EPA/530-SW-88-031S
FINAL
BEST DEMONSTRATED AVAILABLE TECHNOLOGY (BOAT)
BACKGROUND DOCUMENT FOR
K099
(Non CBI Version)
James R. Berlow, Chief
Treatment Technology Section
Jerry Vorbach
Project Manager
U.S. Environmental Protection Agency
Office of Solid Waste
401 M Street, S.W.
Washington, D.C. 20460
August 1988
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TABLE OF CONTENTS
Section Page
EXECUTIVE SUMMARY vi
1. INTRODUCTION 1-1
1.1 Legal Background 1-1
1.1.1 Requirements Under HSWA 1-1
1.1.2 Schedule for Developing Restrictions 1-4
1.2 Summary of Promulgated BOAT Methodology 1-5
1.2.1 Waste Treatability Groups 1-7
1.2.2 Demonstrated and Available Treatment
Technologies 1-7
1.2.3 Collection of Performance Data 1-11
1.2.4 Hazardous Constituents Considered and
Selected for Regulation 1-17
1.2.5 Compliance with Performance Standards 1-30
1.2.6 Identification of BOAT 1-32
- 1.2.7 BOAT Treatment Standards for "Derived-From"
and "Mixed" Wastes 1-36
1.2.8 Transfer of Treatment Standards 1-40
1.3 Variance from the BOAT Treatment Standard 1-41
2. INDUSTRY AFFECTED AND WASTE CHARACTERIZATION 2-1
2.1 Industry Affected and Process Description 2-1
2.2 Waste Characterization 2-1
3. APPLICABLE AND DEMONSTRATED TREATMENT TECHNOLOGIES 3-1
3.1 Applicable Treatment Technologies 3-1
3.2 Demonstrated Treatment Technologies 3-2
3.2.1 Chemical Oxidation 3-2
4. PERFORMANCE DATA BASE 4-1
5. IDENTIFICATION OF BEST DEMONSTRATED AVAILABLE
TECHNOLOGY (BOAT) 5-1
6. SELECTION OF REGULATED CONSTITUENTS 6-1
6.1 Identification of BOAT List Constituents in the Untreated
and Treated Waste 6-1
6.2 Constituents Selection 6-3
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TABLE OF CONTENTS (Continued)
Section Page
7. CALCULATION OF THE BOAT TREATMENT STANDARDS 7-1
8. ACKNOWLEDGMENTS 8-1
9. REFERENCES 9-1
APPENDIX A STATISTICAL ANALYSIS A-l
APPENDIX B ANALYTICAL QA/QC B-l
APPENDIX C DETECTION LIMITS FOR K099 WASTE SAMPLES C-l
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LIST OF TABLES
Table Page
1-1 BOAT Constituent List 1-18
2-1 Major Constituent Composition of K099 Waste 2-4
2-2 BOAT Constituent Composition and Other Data 2-5
4-1 Performance Data Collected by EPA for
Treatment of K099 Waste by Chemical
Oxidation Using Chlorine 4-2
4-2 Chemical Oxidation Performance Data Submitted by
Dow Chemical USA Showing 2,4-D Concentrations in
the Treated Wastewater 4-4
5-1 Accuracy-Corrected Performance Data for 2,4-D in
Treated K099 Wastewaters 5-3
6-1 Status of BOAT List Constituents Presence
in Untreated K099 Waste 6-4
7-1 Calculation of Wastewater Treatment Standard for
2,4-D 7-3
7-2 BOAT Treatment Standards for K099 Waste 7-4
A-l 95th Percentile Values for the
F Distribution A-2
B-l Analytical Methods for Regulated Constituents B-2
B-2 Matrix Spike Recoveries for K099 Treated
Wastewater--EPA-Collected Data B-3
C-l Detection Limits for K099 Untreated and
Treated Samples C-2
IV
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EXECUTIVE SUMMARY
BOAT Treatment Standards for K099
Pursuant to the Hazardous and Solid Waste Amendments (HSWA) enacted
on November 8, 1984, the Environmental Protection Agency is establishing
best demonstrated available technology (BOAT) treatment standards for the
listed waste identified in 40 CFR 261.32 as K099. Compliance with these
treatment standards is a prerequisite for placement of the waste in units
designated as land disposal units according to 40 CFR Part 268. These
treatment standards become effective as of August 8, 1988.
This background document provides the Agency's rationale and
technical support for selecting the constituents to be regulated in K099
waste and for developing treatment standards for those regulated
constituents. The document also provides waste characterization
information that serves as a basis for determining whether treatment
variances may be warranted. EPA may grant a treatment variance in cases
where the Agency determines that the waste in question is more difficult
to treat than the waste upon which the treatment standards have been
established.
The introductory section, which appears verbatim in all the First
Third background documents, summarizes the Agency's legal authority and
promulgated methodology for establishing treatment standards and
discusses the petition process necessary for requesting a variance from
the treatment standards. The remainder of the document presents
waste-specific information the number and locations of facilities
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affected by the land disposal restrictions for K099 waste, the waste
generating process, waste characterization data, the technologies used to
treat the waste (or similar wastes), and available performance data,
including data on which the treatment standards are based. The document
also explains EPA's determination of BOAT, selection of constituents to
be regulated, and calculation of treatment standards.
K099 waste is defined as untreated wastewater from the production of
2,4-dichlorophenoxyacetic acid (2,4-D). The Agency has identified only
one facility that produces 2,4-D. This facility is Dow Chemical USA,
Midland, Michigan (EPA Region V).
The Agency is regulating seven organic constituents, 2,4-D and six
chlorinated dioxins and furans, in both nonwastewater and wastewater
forms of K099 waste. (For the purpose of determining the applicability
of the BOAT treatment standards, wastewaters are defined a;; wastes
containing less than 1 percent (weight basis) total suspended solids* and
less than 1 percent (weight basis) total organic carbon (TOC). Wastes
not meeting this definition must comply with the treatment standards for
nonwastewaters.) The wastewater treatment standards for 2,4-D are based
on performance data from chemical oxidation using chlorine. Wastewater
treatment standards for the chlorinated dioxins and furans are
transferred from the treatment standards promulgated for dioxin-
*The term "total suspended solids" (TSS) clarifies EPA's previously used
terminology of "total solids" and "filterable solids." Specifically,
total suspended solids is measured by method 209C (Total Suspended Solids
Dried at 103-105°C) in Standard Methods for the Examination of Water
and Wastewater, Sixteenth Edition.
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containing wastes (51 FR 40615, November 7, 1986). Nonwastewater
treatment standards for all seven regulated constituents are transferred
from the wastewater treatment standards.
The following table lists the specific BOAT standards for K099
wastewater and nonwastewater. The treatment standards reflect total
constituent concentrations. The units for nonwastewater are mg/kg (parts
per million on a weight-by-weight basis); the units for wastewater are
mg/1 (parts per million on a weight-by-volume basis). Note that if the
concentrations of the regulated constituents in the waste, as generated,
are lower than or equal to the treatment standards, then treatment is not
required prior to land disposal.
Testing and analysis procedures are specifically identified and
discussed in Appendix B (QA/QC Section) of this background document.
