vvEPA
United States
Environmental Protection
Agency
Office of
Solid Waste
Washington, D C 20460
EPA/530-SW-88-0009-h
April 1988
Solid Waste
Best
Demonstrated
Available Technology
(BOAT) Background
Document for
K024
Proposed
Volume 8
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BEST DEMONSTRATED AVAILABLE TECHNOLOGY (BOAT)
BACKGROUND DOCUMENT FOR K024
Volume VIII
U.S. Environmental Protection Agency
Office of Solid Waste
401 M Street, S.W.
Washington, D.C. 20460
James R. Berlow, Chief ORD
Treatment Technology Section Project Manager
April 1988
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BOAT BACKGROUND DOCUMENT FOR K024
TABLE OF CONTENTS
VOLUME 8 Page
Execut i ve Summary i i i
BOAT Treatment Standards for K024 v
SECTION 1. Introduction 1
SECTION 2. Industries Affected and Waste Characterization 46
SECTION 3. Applicable/Demonstrated Treatment Technologies 52
SECTION 4. Selection of BOAT 73
SECTION 5. Determination of Regulated Constituents 77
SECTION 6. Calculation of Treatment Standard 84
SECTION 7. Conclusions 88
APPENDIX A Statistical Analysis A-l
APPENDIX B Analytical QA/QC B-l
APPENDIX C Analytical Method for Determining the Thermal
Conductivity of a Waste C-l
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EXECUTIVE SUMMARY
Pursuant to the Hazardous and Solid Waste Amendments (HSWA) enacted
on November 8, 1984, and in accordance with the procedures for
establishing treatment standards under Section 3004(m) of the Resource
Conservation and Recovery Act (RCRA), the following treatment standards
have been proposed as Best Demonstrated Available Treatment (BOAT) for
the listed waste identified in 40 CFR Part 261.32 (Code of Federal
Regulations) as K024 (distillation bottoms from the production of
phthalic anhydride from naphthalene). The Agency believes that only one
facility produces phthalic anhydride using naphthalene as a feed stock.
A treatment standard is established for one organic constituent,
namely, phthalic acid, which the Agency believes is an indicator of
effective treatment for the BOAT hazardous constituent phthalic
anhydride. 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, a BOAT
constituent, is present at treatable concentrations in the waste. This
standard is proposed 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 a rotary kiln
incinerator to destruct K024. The listed waste has a low water content
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and high organic solids concentration and is generated in the organic
chemical industry. The Agency has examined all available data submitted
by industry and from open literature. These additional data confirm that
incineration is the best technology to effectively treat K024 waste. The
standards proposed are established based on total concentration analyses
conducted on the total (untreated) waste, ash residues, and scrubber
water generated during the incineration of K024 in a rotary kiln
incinerator.
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 regulations of BOAT metals in the future.
These standards become effective as of August 8, 1988, as per the
schedule set forth in 40 CFR 268.10. Because of the lack of nationwide
'incineration capacity at this time, the Agency has proposed to grant a
2-year nationwide variance to the effective date of the land disposal ban
for this waste.
The following tables present the wastewater and nonwastewater
treatment standards for K024 waste. Note that Table 1 presents treatment
standards given in the preamble while Table 2 provides the revised
treatment standards. The explanation for the revision is given below.
It should be noted that this background document was written after
the completion of the preamble for the proposed rule on establishing
treatment standards (BOAT) for K024. The treatment standards in the
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preamble were determined from limited data available from the Onsite
Engineering Report of Treatment Technology Performance and Operation:
Incineration of K024 Waste at the U.S. Environmental Protection Agency
Combustion Research Facility. Since that time, additional data have been
made available, especially for the detection limits. These revised
detection limits were used to determine the treatment standards discussed
in Section 6 and 7 of this document. The final rule will reflect all
necessary corrected values from these additional data when it is
promulgated.
For the purpose of the land disposal restriction rule, wastewaters
are defined as wastes containing less than one percent (weight basis)
filterable solids and less than one percent (weight basis) total organic
carbon (TOC). The units for the total concentration analysis are in
parts per million (mg/kg for nonwastewaters, and mg/1 for wastewaters).
Testing procedures are specifically identified in Appendix B (QA/QC
Section) of this background document.
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1419g
Table 1
BOAT Treatment Standard for K024
(Preamble - Nonwastewater)
Concentration Preamble
in treated proposed
Regulated organic waste Accuracy Variability standard
constituent (mg/kg) factor factor (mg/kg)
Phthalic* <2.5 .85 2.8 6.00
acid
BOAT Treatment Standard for K024
(Preamble - Wastewater)
Concentration Preamble
in treated proposed
Regulated organic waste Accuracy Variability standard
constituent (mg/kg) factor factor (mg/1)
Phthalic* <.250 1.142 2.8 . .80
acid
*This 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.
Standards based on TCLP are not applicable.
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1419g
Table 2
BOAT Treatment Standards for K024
(Nonwastewater)
Regulated organic Total composition
constituent (mg/kg)
Phthalic acid* 27.5 Not applicable
BOAT Treatment Standards for K024
(Uastewater)
Regulated organic Total composition TCLP
constituent (mg/1) (mg/1)
Phthalic acid* 0.54 Not applicable
*This 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 BOAT treatment standards were
developed, a summary of EPA's promulgated methodology for developing
BOAT, and finally a discussion of the petition process that should be
followed to request a variance from the BOAT treatment standards.
1.1 Legal Background
1.1.1 Requirements Under HSWA
The Hazardous and Solid Waste Amendments of 1984 (HSWA), enacted on
November 8, 1984, and which amended the Resource Conservation and
Recovery Act of 1976 (RCRA), impose substantial new responsibilities on
those who handle hazardous waste. In particular, the amendments require
the Agency to promulgate regulations that restrict the land disposal of
untreated hazardous wastes. In its enactment of HSWA, Congress stated
explicitly that "reliance on land disposal should be minimized or
eliminated, and land disposal, particularly landfill and surface
impoundment, should be the least favored method for managing hazardous
wastes" (RCRA section 1002(b)(7), 42 U.S.C. 6901(b)(7)).
One part of the amendments specifies dates on which particular groups
of untreated hazardous wastes will be prohibited from land disposal
unless "it has been demonstrated to the Administrator, to a reasonable
degree of certainty, that there will be no migration of hazardous
constituents from the disposal unit or injection zone for as long as the
wastes remain hazardous" (RCRA section 3004(d)(l), (e)(l), (g)(5), 42
U.S.C. 6924 (d)(l), (e)(l), (g)(5)).
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For the purpose of the restrictions, HSWA defines land disposal "to
include, but not be limited to, any placement of ... hazardous waste in
a landfill, surface impoundment, waste pile, injection well, land
treatment facility, salt dome formation, salt bed formation, or
underground mine or cave" (RCRA section 3004(k), 42 U.S.C. 6924(k)).
Although HSWA defines land disposal to include injection wells, such
disposal of solvents, dioxins, and certain other wastes, known as the
California List wastes, is covered on a separate schedule (RCRA section
3004(f)(2), 42 U.S.C. 6924 (f)(2)). This schedule requires that EPA
develop land disposal restrictions for deep well injection by
August 8, 1988.
The amendments also require the Agency to set "levels or methods of
treatment, if any, which substantially diminish the toxicity of the waste
or substantially reduce the likelihood of migration of hazardous
constituents from the waste so that short-term and long-term threats to
human health and the environment are minimized" (RCRA section 3004(m)(l),
42 U.S.C. 6924 (m)(l)). Wastes that meet treatment standards established
by EPA are not prohibited and may be land disposed. In setting treatment
standards for listed or characteristic wastes, EPA may establish
different standards for particular wastes within a single waste code with
differing treatability characteristics. One such characteristic is the
physical form of the waste. This frequently leads to different standards
for wastewaters and nonwastewaters.
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Alternatively, EPA can establish a treatment standard that is
applicable to more than one waste code when, in EPA's judgment, all the
waste can be treated to the same concentration. In those instances where
a generator can demonstrate that the standard promulgated for the
generator's waste cannot be achieved, the Agency also can grant a
variance from a treatment standard by revising the treatment standard for
that particular waste through rulemaking procedures. (A further
discussion of treatment variances is provided in Section 1.3.)
The land disposal restrictions are effective when promulgated unless
the Administrator grants a national variance and establishes a different
date (not to exceed 2 years beyond the statutory deadline) based on "the
earliest date on which adequate alternative treatment, recovery, or
disposal capacity which protects human health and the environment will be
available" (RCRA section 3004(h)(2), 42 U.S.C. 6924 (h)(2)).
If EPA fails to set a treatment standard by the statutory deadline
for any hazardous waste in the First Third or Second Third of the
schedule (see section 1.1.2), the waste may not be disposed in a landfill
or surface impoundment unless the facility is in compliance with the
minimum technological requirements specified in section 3004(o) of RCRA.
In addition, prior to disposal, the generator must certify to the
Administrator that the availability of treatment capacity has been
investigated and it has been determined that disposal in a landfill or
surface impoundment is the only practical alternative to treatment
currently available to the generator. This restriction on the use of
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landfills and surface impoundments applies until EPA sets a treatment
standard for the waste or until May 8, 1990, whichever is sooner. If the
Agency fails to set a treatment standard for any ranked hazardous waste
by May 8, 1990, the waste is automatically prohibited from land disposal
unless the waste is placed in a land disposal unit that is the subject of
a successful "no migration" demonstration (RCRA section 3004(g), 42
U.S.C. 6924(g)). "No migration" demonstrations are based on case-
specific petitions that show there will be no migration of hazardous
constituents from the unit for as long as the waste remains hazardous.
1.1.2 Schedule for Developing Restrictions
Under Section 3004(g) of RCRA, EPA was required to establish a
schedule for developing treatment standards for all wastes that the
Agency had listed as hazardous by November 8, 1984. Section 3004(g)
required that this schedule consider the intrinsic hazards and volumes
associated with each of these wastes. The statute required EPA to set
treatment standards according to the following schedule:
(a) Solvents and dioxins standards must be promulgated by
November 8, 1986;
(b) The "California List" must be promulgated by July 8, 1987;
(c) At least one-third of all listed hazardous wastes must be
promulgated by August 8, 1988 (First Third);
(d) At least two-thirds of all listed hazardous wastes must be
promulgated by June 8, 1989 (Second Third); and
(e) All remaining listed hazardous wastes and all hazardous wastes
identified as of November 8, 1984, by one or more of the
characteristics defined in 40 CFR Part 261 must be promulgated
by May 8, 1990 (Third Third).
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The statute specifically identified the solvent wastes as those
covered under waste codes F001, F002, F003, F004, and F005; it identified
the dioxin-containing hazardous wastes as those covered under waste codes
F020, F021, F022, and F023.
Wastes collectively known as the California List wastes, defined
under Section 3004(d) of HSWA, are liquid hazardous wastes containing
metals, free cyanides, PCBs, corrosives (i.e., a pH less than or equal to
2.0), and any liquid or nonliquid hazardous waste containing halogenated
organic compounds (HOCs) above 0.1 percent by weight. Rules for the
California List were proposed on December 11, 1986, and final rules for
PCBs, corrosives, and HOC-containing wastes were established
August 12, 1987. In that rule, EPA elected not to establish standards
for metals. Therefore, the statutory limits became effective.
On May 28, 1986, EPA published a final rule (51 FR 19300) that
delineated the specific waste codes that would be addressed by the First
Third, Second Third, and Third Third. This schedule is incorporated into
40 CFR 268.10, .11, and .12.
1.2 Summary of Promulgated BOAT Methodology
In a November 7, 1986, rulemaking, EPA promulgated a technology-based
approach to establishing treatment standards under section 3004(m).
Section 3004(m) also specifies that treatment standards must "minimize"
long- and short-term threats to human health and the environment arising
from land disposal of hazardous wastes.
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Congress indicated in the legislative history accompanying the HSWA
that "[t]he requisite levels of [sic] methods of treatment established by
the Agency should be the best that has been demonstrated to be
achievable," noting that the intent is "to require utilization of
available technology" and not a "process which contemplates
technology-forcing standards" (Vol. 130 Cong. Rec. S9178 (daily ed.,
July 25, 1984)). EPA has interpreted this legislative history as
suggesting that Congress considered the requirement under 3004(m) to be
met by application of the best demonstrated and achievable (i.e.,
available) technology prior to land disposal of wastes or treatment
residuals. Accordingly, EPA's treatment standards are generally based on
the performance of the best demonstrated available technology (BOAT)
identified for treatment of the hazardous constituents. This approach
involves the identification of potential treatment systems, the
determination of whether they are demonstrated and available, and the
collection of treatment data from well-designed and well-operated systems.
The treatment standards, according to the statute, can represent
levels or methods of treatment, if any, that substantially diminish the
toxicity of the waste or substantially reduce the likelihood of migration
of hazardous constituents. Wherever possible, the Agency prefers to
establish BOAT treatment standards as "levels" of treatment
(i.e., performance standards) rather than adopting an approach that would
require the use of specific treatment "methods." EPA believes that
concentration-based treatment levels offer the regulated community greater
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flexibility to develop and implement compliance strategies as well as an
incentive to develop innovative technologies.
1.2.1 Waste Treatability Group
In developing the treatment standards, EPA first characterizes the
waste(s). As necessary, EPA may establish treatability groups for wastes
having similar physical and chemical properties. That is, if EPA
believes that wastes represented by different waste codes could be
treated to similar concentrations using identical technologies, the
Agency combines the codes into one treatability group. EPA generally
considers wastes to be similar when they are both generated from the same
industry and from similar processing stages. In addition, EPA may
combine two or more separate wastes into the same treatability group when
data are available showing that the waste characteristics affecting
performance are similar or that one waste would be expected to be less
difficult to treat.
Once the treatability groups have been established, EPA collects and
analyzes data on identified technologies used to treat the wastes in each
treatability group. The technologies evaluated must be demonstrated on
the waste or a similar waste and must be available for use.
1.2.2 Demonstrated and Available Treatment Technologies
Consistent with legislative history, EPA considers demonstrated
technologies to be those that are used to treat the waste of interest or
a similar waste with regard to parameters that affect treatment selection
(see November 7, 1986, 51 FR 40588). EPA also will consider as treatment
those technologies used to separate or otherwise process chemicals and
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other materials. Some of these technologies clearly are applicable to
waste treatment, since the wastes are similar to raw materials processed
in industrial applications.
For most of the waste treatability groups for which EPA will
promulgate treatment standards, EPA will identify demonstrated
technologies either through review of literature related to current waste
treatment practices or on the basis of information provided by specific
facilities currently treating the waste or similar wastes. •
In cases where the Agency does not identify any facilities treating
wastes represented by a particular waste treatability group, EPA may
transfer a finding of demonstrated treatment. To do this, EPA will
compare the parameters affecting treatment selection for the waste
treatability group of interest to other wastes for which demonstrated
technologies already have been determined. The parameters affecting
treatment selection and their use for this waste are described in
Section 3.2 of this document. If the parameters affecting treatment
selection are similar, then the Agency will consider the treatment
technology also to be demonstrated for the waste of interest. For
example, EPA considers rotary kiln incineration a demonstrated technology
for many waste codes containing hazardous organic constituents, high
total organic content, and high filterable solids content, regardless of
whether any facility is currently treating these wastes. The basis for
this determination is data found in literature and data generated by EPA
confirming the use of rotary kiln incineration on wastes having the above
characteristics.
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If no commercial treatment or recovery operations are identified for
a waste or wastes with similar physical or chemical characteristics that
affect treatment selection, the Agency will be unable to identify any
demonstrated treatment technologies for the waste, and, accordingly, the
waste will be prohibited from land disposal (unless handled in accordance
with the exemption and variance provisions of the rule). The Agency is,
however, committed to establishing treatment standards as soon as new or
improved treatment processes are demonstrated (and available).
Operations only available at research facilities, pilot- and bench-
scale operations will not be considered in identifying demonstrated
treatment technologies for a waste because these technologies would not
necessarily be "demonstrated." Nevertheless, EPA may use data generated
at research facilities in assessing the performance of demonstrated
technologies.
As discussed earlier, Congress intended that technologies used to
establish treatment standards under Section 3004(m) be not only
"demonstrated," but also available. To decide whether demonstrated
technologies may be considered "available," the Agency determines whether
they (1) are commercially available and (2) substantially diminish the
toxicity of the waste or substantially reduce the likelihood of migration
of hazardous constituents from the waste.
EPA will only set treatment standards based on a technology that
meets the above criteria. Thus, the decision to classify a technology as
"unavailable" will have a direct impact on the treatment standard. If
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the best technology is unavailable, the treatment standard will be based
on the next best treatment technology determined to be available. To the
extent that the resulting treatment standards are less stringent, greater
concentrations of hazardous constituents in the treatment residuals could
be placed in land disposal units.
