&EPA
United States
Environmental Protection
Agency
Office of
Solid Waste
Washington, D C 20460
EPA/530-SW-88-0009-a
April 1988
Solid Waste
Best
Demonstrated
Available Technology
(BOAT) Background
Document for
K015
Proposed
Volume 1
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BEST DEMONSTRATED AVAILABLE TECHNOLOGY (BOAT)
BACKGROUND DOCUMENT FOR K015
Volume 1
U.S. Environmental Protection Agency
Office of Solid Waste
401 M Street, S.W.
Washington, D.C. 20460
James R. Berlow, Chief
Treatment Technology Section
April 1988
U.S. Environmental Protection Agency
Region 5, Library (PL-12J)
77 West Jackson Boulevard, 12th Floor
Chicago, IL 60604-3590
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Table of Contents
EXECUTIVE SUMMARY vi
1. INTRODUCTION 1
1.1 Legal Background 1
1.1.1 Requirements Under HSWA 1
1.1.2 Schedule for Developing Restrictions 4
1.2 Summary of Promulgated BOAT Methodology 5
1.2.1 Waste Treatability Groups 7
1.2.2 Demonstrated and Available Treatment
Technologies 7
(1) Proprietary or Patented Processes 10
(2) Substantial Treatment 10
1.2.3 Collection of Performance Data 11
(1) Identification of Facilities for
Site Visits 12
(2) Engineering Site Visit 14
(3) Sampling and Analysis Plan 14
(4) Sampling Visit 16
(5) Onsite Engineering Report 17
1.2.4 Hazardous Constituents Considered and
Selected for Regulation ,.. 17
(1) Development of BOAT List 17
(2) Constituent Selection Analysis 27
(3) Calculation of Standards 29
1.2.5 Compliance with Performance Standards 30
1.2.6 Identification of BOAT 32
(1) Screening of Treatment Data 32
(2) Comparison of Treatment Data 33
(3) Quality Assurance/Quality Control 34
1.2.7 BOAT Treatment Standards for "Derived-From"
and "Mixed" Wastes 36
(1) Wastes from Treatment Trains
Generating Multiple Residues 36
(2) Mixtures and Other Derived-From
Residues 37
(3) Residues from Managing Listed Wastes
or That Contain Listed Wastes 38
1.2.8 Transfer of Treatment Standards 40
1.3 Variance from the BOAT Treatment Standard 41
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Page
2. INDUSTRY AFFECTED AND WASTE CHARACTERIZATION 46
2.1 Industry Affected and Process Description 46
2.2 Waste Characterization 48
3. APPLICABLE/DEMONSTRATED TREATMENT TECHNOLOGIES 51
3.1 Applicable Treatment Technologies 51
3.2 Demonstrated Treatment Technologies 52
3.2.1 Liquid Injection Incineration 56
(1) Applicability and use of this technology. 56
(2) Underlying principles of operation 57
(3) Description of incineration technologies. 59
(4) Waste characteristics affecting
performance (WCAP) 65
(5) Design and operating parameters 70
3.2.2 Fuel Substitution 76
(1) Applicability and use of this technology. 76
(2) Underlying principles of operation 79
(3) Physical description of the process 79
(4) Waste characteristics affecting
performance 82
(5) Design and operating parameters 86
4. IDENTIFICATION OF BEST DEMONSTRATED AVAILABLE
TECHNOLOGY FOR K015 WASTE 92
5. SELECTION OF REGULATED CONSTITUENTS 95
5.1 Identification of Treatable Constituents in the
Untreated Waste 96
5.2 Comparison of the Untreated and Treated Waste Data
for the Major Treatable Constituents 107
5.3 Evaluation of Waste Characteristics Affecting
Performance (WCAP) and Other Related Factors 110
5.4 Selection of Regulated Constituents 110
6. CALCULATION OF THE BOAT TREATMENT STANDARDS Ill
7. CONCLUSIONS 113
REFERENCES 117
Appendix A 119
A.I F Value Determination for ANOVA Test 120
A.2 Variability Factor 130
Appendix B Analytical QA/QC 133
Appendix C Thermal Conductivity Measurement 139
m
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LIST OF TABLES
Table Number
Executive
Summary
1-1
2-1
2-2
3-1
5-1
5-2
5-3
6-1
7-1
A-l
B-l
B-2
B-3
Title
Page
BOAT Treatment Standards for K015
(Wastewater) and (Nonwastewater) viii
BOAT Constituent List 18
Major Constituent Composition for K015 Waste 49
BOAT Constituent Composition and Other Data 50
Performance Data Collected by EPA for Liquid
Injection Incineration of K015 Waste 53
Detection Status for K015 Untreated and
Treated Waste Constituents 97
K015 Waste Constituents with Treatable
Concentrations 106
Major Constituent Concentration Data 108
Calculation of BOAT Treatment Standards for
Regulated Organic Constituents in
K015 Wastewaters 112
BOAT Treatment Standards for K015 Waste 114
95th Percentile Values for the
F Distribution 123
Analytical Methods 135
Base Neutral Matrix Spike Data for K015
Wastewater 136
Metal Matrix Spike Data for K015 Wastewater.. 138
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LIST OF FIGURES
Figure Number Title Page
2-1 Benzyl Chloride Production by the
Chlorination of Toluene 47
3-1 Liquid Injection Incinerator 60
3-2 Rotary Kiln Incinerator 61
3-3 Fluidized Bed Incinerator 63
3-4 Fixed Hearth Incinerator 64
C-l Schematic Diagram of the Comparative Method . 141
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EXECUTIVE SUMMARY
BOAT Treatment Standards for K015
Pursuant to the Hazardous and Solid Waste Amendments (HSWA) enacted
on November 8, 1984, and in accordance with the procedures for
establishing treatment standards under Section 3004(m) of the Resource
Conservation and Recovery Act, the following treatment standards have
been proposed as Best Demonstrated Available Technology (BOAT) for the
listed waste identified in 40 CFR Part 261.32 as K015 (still bottoms from
the distillation of benzyl chloride). Compliance with these treatment
standards is a prerequisite for disposal of the waste in units designated
as land disposal units according to 40 CFR Part 268.
BOAT treatment standards have been established for wastewater and. EPA
is considering establishing BOAT treatment standards for nonwastewater
forms of K015 waste. While testing conducted by EPA produced no
nonwastewater residuals, EPA is aware that some nonwastewater may be
produced when subsequently treating the BOAT list metallic constituents
of the K015 wastewaters. Until the final determination to establish
standards for these nonwastewaters residuals is made by EPA, the
treatment standard for nonwastewaters will be "no land disposal."
For wastewaters, treatment standards have been established for a
total of five organic constituents and two metals. The regulated organic
constituents are toluene, anthracene, benzal chloride, benzo(b and/or
k)fluoranthene, and phenanthrene. The regulated metals are chromium and
nickel.
VI
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The treatment standards for the organic constituents have been
established based on performance data representing liquid injection
incineration. The wastewater standards for metals have been transferred
from performance achieved using chromium reduction, chemical
precipitation, and dewatering of precipitate. These standards become
effective as of August 8, 1988, as per the schedule set forth in
40 CFR 268.10.
The following table lists the specific BOAT standards for K015
wastewaters. The units for the total waste analyses are in milligrams
per liter (mg/1). Testing and analysis procedures are specifically
identified and discussed in Appendix B (QA/QC Section) of this background
document.
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1541g
BOAT Treatment Standards for K015
(Wastewater)
Maximum for any single grab sample
Total waste Total TCLP
concentration concentration
Constituent (nig/1) (mg/1)
Toluene
Anthracene
Benzal chloride
Benzo(b and/or k)f luoranthene
Phenanthrene
Chromium
Nickel
.148
1.02
0.28
0.29
0.27
0.30
0.44
NA
NA
NA
NA
NA
NA
NA
NA = Not applicable
BOAT Treatment Standards for KOI5
(Nonwastewater)
No land disposal
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1. INTRODUCTION
This section of the background document presents a summary of the
legal authority pursuant to which the BOAT treatment standards were
developed, a summary of EPA's promulgated methodology for developing
BOAT, and finally a discussion of the petition process that should be
followed to request a variance from the BOAT treatment standards.
1.1 Legal Background
1.1.1 Requirements Under HSWA
The Hazardous and Solid Waste Amendments of 1984 (HSWA), enacted on
November 8, 1984, and which amended the Resource Conservation and
Recovery Act of 1976 (RCRA), impose substantial new responsibilities on
those who handle hazardous waste. In particular, the amendments require
the Agency to promulgate regulations that restrict the land disposal of
untreated hazardous wastes. In its enactment of HSWA, Congress stated
explicitly that "reliance on land disposal should be minimized or
eliminated, and land disposal, particularly landfill and surface
impoundment, should be the least favored method for managing hazardous
wastes" (RCRA Section 1002(b)(7), 42 U.S.C. 6901(b)(7)).
One part of the amendments specifies dates on which particular groups
of untreated hazardous wastes will be prohibited from land disposal
unless "it has been demonstrated to the Administrator, to a reasonable
degree of certainty, that there will be no migration of hazardous
constituents from the disposal unit or injection zone for as long as the
wastes remain hazardous" (RCRA Section 3004(d)(l), (e)(l), (g)(5),
42 U.S.C. 6924 (d)(l), (e)(l), (g)(5)).
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For the purpose of the restrictions, HSWA defines land disposal "to
include, but not be limited to, any placement of ... hazardous waste in
a landfill, surface impoundment, waste pile, injection well, land
treatment facility, salt dome formation, salt bed formation, or
underground mine or cave" (RCRA Section 3004(k), 42 U.S.C. 6924(k)).
Although HSWA defines land disposal to include injection wells, such
disposal of solvents, dioxins, and certain other wastes, known as the
California List wastes, is covered on a separate schedule (RCRA Section
3004(f)(2), 42 U.S.C. 6924 (f)(2)). This schedule requires that EPA
develop land disposal restrictions for deep well injection by
August 8, 1988.
The amendments also require the Agency to set "levels or methods of
treatment, if any, which substantially diminish the toxicity of the waste
or substantially reduce the likelihood of migration of hazardous
constituents from the waste so that short-term and long-term threats to
human health and the environment are minimized" (RCRA Section 3004(m)(l),
42 U.S.C. 6924 (m)(l)). Wastes that meet treatment standards established
by EPA are not prohibited and may be land disposed. In setting treatment
standards for listed or characteristic wastes, EPA may establish
different standards for particular wastes within a single waste code with
differing treatability characteristics. One such characteristic is the
physical form of the waste. This frequently leads to different standards
for wastewaters and nonwastewaters.
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alternatively, EPA can establish a treatment standard that is applicable
to more than one waste code when, in EPA's judgment, all the waste can be
treated to the same concentration. In those instances where a generator
can demonstrate that the standard promulgated for the generator's waste
cannot be achieved, the Agency also can grant a variance from a treatment
standard by revising the treatment standard for that particular waste
through rulemaking procedures. (A further discussion of treatment
variances is»provided in Section 1.3.)
The land disposal restrictions are effective when promulgated unless
the Administrator grants a national variance and establishes a different
date (not to exceed 2 years beyond the statutory deadline) based on "the
earliest date on which adequate alternative treatment, recovery, or
disposal capacity which protects human health and the environment will be
available" (RCRA Section 3004(h)(2), 42 U.S.C. 6924 (h)(2)).
If EPA fails to set a treatment standard by the statutory deadline
for any hazardous waste in the First Third or Second Third of the
schedule (see Section 1.1.2), the waste may not be disposed in a landfill
or surface impoundment unless the facility is in compliance with the
minimum technological requirements specified in Section 3004(o) of RCRA.
In addition, prior to disposal, the generator must certify to the
Administrator that the availability of treatment capacity has been
investigated and it has been determined that disposal in a landfill or
surface impoundment is the only practical alternative to treatment
currently available to the generator. This restriction on the use of
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landfills and surface impoundments applies until EPA sets a treatment
standard for the waste or until May 8, 1990, whichever is sooner. If the
Agency fails to set a treatment standard for any ranked hazardous waste
by May 8, 1990, the waste is automatically prohibited from land disposal
unless the waste is placed in a land disposal unit that is the subject of
a successful "no migration" demonstration (RCRA Section 3004(g),
42 U.S.C. 6924(g)). "No migration" demonstrations are based on case-
specific petitions that show there will be no migration of hazardous
constituents from the unit for as long as the waste remains hazardous.
1.1.2 Schedule for Developing Restrictions
Under Section 3004(g) of RCRA, EPA was required to establish a
schedule for developing treatment standards for all wastes that the
Agency had listed as hazardous by November 8, 1984. Section 3004(g)
required that this schedule consider the intrinsic hazards and volumes
associated with each of these wastes. The statute required EPA to set
treatment standards according to the following schedule:
(a) Solvents and dioxins standards must be promulgated by
November 8, 1986;
(b) The "California List" must be promulgated by July 8, 1987;
(c) At least one-third of all listed hazardous wastes must be
promulgated by August 8, 1988 (First Third);
(d) At least two-thirds of all listed hazardous wastes must be
promulgated by June 8, 1989 (Second Third); and
(e) All remaining listed hazardous wastes and all hazardous wastes
identified as of November 8, 1984, by one or more of the
characteristics defined in 40 CFR Part 261 must be promulgated
by May 8, 1990 (Third Third).
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The statute specifically identified the solvent wastes as those
covered under waste codes F001, F002, F003, F004, and F005; it identified
the dioxin-containing hazardous wastes as those covered under waste codes
F020, F021, F022, and F023.
Wastes collectively known as the California List wastes, defined
under Section 3004(d) of HSWA, are liquid hazardous wastes containing
metals, free cyanides, PCBs, corrosives (i.e., a pH less than or equal to
2.0), and any liquid or nonliquid hazardous waste containing halogenated
organic compounds (HOCs) above 0.1 percent by weight. Rules for the
California List were proposed on December 11, 1986, and final rules for
PCBs, corrosives, and HOC-containing wastes were established
August 12, 1987. In that rule, 'EPA elected not to establish standards
for metals. Therefore, the statutory limits became effective.
On May 28, 1986, EPA published a final rule (51 FR 19300) that
delineated the specific waste codes that would be addressed by the First
Third, Second Third, and Third Third. This schedule is incorporated into
40 CFR 268.10, .11, and .12.
1.2 Summary of Promulgated BDAT Methodology
In a November 7, 1986, rulemaking, EPA promulgated a technology-based
approach to establishing treatment standards under Section 3004(m).
Section 3004(m) also specifies that treatment standards must "minimize"
long- and short-term threats to human health and the environment arising
from land disposal of hazardous wastes.
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Congress indicated in the legislative history accompanying the HSWA
that "[t]he requisite levels of [sic] methods of treatment established by
the Agency should be the best that has been demonstrated to be
achievable," noting that the intent is "to require utilization of
available technology" and not a "process which contemplates
technology-forcing standards" (Vol. 130 Cong. Rec. S9178 (daily ed.,
July 25, 1984)). EPA has interpreted this legislative history as
suggesting that Congress considered the requirement under 3004(m) to be
met by application of the best demonstrated and achievable (i.e.,
available) technology prior to land disposal of wastes or treatment
residuals. Accordingly, EPA's treatment standards are generally based on
the performance of the best demonstrated available technology (BOAT)
identified for treatment of the hazardous constituents. This approach
involves the identification of potential treatment systems, the
determination of whether they are demonstrated and available, and the
collection of treatment data from well-designed and well-operated systems.
The treatment standards, according to the statute, can represent
levels or methods of treatment, if any, that substantially diminish the
toxicity of the waste or substantially reduce the likelihood of migration
of hazardous constituents. Wherever possible, the Agency prefers to
establish BOAT treatment standards as "levels" of treatment
(i.e., performance standards) rather than adopting an approach that would
require the use of specific treatment "methods." EPA believes that
concentration-based treatment levels offer the regulated community greater
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flexibility to develop and implement compliance strategies, as well as an
incentive to develop innovative technologies.
1.2.1 Waste Treatability Group
In developing the treatment standards, EPA first characterizes the
waste(s). As necessary, EPA may establish treatability groups for wastes
having similar physical and chemical properties. That is, if EPA
believes that wastes represented by different waste codes could be
treated to similar concentrations using identical technologies, the
Agency combines the codes into one treatability group. EPA generally
considers wastes to be similar when they are both generated from the same
industry and from similar processing stages. In addition, EPA may
combine two or more separate wastes into the same treatability group when
data are available showing that the waste characteristics affecting
performance are similar or that one waste would be expected to be less
difficult to treat.
Once the treatability groups have been established, EPA collects and
analyzes data on identified technologies used to treat the wastes in each
treatability group. The technologies evaluated must be demonstrated on
the waste or a similar waste and must be available for use.
