EPA/530-SW-88-031H
FINAL
BEST DEMONSTRATED AVAILABLE TECHNOLOGY (BOAT)
BACKGROUND DOCUMENT FOR
K024
James R. Berlow, Chief
Treatment Technology Section
Lisa Jones
Project Manager
U.S. Environmental Protection Agency
Office of Solid Waste
401 M Street, S.W.
Washington, D.C. 20460
August 1988
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TABLE OF CONTENTS
Section Page
EXECUTIVE SUMMARY vi i
1. INTRODUCTION 1-1
1.1 Legal Background 1-1
1.1.1 Requirements Under HSWA 1-1
1.1.2 Schedule for Developing Restrictions 1-4
1.2 Summary of Promulgated BOAT Methodology 1-5
1.2.1 Waste Treatability Groups 1-7
1.2.2 Demonstrated and Available Treatment
Technologies 1-7
1.2.3 Collection of Performance Data 1-11
1.2.4 Hazardous Constituents Considered and Selected
for Regul at i on 1-17
1.2.5 Compliance with Performance Standards 1-30
1.2.6 Identification of BOAT 1-32
1.2.7 BOAT Treatment Standards for "Derived-From"
and "Mixed" Wastes 1-36
1.2.8 Transfer of Treatment Standards 1-40
1.3 Variance from the BOAT Treatment Standard 1-41
2. INDUSTRIES AFFECTED AND WASTE CHARACTERIZATION 2-1
2.1 Industry Affected and Process Description 2-1
2.2 Waste Characterization 2-2
3. APPLICABLE/DEMONSTRATED TREATMENT TECHNOLOGIES 3-1
3.1 Applicable Treatment Technology 3-1
3.2 Demonstrated Treatment Technology 3-1
3.2.1 Incineration 3-1
4. PERFORMANCE DATA BASE 4-1
5. IDENTIFICATION OF BEST DEMONSTRATED AVAILABLE
TECHNOLOGY (BOAT) 5-1
5.1 Data Screening 5-2
5.2 Data Accuracy 5-2
5.3 Analysis of Variance 5-3
5.4 Determination of BOAT 5-3
5.4.1 Nonwastewaters 5-4
5.4.2 Wastewaters 5-5
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TABLE OF CONTENTS (Continued)
Section Page
6. SELECTION OF REGULATED CONSTITUENTS 6-1
6.1 Identification of Major Constituents in the Untreated
Waste 6-2
6.2 Comparison of the Untreated and Treated Waste Data for
the Major Constituents 6-2
6.3 Evaluation of Waste Characteristics Affecting
Performance and Other Related Factors 6-4
6.4 Selection of Regulated Constituents 6-5
7. CALCULATION OF BOAT TREATMENT STANDARDS 7-1
7.1 Evaluation of the Performance Data 7-2
7.2 Calculation of Treatment Standards 7-2
8. ACKNOWLEDGMENTS 8-1
9. REFERENCES 9-1
APPENDIX A STATISTICAL METHODS A-l
APPENDIX B ANALYTICAL QA/QC B-l
APPENDIX C METHOD OF MEASUREMENT FOR THERMAL CONDUCTIVITY C-l
m
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LIST OF TABLES
Table Page
1-1 BOAT Constituent List 1-18
2-1 Major Constituent Composition for Untreated K024
Waste 2-4
2-2 BOAT Constituent Composition and Other Data 2-5
4-1 Rotary Kiln Incineration - EPA-Collected Total
Concentration Data for Untreated Waste 4-4
4-2 Rotary Kiln Incineration - EPA-Collected Total
Concentration Data for Scrubber Water 4-5
4-3 Rotary Kiln Incineration - EPA-Collected Total
Concentration Data for Ash 4-6
4-4 Total and TCLP Metals Analyses Data for Ash 4-7
4-5 Design Characteristics of the CRF Rotary Kiln 4-8
4-6 Incinerator Operating Parameters, Rotary Kiln 4-10
4-7 Incinerator Operating Parameters, Afterburner 4-11
4-8 Incinerator Operating Parameters, Scrubber System
(Acurex) 4-12
4-9 Incinerator Operating Parameters, Scrubber Exit
and Stack 4-13
6-1 Status of BOAT List Constituent Presence in
Untreated K024 Waste 6-6
6-2 Comparison of Major Constituents in Untreated and
Treated K024 Waste 6-13
7-1 Calculation of BOAT Treatment Standards for K024 7-4
A-l 95th Percentile Values for the F Distribution A-2
B-l Volatiles Spike Recovery (Accuracy) and Relative
Percent Difference (Precision) for Scrubber Sample . B-6
IV
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LIST OF TABLES (Continued)
Table Page
B-2 Volatiles Spike Recovery (Accuracy) and Relative
Percent Difference (Precision) for Tetraglyme
Extract of Feed Sampl e B-6
B-3 Volatiles Spike Recovery (Accuracy) and Relative
Percent Difference (Precision) for Tetraglyme
Extract of Ash Sample B-7
B-4 Volatiles Spike Recovery (Accuracy) and Relative
Percent Difference (Precision) for TCLP Extract
of Feed Sampl e B-7
B-5 Volatiles Spike Recovery (Accuracy) and Relative
Percent Difference (Precision) for TCLP Extract of
Ash Sample B-8
B-6 Semivolatiles Matrix Spike Extract Surrogate
Recoveries (%) B-9
B-7 Semivolatiles Laboratory Check Standard Extract
Surrogate Recoveries B-10
B-8 Semivolatiles Matrix Spike Recovery (Accuracy) and
Relative Difference (Precision) for Scrubber
Effluent Sample B-ll
B-9 Semivolatiles Matrix Spike Recovery (Accuracy) and
Relative Differences (Precision) for Feed Sample ... B-12
B-10 Semvolatiles Matrix Spike Recovery (Accuracy) and
Relative Differences (Precision) for Ash Sample B-13
B-ll Semivolatiles Matrix Spike Recovery (Accuracy) and
Relative Difference (Precision) for Feed TCLP
Extract B-14
B-12 Semivolatiles Matrix Spike Recovery (Accuracy) and
Relative Difference (Precision) for Ash TCLP
Extract B-15
B-13 Semivolatiles Laboratory Check Standard Results B-16
B-14 Duplicate Matrix Spike Data for Metals Analysis of
Ash Sample CK-34-3-B1 B-17
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LIST OF FIGURES
Figure Page
2-1 Schematic Diagram of the Generation of K024 and
Preparation of K024 for Test Burns 2-3
3-1 Liquid Injection Incineration 3-5
3-2 Rotary Kiln Incineration 3-7
3-3 Fluidized Bed Incinerator 3-8
3-4 Fixed Hearth Incinerator 3-9
4-1 U.S. EPA Rotary Kiln Configuration and Feed/Residuals
Sampling Points During the K024 Test 4-3
C-l Schematic Diagram of the Comparative Method C-2
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EXECUTIVE SUMMARY
BOAT Treatment Standards for K024
Pursuant to section 3004(m) of the Resource Conservation and Recovery
Act as enacted by the Hazardous and Solid Waste Amendments on November 8,
1984, the Environmental Protection Agency (EPA) is establishing best
demonstrated available technology (BOAT) treatment standards for the
listed waste identified in 40 CFR 261.32 as K024. Compliance with these
BOAT treatment standards is a prerequisite for placement of the waste in
units designated as land disposal units according to 40 CFR Part 268.
The effective date of these treatment standards is August 8, 1988.
This background document provides the Agency's rationale and
technical support for selecting the constituents to be regulated in K024
waste and for developing treatment standards for those regulated
constituents. The document also provides waste characterization and
treatment information that serves as a basis for determining whether
variances may be warranted. EPA may grant a treatment variance in cases
where the Agency determines that the waste in question is more difficult
to treat than the wastes upon which the BOAT treatment standards are
based.
The introductory section, which appears verbatim in all the First
Third background documents, summarizes the Agency's legal authority and
promulgated methodology for establishing treatment standards and
discusses the petition process necessary for requesting a variance from
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the treatment standards. The remainder of the document presents
waste-specific information—the number and locations of facilities
affected by the land disposal restrictions for K024 waste, the
waste-generating process, waste characterization data, the technologies
used to treat the waste (or similar wastes), and available performance
data, including data on which the treatment standards are based. The
document also explains EPA's determination of BOAT, selection of
constituents to be regulated, and calculation of treatment standards.
It is EPA's understanding that only one facility produces phthalic
anhydride, using naphthalene as a feedstock.
The Agency is regulating one organic constituent in both
nonwastewater and wastewater forms of K024. (For the purpose of
determining the applicability of the treatment standards, wastewaters are
defined as wastes containing less than 1 percent (weight basis) total
suspended solids* and less than 1 percent (weight basis) total organic
carbon (TOC). Waste not meeting this definition must comply with the
treatment standards for nonwastewaters.)
A treatment standard is established for one organic constituent,
phthalic acid, which the Agency believes is an indicator of effective
treatment for the BOAT hazardous constituent phthalic anhydride.
*The term "total suspended solids" (TSS) clarifies EPA's previously used
terminology of "total solids" and "filterable solids." Specifically,
total suspended solids is measured by method 209C. (Total Suspended
Solids Dried at 103-205°C) in Standard Methods for the Examination
of Water and Wastewater. 16th Edition.
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Phthalic acid is chosen as the surrogate constituent to be regulated
because phthalic anhydride cannot be easily analyzed. (During chemical
analysis, phthalic anhydride undergoes hydrolysis to produce phthalic
acid.) Phthalic acid is chosen as a surrogate treatment evaluation
parameter since its precursor, phthalic anhydride, which is a BOAT
constituent, is present at treatable concentrations in the waste. This
standard is for the total concentration of phthalic acid measured in K024
waste.
BOAT standards for wastewaters and nonwastewaters have been
established based on actual performance data using rotary kiln
incineration.
The following table presents the treatment standards for K024
wastewater and nonwastewater. The treatment standards are established
based on total concentration analyses conducted on the total (untreated)
waste, ash residues, and scrubber water generated during rotary kiln
incineration of K024. If the concentrations of the regulated
constituents in K024 waste, as generated, are lower than or equal to the
proposed BOAT treatment standards, then treatment is not necessary as a
prerequisite to land disposal.
Testing procedures are specifically identified in Appendix B of this
background document.
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BOAT Treatment Standards for K024
Constituent
Maximum for any single grab sample
Nonwastewater
Total
concentration
TCLP leachate
concentration
(mg/1)
Wastewater
Total
concentration
Phthalic acid3
28
NA
0.54
NA = Not applicable.
aThis constituent is regulated as a surrogate for phthalic anhydride,
which cannot be easily analyzed because it is hydrolyzed and converted
to phthalic acid during chemical analysis.
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1. INTRODUCTION
This section of the background document presents a summary of the
legal authority pursuant to which the best demonstrated available
technology (BOAT) treatment standards were developed, a summary of EPA's
promulgated methodology for developing the BOAT treatment standards, and,
finally, a discussion of the petition process that should be followed to
request a variance from the BOAT treatment standards.
1.1 Legal Background
1.1.1 Requirements Under HSWA
The Hazardous and Solid Waste Amendments of 1984 (HSWA), which were
enacted on November 8, 1984, and which amended the Resource Conservation
and Recovery Act of 1976 (RCRA), impose substantial new responsibilities
on those who handle hazardous waste. In particular, the amendments
require the Agency to promulgate regulations that restrict the land
disposal of untreated hazardous wastes. In its enactment of HSWA,
Congress stated explicitly that "reliance on land disposal should be
minimized or eliminated, and land disposal, particularly landfill and
surface impoundment, should be the least favored method for managing
hazardous wastes" (RCRA section 1002(b)(7), 42 U.S.C. 6901(b)(7)).
One part of the amendments specifies dates on which particular groups
of untreated hazardous wastes will be prohibited from land disposal
unless "it has been demonstrated to the Administrator, to a reasonable
degree of certainty, that there will be no migration of hazardous
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constituents from the disposal unit or injection zone for as long as the
wastes remain hazardous" (RCRA section 3004(d)(l), (e)(l), (g)(5),
42 U.S.C. 6924 (d)(l), (e)(l), (g)(5)).
For the purpose of the restrictions, HSWA defines land disposal "to
include, but not be limited to, any placement of ... hazardous waste in
a landfill, surface impoundment, waste pile, injection well, land
treatment facility, salt dome formation, salt bed formation, or
underground mine or cave" (RCRA section 3004(k), 42 U.S.C. 6924(k)).
Although HSWA defines land disposal to include injection wells, such
disposal of solvents, dioxins, and certain other wastes, known as the
California List wastes, is covered on a separate schedule (RCRA section
3004(f)(2), 42 U.S.C. 6924 (f)(2)). This schedule requires that EPA
develop land disposal restrictions for deep well injection by
August 8, 1988.
The amendments also require the Agency to set "levels or methods of
treatment, if any, which substantially diminish the toxicity of the waste
or substantially reduce the likelihood of migration of hazardous
constituents from the waste so that short-term and long-term threats to
human health and the environment are minimized" (RCRA section 3004(m)(l),
42 U.S.C. 6924 (m)(l)). Wastes that satisfy such levels or methods of
treatment established by EPA, i.e., treatment standards, are not
prohibited from being land disposed.
In setting treatment standards for listed or characteristic wastes,
EPA may establish different standards for particular wastes within a
single waste code with differing treatability characteristics. One such
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characteristic is the physical form of the waste. This frequently leads
to different standards for wastewaters and nonwastewaters.
Alternatively, EPA can establish a treatment standard that is applicable
to more than one waste code when, in EPA's judgment, a particular
constituent present in the wastes can be treated to the same
concentration in all the wastes.
In those instances where a generator can demonstrate that the
standard promulgated for the generator's waste cannot be achieved, the
amendments allow the Agency to grant a variance from a treatment standard
by revising the treatment standard for that particular waste through
rulemaking procedures. (A further discussion of treatment variances is
provided in Section 1.3.)
The land disposal restrictions are effective when promulgated unless
the Administrator grants a national variance and establishes a different
date (not to exceed 2 years beyond the statutory deadline) based on "the
earliest date on which adequate alternative treatment, recovery, or
disposal capacity which protects human health and the environment will be
available" (RCRA section 3004(h)(2), 42 U.S.C. 6924 (h)(2)).
If EPA fails to set treatment standards by the statutory deadline for
any hazardous waste in the First Third or Second Third waste groups (see
Section 1.1.2), the waste may not be disposed in a landfill or surface
impoundment unless the facility is in compliance with the minimum
technological requirements specified in section 3004(o) of RCRA. In
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addition, prior to disposal, the generator must certify to the
Administrator that the availability of treatment capacity has been
investigated, and it has been determined that disposal in a landfill or
surface impoundment is the only practical alternative to treatment
currently available to the generator. This restriction on the use of
landfills and surface impoundments applies until EPA sets treatment
standards for the waste or until May 8, 1990, whichever is sooner. If
the Agency fails to set treatment standards for any ranked hazardous
waste by May 8, 1990, the waste is automatically prohibited from land
disposal unless the waste is placed in a land disposal unit that is the
subject of a successful "no migration" demonstration (RCRA section
3004(g), 42 U.S.C. 6924(g)). "No migration" demonstrations are based on
case-specific petitions that show there will be no migration of hazardous
constituents from the unit for as long as the waste remains hazardous.
1.1.2 Schedule for Developing Restrictions
Under section 3004(g) of RCRA, EPA was required to establish a
schedule for developing treatment standards for all wastes that the
Agency had listed as hazardous by November 8, 1984. Section 3004(g)
required that this schedule consider the intrinsic hazards and volumes
associated with each of these wastes. The statute required EPA to set
treatment standards according to the following schedule:
1. Solvent and dioxin wastes by November 8, 1986;
2. The "California List" wastes by July 8, 1987;
3. At least one-third of all listed hazardous wastes by
August 8, 1988 (First Third);
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4. At least two-thirds of all listed hazardous wastes by
June 8, 1989 (Second Third); and
5. All remaining listed hazardous wastes and all hazardous wastes
identified as of November 8, 1984, by one or more of the
characteristics defined in 40 CFR Part 261 by May 8, 1990 (Third
Third).
The statute specifically identified the solvent wastes as those
covered under waste codes F001, F002, F003, F004, and F005; it identified
the dioxin-containing hazardous wastes as those covered under waste codes
F020, F021, F022, and F023.
Wastes collectively known as the California List wastes, defined
under section 3004(d) of HSWA, are liquid hazardous wastes containing
metals, free cyanides, PCBs, corrosives (i.e., a pH less than or equal to
2.0), and any liquid or nonliquid hazardous waste containing halogenated
organic compounds (HOCs) above 0.1 percent by weight. Rules for the
California List were proposed on December 11, 1986, and final rules for
PCBs, corrosives, and HOC-containing wastes were established
August 12, 1987. In that rule, EPA elected not to establish treatment
standards for metals. Therefore, the statutory limits became effective.
On May 28, 1986, EPA published a final rule (51 FR 19300) that
delineated the specific waste codes that would be addressed by the First
Third, Second Third, and Third Third land disposal restriction rules.
This schedule is incorporated into 40 CFR 268.10, 268.11, and 268.12.
1.2 Summary of Promulgated BOAT Methodology
In a November 7, 1986, rulemaking, EPA promulgated a technology-based
approach to establishing treatment standards under section 3JD04(m).
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Congress indicated in the legislative history accompanying the HSWA that
"[t]he requisite levels of [sic] methods of treatment established by the
Agency should be the best that has been demonstrated to be achievable,"
noting that the intent is "to require utilization of available
technology" and not a "process which contemplates technology-forcing
standards" (Vol. 130 Cong. Rec. S9178 (daily ed., July 25, 1984)). EPA
has interpreted this legislative history as suggesting that Congress
considered the requirement under section 3004(m) to be met by application
of the best demonstrated and achievable (i.e., available) technology
prior to land disposal of wastes or treatment residuals. Accordingly,
EPA's treatment standards are generally based on the performance of the
best demonstrated available technology (BOAT) identified for treatment of
the hazardous constituents. This approach involves the identification of
potential treatment systems, the determination of whether they are
demonstrated and available, and the collection of treatment data from
well-designed and well-operated systems.
The treatment standards, according to the statute, can represent
levels or methods of treatment, if any, that substantially diminish the
toxicity of the waste or substantially reduce the likelihood of migration
of hazardous constituents. Wherever possible, the Agency prefers to
establish BOAT treatment standards as "levels" of treatment
(i.e., performance standards), rather than to require the use of specific
treatment "methods." EPA believes that concentration-based treatment
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levels offer the regulated community greater flexibility to develop and
implement compliance strategies, as well as an incentive to develop
innovative technologies.
1.2.1 Waste Treatability Group
In developing the treatment standards, EPA first characterizes the
waste(s). As necessary, EPA may establish treatability groups for wastes
having similar physical and chemical properties. That is, if EPA
believes that hazardous constituents in wastes represented by different
waste codes could be treated to similar concentrations using identical
technologies, the Agency combines the wastes into one treatability
group. EPA generally considers wastes to be similar when they are both
generated from the same industry and from similar processing stages. In
addition, EPA may combine two or more separate wastes into the same
treatability group when data are available showing that the waste
characteristics affecting performance are similar or that one of the
wastes in the group, the waste from which treatment standards are to be
developed, is expected to be most difficult to treat.
Once the treatability groups have been established, EPA collects and
analyzes data on identified technologies used to treat the wastes in each
treatability group. The technologies evaluated must be demonstrated on
the waste or a similar waste and must be available for use.
1.2.2 Demonstrated and Available Treatment Technologies
Consistent with legislative history, EPA considers demonstrated
technologies to be those that are currently used on a full-scale basis to
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treat the waste of interest or a waste judged to be similar (see 51 FR
40588, November 7, 1986). EPA also will consider as demonstrated
treatment those technologies used to separate or otherwise process
chemicals and other materials on a full-scale basis. Some of these
technologies clearly are applicable to waste treatment, since the wastes
are similar to raw materials processed in industrial applications.
For most of the waste treatability groups for which EPA will.
promulgate treatment standards, EPA will identify demonstrated
technologies either through review of literature related to current waste
treatment practices or on the basis of information provided by specific
facilities currently treating the waste or similar wastes.
In cases where the Agency does not identify any facilities treating
wastes represented by a particular waste treatability group, EPA may
transfer a finding of demonstrated treatment. To do this, EPA will
compare the parameters affecting treatment selection for the waste
treatability group of interest to other wastes for which demonstrated
technologies already have been determined. (The parameters affecting
treatment selection and their use for this waste are described in
Section 3.2 of this document.) If the parameters affecting treatment
selection are similar, then the Agency will consider the treatment
technology also to be demonstrated for the waste of interest. For
example, EPA considers rotary kiln incineration to be a demonstrated
technology for many waste codes containing hazardous organic
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constituents, high total organic content, and high filterable solids
content, regardless of whether any facility is currently treating these
wastes. The basis for this determination is data found in literature and
data generated by EPA confirming the use of rotary kiln incineration on
wastes having the above characteristics.
If no full-scale treatment or recovery operations are identified for
a waste or wastes with similar physical or chemical characteristics that
affect treatment selection, the Agency will be unable to identify any
demonstrated treatment technologies for the waste, and, accordingly, the
waste will be prohibited from land disposal (unless handled in accordance
with the exemption and variance provisions of the rule). The Agency is,
however, committed to establishing treatment standards as soon as new or
improved treatment processes are demonstrated (and available).