There also may be circumstances in which EPA concludes that for a
given waste none of the demonstrated treatment technologies are
"available" for purposes of establishing the 3004(m) treatment
performance standards. Subsequently, these wastes will be prohibited
from continued placement in or on the land unless managed in accordance
with applicable exemptions and variance provisions. The Agency is,
however, committed to establishing new treatment standards as soon as new
or improved treatment processes become "available."
(1) Proprietary or Patented Processes. If the demonstrated
treatment technology is a proprietary or patented process that is not
generally available, EPA will not consider the technology in its
determination of the treatment standards. EPA will consider proprietary
or patented processes available if it determines that the treatment
method can be purchased or licensed from the proprietor or is
commercially available treatment. The services of the commercial
facility offering this technology often can be purchased even if the
technology itself cannot be purchased.
(2) Substantial Treatment. To be considered "available," a
demonstrated treatment technology must "substantially diminish the
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toxicity" of the waste or "substantially reduce the likelihood of
migration of hazardous constituents" from the waste in accordance with
section 3004(m). By requiring that substantial treatment be achieved in
order to set a treatment standard, the statute ensures that all wastes
are adequately treated before being placed in or on the land and ensures
that the Agency does not require a treatment method that provides little
or no environmental benefit. Treatment will always be deemed substantial
if it results in nondetectable levels of the hazardous constituents of
concern. If nondetectable levels are not achieved, then a determination
of substantial treatment will be made on a case-by-case basis. This
approach is necessary because of the difficulty of establishing a
meaningful guideline that can be applied broadly to the many wastes and
technologies to be considered. EPA will consider the following factors
in an effort to evaluate whether a technology provides substantial
treatment on a case-by-case basis:
(a) Number and types of constituents treated;
(b) Performance (concentration of the constituents in the
treatment residuals); and
(c) Percent of constituents removed.
If none of the demonstrated treatment technologies achieve
substantial treatment of a waste, the Agency cannot establish treatment
standards for the constituents of concern in that waste.
1.2.3 Collection of Performance Data
Performance data on the demonstrated available technologies are
evaluated by the Agency to determine whether the data are representative
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of well-designed and well-operated treatment systems. Only data from
well-designed and well-operated systems are included in determining
BOAT. The data evaluation includes data already collected directly by
EPA and/or data provided by industry. In those instances where
additional data are needed to supplement existing information, EPA
collects additional data through a sampling and analysis program. The
principal elements of this data collection program are: (a) identifi-
cation of facilities for site visits, (b) engineering site visit,
(c) Sampling and Analysis Plan, (d) sampling visit, and (e) Onsite
Engineering Report.
(1) Identification of Facilities for Site Visits. To identify
facilities that generate and/or treat the waste of concern, EPA uses a
number of information sources. These include Stanford Research
Institute's Directory of Chemical Producers, EPA's Hazardous Waste Data
Management System (HWDMS), the 1986 Treatment, Storage, Disposal Facility
(TSDF) National Screening Survey, and EPA's Industry Studies Data Base.
In addition, EPA contacts trade associations to inform them that the
Agency is considering visits to facilities in their industry and to
solicit assistance in identifying facilities for EPA to consider in its
treatment sampling program.
After identifying facilities that treat the waste, EPA uses this
hierarchy to select sites for engineering visits: (1) generators treating
single wastes on site; (2) generators treating multiple wastes together
on site; (3) commercial treatment, storage, and disposal facilities
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(TSDFs); and (4) EPA in-house treatment.' This hierarchy is based on two
concepts: (1) to the extent possible, EPA should develop treatment
standards from data produced by treatment facilities handling only a
single waste, and (2) facilities that routinely treat a specific waste
have had the best opportunity to optimize design parameters. Although
excellent treatment can occur at many facilities that are not high in
this hierarchy, EPA has adopted this approach to avoid, when possible,
ambiguities related to the mixing of wastes before and during treatment.
When possible, the Agency will evaluate treatment technologies using
commercially operated systems. If performance data from properly
designed and operated commercial treatment methods for a particular waste
or a waste judged to be similar are not available, EPA may use data from
research facilities operations. Whenever research facility data are
used, EPA will explain why such data were used in the preamble and
background document and will request comments on the use of such data.
Although EPA's data bases provide information on treatment for
individual wastes, the data bases rarely provide data that support the
selection of one facility for sampling over another. In cases where
several treatment sites appear to fall into the same level of the
hierarchy, EPA selects sites for visits strictly on the basis of which
facility could most expeditiously be visited and later sampled if
justified by the engineering visit.
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(2) Engineering Site Visit. Once a treatment facility has been
selected, an engineering site visit is made to confirm that a candidate
for sampling meets EPA's criteria for a well-designed facility and to
ensure that the necessary sampling points can be accessed to determine
operating parameters and treatment effectiveness. During the visit, EPA
also confirms that the facility appears to be well operated, although the
actual operation of the treatment system during sampling is the basis for
EPA's decisions regarding proper operation of the treatment unit. In
general, the Agency considers a well-designed facility to be one that
contains the unit operations necessary to treat the various hazardous
constituents of the waste as well as to control other nonhazardous
materials in the waste that may affect treatment performance.
In addition to ensuring that a system is reasonably well designed,
the engineering visit examines whether the facility has a way to measure
the operating parameters that affect performance of the treatment system
during the waste treatment period. For example, EPA may choose not to
sample a treatment sys.tem that operates in a continuous mode, for which
an important operating parameter cannot be continuously recorded. In
such systems, instrumentation is important in determining whether the
treatment system is operating at design values during the waste treatment
period.
(3) Sampling and Analysis Plan. If after the engineering site visit
the Agency decides to sample a particular plant, the Agency will then
develop a site-specific Sampling and Analysis Plan (SAP) according to the
Generic Quality Assurance Project Plan for the Land Disposal Restriction
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Program ("BOAT"), EPA/530-SW-87-011. In brief, the SAP discusses where
the Agency plans to sample, how the samples will be taken, the frequency
of sampling, the constituents to be analyzed and the method of analysis,
operational parameters to be obtained, and specific laboratory quality
control checks on the analytical results.
The Agency will generally produce a draft of the site-specific
Sampling and Analysis Plan within 2 to 3 weeks of the engineering visit.
The draft of the SAP is then sent to the plant for review and comment.
With few exceptions, the draft SAP should be a confirmation of data
collection activities discussed with the plant personnel during the
engineering site visit. EPA encourages plant personnel to recommend any
modifications to the SAP that they believe will improve the quality of
the data.
It is important to note that sampling of a plant by EPA does not mean
that the data will be used in the development of treatment standards for
BOAT. EPA's final decision on whether to use data from a sampled plant
depends on the actual analysis of the waste being treated and on the
operating conditions at the time of sampling. Although EPA would not
plan to sample a facility that was not ostensibly well-designed and
well-operated, there is no way to ensure that at the time of the sampling
the facility will not experience operating problems. Additionally, EPA
statistically compares its test data to suitable industry-provided data,
where available, in its determination of what data to use in developing
treatment standards. The methodology for comparing data is presented
later in this section.
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(Note: Facilities wishing to submit data for consideration in the
development of BOAT standards should, to the extent possible, provide
sampling information similar to that acquired by EPA. Such facilities
should review the Generic Quality Assurance Project Plan for the Land
Disposal Restriction Program ("BOAT"), which delineates all of the
quality control and quality assurance measures associated with sampling
and analysis. Quality assurance and quality control procedures are
summarized in Section 1.2.6 of this document.)
(4) Sampling Visit. The purpose of the sampling visit is to collect
samples that characterize the performance of the treatment system and to
document the operating conditions that existed during the waste treatment
period. At a minimum, the Agency attempts to collect sufficient samples
of the untreated waste and solid and liquid treatment residuals so that
variability in the treatment process can be accounted for in the
development of the treatment standards. To the extent practicable, and
within safety constraints, EPA or its contractors collect all samples and
ensure that chain-of-custody procedures are conducted so that the
integrity of the data is maintained.
In general, the samples collected during the sampling visit will have
already been specified in the SAP. In some instances, however, EPA will
not be able to collect all planned samples because of changes in the
facility operation or plant upsets; EPA will explain any such deviations
from the SAP in its follow-up Onsite Engineering Report.
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(5) Onsite Engineering Report. EPA summarizes all its data
collection activities and associated analytical results for testing at a
facility in a report referred to as the Onsite Engineering Report (OER).
This report characterizes the waste(s) treated, the treated residual
concentrations, the design and operating data, and all analytical results
including methods used and accuracy results. This report also describes
any deviations from EPA's suggested analytical methods for hazardous
wastes (Test Methods for Evaluating Solid Waste, SW-846, Third Edition,
November 1986).
After the Onsite Engineering Report is completed, the report is
submitted to the plant for review. This review provides the plant with a
final opportunity to claim any information contained in the report as
confidential. Following the review and incorporation of comments, as
appropriate, the report is made available to the public with the
exception of any material claimed as confidential by the plant.
1.2.4 Hazardous Constituents Considered and Selected for Regulation
(1) Development of BDAT List. The list of hazardous constituents
within the waste codes that are targeted for treatment is referred to by
the Agency as the BDAT constituent list. This list, provided as Table
1-1, is derived from the constituents presented in 40 CFR Part 261,
Appendix VII and Appendix VIII, as well as several ignitable constituents
used as the basis of listing wastes as F003 and F005. These sources
provide a comprehensive list of hazardous constituents specifically
regulated under RCRA. The BDAT list consists of those constituents that
can be analyzed using methods published in SW-846, Third Edition.
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1521g
Table 1-1 BOAT Constituent List
BOAT
reference
no
222.
1.
o
3
4
5.
6.
223.
7
8.
9
10
11
12.
12
14
15.
16.
17
IS
19
2C
21
7 1
23
:4
'C
15
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la
jj
224
' 1 C
*. I -
226
30
227
31
214
- L
Parameter
Volat i les
Acetone
Acetonitn le
Aero le in
Aery lonitn le
Benzene
Bromod i en loromethane
Bromomethane
n-Butyl alcohol
Carbon tetrachloriae
Carnon disulfide
Chlorobenzene
2-Chioro-l .3 -butadiene
Chloroaibromomethane
Chloroetnane
2-Chloroethyl vinyl ether
Chloroform
Ch loromethane
3-Chloropropene
1 ,2-Oibromo-3-chloropropane
1 ,2-Oibromoethane
Oibromomethane
T rans-1 . 4 -Dich loro-2-butene
Dichloroa if luoromethane
1 . 1-Dicl" ioroethane
1 ,2-Dicrloroethane
1 . 1-Dicr 10 roe thy lene
T rans-1 . 2-Dicnlo-oethene
1 . 2-D icr, loropropane
T rans-1 .3-Dichloropropene
cis-1 ,3-D:cnloroproDene
1 . 4-Oioxane
2-£ t hcxvethano 1
Etr.v ' jreiate
Eth> i be^rene
tthy i c> jntde
Etny 1 etner
Etn> 1 metiacrylate
Ethy lene oxide
luuo-nethjne
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
74-67-3
107-05-1
96-12-8
106-93-4
74-95-3
11C-57-6
75-71-5
75-34-3
107-06-2
75-35-4
156-60-5
7S-67-5
10061-02-6
10C61-01-5
123-81-:
110-60-5
141-'5-6
100-41-4
107-12-J
60-29-'
97-63-2
75-21-s
74-66-4
18
-------
1521g
Table 1-1 (continued)
BOAT
reference
no.
33.
228.
34
2Z9.
35.
37.
38.
230.
39.
40.
41.
42.
43.
44.
45.
46.
47.
48
49.
231.
50.
215.
216.
217.
51.
52.
53.
54.
55.
56.
57
58.
59.
218.
60
61
62
Parameter
Volatiles (continued)
Isobutyl alcohol
Methanoi
Methyl ethyl ketone
Methyl isobutyl ketone
Methyl met hacry late
Methacrylomtri le
Methylene chloride
2-Nitropropane
Pyridme
1.1,1. 2-Tetrachloroethane
1, 1,2,2-Tetrachloroethane
Tetrach loroethene
Toluene
T r i b romome t hane
1.1,1-Tnchloroethane
1 , 1 ,2-Tnchloroethane
Trichloroethene
Tr ich loromonof luoromethane
1 , 2 , 3-Tnchloropropane
l,1.2-Trichloro-1.2,2-trif luoro-
ethane
Vinyl chloride
1.2-Xylene
1.3-Xylene
1.4-Xylene
Senuvolat i les
Acenaphthalene
Acenaphthene
Acetophenone
2-Acetylaminof luorene
4-Aminobiphenyl
Am 1 me
Anthracene
Aramite
Benz(a)anthracene
Benza 1 chloride
Benzenethiol
Deleted
Beruo(a)pyrene
Cas no.
78-83-1
67-56-1
78-93-3
108-10-1
80-62-6
126-98-7
75-09-2
79-46-9
110-86-1
630-20-6
79-34-6
127-18-4
108-88-3
75-25-2
71-55-6
79-00-5
79-01-6
75-69-4
96-18-4
76-13-1
75-01-4
97-47-6
108-38-3
106-44-5
208-96-8
83-32-9
96-86-2
53-96-3
92-67-1
62-53-3
120-12-7
140-57-8
56-55-3
98-87-3
108-98-5
50-32-8
19
-------
ISZlg
Table 1-1 (continued)
BOAT
reference
no.
63.
64.
65.
66.
67.
68.
69.
70.
71.
72.
73.
74.
75
76.
77.
78.
79.
80.
81.
82.
232.
83
84
85.
86. '
87.
88
89.
90.
91
92.
93.
94.
95
96.
97.
98.
99
100.
101.
Parameter
Semivolatiles (continued)
Benzo( b ) f 1 uoranthene
Benzofghi Jperylene
Benzol k ) f 1 uoranthene
p-Benzoquinone
B i s ( 2-ch loroethoxy Jmethane
Bis(2-chloroethyl)ether
Bis(2-chloroisopropyl)ether
Bis(2-ethylhexyl)phthalate
4-Bromopheny 1 phenyl ether
Butyl benzyl phthalate
2-sec-Butyl-4,6-dinitrophenol
p-Chloroani line
Chlorobenzi late
p-Chloro-m-cresol
2-Chloronaphthalene
2-Chlorophenol
3-Chloropropionitri le
Chrysene
ortho-Cresol
para-Cresol
Cyclohexanone
D i benz ( a , h) anthracene
Dibenzo(a.e)pyrene
Dibenzofa. ilpyrene
m-Dtchlorobenzene
o-Oichlorobenzene
p-Oichlorobenzene
3,3'-Dichlorobenzidme
2.4-Dichlorophenol
2,6-Dichlorophenol
Diethyl phthalate
3.3'-Dimethoxybenzidine
p-Oimethylaminoazobenzene
3,3'-Oimethylbenzidine
2.4-Oimethylphenol
Dimethyl phthalate
Di-n-butyl phthalate
1 ,4-Oinitrobenzene
4.6-Oinitro-o-cresol
2,4-Oin i tropheno 1
CAS no.
205-99-2
191-24-2
207-08-9
106-51-4
111-91-1
111-44-4
39638-32-9
117-81-7
101-55-3
85-68-7
88-85-7
106-47-8
510-15-6
59-50-7
91-58-7
95-57-8
542-76-7
218-01-9
95-48-7
106-44-5
108-94-1
53-70-3
19Z-65-4
189-55-9
541-73-1
95-50-1
106-46-7
91-94-1
120-83-2
87-65-0
84-66-2
119-90-4
60-11-7
119-93-7
105-67-9
131-11-3
84-74-2
100-25-4
534-52-1
51-28-5
20
-------
1521g
Table 1-1 (continued)
BOAT
reference
no
102.
103.
104.
105.
106.
219.
107.
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
Parameter
Semivolatl les (continued)
2,4-Dinitrotoluene
2,6-Oinitrotoluene
Di-n-octyl phthalate
Di-n-propylnitrosamine
Diphenylamine
Dipnenylnitrosamine
1,2-Diphenylhydrazine
Fluoranthene
Fluorene
Hexach lorobenzene
Hexach lorobutad i ene
Hexach lorocyclopentadiene
Hexachloroethane
Hexach lorophene
Hexach loropropene
Indeno(1.2,3-cd)pyrene
Isosafrole
Methapyn lene
3-Methylcholanthrene
4,4'-Methylenebis
(2-chloroani 1 me)
Methyl methanesulfonate
Naphthalene
1,4-Naphthoqumone
1-Naphthylamine
2-Naphthylamme
p-Nitroani line
Nitrobenzene
4-Nitrophenol
N-Nitrosodi-n-butylamme
N-Nitrosodiethylamme
N-Nitrosodimethylamine
N-N 1 1 rosomethy lethy lamme
N - N i t rosomorpho 1 i ne
N-Nitrosopipendine
n-Nitrosopyrrol idme
5-Nitro-o-toluidine
Pentach lorobenzene
Pentach loroethane
Pentach loron i trobenzene
CAS no.