1.2.2 Demonstrated and Available Treatment Technologies
Consistent with legislative history, EPA considers demonstrated
technologies to be those that are used to treat the waste of interest or
a similar waste with regard to parameters that affect treatment selection
(see November 7, 1986, 51 FR 40588). EPA also will consider as treatment
those technologies used to separate or otherwise process chemicals and
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other materials. Some of these technologies clearly are applicable to
waste treatment, since the wastes are similar to raw materials processed
in industrial applications.
For most of the waste treatability groups for which EPA will
promulgate treatment standards, EPA will identify demonstrated
technologies either through review of literature related to current waste
treatment practices or on the basis of information provided by specific
facilities currently treating the waste or similar wastes.
In cases where the Agency does not identify any facilities treating
wastes represented by a particular waste treatability group, EPA may
transfer a finding of demonstrated treatment. To do this, EPA will
compare the parameters affecting treatment selection for the waste
treatability group of interest to other wastes for which demonstrated
technologies already have been determined. The parameters affecting
treatment selection and their use for this waste are described in
Section 3.2 of this document. If the parameters affecting treatment
selection are similar, then the Agency will consider the treatment
technology also to be demonstrated for the waste of interest. For
example, EPA considers rotary kiln incineration a demonstrated technology
for many waste codes containing hazardous organic constituents, high
total organic content, and high filterable solids content, regardless of
whether any facility is currently treating these wastes. The bases for
this determination are data found in literature and data generated by EPA
confirming the use of rotary kiln incineration on wastes having the above
characteristics.
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If no commercial treatment or recovery operations are identified for
a waste or wastes with similar physical or chemical characteristics that
affect treatment selection, the Agency will be unable to identify any
demonstrated treatment technologies for the waste, and, accordingly, the
waste will be prohibited from land disposal (unless handled in accordance
with the exemption and variance provisions of the rule). The Agency is,
however, committed to establishing treatment standards as soon as new or
improved treatment processes are demonstrated (and available).
Operations only available at research facilities, pilot- and bench-
scale operations, will not be considered in identifying demonstrated
treatment technologies for a waste because these technologies would not
necessarily be "demonstrated." Nevertheless, EPA may use data generated
at research facilities in assessing the performance of demonstrated
technologies.
As discussed earlier, Congress intended that technologies used to
establish treatment standards under Section 3004(m) be not only
"demonstrated," but also available. To decide whether demonstrated
technologies may be considered "available," the Agency determines whether
they (1) are commercially available and (2) substantially diminish the
toxicity of the waste or substantially reduce the likelihood of migration
of hazardous constituents from the waste.
EPA will only set treatment standards based on a technology that
meets the above criteria. Thus, the decision to classify a technology as
"unavailable" will have a direct impact on the treatment standard. If
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the best technology is unavailable, the treatment standard will be based
on the next best treatment technology determined to be available. To the
extent that the resulting treatment standards are less stringent, greater
concentrations of hazardous constituents in the treatment residuals could
be placed in land disposal units.
There also may be circumstances in which EPA concludes that for a
given waste none of the demonstrated treatment technologies are
"available" for purposes of establishing the 3004(m) treatment
performance standards. Subsequently, these wastes will be prohibited
from continued placement in or on the land unless managed in accordance
with applicable exemptions and variance provisions. The Agency is,
however, committed to establishing new treatment standards as soon as new
or improved treatment processes become "available."
(1) Proprietary or patented processes. If the demonstrated
treatment technology is a proprietary or patented process that is not
generally available, EPA will not consider the technology in its
determination of the treatment standards. EPA will consider proprietary
or patented processes available if it determines that the treatment
method can be purchased or licensed from the proprietor or is
commercially available treatment. The services of the commercial
facility offering this technology often can be purchased even if the
technology itself cannot be purchased.
(2) Substantial treatment. To be considered "available," a
demonstrated treatment technology must "substantially diminish the
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toxicity" of the waste or "substantially reduce the likelihood of
migration of hazardous constituents" from the waste in accordance with
Section 3004(m). By requiring that substantial treatment be achieved in
order to set a treatment standard, the statute ensures that all wastes
are adequately treated before being placed in or on the land and ensures
that the Agency does not require a treatment method that provides little
or no environmental benefit. Treatment will always be deemed substantial
if it results in nondetectable levels of the hazardous constituents of
concern. If nondetectable levels are not achieved, then a determination
of substantial treatment will be made on a case-by-case basis. This
approach is necessary because of the difficulty of establishing a
meaningful guideline that can be applied broadly to the many wastes and
technologies to be considered. EPA will consider the following factors
in an effort to evaluate whether a technology provides substantial
treatment on a case-by-case basis:
(a) Number and types of constituents treated;
(b) Performance (concentration of the constituents in the
treatment residuals); and
(c) Percent of constituents removed.
If none of the demonstrated treatment technologies achieve
substantial treatment of a waste, the Agency cannot establish treatment
standards for the constituents of concern in that waste.
1.2.3 Collection of Performance Data
Performance data on the demonstrated available technologies are
evaluated by the Agency to determine whether the data are representative
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of well-designed and well-operated treatment systems. Only data from
well-designed and well-operated systems are included in determining
BOAT. The data evaluation includes data already collected directly by
EPA and/or data provided by industry. In those instances in which
additional data are needed to supplement existing information, EPA
collects these data through a sampling and analysis program. The
principal elements of this data collection program are: (a) identifi-
cation of facilities for site visits, (b) engineering site visit,
(c) Sampling and Analysis Plan, (d) sampling visit, and (e) Onsite
Engineering Report.
(1) Identification of facilities for site visits. To identify
facilities that generate and/or treat the waste of concern, EPA uses a
number of information sources. These include Stanford Research
Institute's Directory of Chemical Producers, EPA's Hazardous Waste Data
Management System (HWDMS), the 1986 Treatment, Storage, Disposal Facility
(TSDF) National Screening Survey, and EPA's Industry Studies Data Base.
In addition, EPA contacts trade associations to inform them that the
Agency is considering visits to facilities in their industry and to
solicit assistance in identifying facilities for EPA to consider in its
treatment sampling program.
After identifying facilities that treat the waste, EPA uses this
hierarchy to select sites for engineering visits: (1) generators treating
single wastes on site; (2) generators treating multiple wastes together
on site; (3) commercial treatment, storage, and disposal facilities
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(TSDFs); and (4) EPA in-house treatment. This hierarchy is based on two
concepts: (1) to the extent possible, EPA should develop treatment
standards from data produced by treatment facilities handling only a
single waste, and (2) facilities that routinely treat a specific waste
have had the best opportunity to optimize design parameters. Although
excellent treatment can occur at many facilities that are not high in
this hierarchy, EPA has adopted this approach to avoid, when possible,
ambiguities related to the mixing of wastes before and during treatment.
When possible, the Agency will evaluate treatment technologies using
commercially operated systems. If performance data from properly
designed and operated commercial treatment methods for a particular waste
or a waste judged to be similar are not available, EPA may use data from
research facilities operations. Whenever research facility data are
used, EPA will explain why such data were used in the preamble and
background document and will request comments on the use of such data.
Although EPA's data bases provide information on treatment for
individual wastes, the data bases rarely provide data that support the
selection of one facility for sampling over another. In cases in which
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.
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(2) Engineering site visit. Once a treatment facility has been
selected, an engineering site visit is made to confirm that a candidate
for sampling meets EPA's criteria for a well-designed facility and to
ensure that the necessary sampling points can be accessed to determine
operating parameters and treatment effectiveness. During the visit, EPA
also confirms that the facility appears to be well operated, although the
actual operation of the treatment system during sampling is the basis for
EPA's decisions regarding proper operation of the treatment unit. In
general, the Agency considers a well-designed facility to be one that
contains the unit operations necessary to treat the various hazardous
constituents of the waste, as well as to control other nonhazardous
materials in the waste that may affect treatment performance.
In addition to ensuring that a system is reasonably well designed,
the engineering visit examines whether the facility has a way to measure
the operating parameters that affect performance of the treatment system
during the waste treatment period. For example, 'EPA may choose not to
sample a treatment system that operates in a continuous mode, for which
an important operating parameter cannot be continuously recorded. In
such systems, instrumentation is important in determining whether the
treatment system is operating at design values during the waste treatment
period.
(3) Sampling and Analysis Plan. If after the engineering site visit
the Agency decides to sample a particular plant, the Agency will then
develop a site-specific Sampling and Analysis Plan (SAP) according to the
Generic Quality Assurance Project Plan for the Land Disposal Restriction
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Program ("BOAT"), EPA/530-SW-87-011. In brief, the SAP discusses where
the Agency plans to sample, how the samples will be taken, the frequency
of sampling, the constituents to be analyzed and the method of analysis,
operational parameters to be obtained, and specific laboratory quality
control checks on the analytical results.
The Agency will generally produce a draft of the site-specific
Sampling and Analysis Plan within 2 to 3 weeks of the engineering visit.
The draft of the SAP is then sent to the plant for review and comment.
With few exceptions, the draft SAP should be a confirmation of data
collection activities discussed with the plant personnel during the
engineering site visit. EPA encourages plant personnel to recommend any
modifications to the SAP that they believe will improve the quality of
the data.
It is important to note that sampling of a plant by EPA does not mean
that the data will be used in the development of treatment standards for
BOAT. EPA's final decision on whether to use data from a sampled plant
depends on the actual analysis of the waste being treated and on the
operating conditions at the time of sampling. Although EPA would not
plan to sample a facility that was not ostensibly well-designed and
well-operated, there is no way to ensure that at the time of the sampling
the facility will not experience operating problems. Additionally, EPA
statistically compares its test data to suitable industry-provided data,
where available, in its determination of what data to use in developing
treatment standards. The methodology for comparing data is presented
later in this section.
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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 Restriction Program ("BOAT"), which delineates all of the
quality control and quality assurance measures associated with sampling
and analysis. Quality assurance and quality control procedures are
summarized in Section 1.2.6 of this document.)
(4) Sampling visit. The purpose of the sampling visit is to collect
samples that characterize the performance of the treatment system and to
document the operating conditions that existed during the waste treatment
period. At a minimum, the Agency attempts to collect sufficient samples
of the untreated waste and solid and liquid treatment residuals so that
variability in the treatment process can be accounted for in the
development of the treatment standards. To the extent practicable, and
within safety constraints, EPA or its> contractors collect all samples and
ensure that chain-of-custody procedures are conducted so that the
integrity of the data is maintained.
In general, the samples collected during the sampling visit will have
already been specified in the SAP. In some instances, however, EPA will
not be able to collect all planned samples because of changes in the
facility operation or plant upsets; EPA will explain any such deviations
from the SAP in its follow-up Onsite Engineering Report.
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(5) Onsite Engineering Report. EPA summarizes all its data
collection activities and associated analytical results for testing at a
facility in a report referred to as the Onsite Engineering Report (OER).
This report characterizes the waste(s) treated, the treated residual
concentrations, the design and operating data, and all analytical results
including methods used and accuracy results. This report also describes
any deviations from EPA's suggested analytical methods for hazardous
wastes (Test Methods for Evaluating Solid Waste, SW-846, Third Edition,
November 1986).
After the Onsite Engineering Report is completed, the report is
submitted to the plant for review. This review provides the plant with a
final opportunity to claim any information contained in the report as
confidential. Following the review and incorporation of comments, as
appropriate, the report is made available to the public, with the
exception of any material claimed as confidential by the plant.
1.2.4 Hazardous Constituents Considered and Selected for Regulation
(1) Development of BOAT list. The list of hazardous constituents
within the waste codes that are targeted for treatment is referred to by
the Agency as the BOAT constituent list. This list, provided as
Table 1-1, is derived from the constituents presented in 40 CFR Part 261,
Appendix VII and Appendix VIII. It also includes several ignitable
constituents used as the basis for listing wastes as F003 and F005.
These sources provide a comprehensive list of hazardous constituents
specifically regulated under RCRA, The BOAT list consists of those
17
-------
1521q
Table 1-1 BDAT 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
Parameter
Volatiles
Acetone
Acetomtn le
Acrolein
Acrylonitri le
Benzene
Bromodichloromethane
Bromomethane
n-Butyl alcohol
Carbon tetrachlonde
Carbon disulfide
Chlorobenzene
2-Chloro-l,3-butadiene
Chlorodibromomethane
Chloroethane
2-Chloroethyl vinyl ether
Chloroform
Chloromethane
3-Chloropropene
1 ,2-Dibromo-3-chloropropane
1 ,2-Oibromoethane
Dibromomethane
Trans-1 ,4-Dichloro-2-butene
Dichlorodif luoromethane
1 , 1-Dichloroethane
1,2-Dichloroethane
1 , 1-Dichloroethylene
Trans- 1,2-Dichloroethene
1 ,2-Dichloropropane
Trans-1 ,3-Dichloropropene
cis-1 ,3-Dichloropropene
1 ,4-Dioxane
2-Ethoxyethanol
Ethyl acetate
Ethyl benzene
Ethyl cyanide
Ethyl ether
Ethyl methacrylate
Ethylene oxide
lodomethane
CAS no.
67-6,4-1
75-05-6
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
74-86-4
18
-------
Table 1-1 (continued)
BOAT
reference
no
33
228
34
229
35
37
38
230
39
40
41
42
43
44
45
46.
47
48
49
231
50.
215
216.
217
51
52
53
54.
55
56
57
5H
59
218.
60.
61
62
Parameter
Volati les (continued)
Isobutyl alcohol
Methanol
Methyl ethyl ketone
Methyl isobutyl ketone
Methyl methacrylate
Methacrylonitri le
Methylene chloride
2-N itropropane
Pyr idine
1,1, 1 , 2-Tetrachloroethane
1, 1 ,2, 2-Tetrachloroethane
TetrdChloroethene
Toluene
Tribromomethane
1,1,1-Tnchloroethane
1 , 1 ,2-Trichloroethane
Trichloroethene
Tnchloromonof luoromethane
1,2,3-Trichloropropane
1 ,1 ,2-Tnchloro-l,2,2-trif luoro-
ethane
Vinyl chloride
1,2-Xylene
1,3-Xylene
1,4-Xylene
Semwolati les
Acenaphthalene
Acenaphthene
Acetophenone
2-Acetylaminof luorene
4-Aminobiphenyl
Am line
Anthracene
Aramite
Benz(a)anthracene
Benzal chloride
Benzenethiol
Deleted
Benzo(a)pyrene
CAS no.
78-83-1
67-56-1
78-93-3
108-10-1
80-62-6
126-98-7
75-09-2
79-46-9
110-86-1
630-20-&
79-34-6
127-18-4
108-88-3
75-25-2
71-55-6
79-00-5
79-01-6
75-69-4
96-18-4
76-13-1
75-01-4
97-47-6
108-38-3
106-44-5
208-96-8
83-32-9
96-86-2
53-96-3
92-67-1
62-53-3
120-12-7
140-57-8
56-55-3
98-87-3
108-98-5
50-32-8
19
-------
IV-ly
Table 1-1 (continued)
BOAT
ref erence
no
63
64
65
66
67
68
69.
70
71
72
7o
74
75
76
77.
78.
79
80
81.
62
232
83
84
85
86
87
88.
89.
90.
91
92.
93
94
95.
96.
97.
98.
99.
100
101.
Parameter
Seinivolat i les (continued)
Benzo(b)f luoranthene
Benzofghi )perylene
Benzo(k)f luoranthene
p-Benzoqumone
Bis(2-chloroethoxy)methane
Bis(2-chloroethyl)ether
B is (2-chloroisopropyl) ether
Bis(2-ethylhexyl)phthalate
4-Bromophenyl phenyl ether
Butyl benzyl phthalate
2-sec-Butyl-4,6-dmitrophenol
p-Chloroam 1 me
Chlorobenzi late
p-Chloro-m-cresol
2-Chloronaphthalene
2-Chlorophenol
3-Chloropropionitri le
Chrysene
ortho-Cresol
para-Cresol
Cyclohexanone
D ibenz( a, h) anthracene
Dibenzo(a,e)pyrene
Dibenzo(a, ijpyrene
m-Dichlorobenzene
o-Dichlorobenzene
p-Dichlorobenzene
3,3'-Dichlorobenzidme
2,4-Dichlorophenol
2,6-Dichlorophenol
Diethyl phthalate
3 , 3 ' -Dimethoxybenz idine
p-Dimethylaimnoazobenzene
3,3'-Dimethylbenzidine
2,4-Dimethylphenol
Dimethyl phthalate
Di-n-butyl phthalate
1,4-Dmitrobenzene
4,6-Dinitro-o-cresol
2,4-Dinitrophenol
CAS no.
205-99-2
191-24-2
207-08-9
106-51-4
111-91-1
111-44-4
39638-32-9
117-81-7 '
101-55-3
85-S8-7
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
-------
IVlg
Table 1-1 (continued)
BOAT
reference
10?
103
104
105
106.
219
107
108
109
HO
111
112
113.
114
115.
116
117
118.
119
120
36.
121
122
123.
124.
125
126
127.
128.
129.
130.
131
132.
133
134
135.