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BOAT Treatment Standards for K099
Maximum for any single grab sample
Nonwastewater Vlastewater
Constituent Total TCLP leachate Total
concentration concentration concentration
(rag/kg) (mg/1) (mg/1)
Phenoxvocetic Acid Herbicides
2,4-Dichlorophenoxyacetic acid 1.0 NA 1.0
Dioxins and Furans
Hexachlorodibenzo-p-dioxins
Hexachl orod i benzof uran
Pentachlorodibenzo-p-dioxins
Pentachl orodi benzof uran
Tetrachlorodibenzo-p-dioxins
Tetrachl orodi benzof urans
0.001
0.001
0.001
0.001
0.001
0.001
NA
NA
NA
NA
NA
NA
0.001
0.001
0.001
0.001
0.001
0.001
NA = Not applicable.
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LIST OF FIGURES
Figure Page
2-1 Schematic Diagram of the 2,4-Dichlorophenoxyacetic
Acid (2,4-D) Process 2-2
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1. INTRODUCTION
This section of the background document presents a summary of the
legal authority pursuant to which the best demonstrated available
technology (BOAT) treatment standards were developed, a summary of EPA's
promulgated methodology for developing the BOAT treatment standards, and,
finally, a discussion of the petition process that should tie followed to
request a variance from the BOAT treatment standards.
1.1 Legal Background
1.1.1 Requirements Under HSWA
The Hazardous and Solid Waste Amendments of 1984 (HSWA), which were
enacted on November 8, 1984, and which amended the Resource Conservation
and Recovery Act of 1976 (RCRA), impose substantial new responsibilities
on those who handle hazardous waste. In particular, the amendments
require the Agency to promulgate regulations that restrict the land
disposal of untreated hazardous wastes. In its enactment of HSWA,
Congress stated explicitly that "reliance on land disposal should be
minimized or eliminated, and land disposal, particularly landfill and
surface impoundment, should be the least favored method for managing
hazardous wastes" (RCRA section 1002(b)(7), 42 U.S.C. 6901(b)(7)).
One part of the amendments specifies dates on which particular groups
of untreated hazardous wastes will be prohibited from land disposal
unless "it has been demonstrated to the Administrator, to a reasonable
degree of certainty, that there will be no migration of hazardous
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constituents from the disposal unit or injection zone for as long as the
wastes remain hazardous" (RCRA section 3004(d)(l), (e)(l), (g)(5),
42 U.S.C. 6924 (d)(l), (e)(l), (g)(5)).
For the purpose of the restrictions, HSWA defines land disposal "to
include, but not be limited to, any placement of ... hazardous waste in
a landfill, surface impoundment, waste pile, injection well, land
treatment facility, salt dome formation, salt bed formation, or
underground mine or cave" (RCRA section 3004(k), 42 U.S.C. 6924(k)).
Although HSWA defines land disposal to include injection wells, such
disposal of solvents, dioxins, and certain other wastes, known as the
California List wastes, is covered on a separate schedule (RCRA section
3004(f)(2), 42 U.S.C. 6924 (f)(2)). This schedule requires that EPA
develop land disposal restrictions for deep well injection by
August 8, 1988.
The amendments also require the Agency to set "levels or methods of
treatment, if any, which substantially diminish the toxicity of the waste
or substantially reduce the likelihood of migration of hazardous
constituents from the waste so that short-term and long-term threats to
human health and the environment are minimized" (RCRA section 3004(m)(l),
42 U.S.C. 6924 (m)(l)). Wastes that satisfy such levels or methods of
treatment established by EPA, i.e., treatment standards, are not
prohibited from being land disposed.
In setting treatment standards for listed or characteristic wastes,
EPA may establish different standards for particular wastes within a
single waste code with differing treatability characteristics. One such
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characteristic is the physical form of the waste. This frequently leads
to different standards for wastewaters and nonwastewaters.
Alternatively, EPA can establish a treatment standard that is applicable
to more than one waste code when, in EPA's judgment, a particular
constituent present in the wastes can be treated to the same
concentration in all the wastes.
In those instances where a generator can demonstrate that the
standard promulgated for the generator's waste cannot be achieved, the
amendments allow the Agency to grant a variance from a treatment standard
by revising the treatment standard for that particular waste through
rulemaking procedures. (A further discussion of treatment variances is
provided in Section 1.3.)
The land disposal restrictions are effective when promulgated unless
the Administrator grants a national variance and establishes a different
date (not to exceed 2 years beyond the statutory deadline) based on "the
earliest date on which adequate alternative treatment, recovery, or
disposal capacity which protects human health and the environment will be
available" (RCRA section 3004(h)(2), 42 U.S.C. 6924 (h)(2)).
If EPA fails to set treatment standards by the statutory deadline for
any hazardous waste in the First Third or Second Third waste groups (see
Section 1.1.2), the waste may not be disposed in a landfill or surface
impoundment unless the facility is in compliance with the minimum
technological requirements specified in section 3004(o) of RCRA. In
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addition, prior to disposal, the generator must certify to the
Administrator that the availability of treatment capacity has been
investigated, and it has been determined that disposal in a landfill or
surface impoundment is the only practical alternative to treatment
currently available to the generator. This restriction on the use of
landfills and surface impoundments applies until EPA sets treatment
standards for the waste or until May 8, 1990, whichever is sooner. If
the Agency fails to set treatment standards for any ranked hazardous
waste by May 8, 1990, the waste is automatically prohibited from land
disposal unless the waste is placed in a land disposal unil; that is the
subject of a successful "no migration" demonstration (RCRA section
3004(g), 42 U.S.C. 6924(g)). "No migration" demonstrations are based on
case-specific petitions that show there will be no migration of hazardous
constituents from the unit for as long as the waste remains hazardous.
1.1.2 Schedule for Developing Restrictions
Under section 3004(g) of RCRA, EPA was required to establish a
schedule for developing treatment standards for all wastes that the
Agency had listed as hazardous by November 8, 1984. Section 3004(g)
required that this schedule consider the intrinsic hazards and volumes
associated with each of these wastes. The statute required EPA to set
treatment standards according to the following schedule:
1. Solvent and dioxin wastes by November 8, 1986;
2. The "California List" wastes by July 8, 1987;
3. At least one-third of all listed hazardous wastes by
August 8, 1988 (First Third);
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4. At least two-thirds of all listed hazardous wastes by
June 8, 1989 (Second Third); and
5. All remaining listed hazardous wastes and all hazardous wastes
identified as of November 8, 1984, by one or more of the
characteristics defined in 40 CFR Part 261 by May 8, 1990 (Third
Third).
The statute specifically identified the solvent wastes as those
covered under waste codes F001, F002, F003, F004, and F005; it identified
the dioxin-containing hazardous wastes as those covered under waste codes
F020, F021, F022, and F023.
Wastes collectively known as the California List wastes, defined
under section 3004(d) of HSWA, are liquid hazardous wastes containing
metals, free cyanides, PCBs, corrosives (i.e., a pH less than or equal to
2.0), and any liquid or nonliquid hazardous waste containing halogenated
organic compounds (HOCs) above 0.1 percent by weight. Rules for the
California List were proposed on December 11, 1986, and final rules for
PCBs, corrosives, and HOC-containing wastes were established
August 12, 1987. In that rule, EPA elected not to establish treatment
standards for metals. Therefore, the statutory limits became effective.
On May 28, 1986, EPA published a final rule (51 FR 19300) that
delineated the specific waste codes that would be addressed by the First
Third, Second Third, and Third Third land disposal restriction rules.