121-14-2
606-20-2
117-84-0
621-64-7
122-39-4
86-30-6
122-66-7
206-44-0
86-73-7
118-74-1
87-68-3
77-47-4
67-72-1
70-30-4
1888-71-7
193-39-5
120-58-1 '
91-80-5
56-49-5
101-14-4
66-27-3
91-20-3
130-15-4
134-32-7
91-59-8
100-01-6
98-95-3
100-02-7
924-16-3
55-18-5
62-75-9
10595-95-6
59-89-2
100-75-4
930-55-2
99-65-8
608-93-5
76-01-7
82-68-8
21
-------
1521g
Table 1-1 (continued)
BOAT
reference
no.
139.
140.
141.
142
220
143.
144.
145.
146.
147.
148.
149
150.
151.
152.
153.
154
155.
156.
157.
158.
159.
221.
160.
161.
162.
163.
164.
165
166.
167.
168.
169
170
171
Parameter
Semwolati les (continued)
Pentach loropheno 1
Phenacet in
Phenanthrene
Phenol
Phthalic anhydride
2-Picoline
Pronamide
Pyrene
Resorcinol
Safrole
1,2,4, 5-Tet rach lorobenzene
2,3,4, 6-Tetrach loropheno 1
1 , 2, 4 -Tnch lorobenzene
2,4, 5-Trich loropheno 1
2, 4, 6-T rich loropheno 1
Tr i s{ 2 , 3-d i bromopropy 1 )
phosphate
Metals
Ant imony
Arsenic
Ba r i urn
Beryl 1 lum
Cadmium
Chromium (total)
Chromium (hexavalent)
Copper
Lead
Mercury
Nickel
Selenium
Si Iver
Thai 1 lum
Vanadium
Zinc
Inorganics
Cyanide
Fluoride
Sulf ide
CAS no.
87-86-5
62-44-2
85-01-8
108-95-2
85-44-9
109-06-8
23950-58-5
129-00-0
108-46-3
94-59-7
95-94-3
58-90-2
120-82-1
95-95-4
88-06-2
126-72-7
7440-36-0
7440-38-2
7440-39-3
7440-41-7
7440-43-9
7440-47-32
-
7440-50-8
7439-92-1
7439-97-6
7440-02-0
7782-49-2
7440-22-4
7440-28-0
7440-62-2
7440-66-6
57-12-5
16964-48-8
8496-25-8
22
-------
1521g
Table 1-1 (continued)
BOAT
reference
no.
172.
173.
174.
175.
176.
177.
178.
179.
180.
181.
182.
183.
184
185.
186.
187.
188.
189.
190.
191.
192.
193
194.
195.
196.
197.
198.
199.
200
201
202
Parameter
Oraanochlonne oesticides
Aldrin
alpha-BHC
beta-BHC
delta-BHC
gaima-BHC
Chlordane
ODD
DOE
DOT
Oieldnn
Endosulfan I
Endosulfan II
Endnn
Endnn aldehyde
Heptachlor
Heptachlor epoxide
Isodrin
Depone
Methoxyclor
Toxaphene
Phenoxvacet ic acid herbicides
2.4-Oichlorophenoxyacet ic acid
Silvex
2,4.5-T
Orqanophosphorous insecticides
Disulfoton
Famphur
Methyl parathion
Parathion
Phorate
PCBs
Aroclor 1016
Aroclor 1221
Aroclor 1232
CAS no.
309-00-2
319-84-6
319-85-7 .
319-86-8
58-89-9
57-74-9
72-54-8
72-55-9
50-29-3
60-57-1
939-98-8
33213-6-5
72-20-8
7421-93-4
76-44-8
1024-57-3
465-73-6
143-50-0
72-43-5
8001-35-2
94-75-7
93-72-1
93-76-5
298-04-4
52-85-7
298-00-0
56-38-2
298-02-2
12674-11-2
11104-28-2
11141-16-5
23
-------
1521g
Table 1-1 (continued)
BOAT
reference Parameter CAS no.
no.
PCBs (continued)
203. Aroclor 1242 53469-21-9
204. Aroclor 1248 . 12672-29-6
205 Aroclor 1254 11097-69-1
206. Aroclor 1260 11096-82-5
Dioxins and furans
207. Hexachlorodibenzo-p-dioxins
208. Hexachlorodibenzofurans
209. Pentachlorodibenzo-p-dioxins
210. Pentachlorodibenzofurans
211. Tetrachlorodibenzo-p-diox'ns
212. Tetrachlorodibenzofurans
213. 2,3,7,8-Tetrachlorodibenzo-p-dioxin 1746-01-6
24
-------
The initial BOAT constituent list was published in EPA's Generic
Quality Assurance Project Plan, March 1987 (EPA/530-SW-87-011).
Additional constituents will be added to the BOAT constituent list as
additional key constituents are identified for specific waste codes or as
new analytical methods are developed for hazardous constituents. For
example, since the list was published in March 1987, eighteen additional
constituents (hexavalent chromium, xylene (all three isomers), benzal
chloride, phthalic anhydride, ethylene oxide, acetone, n-butyl alcohol,
2-ethoxyethanol, ethyl acetate, ethyl benzene, ethyl ether, methanol,
methyl isobutyl ketone, 2-nitropropane, l,l,2-trichloro-l,2,2-
trifluoroethane, and cyclohexanone) have been added to the list.
Chemicals are listed in Appendix VIII if they are shown in scientific
studies to have toxic, carcinogenic, mutagenic, or teratogenic effects on
humans or other life-forms, and they include such substances as those
identified by the Agency's Carcinogen Assessment Group as being
carcinogenic. Including a constituent in Appendix VIII means that the
constituent can be cited as a basis for listing toxic wastes.
Although Appendix VII, Appendix VIII, and the F003 and F005
ignitables provide a comprehensive list of RCRA-regulated hazardous
constituents, not all of the constituents can be analyzed in a complex
waste matrix. Therefore, constituents that could not be readily analyzed
in an unknown waste matrix were not included on the initial BOAT list.
As mentioned above, however, the BOAT constituent list is a continuously
growing list that does not preclude the addition of new constituents when
analytical methods are developed.
25
-------
There are 5 major reasons that constituents were not included on the
BOAT constituent list:
(a) Constituents are unstable. Based on their chemical structure,
some constituents will either decompose in water or will
ionize. For example, maleic anhydride will form maleic acid
when it comes in contact with water and copper cyanide will
ionize to form copper and cyanide ions. However, EPA may choose
to regulate the decomposition or ionization products.
(b) EPA-approved or verified analytical methods are not available.
Many constituents, such as 1,3,5-trinitrobenzene, are not
measured adequately or even detected using any of EPA's
analytical methods published in SW-846 Third Edition.
(c) The constituent is a member of a chemical group designated in
Appendix VIII as not otherwise specified (N.O.S.). Constituents
listed as N.O.S., such as chlorinated phenols, are a generic
group of some types of chemicals for which a single analytical
procedure is not available. The individual members of each such
group need to be listed to determine whether the constituents
can be analyzed. For each N.O.S. group, all those constituents
that can be readily analyzed are included in the BOAT
constituents list.
(d) Available analytical procedures are not appropriate for a
complex waste matrix. Some compounds, such as auramine, can be
analyzed as a pure constituent. However, in the presence of
other constituents, the recommended analytical method does not
positively identify the constituent. The use of high pressure
liquid chromotography (HPLC) presupposes a high expectation of
finding the specific constituents of interest. In using this
procedure to screen samples, protocols would have to be
developed on a case-specific basis to verify the identity of
constituents present in the samples. Therefore, HPLC is not an
appropriate analytical procedure for complex samples containing
unkown constituents.
(e) Standards for analytical instrument calibration are not
commercially available. For several constituents, such as
benz(c)acridine, commercially available standards of a
"reasonably" pure grade are not available. The unavailability
of a standard was determined by a review of catalogs from
specialty chemical manufacturers.
26
-------
Two constituents (fluoride and sulfide) are not specifically included
in Appendices VII and VIII; however, these compounds are included on the
BOAT list as indicator constituents for compounds from Appendices VII and
VIII such as hydrogen fluoride and hydrogen sulfide, which ionize in
water.
The BOAT constituent list presented in Table 1-1 is divided into the
following nine groups:
Volatile organics
Semivolatile organics
Metals
Other inorganics
Organochlorine pesticides
Phenoxyacetic acid herbicides
Organophosphorous insecticides
PCBs
Dioxins and furans
The constituents were placed in these categories based on their chemical
properties. The constituents in each group are expected to behave
similarily during treatment and are also analyzed, with the exception of
the metals and inorganics, by using the same analytical methods.
(2) Constituent Selection Analysis. The constituents that the
Agency selects for regulation in each treatability group are, in general,
those found in the untreated wastes at treatable concentrations. For
certain waste codes, the target list for the untreated waste may have
been shortened (relative to analyses performed to test treatment
technologies) because of the extreme unlikelihood of the constituent
being present.
27
-------
In selecting constituents for regulation, the first step is to
summarize all the constituents that were found in the untreated waste at
treatable concentrations. This process involves the use of the
statistical analysis of variance (ANOVA) test, described in Section
1.2.6, to determine if constituent reductions were significant. The
Agency interprets a significant reduction in concentration as evidence
that the technology actually "treats" the waste.
There are some instances where EPA may regulate constituents that are
not found in the untreated waste but are detected in the treated
residual. This is generally the case where presence of the constituents
in the untreated waste interferes with the quantification of the
constituent of concern. In such instances, the detection levels of the
constituent are relatively high, resulting in a finding of "not detected"
when, in fact, the constituent is present in the waste.
After determining which of the constituents in the untreated waste
are present at treatable concentrations, EPA develops a list of potential
constituents for regulation. The Agency then reviews this list to
determine if any of these constituents can be excluded from regulation
because they would be controlled by regulation of other constituents in
the list.
EPA performs this indicator analysis for two reasons: (1) it reduces
the analytical cost burdens on the treater and (2) it facilitates
implementation of the compliance and enforcement program. EPA's
rationale for selection of regulated constituents for this waste code is
presented in Section 5 of this background document.
28
-------
(3) Calculation of Standards. The final step in the calculation of
the BOAT treatment standard is the multiplication of the average
treatment value by a factor referred to by the Agency as the variability
factor. This calculation takes into account that even well-designed and
well-operated treatment systems will experience some fluctuations in
performance. EPA expects that fluctuations will result from inherent
mechanical limitations in treatment control systems, collection of
treated samples, and analysis of these samples. All of the above
fluctuations can be expected to occur at well-designed and well-operated
treatment facilities. Therefore, setting treatment standards utilizing a
variability factor should be viewed not as a relaxing of 3004(m)
requirements, but rather as a function of the normal variability of the
treatment processes. A treatment facility will have to be designed to
meet the mean achievable treatment performance level to ensure that the
performance levels remain within the limits of the treatment standard.
The Agency calculates a variability factor for each constituent of
concern within a waste treatability group using the statistical
calculation presented in Appendix A. The equation for calculating the
variability factor is the same as that used by EPA for the development of
numerous regulations in the Effluent Guidelines Program under the Clean
Water Act. The variability factor establishes the instantaneous maximum
based on the 99th percentile value.
There is an additional step in the calculation of the treatment
standards in those instances where the ANOVA analysis shows that more
29
-------
than one technology achieves a level of performance that represents
BOAT. In such instances, the BOAT treatment standard is calculated by
first averaging the mean performance value for each technology for each
constituent of concern and then multiplying that value by the highest
variability factor among the technologies considered. This procedure
ensures that all the BOAT technologies used as the basis for the
standards will achieve full compliance.
1.2.5 Compliance with Performance Standards
All the treatment standards reflect performance achieved by the Best
Demonstrated Available Technology (BOAT). As such, compliance with these
standards only requires that the treatment level be achieved prior to
land disposal. It does not require the use of any particular treatment
technology. While dilution of the waste as a means to comply with the
standard is prohibited, wastes that are generated in such a way as to
naturally meet the standard can be land disposed without treatment. With
the exception of treatment standards that prohibit land disposal, all
treatment standards proposed are expressed as a concentration level.
EPA has used both total constituent concentration and TCLP analyses
of the treated waste as a measure of technology performance. EPA's
rationale for when each of these analytical tests is used is explained in
the following discussion.
For all organic constituents, EPA is basing the treatment standards
on the total constituent concentration found in the treated waste. EPA
based its decision on the fact that technologies exist to destroy the
30
-------
various organics compounds. Accordingly, the best measure of performance
would be the extent to which the various organic compounds have been
destroyed or the total amount of constituent remaining after treatment.
(NOTE: EPA's land disposal restrictions for solvent waste codes
F001-F005 (51 FR 40572) uses the TCLP value as a measure of performance.
At the time that EPA promulgated the treatment standards for F001-F005,
useful data were not available on total constituent concentrations in
treated residuals and, as a result, the TCLP data were considered to be
the best measure of performance.)
For all metal constituents, EPA is using both total constituent
concentration and/or the TCLP as the basis for treatment standards. The
total constituent concentration is being used when the technology basis
includes a metal recovery operation. The underlying principle of metal
recovery is the reduction of the amount of metal in a waste by separating
the metal for recovery; therefore, total constituent concentration in the
treated residual is an important measure of performance for this
technology. Additionally, EPA also believes that it is important that
any remaining metal in a treated residual waste not be in a state that is
easily Teachable; accordingly, EPA is also using the TCLP as a measure of
performance. It is important to note that for wastes for which treatment
standards are based on a metal recovery process, the facility has to
comply with both the total constituent concentration and the TCLP prior
to land disposal.
31
-------
In cases where treatment standards for metals are not based on
recovery techniques but rather on stabilization, EPA is using only the
TCLP as a measure of performance. The Agency's rationale is that
stabilization is not meant to reduce the concentration of metal in a
waste but only to chemically minimize the ability of the metal to leach.
1.2.6 Identification of BOAT
(1) Screening of Treatment Data. This section explains how the
Agency determines which of the treatment technologies represent treatment
by BOAT. The first activity is to screen the treatment performance data
from each of the demonstrated and available technologies according to the
following criteria:
(a) Design and operating data associated with the treatment data
must reflect a well-designed, well-operated system for each
treatment data point. (The specific design and operating
parameters for each demonstrated technology for this waste code
are discussed in Section 3.2 of this document.)
(b) Sufficient QA/QC data must be available to determine the true
values of the data from the treated waste. This screening
criterion involves adjustment of treated data to take into
account that the type value may be different from the measured
value. This discrepancy generally is caused by other
constituents in the waste that can mask results or otherwise
interfere with the analysis of the constituent of concern.
(c) The measure of performance must be consistent with EPA's
approach to evaluating treatment by type of constituents (e.g.,
total concentration data for organics, and total concentration
and TCLP for metals in the leachate from the residual).
In the absence of data needed to perform the screening analysis, EPA
will make decisions on a case-by-case basis of whether to include the
data. The factors included in this case-by-case analysis will be the
32
-------
actual treatment levels achieved, the availability of the treatment data
and their completeness (with respect to the above criteria), and EPA's
assessment of whether the untreated waste represents the waste code of
concern. EPA's application of these screening criteria for this waste
code are provided in Section 4 of this background document.
(2) Comparison of Treatment Data. In cases in which EPA has
treatment data from more than one technology following the screening
activity, EPA uses the statistical method known as analysis of variance
(ANOVA) to determine if one technology performs significantly better.
This statistical method (summarized in Appendix A) provides a measure of
the differences between two data sets. If EPA finds that one technology
performs significantly better (i.e., the data sets are not homogeneous),
BOAT treatment standards are the level of performance achieved by the
best technology multiplied by the corresponding variability factor for
each regulated constituent.
If the differences in the data sets are not statistically
significant, the data sets are said to be homogeneous. Specifically, EPA
uses the analysis of variance to determine whether BOAT represents a
level of performance achieved by only one technology or represents a
level of performance achieved by more than one (or all) of the
technologies. If the Agency finds that the levels of performance for one
or more technologies are not statistically different, EPA averages the
performance values achieved by each technology and then multiplies this
value by the largest variability factor associated with any of the
33
-------
acceptable technologies. A detailed discussion of the treatment
selection method and an example of how EPA chooses BOAT from multiple
treatment systems is provided in Section A-l.