136
137
138
Parameter
Semivolati les (continued)
2,4-Dinitrotoluene
2,6-Dmitrotoluene
Di-n-octyl phthalate
Di-n-propylmtrosamine
Diphenylamine
Diphenylnitrosamme
1 ,2-Diphenylhydrazine
Fluoranthene
Fluorene
Hexach lorobenzene
Hexachlorobutadiene
Hexachlorocyc lopentadlene
Hexachloroethane
Hexach lorophene
Hexach loropropene
I ndeno ( 1 , 2 , 3 -cd ) pyrene
Isosafrole
Methapyri lene
3-Methylcholanthrene
4,4'-Methylenebis
(2-chloroani line)
Methyl methanesulfonate
Naphthalene
1 ,4-Naphthoquinone
1-Naphthylamine
2-Naphthylamme
p-Nitroam 1 me
Nitrobenzene
4-Nitrophenol
N-Nitrosodi-n-butylamme
N-Nitrosodiethylamme
N-Nitrosodimethylamme
N-Nitrosomethylethylamme
N-Nitrosomorphol me
N-Nitrosopiperidme
n-Nitrosopyrrol idme
5-Nitro-o-toluidme
Pentach lorobenzene
Pentachloroethane
Pentach loronltrobenzene
CAS no.
121-14-2
606-20-2
117-84-0
621-64-7
122-39-4
86-30-6
122-66-7
206-44-0
86-73-7
118-74-1
87-68-3
77-47-4
67-72-1
70-30-4
1888-71-7
193-39-5
120-58-1
91-80-5
56-49-5
101-14-4
66-27-3
91-20-3
130-15-4
134-32-7
91-59-8
100-01-6
98-95-3
100-02-7
924-16-3
55-18-5
62-75-9
10595-95-6
59-89-2
100-75-4
930-55-2
99-65-8
608-93-5
76-01-7
82-68-8
21
-------
ISZlg
Table 1-1 (continued)
BOAT
reference
no
139.
140
141
142.
220
143
144
145
146
147
148
149
150
151
152
153.
154
155
156
157.
158.
159.
221
160
161
162.
163.
164
165.
166.
167.
168
169
170.
17i
Parameter
Semivolat i les (continued)
Pentachlorophenol
Phenacetin
Phenanthrene
Phenol
Phthalic anhydride
2-Picoline
Pronamide
Pyrene
Resorcmol
Saf role
1.2,4, 5-Tetrachlorobenzene
2,3,4, 6-Tet rach loropheno 1
1,2,4-Trichlorobenzene
2,4,5-Trichlorophenol
2, 4, 6-Trich loropheno 1
Tris(2,3-dibromopropyl)
phosphate
Metals
Antimony
Arsenic
Barium
Beryl 1 lum
Cadmium
Chromium (total)
Chromium (hexavalent)
Copper
Lead
Mercury
Nickel
Selenium
Si Iver
Thall lum
Vanadium
Zinc
Inorganics
Cyanide
F luoride
Sulf ide
CAS no.
87-86-5
62-44-2
85-01-8
108-95-2
85-44-9
109-06-8
23950-58-5
129-00-0
108-46-3
94-59-7
95-94-3
58-SO-2
120-82-1
95-95-4
88-06-2
126-72-7
7440-36-0
7440-38-2
7440-39-3
7440-41-7
7440-43-9
7440-47-32
-
7440-50-8
7439-92-1
7439-97-6
7440-02-0
77B2-49-2
7440-22-4
7440-28-0
7440-62-2
7440-66-6
57-12-5
16964-48-8
8496-25-8
22
-------
Table 1-1 (continued)
BOAT
reference
no
172
173
174.
175
176.
177
176
179
180
181.
182
183
184.
185
186.
1B7.
188
189
190
191.
192.
193
194
195.
196
197
198
199
200.
201
202
Parameter
Oraanochlorine pesticides
Aldrin
alpha-BHC
beta-BHC
delta-BHC
gamma-BBC
Chlordane
ODD
DDE
DDT
Dieldrin
Endosulfan I
Endosulfan 11
Endrin
Endrin aldehyde
Heptachlor
Heptachlor epoxide
Isodrin
Kepone
Methoxyclor
Toxaphene
Phenoxvacet ic acid herbicides
2,4-Dichlorophenoxyacetic acid
Si Ivex
2,4,5-T
Orqanophosphorous insecticides
Disulfoton
Famphur
Methyl parathion
Parathion
Phorate
PCBs
Aroclor 1016
Aroclor 1221
Aroclor 1232
CAS no.
309-00-2
319-84-6
319-85-7
319-86-8
58-89-9
57-74-9
72-54-8
72-55-9
50-29-3
60-57-1
939-98-8
33213-6-5
72-20-8
7421-93-4
76-44-8
1024-57-3
465-73-6
143-50-0
72-43-5
8001-35-2
94-75-7
93-72-1
93-76-5
298-04-4
52-85-7
298-00-0
56-38-2
298-02-2
12674-11-2
11104-28-2
11141-16-5
23
-------
1521g
Table 1-1 (continued)
BOAT
reference Parameter CAS no.
no
PCBs (continued)
203 Aroclor 1242 53469-21-9
204 Aroclor 1248 12672-29-6
205. Aroclor 1254 11097-69-1
206 Aroclor 1260 11096-82-5
Dioxins and furans
207 Hexachlorodibenzo-p-dioxins
208 Hexachlorodibenzofurans
209. Pentachlorodibenzo-p-dioxins
210 Pentachlorodibenzofurans
211 Tetrachlorodibenzo-p-dioxins
212 Tetrachlorodibenzofurans
213. 2,3,7,8-Tetrachlorodibenzo-p-dioxin 1746-01-6
24
-------
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 Project Plan, March 1987 (EPA/530-SW-87-011).
Additional constituents will be added to the BOAT constituent list as
other 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, xylene (all three isomers), benzal
chloride, phthalic anhydride, ethylene oxide, acetone, n-butyl alcohol,
2-ethoxyethanol, ethyl acetate, ethyl benzene, ethyl ether, methanol,
methyl isobutyl ketone, 2-nitropropane, l,l,2-trichloro-l,2,2-
trifluoroethane, and cyclohexanone) have been added to the list.
Chemicals are listed in Appendix VIII if they are shown in scientific
studies to have toxic, carcinogenic, mutagenic, or teratogenic effects on
humans or other life-forms, and they include such substances as those
identified by the Agency's Carcinogen Assessment Group as being
carcinogenic. Including a constituent in Appendix VIII means that the
constituent can be cited as a basis for listing toxic wastes.
Although Appendix VII, Appendix VIII, and the F003 and F005
ignitables provide a comprehensive list of RCRA-regulated hazardous
constituents, not all of the constituents can be analyzed in a complex
waste matrix. Therefore, constituents that could not be readily analyzed
in an unknown waste matrix were not included on the initial BOAT list.
As mentioned above, however, the BOAT constituent list is a continuously
25
-------
growing list that does not preclude the addition of new constituents when
analytical methods are developed.
There are five major reasons why constituents were not included on
the BOAT constituent list:
(a) Constituents are unstable. Based on their chemical structure,
some constituents will either decompose in water or will
ionize. For example, maleic anhydride will form maleic acid
when it comes in contact with water, and copper cyanide will
ionize to form copper and cyanide ions. However, EPA may choose
to regulate the decomposition or ionization products.
(b) EPA-approved or verified analytical methods are not available.
Many constituents, such as 1,3,5-trinitrobenzene, are not
measured adequately or even detected using any of EPA's
analytical methods published in SW-846 Third Edition.
(c) The constituent is a member of a chemical group designated in
Appendix VIII as not otherwise specified (N.O.S.). Constituents
listed as N.O.S., such as chlorinated phenols, are a generic
group of some types of chemicals for which a single analytical
procedure is not available. The individual members of each such
group need to be listed to determine whether the constituents
can be analyzed. For each N.O.S. group, all those constituents
that can be readily analyzed are included in the BOAT
constituents list.
(d) Available analytical procedures are not appropriate for a
complex waste matrix. Some compounds, such as auramine, can be
analyzed as a pure constituent; however, in the presence of
other constituents, the recommended analytical method does not
positively identify the constituent. The use of high pressure
liquid chromatography (HPLC) presupposes a high expectation that
specific constituents of interest will be found. In using this
procedure to screen samples, protocols would have to be
developed on a case-specific basis to verify the identity of
constituents present in the samples. Therefore, HPLC is not an
appropriate analytical procedure for complex samples containing
unknown constituents.
(e) Standards for analytical instrument calibration are not
commercially available. For several constituents, such as
benz(c)acridine, commercially available standards of a
"reasonably" pure grade are not available. The unavailability
of a standard was determined by a review of catalogs from
specialty chemical manufacturers.
26
-------
Two constituents (fluoride and sulfide) are not specifically included
in Appendices VII and VIII; however, these compounds are included on the
BOAT list as indicator constituents for compounds from Appendices VII and
VIII such as hydrogen fluoride and hydrogen sulfide, which ionize in
water.
The BOAT constituent list presented in Table 1-1 is divided into the
following nine groups:
Volatile organics
Semivolatile organics
Metals
Other inorganics
Organochlorine pesticides
Phenoxyacetic acid herbicides
Organophosphorous insecticides
PCBs
Dioxins and furans.
The constituents were placed in these categories based on their chemical
properties. The constituents in each group are expected to behave
similarly during treatment and are also analyzed, with the exception of
the metals and inorganics, by using the same analytical methods.
(2) Constituent selection analysis. The constituents that the
Agency selects for regulation in each treatability group are, in general,
those found in the untreated wastes at treatable concentrations. For
certain waste codes, the target list for the untreated waste may have
been shortened (relative to analyses performed to test treatment
technologies) because it is extremely unlikely that the constituent will
be present.
27
-------
In selecting constituents for regulation, the first step is to
summarize all the constituents that were found in the untreated waste at
treatable concentrations. This process involves the use of the
statistical analysis of variance (ANOVA) test, described in Section
1.2.6, to determine if constituent reductions were significant. The
Agency interprets a significant reduction in concentration as evidence
that the technology actually "treats" the waste.
There are some instances in which EPA may regulate constituents that
are not found in the untreated waste but are detected in the treated
residual. This is generally the case when the presence of the
constituents in the untreated waste interferes with the quantification of
the constituent of concern. In such instances, the detection levels of
the constituent are relatively high, resulting in a finding of "not
detected" when, in fact, the constituent is present in the waste.
After determining which of the constituents in the untreated waste
are present at treatable concentrations, EPA develops a list of potential
constituents for regulation. The Agency then reviews this list to
determine if any of these constituents can be excluded from regulation
because they would be controlled by regulation of other constituents in
the list.
EPA performs this indicator analysis for two reasons: (1) it reduces
the analytical cost burdens on the treater and (2) it facilitates
implementation of the compliance and enforcement program. EPA's
rationale for selection of regulated constituents for this waste code is
presented in Section 5 of this background document.
28
-------
(3) Calculation of standards. The final step in the calculation of
the BOAT treatment standard is the multiplication of the average
treatment value by a factor referred to by the Agency as the variability
factor. This calculation takes into account that even well-designed and
well-operated treatment systems will experience some fluctuations in
performance. EPA expects that fluctuations will result from inherent
mechanical limitations in treatment control systems, collection of
treated samples, and analysis of these samples. All of the above
fluctuations can be expected to occur at well-designed and well-operated
treatment facilities. Therefore, setting treatment standards utilizing a
variability factor should be viewed not as a relaxing of 3004(m)
requirements, but rather as a function of the normal variability of the
treatment processes. A treatment facility will have to be designed to
meet the mean achievable treatment performance level to ensure that the
performance levels remain within the limits of the treatment standard.
The Agency calculates a variability factor for each constituent of
concern within a waste treatability group using the statistical
calculation presented in Appendix A. The equation for calculating the
variability factor is the same as that used by EPA for the development of
numerous regulations in the Effluent Guidelines Program under the Clean
Water Act. The variability factor establishes the instantaneous maximum
based on the 99th percentile value.
There is an additional step in the calculation of the treatment
standards in those instances in which the ANOVA analysis shows that more
29
-------
than one technology achieves a level of performance that represents
BOAT. In such instances, the BOAT treatment standard is calculated by
first averaging the mean performance value for each technology for each
constituent of concern and then multiplying that value by the highest
variability factor among the technologies considered. This procedure
ensures that all the BOAT technologies used as the basis for the
standards will achieve full compliance.
1.2.5 Compliance with Performance Standards
All the treatment standards reflect performance achieved by the Best
Demonstrated Available Technology (BOAT). As such, compliance with these
standards only requires that the treatment level be achieved prior to
land disposal. It does not require the use of any particular treatment
technology. While dilution of the waste as a means to comply with the
standard is prohibited, wastes that are generated in such a way as to
naturally meet the standard can be land disposed without treatment. With
the exception of treatment standards that prohibit land disposal, all
treatment standards proposed are expressed as a concentration level.
EPA has used both total constituent concentration and TCLP analyses
of the treated waste as a measure of technology performance. EPA's
rationale for when each of these analytical tests is used is explained in
the following discussion.
For all organic constituents, EPA is basing the treatment standards
on the total constituent concentration found in the treated waste. EPA
based its decision on the fact that technologies exist to destroy the
30
-------
various organics compounds. Accordingly, the best measure of performance
would be the extent to which the various organic compounds have been
destroyed or the total amount of constituent remaining after treatment.
(NOTE: EPA's land disposal restrictions for solvent waste codes
F001-F005 (51 FR 40572) use the TCLP value as a measure of performance.
At the time EPA promulgated the treatment standards for F001-F005, useful
data were not available on total constituent concentrations in treated
residuals and, as a result, the TCLP data were considered to be the best
measure of performance.)
For all metal constituents, EPA is using both total constituent
concentration and/or the TCLP as the basis for treatment standards. The
total constituent concentration is being used when the technology basis
includes a metal recovery operation. The underlying principle of metal
recovery is the reduction of the amount of metal in a waste by separating
the metal for recovery; therefore, total constituent concentration in the
treated residual is an important measure of performance for this
technology. Additionally, EPA believes that it is important that any
remaining metal in a treated residual waste not be in a state that is
easily Teachable; accordingly, EPA is also using the TCLP as a measure of
performance. It is important to note that for wastes for which treatment
standards are based on a metal recovery process, the facility has to
comply with both the total constituent concentration and the TCLP prior
to land disposal.
31
-------
In cases in which treatment standards for metals are not based on
recovery techniques but rather on stabilization, EPA is using only the
TCLP as a measure of performance. The Agency's rationale is that
stabilization is not meant to reduce the concentration of metal in a
waste but only to chemically minimize the ability of the metal to leach.
1.2.6 Identification of BOAT
(1) Screening of treatment data. This section explains how the
Agency determines which of the treatment technologies represent treatment
by BOAT. The first activity is to screen the treatment performance data
from each of the demonstrated and available technologies according to the
following criteria:
(a) Design and operating data associated with the treatment data
must reflect a well-designed, well-operated system for each
treatment data point. (The specific design and operating
parameters for each demonstrated technology for this waste code
are discussed in Section 3.2 of this document.)
(b) Sufficient QA/QC data must be available to determine the true
values of the data from the treated waste. This screening
criterion involves adjustment of treated data to take into
account that the type value may be different from the measured
value. This discrepancy generally is caused by other
constituents in the waste that can mask results or otherwise
interfere with the analysis of the constituent of concern.
(c) The measure of performance must be consistent with EPA's
approach to evaluating treatment by type of constituents (e.g.,
total concentration data for organics, and total concentration
and TCLP for metals in the leachate from the residual).
In the absence of data needed to perform the screening analysis, EPA
will make decisions on a case-by-case basis of whether to include the
data. The factors included in this case-by-case analysis will be the
32
-------
actual treatment levels achieved, the availability of the treatment data
and their completeness (with respect to the above criteria), and EPA's
assessment of whether the untreated waste represents the waste code of
concern. EPA's application of these screening criteria for this waste
code are provided in Section 4 of this background document.
(2) Comparison of treatment data. In cases in which EPA has
treatment data from more than one technology following the screening
activity, EPA uses the statistical method known as analysis of variance
(ANOVA) to determine if one technology performs significantly better than.
others. This statistical method (summarized in Appendix A) provides a
measure of the differences between two data sets. If EPA finds that one
technology performs significantly better (i.e., the data sets are not
homogeneous), BOAT treatment standards are the level of performance
achieved by the best technology multiplied by the corresponding
variability factor for each regulated constituent.
If the differences in the data sets are not statistically
significant, the data sets are said to be homogeneous. Specifically, EPA
uses the analysis of variance to determine whether BOAT represents a
level of performance achieved by only one technology or represents a
level of performance achieved by more than one (or all) of the
technologies. If the Agency finds that the levels of performance for one
or more technologies are not statistically different, EPA averages the
performance values achieved by each technology and then multiplies this
value by the largest variability factor associated with any of the
33
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acceptable technologies. A detailed discussion of the treatment
selection method and an example of how EPA chooses BOAT from multiple
treatment systems is provided in Section A-l.