This schedule is incorporated into 40 CFR 268.10, 268.11, and 268.12.
1.2 Summary of Promulgated BOAT Methodology
In a November 7, 1986, rulemaking, EPA promulgated a technology-based
approach to establishing treatment standards under section 3004(m).
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Congress indicated in the legislative history accompanying the HSWA that
"[t]he requisite levels of [sic] methods of treatment established by the
Agency should be the best that has been demonstrated to be achievable,"
noting that the intent is "to require utilization of available
technology" and not a "process which contemplates technology-forcing
standards" (Vol. 130 Cong. Rec. S9178 (daily ed., July 25, 1984)). EPA
has interpreted this legislative history as suggesting that Congress
considered the requirement under section 3004(m) to be met by application
of the best demonstrated and achievable (i.e., available) technology
prior to land disposal of wastes or treatment residuals. Accordingly,
EPA's treatment standards are generally based on the performance of the
best demonstrated available technology (BOAT) identified for treatment of
the hazardous constituents. This approach involves the identification of
potential treatment systems, the determination of whether they are
demonstrated and available, and the collection of treatment data from
well-designed and well-operated systems.
The treatment standards, according to the statute, can represent
levels or methods of treatment, if any, that substantially diminish the
toxicity of the waste or substantially reduce the likelihood of migration
of hazardous constituents. Wherever possible, the Agency prefers to
establish BOAT treatment standards as "levels" of treatment
(i.e., performance standards), rather than to require the use of specific
treatment "methods." EPA believes that concentration-based treatment
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levels offer the regulated community greater flexibility to develop and
implement compliance strategies, as well as an incentive to develop
innovative technologies.
1.2.1 Waste Treatability Group
In developing the treatment standards, EPA first characterizes the
waste(s). As necessary, EPA may establish treatability groups for wastes
having similar physical and chemical properties. That is, if EPA
believes that hazardous constituents in wastes represented by different
waste codes could be treated to similar concentrations using identical
technologies, the Agency combines the wastes into one treatability
group. EPA generally considers wastes to be similar when they are both
generated from the same industry and from similar processing stages. In
addition, EPA may combine two or more separate wastes into the same
treatability group when data are available showing that the waste
characteristics affecting performance are similar or that one of the
wastes in the group, the waste from which treatment standards are to be
developed, is expected to be most difficult to treat.
Once the treatability groups have been established, EPA collects and
analyzes data on identified technologies used to treat the: wastes in each
treatability group. The technologies evaluated must be demonstrated on
the waste or a similar waste and must be available for use.
1.2.2 Demonstrated and Available Treatment Technologies
Consistent with legislative history, EPA considers demonstrated
technologies to be those that are currently used on a full-scale basis to
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treat the waste of interest or a waste judged to be similar (see 51 FR
40588, November 7, 1986). EPA also will consider as demonstrated
treatment those technologies used to separate or otherwise process
chemicals and other materials on a full-scale basis. Some of these
technologies clearly are applicable to waste treatment, since the wastes
are similar to raw materials processed in industrial applications.
For most of the waste treatability groups for which EPA will
promulgate treatment standards, EPA will identify demonstrated
technologies either through review of literature related to current waste
treatment practices or on the basis of information provided by specific
facilities currently treating the waste or similar wastes.
In cases where the Agency does not identify any facilities treating
wastes represented by a particular waste treatability group, EPA may
transfer a finding of demonstrated treatment. To do this, EPA will
compare the parameters affecting treatment selection for the waste
treatability group of interest to other wastes for which demonstrated
technologies already have been determined. (The parameters affecting
treatment selection and their use for this waste are described in
Section 3.2 of this document.) If the parameters affecting treatment
selection are similar, then the Agency will consider the treatment
technology also to be demonstrated for the waste of interest. For
example, EPA considers rotary kiln incineration to be a demonstrated
technology for many waste codes containing hazardous organic
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constituents, high total organic content, and high filterable solids
content, regardless of whether any facility is currently treating these
wastes. The basis for this determination is data found in literature and
data generated by EPA confirming the use of rotary kiln incineration on
wastes having the above characteristics.
If no full-scale treatment or recovery operations are identified for
a waste or wastes with similar physical or chemical characteristics that
affect treatment selection, the Agency will be unable to Identify any
demonstrated treatment technologies for the waste, and, accordingly, the
waste will be prohibited from land disposal (unless handled in accordance
with the exemption and variance provisions of the rule). The Agency is,
however, committed to establishing treatment standards as soon as new or
improved treatment processes are demonstrated (and available).
Operations only available at research facilities, pilot- and bench-
scale operations, will not be considered in identifying demonstrated
treatment technologies for a waste. Nevertheless, EPA may use data
generated at research facilities in assessing the performance of
demonstrated technologies.
As discussed earlier, Congress intended that technologies used to
establish treatment standards under section 3004(m) be not only
"demonstrated," but also "available." To decide whether demonstrated
technologies may be considered "available," the Agency determines whether
they (1) are commercially available and (2) substantially diminish the
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toxicity of the waste or substantially reduce the likelihood of migration
of hazardous constituents from the waste. These criteria are discussed
below.
1. Commercially available treatment. If the demonstrated treatment
technology is a proprietary or patented process that is not
generally available, EPA will not consider the technology in its
determination of the treatment standards. EPA will consider
proprietary or patented processes available if it determines
that the treatment method can be purchased or licensed from the
proprietor or is a commercially available treatment. The
services of the commercial facility offering this technology
often can be purchased even if the technology itself cannot be
purchased.
2. Substantial treatment. To be considered "available," a
demonstrated treatment technology must "substantially diminish
the toxicity" of the waste or "substantially reduce the
likelihood of migration of hazardous constituents" from the
waste in accordance with section 3004(m). By requiring that
substantial treatment be achieved in order to set a treatment
standard, the statute ensures that all wastes are adequately
treated before being placed in or on the land and ensures that
the Agency does not require a treatment method that provides
little or no environmental benefit. Treatment will always be
deemed substantial if it results in nondetectable levels of the
hazardous constituents of concern (provided the nondetectable
levels are low relative to the concentrations in the untreated
waste). If nondetectable levels are not achieved, then a
determination of substantial treatment will be made on a
case-by-case basis. This approach is necessary because of the
difficulty of establishing a meaningful guideline that can be
applied broadly to the many wastes and technologies to be
considered. EPA will consider the following factors in an
effort to evaluate whether a technology provides substantial
treatment on a case-by-case basis:
Number and types of constituents treated;
Performance (concentration of the constituents in the
treatment residuals); and
Percent of constituents removed.
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EPA will only set treatment standards based on a technology that
meets both availability criteria. Thus, the decision to classify a
technology as "unavailable" will have a direct impact on the treatment
standard. If the best demonstrated technology is unavailable, the
treatment standards will be based on the next best demonstrated treatment
technology determined to be available. To the extent that the resulting
treatment standards are less stringent, greater concentrations of
hazardous constituents in the treatment residuals could be placed in land
disposal units.
There also may be circumstances in which EPA concludes that for a
given waste none of the demonstrated treatment technologies; are
"available" for purposes of establishing the 3004(m) treatment
performance standards. Subsequently, these wastes will be prohibited
from continued placement in or on the land unless managed in accordance
with applicable exemptions and variance provisions. The Agency is,
however, committed to establishing new treatment standards as soon as new
or improved treatment processes become available.
