferred to the waste to
achieve volatilization of the various waste constituents. For liquids,
volatilization energy may also be supplied by using pressurized
atomization. The energy used to pressurize the liquid waste allows the
atomized waste to break into smaller particles, thus enhancing its rate
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of volatilization. The volatilized constituents then require additional
energy to destabilize the chemical bonds and allow the constituents to
react with oxygen to form carbon dioxide and water vapor. The energy
needed to destabilize the chemical bonds is referred to as the energy of
activation.
(3) Description of the fuel substitution process. As stated, a
number of industrial applications can use fuel substitution. Therefore,
there is no one process description that will fit all of these
applications. However, the following section provides a general
description of industrial kilns (one form of industrial furnace) and
industrial boilers.
(a) Kilns. Combustible wastes have the potential to be used as
fuel in kilns and, for waste liquids, are often used with oil to co-fire
kilns. Coal-fired kilns are capable of handling some solid wastes. In
the case of cement kilns, there are usually no residuals requiring land
disposal since any ash formed becomes part of the product or is removed
by particulate collection systems and recycled back to the kiln. The
only residuals may be low levels of unburned gases escaping with
combustion products. If this is the case, air pollution control devices
may be required.
Three types of kilns are particularly applicable: cement kilns, lime
kilns, and lightweight aggregate kilns.
(i) Cement kilns. The cement kiln is a rotary furnace, which
is a refractory-lined steel shell used to calcine a mixture of calcium,
silicon, aluminum, iron, and magnesium-containing minerals. The kiln is
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normally fired by coal or oil. Liquid and solid combustible wastes may
then serve as auxiliary fuel. Temperatures within the kiln are typically
between 1,380 and 1,540°C (2,500 to 2,800°F). To date, only
liquid hazardous wastes have been burned in cement kilns.
Most cement kilns have a dry particulate collection device (i.e.,
either an electrostatic precipitator or baghouse), with the collected fly
ash recycled back to the kiln. Buildup of metals or other
noncombustibles is prevented through their incorporation in the product
cement. Since many types of cement require a source of chloride, most
halogenated liquid hazardous wastes currently can be burned in cement
kilns. Available information shows that scrubbers are not used.
(ii) Lime kilns. Quick-lime (CaO) is manufactured in a
calcination process using limestone (CaCO ) or dolomite (CaCO and
O
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(iii) Lightweight aggregate kilns. Lightweight aggregate kilns
heat clay to produce an expanded lightweight inorganic material used in
Portland cement formulations and other applications. The kiln has a
normal temperature range of 1,100 to 1,150°C (2,000 to 2,100'F).
Lightweight aggregate kilns are less amenable to combustion of hazardous
wastes as fuels than the other kilns described above because of the lack
of material in the kiln to adsorb halogens. As a result, burning of
halogenated organics in these kilns would likely require afterburners to
ensure complete destruction of the halogenated organics and scrubbers to
control acid gas production. Such controls would produce a wastewater
residual stream subject to treatment standards.
(b) Industrial boilers. A boiler is a closed vessel in which
water is transformed into steam by the application of heat. Normally,
heat is supplied by the combustion of pulverized coal, fuel oil, or gas.
These fuels are fired into a combustion chamber with nozzles and burners
that provide mixing with air. Liquid wastes, and granulated solid wastes
in the case of grate-fired boilers, can be burned as auxiliary fuel in a
boiler. Few grate-fired boilers burn hazardous wastes, however. For
liquid-fired boilers, residuals requiring land disposal are generated
only when the boiler is shut down and cleaned. This is generally done
once or twice per year. Other residuals from liquid-fired boilers would
be the gas emission stream, which would consist of any products of
incomplete combustion, along with the normal combustion products. For
example, chlorinated'wastes would produce acid gases. If this is the
case, air pollution control devices may be required. For solid-fired
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boilers, an ash normally is generated. This ash may contain residual
amounts of organics from the blended waste/fuels, as well as
noncombustible materials. Land disposal of this ash would require
compliance with applicable BOAT treatment standards.
(4) Waste characteristics affecting performance. For cement kilns
and lime kilns and for lightweight aggregate kilns burning nonhalogenated
wastes (i.e., no scrubber is needed to control acid gases), no residual
waste streams would be produced. Any noncombustible material in the
waste would leave the kiln in the product stream. As a result, in
.transferring standards EPA would not examine waste characteristics
affecting performance but rather would determine the applicability of
fuel substitution. That is, EPA would investigate the parameters
affecting treatment selection. As mentioned previously, for kilns these
parameters are Btu content, percent filterable solids, halogenated
organics content, viscosity, and sulfur content.
Lightweight aggregate kilns burning halogenated organics and boilers
burning wastes containing any noncombustibles will produce residual
streams subject to treatment standards. In determining whether fuel
substitution is likely to achieve the same level of performance on an
untreated waste as on a previously treated waste, EPA will examine:
(1) relative volatility of the waste constituents, (2) the heat transfer
characteristics (for solids), and (3) the activation energy for
combustion.
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(a) Relative volatility. The term relative volatility (a)
refers to the ease with which a substance present in a solid or liquid
waste will vaporize from that waste upon application of heat from an
external source. Hence, it bears a relationship to the equilibrium vapor
pressure of the substance.
EPA recognizes that the relative volatilities cannot be measured or
calculated directly for the types of wastes generally treated in an
industrial boiler or furnace. The Agency believes that the best measure
of relative volatility is the boiling point of the various hazardous
constituents, and will, therefore, use this parameter in assessing
volatility of the organic constituents.
(b) Heat transfer characteristics. Consistent with the
underlying principles of combustion in aggregate kilns or boilers, a
major factor with regard to whether a particular constituent will
volatilize is the transfer of heat through the waste. In the case of
industrial boilers burning solid fuels, heat is transferred through the
waste by three mechanisms: radiation, convection, and conduction. For a
given boiler it can be assumed that the type of waste will have a minimal
impact on the heat transferred from radiation. With regard to
convection, EPA believes that the range of wastes treated would exhibit
similar properties with regard to the amount of heat transferred by
convection. Therefore, EPA will not evaluate radiation convection heat
transfer properties of wastes in determining similar treatability. For
solids, the third heat transfer mechanism, conductivity, is the one
principally operative or most likely to vary between wastes.
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Using thermal conductivity measurements as part of a treatability
comparison for two different wastes through a given boiler or furnace is
most meaningful when applied to wastes that are homogeneous. As wastes
exhibit greater degrees of nonhomogeneity, thermal conductivity becomes
less accurate in predicting treatability because the measurement
essentially reflects heat flow through regions having the greatest
conductivity (i.e., the path of least resistance and not heat flow
through all parts of the waste). Nevertheless, EPA has not identified a
better alternative to thermal conductivity, even for wastes that are
nonhomogeneous.
Other parameters considered for predicting heat transfer
characteristics were Btu value, specific heat, and ash content. These
parameters can neither better account for nonhomogeneity nor better
predict heat transferab.il ity through the waste.
(c) Activation energy. Given an excess of oxygen, an organic
waste in an industrial furnace or boiler would be expected to convert to
carbon dioxide and water provided that the activation energy is
achieved. Activation energy is the quantity of heat (energy) needed to
destabilize molecular bonds and create reactive intermediates so that the
oxidation (combustion) reaction will proceed to completion. As a measure
of activation energy, EPA is using bond dissociation energies. In
theory, the bond dissociation energy would be equal to the activation
energy; in practice, however, this is not always the case.
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In some instances, bond energies will not be available and will have
to be estimated, or other energy effects (e.g., vibrational) and other
reactions will have a significant influence on activation energy.
Because of the shortcomings of bond energies in estimating activation
energy, EPA analyzed other waste characteristic parameters to determine
whether these parameters would provide a better basis for transferring
treatment standards from an untested to a tested waste. These parameters
included heat of combustion, heat of formation, use of available kinetic
data to predict activation energies, and general structural class. All
of these parameters were rejected for the reasons provided below.
The heat of combustion measures only the difference in energy of the
products and reactants; it does not provide information on the transition
state (i.e., the energy input needed to initiate the reaction). Heat of
formation is used as a tool to predict whether reactions are likely to
proceed; however, there-are a significant number of hazardous
constituents for which these data are not available. Use of available
kinetic data was rejected because while such data could be used to
calculate some free energy values (AG), they could not be used for
the wide range of hazardous constituents. Finally, EPA decided not to
use structural classes because the Agency believes that evaluation of
bond dissociation energies allows for a more direct comparison.
(5) Design and operating parameters.
(a) Design parameters. Cement kilns and lime kilns, along with
aggregate kilns burning nonhalogenated wastes, produce no residual
streams. Their design and operation is such that any wastes that are
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incompletely destroyed will be contained in the product. As a result,
the Agency will not look at design and operating values for such devices
since treatment, per se, cannot be measured through detection of
constituents in residual streams. In this instance, it is important
merely to ensure that the waste is appropriate for combustion in the kiln
and that the kiln is operated in a manner that will produce a usable
product.
Specifically, cement, lime, and aggregate kilns are demonstrated only
on liquid hazardous wastes. Such wastes must be sufficiently free of
filterable solids to avoid plugging the burners at the hot end of the
kiln. Viscosity also must be low enough for the waste to be injected
into the kiln through the burners. The sulfur content is not a concern
unless the concentration in the waste is sufficiently high as to exceed
Federal, State, or local air pollution standards promulgated for
industrial boilers.
The design parameters that normally affect the operation of an
industrial boiler (and aggregate kilns with residual streams) with
respect to hazardous waste treatment are (1) the design temperature,
(2) the design retention time of the waste in the combustion chamber, and
(3) turbulence in the combustion chamber. Evaluation of these parameters
would be important in determining whether an industrial boiler or
industrial furnace is adequately designed for effective treatment of
hazardous wastes. The rationale for selection of these three parameters
is given below.
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(i) Design temperature. Industrial boilers are generally
designed based on their steam,generation potential (Btu output). This
factor is related to the design combustion temperature, which in turn
depends on the amount of fuel burned and its Btu value. The fuel feed
rates and combustion temperatures of industrial boilers are generally
fixed based on the Btu values of fuels normally handled (e.g., No. 2
versus No. 6 fuel oils). When wastes are to be blended with fossil fuels
for combustion, the blending, based on Btu values, must be such that the
resulting Btu value of the mixture is close to that of the fuel value
used in design of the boiler. Industrial furnaces also are designed to
operate at specific ranges of temperature in order to produce the desired
product (e.g., lightweight aggregate). The blended waste/fuel mixture
should be capable of maintaining the design temperature range.
(ii) Design retention time. A sufficient retention time of
combustion products is normally necessary to ensure that the hazardous
substances being combusted (or formed during combustion) are completely
oxidized. Retention times on the order of a few seconds are generally
needed at normal operating conditions. For industrial furnaces as well
as boilers, the retention time is a function of the size of the furnace
and the fuel feed rates. For most boilers and furnaces, the retention
time usually exceeds a few seconds.
(iii) Turbulence. Boilers are designed so that fuel and air
are intimately mixed. This helps ensure that complete combustion takes
place. The shape of the boiler and the method of fuel and air feed
3-35
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influence the turbulence required for good mixing. Industrial furnaces
also are designed for turbulent mixing where fuel and air are mixed.
(b) Operating parameters. The operating parameters that
normally affect the performance of an industrial boiler and many
industrial furnaces with respect to treatment of hazardous wastes are
(1) air feed rate, (2) fuel feed rate, (3) steam pressure or rate of
production, and (4) temperature. EPA believes that these four parameters
will be used to determine whether an industrial boiler burning blended
fuels containing hazardous waste constituents is properly operated. The
rationale for selection of these four operating parameters is given
below. Most industrial furnaces will monitor similar parameters, but
some exceptions are noted.
(i) Air feed rate. An important operating parameter in boilers
and many industrial furnaces is the 'oxygen content in the flue gas, which
is a function of the air feed rate. Stable combustion of a fuel
generally occurs within a specific range of air-to-fuel ratios. An
oxygen analyzer in the combustion gases can be used to control the feed
ratio of air to fuel to ensure complete thermal destruction of the waste
and efficient operation .of the boiler. When necessary, the air feed rate
can be increased or decreased to maintain proper fuel-to-oxygen ratios.