(3) Quality assurance/quality control. This section presents the
principal quality assurance/quality control (QA/QC) procedures employed
in screening and adjusting the data to be used in the calculation of
treatment standards. Additional QA/QC procedures used in collecting and
screening data for the BOAT program are presented in EPA's Generic
Quality Assurance Project Plan for Land Disposal Restrictions Program
("BOAT") (EPA/530-SW-87-001, March 1987).
To calculate the treatment standards for the Land Disposal
Restriction Rules, it is first necessary to determine the recovery value
for each constituent (the amount of constituent recovered after spiking,
which is the addition of a known amount of the constituent, minus the
initial concentration in the samples divided by the amount added) for a
spike of the treated residual. Once the recovery value is determined,
the following procedures are used to select the appropriate percent
recovery value to adjust the analytical data:
(a) If duplicate spike recovery values are available for the
constituent of interest, the data are adjusted by the lowest
available percent recovery value (i.e., the value that will
yield the most conservative estimate of treatment achieved).
However, if a spike recovery value of less than 20 percent is
reported for a specific constituent, the data are not used to
set treatment standards because the Agency does not have
sufficient confidence in the reported value to set a national
standard.
34
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(b) If data are not available for a specific constituent but are
available for an isomer, then the spike recovery data are
transferred from the isomer and the data are adjusted using the
percent recovery selected according to the procedure described
in (a) above.
(c) If data are not available for a specific constituent but are
available for a similar class of constituents (e.g., volatile
organics, acid-extractable semivolatiles), then spike recovery
data available for this class of constituents are transferred.
All spike recovery values greater than or equal to 20 percent
for a spiked sample are averaged and the constituent
concentration is adjusted by the average recovery value. If
spiked recovery data are available for more than one sample, the
average is calculated for each sample and the data are adjusted
by the lowest average value.
(d) If matrix spike recovery data are not available for a set of
data to be used to calculate treatment standards, then matrix
spike recovery data are transferred from a waste that the Agency
believes is a similar matrix (e.g., if the data are for an ash
from incineration, then data from other incinerator ashes could
be used). While EPA recognizes that transfer of matrix spike
recovery data from a similar waste is not an exact analysis,
this is considered the best approach for adjusting the data to
account for the fact that most analyses do not result in
extraction of 100 percent of the constituent. In assessing the
recovery data to be transferred, the procedures outlined in (a),
(b), and (c) above are followed.
The analytical procedures employed to generate the data used to
calculate the treatment standards are listed in Appendix B of this
document. In cases in which alternatives or equivalent procedures and/or
equipment are allowed in EPA's SW-846, Third Edition (November 1986)
methods, the specific procedures and equipment used are also documented
in this Appendix. In addition, any deviations from the SW-846, Third
Edition, methods used to analyze the specific waste matrices are
documented. It is important to note that the Agency will use the methods
and procedures delineated in Appendix B to enforce the treatment
35
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standards presented in Section 6 of this document. Accordingly,
facilities should use these procedures in assessing the performance of
their treatment systems.
1.2.7 BOAT Treatment Standards for "Derived-From" and "Mixed" Wastes
(1) Wastes from treatment trains generating multiple residues. In a
number of instances, the proposed BOAT consists of a series of
operations, each of which generates a waste residue. For example, the
proposed BOAT for a certain waste code is based on solvent extraction,
steam stripping, and activated carbon adsorption. Each of these
treatment steps generates a waste requiring treatment -- a
solvent-containing stream from solvent extraction, a stripper overhead,
and spent activated carbon. Treatment of these wastes may generate
further residues; for instance, spent activated carbon (if not
regenerated) could be incinerated, generating an ash and possibly a
scrubber water waste. Ultimately, additional wastes are generated that
may require land disposal. With respect to these wastes, the Agency
wishes to emphasize the following points:
(a) All of the residues from treating the original listed wastes are
likewise considered to be the listed waste by virtue of the
derived-from rule contained in 40 CFR Part 261.3(c)(2). (This
point is discussed more fully in (2) below.) Consequently, all
of the wastes generated in the course of treatment would be
prohibited from land disposal unless they satisfy the treatment
standard or meet one of the exceptions to the prohibition.
(b) The Agency's proposed treatment standards generally contain a
concentration level for wastewaters and a concentration level
for nonwastewaters. The treatment standards apply to all of the
wastes generated in treating the original prohibited waste.
Thus, all solids generated from treating these wastes would have
36
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to meet the treatment standard for nonwastewaters. All
derived-from wastes meeting the Agency definition of wastewater
(less than 1 percent TOC and less than 1 percent total
filterable solids) would have to meet the treatment standard for
wastewaters. EPA wishes to make clear that this approach is not
meant to allow partial treatment in order to comply with the
applicable standard.
(c) The Agency has not performed tests, in all cases, on every waste
that can result from every part of the treatment train.
However, the Agency's treatment standards are based on treatment
- of the most concentrated form of the waste. Consequently, the
Agency believes that the less concentrated wastes generated in
the course of treatment will also be able to be treated to meet
this value.
(2) Mixtures and other derived-from residues. There is a further
question as to the applicability of the BOAT treatment standards to
residues generated not from treating the waste (as discussed above) but
from other types of management. Examples are contaminated soil or
leachate that is derived from managing the waste. In these cases, the
mixture is still deemed to be the listed waste, either because of the
derived-from rule (40 CFR Part 261.3(c)(2)(i)) or the mixture rule
(40 CFR Part 261.3(a)(2)(iii) and (iv) or because the listed waste is
contained in the matrix (see, for example, 40 CFR Part 261.33(d)). The
prohibition for the particular listed waste consequently applies to this
type of waste.
The Agency believes that the majority of these types of residues can
meet the treatment standards for the underlying listed wastes (with the
possible exception of contaminated soil and debris for which the Agency
is currently investigating whether it is appropriate to establish a
separate treatability subcategorization). For the most part, these
37
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residues will be less concentrated than the original listed waste. The
Agency's treatment standards also make a generous allowance for process
variability by assuming that all treatability values used to establish
the standard are lognormally distributed. The waste also might be
amenable to a relatively nonvariable form of treatment technology such as
incineration. Finally, and perhaps most important, the rules contain a
treatability variance that allows a petitioner to demonstrate that its
waste cannot be treated to the level specified in the rule (40 CFR Part
268.44(a). This provision provides a safety valve that allows persons
with unusual waste matrices to demonstrate the appropriateness of a
different standard. The Agency, to date, has not received any petitions
under this provision (for example, for residues contaminated with a
prohibited solvent waste), indicating, in the Agency's view, that the
existing standards are generally achievable.
(3) Residues from managing listed wastes or that contain listed
wastes. The Agency has been asked if and when residues from managing
hazardous wastes, such as leachate and contaminated ground water, become
subject to the land disposal prohibitions. Although the Agency believes
this question to be settled by existing rules and interpretative
statements, it will readdress the question to avoid any possible
confusion.
Residues from managing First Third wastes, listed California List
wastes, and spent solvent and dioxin wastes are all considered to be
subject to the prohibitions for the underlying hazardous waste. Residues
38
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from managing California List wastes likewise are subject to the
California List prohibitions when the residues themselves exhibit a
characteristic of hazardous waste. This determination stems directly
from the derived-from rule in 40 CFR Part 261.3(c)(2) or, in some cases,
from the fact that the waste is mixed with or otherwise contains the
listed waste. The underlying principle stated in all of these provisions
is that listed wastes remain listed until delisted.
The Agency's historic practice in processing delisting petitions
addressing mixing residuals has been to consider them to be the listed
waste and to require that delisting petitioners address all constituents
for which the derived-from waste (or other mixed waste) was listed. The
language in 40 CFR Part 260.22(b) states that mixtures or derived-from
residues can be delisted provided a delisting petitioner makes a
demonstration identical to that which a delisting petitioner would make
for the underlying waste. These residues consequently are treated as the
underlying listed waste for delisting purposes. The statute likewise
takes this position, indicating that soil and debris that are
contaminated with listed spent solvents or dioxin wastes are subject to
the prohibition for these wastes even, though these wastes are not the
originally generated waste but rather are a residual from management
(RCRA Section 3004(e)(3)). It is EPA's view that all such residues are
covered by the existing prohibitions and treatment standards for the
listed hazardous waste that these residues contain and from which they
are derived.
39
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1.2.8 Transfer of Treatment Standards
EPA is proposing some treatment standards that are not based on
testing of the treatment technology of the specific waste subject to the
treatment standard. Instead, the Agency has determined that the
constituents present in the subject waste can be treated to the same
performance levels as those observed in other wastes for which EPA has
previously developed treatment data. EPA believes that transferring
treatment performance for use in establishing treatment standards for
untested wastes is valid technically in cases in which the untested
wastes are generated from similar industries, have similar processing
steps, or have similar waste characteristics affecting performance and
treatment selection. Transfer of treatment standards to similar wastes
or wastes from similar processing steps requires little formal analysis.
However, when only the industry is similar, EPA more closely examines the
waste characteristics prior to concluding that the untested waste
constituents can be treated to levels associated with tested wastes.
EPA undertakes a two-step analysis when determining whether wastes
generated by different processes within a single industry can be treated
to the same level of performance. First, EPA reviews the available waste
characteristic data to identify those parameters that are expected to
affect treatment selection. EPA has identified some of the most
important constituents and other parameters needed to select the
treatment technology appropriate for a given waste. A detailed
discussion of each analysis, including how each parameter was selected
for each waste, can be found in the background document for each waste.
40
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Second, when an individual analysis suggests that an untested waste
can be treated with the same technology as a waste for which treatment
performance data are already available, EPA analyzes a more detailed list
of constituents that represent some of the most important waste
characteristics that the Agency believes will affect the performance of
the technology. By examining and comparing these characteristics, the
Agency determines whether the untested wastes will achieve the same level
of treatment as the tested waste. Where the Agency determines that the
untested waste is easier to treat than the tested waste, the treatment
standards can be transferred. A detailed discussion of this transfer
process for each waste can be found in later sections of this document.
1.3 Variance from the BOAT Treatment Standard
The Agency recognizes that there may exist unique wastes that cannot
be treated to the level specified as the treatment standard. In such a
case, a generator or owner/operator may submit a petition to the
Administrator requesting a variance from the treatment standard. A
particular waste may be significantly different from the wastes
considered in establishing treatability groups because the waste contains
a more cpmplex matrix that makes it more difficult to treat. For
example, complex mixtures may be formed when a restricted waste is mixed
with other waste streams by spills or other forms of inadvertent mixing.
As a result, the treatability of the restricted waste may be altered such
that it cannot meet the applicable treatment standard.
Variance petitions must demonstrate that the treatment standard
established for a given waste cannot be met. This demonstration can be
41
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made by showing that attempts to treat the waste by available
technologies were not successful or by performing appropriate analyses of
the waste, including waste characteristics affecting performance, which
demonstrate that the waste cannot be treated to the specified levels.
Variances will not be granted based solely on a showing that adequate
BOAT treatment capacity is unavailable. (Such demonstrations can be made
according to the provisions in Part 268.5 of RCRA for case-by-case
extensions of the effective date.) The Agency will consider granting
generic petitions provided that representative data are submitted to
support a variance for each facility covered by the petition.
Petitioners should submit at least one copy to:
The Administrator
U.S. Environmental Protection Agency
401 M Street, S.W.
Washington, DC 20460
An additional copy marked "Treatability Variance" should be submitted
to:
Chief, Waste Treatment Branch
Office of Solid Waste (WH-565)
U.S. Environmental Protection Agency
401 M Street, S.W.
Washington, DC 20460
Petitions containing confidential information should be sent with
only the inner envelope marked "Treatability Variance" and "Confidential
Business Information" and with the contents marked in accordance with the
requirements of 40 CFR Part 2 (41 FR 36902, September 1, 1976, amended by
43 FR 4000).
The petition should contain the following information:
42
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(1) The petitioner's name and address.
(2) A statement of the petitioner's interest in the proposed action.
(3) The name, address, and EPA identification number of the facility
generating the waste, and the name and telephone number of the
plant contact.
(4) The process(es) and feed materials generating the waste and an
assessment of whether such process(es) or feed materials may
produce a waste that is not covered by the demonstration.
(5) A description of the waste sufficient for comparison with the
waste considered by the Agency in developing BOAT, and an
estimate of the average and maximum monthly and annual
quantities of waste covered by the demonstration. (Note: The
petitioner should consult the appropriate BOAT background
document for determining the characteristics of the wastes
considered in developing treatment standards.)
(6) If the waste has been treated, a description of the system used
for treating the waste, including the process design and
operating conditions. The petition should include the reasons
the treatment standards are not achievable and/or why the
petitioner believes the standards are based on inappropriate
technology for treating the waste. (Note: The petitioner should
refer to the BOAT background document as guidance for
determining the design and operating parameters that the Agency
used in developing treatment standards.)
(7) A description of the alternative treatment systems examined by
the petitioner (if any); a description of the treatment system
deemed appropriate by the petitioner for the waste in question;
and, as appropriate, the concentrations in the treatment
residual or extract of the treatment residual (i.e., using the
TCLP where appropriate for stabilized metals) that can be
achieved by applying such treatment to the waste.
(8) A description of those parameters affecting treatment selection
and waste characteristics that affect performance, including
results of all analyses. (See Section 3.0 for a discussion of
waste characteristics affecting performance that the Agency has
identified for the technology representing BOAT.)
(9) The dates of the sampling and testing.
(10) A description of the methodologies and equipment used to obtain
representative samples.
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(11) A description of the sample handling and preparation techniques,
including techniques used for extraction, containerization, and
preservation of the samples.
(12) A description of analytical procedures used including QA/QC
methods.
After receiving a petition for a variance, the Administrator may
request any additional information or waste samples that may be required
to evaluate and process the petition. Additionally, all petitioners must
certify that the information provided to the Agency is accurate under
40 CFR Part 268.4(b).
In determining whether a variance will be granted, the Agency will
first look at the design and operation of the treatment system being
used. If EPA determines that the technology and operation are consistent
with BOAT, the Agency will evaluate the waste to determine if the waste
matrix and/or physical parameters are such that the BOAT treatment
standards reflect treatment of this waste. Essentially, this latter
analysis will concern the parameters affecting treatment selection and
waste characteristics affecting performance parameters.
In cases in which BOAT is based on more than one technology, the
petitioner will need to demonstrate that the treatment standard cannot be
met using any of the technologies, or that none of the technologies are
appropriate for treatment of the waste. After the Agency has made a
determination on the petition, the Agency's findings will be published in
the Federal Register, followed by a 30-day period for public comment.
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After review of the public comments, EPA will publish its final
determination in the Federal Register as an amendment to the treatment
standards in 40 CFR Part 268, Subpart D.
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2. INDUSTRY AFFECTED AND WASTE CHARACTERIZATION
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.
As discussed in Section 1, the Agency may establish treatability
groups for wastes having similar physical and chemical properties and
thus similar treatability characteristics. At this time, the Agency has
determined that K015 waste represents a separate treatability group.
2.1 Industry Affected and Process Description
According to 40 CFR Part 261.32 (hazardous wastes from specific
sources), waste identified as K015 is specifically generated by the
organic chemicals industry and is listed as follows:
K015 - 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
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HYDROGEN CHLORIDE GAS UNREACTED TOLUENE
1
I
CHLORINE
TOLUENE
REACTOR
TOLUENE
RECOVERY
^-
BENZYL
CHLORIDE
RECOVERY
I
BENZYL CHLORIDE
K015 WASTE
(SOURCE: LISTING BACKGROUND DOCUMENT 1980)
FIGURE 2-1. BENZYL CHLORIDE PRODUCTION BY THE CHLORINATION OF TOLUENE
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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.
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 and sulfur content were approximately 51
and 0.22 percent, respectively, and the waste had a low filterable solids
content.
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1541g
Table 2-1 Major Constituent Composition for K015 Waste
Constituent
Range of concentrations (percent)
Source (1) Source (2)
Benzal chloride
Benzotrichloride and other
chlorinated benzenes
Benzyl chloride
Toluene
Other BOAT constituents
Water
>88
<5
80-90
8-12
3-10
8-12
Source: (1) USEPA 1987a, p.Z-Z.
(2) USEPA 1987b.
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1541g
Table 2-2 BOAT Constituent Composition and Other Data
Parameter
Untreated waste concentration
BOAT volatile orqanics (uq/kq)
Toluene
BOAT semivolati1e orqanics (uq/kq)
Anthracene
Benzal chloride
Benzo(b and/or k)fluoranthene
Phenanthrene
Other parameters
Ash content (%)
Heating value (Btu/lb)
Carbon content (%)
Dry loss (%)
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)
Source: U.S. Environmental Protection Agency 1987, p. 6-3.