Operations only available at research facilities, pilot- and bench-
scale operations, will not be considered in identifying demonstrated
treatment technologies for a waste. Nevertheless, EPA may use data
generated at research facilities in assessing the performance of
demonstrated technologies.
As discussed earlier, Congress intended that technologies used to
establish treatment standards under section 3004(m) be not only
"demonstrated," but also "available." To decide whether demonstrated
technologies may be considered "available," the Agency determines whether
they (1) are commercially available and (2) substantially diminish the
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toxicity of the waste or substantially reduce the likelihood of migration
of hazardous constituents from the waste. These criteria are discussed
below.
1. Commercially available treatment. If the demonstrated treatment
technology is a proprietary or patented process that is not
generally available, EPA will not consider the technology in its
determination of the treatment standards. EPA will consider
proprietary or patented processes available if it determines
that the treatment method can be purchased or licensed from the
proprietor or is a commercially available treatment. The
services of the commercial facility offering this technology
often can be purchased even if the technology itself cannot be
purchased.
2. Substantial treatment. To be considered "available," a
demonstrated treatment technology must "substantially diminish
the toxicity" of the waste or "substantially reduce the
likelihood of migration of hazardous constituents" from the
waste in accordance with section 3004(m). By requiring that
substantial treatment be achieved in order to set a treatment
standard, the statute ensures that all wastes are adequately
treated before being placed in or on the land and ensures that
the Agency does not require a treatment method that provides
little or no environmental benefit. Treatment will always be
deemed, substantial if it results in nondetectable levels of the
hazardous constituents of concern (provided the nondetectable
levels are low relative to the concentrations in the untreated
waste). If nondetectable levels are not achieved, then a
determination of substantial treatment will be made on a
case-by-case basis. This approach is necessary because of the
difficulty of establishing a meaningful guideline that can be
applied broadly to the many wastes and technologies to be
considered. EPA will consider the following factors in an
effort to evaluate whether a technology provides substantial
treatment on a case-by-case basis:
• Number and types of constituents treated;
• Performance (concentration of the constituents in the
treatment residuals); and
• Percent of constituents removed.
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EPA will only set treatment standards based on a technology that
meets both availability criteria. Thus, the decision to classify a
technology as "unavailable" will have a direct impact on the treatment
standard. If the best demonstrated technology is unavailable, the
treatment standards will be based on the next best demonstrated treatment
technology determined to be available. To the extent that the resulting
treatment standards are less stringent, greater concentrations of
hazardous constituents in the treatment residuals could be placed in land
disposal units.
There also may be circumstances in which EPA concludes that for a
given waste none of the demonstrated treatment technologies are
"available" for purposes of establishing the 3004(m) treatment
performance standards. Subsequently, these wastes will be prohibited
from continued placement in or on the land unless managed in accordance
with applicable exemptions and variance provisions. The Agency is,
however, committed to establishing new treatment standards as soon as new
or improved treatment processes become available.
1.2.3 Collection of Performance Data
Performance data on the demonstrated available technologies are
evaluated by the Agency to determine whether the data are representative
of well-designed and well-operated treatment systems. Only data from
well-designed and well-operated systems are considered in determining
BOAT. The data evaluation includes data already collected directly by
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EPA and/or data provided by industry. In those instances where
additional data are needed to supplement existing information, EPA
collects additional data through a sampling and analysis program. The
principal elements of this data collection program are: (1) the
identification of facilities for site visits, (2) the engineering site
visit, (3) the sampling and analysis plan, (4) the sampling visit, and
(5) the onsite engineering report.
(1) Identification of facilities for site visits. To identify
facilities that generate and/or treat the waste of concern, EPA uses a
number of information sources. These include Stanford Research
Institute's Directory of Chemical Producers; EPA's Hazardous Waste Data
Management System (HWDMS); the 1986 Treatment, Storage, Disposal Facility
(TSDF) National Screening Survey; and EPA's Industry Studies Data Base.
In addition, EPA contacts trade associations to inform them that the
Agency is considering visits to facilities in their industry and to
solicit their assistance in identifying facilities for EPA to consider in
its treatment sampling program.
After identifying facilities that treat the waste, EPA uses this
hierarchy to select sites for engineering visits: (1) generators treating
single wastes on site; (2) generators treating multiple wastes together
on site; (3) commercial treatment, storage, and disposal facilities
(TSDFs); and (4) EPA in-house treatment. This hierarchy is based on two
concepts: (1) to the extent possible, EPA should develop treatment
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standards from data produced by treatment facilities handling only a
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 technologi.es using
full-scale treatment systems. If performance data from properly designed
and operated full-scale systems treating a particular waste or a waste
judged to be similar are not available, EPA may use data from research
facility operations. Whenever research facility data are used, EPA will
explain in the preamble and background document why such data were used
and will request comments on the use of such data.
Although EPA's data bases provide information on treatment for
individual wastes, the data bases rarely provide data that support the
selection of one facility for sampling over another. In cases where
several treatment sites appear to fall into the same level of the
hierarchy, EPA selects sites for visits strictly on the basis of which
facility could most expeditiously be visited and later sampled if
justified by the engineering visit.
(2) Engineering site visit. Once a treatment facility has been
selected, an engineering site visit is made to confirm that a candidate
for sampling meets EPA's criteria for a well-designed facility and to
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ensure that the necessary sampling points can be accessed to determine
operating parameters and treatment effectiveness. During the visit, EPA
also confirms that the facility appears to be well operated, although the
actual operation of the treatment system during sampling is the basis for
EPA's decisions regarding proper operation of the treatment unit. In
general, the Agency considers a well-designed facility to be one that
contains the unit operations necessary to treat the various hazardous
constituents of the waste, as well as to control other nonhazardous
materials in the waste that may affect treatment performance.
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In addition to ensuring that a system is reasonably well designed,
the engineering visit examines whether the facility has a way to measure
the operating parameters that affect performance of the treatment system
during the waste treatment period. For example, EPA may choose not to
sample a treatment system that operates in a continuous mode, for which
an important operating parameter cannot be continuously recorded. In
such systems, instrumentation is important in determining whether the
treatment system is operating at design values during the waste treatment
period.
(3) Sampling and analysis plan. If after the engineering site visit
the Agency decides to sample a particular plant, the Agency will then
develop a site-specific sampling and analysis plan (SAP) according to the
Generic Quality Assurance Pro.iect Plan for the Land Disposal Restrictions
Program ("BOAT"). EPA/530-SW-87-011. In brief, the SAP discusses where
the Agency plans to sample, how the samples will be taken, the frequency
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of sampling, the constituents to be analyzed and the method of analysis,
operational parameters to be obtained, and specific laboratory quality
control checks on the analytical results.
The Agency will generally produce a draft of the site-specific SAP
within 2 to 3 weeks of the engineering visit. The draft of the SAP is
then sent to the plant for review and comment. With few exceptions, the
draft SAP should be a confirmation of data collection activities
discussed with the plant personnel during the engineering site visit.
EPA encourages plant personnel to recommend any modifications to the SAP
that they believe will improve the quality of the data.
It is important to note that sampling of a plant by EPA does not mean
that the data will be used in the development of BOAT treatment
standards. EPA's final decision on whether to use data from a sampled
plant depends on the actual analysis of the waste being treated and on
the operating conditions at the time of sampling. Although EPA would not
plan to sample a facility that was not ostensibly well designed and well
operated, there is no way to ensure that at the time of the sampling the
facility will not experience operating problems. Additionally, EPA
statistically compares its test data to suitable industry-provided data,
where available, in its determination of what data to use in developing
treatment standards. The methodology for comparing data is presented
later in this section.
1-15
-------
(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 Pro.iect Plan for the Land
Disposal Restrictions Program ("BOAT"), which delineates all of the
quality control and quality assurance measures associated with sampling
and analysis. Quality assurance and quality control procedures are
summarized in Section 1.2.6 of this document.)
(4) Sampling visit. The purpose of the sampling visit is to collect
samples that characterize the performance of the treatment system and to
document the operating conditions that existed during the waste treatment
period. At a minimum, the Agency attempts to collect sufficient samples
of the untreated waste and solid and liquid treatment residuals so that
variability in the treatment process can be accounted for in the
development of the treatment standards. To the extent practicable, and
within safety constraints, EPA or its contractors collect all samples and
ensure that chain-of-custody procedures are conducted so that the
integrity of the data is maintained.
In general, the samples collected during the sampling visit will have
already been specified in the SAP. In some instances, however, EPA will
not be able to collect all planned samples because of changes in the
facility operation or plant upsets; EPA will explain any such deviations
from the SAP in its follow-up onsite engineering report.
1-16
-------
(5) Onsite engineering report. EPA summarizes all its data
collection activities and associated analytical results for testing at a
facility in a report referred to as the onsite engineering report (OER).
This report characterizes the waste(s) treated, the treated residual
concentrations, the design and operating data, and all analytical results
including methods used and accuracy results. This report also describes
any deviations from EPA's suggested analytical methods for hazardous
wastes that appear in Test Methods for Evaluating Solid Waste. SW-846,
Third Edition, November 1986.
After the OER is completed, the report is submitted to the waste
generator and/or treater for review. This review provides a final
opportunity for claiming any information contained in the report as
confidential. Following the review and incorporation of comments, as
appropriate, the report is made available to the public with the
exception of any material claimed as confidential.
1.2.4 Hazardous Constituents Considered and Selected for Regulation
(1) Development of BOAT list. The list of hazardous constituents
within the waste codes that are targeted for treatment is referred to by
the Agency as the BOAT constituent list. This list, provided as
Table 1-1, is derived from the constituents presented in 40 CFR Part 261,
Appendices VII and VIII, as well as several ignitable constituents used
as the basis of listing wastes as F003 and F005. These sources provide a
1-17
-------
1521g
Table 1-1 BOAT Constituent List
BOAT
reference
no.
222.
I.
2.
3.
4.
5.
6.
223.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
?3.
24.
25.
26.
27.
28.
29.
224.
225.
226.
30.
227.
31.
214.
32.
33.
228.
34.
Constituent
Volatile orqanics
Acetone
Acetonitrile
Aero le in
Aery Ion itri le
Benzene
Brocnodichlorome thane
Bromomethane
n-Butyl alcohol
Carbon tetrachloride
Carbon disulfide
Chlorobenzene
2-Chloro-1.3-butadiene
Ch lorod ibromome thane
Chloroethane
2-Chloroethyl vinyl ether
Chloroform
Chloromethane
3-Chloropropene
l,2-Oibromo-3-chloropropane
1.2-Dibromoethane
Dibromomethane
trans-1 ,4-Oichloro-2-butene
Oichlorodif luoromethane
1,1-Dichloroethane
1 ,2-Oichloroethane
1 , 1-Dich loroethy lene
trans-1, 2-0 ichloroethene
1 . 2-0 ich loropropane
trans-1, 3-0 ichloropropene
cis-1.3-Dich loropropene
1.4-Dioxane
2-Ethoxyethanol
Ethyl acetate
Ethyl benzene
Ethyl cyanide
Ethyl ether
Ethyl metnacry late
E thy lene oxide
lodomethane
Isobutyl alcohol
Methanol
Methyl ethyl ketone
CAS no.
67-64-1
75-05-8
107-02-8
107-13-1
71-43-2
75-27-4
74-83-9
71-36-3
56-23-5
75-15-0
108-90-7
126-99-8
124-48-1
75-00-3
110-75 8
67-66-3
74-87-3
107-05-1
96-12-8
106-93-4
74-95-3
110-57-6
75-71-8
75-34-3
107-06-2
75-35-4
156-60-5
78-87-5
10061-02-6
10061-01-5
123-91-1
110-80-5
141-78-6
100-41-4
107-12-0
60-29-7
97-63-2
75-21-8
74-88-4
78-83-1
67-56-1
78-93-3
1-18
-------
1521g
Table 1-1 (Continued)
BOAT
reference
no.
229.
35.
37.
38.
230.
39.
40.
41.
42.
43.
44.
45.
46.
47.
48.
49.
231.
50.
215.
216.
217.
51.
52.
53.
54.
55.
56.
57.
58.
59.
218.
60.
61.
62.
63.
64.
65.
66.
Constituent
Volatile organ ics (continued)
Methyl isobutyl ketone
Methyl methacrylate
Methacrylonitn le
Methylene chloride
2-Nitropropane
Pyridine
1,1. 1 ,2-Tetrach loroethane
1,1,2. 2- Tetrach loroethane
Tetrach loroethene
Toluene
Tnbromomethane
1. 1,1-Trich loroethane
1,1.2-Trich loroethane
Trich loroethene
Inch loromonof luoromethane
1 ,2.3-frichloropropdne
l,1.2-Trichloro-l,2,2-trif luoro-
ethane
Vinyl chloride
1.2-Xylene
1 ,3-Xylene
1.4 Xylene
Semivolat i le organ ics
Acenaphthalene
Acenaphthene
Acetophenone
2-Acetylaminof luorene
4-Aminobipheny 1
Aniline
Anthracene
Aram He
Benz(a)anthracene
Benzal chloride
Benzenethiol
Deleted
Benzo(a)pyrene
8enzo( b ) f luoranthene
Benzo(ghi Ipery lene
Benzo(k)f luoranthene
p-Benzoquinone
CAS no.
108-10-1
80-62-6
126-98-7
75-09-2
79-46-9
110-86-1
630-20-6
79-34-6
127-18-4
108-88-3
75-25-2
71-55-6
79-00-5
79-01-6
75-69-4
96-18-4
76-13-1
75-01-4
97-47-6
108-38-3
106-44-5
208-96-8
83-32-9
96-86-2
53-96-3
92-67-1
62-53-3
120-12-7
140-57-8
56-55-3
98-87-3
108-98-5
50-32-8
205-99-2
191-24-2
207-08-9
106-51-4
1-19
-------
1521g
Table 1-1 (Continued)
BOA!
reference
no.
67.
68.
69.
70.
71.
72.
73.
74.
75.
76.
77.
78.
79.
80.
81.
82.
232.
83.
84.
85.
86.
87.
88.
89.
90.
91.
92.
93.
94.
95.
96.
97.
98.
99.
100.
101.
102.
103.
104.
105.
106.
219.
Constituent
Semivolatile organ ics (continued)
B i s ( 2 -ch loroethoxy ) me thane
Bis(2-chloroethyl)ether
Bis(2-chloroisopropyl) ether
Bis(2-ethylhexyl)phthalate
4-Bromophenyl phenyl ether
Butyl benzyl phthalate
2-sec -Buty 1 -4 . 6-d i n i tropheno 1
p-Chloroani line
Chlorobenzi late
p-Ch loro-m-creso 1
2-Ch loronaphtha lene
2-Chlorophenol
3-Chloropropionitri le
Chrysene
ortho-Cresol
para-Cresol
Cyclohexanone
0 1 ben/ ( a. h) anthracene
0 i benzo ( a . e ) py rene
Dibenzo(a, i)pyrene
m D ich lorobenzene
o-O ich lorobenzene
p-D ich lorobenzene
3 ,3 ' -0 ich lorobcru id ine
2 . 4 - D i ch loropheno 1
2.6-Dichlorophenol
Diethyl phthalate
3 . 3 ' -0 imethoxybenz id ine
p • D imethy lam i noazobenzene
3,3'-Oimethylbenzidine
2. 4-D imethy 1 phenol
Dimethyl phthalate
Di-n-butyl phthalate
1.4-Dinitrobenzene
4,6-Dinitro-o-cresol
2. 4-0 in i tropheno 1
2.4-Oinitrotoluene
2.6-Dinitrotoluene
Di-n-octyl phthalate
Di-n-propylnitrosamine
Oiphenylamine
0 i pheny 1 n i t rosam i ne
CAS no.
111-91-1
111-44-4
39638-32-9
117-81-7
101-55-3
85-68-7
88-8S-7
106-47-8
510-15-6
59-50-7
91-58-7
95-57-8
542-76-7
218-01-9
95-48-7
106-44-5
108-94 1
53-70-3
192-65-4
189-55-9
541-73-1
95-50-1
106-46-7
91-94-1
120-83 2
87-65-0
84-66-2
119-90-4
60-11-7
119-93-7
105-67-9
131-11-3
84-74-2
100-25-4
534-52-1
51-28-5
121-14-2
606-20-2
117-84-0
621-64-7
122-39-4
86-30-6
1-20
-------
I521g
Table 1-1 (Continued)
BOAT
reference
no.
107.
108.
109.
110.
111.
113.
113.
114.
115.
116.
117.
118,
119.
120.
36.
121.
122.
123.
124.
125.
126.
127.
128.
129.
130.
131.
132.
133.
134.
135.
136.
137.
138.
139.
140.
141.
142.
220.
143.
144.
145.
146.
Constituent
Semivolat i le organ ics (continued)
1 . 2 - D 1 pheny 1 hydraz i ne
Fluoranthene
F luorene
Hexach lorobenzene
Hexach lorobutad iene
Hexach lorocyc lopentadiene
Hexach loroethane
Hexach lorophene
Hexach loropropene
Indeno(1.2.3-cd)pyrene
Isosafrole
Methapyr i Iene
3-Methylcholanthrene
4.4'-Methylenebis
{2-chloroani line)
Methyl methanesulfonate
Naphthalene '
1.4-Napht hoqu i none
1-Naphthy lamine
2-Naphthylamine
p-N it roan i line
Nitrobenzene
4-Nitrophenol
N-Nitrosodi-n-buty lamine
N-Nitrosodiethy lamine
N-Nitrosodimethy lamine
N-N i trosomethy lethy lam ine
N-Nitrosomorphol ine
N-Nitrosopiperidine
N-N i trosopyrro 1 id ine
5-Nitro-o-loluidine
Pentach lorobcruene
Pen tach loroethane
Pentach loron i t robenzene
Pen tach lorophcno 1
Phenacetin
Phenanthrene
Phenol
Phtha 1 ic anhydr ide
2-Picoline
Pronamide
Pyrene
Resorcinol
CAS no.
122-66-7
206-44-0
86-73-7
118-74-1
87-68-3
77-47-4
67-72-1
70-30-4
1888-71-7
193-39-5
120-58-1
91-80-5
56-49-5
101-14-4
66-27-3
91-20-3
130-15-4
134-32-/
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
oj-44-9
109-06-8
23950-58-5
129-00-0
108-46-3
1-21
-------
1521q
Table 1-1 (Continued)
BOAT
reference
no.
147.
148.
149.
150.
151.
152.
153.
154.
155.
1S6.
157.
158.
159.
221.
160.
161.
162.
163.
164.
165.
166.
16/.
168.
169.
170.
1/1.
172.
1/3.
174.
175.
Constituent
Semivolati 1e organ ics (continued)
Safrole
1,2,4.5- Tetrach lorobenzene
2,3,4, 6-Tet rach loropheno 1
1,2.4-Trichlorobenzene
2. 4, 5-Trich loropheno 1
2 , 4 , 6-Tr ich loropheno 1
Tris(2,3-dibromopropyl)
phosphate
Metals
Antimony
Arsenic
Barium
Beryl 1 ium
Cadmium
Chromium (total)
Chromium (hexava lent)
Copper
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Inorganics other than metals
Cyanide
fluoride
Sulfide
Orqanochlorine pesticides
Aldrin
a Ipha-BHC
beta-BHC
delta-BHC
CAS no.
94-59-7
95-94-3
58-90-2
120-82-1
95-95-4
88-06-2
126-72-7
7440-36-0
7440-38-2
7440-39-3
7440-41-7
7440-43-9
7440-47-3
-
7440-50-8
7439-92-1
7439-97-6
7440-02-0
7782-49-2
7440-22 4
7440-28-0
7440-62-2
7440-66-6
57-12-5
16964-48-8
8496-25-8
309-00-2
319-84-6
319-85-7
319-86-8
1-22
-------
1521g
Table 1-1 (Continued)
BOAT
reference
no.
176.
177.
178.
179.
180.
181.
182.
183.
184.
185.
186.
187.
188.
189.
190.
191.
192.
193.
194.
195.
196.
197.
198.
199.
200.
201.
202.
203.
204.
205.
206.
Constituent
Orqanochlorine pesticides (continued)
ganma-BHC
Chlordane
ODD
ODE
DOT
Oieldr in
Endosulfan I
Endosulfan II
Endrin
Endrin aldehyde
Heptachlor
Heptachlor epoxide
Isodrin
Kepone
Methoxyclor
Toxaphene
Phenoxyacet ic acid herbicides
2,4-Oichlorophenoxyacet ic acid
S i Ivex
2.4.5-T
Orqanophosphorous insecticides
Oisulfoton
Famphur
Methyl pa rath ion
Parathion
Phorate
PCBs
Aroclor 1016
Aroclor 1221
Aroclor 1232
Aroclor 1242
Aroclor 1248
Aroclor 1254
Aroclor 1260
CAS no.
58-89-9
57-74-9
72-54-8
72-55-9
50-29-3
60-57-1
939-98-8
33213-6-5
72-20-8
7421-93-4
76-44-8
1024-57-3
465-73-6
143-50-0
72-43-5
8001-35-2
94-75-7
93-72-1
93-76-5
298-04-4
52-85-7
298-00-0
56-38-2
298-02-2
12674-11-2
11104-28-2
11141-16-5
53469-21-9
12672-29-6
11097-69-1
11096-82-5
1-23
-------
1521g
Table 1-1 (Continued)
BOAT
reference Constituent CAS no.
no.