(3) Quality Assurance/Quality Control. This section presents the
principal quality assurance/quality control (QA/QC) procedures employed
in screening and adjusting the data to be used in the calculation of
treatment standards. Additional QA/QC procedures used in collecting and
screening data for the BOAT program are presented in EPA's Generic
Quality Assurance Project Plan for Land Disposal Restrictions Program
("BOAT") (EPA/530-SW-87-001, March 1987).
To calculate the treatment standards for the Land Disposal
Restriction Rules, it is first necessary to determine the recovery value
for each constituent (the amount of constituent recovered after spiking,
which is the addition of a known amount of the constituent, minus the
initial concentration in the samples divided by the amount added) for a
spike of the treated residual. Once the recovery value is determined,
the following procedures are used to select the appropriate percent
recovery value to adjust the analytical data:
(a) If duplicate spike recovery values are available for the
constituent of interest, the data are adjusted by the lowest
available percent recovery value (i.e., the value that will
yield the most conservative estimate of treatment achieved).
However, if a spike recovery value of less than 20 percent is
reported for a specific constituent, the data are not used to
set treatment standards because the Agency does not have
sufficient confidence in the reported value to set a national
standard.
34
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(b) If data are not available for a specific constituent but are
available for an isomer, then the spike recovery data are
transferred from the isomer and the data are adjusted using the
percent recovery selected according to the procedure described
in (a) above.
(c) If data are not available for a specific constituent but are
available for a similar class of constituents (e.g., volatile
organics, acid-extractable semivolatiles), then spike recovery
data available for this class of constituents are transferred.
All spike recovery values greater than or equal to 20 percent
for a spiked sample are averaged and the constituent
concentration is adjusted by the average recovery value. If
spiked recovery data are available for more than one sample, the
average is calculated for each sample and the data are adjusted
by the lowest average value.
(d) If matrix spike recovery-data are not available for a set of
data to be used to calculate treatment standards, then matrix
spike recovery data are transferred from a waste that the Agency
believes is a similar matrix (e.g., if the data are for an ash
from incineration, then data from other incinerator ashes could
be used). While EPA recognizes that transfer of matrix spike
recovery data from a similar waste is not an exact analysis,
this is considered the best approach for adjusting the data to
account for the fact that most analyses do not result in
extraction of 100 percent of the constituent. In assessing the
recovery data to be transferred, the procedures outlined in (a),
(b), and (c) above are followed.
The analytical procedures employed to generate the data used to
calculate the treatment standards are listed in Appendix B of this
document. In cases where alternatives or equivalent procedures and/or
equipment are allowed in EPA's SW-846, Third Edition (November 1986)
methods, the specific procedures and equipment used are also documented
in this Appendix. In addition, any deviations from the SW-846, Third
Edition, methods used to analyze the specific waste matrices are
documented. It is important to note that the Agency will use the methods
and procedures delineated in Appendix B to enforce the treatment
35
-------
standards presented in Section 6 of this document. Accordingly,
facilities should use these procedures in assessing the performance of
their treatment systems.
1.2.7 BOAT Treatment Standards for "Derived-From" and "Mixed" Wastes
(1) Wastes from Treatment Trains Generating Multiple Residues. In a
number of instances, the proposed BOAT consists of a series of operations
each of which generates a waste residue. For example, the proposed BOAT
for a certain waste code is based on solvent extraction, steam stripping,
and activated carbon adsorption. Each of these treatment steps generates
a waste requiring treatment -- a solvent-containing stream from solvent
extraction, a stripper overhead, and spent activated carbon. Treatment
of these wastes may generate further residues; for instance, spent
activated carbon (if not regenerated) could be incinerated, generating an
ash and possibly a scrubber water waste. Ultimately, additional wastes
are generated that may require land disposal. With respect to these
wastes, the Agency wishes to emphasize the following points:
(a) All of the residues from treating the original listed wastes are
likewise considered to be the listed waste by virtue of the
derived-from rule contained in 40 CFR Part 261.3(c)(2). (This
point is discussed more fully in (2) below.) Consequently, all
of the wastes generated in the course of treatment would be
prohibited from land disposal unless they satisfy the treatment
standard or meet one of the exceptions to the prohibition.
(b) The Agency's proposed treatment standards generally contain a
concentration level for wastewaters and a concentration level
for nonwastewaters. The treatment standards apply to all of the
wastes generated in treating the original prohibited waste.
Thus, all solids generated from treating these wastes would have
36
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to meet the treatment standard for nonwastewaters. All
derived-from wastes meeting the Agency definition of wastewater
(less than 1 percent TOC and less than 1 percent total
filterable solids) would have to meet the treatment standard for
wastewaters. EPA wishes to make clear that this approach is not
meant to allow partial treatment in order to comply with the
applicable standard.
(c) The Agency has not performed tests, in all cases, on every waste
that can result from every part of the treatment train.
However, the Agency's treatment standards are based on treatment
of the most concentrated form of the waste. Consequently, the
Agency believes that the less concentrated wastes generated in
the course of treatment will also be able to be treated to meet
this value.
(2) Mixtures and Other Derived-From Residues. There is a further
question as to the applicability of the BOAT treatment standards to
residues generated not from treating the waste {as discussed above), but
from other types of management. Examples are contaminated soil or
leachate that is derived from managing the waste. In these cases, the
mixture is still deemed to be the listed waste, either because of the
derived-from rule (40 CFR Part 261.3(c)(2)(i)) or the mixture rule
(40 CFR Part 261.3(a)(2)(iii) and (iv) or because the listed waste is
contained in the matrix (see, for example, 40 CFR Part 261.33(d)). The
prohibition for the particular listed waste consequently applies to this
type of waste.
The Agency believes that the majority of these types of residues can
meet the treatment standards for the underlying listed wastes (with the
possible exception of contaminated soil and debris for which the Agency
is currently investigating whether it is appropriate to establish a
separate treatability subcategorization). For the most part, these
37
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residues will be less concentrated than the original listed waste. The
Agency's treatment standards also make a generous allowance for process
variability by assuming that all treatability values used to establish
the standard are lognormally distributed. The waste also might be
amenable to a relatively nonvariable form of treatment technology such as
incineration. Finally, and perhaps most important, the rules contain a
treatability variance that allows a petitioner to demonstrate that its
waste cannot be treated to the level specified in the rule (40 CFR Part
268.44(a). This provision provides a safety valve that allows persons
with unusual waste matrices to demonstrate the appropriateness of a
different standard. The Agency, to date, has not received any petitions
under this provision (for example, for residues contaminated with a
prohibited solvent waste), indicating, in the Agency's view, that the
existing standards are generally achievable.
(3) Residues from Managing Listed Wastes or that Contain Listed
Wastes. The Agency has been asked if and when residues from
managing hazardous wastes, such as leachate and contaminated ground
water, become subject to the land disposal prohibitions. Although the
Agency believes this question to be settled by existing rules and
interpretative statements, to avoid any possible confusion the Agency
will address the question again.
Residues from managing First Third wastes, listed California List
wastes, and spent solvent and dioxin wastes are all considered to be
subject to the prohibitions for the underlying hazardous waste. Residues
38
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from managing California List wastes likewise are subject to the
California List prohibitions when the residues themselves exhibit a
characteristic of hazardous waste. This determination stems directly
from the derived-from rule in 40 CFR Part 261.3(c)(2) or in some cases
from the fact that the waste is mixed with or otherwise contains the
listed waste. The underlying principle stated in all of these provisions
is that listed wastes remain listed until delisted.
The Agency's historic practice in processing delisting petitions
addressing mixing residuals has been to consider them to be the listed
waste and to require that delisting petitioners address all constituents
for which the derived-from waste (or other mixed waste) was listed. The
language in 40 CFR Part 260.22(b) states that mixtures or derived-from
residues can be delisted provided a delisting petitioner makes a
demonstration identical to that which a delisting petitioner would make
for the underlying waste. These residues consequently are treated as the
underlying listed waste for delisting purposes. The statute likewise
takes this position, indicating that soil and debris that are
contaminated with listed spent solvents or dioxin wastes are subject to
the prohibition for these wastes even though these wastes are not the
originally generated waste, but rather are a residual from management
(RCRA section 3004(e)(3)). It is EPA's view that all such residues are
covered by the existing prohibitions and treatment standards for the
listed hazardous waste that these residues contain and from which they
are derived.
39
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1.2.8 Transfer of Treatment Standards
EPA is proposing some treatment standards that are not based on
testing of the treatment technology of the specific waste subject to the
treatment standard. Instead, the Agency has determined that the
constituents present in the subject waste can be treated to the same
performance levels as those observed in other wastes for which EPA has
previously developed treatment data. EPA believes that transferring
treatment performance for use in establishing treatment standards for
untested wastes is valid technically in cases where the untested wastes
are generated from similar industries, similar processing steps, or have
similar waste characteristics affecting performance and treatment
selection. Transfer of treatment standards to similar wastes or wastes
from similar processing steps requires little formal analysis. However,
in the case where only the industry is similar, EPA more closely examines
the waste characteristics prior to concluding that the untested waste
constituents can be treated to levels associated with tested wastes.
EPA undertakes a two-step analysis when determining whether wastes
generated by different processes within a single industry can be treated
to the same level of performance. First, EPA reviews the available waste
characteristic data to identify those parameters that are expected to
affect treatment selection. EPA has identified some of the most
important constituents and other parameters needed to select the
treatment technology appropriate for a given waste. A detailed
discussion of each analysis, including how each parameter was selected
for each waste, can be found in the background document for each waste.
40
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Second, when an individual analysis suggests that an untested waste
can be treated with the same technology as a waste for which treatment
performance data are already available, EPA analyzes a more detailed list
of constituents that represent some of the most important waste
characteristics that the Agency believes will affect the performance of
the technology. By examining and comparing these characteristics, the
Agency determines whether the untested wastes will achieve the same level
of treatment as the tested waste. Where the Agency determines that the
untested waste is easier to treat than the tested waste, the treatment
standards can be transferred. A detailed discussion of this transfer
process for each waste can be found in later sections of this document.
1.3 Variance from the BOAT Treatment Standard
The Agency recognizes that there may exist unique wastes that cannot
be treated to the level specified as the treatment standard. In such a
case, a generator or owner/operator may submit a petition to the
Administrator requesting a variance from the treatment standard. A
particular waste may be significantly different from the wastes
considered in establishing treatability groups because the waste contains
a more complex matrix that makes it more difficult to treat. For
example, complex mixtures may be formed when a restricted waste is mixed
with other waste streams by spills or other forms of inadvertent mixing.
As a result, the treatability of the restricted waste may be altered such
that it cannot meet the applicable treatment standard.
Variance petitions must demonstrate that the treatment standard
established for a given waste cannot be met. This demonstration can be
41
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made by showing that attempts to treat the waste by available
technologies were not successful or by performing appropriate analyses of
the waste, including waste characteristics affecting performance, which
demonstrate that the waste cannot be treated to the specified levels.
Variances will not be granted based solely on a showing that adequate
BOAT treatment capacity is unavailable. (Such demonstrations can be made
according to the provisions in Part 268.5 of RCRA for case-by-case
extensions of the effective date.) The Agency will consider granting
generic petitions provided that representative data are submitted to
support a variance for each facility covered by the petition.
Petitioners should submit at least one copy to:
The Administrator
U.S. Environmental Protection Agency
401 M Street, S.W.
Washington, DC 20460
An additional copy marked "Treatability Variance" should be submitted
to:
Chief, Waste Treatment Branch
Office of Solid Waste (WH-565)
U.S. Environmental Protection Agency
401 M Street, S.W.
Washington, DC 20460
Petitions containing confidential information should be sent with
only the inner envelope marked "Treatability Variance" and "Confidential
Business Information" and with the contents marked in accordance with the
requirements of 40 CFR Part 2 (41 FR 36902, September 1, 1976, amended by
43 FR 4000).
The petition should contain the following information:
42
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(1) The petitioner's name and address.
(2) A statement of the petitioner's interest in the proposed action.
(3) The name, address, and EPA identification number of the facility
generating the waste, and the name and telephone number of the
plant contact.
(4) The process(es) and feed materials generating the waste and an
assessment of whether such process(es) or feed materials may
produce a waste that is not covered by the demonstration.
(5) A description of the waste sufficient for comparison with the
waste considered by the Agency in developing BOAT, and an
estimate of the average and maximum monthly and annual
quantities of waste covered by the demonstration. (Note: The
petitioner should consult the appropriate BOAT background
document for determining the characteristics of the wastes
considered in developing treatment standards.)
(6) If the waste has been treated, a description of the system used
for treating the waste, including the process design and
operating conditions. The petition should include the reasons
the treatment standards are not achievable and/or why the
petitioner believes the standards are based on inappropriate
technology for treating the waste. (Note: The petitioner should
refer to the BOAT background document as guidance for
determining the design and operating parameters that the Agency
used in developing treatment standards.)
(7) A description of the alternative treatment systems examined by
the petitioner (if any); a description of the treatment system
deemed appropriate by the petitioner for the waste in question;
and, as appropriate, the concentrations in the treatment
residual or extract of the treatment residual (i.e., using the
TCLP where appropriate for stabilized metals) that can be
achieved by applying such treatment to the waste.
(8) A description of those parameters affecting treatment selection
and waste characteristics that affect performance, including
results of all analyses. (See Section 3.0 for a discussion of
waste characteristics affecting performance that the Agency has
identified for the technology representing BOAT.)
(9) The dates of the sampling and testing.
(10) A description of the methodologies and equipment used to obtain
representative samples.
43
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(11) A description of the sample handling and preparation techniques,
including techniques used for extraction, containerization, and
preservation of the samples.
(12) A description of analytical procedures used including QA/QC
methods.
After receiving a petition for a variance, the Administrator may
request any additional information or waste samples that may be required
to evaluate and process the petition. Additionally, all petitioners must
certify that the information provided to the Agency is accurate under
40 CFR Part 268.4(b).
In determining whether a variance will be granted, the Agency will
first look at the design and operation of the treatment system being
used. If EPA determines that the technology and operation are consistent
with BOAT, the Agency will evaluate the waste to determine if the waste
matrix and/or physical parameters are such that the BOAT treatment
standards reflect treatment of this waste. Essentially, this latter
analysis will concern the parameters affecting treatment selection and
waste characteristics affecting performance parameters.
In cases where BOAT is based on more than one technology, the
petitioner will need to demonstrate that the treatment standard cannot be
met using any of the technologies, or that none of the technologies are
appropriate for treatment of the waste. After the Agency has made a
determination on the petition, the Agency's findings will be published in
the Federal Register, followed by a 30-day period for public comment.
44
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After review of the public comments, EPA will publish its final
determination in the Federal Register as an amendment to the treatment
standards in 40 CFR Part 268, Subpart D.
45
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2. INDUSTRIES AFFECTED AND WASTE CHARACTERIZATION
2.1 Industries Affected
This section discusses the industries that generate K024 and presents
waste characterization data.
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.
2.2 Process Description
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 time for purification. These
chemicals include sodium carbonate, sodium hydroxide, or a material
46
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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 gives
the process schematic for the manufacture of phthalic anhydride and the
generation of the listed waste K024. K024 from the distillation column
at about 250°C temperature is directly drummed where it is allowed to
cool prior to disposal.
2.3 Waste Characterization
All waste characterization data available to the Agency for the 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 comprised of BOAT
constituents (for BDAT 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 BDAT constituent composition and other data are presented in
Table 2-2. No BDAT constituents of interest, except phthalic anhydride,
were detected at significant concentrations in the untreated waste sample.
2.4 Determination of Waste Treatability Group
Fundamental to waste treatment is the concept that the type of
treatment technology used and the level of treatment achieved depend on
the physical and chemical characteristics of the waste. The data
47
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-pi
co
NAPHTHALENE
AIR
1 ^
— H " CAT
FIXED- RE(
BED REACTOR
-u
| | MULTIPLE -
F\\ TFR fc- SWfTCH
| | CONDENSERS
1
ALYST CRUDE
;YCLE STORAGE
PRI
»
JF
A
ITREATME
TANK
HL<
/(
*?' / •*
MBItttlHUt
^
»
i
i
NT Dl:
LIGHT
k^ r»ir.o
3T1LLATI
COLUMN
(K023)
DN
PHTHALIC
-^•ANHYDRIDE
PRODUCT
1 BOTTOMS
(K024)
fc^^^C
) V
- c
VATER- COOLED
JONVEYOR BELT
FLAKED K024
Figure 2-1 Schematic diagram of the generation of K024 and preparation of K024 for test burns.