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3. APPLICABLE/DEMONSTRATED TREATMENT TECHNOLOGIES
This section identifies the applicable treatment technologies,
describes the demonstrated technologies, and presents performance data
for K015 waste. As shown in Section 2, K015 waste primarily contains
high concentrations of organic compounds and has a low filterable solids
concentration and a low water content. The technologies considered to be
applicable for K015 waste are those that reduce the hazardous organic
constituent concentrations and/or reduce the volume of the waste.
3.1 Applicable Treatment Technologies
The Agency has identified two treatment technologies as applicable
for K015 waste: liquid injection incineration and fuel substitution.
Information for K015 waste is available from current literature sources,
field testing, engineering site visits, and data submitted by industry.
Liquid injection incineration destroys the hazardous organic
constituents in the waste; the technology also results in the formation
of residual wastewater (i.e., quench and scrubber water) with reduced
concentrations of organic constituents and with concentrations of BOAT
metals. If EPA establishes nonwastewater treatment standards for
subsequent treatment of metals in the K015 wastewater, EPA has identified
the following demonstrated technologies: chromium reduction followed by
chemical precipitation and, finally, stabilization of the precipitated
residuals. These technologies are commonly practiced for metal-
containing wastewaters. Chromium reduction reduces hexavalent chromium
to the less soluble trivalent form. Chemical precipitation converts
51
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soluble metals in the wastewater to an insoluble sludge suitable for
stabilization. The technology is described in greater detail in
Section 3.2.1.
Fuel substitution, similar to liquid injection incineration, destroys
the organic constituents in the waste. In doing so, however, fuel
substitution also derives fuel value from the waste. This technology is
explained further in Section 3.2.2.
3.2 Demonstrated Treatment Technologies
Liquid injection incineration and fuel substitution have been
identified as demonstrated treatment technologies for K015 waste.
The Agency tested liquid injection incineration for K015 waste,
obtaining three sample sets of performance data. The performance data
include constituent concentration information on both the untreated and
treated forms of the waste incinerated during the interval, as well as
design and operating information. Performance data for this technology
are presented in Table 3-1. Further discussion of how these data were
obtained is presented in USEPA 1987 (Onsite Engineering Report of
Treatment Technology Performance and Operation for Incineration of K015
Waste at the John Zink Company Test Facility).
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
detected were greater than 90 percent. Benzal chloride concentrations in
the treated wastewaters ranged from less than 50 to 94 /ig/1. Other
organic constituents found in the treated waste were toluene, anthracene,
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1541g
Table 3-1 Performance Ddta Collected by EPA for Liquid Injection
Incineration of k015 Waste
Sample set fl
Concentration data
BOAT constituent concentration3
Constituent Untreated waste Treated waste
Ug/g) (*
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1541g
Table 3-1 (continued)
Sample set
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1541g
Table 3-1 (continued)
Sample set #3
Concentration data
BOAT constituent concentration3
Constituent Untreated waste Treated waste
Ug/g) Ug/i)
Volat lies
Toluene <10
Semivol.n i les
Anthracene <5,000
Benzal chloride 1,100,000
Benzo(b and/or k)f luoranthene <5,000
Phenanthrene <5,000
Metals
Si Iver
Arsenic
Barium
Beryllium
Cadmium
Chromium
Copper
Mercury
Nickel
Lead
Antimony
Selenium
Thallium
Vanadium
Zinc
15
210
94
96
<50
<35
530
550
<5
<20
34,000
3,500
60
25,000
300
160
60
<750
390
930
Design and operating data
ki In
Temperature
Feed rate
Excess oxygen
Carbon monoxide
1780-2065'F
4.18-6.22 Ib/min
3 17-5.77%
0-614 ppm
Scrubber
Flow
Pressure drop
17 44 gal/mm
36-40 in. of water
Concentration data have not been adjusted for accuracy
Treated waste concentration data reflect the worst-case concentration from
quench water sampling to ensure conservancy in determining a wastewater
standard
55
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benzo(b and/or k)fluoranthene, and phenanthrene. These constituents were
detected at concentrations up to 210 ^9/1- While not detected in the
untreated waste, EPA's analysis of the process shows that these organic
constituents could be present.
As shown in the table, chromium, copper, and nickel were detected in
the wastewater at substantial concentrations.
No performance data were collected for fuel substitution and recovery.
3.2.1 Liquid Injection Incineration
Liquid injection incineration is discussed within the context of the
incineration technology description that follows.
This section addresses the commonly used incineration technologies:
liquid injection, rotary kiln, fluidized bed incineration, and fixed
hearth. A discussion is provided regarding the applicability of these
technologies, the underlying principles of operation, a technology
description, the 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 this technology
(a) Liquid injection. Liquid injection is applicable to wastes that
have viscosity values low enough so that the waste can be atomized in the
combustion chamber. A range of maximum viscosity values is reported in
the literature, with the low being 100 Saybolt Seconds Universal (SSU)
and the high being 10,000 SSU. It is important to note that viscosity is
temperature dependent; therefore, while liquid injection may not be
56
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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
demonstrated on wastes that are comprised essentially of metals with low
organic concentrations. In addition, the Agency expects that some of the
high metal content wastes may not be compatible with existing and future
air emission limits unless emission controls are far more extensive than
currently practiced.
(2) Underlying principles of operation
(a) Liquid injection. The basic operating principle of this
incineration technology is that incoming liquid wastes are first
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.
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(b) Rotary kiln and fixed hearth. These incineration technologies
have two distinct principles of operation, 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 (CO ) and water
2
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 liquid injection.
(c) Fluidized bed. The principle of operation for this incinerator
technology differs somewhat from that for rotary kiln and fixed hearth
incineration in that there is only one chamber which contains the
fluidizing sand and a freeboard section above the sand. The purpose of
the fluidized bed is to both volatilize the waste and combust the waste.
Destruction of the waste organics can be better accomplished in the
primary chamber 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 freeboard generally does not have
an afterburner; however, additional time is provided for the organic
58
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constituents to convert to carbon dioxide, water vapor, and hydrochloric
acid if chlorine is present in the waste.
(3) Description of incineration technologies
(a) Liquid injection. The liquid injection system is capable of
incinerating a wide range of gases and liquids. The design of the
combustion system is simple, having 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 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.
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WATER
AUXILIARY FUEL
-HBURNER
cr>
O
AIR-
LIQUID OR GASEOUS.
WASTE INJECTION
PRIMARY
COMBUSTION
CHAMBER
AFTERBURNER
(SECONDARY
COMBUSTION
CHAMBER)
SPRAY
CHAMBER
1
1
GAS TO AIR
POLLUTION
CONTROL
HORIZONTALLY FIRED
LIQUID INJECTION
INCINERATOR
ASH
WATER
FIGURE 3-1. LIQUID INJECTION INCINERATOR
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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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(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).
(d) Fixed hearth incineration. Fixed hearth incinerators, also
called controlled air or starved air incinerators, are 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
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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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AIR
cr
WASTE
INJECTION'
-MBURNER
AIR
1
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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the starved air conditions so that participate entrainment and carryover
are minimized.
(e) Air pollution controls. Following incineration of hazardous
wastes, combustion gases generally are 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 hydrogen
chloride (HC1) 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 either exit 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 less
than 1 micron and require high efficiency collection devices to minimize
air emissions. In addition, scrubber systems provide an additional
buffer against accidental releases of incompletely destroyed waste
products resulting from poor combustion efficiency or combustion upsets
such as flameouts.
(4) Waste characteristics affecting performance (WCAP)
(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,
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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, 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
if 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
cited below.
The heat of combustion only measures 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). While
heat of formation is used as a predictive tool for determining whether
reactions are likely to proceed, 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 numerous hazardous
constituents to be addressed by this rule. Finally, EPA decided not to
use structural classes because the Agency believes that evaluation of
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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, to determine 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 the 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 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 in determining 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
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through various wastes by radiation is more a function of the design and
type of incinerator than 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 considering particle size as a waste characteristic that may
significantly impact the amount of heat transferred to a waste by
convection and thus may impact volatilization of the various organic
compounds. The final type of heat transfer, conduction, is the mechanism
believed by EPA to have 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.
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 identified by EPA for measurement of thermal
conductivity is named the "Guarded, Comparative, Longitudinal Heat Flow
Technique"; it is described in more detail in Appendix C) In theory,
thermal conductivity would always provide a good indication as to 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, however, thermal conductivity has some
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limitations in assessing the transferability of treatment standards.
Nevertheless, EPA has not identified a parameter that can provide a
better indication of heat transfer characteristics of a waste. A
discussion of both the limitations associated with thermal conductivity,
as well as the other parameters considered follows.
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), 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.
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 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. As a surrogate of volatility, EPA is using boiling point
of the constituent. Compounds with lower boiling points have higher
vapor pressures and therefore would be more likely to vaporize. The
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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 be easily 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 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 review of how
these parameters will be monitored during operation.
It is important to point out that, relative to the development of
land disposed restriction standards, EPA is only concerned with these
design parameters 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 only be concerned with the waste
characteristics that affect selection of the unit, not the
above-mentioned design parameters.
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(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, the more likely it is that the molecular bonds will be
destabilized and the reaction completed.
The temperature is normally controlled 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
know not only the exact location in the incinerator that 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
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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 from 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 CO and water vapor.
As the carbon monoxide level increases, it indicates that greater amounts
of organic waste constituents are 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, the volume of combustion gas can be calculated. Having determined
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both the Btu content and the expected combustion gas volume, the feed
rate can be fixed at the desired residence time. Continuous monitoring
of the feed rate will determine whether the unit was 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 in order to volatilize the waste constituents. For the secondary
chamber, analogous to the sole liquid injection incineration chamber, EPA
will examine the same parameters discussed for liquid injection
incineration. These parameters will not be reviewed 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 review of how these parameters will be monitored
during operation.
(i) Temperature. The primary chamber temperature is important
because it provides an indirect measure of the energy input (i.e.,
BTU/hr) that is 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 previously under "Liquid
Injection," temperature should be continuously monitored and recorded.
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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 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. As the RPM
value increases, however, 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 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
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temperature, residence time, and bed pressure differential. The first
two were discussed under rotary kiln and will not be addressed here. Bed
pressure differential is important in that it provides an indication of
the amount of turbulence and, thus, indirectly the amount of heat
supplied to the waste. In general, as the pressure drop increases, both
the turbulence and heat supplied increase. The pressure drop through the
bed should be continuously monitored and recorded to ensure that the
designed valued is achieved.
(d) Fixed hearth. The design considerations for this incineration
unit are similar to a rotary kiln, except 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 discussed under rotary kiln;
for the secondary chamber (i.e., afterburner), the design and operating
parameters of concern are the same as were cited under "Liquid Injection."
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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 this technology. 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 manufacturing 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 variety of industrial processes that produce heat and/or 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,
including:
• 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);
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• 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. To minimize such problems, halogenated wastes are blended
into fuels only at very low concentrations. High chlorine content can
also lead to the incidental production (at very low concentrations) of
other hazardous compounds such as PCBs (polychlorinated biphenyls), PCDDs
(chlorinated dibenzo-p-dioxins), PCDFs (chlorinated dibenzofurans), and
chlorinated phenols.
High inorganic solids content (i.e., ash content) of wastes may cause
two problems: (1) scaling in the boiler and (2) particulate 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 they 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 either in the gaseous emissions from the
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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 not release sufficient 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) 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 of the combustion device.
In combustion devices designed to burn liquid fuels, the viscosity of
liquid waste must be low enough that it can be atomized in the combustion
chamber. If 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.
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If filterable material suspended in the liquid fuel prevents or
hinders pumping or atomization, it will be unacceptable.
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
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) Physical Description of the 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.
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(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 that is a
refractory-lined steel shell used to calcine a mixture of calcium,
silicon, aluminum, iron, and magnesium-containing minerals. The kiln is
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 a baghouse), with the collected
fly ash recycled back to the kiln. Buildup of metals or other
noncombustibles is prevented through their incorporation into the product
cement. Many types of cement require a source of chloride so that most
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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 MgCO ).
3 O O
These raw materials are also heated in a refractory-lined rotary kiln,
typically to temperatures of 980 to 1,260°C (1,800° to
2,300°F). Lime kilns are less likely than cement kilns to burn
hazardous wastes because product lime is often added to potable water
systems. Only one lime kiln currently burns hazardous waste in the U.S.
That particular facility sells its product lime for use as flux or as
refractory in blast furnaces.
As with cement kilns, any collected fly ash is re'cycled back to the
lime kiln; thus, no residual streams result from the kiln. Available
information shows that scrubbers are not used.
(ii) 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 these kilns
lack the material to adsorb halogens. As a result, burning of
halogenated organics in these kilns would likely require afterburners to
ensure the 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.
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(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 only
generated 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 th.is is the
case, air pollution control devices may be required. For solid-fired
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,
lime kilns, and 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
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performance, but rather would determine the applicability of fuel
substitution. That is, EPA would investigate the parameters affecting
treatment selection. For kilns, these parameters (as mentioned
previously) 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 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.
(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.
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(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 change between wastes.
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, then 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.
84
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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 transferability 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 CO
and HO 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.
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
if these parameters would provide a better basis for transferring
treatment standards from an untested waste 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.
85
-------
The heat of combustion only measures 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 predictive tool for determining 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 were rejected because, while it could be used to
calculate some free energy values (AG), it 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 are such that any wastes that are
incompletely destroyed will be contained in the product. As a result,
the Agency will not consider 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
kilns and that the kiln is operated in a manner that will produce a
usable product.
Specifically, cement, lime, and aggregate kilns are only demonstrated
on liquid hazardous wastes. Such wastes must be sufficiently free of
filterable solids as to avoid plugging the burners at the hot end of the
86
-------
kiln. Viscosity also must be low enough to inject the waste 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 if 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.
(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 the design of the boiler. Industrial furnaces also are designed
to operate at specific ranges of temperature in order to produce the
87
-------
desired product (e.g., lightweight aggregate). The blended waste/fuel
mixture should be capable of maintaining the design temperature range.
(ii) 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 and 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
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 flow
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 if an industrial boiler that burns blended fuels containing
hazardous waste constituents is properly operated. The rationale for
selection of these four operating parameters is given below. Most
88
-------
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 assure complete thermal destruction of the waste and efficient
operation of the boiler. When necessary, the air flow 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); hence, oxygen concentration in the flue gas is a
meaningless variable.
(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 if 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 caused by increasing or decreasing the
fuel and air feed rates within certain operating design limits. Most
89
-------
industrial furnaces do not produce steam, but instead a product (e.g.,
cement, aggregate), and they also monitor the rate of production.
(iv) Temperature. Temperatures are monitored and controlled in
industrial boilers to assure the quality and flow rate of steam.
Therefore, complex monitoring systems are frequently installed in the
combustion unit to provide a direct temperature reading. The efficiency
of combustion in industrial boilers is dependent on combustion
temperatures. Temperature may be adjusted to design settings by
increasing or decreasing 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.
Monitoring and control of temperature in industrial furnaces are also
critical to the product quality; e.g., 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 flow 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
the electrical power to the combustion air fan, and loss of primary fuel
flow.
90
-------
(c) Other operating parameters. In addition to the four operating
parameters discussed above, EPA considered and then discarded one
additional parameter. Fuel-to-waste blending ratios were also
considered. However, while the blending is done to yield a uniform Btu
content fuel, blending ratios will vary on a wide range dependent on the
Btu content of the wastes and fuels being used.
91
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4. IDENTIFICATION OF BEST DEMONSTRATED AVAILABLE
TECHNOLOGY FOR K015 WASTE
In this section, EPA explains its determination of which technology
represents the "best" level of performance, as well as being demonstrated
and available. As discussed in Section 3, the demonstrated treatment
technologies for K015 waste are liquid injection incineration and fuel
substitution.
For the two technologies identified as demonstrated, the Agency has
performance data for liquid injection incineration only. Accordingly, it
is not possible to perform the statistical comparison test (ANOVA)
between these technologies as discussed in Section 1 of this document.
While performance data are not available for fuel substitution, EPA
would not expect this technology to improve the BOAT list organic
constituent removal achieved by liquid injection incineration for two
reasons. First, the concentrations of the BOAT list organics in the
treated waste are essentially at the level of treatability, with
anthracene (present at .414 ppm), the highest organic constituent
concentration. Second, the temperature and residence time of the liquid
injection incinerator are equal or higher and equal or longer,
respectively, to the temperature and residence times found in fuel
substitution devices. For these reasons, EPA believes that the
performance achieved by liquid injection represents "best" technology.
Demonstrated technologies are considered "available" if they (1) are
commercially available and (2) substantially diminish the toxicity of the
waste or substantially reduce the likelihood that hazardous constituents
92
-------
will migrate from the waste. Because the two demonstrated technologies
for K015 waste meet all of the above criteria, .they are also considered
"available."
In addition to meeting the criteria of "availability," EPA believes
that liquid injection provides "substantial" treatment by significantly
reducing the concentrations of the hazardous organic constituents of
concern. For example, anthracene, benzal chloride, and phenanthrene were
detected in the untreated waste at concentrations of less than
5,000 M9/1. 910,000 M9/"l> and less than 5,000 /jg/1,
respectively. Treated waste concentrations ranged from 210 to greater
than 50 ^g/1 for anthracene; 94 to greater than 50 /^g/1 for
benzal chloride and 58 to greater than 50 /^g/1 for phenanthrene.