1.2.3 Collection of Performance Data
Performance data on the demonstrated available technologies are
evaluated by the Agency to determine whether the data are representative
of well-designed and well-operated treatment systems. Only data from
well-designed and well-operated systems are considered in determining
BOAT. The data evaluation includes data already collected directly by
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EPA and/or data provided by industry. In those instances where
additional data are needed to supplement existing information, EPA
collects additional data through a sampling and analysis program. The
principal elements of this data collection program are: (1) the
identification of facilities for site visits, (2) the engineering site
visit, (3) the sampling and analysis plan, (4) the sampling visit, and
(5) the onsite engineering report.
(1) Identification of facilities for site visits. To identify
facilities that generate and/or treat the waste of concern, EPA uses a
number of information sources. These include Stanford Research
Institute's Directory of Chemical Producers; EPA's Hazardous Waste Data
Management System (HWDMS); the 1986 Treatment, Storage, Disposal Facility
(TSDF) National Screening Survey; and EPA's Industry Studies Data Base.
In addition, EPA contacts trade associations to inform them that the
Agency is considering visits to facilities in their industry and to
solicit their assistance in identifying facilities for EPA to consider in
its treatment sampling program.
After identifying facilities that treat the waste, EPA uses this
hierarchy to select sites for engineering visits: (1) generators treating
single wastes on site; (2) generators treating multiple wastes together
on site; (3) commercial treatment, storage, and disposal facilities
(TSDFs); and (4) EPA in-house treatment. This hierarchy is based on two
concepts: (1) to the extent possible, EPA should develop treatment
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standards from data produced by treatment facilities handling only a
single .waste., and (2) facilities that routinely treat a specific waste
have had the best opportunity to optimize design parameters. Although
excellent treatment can occur at many facilities that are not high in
this hierarchy, EPA has adopted this approach to avoid, when possible,
ambiguities related to the mixing of wastes before and during treatment.
When possible, the Agency will evaluate treatment technologies using
full-scale treatment systems. If performance data from properly designed
and operated full-scale systems treating a particular waste or a waste
judged to be similar are not available, EPA may use data from research
facility operations. Whenever research facility data are used, EPA will
explain in the preamble and background document why such data were used
and will request comments on the use of such data.
Although EPA's data bases provide information on treatment for
individual wastes, the data bases rarely provide data that support the
selection of one facility for sampling over another. In cases where
several treatment sites appear to fall into the same level of the
hierarchy, IIPA selects sites for visits strictly on the basis of which
facility could most expeditiously be visited and later sampled if
justified by the engineering visit.
(2) Engineering site visit. Once a treatment facility has been
selected, an engineering site visit is made to confirm that a candidate
for sampling meets EPA's criteria for a well-designed facility and to
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ensure that the necessary sampling points can be accessed to determine
operating parameters and treatment effectiveness. During the visit, EPA
also confirms that the facility appears to be well operated, although the
actual operation of the treatment system during sampling is the basis for
EPA's decisions regarding proper operation of the treatment unit. In
general, the Agency considers a well-designed facility to be one that
contains the unit operations necessary to treat the various hazardous
constituents of the waste, as well as to control other nonhazardous
materials in the waste that may affect treatment performance.
In addition to ensuring that a system is reasonably well designed,
the engineering visit examines whether the facility has a way to measure
the operating parameters that affect performance of the treatment system
during the waste treatment period. For example, EPA may choose not to
sample a treatment system that operates in a continuous mode, for which
an important operating parameter cannot be continuously recorded. In
such systems, instrumentation is important in determining whether the
treatment system is operating at design values during the waste treatment
period.
(3) Sampling and analysis plan. If after the engineering site visit
the Agency decides to sample a particular plant, the Agency will then
develop a site-specific sampling and analysis plan (SAP) according to the
Generic Quality Assurance Pro.lect Plan for the Land Disposal Restrictions
Program ("BDAT"K EPA/530-SW-87-011. In brief, the SAP discusses where
the Agency plans to sample, how the samples will be taken, the frequency
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of sampling, the constituents to be analyzed and the method of analysis,
operational parameters to be obtained, and specific laboratory quality
control checks on the analytical results.
The Agency will generally produce a draft of the site-specific SAP
within 2 to 3 weeks of the engineering visit. The draft of the SAP is
then sent to the plant for review and comment. With few exceptions, the
draft SAP should be a confirmation of data collection activities
discussed with the plant personnel during the engineering site visit.
EPA encourages plant personnel to recommend any modifications to the SAP
that they believe will improve the quality of the data.
It is important to note that sampling of a plant by EPA does not mean
that the data will be used in the development of BOAT treatment
standards. EPA's final decision on whether to use data from a sampled
plant depends on the actual analysis of the waste being treated and on
the operating conditions at the time of sampling. Although EPA would not
plan to sample a facility that was not ostensibly well designed and well
operated, there is no way to ensure that at the time of the sampling the
facility will not experience operating problems. Additionally, EPA
statistically compares its test data to suitable industry-provided data,
where available, in its determination of what data to use in developing
treatment standards. The methodology for comparing data is presented
later in this section.
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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 Pro.lect Plan for the Land
Disposal Restrictions Program ("BOAT"), which delineates all of the
quality control and quality assurance measures associated with sampling
and analysis. Quality assurance and quality control procedures are
summarized in Section 1.2.6 of this document.)
(4) Sampling visit. The purpose of the sampling visit, is to collect
samples that characterize the performance of the treatment system and to
document the operating conditions that existed during the v/aste 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 that appear in Test Methods for Evaluating Solid Wasite. SW-846,
Third Edition, November 1986.
After the OER is completed, the report is submitted to the waste
generator and/or treater for review. This review provides a final
opportunity for claiming any information contained in the report as
confidential. Following the review and incorporation of comments, as
appropriate, the report is made available to the public with the
exception of any material claimed as confidential.
1.2.4 Hazardous Constituents Considered and Selected for Regulation
(1) Development of BOAT list. The list of hazardous constituents
within the waste codes that are targeted for treatment is referred to by
the Agency as the BOAT constituent list. This list, provided as
Table 1-1, is derived from the constituents presented in 40 CFR Part 261,
Appendices VII and VIII, as well as several ignitable constituents used
as the basis of listing wastes as F003 and F005. These sources provide a
1-17
-------
1521c|
Table 1-1 BOAT Constituent List
BOAT
reference
no.
222.
I.
2.
3.
4.
5.
6.
223.
;.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
25.
26.
27.
28.
29.
224.
225.
226.
30.
227.
31.
214.
32.
33.
228.
34.
Constituent
Volat i 1e organ ics
Acetone
Acetonitrile
Acrolein
Acrylonitri le
Benzene
Bromod ich lorome thane
Bromomethane
n-Butyl alcohol
Carbon tetrachloride
Carbon disulfide
Chlorobenzene
2-Chloro-1.3-butadiene
Ch lorod i bromome thane
Chloroe thane
2-Chloroethyl vinyl ether
Chloroform
Chloronethane
3-Ch loropropene
1.2-Dibromo-3-chloropropane
1.2-Oibromoethane
Di bromome thane
trans-1 ,4-Oichloro-2-butene
0 ich lorod i f luoromethane
1 , 1-Dichloroethane
1 ,2-Oichloroethane
1 . 1 -0 ich loroethy lene
trans-1 ,2-Oichloroethene
1.2-Dichloropropane
trans-1 , 3-D ich loropropene
cis-l,3-Dich loropropene
1,4-Oioxane
2-Ethoxyethanol
Ethyl acetate
Ethyl benzene
Ethyl cyanide
Ethyl ether
Ethyl methacry late
Ethylene oxide
lodomethane
Isobutyl alcohol
Methanol
Methyl ethyl ketone
CAS no.