Some industrial furnaces do not completely combust fuels (e.g., coke
ovens and blast furnaces); therefore, oxygen concentration in the flue
gas is a meaningless variable.
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(ii) Fuel feed rate. The rate at which fuel is injected into
the boiler or industrial furnace will determine the thermal output of the
system per unit of time (Btu/hr). If steam is produced, steam pressure
monitoring will indirectly determine whether the fuel feed rate is
adequate. However, various velocity and mass measurement devices can be
used to monitor fuel flow directly.
(iii) Steam pressure or rate of production. Steam pressure in
boilers provides a direct measure of the thermal output of the system and
is directly monitored by use of in-system pressure gauges. Increases or
decreases in steam pressure can be effected by increasing or decreasing
the fuel and air feed rates within certain operating design limits. Most
industrial furnaces do not produce steam, but instead produce a product
(e.g., cement, aggregate) and monitor the rate of production.
(iv) Temperature. Temperatures are monitored and controlled in
industrial boilers to ensure the quality and flow rate of steam.
Therefore, complex monitoring systems are frequently installed in the
combustion unit to provide a direct reading of temperature. The
efficiency of combustion in industrial boilers is dependent on combustion
temperatures. Temperature may be adjusted to design settings by
increasing or decreasing the air and fuel feed rates.
Wastes should not be added to primary fuels until the boiler
temperature reaches the minimum needed for destruction of the wastes.
Temperature instrumentation and control should be designed to stop waste
addition in the event of process upsets.
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Monitoring and control of temperature in industrial furnaces are also
critical to the product quality. For example, lime, cement, or aggregate
kilns require minimum operating temperatures. Kilns have very high
thermal inertia in the refractory and in-process product, high residence
times, and high air feed rates, so that even in the case of a momentary
stoppage of fuel flow to the kiln, organic constituents are likely to
continue to be destroyed. The main operational control required for
wastes burned in kilns is to stop waste flow in the event of low kiln
temperature, loss of electrical power to the combustion air fan, and loss
of primary fuel flow.
(v) Other operating parameters. In addition to the four
operating parameters discussed above, EPA considered and then discarded
one additional parameterfuel-to-waste blending ratios. While the
blending is done to yield a uniform Btu content fuel, blending ratios
will vary widely depending on the Btu content of the wastes and the fuels
being used.
3.2.3 Chromium Reduction
(1) Applicability and use of chromium reduction. The process of
6+
hexavalent chromium (Cr ) reduction involves conversion from the
hexavalent form to the trivalent form of chromium. This technology has
wide application to hexavalent chromium wastes, including plating
solutions, stainless steel acid baths and rinses, "chrome conversion"
coating process rinses, and chromium pigment manufacturing wastes.
Because this technology requires the pH to be in the acidic range, it
would not be applicable to a waste that contains significant amounts of
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cyanide or sulfide. In such cases, lowering of the pH can generate toxic
gases such as hydrogen cyanide or hydrogen sulfide. It is important to
note that additional treatment is required to remove trivalent chromium
from solution.
(2) Underlying principles of operation. The basic principle of
treatment is to reduce the valence of chromium in solution (in the form
of chromate or dichromate ions) from the valence state of six (+6) to the
trivalent (+3) state. "Reducing agents" used to effect the reduction
include sodium bisulfite, sodium metabisulfite, sulfur dioxide, sodium
hydrosulfide, or the ferrous form of iron.
A typical reduction equation, using sodium sulfite as the reducing
agent, is:
H2Cr20? + 3Na2S03 + (S04)3 - Cr2(S04)3 + 3Na2$04 + 4H20
The reaction is usually accomplished at pH values in the range of 2 to 3.
At the completion of the chromium reduction step, the trivalent
chromium compounds are precipitated from solution by raising the pH to a
value exceeding about 8. The less soluble trivalent chromium (in the
form of chromium hydroxide) is then allowed to settle from solution. The
precipitation reaction is as follows:
Cr2(S04)3 + 3Ca(OH)2 -* 2Cr(OH)3 + CaS04
(3) Description of the chromium reduction process. The chromium
reduction treatment process can be operated in a batch or continuous
mode. A batch system will consist of a reaction tank, a mixer to
homogenize the contents of the tank, a supply of reducing agent, and a
source of acid and base for pH control.
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A continuous chromium reduction treatment system, as shown in
Figure 3-5, will usually include a holding tank upstream of the reaction
tank for flow and concentration equalization. It will also include
instrumentation to automatically control the amount of reducing agent
added and the pH of the reaction tank. The amount of reducing agent is
controlled by the use of a sensor called an oxidation reduction potential
(ORP) cell. The ORP sensor electronically measures, in millivolts, the
level to which the redox reaction has proceeded at any given time. It
must be noted, however, that the ORP reading is very pH dependent.
Consequently, if the pH is not maintained at a steady value, the ORP will
vary somewhat, regardless of the level of chromate reduction.
(4) Waste characteristics affecting performance. In determining
whether chromium reduction can treat an untested waste to the same level
of performance as a previously tested waste, EPA will examine waste
characteristics that affect the reaction involved with either lowering
the pH or reducing the hexavalent chromium. EPA believes that such
characteristics include the oil and grease content of the waste, total
dissolved solids, and the presence of other compounds that would undergo
reduction reaction.
(a) Oil and grease. EPA believes that these compounds could
potentially interfere with the oxidation-reduction reactions, as well as
cause monitoring problems by fouling of instrumentation (e.g.,
electrodes). Oil and grease concentrations can be measured by EPA
Methods 9070 and 9071.
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REDUCING
AGENT
FEED
SYSTEM
ACID
FEED
SYSTEM
HEXAVALENT-
CMROMIUM
CONTAINING
WASTEWATER
OJ
i
J
ALKALI
FEED
SYSTEM
r
D
ORP pH
SENSORS
TO SETTLING
REDUCTION
PRECIPITATION
ELECTRICAL CONTROLS
o
MIXER
FIGURE 3-5
CONTINUOUS HEXAVALENT
CHROMIUM REDUCTION SYSTEM
-------
(b) Total dissolved solids. These compounds can interfere with
the addition of treatment chemicals into solution and possibly cause
monitoring problems.
(c) Other reducible compounds. These compounds would generally
consist of other metals in the waste. Accordingly, EPA will evaluate the
type and concentration of other metals in the waste in evaluating
transfer of treatment performances.
(5) Design and operating parameters. The parameters that EPA will
examine in assessing the design and operation of a chromium reduction
treatment system are discussed below.
(a) Treated and untreated design concentration. EPA will need
to know the level of performance that the facility is designed to achieve
in order to ensure that the design is consistent with best demonstrated
practices. This parameter is important in that a system will not usually
perform better than its design. In addition to knowing the treated
design concentration, it is important to know the characteristics of the
untreated waste that the system is designed to handle. Accordingly, EPA
will obtain data on the untreated wastes to ensure that waste
characteristics fall within design specifications.
(b) Reducing agent. The choice of a reducing agent establishes
the chemical reaction upon which the chromium reduction system is based.
The amount of reducing agent needs to be monitored and controlled in both
batch and continuous systems. In batch systems, reducing agent is
usually controlled by analysis of the hexavalent chromium remaining in
solution. For continuous systems, the ORP reading is used to monitor and
control the addition of reducing agent.
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ORP will change slowly until the correct amount of reducing agent has
been added, at which point ORP will change rapidly, indicating reaction
completion. The set point for the ORP monitor is approximately the
reading just after the rapid change has begun. The reduction system must
then be monitored periodically to determine whether the selected setpoint
needs further adjustment.
. (c) pH. For batch and continuous systems, pH is an important
parameter because of its effect on the reduction reaction. For a batch
system, pH can be monitored intermittently during treatment. For
continuous systems, the pH should be continuously monitored because of
its effect on ORP. In evaluating the design and operation of a
continuous chromium reduction system, it is important to know the pH on
which the design ORP value is based, as well as the designed ORP value.
(d) Retention time. Retention time should be adequate to
ensure that the hexavalent chromium reduction reaction goes to
completion. In the case of the batch reactor, the retention time is
varied by adjusting treatment time in the reaction tank. If the process
is continuous, it is important to monitor the feed rate to ensure that
the designed residence time is achieved.
3.2.4 Chemical Precipitation
(1) Applicability and use of chemical precipitation. Chemical
precipitation is used when dissolved metals are to be removed from
solution. This technology can be applied to a wide range of wastewaters
containing dissolved BOAT list metals and other metals as well. This
treatment 'process has been practiced widely by industrial facilities
since the 1940s.
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(2) Underlying principles of operation. The underlying principle of
chemical precipitation is that metals in wastewater are removed by the
addition of a treatment chemical that converts the dissolved metal to a
metal precipitate. This precipitate is less soluble than the original
metal compound and therefore settles out of solution, leaving a lower
concentration of the metal present in the solution. The principal
chemicals used to convert soluble metal compounds to the less soluble
forms include lime (Ca(OH) ), caustic (NaOH), sodium sulfide (Na S),
and, to a lesser extent, soda ash (Na CO ), phosphate, and ferrous
sulfide (FeS).
The solubility of a particular compound depends on the extent to
which the electrostatic forces holding the ions of the compound together
can be overcome. The solubility changes significantly with temperature;
most metal compounds are more soluble as the temperature increases.
Additionally, the solubility is affected by the other constituents
present in a waste. As a general rule, nitrates, chlorides, and sulfates
are more soluble than hydroxides, sulfides, carbonates, and phosphates.
An important concept related to treatment of the soluble metal
compounds is pH. This term provides a measure of the extent to which a
solution contains an excess of either hydrogen or hydroxide ions. The pH
scale ranges from 0 to 14, with 0 being the most acidic, 14 representing
the highest alkalinity or hydroxide ion (OH ) content, and 7.0 being
neutral.
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When hydroxide is used, as is often the case, to precipitate the
soluble metal compounds, the pH is frequently monitored to ensure that
sufficient treatment chemicals are added. It is important to point out
that pH is not a good measure of treatment chemical addition for
compounds other than hydroxides; when sulfide is used, for example,
facilities might use an oxidation-reduction potential (ORP) meter
correlation to ensure that sufficient treatment chemical is used.
Following conversion of the relatively soluble metal compounds to
metal precipitates, the effectiveness of chemical precipitation is a
function of the physical removal, which usually relies on a settling
process. A particle of a specific size, shape, and composition will
settle at a specific velocity, as described by Stokes' Law. For a batch
system, Stokes' Law is a good predictor of settling time because the
pertinent particle parameters remain essentially constant. Nevertheless,
in practice, settling time for a batch system is normally determined by
empirical testing. For a continuous system, the theory of settling is
complicated by factors such as turbulence, short-circuiting, and velocity
gradients, thereby increasing the importance of the empirical tests.
(3) Description of the chemical precipitation process. The
equipment and instrumentation required for chemical precipitation vary
depending on whether the system is batch or continuous. Both operations
are discussed below; a schematic of the continuous system is shown in
Figure 3-6.
3-45
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WASTEWATEH
FEED
CO
EQUALIZATION
TANK
PUMP
ELECTRICAL CONTROLS
WASTEWATER FLOW
MIXER
X
Q
>
9
4
"
\^
TREATMENT
CHEMICAL
FEED
SVSTEM
,1 to
1 fr«
COAGULANT OR
FLOCCULANT FEED SVSTEM
d
pH
MONITOR
EFFLUENT TO
DISCHARGE OR
SUBSEQUENT
TREATMENT
SLUDGE TO
OEWATEHING
FIGURE 3-6 CONTINUOUS CHEMICAL PRECIPITATION
-------
For a batch system, chemical precipitation requires only a feed
system for the treatment chemicals and a second tank where the waste can
be treated and allowed to settle. When lime is used, it is usually added
to the reaction tank in a slurry form. In a batch system, the supernate
is usually analyzed before discharge, thus minimizing the need for
instrumentation.
In a continuous system, additional tanks are necessary, as well as
instrumentation to ensure that the system is operating properly. In this
system, the first tank that the wastewater enters is referred to as an
equalization tank. This is where the waste can be mixed to provide more
uniformity, minimizing wide swings in the type and concentration of
constituents being sent to the reaction tank. It is important to reduce
the variability of the waste sent to the reaction tank because control
systems inherently are limited with regard to the maximum fluctuations
that can be managed.