Therefore, liquid injection incineration is believed to ensure adequate
waste treatment by reducing both the toxicity of the waste and the
likelihood that the hazardous constituents will migrate from the waste.
For the reasons stated above, EPA believes that liquid injection
incineration represents the best demonstrated available technology for
K015 organic constituents.
For the BOAT list metals present in the wastewater residual from the
scrubber water used in the liquid injection incinerator, EPA is
transferring performance achieved by hexavalent chromium reduction,
followed by chemical precipitation, followed by dewatering of the
precipitate.
93
-------
These treatment technologies have been used with K062 (spent pickle
liquor from steel finishing operations producing iron and steel)
wastewaters and their performance levels have been determined. The
concentration of metals in K062 wastewaters is relatively high compared
to the K015 scrubber wastewater. Accordingly, EPA believes that K015
scrubber water is less difficult to treat and this transfer of technology
performance is thereby warranted. This transfer technology train also
provides a nonwastewater (the dewatered precipitate), that could be
subject to regulation (as discussed in Section 3.1). For treatment of
this nonwastewater, EPA might consider transferring performance achieved
by stabilization. Performance by stabilization has been measured for a
number of hazardous wastes. EPA believes that the nonwastewater
generated from treatment of F006 (wastewater treatment sludges from
electroplating operations) would be sufficiently similar to the K015
dewatered precipitate because of its metals content.
94
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5. SELECTION OF REGULATED CONSTITUENTS
This section describes the step-by-step process used to select the
pollutants to be regulated. The selected pollutants must be present in
the untreated waste and must be treatable by the chosen BOAT, as
discussed in Section 4. The analytical data from the three sets of
performance data from liquid injection incineration of K015 waste were
examined to identify the major BOAT constituents present in the waste.
As discussed in Section 1, the Agency has developed a list of
hazardous constituents (Table 1-1) from which the constituents to be
regulated are selected. The list is a "growing list", which means that
it does not preclude the addition of new constituents as additional key
data and information are identified. The list is divided into the
following categories: volatile organics, semivolatile organics, metals,
inorganics other than metals, organochlorine pesticides, phenoxyacetic
acid herbicides, organophosphorous pesticides, PCBs, and dioxins and
furans.
Also discussed in Section 1 is EPA's procedure for selecting BOAT
constituents to regulate. Essentially, this process comprises a number
of steps. The first step involves summarizing all the constituents that
were found in the untreated waste at treatable concentrations. The
statistical ANOVA is used (also described in Section 1 and Appendix A) to
ascertain if there were significant reductions in the constituent
levels. This significant reduction is viewed by the Agency as evidence
that the technology "treats" the waste.
95
-------
In some cases, constituents may be regulated by EPA even though they
were not present in the untreated waste but were found in the treated
residual. This can occur when other constituents in the untreated waste
interfere with or "mask" the quantification of the constituent of
concern. The detection levels for the constituent of concern, then, are
fairly high, and a "not detected" finding can result even though the
constituent may be present in the waste.
After it is determined that the constituents are present at treatable
concentrations, EPA will develop a list of potential regulated
constituents. EPA will then review this regulated constituent list to
eliminate any constituents that could be controlled by the subsequent
regulation of other constituents on that list.
5.1 Identification of Treatable Constituents in the Untreated Waste
Table 5-1 presents the BOAT list of constituents and indicates which
of the BOAT list constituents were analyzed in the untreated waste and of
those that were analyzed which were detected. A few compounds have been
added to the BOAT list of constituents since the treatment analysis for
K015 was performed; 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 5-1. 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
96
-------
154)g
Table 5-1 Detection Status for kOlS Untreated and Treated Waste Constituents
Detection limit
BOAT
no
BOAT
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
Parameter
volat i le orqanics
Acetone
Acetomtr i le
Acrolein
Acrylomtri le
Benzene
Brornodichloromethane
Bromomethane
n-Butyl alcohol
Carbon Tetrachloride
Carbon disulfide
Chlorobenzene
2-Chloro-l ,3-butadiene
Chlorodibromomethane
Chloroethane
2-Chloroethyl vinyl ether
Chloroform
Chloromethane
3-Chloropropene
1 , 2-Dibromo-3-chloropropane
1 ,2-Dibromoethane
Dibromomethane
Trans-1 ,4-Dichloro-2-butene
Dichlorod if luoromethane
1, 1-Dichloroethane
1,2-Dichloroethane
1,1-Dichloroethylene
Trans-1 ,2-Dichloroethene
1 ,2-Dichloropropane
Trans-1 ,3-Dichloropropene
cis-1 ,3-Dichloropropene
1 ,4-Dioxane
2-Ethoxyethanol
Ethyl acetate
Ethyl benzene
Ethyl cyanide
Ethyl ether
Ethyl methacrylate
Ethylene oxide
lodomethane
Isobutyl alcohol
Methanol
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
108-90-7
75-00-3
110-75-8
67-66-3
74-8-7-3
107-05-1
96-12-8
106-93-4
74-95-3
110-57-6
75-71-8
75-35-3
105-06-2
75-35-4
156-60-5
78-87-5
10061-02-6
10061-01-5
123-91-1
60-29-7
141-78-6
100-41-4
10712-0
60-29-7
97-63-2
75-21-8
74-88-4
78-83-1
67-56-1
Untreated waste
Ug/g)
10
250
250
50
10
10
10
-b
10
10
10
0.25
10
10
50
10
10
10
10
10
10
0.25
10
10
10
10
10
25
;?5
25
_a
_b
250
10
0.5
250
10
250
10
NA
-b
Treated waste
1*9/1)
250
250
250
50
10
10
10
_b
10
10
10
250
10
10
50
10
10
10
10
10
10
250
10
10
10
10
10
25
25
25
_a
.b
10
10
500
250
10
250
10
NA
-b
Detection
status
ND
ND
ND
ND
ND
ND
ND
NA
ND
ND
ND
ND
ND
NO
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NA
ND
ND
ND
ND
ND
ND
ND
NA
NA
97
-------
1541g
Table 5-1 (continued)
Detection limit
BOAT
no
BOAT
34
229
35
37
38
230
39
40
41
42
43
44
45
46
47
48
49
231
50
215
216
217
BDAT
51
52
53
54
55
56
57
58
59
218
60
62
63
or
64
66
Parameter
volatile orqanics (continued)
Methyl ethyl ketone
Methyl isobutyl ketone
Methyl methacrylate
Methylacrylomtn le
Methylene chloride
2-Nitropropane
Pyridine
1,1,1 ,2-Tetrachloroethane
1,1,2 , 2-Tetrachloroethane
Tetrachloroethene
Toluene*
Tnbromomethane
1.1, 1-Tnchloroethane
1 , 1 ,2-Trichloroethane
Trichloroethene
Trichloromonof luoromethane
1,2,3-Trichloropropane
l,l,2-Trichloro-l,2,2-tnf luoro-
ethane
Vinyl chloride
1 ,2-Xylene
1 ,3-Xylene
1 ,4-Xylene
semivolat i les
Acenaphthalene
Acenaphthene
Acetophenone
2-Acetylaminof luorene
4-Aminobiphenyl
Am 1 me
Anthracene*
Aramite
Benz(a)anthracene
Benzal chloride*
Benzenethiol
Benzo(a)pyrene
and/ Benzo(b and/or k)f luoranthene*
65
Benzo(ghi )perylene
p-Benzoquinone
CAS no
78-93-3
108-10-1
80-62-6
126-98-7
75-09-2
79-46-9
110-86-1
630-20-6
79-34-5
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,
207-08-9
191-24-2
106-51-4
Untreated waste
Ug/g)
50
250
10
_a
50
_b
25
10
10
10
10
10
10
10
10
10
250
_b
10
_b
_b
_b
5,000
5,000
5,000
500,000
100,000
10,000
5,000
_a
5,000
5,000
500,000
5,000
5,000
5,000
500,000
Treated waste
Ug/D
50
50
10
_a
. 50
_b
25
10
10
10
10
10
10
10
10
10
250
_b
10
_b
_b
_b
50
50
50
5,000
1,000
100
50
_a
50
50
5,000
50
50
50
50
Detection
status
ND
NO
ND
ND
ND
NA
ND
ND
ND
ND
D
ND
ND
ND
ND
ND
ND
NA
ND
NA
NA
NA
ND
ND
ND
ND
ND
ND
D
ND
ND
D
ND
ND
D
ND
NDC
98
-------
1541q
Table 5-1 (continued)
Detection limit
BOAT
no
BOAT
67
68
69
70
71
73
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
Parameter
semivolat i les (continued)
Bis(2-chloroethoxy)methane
Bis(2-chloroethy])etber
Bis(2-chloroisopropyl)ether
Bis(2-ethylhexyl)phthalate
4-'Bromophenyl phenyl ether
Butyl benzyl phthalate
2-sec-Butyl-4,6-chnitrophenol
p-Chloroam line
Chlorobenzi late
p-Chloro-m-cresol
2-Chloronaphthalene
2-Chlorophenol
3-Chloropropionitri le
Chrysene
ortho-Cresol
para-Cresol
Cyclohexanone
D i benz( a, h) anthracene
Dibenzo(a,e)pyrene
Dibenzo(a, i )pyrene
m-Dicblorobenzene
o-Dichlorobenzene
p-Oichlorobenzene
3,3' -Dichlorobenzidine
2,4-Dichlorophenol
2,6-Dichlorophenol
Diethyl phthalate
3,3'-Dimethoxybenzidine
p-Dimethylaminoazobenzene
3,3'-Dimethylbenzidine
2, 4- Dimethyl phenol
Dimethyl phthalate
Di-n-butyl phthalate
1 ,4-Dimtrobenzene
4,6-Dinitro-o-cresol
2,4-Dinitrophenol
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Di-n-octyl phthalate
Di-n-propylnitrosamine
Diphenylamine
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
Untreated waste
Ug/g)
5,000
5,000
5,000
5,000
5,000
5,000
_a
50,000
_a
5,000
5,000
5,000
5,000
5,000
5,000
5,000
_b
5,000
5,000
5,000
5,000
5,000
5,000
10,000
5,000
5,000
5,000
5,000,000
100,000
5,000,000
5,000
5,000
5,000
50,000
25,000
25,000
5,000
5,000
5,000
_a
5,000
Treated waste
Ug/D
50
50
50
50
50
50
_a
500
_a
50
50
50
50
50
50
50
_b
50
50
50
50
50
50
50
50
50
50
50.000
1,000
50,000
50
50
50
500
250
250
50
50
50
_a
50
Detection
status
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NA
ND
ND
ND
ND
ND
ND
NO
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
99
-------
1541g
Table 5-1 (continued)
Detection limit
BOAT
no
BOAT
219
107
108
109
110
111
112
113
114
116
117
118
119
130
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
147
Parameter
semivolat i les (continued)
Oiphenylnitrosamine
1 , 2-Diphenylhydraz me
Fluoranthene
Fluorene
Hexach lorobenzene
Hexachlorobutadiene
Hexachlorocyc lopentadlene
Hexach loroethane
Hexachlorophene
Indeno(l ,2,3-cd)pyrene
Isosaf role
Methapyn lene
3-Methylcholanthrene
4,4 '-Hethylenebis
(2-chloroani 1 me)
Methyl methanesulfonate
Naphthalene
1 ,4-Naphthoqumone
1-Naphthylamme
2-Naphthylamme
p-Nitroam 1 me
Nitrobenzene
4-Nitrophenol
N-Nitrosodi-n-butylamme
N-Nitrosodiethylamme
N-Nitrosodimethylamme
N-Nitrosomethylethylamme
N-Nitrosomorpholme
N-Nitrosopipendme
n-Nitrosopyrrol idine
5-Nitro-o-toluidme
Pentach lorobenzene
Pent ach loroethane
Pentach loron i t robenzene
Pentachlorophenol
Phenacet in
Phenanthrene*
Phenol
Phthalic anhydride
2-Picolme
Pronamide
Pyrene
Resorcmol
Safrole
CAS no
86-30-6
122-66-7
206-44-0
86-73-7
118-74-1
87-68-3
77-47-4
67-72-1
70-30-4
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
94-59-7
Untreated waste
Ug/g)
5,000
5,000
5,000
5,000
5,000
5,000
5,000
5,000
_a
5,000
50,000
_a
50,000
100,000
25
5,000
50,000
50,000
50,000
25,000
5,000
25,000
50,000
50,000
50,000
NA
100,000
100.000
100,000
100,000
5,000
5,000
50,000
25,000
50.000
5,000
5,000
_b
50,000
50,000
5,000
5,000
50,000
Treated waste
Ug/D
50
50
50
50
50
50
50
50
_a
50
500
_a
500
1,000
25
50
500
500
500
250
50
250
500
500
500
NA
1,000
1.000
1,000
1,000
50
50
500
250
500
50
50
_b
500
500
50
50
500
Detection
status
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NA
ND
ND
ND
ND
ND
ND
ND
ND
ND
D
ND
NA
ND
ND
ND
ND
ND
100
-------
1541g
Table 5-1 (continued)
BOAT
no
Parameter
CAS no.
Detection limit
Untreated waste Treated waste
Ug/g) Ug/D
Detection
status
BOAT semwolat i les (continued)
148
149
150
151
152
153
Metals (jig/
154
155
156
157
158
159
221
160
161
162
163
164
165
166
167
168
Inorganics
169
170
171
2,4, 5- Tetrach lorobenzene
2,3,4,6-Tetrachlorophenol
1,2, 4 -Inch lorobenzene
2,4, 5-Tnchlorophenol
2,4,6-Trichlorophenol
Tns(2,3-dibromopropyl)
phosphate
'ml)c
Antimony
Arsenic
Barium
Beryl 1 lum
Cadmium
Chromium (total)*
Chromium (hexavalent)
Copper
Lead
Mercury
Nickel*
Selenium
Silver
Thallium
Vanadium
Zinc
Cyanide
Fluoride
Sulf ide
95-94-3
58-90-2
120-82-1
95-95-4
88-06-2
126-72-7
7440-36-0
7440-38-2
7440-39-3
7440-41-7
7440-43-9
7440-47-32
-
7440-50-8
7439-92-1
7439-97-6
7440-02-0
7782-49-2
7440-22-4
7440-28-0
7440-62-2
7440-66-6
57-12-5
16964-48-8
8496-25-8
50.000 500
50,000 500
5,000 50
25,000 250
5,000 50
_a _a
.17/.3
.020/1.0
.010/.045
.005
.020
.035
_b _b
.030
.010/.05
0025/.001
075/.1
.020/1.0
0.035
0.75/.015
.040
.010/.03
NA NA
NA NA
NA NA
ND
ND
ND
ND
ND
ND
D
D
D
ND
D
D
NA
D
D
D
D
D
D
D
D
D
NA
NA
NA
Orqanocnlonne Pesticides
172
173
174
175
Aldrin
alpha-BHC
beta-BHC
delta-BHC
309-00-2
319-84-6
319-85-7
319-86-8
NA NA
NA NA
NA NA
NA NA
NA
NA
NA
NA
101
-------
1541g
Table 5-1 (continued)
Detection limit
BOAT
no
Parameter
CAS no
Untreated waste
(MQ/Q)
Treated waste
Ug/D
Detection
status
Orqanochlorine Pesticides (continued)
176
177
178
179
180
181
18?
183
184
185
186
187
188
189
190
191
gamma-BHC
Chlordane
ODD
ODE
DDT
Dieldrin
Endosulfan I
Endosulfan 11
Endrm
Endrin aldehyde
Heptachlor
Heptachlor epoxide
Isodnn
Kepone
Methoxyclor
Toxaphene
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
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
Phenoxyacet ic acid herbicides
192
193
194
2,4-Dichlorophenoxyacet ic acid
Si Ivex
2,4,5-T
94-75-7
93-72-1
93-76-5
NA
NA
NA
NA
NA
NA
NA
NA
NA
Orqanophosphorous insecticides
195
196
197
198
199
PCBs
200
201
202
203
204
205
206
Disulfoton
Famphur
Methyl parathion
Parathion
Phorate
Aroclor 1016
Aroclor 1221
Aroclor 1232
Aroclor 1242
Aroclor 1248
Aroclor 1254
Aroclor 1260
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
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
102
-------
1541g
Table 5-1 (continued)
BOAT
no Parameter
Detection limit
Untreated waste Treated waste
CAS no Ug/g) Ug/l)
Detection
status
Diox iris and furans
207
208
209
210
211
212
213
ND -
NA -
D -
Hexachlorodibenzo-p-dioxins
Hexachlorodibenzofuran
Pentachlorodibenzo-p-dioxins
Pentachlorodibenzofuran
Tetrachlorodibenzo-p-dioxins
Tetrachlorodibenzofuran
2,3, 7,8-Tetrachlorodibenzo-p-dioxin
Not detected.