-------
1419g
Table 2-1 Major Constituent Composition for
Untreated K.024 Waste
Major Constituents Concentration (%)
Phthalic anhydride 5
Ash 10
Water <1
Other BOAT constituents <1
P
Polymer material 83
TOTAL 100%
This is the product that remains in the waste.
r\
Reported by toppers to be produced from reactions of sodium
carbonate, 1,4-naphthaquinone, and other organic and inorganic
impurities from process feed materials.
Source: Data provided in Section 2.1.2, Onsite Engineering Report of
Treatment Technology Performance and Operation: Incineration of
K024 Waste at the U.S. Environmental Protection Agency,
Combustion Research Facility, EPA 1987.
49
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1419g
Table 2-2. BOAT Constituent Composition and Other Data
Constituent
CAS No.
Untreated waste concentration, ppm
Volati1e orqanics
15.
a
Chloromethane
17. 1.2-Dibromo-3-chloropropane
21. Dichlorodlfluoro-methane
34. Methyl ethyl ketone
Semivolatile orqanics
220.b Phthalic acidc'd
9,10-Anthracenedionec
Metals
155.
156.
158.
159.
160.
161.
163.
168.
Arsenic
Barium
Cadm i urn
Chromium
Copper
Lead
Nickel
Zinc
Other parameters
Btu Content (Btu/lb)
Ash %
Water %
Volatile matter (dry basis)%
Sulfur %
Carbon %
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
65.42
<10-40
200-700
13,000-220,000
5,400-6,700
No metal analyses were
performed
10,000-20,000
5-10
1.61
71.55
a - BOAT constituent number
b - This BOAT constituent number is given to phthalic anhydride.
c - Non-BDAT constituent.
d - Phthalic acid is chosen as a surrogate constituent for phthalic anhydride. Phthalic
anhydride is not detectable or measureable because during the analysis it gets hydrolyzed
to phthalic acid and therefore the presence of phthalic anhydride in the waste can be
only detected in the form of phthalic acid.
Source: Data compiled from Section 2.1.2, and Tables 2-1, 6-4 to 6-6, Onsite Engineering
Report of Treatment Technology Performance and Operation of Incineration, EPA 1987.
50
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available in literature and provided to the Agency indicate that this
waste material has a heating value of between 10,000 and 20,000 Btu per
pound, contains less than one percent water, is expected to have metals
at untreatable concentrations, and contains approximately 65 percent
volatile matter and more than 71 percent carbon. It will be shown in the
next section that incineration would be the primary destruction
technology to treat K024 waste.
51
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3. APPLICABLE/DEMONSTRATED TREATMENT TECHNOLOGIES
The previous section discusses the industries producing K024 and
lists its major constituents. This section describes the applicable
treatment technologies and performance data for treatment of K024. The
technologies that were considered to be applicable are those that treat
hazardous constituents by reducing their concentration in the treatment
residues. This section also includes a discussion of those applicable
treatment technologies that have been demonstrated on a commercial basis
to treat the waste of interest. The treatment technology tested by the
Agency, along with the performance data, is presented here. No other
applicable technologies were identified by the Agency.
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.
3.1 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; therefore, no treatment technology
data were available. Because K024 is a high Btu-content organic solid,
52
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EPA tested rotary kiln incineration technology as part of the development
of treatment standards for K024. Figure 3-1 is treatment process
schematic. The Agency believes that other forms of incineration, such as
fluidized bed incineration, might perform equally well.
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 3-1.
The analytical data collected by EPA for rotary kiln incineration are
presented in Tables 3-1 through 3-4. 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. A more detailed discussion of this treatment technology
is presented below.
3.1.1 Applicability and Use of This Technology
Rotary kiln/fluidized bed incineration is applicable to a wide range
of hazardous wastes. They can be used on wastes that contain high or low
filterable solids, high or low total organic content (TOC), various
viscosity ranges, and a range of other parameters. EPA has not found
these technologies to be demonstrated on wastes that comprise essentially
metals with low TOC concentrations; the Agency expects that these wastes
would pose a problem in regard to upcoming metal emission limitation on
hazardous waste incinerators.
53
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SAMPLE
D
A
B
C
0
SITE
DESCRPTION
Drums
Ash Bin
Venlurt Scrubber
Recirculatlon Tank
SAMPLE
DESCRIPTION
Waste Feed Before Packing
K024 Ash
Scrubber Makeup
Scrubber Slowdown
SCRUBBER
NFLUENT
FROM
RECIRCULATION
TANK
SLOWDOWN
T0
STORAGE
TANKS
Figure 3-1 U.S. EPA rotary kiln configuration and feed and residuals
sampling points during the K024 test burn.
-------
1419g
in
in
Table 3-1. Rotary Kiln Incineration - EPA-Collected Total Concentration Data for Untreated Waste
Volatile Orqanics
Chloromethane
Methyl ethyl ketone
Semivolatile Orqanics
Phthalic acid*lb
Anthracene dione*
Metals
(Not analyzed)
Sample 1 Sample 2 Sample 3
(ppm) (ppm) (ppm)
<10 32 <10
240 200 210
220,000C 83,000° 110,000°
6,700 5,600 6,300
Sample 4 Sample 5a
(ppm) (ppm)
40 <10
210 680
13,000C N/A
5,900 N/A
Sample 6a
(ppm)
10
600
N/A
N/A
Sample 7a Sample 8a
(ppm) (ppm)
<10 <10
690 700
N/A N/A
N/A N/A
*Non-BOAT parameter.
a
b
3 Using methanol extract, a methanol blank for methyl ethyl ketone was reported as 770 ppm.
Phthalic acid is used as a surrogate constituent for phthalic anhydride since phthalic anhydride is converted to
phthalic acid during the chemical analysis.
c Memo to Fred Hall, PEI Associated, Cincinnati, OH, from Patrick Meehan, Radian Corp.,
Austin, TX, dated 15 December 1987
N/A Not analyzed
Source; Data compiled from Tables 6-5, 6-6, and 6-10, Onsite Engineering Report, EPA 1987.
-------
1419g
Table 3-2. Rotary Kiln Incineration - EPA-Collected Total Concentration Data for Scrubber Water
Parameter
Sample 1 Sample 2 Sample 3 Sample 4 Sample 5 Sample 6 Sample 7 Sample 8 Sample 9 Sample 10
Volatile Orqanics (jig/1)
Chloromethane
1 , 2-Dibromo-3-chloropropane
Dichlorodif luoromethane
Methy ethyl ketone
<10 <10 <10 <10 <10 <10 <10 <10 <10 <10
12 <10 <10 <10 <10 <10 <10 <10 <10 <10
<10 <10 <10 <10 23 <10 <10 <10 <10 <10
<50 <50 <50 <50 <50 <50 <50 <50 <50 <50
Semivolatile Orqanics
Phthalic acid (surrogate for
phthalic anhydride)
Anthracene dione
C71
01
Hetals (mg/l)
Arsenic
Barium
Cadmium
Chromium
Copper
Nickel
Lead
Zinc
<160a
<250
0.
0.
0.
0.
0.
0.
2.
1.
22
10
082
036
81
11
,0
5
<160
<250
0.063
0.077
0.072
0.096
0.118
0.12
5.2
1.9
<160
<250
0.047
0.11
0.038
<0.035
0.32
0.13
10.0
1.7
<160
<250
0.041
0.16
0.025
<0.035
<0.030
0.13
9.2
1.4
<160
<250
0.066
0.41
<0.02
<0.035
<0.030
0.10
16
1.3
<160
<250
0.059
0.039
<0.02
<0.53
<0.030
0.10
1.7
2.0
<160
<250
<0.02
0.35
<0.02
<0.53
<0.030
<0.075
2.7
0.33
<160
<250
0.022
0.037
<0.02
<0.035
<0.030
<0.075
1.5
0.70
<160
<250
0.024
0.097
<0.02
0.65
<0.030
<0.075
1.4
0.79
<160
<250
0.035
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1419g
Table 3-3. Rotary Kiln Incineration - EPA-Collected Total Concentration Data for Ash
in
Volat i 1e Orqanics
Chloromethane
Methyl ethyl ketone
Semivolat i le Orqanics
Phthalic acid (surrogate for
phthalic anhydride)
Anthracene dione
Hetals
Arsenic
Barium
Cadmium
Chromium
Copper
Nickel
Lead
Vanadium
Zinc
Sample 1
(ug/g)
<10
<50
<8.2
<2.5
12
3900
2.2
20
46
11
1100
64
170
Sample 2
(ug/g)
<10
<50
<8.2
<2.5
2.5
85
<1.5
45
25
44
110
10
110
Sample 3 Sample 4a Sample 5a
(ug/g) (ug/g) (ug/g)
<10 <10 <10
<50 1100 780
<8.2 NA NA
<2.5 NA NA
2.1
35
<1 .5 Not analyzed
52
21
55
20
<10
29
Sample 6a
(ug/g)
<10
440
NA
NA
a Use of methanol extract; a methanol blank for methyl ethyl ketone was reported as 770 itg/
NA - Not analyzed.
Source: Date compiled from Tables 6-4 to 6-6 and 6-12, Onsite Engineering Report, EPA 1987.
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1419g
Table 3-4. Total and TCLP Metals Analyses Data for Ash
CO
Parameter
Arsenic
Barium
Cadmium
Chromium
Copper
Nickel
Lead
Thai lium
Zinc
Total
(/ig/g)
12
3900
2.2
20
46
11
1100
1.0
170
Sample 1
TCLP
(ppm)
<1.5
0.38
<0.015
<0.045
0.14
<0.10
2.3
<0.45
0.30
Total
(cg/g)
2.5
85
<1.5
45
25
44
110
. 1.0
no
Sample 2
TCLP
(ppm)
<1.5
0.18
0.004
0.37
<0.05
1.5
<0.25
<0.45
1.6
Sample 3
Total TCLP
(>"g/g) (ppm)
2.1 <1.5
35 0.084
<1.5 <0.015
52 0.051
21 <0.05
55 0.11
20 <0.25
1.0 0.17
29 <0.10
• Blank
Total
NA
NA
NA
NA
NA
NA
NA
NA
NA
TCLP
(ppm)
<1.5
0.34
<0.015
<0.045
0.37
<0.10
<0.25
<0.45
0.26
NA - Not available.
Source. Data compiled from Tables 6-12 and 6-13. Onsite Engineering Report, EPA 1987.
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3.1.2 Underlying Principles of Operation
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 CO 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 liquid injection.
A rotary kiln is a slowly rotating, refractory-lined cylinder that is
mounted at a slight incline from the horizontal. 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.
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
59
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or absorption step to remove HC1 and other halo-acids from the combustion
gases. Ash in the waste is not destroyed in the combustion process.
Depending on its composition, ash will either exit as bottom ash, at the
discharge end of a kiln or hearth for example, or as particulate matter
(fly ash) suspended in the combustion gas stream. Particulate emissions
from most hazardous waste combustion systems generally have particle
diameters less than one micron and require high efficiency collection
devices to minimize air emissions. In addition, scrubber systems provide
additional buffer against accidental releases of incompletely destroyed
waste products due to poor combustion efficiency or combustion upsets,
such as flame-outs.
3.2.3 Waste Characteristics Affecting Performance
Unlike liquid injection, this incineration technology also generates
a residual ash. Accordingly, in determining whether this technology is
likely to achieve the same level of performance on an untested waste as 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
60
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volatilization of organics from the waste; the discussion relative to
bond energies is the same for these technologies as for liquid injection
and will not be repeated here.
(1) Thermal Conductivity. Consistent with the underlying principles
of incineration, a major factor with regard to whether a particular
constituent will volatilize, is the transfer of heat through the waste.
In the case of rotary kiln, fluidized bed, and fixed hearth incineration,
heat is transferred through the waste by three mechanisms: radiation,
convection, and conduction. For a given incinerator, heat transferred
through various wastes by radiation is more a function of the design and
type of incinerator than of the waste being treated. Accordingly, the
type of waste treated will have a minimal impact on the amount of heat
transferred by radiation. With regard to convection, EPA also believes
that the type of heat transfer will generally be more a function of the
type and design of 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.
61
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Heat flow by conduction is proportional to the temperature gradient
across the material. The proportionality constant is a property of the
material and referred to as the thermal conductivity. (Note: The
analytical method that EPA has identified for measurement of thermal
conductivity is named "Guarded, Comparative, Longitudinal Heat Flow
Technique"; it is described in Appendix C.) In theory, thermal
conductivity would always provide a good indication of whether a
constituent in an untested waste would be treated to the same extent in
the primary incinerator chamber as the same constituent in a previously
tested waste.
In practice, thermal conductivity has some limitations in assessing
the transferability of treatment standards; however, EPA has not
identified a parameter that can provide a better indication of heat
transfer characteristics of a waste. Below is a discussion of the
limitations associated with thermal conductivity, as well as 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 that 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
62
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through regions having the greatest conductivity (i.e., the path of least
resistance) and not heat flow through all parts of the waste.
Btu value, specific heat, and ash content were also considered for
predicting heat transfer characteristics. These parameters can account
for nonhomogeneity no better than they can for thermal conductivity;
neither are they directly related to heat transfer characteristics.
Therefore, these parameters do not provide a better indication of heat
transfer that will occur in any specific waste.
(2) 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.
3.2.4 Rotary Kiln Incineration Process Description
The U.S. EPA, at its Combustion Research Facility (CRF) in Jefferson,
Arkansas, operates a pilot-scale rotary kiln incinerator. Even though no
facility currently uses incineration to treat K024, rotary kiln
incineration is a technology that is demonstrated on similar wastes.
Hence, the Agency decided to use this Agency-operated and maintained
facility to demonstrate incineration of K024 specifically. The
63
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principles involve the oxidation of carbon and hydrogen-containing
molecules to form carbon dioxide and water at temperatures of
approximately 1000° C (1830° F). A schematic diagram of the
rotary kiln incinerator is presented in Figure 3-1. Table 3-5 presents
the design characteristics of the incinerator. Tables 3-6 through 3-9
present operating parameters for the kiln, afterburner, scrubber system,
and stack gases. Those tables also show the design and operating
conditions that were maintained during the destruction of K024 waste.
At the CRF, the rotary kiln is operated at temperatures of 1000°C
(1830°F) or more. The combustion gases from the kiln pass through an
afterburner for further incineration. The afterburner maximum operating
temperature is 1200°C (2200°F). Both the kiln and the
afterburner use propane for startup fuel and as supplementary fuel during
a waste burn. A ram feeder is used to inject cylindrical fiber packs
containing the rotary kiln K024 feed material into the ram. The feed
rate is controlled by the ram feed operator.
The hot combustion gases leaving the afterburner enter a venturi
scrubber followed by a packed tower, a carbon bed, and a high energy
particle (HEPA) filter in series. Typical rotary kiln system gas
handling systems include a venturi scrubber for particulate control and a
packed tray tower for gaseous pollutant control (e.g., hydrogen
chloride).
64
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1419g
Table 3-5. Design Characteristics of the CRF Rotary Kiln System
Characteristics of the kiln main chamber
Length
Diameter
Chamber volume
Rotation
Construction
Refractory
Solids retention
time
Burner
Primary fuel
Feed system
2.44 m (8 ft)
1.22 m (4 ft)
2.88 m3 (100 ft3)
Clockwise or counterclockwise 0.1 to 1.5 rpm
0.63 cm (0.25 in.) thick cold rolled steel
12.7 cm (5 in.) thick high-alumina castable refractory,
variable depth to produce a frustroconical effect for
moving inerts
1 h (at 0.5 rpm)
John Zink Model RW3I-FL
Propane
Liquids: Front face, water-cooled lance with
positive-displacement pump
Semiliquids: Front face, water-cooled land with
double-diaphragm pump
Temperature1
Solids:
1000°C (1832°F)
Ram feeder or metered twin-auger
screw feeder
Characteristics of the afterburner chamber
Length
Diameter
Chamber volume
3.05 m (10 ft)
0.91 m (3 ft)
2.096 m3 (74 ft3)
65
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1419g
Table 3-5. (continued)
Construction
Refractory
Retention time
Burner
Primary fuel
Temperature
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
Characteristics of the air pollution control system
System capacity
Pressure drop
Liquid flow
(nominal)
pH control
Packing
Inlet gas flow of 106.8 m3/min (3773 acfm) at 1200°C
(2200°F) and 101 kPa (14.7 psia)
Venturi 7.5 kPa (30 in. WC)b
Packed tower 1.0 kPa (4 in. WC)
Venturi 77.2 liters/min (20.4 gal/min) at 69 kPA
(10 psig)
Tower 115 liters/min (30 gal/min) at 69 kPa
(10 psig)
Slowdown 7.6 to 9.5 liters/min (2 to 2.5 gpm)
Feedback control by NaOH solution addition
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.H20 across the scrubber and up to
8.2 in.H20 across the packed tower have been used.