67-64-1
75-05-8
107-02-8
107-13-1
71-43-2
75-27-4
74-83-9
71-36-3
56-23-5
75-15-0
108-90-7
126-99-8
124-48-1
75-00-3
110-75-8
67-66-3
74-87-3
107-05-1
96-12-8
106-93-4
74-95-3
110-57-6
75-71-8
75-34-3
107-06-2
75-35-4
156-60-5
78-87-5
10061-02-6
10061-01-5
123-91-1
110-80-5
141-78-6
100-41-4
107-12-0
60-29-7
97-63-2
75-21-8
74-88-4
78-83-1
67-56-1
78-93-3
1-18
-------
1521g
Table 1-1 (Continued)
BOAT
reference
no.
229.
35.
37.
38.
230.
39.
40.
41.
42.
43.
44.
45.
46.
47.
48.
49.
231.
50.
215.
216.
217.
51.
52.
53.
54.
55.
56.
57.
58.
59.
218.
60.
61.
62.
63.
64.
65.
66.
Constituent
Volatile organ ics (continued)
Methyl isobutyl ketone
Methyl met hacry late
Methacrylonitri le
Methylene chloride
2-Nitropropane
Pyridine
1.1. 1 ,2-Tetrachloroethane
1.1.2. 2-Tetrach loroethane
Tet rach loroethene
Toluene
Tribromomethane
1 , 1 . 1 - Tr ich loroethane
1 , 1 ,2-Tr ich loroethane
Tr ich loroethene
Tr ich loromonof luoromethane
1 ,2,3-Trichloropropdne
1. 1,2-Tr ich loro- 1.2.2- tr if luoro-
e thane
Vinyl chloride
1.2-Xylene
1.3-Xylene
1.4-Xy lene
Sani volatile organ ics
Acenaphthalene
Acenaphthene
Acetophenone
2-Acetylaminof luorene
4-Aminobiphenyl
Aniline
Anthracene
Aramite
Benz ( a ) anthracene
Benzal chloride
Benzenethio 1
Oe leted
Benzo(a)pyrene
Benzo(b)f luoranthene
Benzo(ghi )pery lene
Benzo(k)f luoranthene
p-Benzoquinone
CAS no.
108-10-1
80-62-6
126-98-7
75-09-2
79-46-9
110-86-1
630-20-6
79-34-6
127-18-4
108-88-3
75-25-2
71-55-6
79-00-5
79-01-6
75-69-4
96-18-4
76-13-1
75-01-4
97-47-6
108-38-3
106-44-5
208-96-8
83-32-9
96-86-2
53-96-3
92-67-1
62-53-3
120-12-/
140-57-8
56-55-3
98-87-3
108-98-5
50-32-8
205-99-2
191-24-2
207-08-9
106-51-4
1-19
-------
1521g
Table 1-1 (Continued)
BOA I
reference
no.
67.
68.
69.
70.
71.
72.
73.
74.
75.
76.
11.
78.
79.
80.
81.
82.
232.
83.
84.
85.
86.
87.
sa.
8<1.
90.
91.
92.
93.
94.
95.
96.
97.
98.
99.
100.
101.
102.
103.
104.
105.
106.
219.
Constituent
Semivolati le orqanics (continued)
B i s ( 2-ch loroethoxy (methane
Bis(2-chloroethyl)ether
B i s( 2-ch loco i sopropy 1 )ether
Bis(2-ethylhexyl)phthalate
4-Bromophenyl phenyl ether
Butyl benzyl phthalate
2-sec-Butyl-4,6-dinitrophenol
p-Chloroaniline
Chlorobenzi late
p-Chloro-m-cresol
2-Ch loronaphtha lene
2-Chlorophenol
3-Chloropropionitri le
Chrysene
ortho-Cresol
para-Cresol
Cyclohexanone
0 i benz ( a , h ) anthracene
0 i benzo ( a , e ) py rene
Dibenzo(a, ijpyrene
m- Q ich lorobenzene
o-O ich lorobenzene
p-D ich lorobenzene
3 . 3 ' -0 ich lorobenz id ine
2 . 4-0 ich loropheno 1
2.6-Oichlorophenol
Diethyl phthalate
3 , 3 ' -0 imethoxybcn/ id ine
p -Dime thy lorn inoazoben/ene
3,3' -Oimethylbenzidine
2.4-Oimethylphenol
Dimethyl phthalate
Oi-n-butyl phthalate
1 ,4-Oinitrobenzene
4.6-Dinitro-o-cresol
2,4-Din itropheno 1
2,4-Oinitrotoluene
2.6-Dinitrotoluene
Di-n-octyl phthalate
Di-n-propylnitrosamine
Oiphenylamine
Diphenylnitrosamine
CAS no.
111-91-1
111-44-4
39638-32-9
117-81-7
101-55-3
85-68-7
88-8b-7
106-47-8
510-15-6
59-50-7
91-58-7
95-57-8
542-76-7
218-01-9
95-48-7
106-44-5
108-94-1
53-70-3
192-65-4
189-55-9
541-73-1
95-50-1
106-46-7
91-94-1
120-83-2
87-65-0
84-66-2
119-90-4
60-11-7
119-93-7
105-67-9
131-11-3
84-74-2
100-25-4
534-52-1
51-28-5
121-14-2
606-20-2
117-84-0
621-64-7
122-39-4
86-30-6
1-20
-------
1521g
Table 1-1 (Continued)
BOAT
reference
no.
107.
108.
109.
110.
111.
112.
113.
114.
115.
116.
117.
118.
119.
120.
36.
121.
122.
123.
124.
125.
126.
127.
128.
129.
130.
131.
132.
133.
134.
13!i.
13(>.
137.
138.
139.
140.
141.
142.
220.
143.
144.
145.
146.
Constituent
Semivolat i le organ ics (continued)
1 . 2 - 0 i pheny 1 hydraz i ne
Fluoranthene
F luorene
Hexach lorobenzene
Hexach lorobu tad i ene
Hexach lorocyc lopentadiene
Hexach loroe thane
Hexach lorophene
Hexach loropropene
Indeno(l,2,3-cd)pyrene
Isosafrole
Methapyri lene
3 -Methy Icho lanthrene
4,4' -Methy lenebis
(2-chloroani 1 ine)
Methyl methanesulfonate
Naphthalene
1 , 4 -Naphthoqu i none
1-Naphthy lamine
2-Naphthylamine
p-Nitroani line
Nitrobenzene
4-Nitrophenol
N-Mitrosodi-n-buty lamine
N-Nitrosodiethy lamine
N-Nitrosodimethy lamine
N-N i trosomethy lethy lamine
N-Nitrosomorphol ine
N-Nitrosopiperidine
N-Nitrosopyrrolidine
5-N i tro-o-to lu id ine
Pentach lorobcnzcne
Pentach loroethane
Pentach loron i t robenzene
Pentach loropheno 1
Phenacetin
Phenanthrene
Phenol
Phlhal ic anhydride
2-Picoline
Pronamide
Pyrene
Kesorc inol
CAS no.