Dioxins and furans
207. Hexachlorodibenzo-p-dioxins
208. Hexachlorodibenzofurans
209. Pentachlorodibenzo-p-dioxins
210. Pentachlorodibenzofurans
211. Tetrachlorodibenzo-p-dioxins
212. Tetrachlorodibenzofurans
213. 2.3.7.8-Tetrachlorodibenzo-p-dioxin 1746-01-6
1-24
-------
comprehensive list of hazardous constituents specifically regulated under
RCRA. The BOAT list consists of those constituents that can be analyzed
.',
using methods published in SW-846, Third Edition.
The initial BOAT constituent list was published in EPA's Generic
Quality Assurance Project Plan for Land Disposal Restrictions Program
("BOAT") in March 1987. Additional constituents are added to the BOAT
constituent list as more key constituents are identified for specific
waste codes or as new analytical methods are developed for hazardous
constituents. For example, since the list was published in March 1987,
18 additional constituents (hexavalent chromium, xylenes (all three
isomers), benzal chloride, phthalic anhydride, ethylene oxide, acetone,
n-butyl alcohol, 2-ethoxyethanol, ethyl acetate, ethyl benzene, ethyl
ether, methanol, methyl isobutyl ketone, 2-nitropropane,
1,l,2-trichloro-l,2,2-trifluoroethane, and cyclohexanone) have been added
to the list.
Chemicals are listed in Appendix VIII if they are shown in scientific
studies to have toxic, carcinogenic, mutagenic, or teratogenic effects on
humans or other life-forms, and they include such substances as those
identified by the Agency's Carcinogen Assessment Group as being
carcinogenic. A waste can be listed as a toxic waste on the basis that
it contains a constituent in Appendix VIII.
Although Appendix VII, Appendix VIII, and the F003 and F005
ignitables provide a comprehensive list of RCRA-regulated hazardous
constituents, not all of the constituents can be analyzed in a complex
1-25
-------
waste matrix. Therefore, constituents that could not be readily analyzed
in an unknown waste matrix were not included on the initial BOAT
constituent list. As mentioned above, however, the BOAT constituent list
is a continuously growing list that does not preclude the addition of new
constituents when analytical methods are developed.
There are five major reasons that constituents were not included on
the BOAT constituent list:
1. Constituents are unstable. Based on their chemical structure,
some constituents will either decompose in water or will
ionize. For example, maleic anhydride will form maleic acid
when it comes in contact with water, and copper cyanide will
ionize to form copper and cyanide ions. However, EPA may choose
to regulate the decomposition or ionization products.
2. EPA-approved or verified analytical methods are not available.
Many constituents, such as 1,3,5-trinitrobenzene, are not
measured adequately or even detected using any of EPA's
analytical methods published in SW-846 Third Edition.
3. The constituent is a member of a chemical group designated in
Appendix VIII as not otherwise specified (N.O.S.). Constituents
listed as N.O.S., such as chlorinated phenols, are a generic
group of some types of chemicals for which a single analytical
procedure is not available. The individual members of each such
group need to be listed to determine whether the constituents
can be analyzed. For each N.O.S. group, all those constituents
that can be readily analyzed are included in the BOAT
constituent list.
4. Available analytical procedures are not appropriate for a
complex waste matrix. Some compounds, such as auramine, can be
analyzed as a pure constituent. However, in the presence of
other constituents, the recommended analytical method does not
positively identify the constituent. The use of high
performance liquid chromatography (HPLC) presupposes a high
expectation of finding the specific constituents of interest.
In using this procedure to screen samples, protocols would have
to be developed on a case-specific basis to verify the identity
of constituents present in the samples. Therefore, HPLC is
usually not an appropriate analytical procedure for complex
samples containing unknown constituents.
1-26
-------
5. Standards for analytical instrument calibration are not
commercially available. For several constituents, such as
benz(c)acridine, commercially available standards of a
"reasonably" pure grade are not available. The unavailability
of a standard was determined by a review of catalogs from
specialty chemical manufacturers.
Two constituents (fluoride and sulfide) are not specifically included
in Appendices VII and VIII; however, these compounds are included on the
BOAT list as indicator constituents for compounds from Appendices VII and
VIII such as hydrogen fluoride and hydrogen sulfide, which ionize in
water.
The BOAT constituent list presented in Table 1-1 is divided into the
following nine groups:
Volatile organics;
Semivolatile organics;
Metals;
Other inorganics;
Organochlorine pesticides;
Phenoxyacetic acid herbicides;
Organophosphorous insecticides;
PCBs; and
Dioxins and furans.
The constituents were placed in these categories based on their chemical
properties. The constituents in each group are expected to behave
similarly during treatment and are also analyzed, with the exception of
the metals and the other inorganics, by using the same analytical methods,
(2) Constituent selection analysis. The constituents that the
Agency selects for regulation in each waste are, in general, those found
in the untreated wastes at treatable concentrations. For certain waste
1-27
-------
codes, the target list for the untreated waste may have been shortened
(relative to analyses performed to test treatment technologies) because
of the extreme unlikelihood that the constituent will be present.
In selecting constituents for regulation, the first step is to
develop of list of potentially regulated constituents by summarizing all
the constituents that are present or are likely to be present in the
untreated waste at treatable concentrations. A constituent is considered
present in a waste if the constituent (1) is detected in the untreated
waste above the detection limit, (2) is detected in any of the treated
residuals above the detection limit, or (3) is likely to be present based
on the Agency's analyses of the waste-generating process. In case (2),
the presence of other constituents in the untreated waste may interfere
with the quantification of the constituent of concern, making the
detection limit relatively high and resulting in a finding of "not
detected" when, in fact, the constituent is present in the waste. Thus,
the Agency reserves the right to regulate such constituents.
After developing a list of potential constituents for regulation.
EPA reviews this list to determine if any of these constituents can be
excluded from regulation because they would be controlled by regulation
of other constituents on the list. This indicator analysis is done for
two reasons: (1) it reduces the analytical cost burdens on the treater
and (2) it facilitates implementation of the compliance and enforcement
program. EPA's rationale for selection of regulated constituents for
this waste code is presented in Section 6 of this background document.
1-28
-------
(3) Calculation of standards. The final step in the calculation of
the BOAT treatment standard is the multiplication of the average
accuracy-corrected treatment value by a factor referred to by the Agency
as the variability factor. This calculation takes into account that even
well-designed and well-operated treatment systems will experience some
fluctuations in performance. EPA expects that fluctuations will result
from inherent mechanical limitations in treatment control systems,
collection of treated samples, and analysis of these samples. All of the
above fluctuations can be expected to occur at well-designed and
well-operated treatment facilities. Therefore, setting treatment
standards utilizing a variability factor should be viewed not as a
relaxing of section 3004(m) requirements, but rather as a function of the
normal variability of the treatment processes. A treatment facility will
have to be designed to meet the mean achievable treatment performance
level to ensure that the performance levels remain within the limits of
the treatment standard.
The Agency calculates a variability factor for each constituent of
concern within a waste treatability group using the statistical
calculation presented in Appendix A. The equation for calculating the
variability factor is the same as that used by EPA for the development of
numerous regulations in the Effluent Guidelines Program under the Clean
Water Act. The variability factor establishes the instantaneous maximum
based on the 99th percentile value.
1-29
-------
There is an additional step in the calculation of the treatment
standards in those instances where the ANOVA analysis shows that more
than one technology achieves a level of performance that represents
BOAT. In such instances, the BOAT treatment standard for each
constituent of concern is calculated by first averaging the mean
performance value for each technology and then multiplying that value by
the highest variability factor among the technologies considered. This
procedure ensures that all the technologies used as the basis for the
BOAT treatment standards will achieve full compliance.
1.2.5 Compliance with Performance Standards
Usually the treatment standards reflect performance achieved by the
best demonstrated available technology (BOAT). As such, compliance with
these numerical standards requires only that the treatment level be
achieved prior to land disposal. It does not require the use of any
particular treatment technology. While dilution of the waste as a means
to comply with the standards is prohibited, wastes that are generated in
such a way as to naturally meet the standards can be land disposed
without treatment. With the exception of treatment standards that
prohibit land disposal or that specify use of certain treatment methods,
all established treatment standards are expressed as concentration levels,
EPA is using both the total constituent concentration and the
concentration of the constituent in the TCLP extract of the treated waste
as a measure of technology performance.
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For all organic constituents, EPA is basing the treatment standards
on the tota-1 constituent concentration found in the treated waste. EPA
is using this measurement because most technologies for treatment of
organics destroy or remove organics compounds. Accordingly, the best
measure of performance would be the total amount of constituent remaining
after treatment. (NOTE: EPA's land disposal restrictions for solvent
waste codes F001-F005 (51 FR 40572) use the TCLP extract value as a
measure of performance. At the time that EPA promulgated the treatment
standards for F001-F005, useful data were not available on total
constituent concentrations in treated residuals, and, as a result, the
TCLP data were considered to be the best measure of performance.)
For all metal constituents, EPA is using both total constituent
concentration and/or the TCLP extract concentration as the basis for
treatment standards. The total constituent concentration is being used
when the technology basis includes a metal recovery operation. The
underlying principle of metal recovery is that it reduces the amount of
metal in a waste by separating the metal for recovery; total constituent
concentration in the treated residual, therefore, is an important measure
of performance for this technology. Additionally, EPA also believes that
it is important that any remaining metal in a treated residual waste not
be in a state that is easily Teachable; accordingly, EPA is also using
the TCLP extract concentration as a measure of performance. It is
important to note that for wastes for which treatment standards are based
1-31
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on a metal recovery process, the facility has to comply with both the
total and the TCLP extract constituent concentrations prior to land
disposing the waste.
In cases where treatment standards for metals are not based on
recovery techniques but rather on stabilization, EPA is using only the
TCLP value as a measure of performance. The Agency's rationale is that
stabilization is not meant to reduce the concentration of metal in a
waste but only to chemically minimize the ability of the metal to leach.
1.2.6 Identification of BOAT
BOAT for a waste must be the "best" of the demonstrated available
technologies. EPA determines which technology constitutes "best" after
screening the available data from each demonstrated technology, adjusting
these data for accuracy, and comparing the performance of each
demonstrated technology to that of the others. If only one technology is
identified as demonstrated, it is considered "best"; if it is available,
the technology is BOAT.
(1) Screening of treatment data. The first activity in
determining which of the treatment technologies represent treatment by
BOAT is to screen the treatment performance data from each of the
demonstrated and available technologies according to the following
criteria:
1. Design and operating data associated with the treatment data
must reflect a well-designed, well-operated system for each
treatment data point. (The specific design and operating
parameters for each demonstrated technology for the waste
code(s) of interest are discussed in Section 3.2 of this
document.)
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2. Sufficient QA/QC data must be available to determine the true
values of the data from the treated waste. This screening
criterion involves adjustment of treated data to take into
account that the true value may be different from the measured
value. This discrepancy generally is caused by other
constituents in the waste that can mask results or otherwise
interfere with the analysis of the constituent of concern.
3. The measure of performance must be consistent with EPA's
approach to evaluating treatment by type of constituents (e.g.,
total concentration data for organics, and total concentration
and TCLP extract concentration for metals from the residual).
In the absence of data needed to perform the screening analysis, EPA
will make decisions on a case-by-case basis as to whether to use the data
as a basis for the treatment standards. The factors included in this
case-by-case analysis will be the actual treatment levels achieved, the
availability of the treatment data and their completeness (with respect
to the above criteria), and EPA's assessment of whether the untreated
waste represents the waste code of concern.
(2) Comparison of treatment data. In cases in which EPA has
treatment data from more than one demonstrated available technology
following the screening activity, EPA uses the statistical method known
as analysis of variance (ANOVA) to determine if one technology performs
significantly better than the others. This statistical method
(summarized in Appendix A) provides a measure of the differences between
two data sets. Specifically, EPA uses the analysis of variance to
determine whether BOAT represents a level of performance achieved by only
one technology or represents a level of performance achieved by more than
one (or all) of the technologies. If EPA finds that one technology
performs significantly better (i.e., is "best"), BOAT treatment standards
1-33
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are the level of performance achieved by that best technology multiplied
by the corresponding variability factor for each regulated constituent.
If the Agency finds that the levels of performance for one or more
technologies are not statistically different, EPA averages the
performance values achieved by each technology and then multiplies this
value by the largest variability factor associated with any of the
technologies.
(3) Quality assurance/quality control. This section presents the
principal quality assurance/quality control (QA/QC) procedures employed
in screening and adjusting the data to be used in the calculation of
treatment standards. Additional QA/QC procedures used in collecting and
screening data for the BOAT program are presented in EPA's Generic
Quality Assurance Project Plan for Land Disposal Restrictions Program
("BOAT"). EPA/530-SW-87-011.
To calculate the treatment standards for the land disposal restriction
rules, it is first necessary to determine the recovery value for each
constituent (the amount of constituent recovered after spiking--which is
the addition of a known amount of the constituent—minus the initial
concentration in the samples, all divided by the spike amount added) for
each spiked sample of the treated residual. Once the recovery values are
determined, the following procedures are used to select the appropriate
percent recovery value to adjust the analytical data:
1-34
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1. If duplicate spike recovery values are available for the
constituent of interest, the data are adjusted by the lowest
available percent recovery value (i.e., the value that will
yield the most conservative estimate of treatment achieved).
However, if a spike recovery value of less than 20 percent is
reported for a specific constituent, the data are not used to
set treatment standards because the Agency does not have
sufficient confidence in the reported value to set a national
standard.
2. If data are not available for a specific constituent but are
available for an isomer, then the spike recovery data are
transferred from the isomer and the data are adjusted using the
percent recovery selected according to the procedure described
in (1) above.
3. If data are not available for a specific constituent but are
available for a similar class of constituents (e.g., volatile
organics, acid-extractable semivolatiles), then spike recovery
data available for this class of constituents are transferred.
All spike recovery values greater than or equal to 20 percent
for a spike sample are averaged and the constituent
concentration is adjusted by the average recovery value. If
spiked recovery data are available for more than one sample, the
average is calculated for each sample and the data are adjusted
by using the lowest average value.
4. If matrix spike recovery data are not available for a set of
data to be used to calculate treatment standards, then matrix
spike recovery data are transferred from a waste that the Agency
believes is similar (e.g., if the data represent an ash from
incineration, then data from other incinerator ashes could be
used). While EPA recognizes that transfer of matrix spike
recovery data from a similar waste is not an exact analysis,
this is considered the best approach for adjusting the data to
account for the fact that most analyses do not result in
extraction of 100 percent of the constituent. In assessing the
recovery data to be transferred, the procedures outlined in (1),
(2), and (3) above are followed.
The analytical procedures employed to generate the data used to
calculate the treatment standards are listed in Appendix B of this
document. In cases where alternatives or equivalent procedures and/or
equipment are allowed in EPA's SW-846, Third Edition methods, the
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specific procedures and equipment used are documented. In addition, any
deviations from the SW-846, Third Edition methods used to analyze the
specific waste matrices are documented. It is important to note that the
Agency will use the methods and procedures delineated in Appendix B to
enforce the treatment standards presented in Section 7 of this document.
Accordingly, facilities should use these procedures in assessing the
performance of their treatment systems.
1.2.7 BOAT Treatment Standards for "Derived-From" and "Mixed" Wastes
(1) Wastes from treatment trains generating multiple residues. In a
number of instances, the proposed BOAT consists of a series of
operations, each of which generates a waste residue. For example, the
proposed BOAT for a certain waste code is based on solvent extraction,
steam stripping, and activated carbon adsorption. Each of these
treatment steps generates a waste requiring treatment — a
solvent-containing stream from solvent extraction, a stripper overhead,
and spent activated carbon. Treatment of these wastes may generate
further residues; for instance, spent activated carbon (if not
regenerated) could be incinerated, generating an ash and possibly a
scrubber water waste. Ultimately, additional wastes are generated that
may require land disposal. With respect to these wastes, the Agency
wishes to emphasize the following points:
1. All of the residues from treating the original listed wastes are
likewise considered to be the listed waste by virtue of the
derived-from rule contained in 40 CFR 261.3(c)(2). (This point
is discussed more fully in (2) below.) Consequently, all of the
wastes generated in the course of treatment would be prohibited
from land disposal unless they satisfy the treatment standard or
meet one of the exceptions to the prohibition.
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2. The Agency's proposed treatment standards generally contain a
concentration level for wastewaters and a concentration level
for nonwastewaters. The treatment standards apply to all of the
wastes generated in treating the original prohibited waste.
Thus, all derived-from wastes meeting the Agency definition of
wastewater (less than 1 percent total organic carbon (TOC) and
less than 1 percent total suspended solids) would have to meet
the treatment standard for wastewaters. All residuals not
meeting this definition would have to meet the treatment
standard for nonwastewaters. EPA wishes to make clear that this
approach is not meant to allow partial treatment in order to
comply with the applicable standard.
3. The Agency has not performed tests, in all cases, on every waste
that can result from every part of the treatment train.
However, the Agency's treatment standards are based on treatment
of the most concentrated form of the waste. Consequently, the
Agency believes that the less concentrated wastes generated in
the course of treatment will also be able to be treated to meet
this value.
(2) Mixtures and other derived-from residues. There is a further
question as to the applicability of the BOAT treatment standards to
residues generated not from treating the waste (as discussed above), but
from other types of management. Examples are contaminated soil or
leachate that is derived from managing the waste. In these cases, the
mixture is still deemed to be the listed waste, either because of the
derived-from rule (40 CFR 261.3(c)(2)(i)) or the mixture rule (40 CFR
261.3(a)(2)(iii) and (iv)) or because the listed waste is contained in
the matrix (see, for example, 40 CFR 261.33(d)). The prohibition for the
particular listed waste consequently applies to this type of waste.
The Agency believes that the majority of these types of residues can
meet the treatment standards for the underlying listed wastes (with the
possible exception of contaminated soil and debris for which the Agency
is currently investigating whether it is appropriate to establish a
1-37
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separate treatability subcategorization). For the most part, these
residues will be less concentrated than the original listed waste. The
Agency's treatment standards also make a generous allowance for process
variability by assuming that all treatability values used to establish
the standard are lognormally distributed. The waste also might be
amenable to a relatively nonvariable form of treatment technology such as
incineration. Finally, and perhaps most important, the rules contain a
treatability variance that allows a petitioner to demonstrate that its
waste cannot be treated to the level specified in the rule (40 CFR Part
268.44(a)). This provision provides a safety valve that allows persons
with unusual waste matrices to demonstrate the appropriateness of a
different standard. The Agency, to date, has not received any petitions
under this provision (for example, for residues contaminated with a
prohibited solvent waste), indicating, in the Agency's view, that the
existing standards are generally achievable.
(3) Residues from managing listed wastes or that contain listed
wastes. The Agency has been asked if and when residues from managing
hazardous wastes, such as leachate and contaminated ground water, become
subject to the land disposal prohibitions. Although the Agency believes
this question to be settled by existing rules and interpretative
statements, to avoid any possible confusion the Agency will address the
question again.
1-38
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Residues from managing First Third wastes, listed California List
wastes, and spent solvent and dioxin wastes are all considered to be
subject to the prohibitions for the listed hazardous waste as originally
generated. Residues from managing California List wastes likewise are
subject to the California List prohibitions when the residues themselves
exhibit a characteristic of hazardous waste. This determination stems
directly from the derived-from rule in 40 CFR 261.3(c)(2) or, in. some
cases, from the fact that the waste is mixed with or otherwise contains
the listed waste. The underlying principle stated in all of these
provisions is that listed wastes remain listed until delisted.
The Agency's historic practice in processing delisting petitions that
address mixing residuals has been to consider them to be the listed waste
and to require that delisting petitioners address all constituents for
which the derived-from waste (or other mixed waste) was listed. The
language in 40 CFR 260.22(b) states that mixtures or derived-from
residues can be delisted provided a delisting petitioner makes a
demonstration identical to that which a delisting petitioner would make
for the original listed waste. Consequently, these residues are treated
as the original listed waste for delisting purposes. The statute
likewise takes this position, indicating that soil and debris that are
contaminated with listed spent solvents or dioxin wastes are subject to
the prohibition for these wastes even though these wastes are not the
originally generated waste, but rather are a residual from management
(RCRA section 3004(e)(3)). It is EPA's view that all such residues are
1-39
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covered by the existing prohibitions and treatment standards for the
listed hazardous waste that these residues contain or from which they are
derived.
1.2.8 Transfer of Treatment Standards
EPA is proposing some treatment standards that are not based on
testing of the treatment technology on the specific waste subject to the
treatment standard. The Agency has determined that the constituents
present in the untested waste can be treated to the same performance
levels as those observed in other wastes for which EPA has previously
developed treatment data. EPA believes that transferring treatment
performance data for use in establishing treatment standards for untested
wastes is technically valid in cases where the untested wastes are
generated from similar industries or processing steps, or have similar
waste characteristics affecting performance and treatment selection.
Transfer of treatment standards to similar wastes or wastes from similar
processing steps requires little formal analysis. However, in a case
where only the industry is similar, EPA more closely examines the waste
characteristics prior to deciding whether the untested waste constituents
can be treated to levels associated with tested wastes.
EPA undertakes a two-step analysis when determining whether
constituents in the untested wastes can be treated to the same level of
performance as in the tested waste. First, EPA reviews the available
waste characterization data to identify those parameters that are
1-40
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expected to affect treatment selection. EPA has identified some of the
most important constituents and other parameters needed, to select the
treatment technology appropriate for the given waste(s) in Section 3.