Source: Table 3-1 from Onsite Engineering Report for K024, EPA 1987.
CG
-------
Table 3-6. Incinerator Operating Parameters, Rotary Kiln
cr>
Propane
range (average)
Test
date
3/17/87
3/18/87
3/19/87
Feed rate,
scfh
336-424
(366)
282-478
(320)
202-342
(311)
Heat
input,
10* Btu/h
0.822-1.040
(0.935)
0.690-1.170
(0.784)
0.496-0.839
(0.763)
Waste
feed
rate,
Ib/h
a
53
b
107
c
104
Combustion
air
feed rate.
scfm
124
124
124
Exit
temperature
range
(average), °F
1573°-1754°
(1707°)
1713°-2026°
(1898°)
1570°-1953°
(1786°)
Rotation
speed,
rpm
0.2
0.2
0.2
Pressure
(draft),
in. H20
-0.12
-0.12
-0.12
a One fiber pack containing about 4.5 Ib waste fed every 5 minutes.
b One fiber pack containing about 4.5 Ib waste fed every 2.5 minutes.
c Two fiber packs containing about 4.5 Ib waste fed every 5 minutes.
Source: Data from Table B-l, Onsite Engineering Report, EPA 1987.
-------
Table 3-7. Incinerator Operating Parameters, Afterburner
cr>
CD
Afterburner parameter
Propane
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,
°F
1963°-2078°
(2055°)
1894°-2155°
(2025°)
1921°-2091°
(2014°)
range (average)
Pressure
(draft)
in. H20 02, %
(-0.12) 5
-0.2 to -0.1
(-0.15) 4
-0.2 to -0.1
(-0.15) 5
Exit gas
C02, % CO, ppm
<10-100b
9 <10
<10-100b
10 <10
<10-100b
10 <10
a Instrument limit on C02 is 10 percent; on CO 100. ppm; actual values therefore could be higher than the
peak values shown.
b One or more CO spikes from 40 to 100 ppm during test period.
Source: Data for Table B-2, Onsite Engineering Report, EPA 1987.
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Table 3-8. Incinerator Operating Parameters, Scrubber System (Acurex)
O-l
UD
Scrubber system parameter range (average)
Venturi
Test
date
3/17/87
3/18/87
3/19/87
Liquid
flow rate,
gal/min
19
19
19
Delta P,
in. H20
25-42
(35)
20-43
(34)
20-38
(34)
Packed
Liquid
flow rate,
gal/min
31
28-29
(29)
29-30
(29)
tower
Delta P,
in. H20
5.0-10
(6.9)
5.0-10
(7.6)
6.1-10
(8.2)
Scrubber liquid
pH
6.2
6.0-6.
(6.1)
5.0-5.
(5.1)
Temperature
°F
147°-165°
(160°)
2 148°-166°
(158°)
1 153°-165°
(161°)
Slowdown
Flow rate,
gal/min
2.1
1.8-2.4
(2.3)
2.2
Temper-
ature,
°F
71-102
(681)
84-112
(94)
86-119
(102)
Makeup
water
feed rate,
gal/min
5.0-10
(6.9)
5.0-10
(7.6)
6.1-10
(8.2)
Source: Data from Table B-3, Onsite Engineering Report, EPA 1987.
-------
Table 3-9. Incinerator Operating Parameters, Scrubber Exit and Stack Gases^
o
Operating conditions range (average)
Test
date
3/17/87
3/18/87
3/19/87
Temperature,
°F
164°-173°
(170°)
164°-173°
(169°)
160°-174°
(170°)
Scrubber exit
Flow
rate,
dscfm 02, %
708 10.5
735 10.0
670 10.5
(prior to
C02, %
6.0
8.1
6.2
charcoal bed)
Temperature,
CO, ppm °F
163°-170°
<10 (167°)
<10 (168°)
<10 (168°)
Stack
Flow
rate,
dscfm
933
679
734
(to atmosphere)
02, *
10.5
10.0
10.5
C02, % CO, ppm
6.0 <10
8.1 <10
6.2 <10
a As measured by the stack MM5 train.
b See Figure Z-l for location of monitoring points.
Source: Data from Table B-4, Onsite Engineering Report, EPA 1987.
-------
Sodium hydroxide is added to the scrubbing system (venturi and packed
tower) to maintain pH near neutral condition. Makeup water is added at a
rate of 5 to 10 gallons per minute, and the water system is blown down
continuously at a rate of 2.0 to 2.5 gallons per minute.
3.1.5 Incineration Design and Operating Parameters
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 it is likely that sufficient energy will be provided to the waste
in order to volatilize the waste constituents. For the secondary chamber,
analogous to the sole liquid injection incineration chamber, EPA will
examine the same parameters discussed 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.
(1) Temperature. The primary chamber temperature is important in
that it provides an indirect measure of the energy input (i.e., Btus/hr)
that is available for heating the waste. The higher the temperature is
designed to be in a given kiln, the more likely it is that the
constituents will volatilize. As discussed earlier under "Liquid
Injection," temperature should be continuously monitored and recorded.
71
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Additionally, it is important to know the location of the temperature
sensing device in the kiln.
(2) Residence Time. This parameter is important in that it affects
whether the heat transferred to a particular constituent is sufficient to
allow 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 is 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.
(3) 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.
3.2 Other Applicable Treatment Technologies
The Agency is unaware of any other treatment technologies applicable
to K024 that would be as effective as or more effective than
incineration. The Agency also does not believe that other technologies
are applicable because various physical and chemical characteristics of
the waste would not allow destruction of the hazardous constituents as
effectively as incineration.
72
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4. IDENTIFICATION OF BEST DEMONSTRATED TECHNOLOGY FOR K024
4.1 Introduction
In the previous section, EPA examined applicable treatment
technologies. In this section, a best technology to treat K024 is
identified based on the information presented in Section 3 on the
applicable and demonstrated treatment technologies. The demonstrated
treatment technology for K024 is incineration for which the Agency
documented design and operating data and collected the performance data
on rotary kiln incineration. Other types of incineration are expected to
perform in an equivalent manner. The residues generated by this
technology may contain metals at treatable concentrations. The Agency
reserves the right to identify BOAT for treatment of these metals.
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
73
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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.
4.2 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.
4.3 Data Accuracy
After the screening tests, EPA adjusted the data values based on the
analytical recovery values in order to take into account analytical
74
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interferences 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.
4.4 Analysis of Variance
In cases were the Agency has data on treatment of the same or similar
wastes using more than one technology, EPA conduct an analysis of
variance (ANOVA) test to determine whether one of the technologies
performs significantly better. In cases where a particular treatment
technology performs better, the treatment standard will be based on this
best technology.
In case of K024, no ANOVA test was necessary since rotary kiln
incineration was the only destruction technology for which data were
avail able.
4.5 Availability of the Demonstrated Technology
Rotary kiln incineration is believed to be an available technology
because (a) it is commercially available, (b) it is not a proprietary
75
-------
process, and (c) the toxicity of the waste is substantially reduced, and
hence the likelihood of hazards is minimized significantly.
76
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5. SELECTION OF REGULATED CONSTITUENTS
The previous section identifies rotary kiln incineration as BOAT for
K024. This section discusses the methodology 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
77
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the untreated waste and must be treatable by the chosen BOAT, as
discussed in Section 4.
The following steps were taken to select the regulated constituents
for K024:
5.1 Identification of Ma.ior 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 constituent 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. A detection limit is
defined as a practical quantitation limit (PQL) which is five times the
method detection limit that is achievable when using an EPA-approved
analytical method specified for a particular analyte (i.e., constituent
of interest) in Test Methods for Evaluating Solid Waste, SW846,
3rd edition, November 1986.
For example, phthalic acid, which is a surrogate for phthalic
anhydride in the untreated waste, is detected at or above 2500 ppm level
and therefore is identified as a major constituent in K024 untreated
waste. Using the similar selection process, other major constituents
are selected. These constituents and their concentrations identified in
the untreated K024 are listed in Table 5-1.
78
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1419g
Table 5-1. Major BOAT Constituents in Untreated K024
BOAT constituent
Concentration range
ppm
Volati1e orqanics
15.* Chloromethane
34. Methyl ethyl ketone
>10 - 40
200 - 700a
Semivolatile orqanics
220 ** Phthalic acid*** (used
as a surrogate for
phthalic anhydride
Anthracene dione***
13,000 - 220,000°
5,400 - 6,700
Metals
155.
156.
158.
159.
160.
161.
163.
166.
168.
Arsenic
Barium
Cadmium
Chromium
Copper
Nickel
Lead
Thai Hum
Zinc
Not analyzed
Not analyzed
Not analyzed
Not analyzed
Not analyzed
Not analyzed
Not analyzed
Not analyzed
Not analyzed
*BDAT constituent number.
**BDAT constituent number for phthalic anhydride.
***Non-BDAT parameter.
a Methyl ethyl ketone concentration in methanol blank reported as
770 ppm.
Memo to Fred Hall, PEI Associates, Cincinnati, OH, from
Patnick Meehan, Radian Corporation, Austin, TX, dated
15 December 1987.
Source: Data compiled from Tables 6.4 to 6.6, Onsite Engineering Report,
EPA 1987.
79
-------
5-2 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
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) and discussed in Section 1,
is used to determine statistically the significance of constituent
concentration. Table 5-2 compares the analytical data for untreated and
80
-------
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
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, as seen from Table 5-2, was found in
treated nonwastewater (i.e., ash), 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.
5.3 Evaluation of Waste Characteristics Affecting Performance and
Other Related Factors
The waste characteristics that would affect treatment performance
which are 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
81
-------
1419g
Table 5-2. Comparison of Major Constituents in Untreated and Treated K024 Waste
Constituent
Concentration range, ppm
Untreated waste
Composite TCLP Composite TCLP Composite TCLP
Treated waste
Scrubber water Ash
Volati1e orqanics
15.* Chloromethane
<10 - 40
NA
34. Methyl ethyl ketone 200 - 240(600-700°) NA
Senmvolat11e orqanics
220. Phthalic acid (used 13,000 - 220,000 NA
as a surrogate
for phthalic
anhydride)
Anthracene dione** 5,400 - 6,700 NA
Metals
<10a
<50a
<160d
<250d
NA
NA
NA
NA
<50(460-1100)
<8.2L
<2.5
NA
NA
NA
NA
155.
156.
158.
159.
160.
161.
163.
166.
168.
Arsenic
Barium
Cadmium
Chromium
Copper
Nickel
Lead
Thallium
Zinc
NT
NT
NT
NT
NT
NT
NT
NT
NT
NT
NT
NT
NT
NT
NT
NT
NT
NT
<0.
<0.
020-0.
,010-0.
<0. 020-0.
<0.
<0.
<0.
1.
NT
0.
035-0.
,030-0.
,075-0.
.4 -
,33 -2.
22
,41
,082
.65
.81
.13
16
,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.
<0.05 - 0,
<0.10 - 1,
<0.25 - 2,
0.17 -<0,
<0.10 - 1,
,37
.14
.5
.3
.45
.6
*BDAT constituent number.
**Non BOAT parameter.
NA = Not applicable.
a = part per billion (ppb)
b = 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.
NT = Not tested.
Source: Data from Table 6-3 to 6-6, 6-8 to 6-11, 6-12, 6-13, and 6-14, Onsite Engineering Report,
EPA 1987.
Memo to Fred Hall, PEI Associates, Cincinnati, OH, from Patrick Meehan, Radian Corporation, Austin, TX,
dated 15 December 1987.
82
-------
to shorten the list of regulated pollutants to those which, when treated,
are likely to ensure that many others in the potential list are treated.
In other words, the 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
case of K024 waste, no additional constituents were added to the list of
constituents already considered for regulation. (Metals may change this
conclusion!)
5.4 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 can not 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.
83
-------
6. DEVELOPMENT OF BOAT TREATMENT STANDARDS
In the previous sections, a demonstrated available technology was
selected, as were the K024 constituents to be regulated. In this
section, actual performance of best demonstrated technology for the
regulated constituent, namely, 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 greatest flexibility in meeting the treatment standards. In
other words, 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 in order to achieve the proposed
performance levels.
The proposed treatment standards are also applicable to those wastes
regulated as "mixture" and "derived from" wastes. Hence, the treatment
standards would 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 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.
84
-------
The BOAT treatment standard for K024 was developed in the following
manner using actual performance data for rotary kiln incineration.
6.1 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.
6.2 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 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 6-1 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
85
-------
Agency has decided not to regulate metals in the waste, but reserves the
right to consider regulation of BOAT metals in the future.
Also shown in Table 6-1 is a variability factor used to derive a
treatment standard for K024 waste. See Appendix A for derivation of the
variability factor.
86
-------
1419g
Table 6-1. Calculation of BOAT Treatment Standards for K024
oo
Concentration
in treated Accuracy
Constituent waste factor
Phthalic acid** in
nonwastewater
(ash) <8.2 ppm 1,19
Phthalic acid** in
wastewater
(scrubber water) <=160 ppb 1.2
Average
accuracy-
corrected
concentrations
9.8 ppm
192 ppb
Proposed
BOAT
Variability* treatment
factor standard
2.8 27.5 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.
-------
7. CONCLUSIONS
The Agency has proposed treatment standards for the listed waste K024
from the organic chemical industry. The treatment standards are
presented for wastewater and nonwastewater in Table 7-1. As previously
noted, these standards do not reflect the treatment standards included in
the preamble to the proposed rule. The treatment standards given here
represent the use of additional data that have since become available.
The treatment standards proposed for K024 have been developed
consistent with EPA's promulgated methodology for BOAT (November 7, 1986,
51 FR 40572). This waste is generated as distillation bottoms in the
production of phthalic anhydride from naphthalene. Currently, only one
facility generates K024 waste in the country. This waste comprises
primarily high-Btu organic solids, very low metal concentrations, and low
concentrations of water.
Although the concentrations of specific constituents will vary from
sample to sample, all of the wastes are expected to contain similar
concentrations of BOAT constituents such as phthalic anhydride and are
expected to be treatable to the same levels using the same technology.
The Agency has developed the treatment standard for only one constituent,
phthalic anhydride, which is an indicator of treatment performance for
K024. (Because of the difficulty in analyzing phthalic anhydride, the
Agency has chosen phthalic acid as a surrogate for phthalic anhydride.)
Following the review of all available data for K024 waste, the Agency
has identified incineration technology as the best demonstrated available
88
-------
1419g
Table 7-1. BOAT Treatment Standards for K024
Regulated organic
constituent
Total composition
(mg/kg)
TCLP
(mg/1)
Phthalic acid*
27.5
Not applicable
BOAT Treatment Standards for K024
(Uastewater)
Regulated organic
constituent
Total composition
(mg/1)
TCLP
(mg/1)
Phthalic acid*
0.54
Not applicable
*This constituent is regulated as a surrogate for phthaTic anhydride
which cannot be easily analyzed in that it is hydrolyzed and converted to
phthalic acid.
89
-------
technology for treatment of organic BOAT constituents present in the
waste. The Agency collected data for rotary kiln incineration of K024 as
discussed in Section 3. At present time, no other treatment technology
has been demonstrated for K024.
The regulated constituent, phthalic acid, was selected based on
careful evaluation of the BOAT constituents found at significant (i.e.,
treatable) levels in the untreated wastes and constituents detected in
the treated residuals. All available waste characterization data and
applicable treatment data consistent with the type and quality of data
needed by the Agency for this program were used to make this
determination.
In the development of treatment standards for K024, the Agency
examined all available treatment data. The Agency conducted an
incineration test burn for K024. The treatment standards for K024 are
based on the treatment data collected by the Agency for incineration in a
rotary kiln unit. The treatment standard for the only regulated
constituent was derived after adjustment of laboratory data to account
for recovery (accuracy). In case of K024 treated waste, the regulated
constituent, phthalic acid (surrogate for phthalic anhydride) was below
the detection limit of 8.2 ppm (Table 3-3)for ash and below the detection
limit of 160 ppb (Table 3-2) for wastewater. As discussed earlier,
phthalic acid is regarded as a surrogate regulated organic constituent
for phthalic anhydride because phthalic anhydride, during the chemical
analysis, gets hydrolyzed easily and is converted to phthalic acid.
90
-------
Phthalic anhydride can be detected and measured only as phthalic acid,
hence phthalic acid is used as a surrogate regulated organic
constituent.
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.
Wastes determined to be K024 may be land disposed if they meet the
treatment standards at the point of disposal. For K024, the treatment
standards are based on the concentration of phthalic acid in the waste.