Following equalization, the waste is pumped to a reaction tank where
treatment chemicals are added; this is done automatically by using
instrumentation that senses the pH of the system and then pneumatically
adjusts the position of the treatment chemical feed valve so that the
design pH value is achieved. Both the complexity and the effectiveness
of the automatic control system will vary depending on the variation in
the waste and the pH range that is needed to properly treat the waste.
An important aspect of the reaction tank design is that the tank's
contents be well'mixed so that the waste and the treatment chemicals are
both dispersed throughout the tank to ensure commingling of the reactant
3-47
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and the treatment chemicals. In addition, effective dispersion of the
treatment chemicals throughout the tank is necessary to properly monitor
and thereby control the amount of treatment chemicals added.
After the waste is reacted with the treatment chemical, it flows to a
quiescent tank where the precipitate is allowed to settle and
subsequently to be removed. Settling can be chemically assisted through
the use of flocculating compounds. Flocculants increase the particle
size and density of the precipitated solids, both of which increase the
rate of settling. The particular flocculating agent that will best
improve settling characteristics will vary depending on the particular
waste; selection of the flocculating agent is generally accomplished by
performing laboratory bench tests. Settling can be conducted in a large
tank by relying solely on gravity or can be mechanically assisted through
the use of a circular clarifier or an inclined separator. Schematics of
the latter two separators are shown in Figures 3-7 and 3-8.
Filtration can be used for further removal of precipitated residuals
both in cases where the settling system is underdesigned and in cases
where the particles are difficult, to settle. Polishing filtration is
discussed in a separate technology section.
(4) Haste characteristics affecting performance. In determining
whether chemical precipitation is likely to achieve the same level of
performance on an untested waste as on a previously tested waste, EPA
will examine the following waste characteristics: (1) the concentration
and type of the metal(s) in the waste, (2) the concentration of total
suspended solids (TSS), (3) the concentration of total dissolved solids
3-48
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EFFLUENT
SLUDGE
INFLUENT
CENTER FEED CLARIFIER WITH SCRAPER SLUDGE REMOVAL SYSTEM
SLUDGE
EFFLUENT
RIM FEED - CENTER TAKEOFF CLARIFIER WITH
HYDRAULIC SUCTION SLUDGE REMOVAL SYSTEM
INFLUENT
EFFLUENT
SLUDGE
RIM FEED - RIM TAKEOFF CLARIFIER
FIGURE 3-7 CIRCULAR CLARIFIERS
3-49
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INFLUENT
EFFLUENT
FIGURE 3-8
INCLINED PLATE SETTLER
3-50
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(IDS), (4) whether the metal exists in the wastewater as a complex, and
(5) the oil and grease content. These parameters affect the chemical
reaction of the metal compound, the solubility of the metal precipitate,
or the ability of the precipitated compound to settle.
(a) Concentration and type of metals. For most metals, there is a
specific pH at which the metal hydroxide is least soluble. As a result,
when a waste contains a mixture of many metals, it is not possible to
operate a treatment system at a single pH that is optimal for the removal
of all metals. The extent to which this situation affects treatment
depends on the particular metals to be removed and their concentrations.
One approach is to operate multiple precipitations, with intermediate
settling, when the optimum pH occurs at markedly different levels for the
metals present. The individual metals and their concentrations can be
measured using EPA Method 6010.
(b) Concentration and type of total suspended solids (TSS).
Certain suspended solid compounds are difficult to settle because of
their particle size or shape. Accordingly, EPA will evaluate this
characteristic in assessing the transfer of treatment performance. Total
suspended solids can be measured by EPA Wastewater Test Method 160.2.
(c) Concentration of total dissolved solids (TDS). Available
information shows that total dissolved solids can inhibit settling. The
literature states that poor flocculation is a consequence of high TDS and
shows that higher concentrations of total suspended solids are found in
treated residuals. Poor flocculation can adversely affect the degree to
which precipitated particles are removed. Total dissolved solids can be
measured by EPA Wastewater Test Method 160.1.
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(d) Complexed metals. Metal complexes consist of a metal ion
surrounded by a group of other inorganic or organic ions or molecules
(often called ligands). In the complexed form, the metals have a greater
solubility and therefore may not be as effectively removed from solution
by chemical precipitation. EPA does not have an analytical method to
determine the amount of complexed metals in the waste. The Agency
believes that the best measure of complexed metals is to analyze for some
common complexing compounds (or complexing agents) generally found in
wastewater for which analytical methods are available. These complexing
agents include ammonia, cyanide, and EDTA. The analytical method for
cyanide is EPA Method 9010, while the method for EDTA is ASTM
Method D3113. Ammonia can be analyzed using EPA Wastewater Test
Method 350.
(e) Oil and grease content. The oil and grease content of a
particular waste directly inhibits the settling of the precipitate.
Suspended oil droplets float in water and tend to suspend particles such
as chemical precipitates that would otherwise settle out of the
solution. Even with the use of coagulants or flocculants, the separation
of the precipitate is less effective. Oil and grease content can be
measured by EPA Method 9071.
(5) Design and operating parameters. The parameters that EPA will
evaluate when determining whether a chemical precipitation system is well
designed are (1) design value for treated metal concentrations, as well
as other characteristics of the waste used for design purposes (e.g.,
total suspended solids); (2) pH; (3) residence time; (4) choice of
3-52
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treatment chemical; (5) choice of coagulant/flocculant; and (6) mixing.
The reasons for which EPA believes these parameters are important to a
design analysis are cited below, along with an explanation of why other
design criteria are not included in this analysis.
(a) Treated and untreated design concentrations. When determining
whether to sample a particular facility, EPA pays close attention to the
treated concentration that the system is designed to achieve. Since the
system will seldom outperform its design, EPA must evaluate whether the
design is consistent with best demonstrated practice.
The untreated concentrations that the system is designed to treat are
important in evaluating any treatment system. Operation of a chemical
precipitation treatment system with untreated waste concentrations in
excess of design values can easily result in poor performance.
(b) pH. The pH is important because it can indicate that
sufficient treatment chemical (e.g., lime) has been added to convert the
metal constituents in the untreated waste to forms that will
precipitate. The pH also affects the solubility of metal hydroxides and
sulfides and thus directly impacts the effectiveness of removal. In
practice, the design pH is determined by empirical bench testing, often
referred to as "jar" testing. The temperature at which the "jar" testing
is conducted is important since it also affects the solubility of the
metal precipitates. Operation of a treatment system at temperatures
above the design temperature can result in poor performance. In
assessing the operation of a chemical precipitation system, EPA prefers
to use continuous data on the pH and periodic temperature conditions
throughout the treatment period.
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(c) Residence time. Residence time is important because it
impacts the completeness of the chemical reaction to form the metal .
precipitate and, to a greater extent, the amount of precipitate that
settles out of solution. In practice, it is determined by "jar"
testing. For continuous systems, EPA will monitor the feed rate to
ensure that the system is operated at design conditions. For batch
systems, EPA will want information on the design parameter used to
determine sufficient settling time (e.g., total suspended solids).
(d) Choice of treatment chemical. A choice must be made as to
what type of precipitating agent (i.e., treatment chemical) will be
used. The factor that most affects this choice is the type of metal
constituents to be treated. Other design parameters, such as pH,
residence time, and choice of coagulant/flocculant agents, are based on
the selection of the treatment chemical.
(e) Choice of coagulant/flocculant. This is important because
these compounds improve the settling rate of the precipitated metals and
allow smaller systems (i.e., those with a lower retention time) to
achieve the same degree of settling as much larger systems. In practice,
the choice of the best agent and the required amount is determined by
"jar" testing.
(f) Mixing. The degree of mixing is a complex assessment that
includes, the energy supplied, the time the material is mixed, and the
related turbulence effects of the specific size and shape of the tank.
In its analysis, EPA will consider whether mixing is provided and whether
3-54
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the type of mixing device is one that could be expected to achieve
uniform mixing. For example, EPA may not use data from a chemical
precipitation treatment system in which an air hose was placed in a large
tank to achieve mixing.
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4. PERFORMANCE DATA BASE.
This section presents performance data associated with the
demonstrated technologies for K015 waste. Performance data include the
BOAT list constituent concentrations in the untreated and treated waste
samples, the operating data collected during treatment of the sampled
waste, design values for the treatment technologies, and data on waste
characteristics that affect performance. EPA has presented all such
data to the extent that they are available.
EPA's use of these data in determining the technologies that
represent BOAT, and in developing treatment standards, is described in
Sections 5 and 7, respectively.
4.1 BOAT List Orqanics Treatment Data
EPA tested liquid injection incineration to demonstrate the actual
performance achievable by the technology for treatment of K015. The
Agency has three data sets (matched pairs of treated and untreated data
points) for BOAT list organics as well as the appropriate design and
operating data. Performance data collected for liquid injection
incineration of K015 are presented in Table 4-1 at the end of this
section. Further discussion of how these data were obtained is presented
in the Onsite Engineering Report of Treatment Technology Performance and
Operation for Incineration of K015 Waste at the John Zink Company Test
Facility (USEPA 1987a).
Unadjusted analytical data show that in the untreated waste for which
detection limits were fairly high (parts per thousand for semivolatile
organic compounds), only benzal chloride was detected. Concentrations
4-1
-------
detected ranged upward from 88 percent. Benzal chloride concentrations
in the treated wastewaters ranged from less than 0.050 to 0.094 mg/1.
Other organic constituents found in the treated waste were toluene,
anthracene, benzo(b and/or k)fluoranthene, and phenanthrene. These
constituents were detected at concentrations up to 0.210 mg/1.
The Agency does not have performance data for treatment of the BOAT
list organics present in K015 using fuel substitutions.
4.2 BDAT List Metals Treatment Data
The treatment wastewater residual from liquid injection incineration
of K015 contains BDAT list metals in treatable concentrations. The
Agency does not have performance data specifically for treatment of BDAT
list metals in the scrubber water generated from liquid injection
incineration of K015. However, EPA does have data from EPA's testing of
a metal-bearing wastewater at Erivirite Corporation that the Agency
believes represent a level of treatment performance that can be achieved
for the K015 scrubber water by using chromium reduction and chemical
precipitation, primarily using lime as the treatment chemical.
The data collected for the Envirite treatment system consist of
11 sample sets. The untreated waste was a metal-containing wastewater
that was a mixture of F006, F002, D003, and K062 wastewaters. The
performance data for the Envirite wastewater treatment system are shown
in Table 4-2 at the end of this section.
EPA reviewed the characterization data for the K015 scrubber water
from liquid injection incineration, as well as data on parameters that
would affect the performance of the Envirite treatment system. The
4-2
-------
concentrations of the untreated metals in the Envirite wastewater are
typically higher than the BOAT list metals in the K015 scrubber water.
Specifically, the principal metals in the K015 scrubber are present at
concentrations less than 35 mg/1 for chromium and 25 mg/1 for nickel. In
the Envirite metal-containing wastewater, the concentrations of chromium
and nickel are as high as 2,581 mg/1 and 16,330 mg/1, respectively. In
addition, both the Envirite wastewater and the K015 scrubber water have
low oil and grease contents. In conclusion, these data indicate that the
BOAT list metals in K015 scrubber water could be treated to the same
levels as the Envirite metal-containing wastewater.
4-3
-------
1541g
Table 4-1 Performance Data Collected by EPA for Liquid Injection
Incineration of K015 Waste
Sample set #1
Constituent
BOAT constituent concentration
Untreated waste Treated waste
(mg/kg) (mg/1)
Volatiles
Toluene <10
Semivolati les
Anthracene <5,000
Benzal chloride 930,000
Benzo(b and/or k)f luoranthene <5,000
Phenanthrene <5,000
Metals
Antimony
Arsenic
Barium
Beryllium
Cadmium
Chromium
Copper
Mercury
Nickel
Lead
Selenium
Silver
Thallium
Vanadium
Zinc
0.059
<0.050
<0.050
<0.050
<0.050
<0.17
0.25
0.11
<0.005
<0.02
4.0
0.58
0.005
2.2
0.06
0.06
0.13
<0.75
0.05
0.11
Design and operating data
Kiln
Temperature
Feed rate
Excess oxygen
Carbon monoxide
Scrubber
Flow
Pressure drop
1841-2013-F
4.14-4.5 Ib/min
3.74-5.297.