Not analyzed.
Detected
1746-01-6
1746-01-6
S746-01-6
1746-01-6
1746-01-6
1746-01-6
1746-01-6
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
a The compound was not detected The detection limit is not given because the analytical standard was not
available. The compound was searched using an NBS data base of 42,000 compounds.
Constituents have been added to the BOAT list since the time that EPA tested and analyzed these
samples for K015. Therefore, data are not available for these particular waste constituents.
c Detection limits for treated metals represent quench samples and scrubber water samples, respectively.
* - Constituents to be regulated.
103
-------
pesticides, phenoxyacetic herbicides, organophosphorous insecticides,
PCBs, and dioxin/furans.
Of the 232 current BOAT list constituents, the Agency analyzed for
158 constituents in the untreated wastes. Eleven BOAT constituents were
not on the BOAT list at the time the K015 waste was analyzed; thus, no
data exist on them. Another 45 BOAT constituents were not analyzed
because the Agency believed that there was no in-process source for
them. For 2 of the BOAT list organics (isobutyl alcohol and
N-nitrosomethylethylamine), there was no information available to
indicate if they had been analyzed; therefore, the Agency will assume
that they were not. The remaining 16 BOAT list metal constituents were
detected in the treated waste.
Of the 158 BOAT list constituents analyzed, the Agency has no data
for 11. Of these 11 constituents, 2 have no data, as discussed in the
preceding paragraph. The remaining 9 constituents could not be detected
because there was no analytical standard available to set detection
limits. Therefore, of the 147 constituents for which there were
laboratory analyses, only 5 were detected; the remaining 142 constituents
were below nondetection levels.
Metals were not analyzed in the untreated waste, but were analyzed in
the treated waste. Of the 16 metals analyzed, 14 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 19 detected BOAT
104
-------
list constituents, EPA has determined that all are treatable. These
constituents will then form the list of potential constituents for
regulation.
Table 5-2 presents those organic constituents determined by EPA to
have treatable concentrations that would be treatable by liquid injection
incineration. This technology would thus significantly reduce these
concentrations. The table also presents those metals thought to be
treatable by the transfer technology train described in Section 4. In
the case of K015, any organic constituent detected in the untreated or
treated waste was identified as treatable for two reasons: (1) detection
limits were fairly high in the untreated waste (parts per thousand for
semivolatile organic compounds), and (2) any constituent detected in the
treated waste was likely to have been present in the untreated waste. (A
detection limit is defined as a practical quantitation limit (PQL) that
is five times the method detection limit achievable when using an
EPA-approved analytical method specified for a particular analyte (i.e.,
constituent of interest) in SW-846, 3rd Edition.
Those organic constituents that were not detected in the treated or
untreated waste are not deemed treatable. They are therefore not
regulated 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
105
-------
1825g
Table 5-2 K015 Waste Constituents with Treatable Concentrations
BOAT
number
43
57
218
63 and/or 65
141
154
155
156
158
159
160
161
162
163
164
165
166
167
168
Constituent
Toluene
Anthracene
Benzal chloride
Benzo (b and/or k)
f luoranthene
Phenanthrene
Ant imony
Arsenic
Ba r i urn
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Si Iver
Thai lium
Vanadium
Zinc
CAS number
108-88-3
120-12-7
98-87-3
205-99-2/
207-08-9
85-01-8
7440-36-0
7440-38-2
7440-39-3
7440-43-9
7440-47-32
7440-50-8
7439-92-1
7439-97-6
7440-02-0
7782-49-2
7440-22-4
7440-28-0
7440-62-2
7440-66-6
Concentration in
untreated waste
(ug/g)
-10
<5,000
930.000-1,100,000
<5.000
<5,000
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
Concentration in
treated waste
(ug/1)
15 59
'50-210
'50-94
<50-96
<50-58
<120-160
100-530
110-550
<20
4,000-34,000*
580-3.500
60-300
<2.5-60
2,200-25,000*
60-90
<35-300
'750
50-390
110-930
NA - Not analyzed in the untreated waste. See Section 5.1.
* Those K015 waste constituents believed to be treatable by transfer technology.
-------
treatable organic BOAT list constituents determined by EPA during the
liquid injection incineration.
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, cadmium, chromium, copper, lead, mercury, nickel,
selenium, silver, thallium, vanadium, and zinc). Concentration data from
the testing of K015 waste for these constituents are summarized in
Table 5-3. The table shows concentrations detected in the untreated
waste, as well as those in the treated waste. Values in parentheses
under treated waste are accuracy-corrected data. Data accuracy is
discussed in Section 1.2.6. The correction factors are derived as
described in Appendix B.
5.2 Comparison of the Untreated and Treated Haste Data for the Ma.ior
Treatable Constituents
Having identified the major treatable BOAT list constituents present
in the waste, EPA compared the analytical data to determine if the
constituent concentration was reduced significantly from the untreated to
the treated waste. When the concentration of a constituent was above the
detection limit, comparisons were based on percent reduction, defined as
the ratio of the concentration of the constituent in the untreated waste
to the concentration in 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
107
-------
1584g
O
oo
Table 5-3 Major Constituent Concentration Data
a
Concentration (accuracy-corrected concentration)
Maior constituent Untreated waste (mq/kq)
Sample set
idl #2 #3
Volat i 1e 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
Benzo(b and/or k)-
fluoranthene <5,000 <5,000 <5,000
Phenanthrene <5,000 <5,000 <5,000
Meta1sb
Silver -
Arsenic -
Barium -
Chromium -
Copper - - -
Mercury -
Nickel
Lead
Ant imony -
Selenium -
Vanadium -
Zinc - - -
#1
59
<50
<50
<50
<50
130
250
110
4,000
580
5
2,200
60
<120
60
50
110
Treated waste (
uq/1)
Correct ion
factor
Sample set
#2
(59)
(<98.6)
(<98.6)
(<98.6)
(<98.6)
(160)
(260)
(150)
(5,000)
(660)
(5)
(2.900)
(130)
(<250)
(80)
(66)
(130)
30
68
66
<50
58
300
100
250
18.000
1,600
<2.5
11,000
240
120
90
170
750
(30)
(134)
(130)
(<98.6)
(114)
(370)
(100)
(330)
(23.000)
(1.820)
(<2.5)
(14,500)
(510)
(250)
(130)
(220)
(850)
15
210
94
96
110
<35
530
550
34,000
3,500
60
25,000
300
160
60
390
930
#3
(15)
(414)
(185)
(189)
(217)
(<43)
(540)
(720)
(44,000)
(3,980)
(60)
(32.900)
(640)
(340)
(80)
(510)
(1.050)
1 00
1.97
1.97
1.97
1 97
1.23
1.02
1.32
1.28
1.14
1.00
1.32
2.13
2.13C
1.39
1.32
1.14
a The data in parentheses have been adjusted for accuracy using the correction factors provided.
As stated in Section 3, metals were not analyzed in the untreated waste.
c The wastewater matrix spike was not analyzed for antimony; accuracy-corrected values were calculated using an assumed correction factor
of 2.13. (See Appendix B.)
-------
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. 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 shown in Table 5-3, all
identified organic constituents in K015 waste were significantly reduced
by liquid injection incineration. As discussed in Section 5.1, liquid
injection incineration of K015 waste was not expected to treat metals,
but metals were found in the treated wastewater. Except for chromium and
nickel, all metals were eliminated from consideration as regulated
pollutants. Chromium and nickel were present in the treated waste at
concentrations for which treatment has been demonstrated by other
technologies (i.e., BOAT for K062 wastewaters). The Agency is still
considering possible regulation of copper at this time, since it is also
present at relatively higher concentrations than the other metals but not
as high as chromium and nickel. The Agency believes that treatment of
chromium and nickel will result in subsequent treatment of the other
detected metals, since they are present at relatively lower
concentrations.
109
-------
5.3 Evaluation of Waste Characteristics Affecting Performance (WCAP)
and Other Related Factors
The WCAPs given in Sections 3.2.1 and 3.2.2 are used to evaluate the
major constituents to determine which organic constituents should be
given priority in the final selection of the regulated constituents.
Such an evaluation is necessary and is generally performed when a
significant number of major constituents have been identified as
potential regulated constituents. Under these circumstances, the major
constituents need to be prioritized based on either of two criteria:
(1) the greatest attenuation in concentration or (2) the identification
of those constituents that are the most difficult to remove and which
may, in many instances, require further treatment. For example, in the
case of K015 waste, toluene was given the lowest priority for regulatory
selection since its reduction in concentration from the untreated waste
was not readily apparent yet it was still detected in the treated
waste. Furthermore, its chemical structure is considered easier to
treat by liquid injection than are the other major organic constituents
in the waste. Moreover, if toluene were present in any concentration, it
would be treated more quickly than the other major organic constituents.
5.4 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. (As stated in Section 5.2,
the Agency is still considering copper as a potential regulated metal
constituent.)
110 (
-------
6. CALCULATION OF THE BOAT TREATMENT STANDARDS
The purpose of this section is to present the calculation of the
actual treatment standards for the regulated constituents determined in
Section 5. EPA has three sets of influent and effluent data from one
facility for treatment of KOI5 using liquid injection incineration. EPA
believes that the treated constituent concentrations substantially
diminish the toxicity or mobility of K015 waste. As discussed in the
introduction, the following steps were taken to derive the BOAT treatment
standards for K015 waste.
1. The Agency evaluated the data collected from the liquid
injection treatment system to determine whether any of the data
represented poor design or operation of the treatment system.
The available data show that all three data sets do not
represent poor design or operation. All three data sets for
liquid injection incineration are used for establishing
treatment standards for regulation of the organic constituents
in K015 wastewaters. For the regulated constituents chromium
and nickel, treatment data were transferred from standards
established for those metals in K062 wastewaters (see the
Background Document for K062 waste).
2. 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. These are
shown for the organic constituents in Table 6-1. The
calculation of the variability factor is explained in Appendix A.
3. 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 BOAT treatment standards for the
organic constituents are also shown in Table 6-1.
Ill
-------
Table 6-1 Calculation of BOAT Treatment Standards for
Regulated Organic Constituents in K015 Wastewaters
Accuracv-corrected concentration Average Variability
Constituent (units)
Toluene (ng/1)
Anthracene (/ig/1)
Benzal chloride (ng/1)
Benzo(b and/or k)
fluoranthene (ng/1)
Phenanthrene (ng/1)
Sample set
#1
59
<98.6
<98.6
<98.6
<98.6
Sample set Sample set treated waste factor Treatment standard
#2 #3 concentration (VF) (average x VF)
30 15 34 7 4.26 148
134 414 216 4 15 1,020
130 185 138 2.02 280
<98.6 189 129 2.28 290
114 217 107 2 50 270
-------
7. CONCLUSIONS
The Agency has proposed treatment standards for the listed waste code
K015. Standards for nonwastewater and wastewater forms of this waste are
presented in Table 7-1.
The treatment standards proposed for K015 waste have been developed
consistent with EPA's promulgated methodology for BOAT (November 7, 1986,
51FR 40572). Only two facilities are known to produce benzyl chloride
and to generate K015 waste. The BOAT constituents generally present in
the K015 waste are benzal chloride and toluene.
Through available data bases, EPA's technology testing program, and
data submitted by industry, the Agency has identified the following
demonstrated technologies for treatment of organic constituents present
in the K015 waste: liquid injection incineration and fuel substitution.
Regulated constituents were selected based on a careful evaluation of
the constituents detected at treatable levels in the untreated wastes and
constituents detected in the treated wastes. All available waste
characterization data and applicable treatment data consistent with the
type and quality of data required by the Agency for this program were
used to make this determination.
In the development of treatment standards for K015 wastes, the Agency
examined all available data, conducted tests on liquid injection
incineration of the waste, and collected performance data for three
sample sets. Design and operating data collected during the testing of
113
-------
1590g
Table 7-1 BOAT Treatment Standards for K015 Waste
NONWASTEWATER
No land disposal
WASTEWATER
Maximum for any single grab sample
Total constitution TCLP
Constituent (mg/1) (mg/1)
Toluene -1478 NA
Anthracene 1-02 NA
Benzal chloride 0.28 NA
Benzo(b and/or k)fluoranthene 0.29 NA
Phenanthrene ' 0.27 NA
Chromium 0 3f6 NA
Nickel 0 44' NA
NA = Not applicable.
114
-------
the technology indicate that the technology was properly operated during
all three sample sets; accordingly, the treatment performance data were
used in the development of the BOAT treatment standards.
Two categories of treatment standards were developed for K015 waste:
wastewater and nonwastewater. (For the purpose of the land disposal
restrictions rule, wastewaters are defined as wastes containing less than
1 percent (weight basis) filterable solids and less than 1 percent
(weight basis) total organic carbon.) The nonwastewater standard is "no
land disposal" for K015 as generated. Wastewater standards for organic
constituents in K015 waste are based on the performance data from EPA's
test of liquid injection incineration. Wastewater standards for metal
constituents in K015 are based on the transfer of BOAT standards for K062
waste.
Treatment standards for these wastes were derived after adjustment of
laboratory data to account for recovery. Subsequently, the mean of the
adjusted data points was multiplied by a variability factor to derive the
standard. The variability factor represents the variability inherent in
the treatment process and sampling and analytical methods. Variability
factors were determined by statistically calculating the variability seen
for a number of data points for a given constituent. For constituents
for which specific variability factors could not be calculated, a
variability factor of 2.8 was used (although this was not necessary for
K015).
115
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Wastes determined to be K015 residuals may be land disposed if they
meet the standards at the point of disposal. The BOAT upon which the
treatment standards are based need not be specifically utilized prior to
land disposal, provided the alternative technology used achieves the
standards.
These standards were to become effective as of August 8, 1986, as per
the schedule set forth in 40 CFR 268.10. Because of the lack of
nationwide incineration capacity at this time, the Agency has proposed to
grant a 2-year nationwide variance to the effective date of the land
disposal ban for K015 waste. A detailed discussion of the Agency's
determination that a lack of nationwide incineration capacity exists is
presented in the Capacity Background Document, which is available in the
Administrative Record for the First Sixths' Rule.
Consistent with Executive Order 12291, EPA prepared a regulatory
impact analysis (RIA) to assess the economic effect of compliance with
this proposed rule. The RIA prepared for this proposed rule is available
in the Administrative Record for the First Sixths' Rule.
116
-------
REFERENCES
Ackerman, D.G., McGaughey, J.F., Wagoner D.E.1983., At sea incineration
of PCB-containinq wastes on board the M/T Vulcanus. 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. Prepared by Monsanto Research Corporation for U.S.
Environmental Protection Agency. NTIS PB 81-248163. June 1981.
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., Incineration of hazardous waste. 1987. 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 K015.
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, November 1986.
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.
117
-------
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 and evaluation for "California List"
waste streams. Contract No. 68-01-7053. 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.
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. 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. Cincinnati, Ohio.
April 1986.
118
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APPENDIX A
119
-------
APPENDIX A
A.I F Value Determination for ANOVA Test
As noted earlier in Section 1.0, EPA is using the statistical method
known as analysis of variance in the determination of the level of
performance that represents "best" treatment where more than one
technology is demonstrated. This method provides a measure of the
differences between data sets. If the differences are not statistically
different, the data sets are said to be homogeneous.
If the Agency found that the levels of performance for one or more
technologies are not statistically different (i.e., the data sets are
homogeneous), EPA would average the long-term performance values achieved
by each technology and then multiply this value by the largest
variability factor associated with any of the acceptable technologies.
If EPA found that one technology performs significantly better (i.e., the
data sets are not homogeneous), BOAT would be the level of performance
achieved by the best technology multiplied by its variability factor.
To determine whether any or all of the treatment performance data
sets are homogeneous using the analysis of variance method, it is
necessary to compare a calculated "F value" to what is known as a
"critical value." These critical values are available in most statistics
texts (see, for example, Statistical Concepts and Methods by
Bhattacharyya and Johnson, 1977, John Wiley Publications, New York).
Where the F value is less than the critical value, all treatment data
sets are homogeneous. If the F value exceeds the critical value, it is
120
-------
necessary to perform a "pair wise F" test to determine if any of the sets
are homogeneous. The "pair wise F" test must be done for all of the
various combinations of data sets using the same method and equation as
the general F test.
The F value is calculated as follows:
(i) All data are natural logtransformed.
(ii) The sum of the data points for each data set is computed (T.).
(iii) The statistical parameter known as the sum of the squares
between data sets (SSB) is computed:
SSB
k
I
•i-1
i — i
T,2'
N~
—
r k
^
N
i -
where:
k = number of treatment technologies
n^ = number of data points for technology i
N = number of data points for all technologies
T^ = sum of natural logtransformed data points for each technology.
(iv) The sum of the squares within data sets (SSW) is computed:
SSW =
where:
Xi i
X X
1=1 j=l
,2,
i,J
k
- X
= the natural logtransformed observations (j) for treatment
technology (i).