The BOAT technology upon which the treatment standards are based
(incineration) need not be specifically utilized prior to land disposal,
provided an alternative technology achieves the standards and does not
pose a greater risk to human health and the environment than land
disposal.
These standards become effective as of August 8, 1988, according to
the schedule set forth in 40 CFR 268.10. Because of the lack of
nationwide incineration capacity at this time, the Agency has proposed to
grant a 2-year nationwide variance to the effective date of the land
disposal ban for these wastes. A detailed discussion of the Agency's
determination that a lack of capacity exists is presented in the Capacity
Background Document, which is available in the Administrative Record for
the First Sixths rule.
91
-------
Consistent with Executive Order 12291, EPA prepared a regulatory
impact analysis (RIA) to assess the economic effect of compliance with
this proposed rule. The RIA prepared for this proposed rule is available
in the Administrative Record for the First Sixths Rule.
92
-------
REFERENCES
1. Ackerman DG, McGaughey JF, Wagoner D.E., At Sea Incineration of
PCB-Containing Wastes on Board the M/T Vulcanus, USEPA,
600/7-83-024, April 1983.
2. Bonner TA, et al., Engineering Handbook for Hazardous Waste
Incineration. SW889. Prepared by Monsanto Research Corporation for
U.S. NTIS PB 81-248163. June 1981.
3. Novak RG, Troxler WL, Dehnke TH, Recovering Energy from Hazardous
Waste Incineration, Chemical Engineering Progress 91:146 (1984).
4. Oppelt ET, Incineration of Hazardous Waste; JAPCA; Volume 37, No. 5;
May 1987.
5. Santoleri JJ, 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, 1983.
6. USEPA, Best Demonstrated Available Technology (BOAT) Background
Document for F001-F005 Spent Solvents, Volume 1, EPA/530-SW-86-056,
November 1986.
7. Vogel G, et al., Incineration and Cement Kiln Capacity for Hazardous
Waste Treatment, in Proceedings of the 12th Annual Research
Symposium. Incineration and Treatment of Hazardous Wastes.
Cincinnati, Ohio. April 1986.
8. USEPA. 1987a. Memorandum Concerning Adjusted Concentration Values
and Detection Limits. U.S. Environmental Protection Agency, Office
of Solid Waste; Contract No. 68-03-3389, Work Assignment No. 11A.
9. USEPA. 1987b. Onsite Engineering Report of Treatment Technology
Performance and Operation: Incineration of K024 Waste at the U.S.
Environmental Protection Agency's Combustion Research Facility.
U.S. Environmental Protection Agency, Office of Solid Waste.
93
-------
-------
APPENDIX A
A.I F Value Determination for ANOVA Test
As noted earlier in Section 1.0, EPA is using the statistical method
known as analysis of variance in the determination of the level of
performance that represents "best" treatment where more than one
technology is demonstrated. This method provides a measure of the
differences between data sets. If the differences are not statistically
significant, the data sets are said to be homogeneous.
If the Agency found that the levels of performance for one or more
technologies are not statistically different (i.e., the data sets are
homogeneous), EPA would average the long term performance values achieved
by each technology and then multiply this value by the largest
variability factor associated with any of the acceptable technologies.
If EPA found that one technology performs significantly better (i.e., the
data sets are not homogeneous), BOAT would be the level of performance
achieved by the best technology multiplied by its variability factor.
To determine whether any or all of the treatment performance data
sets are homogeneous using the analysis of variance method, it is
necessary to compare a calculated "F value" to what is known as a
"critical value." (See Table A-l.) These critical values are available
in most statistics texts (see, for example, Statistical Concepts and
Methods by Bhattacharyya and Johnson, 1977, John Wiley Publications, New
York).
Where the F value is less than the critical value, all treatment data
sets are homogeneous. If the F value exceeds the critical value, it is
A-l
-------
Table A-l
95th PERCENTILE VALUES FOR
THE F DISTRIBUTION
MI = degrees of freedom for numerator
n2 = degrees of freedom for denominator
X^v
^95
^
1
2
3
4
5
6
1
8
9
10
11
12
13
14
15
16
17
18
19
20
"2
24
26
28
30
40
50
60
70
80
100
150
200
400
BO
1
1G1.4
18.51
10.13
7.71
6.61
5.99
5.59
5.32
5.12
4.96
4.84
4.75
4.67
4.60
4.54
4.49
4.45
4.41
4.38
4.35
4.30
4.26
4.23
4.20
4.17
4.08
4.03
4.00
3.98
3.96
3.94
3.91
3.89
3.86
3.84
2
199.5
19.00
9.55
6.94
5.79
5.14
4.74
4. -16
4.26
4.10
3.98
3.89
3.81
3.74
3.68
3.63
3.59
3.55
3.52
3.49
3.44
3.40
3.37
3.34
3.32
3.23
3.18
3.15
3.13
3.11
3.09
3.06
3.04
3.02
2.99
3
215.7
19.16
9.28
6.59
5.41
4.76
4.35
4.07
S.86
3.71
3.59
3.49
3.41
3.34
3.29
3.24
3.20
3.16
3.13
3.10
3.05
3.01
2.98
2.95
2.92
2.84
2.79
2.76
2.74
2.72
2.70
2.67
2.65
2.62
2.60
4
224.6
19.25
9.12
6.39
5.19
4.53
4.12
3.84
•3.G3
3.48
3.36
3.26
3.18
3.11
3.06
3.01
2.96
2.93
2.90
2.87
2.82
2.78 '
2.74
2.71
2.69
2.61
2.56
2.53
2.50
2.48
2.46
2.43
2.41
2.39
2.37
5
230.2
19.30
9.01
6.26
5.05
4.39
3.97
3.69
3.48
3.33
3.20
3.11
3.03
2.96
2.90
2.85
2.81
2.77
2.74
2.71
2.66
2.62
2.59
2.56
2.53
2.45
2.40
2.37
2.35
2.33
2.30
2.27
2.26
2.23
2.21
6
234.0
19.33
8.94
6.16
4.95
4.28
3.87
3.58
3.37
3.22
3.09
3.00
2.92
2.85
2.79
2.74
2.70
2.66
2.63
2.60
2.55
2.51
2.47
2.45
2.42
2.34
2.29
2.25
2.23
2.21
2.19
2.16
2.14
2.12
2.09
8
238.9
19.37
8.85
6.04
4.82
4.15
3.73
3.44
3.23
3.07
2.95
2.85
2.77
2.70
2.64
2.59
2.55
2.51
2.48
2.45
2.40
2.36
2.32
2.29
2.27
2.18
2.13
2.10
2.07
2.05
2.03
2.00
1.98
1.96
1.94
12
243.9
19.41
8.74
5.91
4.68
4.00
3.57
3.28
3.07
2.91
2.79
2.69
2.60
2.53
2.48
2.42
2.38
2.34
2.31
2.28
2.23
2.18
2.15
2.12
2.09
2.00
1.95
1.92
1.89
1.88
1.85
1.82
1.80
1.78
1.75
16
246.3
19.43
8.69
5.84
4.60
3.92
3.49
3.20
2.98
2.82
2.70
2.60
2.51
2.44
2.39
2.33
2.29
2.25
2.21
2.18
2.13
2.09
2.05
2.02
1.99
1.90
1.85
1.81
1.79
1.77
1.75
1.71
1.69
1.67
1.64
20
248.0
19.45
8.66
5.80
4.56
3.87
3.44
3.15
2.93
2.77
2.65
2.54
2.46
2.39
2.33
2.28
2.23
2.19
2.15
2.12
2.07
2.03
1.99
1.96
1.93
1.84
1.78
1.75
1.72
1.70
1.68
1.64
1.62
1.60
1.57
30
250.1
19.46
8.62
5.75
4.50
3.81
3.38
3.08
2.86
2.70
2.57
2.46
2.38
2.31
2.25
2.20
2.15
2.11
2.07
2.04
1.98
1.94
1.90
1.S7
1.84
1.74
1.69
1.65
1.62
1.60
1.57
1.54
1.52
1.49
1.46
40
251.1
19.46
8.60
5.71
4.46
3.77
3.34
3.05
2.82
2.67
2.53
2.42
2.34
2.27
2 °1
2.16
2.11
2.07
2.02
1.99
1.93
1.89
1.85
1.81
1.79
1.69
1.63
1.59
1.56
1.54
1.51
1.47
1.45
1.42
1.40
50
252.2
19.47
8.58
5.70
4.44
3.75
3.32
3.03
2.80
2.64
2.50
2.40
2.32
2.24
2.18
2.13
2.08
2.04
2.00
1.96
1.91
1.86
1.82
1.78
1.76
1.66
1.60
1.56
1.53
1.51
1.48
1.44
1.42
1.38
1.32
100
253.0
19.49
8.56
5.66
4.40
3.71
3.28
2.98
2.76
2.59
2.45
2.35
2.26
2.19
2.12
2.07
2.02
1.98
1.94
1.90
1.84
1.80
1.76
1.72
1.69
1.59
1.52
1.48
1.45
1.42
1.39
1.34
1.32
1.28
1.24
ee
254.3
19.50
8.53
5.63
4.35
3.67
3.23
2.93
2.71
2.54
2.40
2.30
2.21
2.13
2.07
2.01
1.96
1.92
1.8S
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
-------
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
T^ = sum of natural logtransformed data points for each technology.
(iv) The sum of the squares within data sets (SSW) is computed:
k
I
i=l
I11']
ni
r k i
&T<
N
-------
(vi) Using the above parameters, the F value is calculated as
follows:
MSB
F = MSW
where:
MSB = SSB/(k-l) and
MSW = SSW/(N-k).
A computational table summarizing the above parameters is shown below.
Computational Table for the F Value
Source
Between
Within
Degrees of
freedom
K-l
N-k
Sum of
squares
SSB
SSW
Mean square
MSB = SSB/k-1
MSW = SSW/N-k
F
MSB/MSW
Below are three examples of the ANOVA calculation. The first two
represent treatment by different technologies that achieve statistically
similar treatment; the last example represents a case where one
technology achieves significantly better treatment than the other
technology.
A-4
-------
1790g
Example 1
Methylene Chloride
Steam stripping
Influent Effluent
Us/D
1550.00
1290.00
1640.00
5100.00
1450.00
4600.00
1760.00
2400.00
4800.00
12100.00
Ug/l)
10.00
10.00
10.00
12.00
10.00
10.00
10.00
10.00
10.00
10.00
Biological treatment
In(effluent) [ln(eff luent)]2 Influent Effluent In(effluent)
2.30
2.30
2.30
2.48
2.30
2.30
2.30
2.30
2.30
2.30
Ug/i) (rt>/i)
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 Size:
10 10
Mean:
3669 10.2
Standard Deviation:
3328.67 .63
Variability Factor:
10
2.32
.06
2378
923.04
1.15
13.2
7.15
2.48
2.49
.43
ANOVA Calculations:
SSB =
SSW =
r MT]21
i=l ni
1 J .
k n1 x2- 1
. 1=1 3=1 X 1>J J
MSB = SS8/(k-l)
MSW = SSW/(N-k)
r k
N
2 '
-U-l
1=1 (. ni J
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 log transformed data points for all technologies
T. = sum of log transformed data points for each technology
X . = the nat. log transformed observations (j) for treatment technology (1)
n = 10, n = 5. N = 15. k = 2. T = 23.18, T = 12.46, T = 35.64, T = 1270.21
T = 537.31 T2 = 155.25
SSB -
10
1270.21
15
0.10
SSW = (53.76 + 31.79) -
MSB = 0.10/1 = 0.10
MSW = 0.77/13 = 0.06
F = =1.67
0.06
10
= 0.77
ANOVA Table
Source
Between (B)
Within(U)
Degrees of
freedom
1
13
SS MS F
0.10 0.10 1.67
0.77 0.06
The critical value of the F test at the 0.05 significance level is 4.67. Since
the F value is less than the critical value, the means are not significantly
different (i.e., they are homogeneous).
Note: All calculations were rounded to two decimal places. Results may differ
depending upon the number of decimal places used in each step of the calculations.
A-6
-------
1790g
Example 2
Trichloroethylene
^team stripping
Influent
Ug/D
1650.00
5300.00
5000.00
1720.00
1560.00
10300.00
210.00
1600.00
204.00
160.00
Effluent
(/•9/D
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
[In(effluent)]2
5.29
5.29
5.29
5.29
5.29
5.29
5.29
10.89
19.71
5.29
Influent
WD
200.00
224.00
134.00
150.00
484.00
163.00
182.00
Biological treatment
Effluent
Ug/D
10.00
10.00
10.00
10.00
16.25
10.00
10.00
In(effluent)
2.30
2.30
2.30
2.30
2.79
2.30
2.30
[In(effluent)]2
5.29
5.29
5.29
5.29
7.78
5.29
5.29
Sum:
Sample Size:
10 10
Mean:
2760
19.2
Standard Deviation:
3209.6 23.7
Variability Factor:
3.70
26.14
10
2.61
.71
72.92
220
120.5
10.89
2.36
1.53
16.59
2.37
.19
39.52
ANOVA Calculations
Ti?
SSB
k
ssw
MSB = SSBX(k-l)
MSW = SSW/(N-k)
k . 1
A-7
-------
1790g
Example 2 (continued)
F = MSB/MSW
where:
k = number of treatment technologies
n = number of data points for technology i
N = number of data points for all technologies
T. = sum of natural log transformed data points for each technology
X.. = the natural log transformed observations (j) for treatment technology (i)
= 10, N = 7, N = 17, k = 2, T = 26.14,
= 275.23
(683.30 275.23
SSB =1 +
10
1825.85
17
SSW - (72.92 + 39.52)- I ^-30^275.23
10
16.59, T = 42.73, J= 1825.85, J = 683.30,
0.25
4.79
MSB = 0.25/1 = 0.25
MSW = 4 79/15 = 0.32
F=!±_=0.78
0.32
ANOVA Table
Source
Between(B)
Within(W)
Degrees of
freedom
1
15
SS
0.25
4.79
MS
0.25
0.32
F
0.78
The critical value of the F test at the 0.05 significance level is 4.54. Since
the F value is less than the critical value, the means are not significantly
different (i.e., they are homogeneous).
Note: All calculations were rounded to two decimal places. Results may differ
depending upon the number of decimal places used in each step of the calculations.
A-8
-------
1790g
Example 3
Chlorobenzene
Activated sludqe followed by carbon adsorption
Influent Effluent In(effluent) [ln(eff luent)]2
Ug/1) Ug/D
7200.00 80.00 4.38 19.18
6500.00 70.00 4.25 18.06
6075.00 35.00 3.56 12.67
3040.00 10.00 2.30 5.29
Sum:
14.49 55.20
Sample Size:
444
Mean:
5703 49 3.62
Biological
Influent
Ug/D
9206.00
16646.00
49775.00
14731.00
3159.00
6756.00
3040.00
-
7
14759
treatment
Effluent
(rt/U
1083.00
709.50
460.00
142.00
603.00
153.00
17.00
_
7
452.5
In(effluent) ln[(eff luent)]2
6.99 48.86
6.56 43.03
6.13 37.58
4.96 24.60
6.40 40.96
5.03 25.30
2.83 8.01
38.90 228.34
7
5.56
Standard Deviation:
1835.4 32.24
.95
16311.86
379.04
1.42
Variability Factor:
7.00
15.79
ANOVA Calculations:
SSB
A-9
-------
1790g
Example 3 (continued)
where,
k = number of treatment technologies
n. = number of data points for technology i
N = number of data points for all technologies
T. = sum of natural log transformed data points for each technology
X = the natural log transformed observations (j) for treatment technology (i)
NI = 4, N2= 7, N = 11, k = 2, TI = 14.49, 1^ = 38.90, T = 53.39, T?= 2850.49. T2
209.96
1513.21
2850.49
11
= 9.52
SSW = (55.20 + 228.34) -
2°9'96 1513'21
14.88
MSB = 9.52/1 = 9.52
MSW = 14.88/9 =1.65
F = 9.52/1.65 = 5.77
Degrees of
Source freedom
ANOVA Table
SS
MS
Between (B)
Within(W)
1
9
9.53
14.89
9.53
1.65
5.77
The critical value of the F test at the 0.05 significance level is 5.12. Since
the F value is larger than the critical value, the means are significantly
different (i.e., they are heterogeneous).
Note: All calculations were rounded to two decimal places. Results may differ depending
upon the number of decimal places used in each step of the calculations.
A-10
-------
A.2. Variability Factor
-£99-
VF = Mean
where:
VF = estimate of daily maximum variability factor determined from
a sample population of daily data.