Second, when analysis suggests that an untested waste can be treated
with the same technology as a waste for which treatment performance data
are already available, EPA analyzes a more detailed list of
characteristics that the Agency believes will affect the performance of
the technology. By examining and comparing these characteristics, the
Agency determines whether the untested wastes will achieve the same level
of treatment as the tested waste. Where the Agency determines that the
untested waste can be treated as well or better than the tested waste,
the treatment standards can be transferred.
1.3 Variance from the BOAT Treatment Standard
The Agency recognizes that there may exist unique wastes that cannot
be treated to the level specified as the treatment standard. In such a
case, a generator or owner/operator may submit a petition to the
Administrator requesting a variance from the treatment standard. A
particular waste may be significantly different from the wastes on which
the treatment standards are based because the subject waste contains a
more complex matrix that makes it more difficult to treat. For example,
complex mixtures may be formed when a restricted waste is mixed with
other waste streams by spills or other forms of inadvertent mixing. As a
result, the treatability of the restricted waste may be altered such that
it cannot meet the applicable treatment standard.
1-41
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Variance petitions must demonstrate that the treatment standard
established for a given waste cannot be met. This demonstration can be
made by showing that attempts to treat the waste by available
technologies were not successful or by performing appropriate analyses of
the waste, including waste characteristics affecting performance, which
demonstrate that the waste cannot be treated to the specified levels.
Variances will not be granted based solely on a showing that adequate
BOAT treatment capacity is unavailable. (Such demonstrations can be made
according to the provisions in Part 268.5 of RCRA for case-by-case
extensions of the effective date.) The Agency will consider granting
generic petitions provided that representative data are submitted to
support a variance for each facility covered by the petition.
Petitioners should submit at least one copy to:
The Administrator
U.S. Environmental Protection Agency
401 M Street, S.W.
Washington, DC 20460
An additional copy marked "Treatability Variance" should be submitted
to:
Chief, Waste Treatment Branch
Office of Solid Waste (WH-565)
U.S. Environmental Protection Agency
401 M Street, S.W.
Washington, DC 20460
Petitions containing confidential information should be sent with
only the inner envelope marked "Treatability Variance" and "Confidential
Business Information" and with the contents marked in accordance with the
1-42
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requirements of 40 CFR Part 2 (41 FR 36902, September 1, 1976, amended by
43 FR 4000).
The petition should contain the following information:
1. The petttioner'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 for a discussion of
1.-43
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waste characteristics affecting performance that the Agency has
identified for the technology representing BOAT.)
9. The dates of the sampling and testing.
10. A description of the methodologies and equipment used to obtain
representative samples.
11. A description of the sample handling and preparation techniques,
including techniques used for extraction, containerization, and
preservation of the samples.
12. A description of analytical procedures used, including .QA/QC
methods.
After receiving a petition for a variance, the Administrator may
request any additional information or waste samples that may be required
to evaluate and process the petition. Additionally, all petitioners must
certify that the information provided to the Agency is accurate under
40 CFR 268.4(b).
In determining whether a variance will be granted, the Agency will
first look at the design and operation of the treatment system being
used. If EPA determines that the technology and operation are consistent
with BOAT, the Agency will evaluate the waste to determine if the waste
matrix and/or physical parameters are such that the BOAT treatment
standards reflect treatment of this waste. Essentially, this latter
analysis will concern the parameters affecting treatment selection and
waste characteristics affecting performance parameters.
In cases where BOAT is based on more than one technology, the
petitioner will need to demonstrate that the treatment standard cannot be
met using any of the technologies, or that none of the technologies are
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appropriate for treatment of the waste. After the Agency has made a
determination on the petition, the Agency's findings will be published in
the Federal Register, followed by a 30-day period for public comment.
After review of the public comments, EPA will publish its final
determination in the Federal Register as an amendment to the treatment
standards in 40 CFR Part 268, Subpart D.
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2. INDUSTRIES AFFECTED AND WASTE CHARACTERIZATION
This section discusses the industries that generate K024, describes
the process that generates the waste, and presents waste characterization
data.
2.1 Industry Affected and Process Description
The listed waste K024 is generated in a distillation column as bottom
residues during the production of phthalic anhydride from napthalene in
the organic chemical industry. The Agency estimates that only one
facility uses this process and generates K024 waste. This facility is
located in the State of Illinois (EPA Region V) and generates a maximum
of 600 tons of K024 waste per year.
Phthalic anhydride is manufactured by a process that uses a vaporized
napthalene and air mixture fed into a fixed-bed reactor with a vanadium
pentoxide catalyst. The naphthalene is oxidized to phthalic anhydride,
carbon dioxide, and water at a temperature of about 350°C. These
gases pass through a vapor cooler that reduces the gas temperature just
below the dew point (approximately 126°C). The condensed liquid is
then routed into crude phthalic anhydride storage.
The crude phthalic anhydride is subsequently heated at atmospheric
pressure to dehydrate traces of phthalic acid and to convert other
compounds to high boiling compounds that can be separated from the
product during distillation. Other chemicals are added to promote
condensation reactions and to shorten the time required for
purification. These chemicals include sodium carbonate, sodium
2-1
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hydroxide, or a material to tie up naphthoquinone in a polymer state so
that it will be easily removed from the product. The bottoms or heavy
ends from the distillation column constitute the waste stream K024.
Figure 2-1 is a process schematic of the manufacture of phthalic
anhydride and the generation of the listed waste K024. K024 from the
distillation column is directly drummed at a temperature of 250°C and
then allowed to cool prior to disposal.
2.2 Waste Characterization
All waste characterization data available to the Agency for K024
waste are presented below. The major constituents in the waste and their
approximate concentrations are presented in Table 2-1. The percent
concentration of each major constituent in the waste was determined from
best estimates based on chemical analyses and discussion with the
generator. Less than 6 percent of the waste is composed of BOAT
constituents (for BOAT constituent list, refer to Section 1.2.4), of
which 5 percent is phthalic anhydride. (Analytical results upon which
the estimate is based are reported in the Onsite Engineering Report for
K024.) The BOAT constituent composition and other data are presented in
Table 2-2. No BOAT constituents of interest, except phthalic anhydride,
were detected at significant concentrations in the untreated waste sample.
-------
ro
i
CO
NAPHTHALENE
AIR
-Jr
FIXED-
BED REACTOR
•^FILTER-
I I
CATALYST
RECYCLE
MULTIPLE -
SWITCH
CONDENSERS
I
CRUDE
STORAGE
LIGHT
(K023)
PRETREATMENT
TANK
DISTILLATION
COLUMN
BOTTOMS
,K024,
PHTHALIC
ANHYDRIDE
PRODUCT
WATER-COOLED
CONVEYOR BELT
FLAKED K024
Figure 2-1 Schematic Diagram of the Generation of K024 and Preparation of K024 for Test Burns
-------
1419g/p 1
Table 2-1 Major Constituent Composition for
Untreated K024 Waste
Major constituents Concentration (%)
Phthalic anhydride3 5
Ash 10
Water <1
Other BOAT constituents <1
Polymer material 83
TOTAL 100
This is the product that remains in the waste.
Reported by Koppers to be produced from reactions of sodium carbonate,
1,4-naphthaquinone, and other organic and inorganic impurities from
process feed materials.
Reference: USEPA 1987b.
2-4
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1419g/p 18
Table 2-2 BOAT Constituent Composition and Other Data
Constituent
CAS no. Untreated waste concentration (ppm)
Volati1e orqanics
15. Chloromethane
17. 1.2-Dibromo-3-chloropropane
21. Dichlorodifluoro-methane
34. Methyl ethyl ketone
Semivolatile orqanics
220.'
Metals
155.
156.
158.
159.
160.
161.
163.
168.
Phthalic acidCld
9,10-Anthracenedionec
Arsenic
Barium
Cadmium
Chromium
Copper
Lead
Nickel
Zinc
74-87-3
96-12-8
75-71-8
78-93-3
85-44-9
84-65-1
7440-36-0
7440-39-3
7440-43-9
7440-47-3
7440-50-8
7439-92-1
7440-02-0
7440-66-6
<10-40
200-700
13.000-220.000
5,400-6.700
No metal analyses were
performed
Other parameters
Btu Content (Btu/lb)
Ash X
Water %
Volatile matter (dry basis) %
Sulfur %
Carbon %
65.42
10,000-20,000
5-10
1.61
71.55
BOAT constituent number.
This BOAT constituent number is given to phthalic anhydride.
cNon-BDAT constituent.
Phthalic acid is chosen as a surrogate constituent for phthalic anhydride. Phthalic
anhydride is not detectable or measureable because it is hydrolyzed to phthalic acid during
analysis and therefore the presence of phthalic anhydride in the waste can be detected only
in the form of phthalic acid.
Reference: USEPA 1987b. Section 2.1.2 and Tables 2-i and 6-1 to 6-6.
2-5
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3. APPLICABLE/DEMONSTRATED TREATMENT TECHNOLOGIES
This section identifies the applicable and demonstrated treatment
technology for K024 waste. A detailed discussion is provided for the
technology that is demonstrated.
3.1 Applicable Treatment Technology
As shown in Section 2.3, K024 waste contains BOAT list organic
constituents. The Agency has identified incineration as the applicable
destruction technology because this technology is applicable for organic
wastes such as K024, with high Btu content, high solids, low untreatable
metals concentrations, and low water content. This selection is based on
information in literature, information obtained from engineering site
visits, and information submitted by industry. No other applicable
technologies were identified.
3.2 Demonstrated Treatment Technology
Currently, the sole generator of K024 does not treat the waste
generated during the production of phthalic anhydride from naphthalene
but disposes of it as a drummed waste. The Agency cannot identify any
facilities that currently use incinerators to treat K024 waste. However,
incineration is demonstrated on wastes that are similar to K024 (high BTU
content and organic solids) and therefore the Agency believes that
incineration is demonstrated on K024 waste.
3.2.1 Incineration
This section addresses the commonly used incineration technologies:
liquid injection, rotary kiln, fluidized bed, and fixed hearth. A
discussion is provided regarding the applicability of these technologies,
3-1
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the underlying principles of operation, a technology description, waste
characteristics that affect performance, and, finally, important design
and operating parameters. As appropriate, the subsections are divided by
type of incineration unit.
(1) Applicability and use of incineration.
(a) Liquid injection. Liquid injection is applicable to wastes
that have viscosity values low enough that the waste can be atomized in
the combustion chamber. A range of literature maximum viscosity values
are reported with the low being 100 SSU and the high being 10,000 SSU.
It is important to note that viscosity is temperature dependent so that
while liquid injection may not be applicable to a waste at ambient
conditions, it may be applicable when the waste is heated. Other factors
that affect the use of liquid injection are particle size and the
presence of suspended solids. Both of these waste parameters can cause
plugging of the burner nozzle.
(b) Rotary kiln/fluidized bed/fixed hearth. These incineration
technologies are applicable to a wide range of hazardous wastes. They
can be used on wastes that contain high or low total organic content,
high or low filterable solids, various viscosity ranges, and a range of
other waste parameters. EPA has not found these technologies to be
demonstrated on wastes that are composed 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 without emission controls far more extensive than
those currently used.
3-2
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(2) Underlying principles of operation.
(a) Liquid injection. The basic operating principle of this
incineration technology is that incoming liquid wastes are volatilized
and then additional heat is supplied to the waste to destabilize the
chemical bonds. Once the chemical bonds are broken, these constituents
react with oxygen to form carbon dioxide and water vapor. The energy
needed to destabilize the bonds is referred to as the energy of
activation.
(b) Rotary kiln and fixed hearth. There are two distinct
principles of operation for these incineration technologies, one for each
of the chambers involved. In the primary chamber, energy, in the form of
heat, is transferred to the waste to achieve volatilization of the
various organic waste constituents. During this volatilization process
some of the organic constituents will oxidize to carbon dioxide and water
vapor. In the secondary chamber, additional heat is supplied to overcome
the energy requirements needed to destabilize the chemical bonds and
allow the constituents to react with excess oxygen to form carbon dioxide
and water vapor. The principle of operation for the secondary chamber is
similar to that of liquid injection.
(c) Fluidized bed. The principle of operation for this
incineration technology is somewhat different than that for rotary kiln
and fixed hearth incineration relative to the functions of the primary
and secondary chambers. In fluidized bed incineration, the purpose of
the primary chamber is not only to volatilize the wastes but also to
3-3
-------
essentially combust the waste. Destruction of the waste organics can be
accomplished to a better degree in the primary chamber of a fluidized bed
incinerator than in that of a rotary kiln or fixed hearth incinerator
because of (1) improved heat transfer from fluidization of the waste
using forced air and (2) the fact that the fluidization process provides
sufficient oxygen and turbulence to convert the organics to carbon
dioxide and water vapor. The secondary chamber (referred to as the
freeboard) generally does not have an afterburner; however, additional
time is provided for conversion of the organic constituents to carbon
dioxide, water vapor, and hydrochloric acid if chlorine is present in the
waste.
(3) Description of the incineration process.
(a) Liquid injection. The liquid injection system is capable
of incinerating a wide range of gases and liquids. The combustion system
has a simple design with virtually no moving parts. A burner or nozzle
atomizes the liquid waste and injects it into the combustion chamber,
where it burns in the presence of air or oxygen. A forced draft system
supplies the combustion chamber with air to provide oxygen for combustion
and turbulence for mixing. The combustion chamber is usually a cyclinder
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 cyclinder that is mounted at a slight incline from the
3-4
-------
WATER
AUXILIARY FUEL
BURNER
AIR
CO
en
LIQUID OR GASEOUS.
WASTE INJECTION
BURNER
nu
nni..«n%/
PRIMARY
COMBUSTION
ruAMncn
CHAMBER
AFTERBURNER
(SECONDARY
COMBUSTION
COMBUSTION
CHAMBER)
SPRAY
CHAMBER
I
1
GAS TO
POLLUTION
CONTROL
HORIZONTALLY FIRED
LIQUID INJECTION
INCINERATOR
ASH
WATER
FIGURE 3-1
LIQUID INJECTION INCINERATOR
-------
horizontal (see Figure 3-2). Solid wastes enter at the high end of the
kiln, and liquid or gaseous wastes enter through atomizing nozzles in the
kiln or afterburner section. Rotation of the kiln exposes the solids to
the heat, vaporizes them, and allows them to combust by mixing with air.
The rotation also causes the ash to move to the lower end of the kiln,
where it can be removed. Rotary kiln systems usually have a secondary
combustion chamber or afterburner following the kiln for further
combustion of the volatilized components of solid wastes.
(c) Fluidized bed. A fluidized bed incinerator consists of a
column containing inert particles such as sand, which is referred to as
the bed. Air, driven by a blower, enters the bottom of the bed to
fluidize the sand. Air passage through the bed promotes rapid and
uniform mixing of the injected waste material within the fluidized bed.
The fluidized bed has an extremely high heat capacity (approximately
three times that of flue gas at the same temperature), thereby providing
a large heat reservoir. The injected waste reaches ignition temperature
quickly and transfers the heat of combustion back to the bed. Continued
bed agitation by the fluidizing air allows larger particles to remain
suspended in the combustion zone (see Figure 3-3).
(d) Fixed hearth incineration. Fixed hearth incineration, also
called controlled air or starved air incineration, is another major
technology used for hazardous waste incineration. Fixed hearth
incineration is a two-stage combustion process (see Figure 3-4). Waste
is ram-fed into the first stage, or primary chamber, and burned at less
3-6
-------
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
3-7
-------
WASTE
INJECTION
ASH
FIGURE 3-3
FLUIDIZED BED INCINERATOR
GAS TO
AIR POLLUTION
CONTROL
MAKE-UP
SAND
AIR
3-8
-------
CO
10
WASTE
INJECTION
AIR
GAS TO AIR
POLLUTION
CONTROL
PRIMARY
COMBUSTION
CHAMBER
GRATE
SECONDARY
CHAMBER
AUXILIARY
FUEL
2-STAGE FIXED HEARTH
INCINERATOR
ASH
FIGURE 3-4
FIXED HEARTH INCINERATOR
-------
than stoichiometric conditions. The resultant smoke and pyrolysis
products, consisting primarily of volatile hydrocarbons and carbon
monoxide, along with the normal products of combustion, pass to the
secondary chamber. Here, additional air is injected to complete the
combustion. This two-stage process generally yields low stack
particulate and carbon monoxide (CO) emissions. The primary chamber
combustion reactions and combustion gas are maintained at low levels by
the starved air conditions so that particulate entrainment and carryover
are minimized.
(e) Air pollution controls. Following incineration of
hazardous wastes, combustion gases are generally further treated in an
air pollution control system. The presence of chlorine or other halogens
in the waste requires a scrubbing or absorption step to remove
hydrochloric acid and other halo-acids from the combustion gases. Ash in
the waste is not destroyed in the combustion process. Depending on its
composition, ash will 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 of
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 as a result of poor combustion efficiency or combustion
upsets, such as flameouts.
3-10
-------
(4) Waste characteristics affecting performance.
(a) Liquid injection. In determining whether liquid injection
is likely to achieve the same level of performance on an untested waste
as on a previously tested waste, the Agency will compare dissociation
bond energies of the constituents in the untested and tested waste. This
parameter is being used as a surrogate indicator of activation energy
which, as discussed previously, destabilized molecular bonds. In theory,
the bond dissociation energy would be equal to the activation energy;
however, in practice this is not always the case. Other energy effects
(e.g., vibrational effects, the formation of intermediates, and
interactions between different molecular bonds) may have a significant
influence on activation energy.
Because of the shortcomings of bond energies in estimating activation
energy, EPA analyzed other waste characteristic parameters to determine
whether these parameters would provide a better basis for transferring
treatment standards from an untested waste to a tested waste. These
parameters include heat of combustion, heat of formation, use of
available kinetic data to predict activation energies, and general
structural class. All of these were rejected for reasons provided below.
The heat of combustion measures only the difference in energy of the
products and reactants; it does not provide information on the transition
state. Heat of formation is used as a tool to predict whether reactions
are likely to proceed; however, there are a significant number of
hazardous constituents for which these data are not available. Use of
3-11
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kinetic data was rejected because these data are limited and could not be
used to calculate free energy values (AG) for the wide range of
hazardous constituents to be addressed by this rule. Finally, EPA
decided not to use structural classes because the Agency believes that
evaluation of bond dissociation energies allows for a more direct
determination of whether a constituent will be destabilized.
(b) Rotary kiln/fluidized bed/fixed hearth. Unlike liquid
injection, these incineration technologies also generate a residual ash.
Accordingly, in determining whether these technologies are likely to
achieve the same level of performance on an untested waste as on a
previously tested waste, EPA would need to examine the waste
characteristics that affect volatilization of organics from the waste, as
well as destruction of the organics, once volatilized. Relative to
volatilization, EPA will examine thermal conductivity of the entire waste
and boiling point of the various constituents. As with liquid injection,
EPA will examine bond energies in determining whether treatment standards
for scrubber water residuals can be transferred from a tested waste to an
untested waste. Below is a discussion of how EPA arrived at thermal
conductivity and boiling point as the best method to assess
volatilization of organics from the waste; the discussion relative to
bond energies is the same for these technologies as for liquid injection
and will not be repeated here.
(i) Thermal conductivity. Consistent with the underlying
principles of incineration, a major factor with regard to whether a
3-12
-------
particular constituent will volatilize is the transfer of heat through
the waste. In the case of rotary kiln, fluidized bed, and fixed hearth
\
incineration, heat is transferred through the waste by three mechanisms:
radiation, convection, and conduction. For a given incinerator, heat
transferred through various wastes by radiation is more a function of the
design and type of incinerator than of the waste being treated.
Accordingly, the type of waste treated will have a minimal impact on the
amount of heat transferred by radiation. With regard to convection, EPA
also believes that the type of heat transfer will generally be more a
function of the type and design of incinerator than of the waste itself.
However, EPA is examining particle size as a waste characteristic that
may significantly impact the amount of heat transferred to a waste by
convection and thus impact volatilization of the various organic
compounds. The final type of heat transfer, conduction, is the one that
EPA believes will have the greatest impact on volatilization of organic
constituents. To measure this characteristic, EPA will use thermal
conductivity; an explanation of this parameter, as well as how it can be
measured, is provided below.
Heat flow by conduction is proportional to the temperature gradient
across the material. The proportionality constant is a property of the
material and is referred to as the thermal conductivity. (Note: The
analytical method that EPA has identified for measurement of thermal
conductivity is named "Guarded, Comparative, Longitudinal Heat Flow
Technique"; it is described in Appendix C.) In theory, thermal
3-13
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conductivity would always provide a good indication of whether a
constituent in an untested waste would be treated to the same extent in
the primary incinerator chamber as the same constituent in a previously
tested waste.
In practice, thermal conductivity has some limitations in assessing
the transferability of treatment standards; however, EPA has not
identified a parameter that can provide a better indication of heat
transfer characteristics of a waste. Below is a discussion of both the
limitations associated with thermal conductivity and the other parameters
considered.
Thermal conductivity measurements, as part of a treatability
comparison for two different wastes through a single incinerator, are
most meaningful when applied to wastes that are homogeneous (i.e., major
constituents are essentially the same). As wastes exhibit greater
degrees of nonhomogeneity (e.g., significant concentration of metals in
soil), then thermal conductivity becomes less accurate in predicting
treatability because the measurement essentially reflects heat flow
through regions having the greatest conductivity (i.e., the path of least
resistance) and not heat flow through all parts of the waste.
BTU value, specific heat, and ash content were also considered for
predicting heat transfer characteristics. These parameters can no better
account for nonhomogeneity than can thermal conductivity; additionally,
they are not directly related to heat transfer characteristics.