122-66-7
206-44-0
86-73-7
118-74-1
87-68-3
77-47-4
67-72-1
70-30-4
1888-71-7
193-39-5
120-58-1
91-80-5
56-49-5
101-14-4
66-27-3
91-20-3
130-15-4
134-32-7
91-59-8
100-01 6
98-95-3
100-02-7
924-16-3
55-18-5
62-75-9
10595-95-6
59-89-2
100-75-4
930-55-2
99-65-8
608-93-5
76-01-7
82-68-8
87-86-5
62-44-2
85-01-8
108-95-2
85-44-9
109-06-8
23950-58-5
129-00-0
108-46-3
1-21
-------
1521q
Table 1-1 (Continued)
BOAT
reference
no.
147.
148.
149.
150.
151.
152.
153.
154.
155.
156.
157.
158.
159.
221.
160.
161.
162.
163.
164.
165.
166.
16/.
168.
169.
170.
1/1.
172.
1/3.
174.
175.
Constituent
Semivolat 1 1e organ ics (continued)
Safrole
1.2,4, 5-Tetrach lorobenzene
2,3,4, 6-Tet rach loropheno 1
1.2,4-Trich lorobenzene
2, 4, 5-Trich loropheno 1
2 . 4 , 6-Tr ich loropheno 1
Tris(2,3-dibromopropyl)
phosphate
Hetals
Antimony
Arsenic
Barium
Beryl 1 ium
Cadmium
Chromium (total)
Chromium (hexavalent)
Copper
Lead
Mercury
Nickel
Selenium
S i Iver
Thallium
Vanadium
Zinc
Inorganics other than metals
Cyanide
fluoride
Sulf ide
Orqanochlorine pesticides
Aldrin
alpha-BHC
beta-BHC
delta-BHC
CAS no.
94-59-7
95-94-3
58-90-2
120-82-1
95-95-4
88-06-2
126-72-7
7440-36-0
7440-38-2
/440-39-3
7440-41-7
7440-43-9
7440-47-3
-
7440-50-8
7439-92-1
7439-97-6
7440-02-0
7782-49-2
7440-22-4
7440-28-0
7440-62-2
7440-66-6
57-12-5
16964-48-8
8496-25-8
309-00-2
319-84-6
319-85-7
319-86-8
1-22
-------
1521c|
Table 1-1 (Continued)
BOAT
reference
no.
176.
177.
178.
179.
180.
181.
182.
183.
184.
185.
186.
187.
188.
189.
190.
191.
192.
193.
194.
195.
196.
197.
198.
199.
200.
201.
202.
203.
204.
205.
206.
Constituent
Orqanochlorine pesticides (continued)
ganma-BHC
Ch lordane
ODD
DOE
DOT
Oieldrin
Endosulfan I
Endosulfan II
Endrin
Endrin aldehyde
Heptachlor
Heptachlor epoxide
Isodrin
Kepone
Methoxyc lor
Toxaphene
Phenoxyacet ic acid herbicides
2,4-Oichlorophenoxyacetic acid
Si Ivex
2.4.5-T
Orqanophosohorous insecticides
Oisulfoton
Famphur
Methyl parathion
Para th ion
Phorate
PCBs
Aroclor 1016
Aroclor 1221
Aroclor 1232
Aroclor 1242
Aroclor 1248
Aroclor 1254
Aroclor 1260
CAS no.
58-89-9
57-74-9
72-54-8
72-55-9
50-29-3
60-57-1
939-98-8
33213-6-5
72-20-8
7421-93-4
76-44-8
1024-57-3
465-73-6
143-50-0
72-43-5
8001-35-2
94-75-7
93-72-1
93-76-5
298-04-4
52-85-7
298-00-0
56-38-2
298-02-2
12674-11-2
11104 28-2
11141-16-5
53469-21-9
12672-29-6
11097-69-1
11096-82-5
1-23
-------
1521g
Table 1-1 (Continued)
BOAT
reference Constituent CAS no.
Dioxins and furans
207. Hexachlorodibenzo-p-dioxins
208. Hexachlorodibenzofurans
209. Pentachlorodibenzo-p-dioxins
210. Pentachlorodibenzofurans
211. Tetrach)orodibenzo-p-dioxins.
212. Tetrachlorodibenzofurans
213. 2.3.7.8-Tetrachlorodibenzo-p-dioxin 1746-01-6
1-24
-------
comprehensive list of hazardous constituents specifically regulated under
RCRA. The BOAT list consists of those constituents that can be analyzed
using methods published in SW-846, Third Edition.
The initial BOAT constituent list was published in EPA's Generic
Quality Assurance Pro.lect Plan for Land Disposal Restrictions Program
("BOAT") in March 1987. Additional constituents are added to the BOAT
constituent list as more key constituents are identified for specific
waste codes or as new analytical methods are developed for hazardous
constituents. For example, since the list was published in March 1987,
18 additional constituents (hexavalent chromium, xylenes (all three
isomers), benzal chloride, phthalic anhydride, ethylene oxide, acetone,
n-butyl alcohol, 2-ethoxyethanol, ethyl acetate, ethyl benzene, ethyl
ether, methanol, methyl isobutyl ketone, 2-nitropropane,
1,l,2-trichloro-l,2,2-trifluoroethane, and cyclohexanone) have been added
to the list.
Chemicals are listed in Appendix VIII if they are shown in scientific
studies to have toxic, carcinogenic, mutagenic, or teratogenic effects on
humans or other life-forms, and they include such substances as those
identified by the Agency's Carcinogen Assessment Group as being
carcinogenic. A waste can be listed as a toxic waste on the basis that
it contains a constituent in Appendix VIII.
Although Appendix VII, Appendix VIII, and the F003 and F005
ignitables provide a comprehensive list of RCRA-regulated hazardous
constituents, not all of the constituents can be analyzed in a complex
1-25
-------
waste matrix. Therefore, constituents that could not be readily analyzed
in an unknown waste matrix were not included on the initial BOAT
constituent list. As mentioned above, however, the BOAT constituent list
is a continuously growing list that does not preclude the addition of new
constituents when analytical methods are developed.
There are five major reasons that constituents were not included on
the BOAT constituent list:
1. Constituents are unstable. Based on their chemical structure,
some constituents will either decompose in water or will
ionize. For example, maleic anhydride will form rnaleic acid
when it comes in contact with water, and copper cyanide will
ionize to form copper and cyanide ions. However, EPA may choose
to regulate the decomposition or ionization products.
2. EPA-approved or verified analytical methods are not available.
Many constituents, such as 1,3,5-trinitrobenzene, are not
measured adequately or even detected using any of EPA's
analytical methods published in SW-846 Third Edition.
3. The constituent is a member of a chemical group designated in
Appendix VIII as not otherwise specified (N.O.S.). Constituents
listed as N.O.S., such as chlorinated phenols, are a generic
group of some types of chemicals for which a single analytical
procedure is not available. The individual members of each such
group need to be listed to determine whether the constituents
can be analyzed. For each N.O.S. group, all those constituents
that can be readily analyzed are included in the BOAT
constituent list.