0-520 ppm
17.44 gal/mm
40-44 in. of water
a Concentration data have not been adjusted for accuracy. Accuracy-adjusted
data are shown in Section 6 and Appendix B.
The concentrations represent scrubber water residuals and are considered
treated relative to organics and not relative to metals.
4-4
-------
1541g
Table 4-1 (continued)
Sample set w2
Constituent
BOAT constituent concentration
Untreated waste Treated waste
(mg/kg) (mg/1)
Volatiles
Toluene <10
Semivolat i les
Anthracene <5,000
Benzal chloride 910,000
Benzofb and/or k)f luoranthene <5,000
Phenanthrene <5,000
Metals
Antimony
Arsenic
Barium
Beryllium
Cadmium
Chromium
Copper
Mercury
Nickel
Lead
Selenium
Silver
Thallium
Vanadium
Zinc
0.030
0.068
0.066
<0.050
0.058
<0.12
0.10
0.25
<0.005
<0.02
18
1.6
<0.0025
11
0.24
0.09
0.30
<0.75
0.170
0.75
Design and operating data
iln
Temperature
Feed rate
Excess oxygen
Carbon monoxide
Scrubber
Flow
Pressure drop
2001-2077"F
4.48-4.55 Ib/min
3.29-5.12%
0-80 ppm
17.44 gal/min
40-41 in. of water
Concentration data have not oeen adjusted for accuracy. Accuracy-adjusted
data are shown in Section 6 and Appendix B.
The concentrations represent scrubber water residuals and are considered
treated relative to organics and not relative to metals.
4-5
-------
1541g
Table 4-1 (continued)
Sample set ff3
Constituent
BOAT constituent concentration
Untreated waste Treated waste
(mg/kg) (mg/1)
Volatiles
Toluene <10
Semivolati les
Anthracene <5,000
Benzal chloride 1,100,000
Benzolb and/or k)f luoranthene <5,000
Phenanthrene <5,000
Metals
Antimony
Arsenic
Barium . -
Beryllium
Cadmium
Chromium
Copper
Mercury
Nickel
Lead
Selenium
Silver
Thallium
Vanadium
Zinc
0.015
0.210
0.094
0.096
0.110
0.16
0.53
0.55
<0.005
<0.02
34
3.5
0.06
25
0.30
0.06
<0 . 035
<0.75
0.39
0.93
Design and operating data
Kiln
Temperature
Feed rate
Excess oxygen
Carbon monoxide
Scrubber
Flow
Pressure drop
1780-2065'F
4.18-6.22 Ib/min
3.17-5.77%
0-614 ppm
17.44 gal/min
38-40 in. of water
Concentration data have not been adjusted for accuracy. Accuracy adjusted
data are shown in Section 6 and Appendix 8.
Treated waste concentration data reflect the worst-case concentration from
quench water sampling to ensure conservatism in determining a wastewater
standard. . c
-------
Total organic carbon
Total solids
Total chlorides
Total organic halides
Table 4-2 Performance Data for Chromium Reduction and Chemical Precipitation
on Mixed Waste Sampled by EPA at Envirite Co.
Concentration (ppm)
Const ituent/parameter
BOAT Metals
Ant imony
Arsenic
Barium
Beryl 1 ium
Cadmium
Chromium (hexavalent)
Chromium (total)
Copper
Lead
Mercury
Nickel
Selenium
Si Iver
Thallium
Zinc
Other Parameters
Sample
Treatment
tank composite
<10
-------
Table 4-2 (continued)
Concentration (com)
Const ituent/parameter
BOAT Metals
Antimony
Arsenic
Barium
Beryllium
Cadmium
Chromium (hexavalent)
Chromium (total)
Copper
Lead
Mercury
Nickel
Selenium
-p> Silver
oo Thallium
Zinc
Other Parameters
Sample
Treatment
tank composite
<10
<1
<10
<2
<5
917
2.236
91
18
1
1,414
<10
<2
<10
71
Set #5
Filtrate
<1
<0.1
<1
<0.2
<0.5
0.058
0.11
0.14
<0.01
<0.1
0.310
<1
<0.2
<1
0.125
Sample
Treatment
tank composite
<10
<1
<10
<2
<5
734
2.548
149
<10
<1
588
<10
<2
<10
4
Set #6
Filtrate
<1
<0.1
<2
<0.2
<0.5
_a
0.10
0.12
<0.01
<0.1
0.33
<1
<0.2
<1
0.095
Sample
Treatment
tank composite
<10
<1
<10
<2
10
769
2.314
72
108
<1
426
<10
<2
<10
171
Set #7
Filtrate
<1
<0.1
<1
<0.2
<0.5
0.121
0.12
0.16
<0.01
<0.01
0.40
<1
<0.2
<1
0.115
Sample
Treatment
tank composite
<10
<1
<10
<2
<5
0.13
831
217
212
<1
669
<10
<2
<10
151
Set #8
Filtrate
<1
<0.1
<1
<0.2
<0.5
<0.01
0.15
0.16
<0.01
<0.1
0.36
<1
<0.2
<1
0.130
Total organic carbon
Total solids
Total chlorides
Total organic ha 1 ides
200
700
700
3400
1900
5900
800
-------
Table 4-2 (continued)
Concentration (opm)
Const ituent/parameter
BOAT Metals
Ant imony
Arsenic
Barium
Beryll ium
Cadmium
Chromium (hexavalent)
Chromium (total)
Copper
Lead
Mercury
Nickel
Selenium
1 Si Iver
10
1 ha 1 1 ium
Zinc
Other Parameters
Total organic carbon
Total solids
Total chlorides
Total organic ha 1 ides
Sample Set #9
Treatment
tank composite Filtrate
<10 <1
<1 <0.1
<10 <1
<2 <0.2
<5 <0.5
0.07 0.041
939 0.10
225 0.08
<10 <0.01
<1 <0.1
940 0.33
<10 <1.0
<2 <0.2
5 0.06
2100
-
-
0
Sample Set #10
Treatment
tank composite Filtrate
<10 <1
<1 <0.1
<10 <1
<2 <0.2
<5 <0.5
0.08 0.106
395 0.12
191 0.14
<10 <0.01
<1 <0.1
712 0.33
<\0
-------
5. IDENTIFICATION OF THE BEST DEMONSTRATED AVAILABLE TECHNOLOGY (BOAT)
This section presents the rationale for the determination of best
demonstrated available technology (BOAT) for K015 organics and metals
treatment. As discussed in Section 1, the Agency examines all the
available data for the demonstrated technologies to determine.whether one
of the technologies performs significantly better than the others. Next,
the "best" performing treatment technology is evaluated to determine
whether the resulting treatment is available. To be "available," a
technology (1) must provide substantial treatment, and (2) must be
commercially available to the affected industry. If the "best"
technology is "available," then the technology represents BOAT.
5.1 BOAT for Treatment of Orqanics
For treatment of organics in K015, the Agency has data only from
liquid injection incineration. The three data sets were collected during
tests in which the K015 waste was incinerated. Because data from the
other demonstrated technologies are not available, the Agency cannot
compare performance to determine which technology is "best." However,
the Agency would not expect the level of performance to be improved by
other forms of incineration such as rotary kiln or fixed hearth. In
addition, EPA believes that well-designed and well-operated fuel
substitution systems could not achieve better treatment since they
operate at approximately the same temperatures and turbulent conditions
as a liquid injection incineration system.
5-1
-------
Consistent with EPA's methodology for determining BOAT, the Agency
evaluated the liquid injection incineration performance data to determine
whether the technology provides substantial treatment for BOAT list
organic constituents in K015.
As a first step in determining whether substantial treatment is
provided, the available treatment data described in Section 4 were
reviewed and assessed with regard to the design and operation of the
treatment system, the analytical testing, and the quality assurance/
quality control analyses of the data. In general, all of the performance
data collected for liquid injection incineration of K015 were of
sufficient quality for the determination of substantial treatment.
Design and operating data were collected for the liquid injection
incineration system used for treating BOAT list organic constituents in
K015 wastes. These data indicate that the system was well designed and
well operated during the test burn. In addition, the proper analytical
tests were performed for the untreated wastes and the treated residuals.
Specifically, because incineration is a destruction technology for
organics, total constituent concentration of organics is used to measure
treatment performance.
Next, EPA adjusted the data values based on the analytical recovery
values to take into account analytical interferences associated with the
chemical makeup of the treated sample. In summary, EPA first analyzes a
waste for a constituent and then adds a known amount of the same
constituent (i.e., spike) to the waste material. The total amount
5-2
-------
recovered after spiking minus the initial concentration in the sample,
all divided by the amount added, is the recovery value. The reciprocal
of the recovery (EPA uses the lower value of the matrix spike and matrix
duplicate recoveries, in general), multiplied by the performance data
value, is the accuracy-corrected value used in determining substantial
treatment and subsequently calculating treatment standards. Percent
recovery values for the BOAT list constituents in the K015 performance
data are presented in Appendix B. The accuracy correction values for the
regulated organic constituents are presented in Table 7-1. (The
methodology for adjusting the performance data is discussed in Section 1.)
EPA's determination that substantial treatment occurs is based on the
reduction of the concentration of BOAT list organic constituents. For
example, benzal chloride was detected in the untreated waste at
concentrations greater than 910,000 mg/kg. Treated waste concentrations
in the scrubber water ranged from <0.050 to 0.094 mg/1 for benzal
chloride. In addition to the substantial reduction, liquid injection
incineration is commercially available and therefore meets the second
criterion for "availability." As "best," "demonstrated," and
"available," the technology represents BOAT for the organics present in
K015.
5.2 BOAT for Treatment of Metals
Treatment of the BOAT list organics present in K015 using liquid
injection incineration generates a wastewater residual that requires
treatment for BOAT list metals. As discussed earlier, EPA does not
5-3
-------
have treatment data specifically for K015 wastewaters generated from
liquid injection incineration; however, EPA does have treatment data
specifically for metal-containing wastewaters (Envirite) believed to be
similar to K015 scrubber water. The demonstrated technologies identified
for treatment of BOAT list metals in K015 scrubber water for which the
Agency has data are chromium reduction and chemical precipitation. The
treatment performance data for the BOAT list metals by chromium reduction
and chemical precipitation were examined to determine whether substantial
treatment had occurred. Since the operating data collected during
treatment of this waste represent the performance of a well-designed,
well-operated treatment system, all data were used in determining
substantial treatment.
EPA's determination of substantial wastewater treatment for the
Envirite treatment system is based on the reductions of hexavalent
chromium from 917 mg/1 to 0.058 mg/1, chromium from 2,581 mg/1 to
0.12 mg/1, lead from 212 mg/1 to 0.01 mg/1, copper from 225 mg/1 to
0.08 mg/1, nickel from 16,330 mg/1 to 0.33 mg/1, and zinc from 171 mg/1
to 0.115 mg/1. The treated concentrations are accuracy-corrected values
adjusted in the same manner described for the organic constituents.
The Agency has no reason to expect that the use of other processes
could improve the level of performance; therefore, chromium reduction and
chemical precipitation are "best." The treatment system consisting of
chromium reduction followed by chemical precipitation is "available"
because the components of the treatment system are commercially available
5-4
-------
and the treatment provides substantial treatment. Therefore, this
treatment system represents BOAT for BOAT list metals in K015 wastewaters,
5-5
-------
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 organics, semivolatile organics, metals, inorganics
other than metals, organochlorine pesticides, phenoxyacetic acid
herbicides, organophosphorus insecticides, PCBs, and dioxins and furans.
This section describes the process used to select the constituents to
be regulated. The process involves developing a list of potential
regulated constituents and then eliminating those constituents that would
not be treated by the chosen BOAT or that would be controlled by
regulation of the remaining constituents.