Therefore, these parameters do not provide a better indication of the
heat transfer that will occur in any specific waste.
3-14
-------
(ii) Boiling point. Once heat is transferred to a constituent
within a waste, then 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 Agency recognizes that this parameter does not take into
consideration the impact of other compounds in the waste on the boiling
point of a constituent in a mixture; however, the Agency is not aware of
a better measure of volatility that can easily be determined.
(5) Design and operating parameters.
(a) Liquid injection. For a liquid injection unit, EPA's
analysis of whether the unit is well designed will focus on (1) the
likelihood that sufficient energy is provided to the waste to overcome
the activation level for breaking molecular bonds and (2) whether
sufficient oxygen is present to convert the waste constituents to carbon
dioxide and water vapor. The specific design parameters that the Agency
will evaluate to assess whether these conditions are met are temperature,
excess oxygen, and residence time. Below is a discussion of why EPA
believes these parameters to be important, as well as a discussion of how
these parameters will be monitored during operation.
It is important to point out that, relative to the development of
land disposal restriction standards, EPA is concerned with these design
parameters only when a quench water or scrubber water residual is
generated from treatment of a particular waste. If treatment of a
3-15
-------
particular waste in a liquid injection unit would not generate a
wastewater stream, then the Agency, for purposes of land disposal
treatment standards, would be concerned with only the waste
characteristics that affect selection of the unit, not the
above-mentioned design parameters.
(i) Temperature. Temperature is important in that it provides
an indirect measure of the energy available (i.e., Btu/hr) to overcome
the activation energy of waste constituents. As the design temperature
increases, it is more likely that the molecular bonds will be
destabilized and the reaction completed.
The temperature is normally controlled automatically through the use
of instrumentation that senses the temperature and automatically adjusts
the amount of fuel and/or waste being fed. The temperature signal
transmitted to the controller can be simultaneously transmitted to a
recording device, referred to as a strip chart, and thereby continuously
recorded. To fully assess the operation of the unit, it is important to
know not only the exact location in the incinerator at which the
temperature is being monitored but also the location of the design
temperature.
(ii) Excess oxygen. It is important that the incinerator
contain oxygen in excess of the stiochiometric 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
3-16
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potentially cause the scrubber water to contain higher concentrations of
BOAT list constituents than would be the case for a well-operated unit.
In practice, the amount of oxygen fed to the incinerator is
controlled by continuous sampling and analysis of the stack gas. If the
amount of oxygen drops below the design value, then the analyzer
transmits a signal to the valve controlling the air supply and thereby
increases the flow of oxygen to the afterburner. The analyzer
simultaneously transmits a signal to a recording device so that the
amount of excess oxygen can be continuously recorded. Again, as with
temperature, it is important to know the location at which the combustion
gas is being sampled.
(iii) Carbon monoxide. Carbon monoxide is an important
operating parameter because it provides an indication of the extent to
which the waste organic constituents are being converted to carbon
dioxide and water vapor. An increase in the carbon monoxide level
indicates that greater amounts of organic waste constituents are
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
3-17
-------
devise known as a bomb calorimeter. The volume of combustion gas
generated from the waste to be incinerated is determined from an analysis
referred to as an ultimate analysis. This analysis determines the amount
of elemental constituents present, which include carbon, hydrogen,
sulfur, oxygen, nitrogen, and halogens. Using this analysis plus the
total amount of air added, one can calculate the volume of combustion
gas. After both the Btu content and the expected combustion gas volume
have been determined, the feed rate can be fixed at the desired residence
time. Continuous monitoring of the feed rate will determine whether the
unit is being operated at a rate corresponding to the designed residence
time.
(b) Rotary kiln. For this incineration, EPA will examine both
the primary and secondary chamber in evaluating the design of a
particular incinerator. Relative to the primary chamber, EPA's
assessment of design will focus on whether sufficient energy is likely to
be provided to the waste to volatilize the waste constituents. For the
secondary chamber, analogous to the sole liquid injection incineration
chamber, EPA will examine the same parameters discussed previously under
liquid injection incineration. These parameters will not be discussed
again here.
The particular design parameters to be evaluated for the primary
chamber are kiln temperature, residence time, and revolutions per
minute. Below is a discussion of why EPA believes these parameters to be
important, as well as a discussion of how these parameters will be
monitored during operation.
3-18
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(i) Temperature. The primary chamber temperature is important
in that it provides an indirect measure of the energy input (i.e.,
Btu/hr) available for heating the waste. The higher the temperature is
designed to be in a given kiln, the more likely it is that the
constituents will volatilize. As discussed earlier under "Liquid
injection," temperature should be continuously monitored and recorded.
Additionally, it is important to know the location of the temperature
sensing device in the kiln.
(ii) Residence time. This parameter is important in that it
affects whether sufficient heat is transferred to a particular
constituent in order for volatilization to occur. As the time that the
waste is in the kiln is increased, a greater quantity of heat is
transferred to the hazardous waste constituents. The residence time will
be a function of the specific configuration of the rotary kiln, including
the length and diameter of the kiln, the waste feed rate, and the rate of
rotation.
(iii) Revolutions per minute (RPM). This parameter provides an
indication of the turbulence that occurs in the primary chamber of a
rotary kiln. As the turbulence increases, the quantity of heat
transferred to the waste would also be expected to increase. However, as
the RPM value increases, the residence time decreases, resulting in a
reduction of the quantity of heat transferred to the waste. This
parameter needs to be carefully evaluated because it provides a balance
between turbulence and residence time.
3-19
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(c) Fluidized bed. As discussed previously in the section on
"Underlying Principles of Operation," the primary chamber accounts for
almost all of the conversion of organic wastes to carbon dioxide, water
vapor, and acid gas if halogens are present. The secondary chamber will
generally provide additional residence time for thermal oxidation of the
waste constituents. Relative to the primary chamber, the parameters that
the Agency will examine in assessing the effectiveness of the design are
temperature, residence time, and bed pressure differential. The first
two were included in the discussion of the rotary kiln and will not be
discussed here. The latter, bed pressure differential, is important in
that it provides an indication of the amount of turbulence and,
therefore, indirectly the amount of heat supplied to the waste. In
general, as the pressure drop increases, both the turbulence and heat
supplied increase. The pressure drop through the bed should be
continuously monitored and recorded to ensure that the designed value is
achieved.
(d) Fixed hearth. The design considerations for this
incineration unit are similar to those for a rotary kiln with the
exception that rate of rotation (i.e., RPM) is not an applicable design
parameter. For the primary chamber of this unit, the parameters that the
Agency will examine in assessing how well the unit is designed are the
same as those discussed under "Rotary kiln"; for the secondary chamber
(i.e., afterburner), the design and operating parameters of concern are
the same as those previously discussed under "Liquid injection."
3-20
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4. PERFORMANCE DATA BASE
This section discusses the available performance data associated with
the demonstrated technology for K024 waste. Performance data include the
constituent concentrations in untreated and treated waste samples, the
operating data collected during treatment of the sampled waste, design
values for the treatment technology, and data on waste characteristics
that affect performance. EPA has presented all such data to the extent
that they are available.
EPA's use of these data in determining the technology that represents
BOAT, and in developing treatment standards, is described in Sections 5
and 7, respectively.
EPA tested rotary kiln incineration technology as part of the
development of treatment standards for K024. Figure 4-1 at the end of
this section, is the treatment process schematic.
During the treatment of K024 waste in the rotary kiln incinerator,
two treatment residue streams are generated: a wastewater stream (i.e.,
scrubber water) and a nonwastewater stream (i.e., ash). Residue samples
for ash and scrubber water were taken for analysis at sampling points B
and C, respectively, and the raw untreated waste was sampled at sampling
point A shown in Figure 4-1.
The analytical data collected by EPA for rotary kiln incineration are
presented in Tables 4-1 through 4-4 at the end of this section. The
treatment performance data show that in almost all cases the BOAT
constituents are reduced to levels below the detection limits. Hence, it
can be concluded that treatment is very effective.
4-1
-------
The Agency has data on 8 sets of untreated waste samples, 6 kiln ash
samples, and 10 scrubber water samples from an EPA incineration facility
that show treatment of BOAT list organic constituents in K024 waste.
These analytical data, collected during a test burn using rotary kiln
incineration, have been reported in the K024 onsite engineering report
(USEPA 1987b), along with design and operating information on the
treatment system. The analytical data are presented in Tables 4-1
through 4-4 at the end of this section. These data show total waste
concentrations for all BOAT list constituents in the untreated waste
(Table 4-1), the scrubber water (Table 4-2), and the residual ash (Table
4-3). Total concentrations and TCLP leachate concentrations for metals
in the ash are also shown (Table 4-4). Tables 4-5 through 4-9 present
design and operating parameters of the CRF rotary kiln system.
4-2
-------
CJ
SAMPLE
D
A
B
C
0
SITE
OESCRPTON
Drum
Ash Bin
Venlurl Scrubber
Redrculadon Tank
SAMPLE
DESCRIPTION
Waste Feed Before Packing
K024 Ash
Scrubber Makeup
Scrubber Bto*do«m
SCRUBBER
NflUENT
FROM
RECIRCULATIOM
TANK
BLOWDOWN
10
STORAGE
TANKS
Figure 4-1 U.S. EPA Rotary Kiln Configuration and Feed/Residuals Sampling
Points During the K024 Test Burn
-------
Table 4-1 Rotary Kiln Incineration - EPA-Collected Total Concentration Data for Untreated Waste
Untreated waste concentration
Constituent Sample 1 Sample 2 Sample 3 Sample 4 Sample 5a Sample 6a Sample 7a
Volatile oraanics loom]
Chloromethane <10 32 <10 40 <10 10 ' <10
Methyl ethyl ketone 240 200 210 210 680 600 690
Semivolatile orcjanics (ppm)
Phthalic acidb>c 220,000d 83.000d 110,000d 13.000d NA NA NA
Anthracene dioneb 6.700 5,600 6,300 5,900 NA NA NA
Metals
(Not analyzed)
Sample 8a
<10 •
700
NA
NA
aUsing methanol extract, a methanol blank for methyl ethyl ketone was reported as 770 ppm.
Non-BDAT parameter.
cPhthalic acid is used as a surrogate constituent for phthalic anhydride since phthalic anhydride is converted to phthalic acid during the
chemical analysis.
clMemo to Fred Hall, PEI Associated, Cincinnati. Ohio, from Patrick Meehan, Radian Corp., Austin, Texas, dated December 15, 1987.
NA = Hot analyzed.
Reference: EPA 1987b. Tables 6-5. 6-6. and 6-10.
-------
Table 4-2 Rotary Kiln Incineration - EPA-Collected Total Concentration Data for Scrubber Water
Constituent
Scrubber water concentration
Sample 1 Sample 2 Sample 3 Sample 4 Sample 5 Sample 6 Sample 7 Sample 8 Sample 9 Sample 10
tn
Volat ile orqanics (ng/1)
Chloromethane
1,2-Oibromo-3-chloropropane
Dichlorodifluoromethane
Methy ethyl ketone
Semivolatile orqanics («ig/l)
Phthalic acid (surrogate for
phthalic anhydride)
Anthracene dione
Metals (mg/1)
12
<50
<160a
<250
<50
<160
<250
<50
<160
<250
<50
<160
<250
23
<50
<160
<250
<50
<160
<250
<50
<160
<250
<50
<160
<250
<50
<160
<250
Memo to Fred Hall, PEI Associated. Cincinnati. Ohio, from Patrick Meehan, Radian Corp.. Austin. Texas, dated December 15, 1987.
Reference: EPA 1987b, Tables 6-3, 6-7 to 6-9, and 6-14.
<50
<160
<250
Arsenic
Barium
Cadmium
Chromium
Copper
Nickel
Lead
Zinc
0.
0
0.
0.
0.
0.
2.
1.
,22
.10
.082
.036
.81
11
0
.5
0.063
0.077
0.072
0.096
0.118
0.12
5.2
1.9
0.047
0.11
0.038
<0.035
0.32
0.13
10.0
1.7
0.041
0.16
0.025
<0.035
<0.030
0.13
9.2
1.4
0.066
0.41
<0.02
<0.035
<0.030
0.10
16
1.3
0.059
0.039
<0.02
<0.53
<0.030
0.10
1.7
2.0
<0.02
0.35
<0.02
<0.53
<0.030
<0.075
2.7
0.33
0.022
0.037
<0.02
<0.035
<0.030
<0.075
1.5
0.70
0.024
0.097
<0.02
0.65
<0.030
<0.075
1.4
0.79
0.035
<0.01
<0.025
<0.035
<0.030
<0.075
1.7
1.1
-------
Table 4-3 Rotary Kiln Incineration - EPA-Collected Total Concentration Data for Ash
a-.
Constituent
Volat i 1e organics (»
-------
1419g/p 5
Table 4-4 Total and TCLP Metals Analyses Data for Ash
Const ituent
Arsenic
Barium
Cadmium
Chromium
Copper
Nickel
Lead
Thai 1 lum
Zinc
Ash concentration
Sample 1 Sample 2 Sample 3 Blank
Total TCLP Total TCLP Total TCLP Total TCLP
(;*g/g) (ppm) (ng/g) (ppm) Ug/g) (ppm) (ppm)
12 <1.5 2.5 <1.5 2.1 <1.5 NA <1.5
3900 0.38 85 0.18 35 0.084 NA 0.34
2.2 <0.015 <1.5 0.004 <1.5 <0.015 NA <0.015
20 <0.045 45 0.37 52 0.051 NA <0.045
46 0.14 25 <0.05 21 <0.05 NA 0.37
11 <0.10 44 1.5 55 0.11 NA <0.10
1100 2.3 110 <0.25 20 <0.25 NA <0.25
1.0 <0.45 1.0 <0.45 1.0 0.17 NA ' <0.45
170 0.30 110 1.6 29 <0.10 NA 0.26
NA = Not available.
Reference: EPA 1987b, Tables 6-12 and 6-13.
-------
1419g/p 14
Table 4-5 Design Characteristics of the CRF Rotary Kiln System
Characteristics of the kiln main chamber
Length 2.44 m (8 ft)
Diameter 1.22 m (4 ft)
Chamber volume 2.88 m3 (100 ft3)
Rotation Clockwise or counterclockwise 0.1 to 1.5 rpm
Construction 0.63 cm (0.25 in.) thick cold rolled steel
Refractory 12.7 cm (5 in.) thick high-alumina castable
refractory, variable depth to produce a frustroconical
effect for moving inerts
Solids retention 1 h (at 0.5 rpm)
time
Burner John Zink Model RW31-FL
Primary fuel Propane
Feed system Liquids: Front face, water-cooled lance
with positive-displacement pump
Semi liquids: Front face, water-cooled lance
with double-diaphragm pump
Solids: Ram feeder or metered twin-auger
screw feeder
Temperature3 1000'C (1832'F)
Characteristics of the afterburner chamber
Length 3.05 m (10 ft)
Diameter 0.91 m (3 ft)
Chamber volume 2.096 m3 (74 ft3)
4-8
-------
1419g/p 21
Construction
Refractory
Retention time
Burner
Primary fuel
Temperature
Characteristics
Table 4-5 (Continued)
0.63-cm (0.25-in.) thick cold rolled steel
15.24-cm (6-in.) thick high-alumina castable refractory
Depends on temperature and excess air (1.2 to 2.5 sec)
Iron Fireman. Model C-120-G-SMG, rated at 530 kW
(1.8 x 106 Btu/h or 31.6 MJ/s)
Propane
1200"C (2200"F) maximum operating
of the air pollution control system
System capacity Inlet gas flow of 106.8 m /min (3773 acfm) at
1200'C (2200'F) and 101 kPa (14.7 psia)
Pressure drop Venturi 7.5 kPa (30 in. WC)
Packed tower 1.0 kPa (4 in. WC)
Liquid flow Venturi 77.2 1/min (20.4 gal/min) at 69 kPA
(nominal) (10 psig)
Tower 115 1/min (30 gal/min) at 69 kPa
(10 psig)
Blowdown 7.6 to 9.5 1/min (2 to 2.5 gpm)
pH control Feedback control by NaOH solution addition
Packing Saddles
Operating temperatures in excess of 1837"F have been generated.
Waste treatment effectiveness should not be affected under these
conditions.
Operating pressure drops of 30 to 35 in. H^O across the scrubber and
up to 8.2 in.H^O across the packed tower have been used.
Reference: EPA 1987b, Table 3-1.
4-9
-------
Table 4-6 Incinerator Operating Parameters, Rotary Kiln
I
I—•
o
Test
date
3/17/87
3/18/87
3/19/87
Propane
Feed rate
(scfh)
336-424
(366)
282-478
(320)
202-342
(311)
range (average)
Heat input
(106 Btu/h)
0.822-1.040
(0.935)
0.690-1.170
(0.784)
0.496-0.839
(0.763)
Waste Combustion
feed air
rate feed rate
(Ib/h) (scfm)
53a 124
124
107b
104C 124
Exit
temperature
range
(average) (*F)
1573' - 1754*
(1707')
1713' - 2026'
(1898-)
1510" - 1953'
(1786-)
Rotation
speed
(rpm)
0.2
0.2
0.2
Pressure
(draft)
(in. H20)
-0.12
-0.12
-0.12
One fiber pack containing about 4.5 Ib waste fed every 5 minutes.
One fiber pack containing about 4.5 Ib waste fed every 2.5 minutes.
cTwo fiber packs containing about 4.5 Ib waste fed every 5 minutes.
Reference: Onsite Engineering Report. EPA 1987b, Table B-l.
-------
Table 4-7 Incinerator Operating Parameters, Afterburner
Afterburner parameter range (averaqe)
Propane ranqe
Test
date
3/17/87
3/18/87
3/19/87
Feed rate
(scfh)
367-561
(488)
378-564
(440)
367-636
(311)
Heat input
(106 Btu/h)
0.901-1.377
(1.196)
0.925-1.381
(1.078)
0.897-1.599
(1.172)
Combustion
air
feed rate
(scfm)
111-118
(113)
118-124
(120)
(111)
Exit
temperature
CF)
1963" - 2078'
(2055-)
1894* - 2155'
(2025-)
192K - 2091'
(2014°)
Pressure
(draft)
(in. H20) 02(%)
5
(-0.12)
-0.2 to -0.1 4
(-0.15)
-0.2 to -0.1 5
(-0.15)
Exit Gas
C02('/,)b C0(ppm)a
9 <10-100b
<10
10 <10-100b
<10
10 <10-100b
<10
Instrument limit on CO, is 10 percent; on CO. 100 ppm; actual values therefore could be higher than the
peak values shown.
One or more CO spikes from 40 to 100 ppm during test period.
Reference: EPA 1987b. Table B-2.
-------
Table 4-8 Incinerator Operating Parameters, Scrubber System (Acurex)
Scrubber system parameter range (average)
Venturi
Liquid
Test flow rate Delta P
date (gal/min) (in. rUO)
3/17/87 25-42
19 (35)
3/18/87 20-43
19 (34)
f" 3/19/87 20-38
£ 19 (34)
Packed tower
L iquid
flow rate
(gal/min)
(31)
28-29
(29)
29-30
(29)
Delta P
(in. H20)
5.0-10
(6.9)
5.0-10
(7.6)
6.1-10
(8.2)
Scrubber liquid
Temperature
pH (-F)
147' - 165'
(6.2) (160-)
6.0-6.2 148" - 166°
6.1 (158-)
5.0-5.1 153* - 165-
5.1 (161") -
Slowdown
Flow rate Temperature
(gal/min) CF)
71-102
2.1 (681)
1.8-2.4 84-112
(2.3) (94)
86-119
2.2 (102)
Makeup water
feed rate
(gal/min)
5.0-10
(6.9)
5.0-10
(7.6)
6.1-10
(8.2)
Reference: EPA 1987b. Table B-3.
-------
Table 4-9. Incinerator Operating Parameters, Scrubber Exit and Stack
Operating conditions range (average)
Scrubber exit (prior to charcoal bed)
Test Temperature Flow rate
date (*F) (dscfm) 02(;0
1
3/17/87 164' - 173"
(170-) 708 10.5
^ 3/18/87 164- - 173'
^ (169*) 735 10.0
3/19/87 160" - 174'
(170') 670 10.5
Stack (to atmosphere)
Temperature Flow rate3
C02(%) CO (ppm) (-F) (dscfm) 02 (%) C02 (%] CQ (ppm)
163* - 170'
6.0 <10 (167") 933 10.5 6.0 <10
163" - 170-
8.1 <10 (168-) 679 10.0 8.1 <10
161" - 172*
6.2 <10 (168-) 734 10.5 6.2 <10
As measured by the stack MM5 train.
See Figure 2-1 for location of monitoring points.
Reference: EPA 1987b, Table B-4.
-------
5. IDENTIFICATION OF BEST DEMONSTRATED AVAILABLE TECHNOLOGY (BOAT)
This section explains EPA's determination of the best demonstrated
available technology (BOAT) for K024 waste. As discussed in Section 1,
the BOAT for a waste must be the "best" of the "demonstrated"
technologies; the BOAT must also be "available." In general, the
technology that constitutes "best" is determined after screening the
available data from each demonstrated technology, adjusting these data
for accuracy, and comparing the performance of each technology to that of
the others. If only one technology is identified as demonstrated, this
technology is considered "best." To be "available" a technology (1) must
be commercially available and (2) must provide substantial treatment.