4. Available analytical procedures are not appropriate for a
complex waste matrix. Some compounds, such as auramine, can be
analyzed as a pure constituent. However, in the presence of
other constituents, the recommended analytical method does not
positively identify the constituent. The use of high
performance liquid chromatography (HPLC) presupposes a high
expectation of finding the specific constituents of interest.
In using this procedure to screen samples, protocols would have
to be developed on a case-specific basis to verify the identity
of constituents present in the samples. Therefore, HPLC is
usually not an appropriate analytical procedure for complex
samples containing unknown constituents.
1-26
-------
5. Standards for analytical instrument calibration arc; not
commercially available. For several constituents, such as
benz(c)acridine, commercially available standards of a
"reasonably" pure grade are not available. The unavailability
of a standard was determined by a review of catalogs from
specialty chemical manufacturers.
Two constituents (fluoride and sulfide) are not specifically included
in Appendices VII and VIII; however, these compounds are included on the
BOAT list as indicator constituents for compounds from Appendices VII and
VIII such as hydrogen fluoride and hydrogen sulfide, which ionize in
water.
The BOAT constituent list presented in Table 1-1 is divided into the
following nine groups:
Volatile organics;
Semivolatile organics;
Metals;
Other inorganics;
Organochlorine pesticides;
Phenoxyacetic acid herbicides;
Organophosphorous insecticides;
PCBs; and
Dioxins and furans.
The constituents were placed in these categories based on their chemical
properties. The constituents in each group are expected to behave
similarly during treatment and are also analyzed, with the exception of
the metals and the other inorganics, by using the same analytical methods,
(2) Constituent selection analysis. The constituents that the
Agency selects for regulation in each waste are, in general, those found
in the untreated wastes at treatable concentrations. For certain waste
1-27
-------
codes, the target list for the untreated waste may have been shortened
(relative to analyses performed to test treatment technologies) because
of the extreme unlikelihood that the constituent will be present.
In selecting constituents for regulation, the first step is to
develop of list of potentially regulated constituents by summarizing all
the constituents that are present or are likely to be present in the
untreated waste at treatable concentrations. A constituent is considered
present in a waste if the constituent (1) is detected in the untreated
waste above the detection limit, (2) is detected in any of the treated
residuals above the detection limit, or (3) is likely to be present based
on the Agency's analyses of the waste-generating process. In case (2),
the presence of other constituents in the untreated waste may interfere
with the quantification of the constituent of concern, making the
detection limit relatively high and resulting in a finding of "not
detected" when, in fact, the constituent is present in the waste. Thus,
the Agency reserves the right to regulate such constituents.
After developing a list of potential constituents for regulation.
EPA reviews this list to determine if any of these constituents can be
excluded from regulation because they would be controlled by regulation
of other constituents on the list. This indicator analysis is done for
two reasons: (1) it reduces the analytical cost burdens on the treater
and (2) it facilitates implementation of the compliance and enforcement
program. EPA's rationale for selection of regulated constituents for
this waste code is presented in Section 6 of this background document.
1-28
-------
(3) Calculation of standards. The final step in the calculation of
the BOAT treatment standard is the multiplication of the average
accuracy-corrected treatment value by a factor referred to by the Agency
as the variability factor. This calculation takes into account that even
well-designed and well-operated treatment systems will experience some
fluctuations in performance. EPA expects that fluctuations will result
from inherent mechanical limitations in treatment control systems,
collection of treated samples, and analysis of these samples. All of the
above fluctuations can be expected to occur at well-designed and
well-operated treatment facilities. Therefore, setting treatment
standards' utilizing a variability factor should be viewed not as a
relaxing of section 3004(m) requirements, but rather as a function of the
normal variability of the treatment processes. A treatment facility will
have to be designed to meet the mean achievable treatment performance
level to ensure that the performance levels remain within the limits of
the treatment standard.
The Agency calculates a variability factor for each constituent of
concern within a waste treatability group using the statistical
calculation presented in Appendix A. The equation for calculating the
variability factor is the same as that used by EPA for the development of
numerous regulations in the Effluent Guidelines Program under the Clean
Water Act. The variability factor establishes the instantaneous maximum
based on the 99th percentile value.
1-29
-------
There is an additional step in the calculation of the treatment
standards in those instances where the ANOVA analysis shows that more
than one technology achieves a level of performance that represents
BOAT. In such instances, the BOAT treatment standard for each
constituent of concern is calculated by first^averaging the mean
performance value for each technology and then multiplying that value by
the highest variability factor among the technologies considered. This
procedure ensures that all the technologies used as the basis for the
BOAT treatment standards will achieve full compliance.
1.2.5 Compliance with Performance Standards
Usually the treatment standards reflect performance achieved by the
best demonstrated available technology (BOAT). As such, compliance with
these numerical standards requires only that the treatment level be
achieved prior to land disposal. It does not require the use of any
particular treatment technology. While dilution of the waste as a means
to comply with the standards is prohibited, wastes that are generated in
such a way as to naturally meet the standards can be land disposed
without treatment. With the exception of treatment standards that
prohibit land disposal, or that specify use of certain treatment methods,
all established treatment standards are expressed as concentration levels,
EPA is using both the total constituent concentration and the
concentration of the constituent in the TCLP extract of the treated waste
as a measure of technology performance.
1-30
-------
For all organic constituents, EPA is basing the treatment standards
on the total constituent concentration found in the treated waste. EPA
is using this measurement because most technologies for treatment of
organics destroy or remove organics compounds. Accordingly, the best
measure of performance would be the total amount of constituent remaining
after treatment. (NOTE: EPA's land disposal restrictions for solvent
waste codes F001-F005 (51 FR 40572) use the TCLP extract value as a
measure of performance. At the time that EPA promulgated the treatment
standards for F001-F005, useful data were not available on total
constituent concentrations in treated residuals, and, as a result, the
TCLP data were considered to be the best measure of performance.)
For all metal constituents, EPA is using both total constituent
concentration and/or the TCLP extract concentration as the basis for
treatment standards. The total constituent concentration is being used
when the technology basis includes a metal recovery operation. The
underlying principle of metal recovery is that it reduces the amount of
metal in a waste by stparating the metal for recovery, total constituent
concentration in the treated residual, therefore, is an important measure
of performance for this technology. Additionally, EPA also believes that
it is important that any remaining metal in a treated residual waste not
be in a state that is easily Teachable; accordingly, EPA is Slso using
the TCLP extract concentration as a measure of performance. It is
important to note that for wastes for which treatment standards are based
1-31
-------
on a metal recovery process, the facility has to comply with both the
total and the TCLP extract constituent concentrations prior to land
disposing the waste.
In cases where treatment standards for metals are not based on
recovery techniques but rather on stabilization, EPA is using only the
TCLP value as a measure of performance. The Agency's rationale is that
stabilization is not meant to reduce the concentration of metal in a
waste but only to chemically minimize the ability of the metal to leach.
1.2.6 Identification of BOAT
BOAT for a waste must be the "best" of the demonstrated available
technologies. EPA determines which technology constitutes "best" after
screening the available data from each demonstrated technology, adjusting
these data for accuracy, and comparing the performance of each
demonstrated technology to that of the others. If only one technology is
identified as demonstrated, it is considered "best"; if it is available,
the technology is BOAT.