6.1 Identification of BOAT List Constituents in K015
As discussed in Sections 2 and 4, the Agency has characterization
data as well as performance data from treatment of K015 waste. These
data, as well as information on the waste generating process, have.been
used to determine which BOAT list constituents may be present in the
waste and thus which ones are potential candidates for regulation in
wastewater forms of K015.
Table 6-1, at the end of this section, indicates, for the untreated
waste, which constituents were analyzed, which constituents were
detected, and which constituents the Agency believes could be present
though not detected. A few compounds have been added to the BOAT list of
constituents since the treatment analysis for K015 was performed;
6-1
-------
therefore, no analytical data exist for these constituents. While the
Agency does not expect -any of the additional compounds to be present in
the K015 waste, these additional compounds are also noted on Table 6-1.
Certain BOAT list categories were not analyzed in the untreated waste
because there was not thought to be an in-process source of these
constituents. These categories include all the constituents listed in
the inorganics other than metals, organochlorine pesticides,
phenoxyacetic herbicides, organophosphorus insecticides, PCBs, and
dioxin/furans.
Under the column "Believed to be present," constituents other than
those detected in the untreated waste are marked with Y if EPA believes
they are likely to be present in the untreated waste. Those constituents
marked with Y have been detected in the treated residual and therefore
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 those
constituents, (2) masking or interference by other constituents prevented
detection, or (3) the constituent indeed was not present.
Of the 231 current BOAT list constituents, the Agency analyzed for
162 constituents in the untreated waste. Eighteen BOAT constituents were
not on the BOAT list at the time the K015 waste was analyzed; thus data
do not exist for some of them. Other BOAT list constituents were not
analyzed because the Agency believed that there was no in-process source
for them.
6-2
-------
Of the 162 BOAT list constituents analyzed in the untreated waste,
only 1 was detected Denial chloride. In the treated waste, i.e.,
scrubber water, 5 BOAT list organic constituents were detected.
BOAT list metals were not analyzed in the untreated waste but were
analyzed in the treated waste (scrubber water). Of the 15 metals
analyzed, 12 were detected in the treated waste stream. These BOAT list
metals are thought to result from reaction of stainless steel process
equipment with hydrogen chloride gas liberated from the process
reactions. They must therefore be considered a part of the BOAT list
selected constituents. Of these 12 detected BOAT list constituents, EPA
has determined that all are treatable.
The constituents identified as major treatable constituents of K015
waste are toluene, anthracene, benzal chloride, benzo(b and/or k)
fluoranthene, phenanthrene, and several metals (i.e., antimony, arsenic,
barium, chromium, copper, lead, mercury, nickel, selenium, silver,
vanadium, and zinc). Concentration data from the testing of K015 waste
for these constituents are summarized in Table 6-2. The table shows
concentrations detected in the untreated waste, as well as those in the
treated waste.
6.2 Determination of Significant Treatment from BOAT
The next step in selecting the constituents to be regulated is to
eliminate those identified constituents in the waste that cannot be
significantly treated by the technologies designated as BOAT.
Having identified the major treatable BOAT list constituents present
in the waste, EPA compared the analytical data to determine whether the
6-3
-------
constituent concentration was reduced significantly from the untreated to
the treated waste. For constituents present in the treated waste but not
detected in the untreated waste, it was assumed that the constituent was
present in the untreated waste at or near the detection limit. -This
assumption was based on the likelihood that the constituents would be
masked by other constituents in the untreated waste.
If the concentration of a major treatable constituent is not reduced
significantly by treatment deemed BOAT, the Agency eliminates the
constituent from the list of identified constituents to be considered as
regulated unless the concentration in the treated waste is high. Table
6-3 presents those BOAT list organic constituents determined by EPA to be
treatable by liquid injection incineration. This technology would thus
significantly reduce these concentrations. Those organic constituents
that were not detected in the treated or untreated waste are not deemed
treatable. They are therefore not considered for regulation because
(1) the currently available analytical methods and recommended procedures
are inadequate for these constituents and thus are considered unreliable;
(2) the constituents, if present, are likely to be at low-level
concentrations; or (3) it is assumed that the majority of these
constituents are treated, if present at low levels, along with the
treatable organic BOAT list constituents determined by EPA during the
liquid injection incineration. As shown in Table 6-3, all identified
«
organic constituents in K015 waste were significantly treated by liquid
injection incineration.
6-4
-------
BOAT list metals were found at high concentrations in the scrubber
water residual. In such a case, treatment standards may be established
for that constituent using some other demonstrated and available
technology on a matrix similar to the treated residual. As discussed in
Section 6.1, liquid injection incineration of K015 waste was. not expected
to treat metals, but metals were found in the treated wastewater.
Chromium and nickel were present in the treated waste at the highest
concentrations. In addition, these two BOAT list metals were present in
concentrations for which treatment has been demonstrated by chromium
reduction and chemical precipitation. The Agency believes that treatment
of chromium and nickel will result in treatment of the other detected
metals, since they are present at considerably lower concentrations.
6.3 Selection of Regulated Constituents
In summary, EPA has selected five BOAT organic constituents, toluene,
anthracene, benzal chloride, benzo(b and/or k)fluoranthene, and
phenanthrene, and two metal constituents, chromium and nickel, as the
regulated constituents for K015 wastewaters.
6-5
-------
2154g
Table 6-1 Status of BOAT List Constituent Presence
in Untreated K.015 Waste
BOAT
reference
no.
222.
1.
2.
3.
4.
5.
6.
223.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
25.
26.
27.
28.
29.
224.
225.
226.
30.
227.
31.
214.
32.
33.
228.
34.
Constituent
Volati 1e orqanics
Acetone
Acetonitri le
Acrolein
Aery lonitri le
Benzene
Bromod i ch loromethane
Bromomethane
n-Butyl alcohol
Carbon tetrachloride
Carbon disulfide
Chlorobenzene
2-Chloro-l,3-butadiene
Ch lorod i bromomethane
Chloroethane
2-Chloroethyl vinyl ether
Chloroform
Ch loromethane
3-Chloropropene
l,2-Dibromo-3-chloropropane
1 ,2-Oibromoethans
Dibromomethane
trans- l,4-Dichloro-2-butene
D ich lorod if luoromethane
1,1-Oichloroethane
1,2-Oichloroethane
1 , 1-Dichloroethylene
trans- 1,2-0 ich loroethene
1,2-Oichloropropane
trans-1 ,3-Oichloropropene
cis-1.3-Dichloropropene
1,4-Dioxane
2-Ethoxyethanol
Ethyl acetate
Ethyl benzene
Ethyl cyanide
Ethyl ether
Ethyl methacrylate
Ethylene oxide
lodomethane
Isobutyl alcohol
Methanol
Methyl ethyl ketone
Detection Believed to
status3 be present
NO
NO
NO
NO
NO
NO
NO
NA
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NA
NO
NO
NO
NO
NO
NO
NO
NA
NA
NO
6-6
-------
2154g
Table 6-1 (continued)
BOAT
reference
no.
229.
35.
37.
38.
230.
39.
40.
41.
42.
43.
44.
45.
46.
47.
48.
49.
231.
50.
215.
216.
217.
51.
52.
53.
54.
55.
56.
57.
58.
59.
218.
60.
61.
62.
63.
64.
'65.
66.
Constituent
Volat i 1e orqanics (continued)
Methyl isobutyl ketone
Methyl methacrylate
Methacrylonitri le
Methylene chloride
2-Nitropropane
Pyridine
1, 1,1,2-Tetrachloroethane
1,1,2 , 2-Tetrach loroethane
Tetrachloroethene
Toluene
Tribromomethane
1,1,1-Trichloroethane
1, 1,2-Trichloroethane
Trichloroethene
Trichloromonof luoromethane
1,2,3-Trichloropropane
l,l,2-Trichloro-l,2.2-
trif luoroethane
Vinyl chloride
1,2-Xylene
1,3-Xylene
1,4-Xylene
Semivolat i le orcianics
Acenaphthalene
Acenaphthene
Acetophenone
2-Acetylaminof luorene
4-Aminobiphenyl
Ani line
Anthracene
Aramite
Benz(a)anthracene
Benzal chloride
Benzenethiol
Deleted
Benzo(a)pyrene
Benzo(b)f luoranthene
Benzo(ghi (perylene
Benzo(k)f luoranthene
p-Benzoquinone
Detection Believed to
status3 be present
' NO
ND
NO
ND
NA
ND
ND
ND
ND
ND Y
ND
ND
ND
ND
ND
ND
NA
ND '
ND
ND
ND
ND
ND
ND
NO
ND
ND
ND Y
ND
ND
880,000-1,100,000
ND
ND
ND Y
NO
ND Y
ND
6-7
-------
2154g
Table 6-1 (continued)
BOAT
reference
no.
67.
68.
69.
70.
71.
72.
73.
74.
75.
76.
77.
78.
79.
80.
81.
82.
232.
83.
84.
85.
86.
87.
88.
89.
90.
91.
92.
93.
94.
95.
96.
97.
98.
99.
100.
101.
102.
103.
104.
10-5.
106.
219.
Constituent
Semivolati 1e orqanics (continued)
B i s ( 2-ch.loroethoxy )met hane
Bis(2-chloroethyl)ether
Bis(2-chloroisopropyl)ether
Bis(2-ethylhexyl)phthalate
4-Bromophenyl phenyl ether
Butyl benzyl phthalate
2-sec-Buty 1-4,6-dinitrophenol
p-Chloroani 1 ine
Chlorobenzilate
p-Chloro-m-creso'i
2-Chloronaphtha lene
2-Chlorophenol
3-Chloropropionitri le
Chrysene
ortho-Cresol
para-Cresol
Cyclohexanone
Oibenzt a, h) anthracene
Dibenzo(a,e)pyrene
Dibenzo(a, i jpyrene
m-Dichlorobenzeng
o-Dichlorobenzene
p-Oichlorobenzene
3,3'-Oichlorobenzidine
2,4-Oichlorophenol
2,6-Dichlorophenol
Oiethyl phthalate
3 . 3 ' -0 imet hoxybenz i d i ne
p-Dimethylaminoazobenzene
3,3 '-Dimethylbenzidine
2 , 4-D imethy Ipheno 1
Dimethyl phthalate
Di-n-butyl phthalate
1 ,4-Dinitrobenzeme
4,6-Oinitro-o-cresol
2,4-Oinitrophenol
2,4-DinitrotoluRne
2,6-Dinitrotolufine
Di-n-octyl phthalate
Di-n-propylnitrosamine
Diphenylamine
D i pheny In i t rosam i ne
Detection Bel ieved to
status be present
NO
ND
ND
ND
ND
ND
ND
ND
ND
ND.
ND
ND
ND
ND
ND
ND
NA
NO
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NO
ND
ND
ND
ND
ND
ND
ND
ND
ND
NO
6-8
-------
2154g
Table 6-1 . (continued)
BOAT
reference
no.
107.
108.
109.
110.
111.
112.
113.
114.
115.
116.
117.
118.
119.
120.
36.
121.
122.
123.
124.
125.
126.
127.
128.
129.
130.
131.
132.
133.
134.
135.
136.
137.
.138.
139.
140.
141.
142.
220.
143.
144.
145.
146.
Constituent
Semivolati le orqanics (continued)
1,2-Diphenylhydrazine
Fluoranthene
Fluorene
Hexachlorobenzene
Hexachlorobutadiene
Hexach lorocyc lopentad iene
Hexachloroe thane
Hexachlorophene
Hexach loropropene
Indeno(l,2,3-cd)pyrene
Isosafrole
Methapyri Iene
3-Methylcholanthrene
4,4'-Methylenebis
(2-chloroani 1 ine)
Methyl methanesulfonate
Naphthalene
1,4-Naphthoquinone
1-Naphthylamine
2-Naphthylamine
p-Nitroani 1 ine
Nitrobenzene
4-Nitrophenol
N-Nitrosodi-n-butylamine
N-Nitrosodiethylamine
N-Nitrosodi methyl am Ine
N-Nitrosomethylethylamine
N-Nitrosomorpholine
N-Nitrosopiperidine
N-Nitrosopyrrol id ine
5-Nitro-o-toluidine
Pentachlorobenzene
Pent achloroe thane
Pentachloronitrobenzene
Pentachlorophenol
Phenacet in
Phenanthrene
Phenol
Phthal ic anhydride
2-Picoline
Pronamide
Pyrene
Resorcinol
Detection Believed to
status3 be present
NO
NO
NO
ND
ND
NO
NO
ND
NO
ND
ND
NO
NO
ND
NO
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NO
ND
ND
ND
NO
ND
ND
ND
ND
ND
ND
NA
ND
NO
ND
ND
6-9
-------
2154g
Table 6-1 (continued)
BOAT
reference
no.