Included in this section is a discussion on how the Agency selected a
BOAT technology based on the treatment/destruction technology performance
data developed during the treatment demonstration and laboratory
analysis. All the analytical data generated specific to the BOAT
constituents are screened using the acceptable design and operating
characteristics of the treatment technology, the quality assurance/
quality control objectives of the BOAT treatment standards development
process, and the statistical analysis methods used to assess the data
quality. Performance data that did not meet any or all of these
screening criteria are deleted from consideration as BOAT. The remaining
performance data are corrected for accuracy, precision, and recovery to
account for any analytical problems related to interferences associated
5-1
-------
with the sample matrix. Finally, in cases where the Agency has data on
treatment of the same wastes using more than one applicable and
demonstrated technology, the analysis of variance (ANOVA) test is used to
determine which technology provides the best performance data and
treatment efficiencies.
5.1 Data Screening
The available treatment data for K024 were reviewed and assessed with
regard to the design and operation of the treatment system, the quality
assurance/quality control objectives that must be met during the data
generation and analysis, and the statistical analysis performed to assess
treatment efficiencies based on the treatment performance data. Data
that did not meet data quality objectives were regarded as "unacceptable"
data and were deleted. Only the "acceptable" performance data were used
for developing BOAT. The BOAT development objectives are given in
Section 1 of this report.
For rotary kiln incineration, analytical data are reported for 8
untreated waste samples, 10 scrubber water samples, and 6 ash samples
that were collected. All the available data have been used for the
development of treatment standards. The Agency believes the incineration
data represent acceptable performance of rotary kiln incineration, and
the data were used for the development of treatment standards for K024.
5.2 Data Accuracy
After the screening tests, EPA adjusted the data values based on the
analytical recovery values to take into account analytical interferences
5-2
-------
associated with the chemical makeup of the treated sample. In developing
recovery data (also referred to as accuracy data), EPA first analyzed the
waste for a constituent and then added a known amount of the same
constituent (i.e., spike) to the waste material. The total amount
recovered after spiking minus the initial concentration in the sample,
divided by the amount added, is the recovery value. The analytical data
were adjusted for accuracy using the lowest recovery value for each
constituent. These adjusted values for rotary kiln incineration were
then used to determine BOAT for K024.
5.3 Analysis of Variance
In cases were the Agency has data on treatment of the same or similar
wastes using more than one technology, EPA conducts an analysis of
variance (ANOVA) test to determine whether one of the technologies
performs significantly better than the others. In cases where a
particular treatment technology performs better, the treatment standard
will be based on this best technology.
In the case of K024, no ANOVA test was necessary since rotary kiln
incineration was the only destruction technology for which data were
available.
5.4 Determination of BOAT
K024 waste is an organic nonwastewater for the purpose of determining
the applicability of the BOAT treatment standards, since wastewaters are
defined as wastes containing less than 1 percent (weight basis)
filterable solids and less than 1 percent (weight basis) total organic
5-3
-------
carbon. However, the demonstrated technology for K024 nonwastewaters
produces both nonwastewater and wastewater residuals. BOAT must
therefore be identified for both types of waste streams.
5.4.1 Nonwastewaters
The only demonstrated technology for this waste is incineration. The
Agency has data on incineration of K024 nonwastewaters only for rotary
kiln incineration. It is therefore not possible to compare rotary kiln
incineration with other forms of incineration, such as fluidized bed.
However, the Agency has no reason to expect that fluidized bed
incineration would provide better treatment than rotary kiln incineration
because operating temperatures in fluidized bed units are lower than
those in rotary kilns. EPA therefore has determined that incineration in
a rotary kiln is the best demonstrated technology for K024 nonwastewaters.
Rotary kiln incineration is commonly available commercially. As
shown in the performance data in Section 4.0, it also achieves
substantial treatment. Phthalic acid in the untreated waste* of between
13,000 and 220,000 ppm is treated to nondetectable levels in both the
incinerator ash and the incinerator scrubber water. Methyl ethyl ketone
levels of 200 and 700 ppm in the untreated waste are also treated to
nondetectable levels in both ash and scrubber waters.
* As noted elsewhere, phthalic acid, a non-BDAT parameter, is used as a
surrogate for phthalic anhydride because phthalic anhydride is
converted to phthalic acid during chemical analysis.
5-4
-------
EPA therefore concludes that rotary kiln incineration is the best
demonstrated available technology (BOAT) for treatment of K024
nonwastewaters.
As noted, incineration produces one nonwastewater residual,
incinerator ash. Since organic constituent levels in this residual are
below detection limits, EPA concludes that no further treatment could
improve upon the levels of performance achieved by rotary kiln
incineration alone and that no further treatment is necessary. Rotary
kiln incineration is therefore also BOAT for nonwastewater residuals from
incineration of K024 nonwastewaters.
5,4.2 Wastewaters
Scrubber water is the other residual produced by incineration of K024
nonwastewaters. Since performance data indicate that levels of phthalic
acid and other constituent organics in this wastewater are below
detection limits, the Agency concludes that no further treatment of this
residual stream could improve upon the level of performance achieved by
rotary kiln incineration alone and that no further treatment is
required. Rotary kiln incineration is therefore BOAT for wastewater
residuals from incineration of K024 nonwastewaters.
5-5
-------
6. SELECTION OF REGULATED CONSTITUENTS
This section discusses the methodology used to select regulated
constituents for K024. As discussed in Section 1, the Agency has
developed a list of hazardous constituents (Table 1-1) from which the
pollutants to be regulated are selected. The list is a "growing list"
that does not preclude the addition of new constituents as additional key
parameters are identified. The list is divided into the following
categories: volatile organics, semivolatile organics, metals, other
inorganics, organochlorine pesticides, phenoxyacetic acid herbicides,
organophosphorous pesticides, PCBs, and dioxins and furans. The
constituents in each category have similar chemical properties and are
expected to behave similarly during treatment, with the exception of the
inorganics.
The selection process resulted primarily in reducing the list of 251
BOAT constituents to those BOAT constituents that are found in the
untreated wastes at significant (i.e., treatable) concentrations and
those that were prioritized for regulation based on difficulties
encountered or expected during treatment. Where applicable, certain
other BOAT constituents are not regulated because the waste treatment
performance data show that these would be controlled in the course of
achieving the limit set for other constituents.
This section describes the step-by-step process used to select the
pollutants to be regulated. The selected pollutants must be present in
6-1
-------
the untreated waste and must be treatable by the chosen BOAT, as
discussed in Section 5.
6.1 Identification of Major Constituents in the Untreated Waste
The analytical data gathered or generated as part of the BOAT program
were analyzed and reviewed to select major constituents in the untreated
waste. The selection of these constituents was based primarily on the
presence of particular constituents in the waste at a concentration at or
above the detection limit in the untreated waste. As a general rule, any
constituent present in the waste at a concentration above the analytical
detection limit would be eligible for selection.
For example, phthalic acid, which is a surrogate for phthalic
anhydride in the untreated waste, is detected at or above the 2500-ppm
level and therefore is identified as a major constituent in K024
untreated waste. Using a similar selection process, other major
constituents are selected. These constituents and their concentrations
identified in the untreated K024 are listed in Table 6-1 at the end of
this section.
6.2 Comparison of the Untreated and Treated Waste Data for the Ma.ior
Constituents
A comparison of analytical data for the major constituents in the
untreated and treated waste demonstrated whether the major constituents
were significantly reduced and the concentrations of the major
constituents were below the detection limits or practical quantitation
limits (PQLs).
When the concentrations of constituents were not below the detection
limit, the comparison was based on percent reduction. The reduction is
6-2
-------
defined as the ratio of the concentration of the major 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 detection limit. This assumption is based
on the likelihood of masking of the constituent by other constituents in
the untreated waste.
In general, where the concentration of a major constituent in the
waste was reduced by a factor of less than 10 after the treatment of the
waste, the Agency concluded that this reduction in constituent
concentration may not be significant treatment and that, therefore,
further analysis of the analytical data is required to determine whether
the reduction that has been achieved is significant. A statistical
method known as analysis of variance (ANOVA), which is discussed in
Section 1, is used to determine statistically the significance of
constituent concentrations. Table 6-2, at the end of this section,
compares the analytical data for untreated and treated waste for
chloromethane, methyl ethyl ketone, phthalic anhydride, anthracene dione,
and BOAT metals.
EPA recognizes that some BOAT metals were detected in the residue
wastewater and nonwastewater. The TCLP for nonwastewater (i.e., ash) did
not show that BOAT metals are present in the ash at treatable
concentrations. The average TCLP concentration in treated nonwastewater
for any given metal is below treatable levels. In contrast, two BOAT
metals were found in the residue wastewater at levels that may be
6-3
-------
considered treatable. EPA has not chosen to regulate metals for K024 at
this time, but reserves the right to do so at a later date.
Even though methyl ethyl ketone was found in treated nonwastewater
(i.e., ash), as seen from Table 6-2, the concentration was very similar
to the level of 770 ppm detected in methanol blank. This suggests that
methyl ethyl ketone does not exist in nonwastewater. In addition, EPA
believes that methyl ethyl ketone is much more volatile than the
constituent that is being regulated and that, if present, methyl ethyl
ketone would be adequately controlled.
6.3 Evaluation of Waste Characteristics Affecting Performance and
Other Related Factors
The waste characteristics that would affect treatment performance,
discussed in Section 3, are used to evaluate the constituents to
determine whether any additional constituents must be selected for
regulation. Such an evaluation is generally performed when a significant
number of constituents are identified for potential regulation, in order
to shorten the list of regulated pollutants to those that, when treated,
are likely to ensure that many others in the potential list are treated.
In other words, the constituents that are most difficult to treat are
selected, based on the waste characteristics affecting performance of the
technology. For example, aniline is less volatile than benzene, and
therefore it is likely to be more difficult to remove by thermal
processes than benzene. Hence, aniline might be regulated if it were
inadequately removed. In the case of K024 waste, no additional
6-4
-------
constituents were added to the list of constituents already considered
for regulation.
6.4 Selection of Regulated Constituents
Phthalic anhydride is selected as the only regulated constituent for
K024 because this constituent is present in the untreated waste at a
5 percent or higher concentration while all other BOAT constituents are
present at nondetectable levels. This constituent cannot easily be
analyzed, in that the analytical method readily hydrolyzes the compound
to phthalic acid. Therefore, phthalic acid, although not listed as a
hazardous constituent in Part 261 Appendix VIII, is being regulated as a
surrogate for phthalic anhydride. The Agency detected BOAT metals at
potentially treatable concentrations in the wastewater residue (i.e.,
scrubber water) from incineration. At this time, the Agency has decided
not to regulate metals in the wastewater, but reserves the right to
consider regulation of BOAT metals in the future.
6-5
-------
2170g
Table 6-1 Status of BOAT List Constituent Presence
in Untreated K024 Waste
BOAT
reference
no.
222.
1.
2.
3.
4.
5.
6.
223.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
25.
26.
27.
28.
29.
224.
225.
226.
30.
227.
31.
214.
32.
33.
228.
34.
Constituent
Volati 1e oroanics
Acetone
Acetonitrile
Acrolein
Acrylonitri le
Benzene
Bromodichloromethane
Bromomethane
n-Butyl alcohol
Carbon tetrachloride
Carbon disulfide
Chlorobenzene
2-Chloro-l ,3-butadiene
Chlorodibromomethane
Chloroethane
2-Chloroethyl vinyl ether
Chloroform
Chloromethane
3-Chloropropene
1 ,2-Dibromo-3-chloropropane
1 , 2-Oibromoethane
Dibromomethane
trans-l,4-Dichloro-2-butene
Dichlorodif luorome thane
1 . 1-Dichloroethane
1,2-Oichloroethane
1.1-Dichloroethylene
trans-1.2-Dichloroethene
1 ,2-Dichloropropane
trans-1 ,3-Oichloropropene
cis-1 ,3-Dichloropropene
1.4-Dioxane
2-Ethoxyethanol
Ethyl acetate
Ethyl benzene
Ethyl cyanide
Ethyl ether
Ethyl methacrylate
Ethylene oxide
lodomethane
Isobutyl alcohol
Methanol
Methyl ethyl ketone
Detection Believed to
status3 be present
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
<10-40b
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
6-6
-------
2170g
Table 6-1 (Continued)
BOAT
reference
no.
229.
35.
37.
38.
230.
39.
40.
41.
42.
43.
44.
45.
46.
47.
48.
49.
231.
50.
215.
216.
217.
51.
52.
53.
54.
55.
56.
57.
58.
59.
218.
60.
61.
62.
63.
64.
65.
66.
Constituent
Volati 1e orqanics (continued)
Methyl isobutyl ketone
Methyl methacrylate
Methacrylonitri le
Methylene chloride
2-Nitropropane
Pyridine
1. 1,1,2-Tetrachloroethane
1,1 ,2.2-Tetrachloroethane
Tetrachloroethene
Toluene
Tribromomethane
1,1, 1-Trichloroethane
1 , 1 ,2-Trichloroethane
Trichloroethene
Trichloromonof luoromethane
1,2,3-Trichloropropane
l,l,2-Trichloro-l,2.2-
trif luoroethane
Vinyl chloride
1,2-Xylene
1.3-Xylene
1,4-Xylene
Semivolat i le orqanics
Acenaphthalene
Acenaphthene
Acetophenone
2-Acetylaminof luorene
4-Aminobiphenyl
Ani 1 ine
Anthracene
Aramite
Benz(a)anthracene
Benzal chloride
Benzenethiol
Deleted
Benzo(a)pyrene
Benzo(b)f luoranthene
Benzo(ghi)perylene
Benzo( k ) f 1 uoranthene
p-Benzoquinone
Detection Believed to
status3 be present
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
6-7
-------
2170g
Table 6-1 (Continued)
BOAT
reference
no.
67.
68.
69.
70.
71.
72.
73.
74.
75.
76.
77.
78.
79.
80.
81.
82.
232.
83.
84.
85.
«6.
87.
88.
89.
90.
91.
92.
93.
94.
95.
96.
97.
98.
99.
100.
101.
102.
103.
104.
105.
106.
219.
Constituent
Semivolati 1e organ ics (continued)
Bis(2-chloroethoxy)methane
Bis(2-chloroethyl)ether
8is(2-chloroisopropyl)ether
Bis(2-ethy1hexyl)phthalate
4-Bromophenyl phenyl ether
Butyl benzyl phthalate
2-sec-Butyl-4,6-dinitrophenol
p-Chloroani line
Chlorobenzi late
p-Chloro-m-cresol
2-Chloronaphtha lene
2-Chlorophenol
3-Chloropropionitri le
Chrysene
ortho-Cresol
para-Cresol
Cyclohexanone
Dibenzf a, h) anthracene
Dibenzo(a,e)pyrene
Dibenzofa, i)pyrene
m-Dichlorobenzene
o-O ich lorobenzene
p-Dichlorobenzene
3,3'-Oichlorobenzidine
2,4-Oichlorophenol
2,6-Dichlorophenol
Diethyl phthalate
3 . 3 ' -0 imet hoxybenz i d i ne
p-Dimethylaminoazobenzene
3,3'-Oimethylbenzidine
2,4-Oimethylphenol
Dimethyl phthalate
Oi-n-butyl phthalate
1 ,4-Dinitrobenzene
4,6-Dinitro-o-cresol
2,4-Dinitrophenol
2,4-Oinitrotoluene
2,6-Dinitrotoluene
Oi-n-octyl phthalate
Di-n-propylnitrosamine
Diphenylamine
Diphenylnitrosamine
Detection Believed to
status3 be present
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
6-8
-------
2170g
Table 6-1 (Continued)
BOAT Detection Believed to
reference Constituent status3 be present
no.
107.
108.
109.
110.
111.
112.
113.
114.
115.
116.
117.
118.
119.
120.
36.
121.
122.
123.
124.
125.
126.
127.
128.
129.
130.
131.
132.
133.
134.
135.
136.
137.
138.
139.
140.
141.
142.
220.
143.
144.
145.
146.
Semivolatile Orqanics (continued)
1,2-Oiphenylhydrazine
Fluoranthene
Fluorene
Hexachlorobenzene
Hexachlorobutadiene
. Hexachlorocyclopentadiene
Hexachloroethane
Hexachlorophene
Hexachloropropene
Indeno(l ,2,3-cd)pyrene
Isosafrole
Methapyri lene
3-Methylcholanthrene
4,4'-Methylenebis
(2-chloroani line)
Methyl methanesulfonate
Naphthalene
1,4-Naphthoquinone
1-Naphthylamine
2-Naphthylamine
p-Nitroani 1 ine
Nitrobenzene
4-Nitrophenol
N-Nitrosodi-n-butylamine
N-Nitrosodiethylamine
N-Nitrosodimethylamine
N-Nitrosomethylethylamine
N-Nitrosomorphol ine
N-Nitrosopiperidine
n-Nitrosopyrrol idine
5-Nitro-o-toluidine
Pentachlorobenzene
Pentachloroethane
Pentach loron i t robenzene
Pentachlorophenol
Phenacetin
Phenanthrene
Phenol
Phthalic acid (used as a surrogate
for phthalic anhydride)
2-Picotine
Pronamide
Pyrene
Resorcinol
6-9
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
13, 000-22.000°
NA
NA
NA
NA
-------
2170g
Table 6-1 (Continued)
6DAT Detection Believed to
reference Constituent status6 be present
no.
Semivolati1e organics (continued)
147. Safrole NA
148. 1.2,4.5-Tetrachlorobenzene NA
149. 2,3,4.6-Tetrachlorophenol NA
150. 1,2,4-Trichlorobenzene NA
151. 2,4.5-Trichlorophenol NA
152. 2.4,6-Trichlorophenol NA
153. Tris(2.3-dibromopropyl) NA
phosphate
Anthracene dioned 5,400-6,700
154.
155..
156.
157.
158.
159.
221.
160.
161.
162.
163.
164.
165.
166.
167.
168.
Antimony
Arsenic
Barium
Beryll turn
Cadmium
Chromium (total)
Chromium (hexavalent)
Copper
Lead
Mercury
Nickel
Selen ium
Si Iver
Thallium
Vanadium
Zinc
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
Inorganics other than metals
169. Cyanide NA
170. Fluoride NA
171. Sulfide NA
Orqanochlorine pesticides
172. Aldrin NA
173. alpha-BHC NA
174. beta-BHC NA
175. delta-BHC NA
6-10
-------
2170g
Table 6-1 (Continued)
BOAT
reference
no.
Constituent
Detection Believed to
status3 he present
Orqanochlorine pesticides (continued)
176.
177.
178.
179.
180.
181.
182.
183.
184.
185.
1B6.
187.
188.
189.
190.
191.
192.
193.
194.
195.
196.
197.
198.
199.
200.
201.
202.
203.
204.
205.
206.
gamma -BHC
Chlordane
ODD
ODE
DDT
Dieldrin
Endosulfan 1
Endosulfan II
Endrin
Endrin aldehyde
Heptachlor
Heptachlor epoxide
Isodrin
Kepone
Methoxyclor
Toxaphene
Phenoxyacet ic acid herbicides
2.4-Dichlorophenoxyacet ic acid
Si Ivex
2.4.5-T
Orqanophorjnnorous insecticides
Oisulfoton
Famphur
Methyl parathion
Parathion
Phorate
PCBs
Aroclor 1016
Aroclor 1221
Aroclor 1232
Aroclor 1242
Aroclor 1248
Aroclor 1254
Aroclor 1260
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
6-11
-------
2170g
Table 6-1 (Continued)
BOAT
reference
no.
Constituent
Detection
status3
Believed to
be present •
207.
208.
209.
210.
211.
212.
213.
Dioxins and furans
Hexachlorodibenzo-p-dioxins
Hexachlorod i benzofurans
Pentachlorodibenzo-p-dioxins
Pentachlorodibenzofurans
Tetrachlorodibenzo-p-diox ins
Tetrachlorodibenzofurans
2,3,7.8-Tetrachlorodibenzo-
p-dioxin
NA
NA
NA
NA
NA
NA
NA
NA = Not analyzed.
a Where concentrations are shown, units are mg/kg.
Methyl ethyl ketone concentration in methanol blank reported as 770 ppm.
0 Memo to Fred Hall, PEI Associates, Cincinnati, Ohio, from Patrick Meehan,
Radian Corporation, Austin, Texas, dated December 15, 1987.
Non-BDAT parameter.
Reference: EPA 1987b, Tables 6-4 to 6-6.
6-12
-------
1419g/p 16
Table 6-2 Comparison of Major Constituents in Untreated and Treated K024 Waste
Concentration range (ppm)
Untreated waste
Constituent
Composite
Treated waste
Scrubber water
Ash
TCLP Composite TCLP Composite
TCLP
Volatile orqanics
15.a Chloromethane
<10 - 40
NA
34. Methyl ethyl ketone 200 - 240(600-700)c NA
Semivolatile organics
220. Phthalic acid (used 13.000 - 220,000
as a surrogate
for phthalic
anhydride)
Anthracene dione
5,400 - 6,700
NA
NA
<50
<160U
<250I]
NA
NA
NA
NA
<50(460-1100)c
<8.2L
-2.5
NA
NA
NA
NA
155.
156.
158.
159.
160.
161.
163.
166.
168.