(v) The degrees of freedom corresponding to SSB and SSW are
calculated. For SSB, the degree of freedom is given by k-1. For SSW,
the degree of freedom is given by N-k.
121
-------
(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
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.
122
-------
Table A-l
95th PERCENTILE VALUES FOR
THE F DISTRIBUTION
degrees of freedom for numerator
degrees of freedom for denominator
„ . . (shaded area = .95)
^
4
i
*
8
9
10
11
12
13
14
15
16
17
18
19
20
22
24
26
28
30
40
50
60
70
80
100
150
200
400
80
1 1
>t
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
3.81
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
5.86
3.71
3.59
3.49
3.41
3.34
3.29
3.24
3.20
3.16
3.13
3.10
3.05
3.01
2.98
2.95
2.92
2.84
2.79
2.76
2.74
2.72
2.70
2.67
2.65
2.62
2.60
4
224.6
19.25
9.12
6.39
5.19
4.53
4.12
3.84
3.63
3.48
3.36
3.26
3.18
3.11
3.06
3.01
2.96
2.93
2.90
2.87
2.82 .
2.78 '
2.74
2.71
2.69
2.61
2.56
2.53
2.50
2.48
2.46
2.43
2.41
2.39
2.37
5
230.2
19.30
9.01
6.26
5.05
4.39
3.97
3.69
3.48
3.33
3.20
3.11
3.03
2.96
2.90
2.85
2.81
2.77
2.74
2.71
2.66
2.62
2.59
2.56
2.53
2.45
2.40
2.37
2.35
2.33
2.30
2.27
2.26
2.23
2.21
6
234.0
19.33
8.94
6.16
4.95
4.28
3.87
3.58
3.37
3.22
3.09
3.00
2.92
2.85
2.79
2.74
2.70
2.66
2.63
2.60
2.55
2.51
2.47
2.45
2.42
2.34
2.29
2.25
2.23
2.21
2.19
2.16
2.14
2.12
2.09
8
238.9
19.37
8.85
6.04
4.82
4.15
3.73
3.44
3.23
3.07
2.95
2.85
2.77
2.70
2.64
2.59
2.55
2.51
2.48
2.45
2.40
2.36
2.32
2 29
2.27
2.18
2.13
2.10
2.07
2.05
2.03
2.00
1.98
1.96
1.94
12
243.9
19.41
8.74
5.91
4.68
4.00
3.57
3.28
3.07
2.91
2.79
2.69
2.60
2.53
2.48
2.42
2.38
2.34
2.31
2.28
2.23
2.18
2.15
2.12
2.09
2.00
1.95
1.92
1.89
1.88
1.85
1.82
1.80
1.78
1.75
16
24G.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
2.29
2.25
2 21
2.18
2.13
2.09
2.05
2.02
1.99
1.90
1.85
1.81
1.79
1.77
1.75
1.71
1.69
1.67
1.64
20
248.0
19.45
8.66
5.80
4.56
3.87
3.44
3.15
2.93
2.77
2.65
2.54
2.46
2.39
2.33
2.28
2.23
2.19
2.15
2.12
2.07
2.03
1.99
1.96
1.93
1.84
1.78
1.75
1.72
1.70
1.68
1.64
1.62
1.60
1.57
30
250.1
19.46
8.62
5.75
4.50
3.81
§.38
3.08
2.86
2.70
2.57
2.46
2.38
2.31
2.25
2.20
2.15
2.11
2.07
2.04
1.98
1.94
1.90
1.87
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
1.45
1.42
1.40
50
252.2
19.47
8.58
5.70
4.44
3.75
3.32
3.03
2.80
2.64
2.50
2.40
2.32
2.24
2.18
2.13
2.08
2.04
2.00
1.96
1.91
1.86
1.82
1.78
1.76
1.66
1.60
1.56
1.53
1.51
1.48
1.44
1.42
1.38
1.32
100
253.0
19.49
8.56
5.66
4.40
3.71
3.28
2.98
2.76
2.59
2.45
2.35
2.26
2.19
2.12
2.07
2.02
1.98
1.94
1.90
1.84
1.80
1.76
1.72
1.69
1.59
1.52
1.48
1.45
1.42
1.39
1.34
1.32
1.28
1.24
*
254.3
19.50
8.53
5.63
4.36
3.67
3.23
2.93
2.71
2.54
2.40
2.30
2.21
2.13
2.07
2.01
1.96
1.92
1.88
1.84
1.78
1.73
1.69
1.65
1.62
1.51
1.44
1.39
1.35
1.32
1.28
1.22
1.19
1.13
1.00
123
-------
1790g
Example 1
Methylene Chloride
Steam stripping Biological treatment
Influent Effluent In(effluent) [ln|effluent)]2 Influent Effluent In(effluent)
(Mg/D Ug/D Ug/D Ug/1)
Sum.
[In(effluent)]
2
1550 00
1290.00
1540.00
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
Mean:
3669 10.2
Standard Deviation:
3328.67 .63
Variability Factor:
10
2.32
.06
2378
923.04
1.15
13.2
7.15
2.48
2.49
.43
ANOVA Calculations-
SSB =
1=1 ~
ssw =
MSB = SSB/(k-l)
MSW-= SSW/(N-k)
124
-------
1790g
Example 1 (continued)
F = MSB/MSW
where
k = number of treatment technologies
n = number of data points for technology i
i
N = number of natural log transformed data points for all technologies
T = sum of log transformed data points for each technology
X = the nat log transformed observations (j) for treatment technology (i)
n = 10, n = 5, H = 15, k = 2, T = 33 18, T = 12.46, T = 35.64, T = 1270.21
T2 = 537.31 T2 = 155 25
SSB =
537.31 155.25
10
1270.21
15
= 0.10
SSW = (53.76 + 31.79) -
537.31 155.25'
10
= 0.77
MSB = 0 10/1 = 0 10
MSW = 0.77/13 = 0.06
010
F = = I.b7
0.06
ANOVA Table
Source
Degrees of
freedom
SS
MS
Between(B)
Within(W)
1
13
0.10
0.77
0.10
0.06
1.67
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.
125
-------
1790g
Example 2
Tnchloroethy lene
Influent
Ug/D
1650.00
5200.00
5000.00
1720.00
1560.00
10300 00
210.00
1600.00
204 00
160 00
Steam stripping
Effluent
Ug/l)
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(eff luent)]2
5.29
5.29
5.29
5.29
5.29
5.29
5 29
10.89
19 71
5 29
Influent
Ug/D
200.00
224.00
134.00
150.00
484.00
163 00
182.00
Biological treatment
Effluent In(effluent)
Ug/D
10.00
10.00
10.00
10.00
16.25
10.00
10.00
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
Variability 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:
SSB =
F k
ssw =
MSB = SSB/(k-l)
MSW = SSW/(N-k)
V'
1=1
126
-------
1790g
Example 2 (continued)
F = MSB/MSW
where
k = number of treatment technologies
n = number of data points for technology i
N = number of data points for all technologies
T = sum of natural log transformed data points for each technology
X = the natural log transformed observations (j) for treatment technology (i)
2 2
N = 10, N = 7, N = 17, k = 2, T = 26.14, T = 16.59, T = 42.73, T = 1825.85, T = 683.30,
T2 = 275.23
SSB -f683'30 , 275'23 ] - 1825'85 - 0.25
10 7 I 17
SSWM72.92. 39.52) . , «"0 + 275f| = 4.79
10 7
MSB = 0.25/1 = 0.25
MSW = 4.79/15 = 0 32
0.32
ANOVA Table
Degrees of
Source freedom
Between (B) 1
Within(W) 15
SS MS
0.25 0.25
4.79 0.32
F
0.78
The critical value of the F test at the 0.05 significance level is 4.54. Since
the F value is less than the critical value, the means are not significantly
different (i.e., they are homogeneous).
Note: All calculations were rounded to two decimal places. Results may differ
depending upon the number of decimal places used in each step of the calculations.
127
-------
1790g
Example 3
Ch lorobenzene
Activated sludqe followed by carbon adsorption
Influent Effluent In(effluent) [ln(effluent)]
Ug/D Ug/D
Sum
Sample Size:
4 4
Mean.
5703
49
Standard Deviation:
1835.4 32.24
Variability Factor:
14 49
3 62
.95
Biological treatment
2 Influent Effluent
{(ig/l) Ug/1)
In(effluent)
55.20
14759
16311.86
7.00
452.5
379.04
15.79
38.90
5.56
1.42
In [(effluent)]
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
228.34
ANOVA Calculations:
SSB =
n,
12
k
SSW =
MSB = SSB/(k-l)
MSW = SSU/(N-k)
F = MSB/MSW
-U-l
i=l I n, J
128
-------
1790g
where,
Example 3 (continued)
k = number of treatment technologies
n = number of data points for technology i
N = number of data points for all technologies
T = sum of natural log transformed data points for each technology
X = the natural log transformed observations (j) for treatment technology (i)
N = 4, N = 7. N = 11. k = 2, T = 14.49, T = 38.90, T = 53.39, T?= 2850.49, T2 = 209.96
T = 1513.21
SSB =
209.96 1513.21
2850.49
11
9.52
SSW = (55.20 + 228.34)
209.96 1513.21
4 7
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
Between! B)
Within(W)
1
9
9.53
14.89
9.53
1.65
5.77
The critical value of the F test at the 0.05 significance level is 5.12. Since
the F value is larger than the critical value, the means are significantly
different (i.e., they are heterogeneous).
Note. All calculations were rounded to two decimal places. Results may differ depending
upon the number of decimal places used in each step of the calculations.
129
-------
A. 2 Variability Factor
-£•99-
VF = Mean
where:
VF = estimate of daily maximum variability factor determined from
a sample population of daily data.
Cgg = Estimate of performance values for which 99 percent of the
daily observations will be below. Cgg is calculated using
the following equation: Cgg = Exp(y + 2.33 Sy) where y and
Sy are the mean and standard deviation, respectively, of the
logtransformed data.
Mean = average of the individual performance values.
In several cases, all the results from analysis of the residuals from
BOAT treatment are found at concentrations less than the detection
limit. In such cases, all the actual concentration values are considered
unknown and hence, cannot be used to estimate the variability factor of
the analytical results. Below is a description of EPA's approach for
calculating the variability factor for such cases with all concentrations
below the detection limit.
It has been postulated as a general rule that a lognormal
distribution adequately describes the variation among concentrations.
Agency data shows that the treatment residual concentrations are
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
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percentile (C ) of the lognormal distribution to its arithmetic mean
(Mean).
VF = C99
Mean
The relationship between the parameters of the lognormal distribution
and the parameters of the normal distribution created by taking the
natural logarithms of the lognormally-distributed concentrations can be
found in most mathematical statistics texts (see for example:
Distribution in Statistics-Volume 1 by Johnson and Kotz, 1970). The mean
of the lognormal distribution can be expressed in terms of the
mean (M) and standard deviation (a) of the normal distribution as
follows:
C9g = Exp („ + 2.33a) (2)
Mean = Exp (M + .5a2) (3)
Substituting (2) and (3) in (1) the variability factor can then be
expressed in terms of a as follows:
VF = Exp (2.33 a - .5a2) (4)
For residuals with concentrations that are not all below the
detection limit, the 99 percentile and the mean can be estimated from
the actual analytical data and accordingly, the variability factor (VF)
can be estimated using equation (1). For residuals with concentrations
that are below the detection limit, the above equations can be used in
conjunction with the assumptions below to develop a variability factor.
Step 1: The actual concentrations follow a lognormal distribution. The
upper limit (UL) is equal to the detection limit. The lower limit (LL)
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is assumed to be equal to one tenth of the detection limit. This
assumption is based on the fact that data from well-designed and
well-operated treatment systems generally falls within one order of
magnitude.
Step 2: The natural logarithms of the concentrations have a normal
distribution with an upper limit equal to In (UL) and a lower limit equal
to In (LL).
Step 3: The standard deviation (a) of the normal distribution is
approximated by
a = [(In (UL) - In (LL)] / [(2)(2.33)] = [ln(UL/LLJ] / 4.66
when LL = (0.1)(UL) then a = (InlO) / 4.66 = 0.494
Step 4: Substitution of the value from Step 3 in equation (4) yields the
variability factor, VF.
VF = 2.8
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APPENDIX B
133
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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 multipled 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.
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1541g
Table B-l Analytical Methods
Analysis/methods Method Reference
Volati1e Orqanics
Purge-and-trap 5030 1
Gas chromatography/mass spectrometry for
volatile orgamcs 8240 1
Semivolati1e Orqanics
Continuous liquid-liquid extraction (treated waste) 3520 1
Soxhlet extraction (untreated waste) 3540 1
Gas chromatography/mass spectrometry for semi-
volatile organics- Capillary Column Technique 8270 1
Metals
Digestion
Aqueous liquids analyzed by ICP 3010 1
Aqueous liquids analyzed by graphite furnace 3020 1
Inductively coupled plasma atomic emission
spectroscopy (ant imony/banum/chromiurn/copper/
nickel/siIver/vanadium/zinc) 6010 1
Arsenic (atomic absorption, furnace technique) 7060 1
Selenium (atomic absorption, furnace technique) 7740 1
Mercury in solid or semisolid waste 7471 1
(manual cold-vapor technique)
Lead (atomic absorption, furnace technique) 7421 1
Reference 1. (US EPA 1986b).
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1541g
Table 6-2 Base Neutral Matrix Spike Data for ICO 15 Uastewater
Compound
1,4-Dichlorobenzene
N-nitroso-di-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
SO
25
62
.83 50.66
50.7
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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.
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1541g
Table B-3 Metal Matrix Spike Data for 10)15 Uastewater
Compound
Lowest percent recovery
Correction factor
Silver
Arsenic
Barium
Chromium
Copper
Mercury
Nickel
Lead
Antimony
Selenium
Vanadium
Zinc
81
98
76
78-
88
100
76
47
47a -
72
76
88
1.23
1.02
1.32
1.28
1.14
1.00
1.32
2.13
2.13a
1.39
1.32
1.14
These are assumed values See text.
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APPENDIX C
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APPENDIX C
The comparative method of measuring thermal conductivity has been
proposed as an ASTM test method under the name "Guarded, Comparative,
Longitudinal Heat Flow Technique." A thermal heat flow circuit is used
which is the analog of an electrical circuit with resistances in series.
A reference material is chosen to have a thermal conductivity close to
that estimated for the sample. Reference standards (also known as heat
meters) having the same cross-sectional dimensions as the sample are
placed above and below the sample. An upper heater, a lower heater, and
a heat sink are added to the "stack" to complete the heat flow circuit.
See Figure 1.
The temperature gradients (analogous to potential differences) along
the stack are measured with type K (chromel/alumel) thermocouples placed
at known separations. The thermocouples are placed into holes or grooves
in the references and also in the sample whenever the sample is thick
enough to accommodate them.
For molten samples, pastes, greases, and other materials that must be
contained, the material is placed into a cell consisting of a top and
bottom of Pyrex 7740 and a containment ring of marinite. The sample is 2
inch in diameter and .5 inch thick. Thermocouples are not placed into
the sample but rather the temperatures measured in the Pyrex are
extrapolated to give the temperature at the top and bottom surfaces of
the sample material. The Pyrex disks also serve as the thermal
conductivity reference material.
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CLAMP
THERMOCOUPLE
GUARD
GRADIENT,
STACK
GRADIENT
->c
UPPER STACK
HEATER
I
TOP REFERENCE yf
SAMPLE I//
I
J
*
TEST/SAMPLE
' BOTTOM
REFERENCE
SAMPLE
HEAT FLOW
DIRECTION
I
LOWER STACK
HEATER
I
LIQUID 'COOLED
HEAT SINK
I
UPPER
GUARD
HEATER
V
J
LOWER
GUARD
HEATER
Figure C-l
SCHEMATIC DIAGRAM OF THE COMPARATIVE METHOD
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The stack is clamped with a reproducible load to insure intimate
contact between the components. In order to produce a linear flow of
heat down the stack and reduce the amount of heat that flows radially, a
guard tube is placed around the stack and the intervening space is filled
with insulating grains or powder. The temperature gradient in the guard
is matched to that in the stack to further reduce radial heat flow.
The comparative method is a steady state method of measuring thermal
conductivity. When equilibrium is reached the heat flux {analogous to
current flow) down the stack can be determined from the references. The
heat into the sample is given by
Q. = A (dT/dx1
in top top
and the heat out of the sample is given by
Qout = Ak „ (dT/dx)k ..
bottom bottom
where
A = thermal conductivity
dT/dx = temperature gradient
and top refers to the upper reference while bottom refers to the lower
reference. If the heat was confined to flow just down the stack, then
Q and Q would be equal. If Q. and Q are in reasonable
in out in out
agreement, the average heat flow is calculated from
Q = (Q. + Q J/2
in out
The sample thermal conductivity is then found from
A . = Q/(dT/dx) •
sample sample
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