147.
148.
149.
150.
151.
152.
153.
154.
155.
156.
157.
158.
159.
221.
160.
1'61.
162.
163.
164.
165.
166.
167.
168.
169.
170.
171.
172.
173.
174.
175.
Constituent
Semivolat ile Orqanics (continued)
Safrole
1,2,4, 5-Tet rach lorobenzene
2,3,4, 6-Tet rach loropheno 1
1, 2, 4-Trich lorobenzene
2, 4, 5-Trich loropheno 1
2, 4, 6-Trich loropheno 1
Tris(2,3-dibromopropyl)
phosphate
Heta1sb
Antimony
Arsenic
Barium
Beryllium
Cadmium
Chromium (total)
Chromium (hexavalent)
Copper
Lead
Mercury
Nickel
Selenium
Si Iver
Thai 1 ium
Vanadium
Zinc
Inoraanics other than metals
Cyanide
Fluoride
Sulfide
Orqanocnlorine pesticides
Aldrin
alpha-BHC
beta-BHC
delta-BHC
Detection
Status3
NO
NO
ND
NO
ND
ND
ND
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
Believed to
be present
Y
Y
Y
Y
Y
Y
Y
Y '
Y
Y
Y
Y
6-10
-------
2154g
Table 6-1 (continued)
BOAT
reference
no.
Detection Believed to
Constituent Status be present
Orqanochlorine pesticides (continued)
176.
177.
178.
179.
180.
181.
182.
183.
184.
185.
186.
187.
188.
189.
190.
191.
192.
193.
194.
195.
196.
197.
198.
199.
200.
201.
202.
203.
204.
205.
206.
ganma-BHC
Chlordane
ODD
DDE
DDT
Dieldrin
Endosulfan I
Endosulfan II
Endrin
Endrin aldehyde
Heptachlor
Heptachlor epoxide
Isodrin
Kepone
Methoxyclor
Toxaphene
Phenoxyacetic acid herbicides
2,4-Oichlorophenoxyacet ic acid
Si Ivex
2,4.5-T
Oraanophosohorous insecticides
Oisulfoton
Famphur
Methyl parathion
Parathion
Phorate
PCBs
Aroclor 1016
Aroclor 1221
Aroclor 1232
Aroclor 1242
Aroclor 1248
Aroclor 1254
Aroclor 1260
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NO
NO
NO
NO
ND
ND
NO
ND
NA
NA
NA
NA
NA
NA
NA
6-11
-------
2154g
Table 6-1 (continued)
BOAT
reference
no.
Constituent
Detection
Status3
Believed to
be present
207.
208.
209.
210.
211.
212.
213.
Dioxins and furans
Hexachlorod ibenzo-p-d iox ins
Hexachlorodibenzofurans
Pentachlorodibenzo-p-dioxins
Pentachlorodibenzofurans
Tetrachlorod iben;:o-p-d iox ins
Tetrachlorodibenzofurans
2,3,7,8-Tetrachlorodibenzo-
p-dioxin
NA
NA
NA
NA
NA
NA
NA
ND = Not detected.
NA = Not analyzed.
X = Believed to be present based on engineering analysis of waste generating
process.
Y = Believed to be present based on detection in treated residuals.
alf detected, concentrations are shown; units are mg/kg.
BOAT list metals were not analyzed in the untreated waste.
6-12
-------
1825g
Table 6-2 K015 Waste Constituents with Treatable Concentrations
BOAT
number
43
57
218
63 and/or 65
Ml
154
155
156
159
160
161
162
163
164
. 165
167
168
Constituent
Toluene
Anthracene
Benzal chloride
Benzo (b and/or k)
f luoranthene
Phenanthrene
Ant imony
Arsenic
Barium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Silver
Vanadium
Zinc
CAS number
108-88-3
120-12-7
98-87-3
205-99-2/
207-08-9
85-01-6
7440-36-0
7440-38-2
7440-39-3
7440-47-32
7440-50-8
7439-92-1
7439-97-6
7440-02-0
7782-49-2
7440-22-4
7440-62-2
7440-66-6
Concentration in
untreated waste
(mg/kg)
<10
<5,000
910.000-1,100,000
<5,000
<5.000
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
Concentration in
treated waste
(mg/D
0.015-0.059
<0. 050-0. 210
<0. 050-0. 094
<0. 050-0. 096
<0. 050-0. 058
<0. 120-0. 160
0.100-0.530
0.110-0.530
4.0-34
0.580-0.35
0.060-0.300
<0. 0025-0. 06
2.2-25
0.06-0.90
<0. 035-0. 300
0.050-0.390
0.110-0.930
NA = Not analyzed in the untreated waste. See Section 6.1
-------
1584
Table 6-3 Major Constituent Concentration Data
a
Concentration (accuracy-corrected concentration)
Major constituent Untreated waste (mq/kq)
Sample set
*1 #2 #3
Volatile orqanics
Toluene <10 <10 <10
Semivolat i 1e orqanics
Anthracene <5,000 <5.000 <5,000
Benzal chloride 930.000 910.000 1,100,000
Benzol b and/or k)-
fluoranthene <5..000 <5.000 <5,000
Phenanthrene <5,000 <5,000 <5,000
7* Hetalsb
|_»1
4^
Antimony -
Arsenic -
' Barium
Chromium -
Copper -
Mercury -
Nickel
Lead
Selenium -
Silver -
Vanadium . - -
Zinc
Treated waste
0.059
<0.050
<0.050
<0.050
<0.050
<0.12
0.25
0.11
4.0
0.58
0.005
2.2
0.06
0.06
0.13
0.05
0.11
#1
(0.059)
(<0.0986)
(<0.0986)
(<0.0986)
(<0.0986)
(<0.250)
(0.260)
(0.150)
(5.0)
(0.660)
(0.005)
(2.9)
(0.130)
(0.080)
(0.160)
(0.066)
(0.130)
(mq/1)
Correct ion
factor
Sample set
n
0.030
0.068
0.068
0.050
0.058
.0.120
0.10
0.25
18
1.6
<0.0025
11
0.24
0.09
0.30
0.17
0.75
(0.030)
(0.134)
(0.130)
(<0.0986)
(0.114)
(0.250)
(0.100)
(0.330)
(23)
(1.82)
(<0.0025)
(14.5)
(0.510)
(0.130)
(0.370)'
(0.220)
(0.850)
0.015
0.210
0.094
0.096
0.110
0.16
0.53
0.55
34
3.5
0.06
25
' 0.30
0.06
<0.035
0.390
0.93
#3
(0.015)
(0.414)
(0.185)
(0.189)
(0.217)
(0.340)
(0.540)
(0.720)
(44)
(3.98)
(0.060)
(32.9)
(0.640)
(0.080)
(<0.043)
(0.510)
(1.05)
1.00
1.97
1.97
1.97
1.97
2.13C
1.02
1.32
1.28
1.14
1.00
1.32
2.13
1.39
1.23
1.32
1.14
The data in parentheses have been adjusted for accuracy using the correction factors provided.
'As stated in Section 4, metals were not analyzed in the untreated waste.
cThe wastewater matrix spike was not analyzed for antimony; accuracy-corrected values were calculated using an assumed correction factor
of 2. 13. (See Appendix B.)
-------
7. CALCULATION OF BOAT TREATMENT STANDARDS
This section presents the calculation of the actual treatment
standards for the regulated constituents determined in Section 6. EPA
has three sets of untreated and treated data from one facility for
treatment of K015 using liquid injection incineration. EPA also has
11 data sets for treatment of metal-bearing wastewaters by chromium
reduction and chemical precipitation. As discussed in Section 1, the
following steps were taken to derive the BOAT treatment standards for
K015 wastewaters.
The Agency evaluated the three data sets collected from the liquid
injection incineration treatment system to determine whether any of the
data represented poor design or poor operation of the treatment system.
The available data show that all three data sets do not represent poor
design or poor operation. All three data sets for liquid injection
incineration are used for establishing treatment standards for regulation
of the BOAT list organic constituents in K015 wastewaters.
For the regulated BOAT list metal constituents chromium and nickel,
treatment data were transferred from Envirite. The.design and operating
data were examined and indicated that the system was well designed and
well operated. However, recovery values were not available for metal
spikes and metal spike duplicating from the treatment data collected at
Envirite. The recovery data used to correct the nickel and chromium data
were transferred from the Onsite Engineering Report for Horsehead
Resource Development Company for K061. This was determined to be the
appropriate source for recovery data for BOAT list metals in wastewaters.
7-1
-------
Accuracy-corrected constituent concentrations were calculated for all
BOAT list constituents. An arithmetic average concentration level and a
variability factor were determined for each BOAT list constituent
regulated in this waste. The variability factor represents the
variability inherent in the treatment process and the sampling and
analytical methods. Variability factors are calculated based on the
treatment data for each of the regulated constituents. The general
methodology for calculating variability factors is presented in
Appendix A.
The BOAT treatment standard for each constituent regulated in this
rulemaking was determined by multiplying the average accuracy-corrected
total composition by the appropriate variability factor. The treatment
standards for the organic constituents are shown in Table 7-1. The
calculation of the treatment standards for chromium and nickel is
presented in Table 7-2.
7-2
-------
1566g
Table 7-1 Calculation of BOAT Treatment Standards for
Regulated Organic Constituents in K015 Wastewaters
Constituent
Accuracy-corrected concentration (mq/1)
Sample set Sample set Sample set
#1 #2 #3
Average Variability
treated waste factor
concentration (mg/1) (VF)
Treatment standard
(average x VF)
-»J
1
CO
Toluene
Anthracene
Benzal chloride
Benzo(b and/or k)
f luoranthene
Phenanthrene
0.059
<0.099
<0.099
<0.099
<0.099
0.030
0.134
0.130
<0.099
0.114
0.015
0.414
0.185
0.189
0.217
0.035
0.216
0.138
0.129
0.107
4.26
4.15
2.02
2.28
2.50
0.15
1.0
0.28
0.29
0.27
-------
1586g
Table 7-2 Treated Standards for KOIS Wastewater Regulated Metal Constituents
Treated by Chromium Reduction and Chemical Precipitation
Accuracy-corrected concentration
Correction
Constituent factor 1 2
BOAT Metals
Chromium 1.47 0,176 0.176
Nickel 1.08 0.355 0.355
Sample
3 4 5
0.294 0.147 0.162
0.355 0.355 0.333
Set t
6
0.147 0
0.355 0.
(mg/1)
7 6 9 10
.176 0.221 0.147 0.176
.430 0.387 0.355 0.355
11 Average
(mg/1)
0.264 0.19
0.419 0.37
Variabi lity
factor
(VF)
1.69
1.20
Treatment
standard
Avg * VF)
0.32
0.44
-------
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 K015 waste. The technical project officer for the waste was
Ms. Lisa Jones. Mr. Steven Silverman served as legal advisor.
Versar personnel involved with preparing this document included
Mr. Jerome Strauss, Program Manager; Ms. Peggy Redmond, Engineering Team
Leader; Ms. Justine Alchowiak, Quality Assurance Officer; Mr. David
Pepson, Senior Technical Reviewer; Mr. David Bottimore, Technical
Reviewer; Ms. Juliet Crumrine, Technical Editor; and the Versar
secretarial staff, Ms. Linda Gardiner and Ms. Mary Burton.
The K015 treatment tests were executed at the John Zink Test
Facility, Tulsa, Oklahoma, by PEI Associates, contractors to the Office
of Research and Development. Field sampling for the tests was conducted
under the leadership of Mr. Ronald J. Turner of the EPA Office of
Research and Development and Mr. Robert Hoye of PEI Associates.
We greatly appreciate the cooperation of Monsanto Company,
Bridgeport, New Jersey, whose plant was sampled for the K015 waste
incinerated at the test facility.