Arsenic
Barium
Cadmium
Chromium
Copper
Nickel
Lead
Thai 1 ium
Zinc
NT
NT
NT
NT
NT
NT
NT
NT
NT
NT
NT
NT
NT
NT
NT
NT
NT
NT
<0. 020-0. 22
<0. 010-0. 41
<0. 020-0. 082
<0. 035-0. 65
<0. 030-0. 81
<0. 075-0. 13
1.4 - 16
NT
0.33 -2.1
NA
NA
NA
NA
NA
NA
NA
NA
NA
2.1 -
35 -
'1.5 -
20 -
21 -
11 -
20 -
1.0
29 -
12
3900
2.2
52
46
55
1100
170
-1.5
0.084- 0.38
0.004-0.015
0.004- 0.37
<0.05 - 0. 14
«0.10 - 1.5
-•0.25 - 2.3
0.17 -<0.45
<0.10 - 1.6
NA = Not applicable.
NT = Hot tested.
aBDAT constituent number.
part per billion (ppb)
Numbers given in parenthesis are for methanol extraction procedure where the reading for methyl ethyl
ketone is reported to be 770 ppm. Other methyl ethyl ketone values are for tetraglyme extract.
Memo to Fred Hall, PEI Associates, Cincinnati, Ohio, from Patrick Meehan, Radian Corporation, Austin,
Texas, dated December 15, 1987.
eNon BOAT parameter.
Reference: EPA 1987b. Table 6-3 to 6-6, 6-8 to 6-11, 6-12, 6-13, and 6-14.
6-13
-------
7. CALCULATION OF BOAT TREATMENT STANDARDS
In this section, actual performance of best demonstrated available
technology for the regulated constituent, phthalic anhydride, is
evaluated to calculate a treatment standard. Development of BOAT
treatment standards requires a step-by-step approach. Different
engineering and analytical steps and statistical methods discussed in
Section 1 contribute to this final step of BOAT treatment standards
development. The Agency chooses to establish treatment standards as
performance levels because this provides the greatest flexibility in
meeting the treatment standards. When treatment standards are set as
performance levels, the regulated community may use any technology except
dilution (prohibited under 40CFR 268.3) to treat the waste to achieve the
proposed performance levels.
The treatment standards are also applicable to those wastes regulated
as "mixture" and "derived from" wastes. Hence, the treatment standards
apply to all nonwastewaters and wastewaters derived from or mixed with
the specific waste code.
The BOAT treatment standards (1) are reflective of treatment data for
well-designed and well-operated treatment systems; (2) account for
analytical deficiencies due to masking, interference, or deviation from
the recommended analytical procedures; and (3) adjust for variability due
to treatment, sampling, and analytical techniques and procedures.
The BOAT treatment standard for K024 was developed in the following
manner using actual performance data for rotary kiln incineration.
7-1
-------
7.1 Evaluation of the Performance Data
All the data collected by the Agency for the development of treatment
standards were evaluated to determine (a) whether any of the data
represented poor design or operation of the treatment system; (b) whether
data quality objectives were met; and (c) whether any data sets were
homogeneous, i.e., indicated that more than one treatment technology
achieved the same level of treatment.
7.2 Calculation of Treatment Standards
Treatment standards are calculated using recovery (accuracy) and
precision data generated as part of laboratory QA/QC procedure. All the
relevant data are presented in Appendix B. Because there were no quality
assessments such as matrix spikes and duplicates specifically for
phthalic anhydride (or phthalic acid) the accuracy-corrected
concentrations are calculated using the matrix spike data for other
semivolatile organics such as 1,2,4-trichlorobenzene, acenaphthene,
2,4-dinitrotoluene, pyrene, 1,4-dichlorobenzene, and
N-Nitrosodin-n-propylamine. The spike recovery and spike recovery
(duplicate) values were averaged for these constituents to obtain an
accuracy factor. Table 7-1 presents the accuracy-corrected concentration
for the regulated constituent in each of the residue streams.
EPA recognizes that some BOAT metals were detected in the residue
wastewater and nonwastewater from incineration. At this time, the Agency
has decided not to regulate metals in the waste, but reserves the right
to consider regulation of BOAT metals in the future.
7-2
-------
Also shown in Table 7-1 is a variability factor used to derive a
treatment standard for K024 waste. See Appendix A for derivation of the
variability factor.
7-3
-------
Table 7-1 Calculation of BOAT Treatment Standards fon K024
Constituent
Phthalic acid in
nonwastewater
(ash)
Phthalic acidb in
wastewater
(scrubber water)
Average
Concentration accuracy- BOAT
in treated Accuracy corrected Variability3 treatment
waste factor concentration factor standard
<8.2 ppm 1.19 9.8 ppm 2.8 27.5 ppm
<0.160 ppm 1.2 0.192 ppm 2.8 0.54 ppm
Variability factor of 2.8 is used when all samples are below the detection limit for the constituent.
Used as a surrogate for phthalic anhydride.
-------
8. ACKNOWLEDGMENTS
This document was prepared for the U.S. Environmental Protection
Agency, Office of Solid Waste, by Versar Inc. under Contract
No. 68-01-7053. Mr. James Berlow, Chief, Treatment Technology Section,
Waste Treatment Branch, served as the EPA Program Manager during the
preparation of this document and the development of treatment standards
for the K024 waste. The technical project officer for the waste was
Ms. Lisa Jones. Mr. Steven Silverman served as legal advisor.
Versar personnel involved in the preparation of this document
included Mr. Jerome Strauss, Program Manager; Ms. Rajani Joglekar,
Engineering Team Leader; Ms. Justine Alchowiak, Quality Assurance
Officer; Mr. David Pepson, Senior Technical Reviewer; Mr. James Morgan,
Technical Reviewer; Ms. Juliet Crumrine, Technical Editor; and the Versar
secretarial staff, Ms. Linda Gardiner and Ms. Mary Burton.
Mr. Benjamin Blaney, Chief, Treatment Technology Staff, served as the
Office of Research and Development (ORD) Program Manager for collection
of treatment data for K024 waste. The ORD technical project officer was
Mr. Ronald Turner. The K024 treatment test was executed at the U.S. EPA
Combustion Research Facility by Acurex Corporation, contractor to ORD.
Sampling and analysis for the test were conducted under the leadership of
PEI Associates.
We greatly appreciate the cooperation of the company that permitted
its plant to be sampled and submitted detailed information to the U.S.
EPA.
8-1
-------
9. REFERENCES
Ackennan D.G., McGaughey J.F., and Wagoner D.E. 1983. At sea
incineration of PCB-containing wastes on board the M/T Vulcanus.
EPA 600/7-83-024. Washington, D.C.: U.S. Environmental Protection
Agency.
Bonner T.A., et al. 1981. Engineering handbook for hazardous waste
incineration. SW-889. NTIS PB 81-248163. Prepared by Monsanto
Research Corporation under Contract no. 68-03-3025 for U.S.
Environmental Protection Agency.
Novak R.G., Troxler, W.L., Dehnke, T.H., 1984. Recovering energy from
hazardous waste incineration. Chemical Engineering Progress 91:146.
Oppelt E.T. 1987. Incineration of hazardous waste. JAPCA 37(5).
Santoleri J.J. 1983. Energy recovery—A by-product of hazardous waste
incineration systems. In Proceedings of the 15th Mid-Atlantic
Industrial Waste Conference on Toxic and Hazardous Waste.
USEPA. 1986. U.S. Environmental Protection Agency. Best demonstrated
available technology (BOAT) background document for F001-F005 spent
solvents. Vol. 1. EPA/530-SW-86-056. Washington, D.C.: U.S.
Environmental Protection Agency.
USEPA. 1987a. U.S. Environmental Protection Agency, Office of Solid
Waste. Memorandum concerning adjusted concentration values and
detection limits. Contract no. 68-03-3389, Work Assignment no. 11A.
Washington, D.C.: U.S. Environmental Protection Agency.
USEPA. 1987b. U.S. Environmental Protection Agency. Onsite engineering
report of treatment technology performance and operation: incineration
of K024 waste at the U.S. Environmental Protection Agency's Combustion
Research Facility. Washington, D.C.: U.S. Environmental Protection
Agency.
Vogel G., et al. Incineration and cement kiln capacity for hazardous
waste treatment. In Proceedings of the 12th Annual Research Symposium
on Incineration and Treatment of Hazardous Wastes. April 1986,
Cincinnati, Ohio.
9-1
-------
APPENDIX A
STATISTICAL METHODS
A.I F Value Determination for ANOVA Test
As noted in Section 1.2, EPA is using the statistical method known as
analysis of variance (ANOVA) to determine the level of performance that
represents "best" treatment where more than one technology is
demonstrated. This method provides a measure of the differences between
data sets.
If the Agency found that the levels of performance for one or more
technologies are not statistically different (i.e., the data sets are
homogeneous), EPA would average the long-term performance values achieved
by each technology and then multiply this value by the largest
variability factor associated with any of the acceptable technologies.
If EPA found that one technology performs significantly better (i.e., the
data sets are not homogeneous), the "best" technology would be the
technology that achieves the best level of performance, i.e., the
technology with the lowest mean value.
To determine whether any or all of the treatment performance data
sets are homogeneous using the analysis of variance method, it is
necessary to compare a calculated "F value" to what is known as a
"critical value." (See Table A-l.) These critical values are available
in most statistics texts (see, for example, Statistical Concepts and
Methods by Bhattacharyya and Johnson, 1977, John Wiley Publications,
New York).
A-l
-------
Table A-l
95th PERCENTILE VALUES FOR
THE F DISTRIBUTION
degrees of freedom for numerator
degrees of freedom for denominator
(shaded area = .95)
^
1
2
3
4
5
6
1
8
9
10
11
12
13
14
15
16
17
IB
19
20
no
24
26
28
30
40
50
60
70
80
100
150
200
400
•
1
^
161.4
16.51
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
4.4C
4.2C
4.10
3.98
3.89
3.31
3.74
3.68
3.63
3.59
3.55
3.52
3.49
3.44
3.40
3.37
3.34
3.32
3.23
3.18
3.15
3.13
3.11
3.09
3.06
3.04
3.02
2.99
3
215.7
19.16
9.28
6.59
5.41
4.76
4.35
4.07
3.86
3.71
3.59
3.49
3.41
3.34
3.29
3.24
3.20
3.16
3.13
3.10
3.05
3.01
2.98
2.95
2.92
2.84
2.79
2.76
2.74
2.72
2.70
2.67
2.65
2.62
2.60
4
224.6
19.25
9.12
6.39
5.19
4.53
4.12
3.84
3.G3
3.48
3.36
3.26
3.18
3.11
3.06
3.01
2.96
2.93
2JO
2.S7
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
2JZ7
2.25
2^3
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
2JI3
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
2J6
2.32
2J19
2JI7
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
2^3
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
1.76
16
24G.3
19.43
8.69
5.84
4.GO
3.92
3.49
3.20
2.98
2.82
2.70
2.60
2.51
2.44
2.39
2.33
2^9
2.25
2.21
2.18
2J3
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
1L23
2.19
2.15
2.12
2.07
2.03
1.99
1.96
1.93
1.84
1.78
1.75
1.72
1.70
1.68
1.64
1.62
1.60
1.57
30
250.1
19.46
8.62
5.75
4.50
3.81
3.38
3.08
2.86
2.70
2.57
2.46
2.38
2.31
2 °5
2.20
2.15
2.11
2.07
2.04
1.98
1.94
1.90
1.S7
1.84
1.74
1.69
1.65
1.62
1.60
1.57
1.54
1.52
1.49
1.46
40
251.1
19.46
8.GO
5.71
4.4G
3.77
3.34
3.05
2.82
2.67
2.53
2.42
2.34
2 27
O ">1
2.16
2,11
2.07
2.02
1.99
1.93
1.89
1.85
1.81
1.79
1.69
1.63
1.59
1.56
1.54
1.51
1.47
1.46
1.42
1.40
50
252JJ
19.47
8.58
5.70
4.44
3.75
3.32
3.03
2.80
2.64
2.50
2.40
2.32
2^4
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
5.6G
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
-
25-1.3
19.50
S.53
5.63
4.35
3.67
3.23
2.93
2.71
2.5;
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
A-2
-------
Where the F value is less than the critical value, all treatment data
sets are homogeneous. If the F value exceeds the critical value, it is
necessary to perform a "pair wise F" test to determine if any of the sets
are homogeneous. The "pair wise F" test must be done for all of the
various combinations of data sets using the same method and equation as
the general F test.
The F value is calculated as follows:
(i) All data are natural logtransformed.
(ii) The sum of the data points for each data set is computed (T.).
(iii) The statistical parameter known as the sum of the squares
between data sets (SSB) is computed:
SSB '
where:
k = number of treatment technologies
n^ = number of data points for technology i
N = number of data points for all technologies
Ti = sum of natural logtransformed data points for each technology.
(iv) The sum of the squares within data sets (SSW) is computed:
SSW =
where:
' k
Z
. 1=1
ni 9
£ x i,J
j-1
k
- I
Ti '
. ni -
= the natural logtransformed observations (j) for treatment
technology (i).
A-3
-------
(v) The degrees of freedom corresponding to SSB and SSW are
calculated. For SSB, the degree of freedom is given by k-1. For SSW,
the degree of freedom is given by N-k.
(vi) Using the above parameters, the F value is calculated as
follows:
MSB
F = MSW
where:
MSB = SSB/(k-l) and
MSW = SSW/(N-k).
A computational table summarizing the above parameters is shown below.
Computational Table for the F Value
Source
Between
Within
Degrees of
freedom
k-1
N-k
Sum of
squares
SSB
SSW
Mean square
MSB = SSB/k-1
MSW = SSW/N-k
F value
MSB/MSW
Below are three examples of the ANOVA calculation. The first two
represent treatment by different technologies that achieve statistically
similar treatment; the last example represents a case in which one
technology achieves significantly better treatment than the other
technology.
A-4
-------
1790g
Example 1
Methylene Chloride
Steam stripping
Influent bf fluent
Ug/D
1550.00
1290.00
1640.00
5100.00
1450.00
4600.00
1760.00
2400.00
4800.00
12100.00
Ug/i)
10.00
10.00
10.00
12.00
10.00
10.00
10.00
10.00
10.00
10.00
Biological treatment
ln(ef fluent) [ln(eff luent)]2 Influent bffluent In(effluent)
2.30
2.30
2.30
2.48
2.30
2.30
2.30
2.30
2.30
2.30
Ug/D (M9/D
5.29 1960.00 10.00 2.30
5.29 2568.00 10.00 2.30
5.29 1817.00 10.00 2.30
6.15 1640.00 26.00 3.26
5.29 3907.00 10.00 2.30
5.29
5.29
5.29
5.29
5.29
[In(effluent)]2
5.29
5.29
5.29
10.63
5.29
Sum:
23.18
53.76
12.46
31.79
Sample Si/e:
10 10
Mean:
3669
10.2
Standard Oev\ation:
3328.67 .63
Variabi1ity Factor:
10
2.32
.06
2378
923.04
1.15
13.2
7.15
2.48
2.49
.43
ANOVA Calculations:
if IL
'=1 I n~
MSB = SSB/(k-l)
MSW = SSW/(N-k)
-M£]
A-5
-------
1790g
Example 1 (Continued)
F = MSB/MSW
where:
k = number of treatment technologies
n. = number of data points for technology i
N - number of natural logtransfortned data points for all technologies
T. = sum of logtransformed data points for each technology
X = the nat. logtransformed observations (j) for treatment technology (i)
ij
n = 10, n = 5. N = 15. k = 2. T = 23.18. T = 12.46. T = 35.64. T = 1270.21
T = 537.31 T = 155.25
SSB
10
SSW - (53.76 + 31.79) -
MSB = 0.10/1 = 0.10
MSW = 0./7/13 - 0.06
0.10
1270.21
15
537.31 155.25
-f
10 5
= 0.10
= 0.77
0.06
1.67
ANOVA Table
Degrees of
Source freedom
Between(B) 1
Within(W) 13
SS MS F value
0.10 0.10 1.67
0.77 0.06
The critical value of the F test at the 0.05 significance level is 4.67. Since
the F value is less than the critical value, the means ore not significantly
different (i.e.. they are homogeneous).
Note: All calculations were rounded to two decimal places. Results may differ
depending upon the number of decimal places used in each step of the calculations.
A-6
-------
1790g
Example 2
Trichloroethylene
£team stripping
Influent
(M9/D
1650.00
5200.00
5000.00
1720.00
1S60.00
10300.00
210.00
1600.00
204.00
160.00
Effluent
(<»g/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
O(effluent)]2
5.29
5.29
5.29
5.29
5.29
5.29
5.29
10.89
19.71
5.29
Influent
(M9/D
200.00
224.00
134.00
150.00
484.00
163.00
182.00
Biological treatment
Effluent
Ug/i)
10.00
10.00
10.00
10.00
16.25
10.00
10.00
ln(eff luent)
2.30
2.30
2.30
2.30
2.79
2.30
2.30
[In(effluent)]2
5.29
5.29
5.29
5.29
7.78
5.29
5.29
Sum:
Sample Size:
10 10
26.14
10
72.92
16.59
. 39.52
Mean:
2760
19.2
Standard Deviation:
3209.6 23.7
Variabi I ity Factor:
3.70
2.61
.71
220
120.5
10.89
2.36
1.53
2.37
.19
ANOVA Calculations:
SSb =
k
2
i = l
1(2 11
n — J
ni ;
f k r 12
N
SSW =|2,-,
1=1 j-1
MSB = SSB/(k-l)
MSW = SSW/(N-k)
A-7
-------
1790g
Example 2 (Continued)
F - MSB/HSU
where:
k = number of treatment technologies
n = number of data points for technology i
i
N = number of data points for all technologies
T. = sum of natural logtransformed data points for each technology
X - the natural logtransformed observations (j) for treatment technology (i)
ij
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,
275.23
SSB =
683'30
10
SSW = (72.92 + 39.52) -
MSB - 0.25/1 = 0.25
MSW = 4.79/15 = 0.32
_ 0.25
1825.85
17
683.30 275.23
10 7
= 0.25
= 4.79
0.78
0.32
ANOVA Table
Source
Between! B)
Within(W)
Degrees of
freedom
1
15
SS MS F value
0.25 0.25 0.78
4.79 0.32
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.
A-8
-------
I790g
Example 3
Chlorobenzene
Activated sludge followed by carbon adsorption
Biological treatment
Influent
Ug/l)
Effluent
Ug/D
In(effluent) [ln(eff luent)]'
Influent
Ug/D
Effluent
Ug/D
ln(effluent)
ln[(effluent)]2
7200.00
6500.00
6075.00
3040.00
80.00
70.00
35.00
10.00
4.38
4.25
3.56
2.30
19.18
18.06
12.67
5.29
9206.00
16646.00
49775.00
14731.00
3159.00
6756.00
3040.00
1083.00
709.50
460.00
142.00
603.00
153.00
17.00
6.99
6.56
6.13
4.96
6.40
5.03
2.83
48.86
43.03
37.58
24.60
40.96
25.30
8.01
Sum:
Sample Size:
4
14.49
55.20
38.90
228.34
Mean:
5703
49
3.62
14759
452.5
5.56
Standard Deviation:
1835.4 32.24
Variabi I ily Factor:
7.00
.95
16311.86
379.04
15.79
1.42
ANOVA Calculations:
SSB -
i=l
T,
,1, " ]
2 1
f k nj , 1 k f Tj2 }
SSW = .E .E x2j.j Z —
I i=l j=l
-------
1790g
where.
Example 3 (Continued)
k = number of treatment technologies
n - number of data points for technology i
i
N = number of data points for all technologies
T = sum of natural logtransformed data points for each technology
i
X - the natural logtransformed observations (j) for treatment technology (i)
ij
N = 4. N = 7, N = 11. k = 2. T = 14.49. T = 38.90. T = 53.39. T'= 2850.49. T* = 209.96
T = 1513.21
209.96 + 1513.21
4 7
SSW = (55.20 + 228.34)
- 9.52
= 14.88
MSB = 9.52/1 = 9.52
MSW - 14.88/9 - 1.65
F = 9.52/1.65 - 5.77
ANOVA Table
Degrees of
Source freedom
SS
MS
F value
Betwecn(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 5.1?. Since
the F value is larger than the critical value, the means are significantly
different (i.e.. they are heterogeneous). Activated sludge followed by carbon
adsorption is "best" in this example because the mean of the long-term performance
value, i.e., the effluent concentration, is lower.
Note: All calculations were rounded to two decimal places. Results may differ depending
upon the number of decimal places used in each step of the calculations.
A-10
-------
A.2 Variabilitv Factor
C99
VF = Mean
where:
VF = estimate of daily maximum variability factor determined
from a sample population of daily data;
Cgg = estimate of performance values for which 99 percent of the
daily observations will be below. Cgg is calculated
using the following equation: Cgq = Exp(y + 2.33 Sy)
where y and Sy are the mean and standard deviation,
respectively, of the logtransformed data; and
Mean = average of the individual performance values.
EPA is establishing this figure as an instantaneous maximum because
the Agency believes that on a day-to-day basis the waste should meet the
applicable treatment standards. In addition, establishing this
requirement makes it easier to check compliance on a single day. The
99th percentile is appropriate because it accounts for almost all process
variability.
In several cases, 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 show that the treatment residual concentrations are
A-ll
-------
distributed approximately lognormally. Therefore, the lognormal model
has been used routinely in the EPA development of numerous regulations in
the Effluent Guidelines program and is being used in the BOAT program.