Cgg = Estimate of performance values for which 99 percent of the
daily observations will be below. Cgg is calculated using
the following equation: Cgg = Exp(y +2.33 Sy) where y and
Sy are the mean and standard deviation, respectively, of the
logtransformed data.
Mean = average of the individual performance values.
EPA is establishing this figure as an instantaneous maximum because
the Agency believes that on a day-to-day basis the waste should meet the
applicable treatment standards. In addition, establishing this
requirement makes it easier to check compliance on a single day. The
99th percentile is appropriate because it accounts for almost all process
variability.
In several cases, all the results from analysis of the residuals from
BOAT treatment are found at concentrations less than the detection
limit. In such cases, all the actual concentration values are considered
unknown and hence, cannot be used to estimate the variability factor of
the analytical results. Below is a description of EPA's approach for
calculating the variability factor for such cases with all concentrations
below the detection limit.
It has been postulated as a general rule that a lognormal
distribution adequately describes the variation among concentrations.
Agency data shows that the treatment residual concentrations are
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).
VF = C99 M
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:
C99 = Exp („ + 2.33a) (2)
Mean = Exp (M + .5a2) (3)
Substituting (2) and (3) in (1) the variability factor can then be
expressed in terms of a as follows:
VF = Exp (2.33 a - .5a2) (4)
For residuals with concentrations that are not all below the
detection limit, the 99 percentile and the mean can be estimated from
the actual analytical data and accordingly, the variability factor (VF)
can be estimated using equation (1). For residuals with concentrations
A-12
-------
that are below the detection limit, the above equations can be used in
conjunction with the assumptions below to develop a variability factor.
Step 1: The actual concentrations follow a lognormal distribution. The
upper limit (UL) is equal to the detection limit. The lower limit (LL)
is assumed to be equal to one tenth of the detection limit. This
assumption is based on the fact that data from well-designed and
well-operated treatment systems generally falls within one order of
magnitude.
Step 2: The natural logarithms of the concentrations have a normal
distribution with an upper limit equal to In (UL) and a lower limit equal
to In (LL).
Step 3: The standard deviation (a) of the normal distribution is
approximated by
a = [(In (UL) - In (LL)] / [(2)(2.33)] = [ln(UL/LL)] / 4.66
when LL = (0.1)(UL) then a = (InlO) / 4.66 = 0.494
Step 4: Substitution of the value from Step 3 in equation (4) yields the
variability factor, VF.
VF = 2.8
A-13
-------
-------
APPENDIX B
QUALITY ASSURANCE/QUALITY CONTROL
Quality assurance/quality control measures taken during the test are
outlined herein.
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 five-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.
PFTB, perfluorotributylamine; BFB, bromof1uorobenzene.
B-l
-------
For analyte calibration, the initial five-point calibration of 5, 10,
50, 100, and 200 /ig/liter standards, used for generating response
factors, also demonstrated a percent relative standard deviation (% PSD)
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's SW-846, 3rd ed:
• 1,1-Dichloroethene
• Trichloroethene
• Toluene
• Benzene
Tables B-l through B-5 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
-------
CO
I
CO
Table B-l Volatiles Spike Recovery (Accuracy) and Relative Percent Olffernce (Precision)
for Scrubber Sample
Matrix spike
Benzene
Chlorobenezene
1 . 1-Dichloroethylene
Toluene
Tnchloroethene
Determined
CK24-2-D2
43532
NO*
NO
NO
ND
ND
concentration, /ig/ 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
CND = hot detected.
Table 6-2. Volatiles Spike Recovery (Accuracy) and Relative Percent Olffernce (Precision)
for Tetraglyme Extract of Feed Sample
Matrix spike
Benzene
Chlorobenezene
1 , 1-Dichloroethylene
Toluene
Tnchloroethene
Determined
TK24-1-AX
43651
2
NDa
ND
ND
ND
concentration, ng/ liter
CK24-1-AX
43728
29
28
28
29
22
CK24-1-AX
43729
29
29
27
29
21
Percent
spike
recovery
116
112
112
116
68
Percent
spike
recovery
duplicate
116
116
106
116
84
Relative
percent
difference
G
4
4
0
5
Nt = Not detected.
-------
ro
i
Table B-3 Volatiles Spike Recovery (Accuracy) and Relative Percent Oiffernce (Precision)
for Tetraglyme Extract of Ash Sample
Matrix spike
Benzene
Chlorobenezene
1 , 1-Oichloroelhylene
Toluene
Tr ichloroelhene
Determined
U24-2-61
43650
3
NDa
NO
2
NO
concentration, ng/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
aND = Net detected
Table E-4. Volatile* Spike Recovery (Accuracy) and Relative Percent Differnce (Precision)
for TCLP Extract of Feed Sample
Determined concentration', ng/ liter
Matrix spike
Benzene
Chlorobenezene
1, 1-Oichloroethylene
Tolutnt
Tr ichloroethene
CK24-3-AX
43634
6
NDa
NO
7
NO
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
106
Relative
percent
difference
3
4
8
11
0
°HD = Not detected
-------
Table B-L Volatiles Spike Recovery (Accuracy) and Relative Percent Oiffernce (Precision)
for TCLP Extract of Ash Sample
00
en
Determined concentration, (ig/liter
Matrix spike
Benzene
Chlorobenezene
1 , l-Dichloroethy lene
Toluene
Trichloroethe'ie
CK24-2-B1-1
4363?
?
N0a
NO
2
NO
CK24-2-B2-1
43633
2B
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
dupl icate
107
108
144
104
104
Relat ive
percent
difference'
4
11
li
4
7
110 = Hot detected
-------
B.2 Semivolatile Organic Compounds
All semivolatile 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 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
(SPCC's) had response factors greater than 0.05 when using the
50 M9/ro1 calibration standard. These SPCC's 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 ^g/ml concentrations. Specific ion response
factors for the following calibration check compounds (CCC's) were
verified to have less than 30 percent relative standard deviation over
the range calibrated:
• Phenol • 2,4,6-Trichlorophenol
• 1,4-Dichlorobenzene • N-nitrosodi-N-phenylamine
B-6
-------
• 2-Nitrophenol • Pentachlorophenol
• 2,4-Dichlorophenol • Fluoranthene
• Hexachlorobutadiene • Di-n-octylphthalate
• 4-Chloro-3-methylphenol • Benzo(a)pyrene
• Acenaphthene
These CCC's 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-Dinitrotoluene
• 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-7
-------
1419g
Table B-6 Semivolatiles Matrix Spike Extract Surrogate Recoveries (%)
CO
i
co
Surrogate
2-F luorophenol
Phenol-d5
Nitrobenzene-dS
2-F Ijorobiphenyl
2.4.6-Tr ibromophenol
lerpneny l-d!4
CK24-2-D3
21
30
S2
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
61
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
Table B-7. Sennvolat)les Laboratory Check Standard
Extract Surrogate Recoveries (X)
Surrogate
2-Fluorophenol
Phenol-d5
Nitrobenzene-d5
2-Fluorobiphenyl
2 . 4 , 6- Tr i bromopheno 1
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-9
-------
U19g
Table B-8. Semivolatiles Matrix Spike Recovery (Accuracy) and Relative
Difference (Precision) for Scrubber Effluent Sample
Determined concentration, nq/ liter
(B/N = SO (ig/tnl)
Matrix spike (Acids = 100 iig/ml)
1 . 2.4-Trichlorobenzene
Arenopnthene
2.4 Dmitrotoluene
Pyrene
1 ,4-Oichlorobenzene
CD
i
O M-Nitrosodin-n-propylamme
Pentachlorophenol
Phenc 1
^-Ch loropheno 1
4 -Chloro- 3 -methyl phenol
4-Hitrophenol
CK24-2-D3
NO
ND
NO
ND
ND
ND
ND
ND
ND
ND
ND
CK24-2-D3
36
48
57
49
34
21
60
36
49
49
77
C24-2-D3
36
49
60
50
34
22
64
34
46
47
90
Spike
recovery. X
72
96
114
98
68
42
60
36
49
49
77
Spike
recovery
duplicate, X
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
f
-------
I419g
Table B-9. Semivolatiles Matrix Spike Recovery (Accuracy) and Relative
Difference (Precision) for Feed Sample
ro
i
(B/N = 50 Mg/ml)
Kdtnx sp'ke (Acids = 100 Mg/ml)
1 , 2.4-Tr ichlorobenzene
Acer.aphthene
2.4-Cinitrotoiuene
Fyrene
1 , 4 -Dich lore-benzene
N-Hitrosodin-n-propylamine
Pent ach loropheno 1
Phenol
2-Chlorophenol
4-Chloro-3-nethylphenol
4-llitropheno'.
Determined
CK24-2-AX
NO
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
concent rat ion.
CK24-2-AX
54
53
64
43
52
27
104
106
123
95
123
nq/liter
C24-1-B1
50
50
60
44
49
24
93
106
119
92
116
Spike
recovery, %
108
106
128
98
104
54
104
100
123
95
123
Spike
recovery
duplicate, X
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
1.0 = Not detected.
-------
]419q
Table 6-10 Semwolat i les Matrix Spike Recovery (Accuracy) and Relative
Difference (Precision) for Ash Sample
(B/N = SO (1g/ml)
Matrix spike (Acids = 100 «g/ml)
1 ,2.4-Tnchlorobenzene
Aceniphthene
'i . 4-Din it rotoluene
Pyrtr.e
1 .^-D'.chlorohenzene
CO
1
]~* (%-Nit rosodin-n-propy lamine
Per.tacnlorophenol
Pnencl
2-Chloi-ophenol
4-Chloro- 3-iriethy Iphenol
4-Nn rophenol
Determined
CK24-1-B1
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
concentration, iiq,
0.24-1-61
45
48
59
4?
45
20
98
96
109
68
120
/liter
C24-1-B1
45
46
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. %
0
0
0
14
1
42
7
2
2
2
5
HO = Not detected
-------
1419g
Table B-ll. Sem\volatiles Matrix Spike Recovery (Accuracy) and Relative
Difference (Precision) for Feed ECLP Extract
(B/N = 50 ng/ml)
Matrix spike (Acids = 100 ttg/m'i)
1 . 2,4-Tr ichlcrobenzene
/kenaplthene
2 , '-Dinit rotcljer.e
Pyrene
1 ,4-Oichlorobenzene
CD
i
£J U-Nitrosodin-n-propylamine
Pentachlorophenol
Phenol
2-Chlorophenol
4-thloro-3-methylphenol
4-Nitrophenol
Determined
CK24-3-AX
ND
ND
hD
ND
ND
NO
11
8
ND
ND
ND
concentration,
CK24-3-AX
22
24
31
32
21
26
32
33
24
23
32
wq/ liter
C24-3-AX
21
23
32
24
21
27
28
27
23
23
22
Spike
recovery, %
68
96
124
128
64
104
84
100
96
96
128
Spike
recovery
duplicate, X
84
92
128
96
64
108
64
76
96
96
88
Relat ive
percent
difference. X
5
4
3
29
0
4
27
27
0
0
37
ND = Not detected.
-------
1419g
Table B-12 Semivolatiles Matrix Spike Recovery (Accuracy) and Relative
Difference (Precision) for Ash TCIP Extract
(B/N * 50 MQ/ml)
Matrix spike (Acids = 100 /ig/ml)
1 ,2,4-Tr ichlorobenjene
Acenaphthene
2,4-Omitrotcluene
Pyrene
1 . <-DichloroLen*ene
CO
»— li-Nitrosodm-n-propylamine
Pentachloropheno)
Pheno 1
2-Chlorophenol
4-Chloro-3-methylphenol
4-Nitrophenol
Determined
CK24-2-B1
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
concentrat ion.
CK24-2B-1
21
24
23
22
20
26
14
24
24
20
23
wQ/liter
C24-2-B1
19
20
15
16
19
21
10
19
20
16
8
Spike
recovery, X
84
96
92
88
80
104
56
96
96
80
92
Spike
recovery
duplicate, %
76
80
60
64
76
84
40
76
60
64
32
Relative
percent
difference, %
10
18
42
32
5
21
33
23
18
22
97
ND = Not detected.
-------
1419g
lable B-13 Semivolatiles Laboratory Check Standard Results
Determined concentration, /iq/ liter with percent error
Run 1 Run 2
Analyte (true concentrat ion) 35993 3C053
Run 3 Run 4 Mean Precision
' 36055 36056 (X error) (X RSD)
1.2.4-Tnchlorobenzene (50 7) 41 6 (185!) 41 7 (18X) 39.8 (18X) 41.5 (18X) 41.2 (18X) 2.2%
Pentachloronitrobenzene (74.5) 56 2 (2WJ 61.1 (18%) 62 9 (16%) 64.8 (13%) 61.3 (18%) 6.0%
cn
-------
B.3 Metals and Other
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
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 (% 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
the ICP methods, but they are also more prone to physical and chemical
matrix interferences.
B-16
-------
1419g
Table B-14. Duplicate Matrix Spike Data for Metals
Analysis of Ash Sample (X-24-3-BI
Clv-24-3-Bl
S i Iver
Arsenic
Ba r i urn
Beryll lum
Cadmium
Chromium
Copper
Mercury
Nickel
lead
Ant imony
Selenium
T ha 1 1 1 urn
Vanadium
Zinc
CK-24-3-B1
ND
2.1
35
ND
ND
52
21
ND
55
20b
ND
ND
ND
9b
29
MS
CK-24-3-B1
89
51a
81
86
87
90
SI
115
89
90
106
0"
65"
87
84
MSD
difference
V,
88
46a
91
85
84
97
84
105
99
90
98
0
69
88
82
Relat ive
percent
Ana lyt<2
V
1
10
12
1
4
7
8
9
11
0
8
c
6
1
2
Data outside of QC/QA limits for this analysis.
Amount is less than five times detection limit
cNot calculated.
B-17
-------
APPENDIX C
Analytical Method for Determining the
Thermal Conductivity of a Waste
The comparative method of measuring thermal conductivity has been
proposed as an ASTM test method under the name "Guarded, Comparative,
Longitudinal Heat Flow Technique." A thermal heat flow circuit is used
which is the analog of an electrical circuit with resistances in series.
A reference material is chosen to have a thermal conductivity close to
that estimated for the sample. Reference standards (also known as heat
meters) having the same cross-sectional dimensions as the sample are
placed above and below the sample. An upper heater, a lower heater, and
a heat sink are added to the "stack" to complete the heat flow circuit.
See Figure 1.
The temperature gradients (analogous to potential differences) along
the stack are measured with type K (chromel/alumel) thermocouples placed
at known separations. The thermocouples are placed into holes or grooves
in the references and also in the sample whenever the sample is thick
enough to accommodate them.
For molten samples, pastes, greases, and other materials that must be
contained, the material is placed into a cell consisting of a top and
bottom of Pyrex 7740 and a containment ring of marinite. The sample is 2
inch in diameter and .5 inch thick. Thermocouples are not placed into
the sample but rather the temperatures measured in the Pyrex are
extrapolated to give the temperature at the top and bottom surfaces of
the sample material. The Pyrex disks also serve as the thermal
conductivity reference material.
C-i
-------
THERMOCOUPLE
v-
GUARD
GRADIENT
STACK
GRADIENT
CLAMP
1
UPPER STACK
HEATER
I
TOP REFERENCE
SAMPLE
I
TEST/SAMPLE
1
BOTTOM
REFERENCE
1
LOWER STACK
HEATER
I
LIQUID 'COOLED
HEAT SINK
I
7"'
HEAT FLOW
DIRECTION
UPPER
GUARD
HEATER
LOWER
GUARD
HEATE
SCHEMATIC DIACILU1 OF THE COMPARATIVE METHOD
C-2
-------
The stack is clamped with a reproducible load to insure intimate
contact between the components. In order to produce a linear flow of
heat down the stack and reduce the amount of heat that flows radially, a
guard tube is placed around the stack and the intervening space is filled
with insulating grains or powder. The temperature gradient in the guard
is matched to that in the stack to further reduce radial heat flow.
The comparative method is a steady state method of measuring thermal
conductivity. When equilibrium is reached the heat flux (analogous to
current flow) down the stack can be determined from the references. The
heat into the sample is given by
Q. = A+ (dT/dx)
in top top
and the heat out of the sample is given by
Qout = A, (dT/dx)k ^
bottom bottom
where
A = thermal conductivity
dT/dx = temperature gradient
and top refers to the upper reference while bottom refers to the lower
reference. If the heat was confined to flow just down the stack, then
Q. and Q would be equal. If Q. and Q are in reasonable
in out in out
agreement, the average heat flow is calculated from
" ' (Qin V Qout>/2
The sample thermal conductivity is then found from ;'
A
.
sample sample
C-3
------- |