8-1
-------
9. REFERENCES
Ackerman D.G., McGaughey J.F,, and Wagoner D.E. 1983. At sea incineration
of PCB-containing wastes on board the M/T Vulcanus. EPA 600/7-83-024.
Washington, D.C.: U.S. Environmental Protection Agency.
Bonner, T.A., et al. 1981. Engineering handbook for hazardous waste
incineration. SW-889. NTIS PB 81-248163. Prepared by Monsanto
Research Corporation for U.S. Environmental Protection Agency.
Castaldini, C., et al. 1986. Disposal of hazardous wastes in industrial
boilers on furnaces. New Jersey: Noyes Publications.
Hughes, C.S., Shimosato, J., and Bakker, J. 1983. CEH product review:
benzyl chloride.- In Chemical economics handbook. Menlo 'Park, Calif.:
Stanford Research Institute International.
Novak, R.G., Troxler, W.L., and Dehnke, T.H. 1984. Recovering energy
from hazardous waste incineration. Chemical Engineering Progress
91:146.
Oppelt, E.T. 1987. Incineration of hazardous waste. JAPCA 37 (5)..
Santoleri, J.J. 1983. Energy recovery a by-product of hazardous waste
incineration systems. In Proceedings of the 15th Mid-Atlantic
Industrial Waste Conference on Toxic and Hazardous Waste.
SRI. 1986. Stanford Research Institute. Benzyl chloride, butyl benzyl
phthalate, p-benzylphenol, and benzyl alcohol. In Directory of
chemical producers United States of America. Menlo Park, Calif.:
Stanford Research Institute International.
USEPA. 1980. U.S. Environmental Protection Agency. RCRA listing
background document waste code K001. Washington, D.C.: U.S.
Environmental Protection Agency.
USEPA. 1986a. U.S. Environmental Protection Agency. Best demonstrated
available technology (BOAT) background document for F001-F005 spent
solvents. Vol. 1. EPA/530-SW-86-056. Washington, D.C.: U.S.
Environmental Protection Agency.
USEPA. 1986b. 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.
9-1
-------
USEPA. 1986c. U.S. Environmental Protection Agency. Summary of available
waste composition data from review of literature and data bases for use
in- treatment technology application evaluation for "California List"
waste streams. Prepared by Versar Inc. under Contract no. 68-01-7053.
Washington, D.C.: U.S. Environmental Protection Agency.
USEPA. 1986d. U.S. Environmental Protection Agency. Onsite engineering
report of treatment technology performance and operation at Envirite
Corporation, York, Pennsylvania. Washington, D.C.: U.S. Environmental
Protection Agency.
USEPA 1987a. U.S. Environmental Protection Agency. Onsite engineering
report of treatment technology performance and operation for
incineration of K015 waste at the John Zink Company test facility.
Washington, D.C.: U.S. Environmental Protection Agency.
USEPA 1987b. Memoranda concerning industry data from Monsanto Company and
Velsicol Chemical Corporation of their handling of K015 hazardous
waste. Contract No. 68-03-3389. Washington, D.C.: U.S. Environmental
Protection Agency.
Versar Inc. 1984. Estimating PMN Incineration Results (Draft). U.S.
Environmental Protection Agency, Exposure Evaluation Division, Office
of Toxic Substances, Washington, D.C. EPA Contract No. 68-01-6271,
Task No. 66.
Vogel, G., et al. 1986. Incineration and cement kiln capacity for
hazardous waste treatment. In Proceedings of the 12th Annual Research
Symposium, Incineration and Treatment of Hazardous Wastes, April 1986,
Cincinnati, Ohio.
9-2
-------
APPENDIX A
STATISTICAL METHODS
A.I 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 value.
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 arid Johnson, 1977, John Wiley Publications,
New York).
A-l
-------
Table A-l
95th PERCENTILE VALUES FOR
THE F DISTRIBUTION
«i = degrees of freedom for numerator
ns = degrees of freedom for denominator
(abided area « .96)
Jlk,
fM
^s
1
2
A
o
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
an
24
26
28
30
40
50
60
70
80
100
150
200
400
V
1
161.4
18.51
10.13
7.71
6.61
5.99
5.59
5.32
5.12
4.96
4.84
4.75
4.67
4.60
4.54
4.49
4.45
4.41
4.38
4.35
4.30
4.26
4.23
4.20
4.17
4.08
4.03
4.00
3.98
3.96
3.94
3.91
3.89
3.86
3.84
2
199.5
19.00
9.55
6.94
5.79
5.14
4.74
4.46
4.26
4.10
3.98
3.89
3.31
3.74
3.68
3.63
3.59
3.55
3.52
3.49
3.44
3.40
3.37
3.34
3.32
3.23
3.18
3.15
3.13
3.11
3.09
3.06
3.04
3.02
2.99
3
215.7
19.16
9.28
6.59
5.41
4.76
4.35
4.07
3.86
3.71
3.59
3.49
3.41
3.34
3.29
3.24
3.20
3.16
3.13
3.10
3.05
3.01
2.98
2.95
2.92
2.84
2.79
2.76
2.74
2.72
2.70
2.67
2.65
2.62
2.60
4
224.6
15.25
9.12
6.39
5.19
4.53
4.12
3.84
3.C3
3.48
3.36
3.26
3.18
3.11
3.06
3.01
2.96
2.93
2.90
2^7
2.82
2.78
2.74
2.71
2.69
2.61
2.56
2.53
2.50
2.48
2.46
2.43
2.41
2.39
2.37
6
230.2
19.30
9.01
6.26
5.05
4.39
3.97
3.69
3.48
3.33
3.20
3.11
3.03
2.96
2.90
2.85
2.81
2.77
2.74
2.71
2.66
2,62
2.59
2,56
2,53
2.45
2.40
2.37
2.35
2.33
2^0
2J!7
2.26
2.23
2.21
6
234.0
19.33
&J94
6.16
4.95
4.28
3.87
3.58
3.37
3.22
3.09
3.00
2.92
2.85
2.79
2.74
2.70
2.66
2.63
2.60
2.55
2.51
2.47
2.45
2.42
2.34
2JJ9
2^5
2.23
2.21
2.19
2.16
2.14
2.12
2.09
8
238.9
19.37
8.85
6.04
4.82
4.15
3.73
3.44
3.23
3.07
2.95
2.85
2.77
2.70
2.64
2.59
2.55
2.51
2.48
2.45
2.40
2J36
2.32
2J>9
2JJ7
2.18
2.13
2JO
2.07
2.05
2.03
2.00
1.98
1.96
1.94
12
243.9
19.41
8.74
5.91
4.68
4.00
3.57
3.28
3.07
2,91
2.79
2.69
2.60
2.53
2.48
2.42
2.38
2.34
2.31
2.28
2.23
2.18
2.15
2.12
2.09
2.00
1.95
1.92
1.89
1.88
1.85
1.82
1.80
1.78
1.75
16
246.3
19.43
8.69
5.84
4.60
3.92
3.49
3.20
2.98
2.82
2.70
2.60
2.51
2.44
2.39
2.33
« 09
2^5
2^1
2.18
2-13
2.09
2.05
2.02
1.99
1.90
1.85
1.81
1.79
1.77
1.75
1.71
1.69
1.67
1.64
20
248.0
19.45
8.66
5.80
4.56
3.87
3.44
3.15
2.93
2.77
2.65
2.54
2.46
2.39
2.33
2.28
2^3
2.19
2.15
2.12
2.07
2.03
1.99
1.96
1.93
1.84
1.78
1.75
1.72
1.70
1.68
1.64
1.62
1.60
1.57
30
250.1
19.46
8.62
5.75
4.50
3.81
138
3.08
2.86
2.70
2.57
2.46
2.38
2.31
2JI5
2.20
2.15
2.11
2.07
2.04
1.98
1.94
1.90
1.S7
1.84
1.74
1.69
1.65
1.62
1.60
1.57
1.54
1.52
1.49
1.46
40
251.1
19.46
8.60
5.71
4.46
3.77
3.34
3.05
2.82
2.67
2.53
2.42
2.34
2.27
2.21
2.16
2.11
2.07
2.02
1.99
1.93
1.89
1.85
1.81
1.79
1.69
1.63
1.59
1.56
1.54
1.51
1.47
1.46
1.42
1.40
50
252,2
19.47
8.58
5.70
4.44
3.75
3.32
3.03
2.80
2.64
2.50
2.40
2.32
1L24
2.18
2.13
2.08
2.04
2.00
1.96
1.91
1.86
1.82
1.78
1.76
1.66
1.60
1.56
1.53
1.51
1.48
1.44
1.42
1.38
1.32
100
253.0
19.49
8.56
5.66
4.40
3.71
3.28
2.98
2.76
2.59
2.45
2.35
2.26
2.19
2.12
2.07
2.02
1.98
1.94
1.90
1.84
1.80
1.76
1.72
1.69
1.59
1.52
1.48
1.45
1.42
1.39
1.34
1.32
1.28
1.24
0
25-i.S
19.50
S.53
5.63
4.35
3.67
3.23
2.93
2.71
2.5;
2.40
2.30
2^1
2.13
2.07
2.01
1.96
1.92
1.88
1.84
1.78
1.73
1.69
1.65
1.62
1.51
1.44
1.39
1.35
1.32
1.28
12
1.19
1.13
1.00
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 to perform a "pair wise F" test to determine if any of the sets
are homogeneous. The "pair wise F" test must be done for all of the
various combinations of data sets using the same method and equation as
the general F test.
The F value is calculated as follows:
(i) All data are natural logtransformed.
(ii) The sum of the data points for each data set is computed (T.).
(iii) The statistical parameter known as the sum of the squares
between data sets (SSB) is computed:
Ir I T!~ I I ? T;
SSB
where:
k
I*mi-Hid
= number of treatment technologies
n^ = number of data points for technology i
N = number of data points for all technologies
T.J = sum of natural logtransformed data points for each technology.
(iv) The sum of the squares within data sets (SSW) is computed:
SSW =
where:
' k
I
. 1-1
I1 *2i J "
jii '*J .
k
- I
1-1
[T(
In,
= 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-1) and
MSW = SSW/(N-k).
A computational table summarizing the above parameters is shown below.
Computational Table for the F Value
Source
Between
Within
Degrees of
freedom
k-1
N-k
Sum of
squares
SSB
SSW
Mean square
MSB = SSB/k-1
MSW = SSW/N-k
F value
MSB/MSW
Below are three examples of the ANOVA calculation. The first two
represent treatment by different technologies that achieve statistically
similar treatment; the last example represents a case in which one
technology achieves significantly better treatment than the other
technology.
A-4
-------
1790g
Example 1
Methylene Chloride
Steam stripping Biological treatment
influent Effluent In(effluent) [ln(effluent}]2 Influent Effluent In(effluent)
Ug/M
Sum:
[In(effluent)]'
1550.00
1290.00
1640.00
5100.00
1450.00
4600.00
1760.00
2400.00
4800.00
12100,00
10.00
10.00
10.00
12.00 .
10.00
10.00
10.00
10.00
10.00
10.00
2.30
2.30
2.30
2.48
2.30
2.30
2.30
2.30
2.30
2.30
5.29
5.29
5.29
6.15
5.29
5.29
5.29
5.29
5.29
5.29
1960.00
2568.00
1817.00
1640.00
3907.00
10.00
10.00
10.00
26.00
10.00
2.30
2.30
2.30
3.26
2.30
5.29
5.29
5.29
10.63
5.29
23.18
53.76
12.46
31.79
Sample Size:
10 10
10
Mean:
3669
10.2
2.32
2378
13.2
2.49
Standard Deviation:
3328.67 .63
Variability Factor:
1.15
.06
923.04
7.15
2.48
.43
ANOVA Calculations:
_ 2
SSB
ssu.(5l
MSB = SSB/fk-1)
MSW = SSW/(N-k)
It
i=l I n.
k f TI? 1
-M-J
A-5
-------
1790g
Example 1 (Continued)
F = MSB/HSU
where:
k = number of treatment technologies
n. = number of data points for technology i
N = number of natural logtransformed data points for all technologies
T. - sum of logtransformed data points for each technology
X = the nat. logtransformed observations (j) for treatment technology (i)
ij
n = 10. n = 5. N = 15. k = 2. T = 23.18. T = 12.46. T = 35.64. T = 1270.21
T2 = 537.31 T2 = 155.25
cco
SSB
537.31 155.25
10
SSW = (53.76 + 31.79) -
MSB = 0.10/1 = 0.10
MSW = 0.77/13 = 0.06
0.10
1270.21
15
537.31 155.25
10
= 0.10
0.77
F =
1.67
0.06
ANOVA Table
Degrees of
Source freedom
Between (B) 1
Within(U) 13
SS MS F value
0.10 0.10 1.67
0.77 0.06
The critical value of the F test at the 0.05 significance level is 4.67. Since
the F value is less than the critical value, the means are not significantly
different (i.e., they are homogeneous).