The variability factor (VF) was defined as the ratio of the 99th
percentile (C ) of the lognormal distribution to its arithmetic mean
(Mean), as follows:
VF = C99. (1)
Mean
The relationship between the parameters of the lognormal distribution
and the parameters of the normal distribution created by taking the
natural logarithms of the 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 (n) and standard deviation (a) of the normal distribution as
follows:
C9g = Exp (M + 2.33a) (2)
Mean = Exp (M + 0.5a2). (3)
By substituting (2) and (3) in (1), the variability factor can then
be expressed in terms of a as follows:
VF = Exp (2.33 a - 0.5a2). (4)
For residuals with concentrations that are not all below the
detection limit, the 99th percentile and the mean can be estimated from
the actual analytical data and, accordingly, the variability factor (VF)
can be estimated using equation (1). For residuals with concentrations
A-12
-------
that are below the detection limit, the above equations can be used in
conjunction with the following assumptions to develop a variability
factor.
• Assumption 1: The actual concentrations follow a lognormal
distribution. The upper limit (UL) is equal to the detection
limit. The lower limit (LL) is assumed to be equal to one-tenth
of the detection limit. This assumption is based on the fact that
data from well-designed and well-operated treatment systems
generally fall within one order of magnitude.
• Assumption 2: The natural logarithms of the concentrations have
a normal distribution with an upper limit equal to In (UL) and a
lower limit equal to In (LL).
• Assumption 3: The standard deviation (a) of the normal
distribution is approximated by:
a = [ln(UL) - ln(LL)] / [(2)(2.33)]
= [ln(UL/LL)] / 4.66. (5)
(Note that when LL = (0.1)(UL) as in Assumption 1, then
a = (InlO) / 4.66 = 0.494.)
Substitution of the a value from equation (5) into equation (4)
yields the variability factor, VF, as shown:
VF = 2.8. (6)
A-13
-------
APPENDIX B
ANALYTICAL QA/QC
Quality assurance/quality control (QA/QC) measures taken during the
test are outlined in this appendix.
B.I Volatile Organic Compounds
The volatile samples were analyzed according to the QA/QC procedures
outlined in SW-845 Method 8240, 3rd ed. Calibration of the instrument
was demonstrated daily with PFTBA to give an acceptable spectrum of BFB.*
System performance was verified initially (beginning with 5-point
calibrations) to ensure a minimum average response factor of 0.3 (0.25
for bromoform) for the following system performance check compounds
(SPCCs):
• Chloromethane
• 1,1-Dichloroethane
• Bromoform
• 1,1,2,2-Tetrachloroethane
• Chlorobenzene
Adherence to these criteria was demonstrated every 12 hours for the
duration of the project.
*PFTBA, perfluorotributyl amine; BFB, bromofluorobenzene.
B-l
-------
For analyte calibration, the initial 5-point calibration of 5, 10,
50, 100, and 200 ^g/liter standards, used for generating response
factors, also demonstrated a percent relative standard deviation (% RSD)
of less than 30 for all of the following calibration check compounds
(CCC's):
1,1-Dichloroethene
Chloroform
1,2-Dichloropropane
Toluene
Ethyl benzene
Vinyl chloride
Adherence to this criterion was also demonstrated every 12 hours for
the duration of the project.
A sample from each matrix type was used to perform duplicate matrix
spike analyses. Each sample was spiked with 125 ng of the following
matrix spike compounds as per EPA SW-846, 3rd ed:
• 1,1-Dichloroethene
• Trichloroethene
• Toluene
• Benzene
Tables B-l through B-5, at the end of this appendix, show the
accuracy and precision of these analyses. The percentage recoveries of
the spikes for 1,1-dichloroethylene in the scrubber effluent are outside
acceptable limits. All other sample recoveries are within the specified
target limits, as are the relative percent differences.
B-2
-------
B.2 Semi volatile Organic Compounds
All semi volatile extracts were analyzed by the QA/QC procedures
outlined in SW-846 Method 8270, 3rd edition, without significant
modification. The mass spectrometer used for these analyses (see
Table B-l) was tuned daily by PFTBA. The stability of this tune was
verified by demonstrating an acceptable spectrum of decafluorotriphenyl-
phosphine (DFTPP) daily (or every 12 hours). Acceptable chromatography
was verified daily by examining the peak shape of benzidine and
pentachlorophenol.
System performance was verified daily, beginning with the 5-point
calibration, by demonstrating that system performance check compounds
(SPCCY's) had response factors greater than 0.05 when using the
50 A*9/rol calibration standard. These SPCCs were:
• N-nitrosodi-n-propylamine
• Hexachlorocyclopentadiene
2,4-Dichlorophenol
• 4-Nitrophenol
For continuing analyte calibration, three 5-point calibrations were
generated during the course of this work with Appendix IX standards at
10, 20, 50, 100, and 200 t^g/m^ concentrations. Specific ion response
factors for the following calibration check compounds (CCCs) were
verified to have less than 30 percent relative standard deviation over
the range calibrated:
Phenol
1,4-Dichlorobenzene
2-Nitrophenol
2,4-Dichlorophenol
Hexachlorobutad i ene
4-Chioro-3-methyl phenol
Acenaphthene
B-3
2,4,6-Trichlorophenol
N-nitrosodiphenylamine
Pentachlorophenol
Fluoranthene
Di-n-octylphthalate
Benzo(a)pyrene
-------
These CCCs were reanalyzed every 12 hours to verify that the response
factor remained within +30 percent of that generated from the average of
the 5-point standard.
For duplicate matrix spike analyses, a sample from each matrix type
was used to perform duplicate matrix spike analyses. Samples were spiked
prior to extraction with a mixture containing the following:
1,2,4-Trichlorobenzene
Acenaphthene
2,4-Oinitrotoluene
Pyrene
1,4-Dichlorobenzene
N-nitrosodi-n-propylamine
Pentachlorophenol
Phenol
2-Chlorophenol
4-Chloro-3-methyl phenol
4-Nitrophenol
The accuracy and precision of these analyses are shown in Tables B-6
through B-13.
B.3 Metals and Other Parameters
All samples were analyzed according to the QA/QC procedures outlined
in the appropriate methods listed in Section 1. All instruments were
calibrated daily with freshly prepared standards.
System performance was verified immediately after calibration with a
calibration verification standard prepared from a different source. When
applicable, an NBS or EPA Quality Assurance sample is used for this
purpose. This standard is then analyzed at 10 percent intervals
throughout the analysis and at the end of the analytical run to verify
system control. For all parameters, the recoveries for the calibration
B-4
-------
verification standards analyzed throughout this project were between 86
and 111 percent.
Ash sample number CK-24-3-B1 was used for the duplicate matrix spike
analysis. These data are presented in Table B-14. Precision, as
measured by relative percent difference, is <20 percent on all of these
analyses, which is the acceptance limit required for this project.
Accuracy (percent recovery) for the metals analyzed by ICP is within the
acceptance range of 75 to 125 percent. Recovery of the elements by
atomic absorption is lower than the ICP acceptance limits. Other
parameters (instrument checks, calibration, and check samples) were
within range for these analyses, which indicates that a matrix effect was
the cause of these low recoveries. Analyses by graphite furnace atomic
absorption for arsenic, selenium, and thallium are more sensitive than
those using the ICP methods, but they are also more prone to physical and
chemical matrix interferences.
B-5
-------
Table B-l Volatiles Spike Recovery (Accuracy) and Relative Percent Difference (Precision)
for Scrubber Sample
Matrix spike
Benzene
Chlorobenezene
1.1-Dichloroethylene
Toluene
Trichloroethene
Determined
CK24-2-D2
43532
N0a
ND
ND
ND
ND
concentration (/jg/liter)
CK24-2-D2
43533
28
30
45
29
21
CK24-2-D2
43534
28
29
41
29
20
Percent
spike
recovery
112
120
180
116
84
Percent
spike
recovery
duplicate
112
116
164
116
80
Relative
percent
difference
0
3
9
0
5
SND = Not detected.
CO
cr>
Table B-2 Volatiles Spike Recovery (Accuracy) and Relative Percent Difference (Precision)
for Tetraglyme Extract of Feed Sample
Matrix spike
Benzene
Chlorobenezene
1 . 1-Dichloroethylene
Toluene
Trichloroethene
Determined
CK24-1-AX
43651
2
NDa
ND
ND
ND
concentration
CK24-1-AX
43728
29
28
28
29
22
(/ig/liter)
CK24-1-AX
43729
29
29
27
29
21
Percent
spike
recovery
116
112
112
116
88
Percent
spike
recovery
duplicate
116
116
108
116
84
Relative
percent
difference
0
4
4
0
5
3ND = Not detected.
-------
Table B-3 Volatiles Spike Recovery (Accuracy) and Relative Percent Difference (Precision)
for Tetraglyme Extract of Ash Sample
Matrix spike
Benzene
Chlorobenezene
1, 1-Oichloroethylene
Toluene
Tr ichloroethene
Determined
CK24-2-B1
43650
3
N0a
ND
2
ND
concentration (/jg/ liter)
CK24-2-B2
43658
29
28
35
33
26
CK24-2-B2
• 43659
29
28
34
29
27
Percent
spike
recovery
104
112
140
122
104
Percent
spike
recovery
duplicate
104
112
136
107
108
Relative
percent
difference
0
0
3
13
4
"ND = Hot detected.
CD
I
—I
Table B-4 Volatiles Spike Recovery (Accuracy) and Relative Percent Difference (Precision)
for TCLP Extract of Feed Sample
Matrix spike
Benzene
Chlorobenezene
1 . 1-Oichloroethy lene
Toluene
Tr ichloroethene
Determined
CK24-3-AX
43634
6
NDa
ND
7
ND
concentration (/jg/liter)
CK24-3-AX-1
43645
32
27
35
30
27
CK24-3-AX-1
43646
31
26
38
27
27
Percent
spike
recovery
103
108
140
94
108
Percent
spike
recovery
duplicate
100
104
152
84
108
Relative
percent
difference
3
4
8
11
0
°ND = Not detected.
-------
Table B-S Volatiles Spike Recovery (Accuracy) and Relative Percent Difference (Precision)
for TCLP Extract of Ash Sample
CO
i
00
Determined concentration (^g/liter)
Matrix spike
+>
Benzene
Chlorobenezene
1 , 1-Dichloroethylene
Toluene
Trichloroethene
CK24-2-B1-1
43632
2
NDa
NO
2
NO
CK24-2-B2-1
43633
28
30
31
29
28
CK24-2-B2-4
43634
29
27
36
28
26
Percent
spike
recovery
104
120
124
107
112
Percent
spike
recovery
duplicate
107
108
144
104
104
Relative
percent
difference
4
11
15
4
7
aND = Not detected.
-------
Table B-6 Semivolatiles Matrix Spike Extract Surrogate Recoveries (%)
Surrogate
2-F luorophenol
Phenol-d5
Nitrobenzene-d5
2-Fluorobiphenyl
2.4.6-Tribromophenol
Terphenyl-dl4
CK24-2-03
21
30
92
67
49
100
CK24-2-D3
26
32
92
65
51
102
CK24-2-AX
108
111
111
75
87
112
CK24-2-AX
105
104
105
69
80
111
CK24-1-B1
95
94
99
67
77
103
CK24-1-B1
90
92
96
68
81
104
CK24-3-AX
78
85
80
57
73
87
CK24-3-AX
63
64
86
61
76
91
CK24-2-B1
89
90
75
42
75
89
CK24-2-B1
64
64
71
42
46
69
-------
1419g/p 7
Table B-7 Semivolatiles Laboratory Check Standard
Extract Surrogate Recoveries (%)
Surrogate
2-Fluorophenol
Phenol-d5
Nitrobenzene-d5
2-Fluorobiphenyl
2,4,6-Tribromophenol
Terphenyl-dl4
Run 1
35993
78
78
85
55
52
100
Run 2
36053
62
64
74
49
44
94
Run 3
36055
71
77
82
54
55
99
Run 4
36056
70
76
84
55
57
100
B-10
-------
Table B-8 Semivolatiles Matrix Spike Recovery (Accuracy) and Relative
Difference (Precision) for Scrubber Effluent Sample
CD
i
(B/N = 50 ^/nil)
Matrix spike (Acids = 100 /ig/ml)
1 , 2.4-Trichlorobenzene
Acenaphthene
2,4-Dinitrotoluene
Pyrene
1 ,4-Dichlorobenzene
N-Nitrosodi-n-propylamine
Pentachlorophenol
Phenol
2-Chlorophenol
4 -Chloro- 3 -methyl phenol
4-Nitrophenol
Determined
CX24-2-D3
NO
ND
NO
ND
ND
ND
ND
ND
ND
ND
ND
concentration
CK24-2-D3
36
48
57
49
34
21
60
36
49
49
77
(wq/liter)
C24-2-D3
36
49
60
50
34
22
64
34
46
47
90
Spike
recovery (%)
72
96
114
98
68
42
60
36
49
49
77
Spike
recovery
duplicate ('/,)
72
98
120
100
68
44
64
34
46
47
90
Relative
percent
difference ('/,)
0
2
5
3
0
5
6
6
6
4
16
ND = Not detected.
-------
Table B-9 Semivolatiles Matrix Spike Recovery (Accuracy) and Relative
Difference (Precision) for Feed Sample
(B/N = 50 Kg/ml)
Matrix spike (Acids = 100 jig/ml)
1.2,4-Trichlorobenzene
Acenaphthene
2.4-Dinitrotoluene
Pyrene
CO
*-• 1 ,4-Dichlorobenzene
ro
N-Nitrosodi-n-propylamine
Pentachlorophenol
Phenol
2-Chlorophenol
4-Chloro-3-methylphenol
4-Nitrophenol
Determined
CX24-2-AX
NO
NO
ND
ND
ND
ND
ND
ND
ND
ND
ND
concent rat ion
CK24-2-AX
54
53
64
49
52
27
104
106
123
95
123
M/liter)
C24-1-B1
50
50
60
44
49
24
93
106
119
92
116
Spike
recovery (%)
108
106
128
98
104
54
104
106
123
95
123
Spike
recovery
duplicate (%)
100
100
120
88
98
48
93
106
119
92
116
Relative
percent
difference (%)
8
6
6
11
6
12
11
0
3
3
6
ND = Not detected.
-------
Table B-10 Semivolatiles Matrix Spike Recovery (Accuracy) and Relative
Difference (Precision) for Ash Sample
CD
I
(B/N = 50 ng/ml)
Matrix spike (Acids = 100 ^g/ml)
1 .2.4-Trichlorobenzene
Acenaphthene
2,4-Dinitrotoluene
Pyrene
1 . 4-D ich lorobenzene
N-Nitrosodi-n-propylamine
Pentachlorophenol
Phenol
2-Chlorophenol
4 -Chloro- 3 -methyl phenol
4-NitrophenoT
Determined
CX24-1-B1
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
concent rat ion
CK24-1-B1
45
48
59
47
45
20
98
96
109
88
120
(jiq/ liter)
C24-1-B1
45
48
59
41
45
13
91
94
107
86
114
Spike
recovery (%)
90 '
96
118
94
89
40
98
96
109
88
120
Spike
recovery
duplicate (%)
90
96
118
82
90
26
91
94
107
86
114
Relative
percent
difference ('4)
0
0
0
14
1
42
7
2
2
2
5
ND = Not detected.
-------
Table B-ll Seimvolat i les Matrix Spike Recovery (Accuracy) and Relative
Difference (Precision) for Feed TCLP Extract
cc
i
(B/N = 50 ug/ml)
Matrix spike (Acids = 100 /ig/ml)
1 . 2.4- T rich lorobenzene
Acenaphthene
2.4-Dimtrotoluene
Pyrene
1 ,4-Dichlorobenzene
N-Nitrosodi-n-propylamine
Pentachlorophenol
Phenol
2-Chlorophenol
4 -Chloro- 3 -methyl phenol
4-Nitrophenol
Determined
CK24-3-AX
NO
NO
NO
NO
NO
NO
11
8
NO
NO
NO
concentrat ion
CK24-3-AX
22
24
31
32
21
26
32
33
24
23
32
[(iq/ liter)
C24-3-AX
21
23
32
24
21
27
28
27
23
23
22
Spike
recovery (%)
88
96
124
128
84
104
84
100
96
96
128
Spike
recovery
duplicate (%)
84
92
128
96
84
108
64
76
96
96
88
Relative
percent
difference (%)
5
4
3
29
0
4
27
27
0
0
37
ND = Not detected.
-------
Table B-12 Semivolatiles Matrix Spike Recovery (Accuracy) and Relative
Difference (Precision) for Ash TCLP Extract
Determined concentration In
(B/N = 50 /.g/ml)
Matrix spike (Acids = 100 /jg/ml)
1 ,2,4-Tr ichlorobenzene
Acenaphthene
2,4-Dinitrotoluene
Pyrene
DO
1
JjJ 1 ,4-Dichlorobenzene
N-Nitrosodi-n-propylamine
Pentachlorophenol
Phenol
2-Chlorophenol
4-Chloro-3-methylphenol
4-Nitrophenol
CK24-2-B1
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
CK24-2B-1
21
24
23
22
20
26
14
24
24
20
23
q/ liter)
C24-2-B1
19
20
15
16
19
21
10
19
20
16
8
Spike
recovery ('/,)
84
96
92
88
80
104
56
96
96
80
92
Spike
recovery
duplicate ('/,)
76
80
60
64
76
84
40
76
80
64
32
Relative
percent
difference ('/)
10
18
42
32
5
21
33
23
18
22
97
ND = Not detected.
-------
Table B-13 Semivolatiles Laboratory Check Standard Results
Analyte (true concentration)
Determined concentration (;jq/1iter with percent error)
Run 1 Run 2 Run 3 Run 4 Mean Precision
35993 36053 36055 36056 (% error) (% RSO)
1.2,4-Trichlorobenzene (50.7)
Pentachloronitrobenzene (74.5)
41.6 (18'/0 41.7 (18X) 39.8 (18%) 41.5 (18%) 41.2 (18'X) 2.2%
56.2 (25'X) 61.1 (18%) 62.9 (16%) 64.8 (13%) 61.3 (187.) 6.07C
oo
i
-------
1419g/p 14
Table B-14 Duplicate Matrix Spike Data for Metals
Analysis of Ash Sample CK-24-3-B1
CK-24-3-81
Si Iver
Arsenic
Barium
Beryl 1 mm
Cadmium
Chromium
Copper
Mercury
Nickel
Lead
Arit imony
Selenium
Tha 1 1 ium
Vanadium
Zinc
CK-24-3-B1
Ug/g)
NO
2.1
35
NO
ND
52
21
ND
55
20b
ND
ND
ND
9b
29
MS
CK-24-3-B1
t%)
89
51d
81
86
87
90
91
115
89
90
106
Oa
65a
87
84
MSD
difference
(%)
88
46a
91
85
84
97
84
105
99
90
98
0
69
88
82
Relative
percent
Analyte
(%)
1
10
12
1
4
7
8
9
11
0
8
c
6
1
2
ND = Not detected.
aData outside of QC/QA limits for this analysis.
Amount is less than five times detection limit.
cNot calculated.
B-17
-------
APPENDIX C
METHOD OF MEASUREMENT FOR THERMAL CONDUCTIVITY
The comparative method of measuring thermal conductivity has been
proposed as an ASTM test method under the name "Guarded, Comparative,
Longitudinal Heat Flow Technique." A thermal heat flow circuit is used
that is the analog of an electrical circuit with resistances in series.
A reference material is chosen to have a thermal conductivity close to
that estimated for the sample. Reference standards (also known as heat
meters) having the same cross-sectional dimensions as the sample are
placed above and below the sample. An upper heater, a lower heater, and
a heat sink are added to the "stack" to complete the heat flow circuit.
See Figure C-l.
The temperature gradients (analogous to potential differences) along
the stack are measured with type K (chromel/alumel) thermocouples placed
at known separations. The thermocouples are placed into holes or grooves
in the references and also in the sample whenever the sample is thick
enough to accommodate them.
For molten samples, pastes, greases, and other materials that must be
contained, the material is placed into a cell consisting of a top and
bottom of Pyrex 7740 and a containment ring of marinite. The sample is
2 inches in diameter and 0.5 inch thick. Thermocouples are not placed
into the sample; rather, the temperatures measured in the Pyrex are
extrapolated to give the temperature at the top and bottom surfaces of
the sample material. The Pyrex disks also serve as the thermal
conductivity reference material.
C-l
-------
UPPER
GUARD
HEATER
THERMOCOUPLE
GUARD
GRADIENTX
STACK
GRADIENT
LOWER
GUARD
HEATER
FIGURE C-l SCHEMATIC DIAGRAM OF THE COMPARATIVE METHOD
C-2
-------
The stack is clamped with a reproducible load to ensure intimate
contact between the components. To produce a linear flow of heat down
the stack and reduce the amount of heat that flows radially, a guard tube
is placed around the stack, and the intervening space is filled with
insulating grains or powder. The temperature gradient in the guard is
matched to that in the stack to further reduce radial heat flow.
The comparative method is a steady-state method of measuring thermal
conductivity. When equilibrium is reached, the heat flux (analogous to
current flow) down the stack can be determined from the references. The
heat into the sample is given by
Q = A (dT/dx)
in top top
and the heat out of the sample is given by
Q = A (dT/dx)
out bottom bottom
where
A = thermal conductivity
dT/dx = temperature gradient
and top refers to the upper reference, while bottom refers to the lower
reference. If the heat were confined to flow down the stack, then 0
in
and Q would be equal. If Q. and Q are in reasonable
out in out
agreement, the average heat flow is calculated from
Q = (Q + Q )/2.
in out
The sample thermal conductivity is then found from
A = Q/(dT/dx)
sample sample.
C-3
------- |