Note: All calculations were rounded to two decimal places. Results may differ
depending upon the number of decimal places used in each step of the calculations.
A-6
-------
1790g
Example 2
Trichloroethylene
^team stripping
Influent
(M9/D
1650.00
5200.00
5000.00
1720.00
1560.00
10300.00
210.00
1600.00
204.00
160.00
Effluent
(M9/1)
10.00
10.00
10.00
10.00
10.00
10.00
10.00
27.00
85.00
10.00
In(effluent)
2.30
2.30
2.30
2.30
2.30
2.30
2.30
3.30
4.44
2.30
[ln(ef Fluent)]2
5.29
5". 29
5.29
5.29
5.29
5.29
5.29
10.89
19.71
5.29
Influent
Ug/l)
200.00
224.00
134.00
150.00
484.00
163.00
182.00
Biological treatment
Effluent
Ug/D
10.00
10.00
10.00
10.00
16.25
10.00
10.00
In(effluent)
2.30
2.30
2.30
2.30
2.79
2.30
2.30
[In(effluent)]2
5.29
5.29
5.29
5.29
7.78
5.29
5.29
Sum:
Sample Size:
10 10
Mean:
2760
19.2
Standard Deviation:
3209.6 23.7
Variabi I ity Factor:
3.70
26.14
10
2.61
.71
72.92
220
120.5
10.89
2.36
1.53
16.59
2.37
.19
39.52
ANOVA Calculations:
2
SSB
MIL) - U")
-11 . J
ssw
MSB = SSB/(k-l)
MSW = SSU/(N-k)
N
Ti2
f k nj , I k C Tj2 1
= Z Z x2j j - s __
L i=l j-1 lj j i=l I ni J
A-7
-------
179043
Example 2 (Continued)
F = HSB/MSU
where:
k = number of treatment technologies
n = number of data points for technology i
i
N = number of data points for all technologies
T. = sum of natural logtransformed data points for each technology
X.. = the natural logtransformed observations (j) for treatment technology (i)
N = 10. N = 7, N = 17, k = 2. T = 26.14, T = 16.59. T = 42.73, T = 1825.85, T = 683.30,
Tg = 275.23
..
SS8 =
683.30 275.23
10
1825.85
17
= 0.25
SSW = (72.92 + 39.52) -
MSB = 0.25/1 = 0.25
HSU = 4.79/15 = 0.32
10
= 4.79
0.78
0.32
ANOVA Table
Degrees of
Source freedom
Between( B) 1
Uithin(W) 15
SS MS F value
0.25 0.25 0.78
4.79 0.32
The critical value of thi! F test at the 0.05 significance level is 4.54. Since
the F value is less than the critical value, the means are not significantly
different (i.e., they am homogeneous).
Note: All calculations were rounded to two decimal places. Results may differ
depending upon the number of decimal places used in each step of the calculations.
A-8
-------
1790g
Example 3
Chlorobenzene
Activated sludge followed by carbon adsorption
Biological treatment
Influent
Effluent
In(effluent) [ln(eff luent)]
Influent
Ug/l)
Effluent
Ug/D
In(effluent)
ln[(eff luent)]
7200.00
6500.00
6075.00
3040.00
80.00
70.00
35.00
10.00
4.38
4.25
3.56
2.30
19.18
18.06
12.67
5.29
9206.00
16646.00
49775.00
14731.00
3159.00
6756.00
3040.00
1083.00
709.50
460.00
142.00
603.00
153.00
17.00
6.99
6.56
6.13
4.96
6.40
5.03
2.83
48.86
43.03
37.58
24.60
40.96
25.30
8.01
Sum:
14.49
55.20
38.90
228.34
Sample Size:
4
Mean:
5703
49
3.62
14759
452.5
5.56
Standard Deviation:
1835.4 32.24
Variability Factor:
7.00
.95
16311.86
379.04
15.79
1.42
ANOVA Calculations:
2
k I I
SSB =
MSB = SSB/(k-l)
MSW = SSW/(N-k)
F = MSB/HSU
k T 12
AT1
N
Ti2
[U-'-'l-Mlr)
A-9
-------
1790g
where.
Example 3 (Continued)
k - number of treatment technologies
n = number of data points for technology i
i
N = number of data points for all technologies
T = sum of natural logtransformed data points for each technology
i
X = the natural logtransformed observations (j) for treatment technology (i)
ij
N = 4. N = 7. N = 11. k = 2, T = 14.49, T = 38.90, T = 53.39. T*= 2850.49. T* = 209.96
T = 1513.21
f209.96 1513.21
SSB =1 +
SSW = (55.20 + 228.34)
= 9.52
14.88
MSB = 9.52/1 = 9.52
MSW = 14.88/9 = 1.65
F = 9.52/1.65 = 5.77
ANOVA Table
Degrees of
Source freedom
SS
MS
F value
Between(B)
Uithin(W)
1
9
9.53
14.89
9.53
1.65
5.77
The critical value of the F test at the 0.05 significance level is 5.12. Since
the F value is larger than the critical value, the means are significantly
different (i.e., they are heterogeneous). Activated sludge followed by carbon
adsorption is "best" in this example because the mean of the long-term performance
value, i.e., the effluent concentration, is lower.
Note: All calculations were rounded to two decimal places. Results may differ depending
upon the number of dec inn I 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;
Cgg = estimate of performance values for which 99 percent of the
daily observations will be below. Cgq is calculated
using the following equation: Cgq = txp(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, all the results from analysis of the residuals from
BOAT treatment are found at concentrations less than the detection
limit. In such cases, all the actual concentration values are considered
unknown and, hence, cannot be used to estimate the variability factor of
the analytical results. Below is a description of EPA's approach for
calculating the variability factor for such cases with all concentrations
below the detection limit.
It has been postulated a:; a general rule that a lognormal
distribution adequately describes the variation among concentrations.
Agency data show that the treatment residual concentrations are
A-ll
-------
distributed approximately lognormally. Therefore, the lognormal model
has been used routinely in the EPA development of numerous regulations in
the Effluent Guidelines program and is being used in the BOAT program.
The variability factor (VF) was defined as the ratio of the 99th
percentile (C ) of the lognormal distribution to its arithmetic mean
(Mean), as follows:
VF = C99. (1)
Mean
The relationship between the parameters of the lognormal distribution
and the parameters of the normal distribution created by taking the
natural logarithms of the locinorrnally distributed concentrations can be
found in most mathematical statistics texts (see, for example,
Distribution in Statistics-Volume 1 by Johnson and Kotz, 1970). The mean
of the lognormal distribution can be expressed in terms of the
mean (^) and standard deviation (a) of the normal distribution as
follows:
C9g = Exp (M + 2.33a) (2)
Mean = Exp (M + 0.5a2). (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<72). (4)
For residuals with concentrations that are not all below the
detection limit, the 99th percentile and the mean can be estimated from
the actual analytical data and, accordingly, the variability factor (VF)
can be estimated using equation (1). For residuals with concentrations
A-12
-------
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 well-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:
o - [ln(UL) - ln(LL)] / [(2)(2.33)]
= [ln(UL/LL)] / 4.66. . (5)
(Note that when LL = (0.1)(UL) as in Assumption 1, then
a = (InlO) / 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
The methods used to analyze the constituents identified in Section 5
are presented in Table B-l. All methods are described in SW-846 Third
Edition (EPA's Test Methods for Evaluating Solid Waste).
The accuracy determination for a constituent is based on matrix spike
recovery values. The inverse of the recovery is the correction factor.
An accuracy-corrected value is simply the analytical result multiplied by
the correction factor as shown in the following example:
Analytical Result Correction Factor Accuracy-Corrected Value
0.13 mg/1 x 1.23 = 0.16 mg/1.
Only one of the organic compounds identified as a major constituent
in K015 wastewaters, toluene, served as a spiking component. Its
recovery was 100 percent. Thus, the detected values and accuracy-
corrected values for toluene are identical. For the remaining organics
in the wastewaters (all semivolatiles), the recovery value for each was
taken to be the average of the recoveries for similar compounds. The
identified semivolatiles were all base neutral compounds; thus, the
average recovery for the base neutral spiking compounds was used as a
recovery value. The matrix spike data for the base neutral semivolatile
compounds in K015 wastewaters; are presented in Table B-2. As shown, the
average recovery is 50.7 percent, corresponding to a correction factor of
1.97.
B-l
-------
For each metal compound identified as a major constituent, the data
were adjusted using the lower of the matrix spike and matrix spike
duplicate recoveries for that compound, except in the case of antimony.
Because the wastewater matrix spike was not analyzed for antimony, the
data were adjusted using the lowest recovery of all major metal
constituents in the waste (i.e., for lead). Table B-3 summarizes the
major constituents in the K015 wastewater, their recovery values, and the
respective correction factors used to obtain the accuracy-corrected
concentrations displayed on Table 5-3.
B-2
-------
1541g
Tajle B-l Analytical Methods
Analysis/methods Method
Volati1e Orqanics
Purge-and-trap 5030
Gas chromatography/mass. spectrometry for
volatile organics 8240
Semivolati1e Qraanics
Continuous liquid-liquid extraction (treated waste) 3520
Soxhlet extraction (unfeated waste) 3540
Gas chromatography/mass spectrometry for semi-
volatile organics: Capillary Column Technique 8270
Metals
Digestion
Aqueous liquids analyzed by 1CP 3010
Aqueous liquids analyzed by graphite furnace 3020
Inductively coupled plasma atomic emission
spectroscopy (antimony/barium/chromium/copper/
nickel/silver/vanadium/zinc) 6010
Arsenic (atomic absorption, Furnace technique) 7060
Selenium (atomic absorption, furnace technique) 7740
Mercury in solid or semisolid waste 7471
(manual cold-vapor technique)
Lead (atomic absorption, furnace technique) 7421
Reference: USEPA 1986b.
B-3
-------
1541g
Table B-2 Base Neutral Matrix Spike Data for K015 Wastewater
Compound
1 ,4-Oichlorobenzene
N-nitrosodi-n-propylamine
1.2, 4-Tr ich lorobenzene
Acenaphthene
2,4-Dinitrotoluene
Pyrene
Average:
Combined
Matrix
40
75
37
76
25
52
50
averages:
Percent recovery
spike Matrix spike duplicate
37
65
35
80
25
62
.83 50.66
50.7
B-4
-------
1541g
Table B-3 Metal Matrix Spike Data for K015 Wastewater
Compound
Lowest percent recovery
Correction factor
Silver
Arsenic
Barium
Beryl! ium
Chromium
Copper
Mercury
Nickel
Lead
Antimony
Selenium
Vanadium
Zinc
81
98
76
77
78
88
100
76
47
47a
72
76
88
1.23
1.02
1.32
1.30
1.28
1.14
1.00
1.32
2.13
2.13a
1.39
1.32
1.14
aThese are assumed values. See text.
B-5
-------
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
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GUARD
GRADIENTX
STACK
GRADIENT
X
CLAMP
THERMOCOUPLE
UPPER STACK
HEATER
TOP
REFERENCE
SAMPLE
BOTTOM
REFERENCE
SAMPLE
i
l
LOWER STACK
HEATER
l
LIQUID COOLED
HEAT SINK
l
HEAT FLOW
DIRECTION
UPPER
GUARD
HEATER
LOWER
GUARD
HEATER
FIGURE C-l SCHEMATIC DIAGRAM OF THE COMPARATIVE METHOD
C-2
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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, ar,d 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 in 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
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