(1) Screening of treatment data. The first activity in
determining which of the treatment technologies represent treatment by
BOAT is to screen the treatment performance data from each of the
demonstrated and available technologies according to the following
criteria:
1. Design and operating data associated with the treatment data
must reflect a well-designed, well-operated system for each
treatment data point. (The specific design and operating
parameters for each demonstrated technology for the waste
code(s) of interest are discussed in Section 3.2 of this
document.)
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2. Sufficient QA/QC data must be available to determine the true
1 values of the data from the treated waste. This screening
criterion involves adjustment of treated data to take into
account that the true value may be different from the measured
value. This discrepancy generally is caused by other
constituents in the waste that can mask results or otherwise
interfere with the analysis of the constituent of concern.
3. The measure of performance must be consistent with EPA's
approach to evaluating treatment by type of constituents (e.g.,
total concentration data for organics, and total concentration
and TCLP extract concentration for metals from the residual).
In the absence of data needed to perform the screening analysis, EPA
will make decisions on a case-by-case basis as to whether to use the data
as a basis for the treatment standards. The factors included in this
case-by-case analysis will be the actual treatment levels achieved, the
availability of the treatment data and their completeness (with respect
to the above criteria), and EPA's assessment of whether the untreated
waste represents the waste code of concern.
(2) Comparison of treatment data. In cases in which EPA has
treatment data from more than one demonstrated available technology
following the screening activity, EPA uses the statistical method known
as analysis of variance (ANOVA) to determine if one technology performs
significantly better than the others. This statistical method
(summarized in Appendix A) provides a measure of the differences between
two data sets. Specifically, EPA uses the analysis of variance to
determine whether BOAT represents a level of performance achieved by only
one technology or represents a level of performance achieved by more than
one (or all) of the technologies. If EPA finds that one technology
performs significantly better (i.e., is "best"), BOAT treatment standards
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are the level of performance achieved by that best technology multiplied
by the corresponding variability factor for each regulated constituent.
If the Agency finds that the levels of performance for one or more
technologies are not statistically different, EPA averages the
performance values achieved by each technology and then multiplies this
value by the largest variability factor associated with any of the
technologies.
(3) Quality assurance/quality control. This section presents the
principal quality assurance/quality control (QA/QC) procedures employed
in screening and adjusting the data to be used in the calculation of
treatment standards. Additional QA/QC procedures used in collecting and
screening data for the BOAT program are presented in EPA's Generic
Quality Assurance Project Plan for Land Disposal Restrictions Program
("BOAT"). EPA/530-SW-87-011.
To calculate the treatment standards for the land disposal restriction
rules, it is first necessary to determine the recovery value for each
constituent (the amount of constituent recovered after spiking--which is
the addition of a known amount of the constituentminus the initial
concentration in the samples, all divided by the spike amount added) for
each spiked sample of the treated residual. Once the recovery values are
determined, the following procedures are used to select the appropriate
percent recovery value to adjust the analytical data:
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1. If duplicate spike recovery values are available for the
constituent of interest, the data are adjusted by the lowest
available percent recovery value (i.e., the value that will
yield the most conservative estimate of treatment achieved).
However, if a spike recovery value of less than 20 percent is
reported for a specific constituent, the data are not used to
set treatment standards because the Agency does not have
sufficient confidence in the reported value to set a national
standard.
2. If data are not available for a specific constituent but are
available for an isomer, then the spike recovery data are
transferred from the isomer and the data are adjusted using the
percent recovery selected according to the procedure described
in (1) above.
3. If data are not available for a specific constituent but are
available for a similar class of constituents (e.g., volatile
organics, acid-extractable semivolatiles), then spike recovery
data available for this class of constituents are transferred.
All spike recovery values greater than or equal to 20 percent
for a spike sample are averaged and the constituent
concentration is adjusted by the average recovery value. If
spiked recovery data are available for more than one sample, the
average is calculated for each sample and the data are adjusted
by using the lowest average value.
4. If matrix spike recovery data are not available for a set of
data to be used to calculate treatment standards, then matrix
spike recovery data are transferred from a waste that the Agency
believes is similar (e.g., if the data represent an ash from
incineration, then data from other incinerator ashes could be
used). While EPA recognizes that transfer of matrix spike
recovery data from a similar waste is not an exact analysis,
this is considered the best approach for adjusting the data to
account for the fact that most analyses do not result in
extraction of 100 percent of the constituent. In assessing the
recovery data to be transferred, the procedures outlined in (1),
(2), and (3) above are followed.
The analytical procedures employed to generate the data used to
calculate the treatment standards are listed in Appendix B of this
document. In cases where alternatives or equivalent procedures and/or
equipment are allowed in EPA's SW-846, Third Edition methods, the
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specific procedures and equipment used are documented. In addition, any
deviations from the SW-846, Third Edition methods used to analyze the
specific waste matrices are documented. It is important to note that the
Agency will use the methods and procedures delineated in Appendix B to
enforce the treatment standards presented in Section 7 of this document.
Accordingly, facilities should use these procedures in assessing the
performance of their treatment systems.
1.2.7 BOAT Treatment Standards for "Derived-From" and "Mixed" Wastes
(1) Hastes from treatment trains generating multiple residues. In a
number of instances, the proposed BOAT consists of a series of
operations, each of which generates a waste residue. For example, the
proposed BOAT for a certain waste code is based on solvent extraction,
steam stripping, and activated carbon adsorption. Each of these
treatment steps generates a waste requiring treatment a
solvent-containing stream from solvent extraction, a stripper overhead,
and spent activated carbon. Treatment of these wastes may generate
further residues; for instance, spent activated carbon (if not
regenerated) could be incinerated, generating an ash and possibly a
scrubber water waste. Ultimately, additional wastes are generated that
may require land disposal. With respect to these wastes, the Agency
wishes to emphasize the following points:
1. All of the residues from treating the original listed wastes are
likewise considered to be the listed waste by virtue of the
derived-from rule contained in 40 CFR 261.3(c)(2). (This point
is discussed more fully in (2) below.) Consequently, all of the
wastes generated in the course of treatment would be prohibited
from land disposal unless they satisfy the treatment standard or
meet one of the exceptions to the prohibition.
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2. The Agency's proposed treatment standards generally contain a
concentration level for wastewaters and a concentration level
for nonwastewaters. The treatment standards apply to all of the
wastes generated in treating the original prohibited waste.
Thus, all derived-from wastes meeting the Agency definition of
wastewater (less than 1 percent total organic carbon (TOC) and
less than 1 percent total suspended solids) would have to meet
the treatment standard for wastewaters. All residuals not
meeting this definition would have to meet the treatment
standard for nonwastewaters. EPA wishes to make clear that this
approach is not meant to allow partial treatment in order to
comply with the applicable standard.
3. The Agency has not performed tests, in all cases, on every waste
that can result from every part of the treatment train.
However, the Agency's treatment standards are based on treatment
of the most concentrated form of the waste. Consequently, the
Agency believes that the less concentrated wastes generated in
the course of treatment will also be able to be treated to meet
this value.
(2) Mixtures and other derived-from residues. There is a further
question as to the applicability of the BOAT treatment standards to
residues generated not from treating the waste (as discussed above), but
from other types of management. Examples are contaminated soil or
leachate that is derived from managing the waste. In these cases, the
mixture is still deemed to be the listed waste, either because of the
derived-from rule (40 CFR 261.3(c)(2)(i)) or the mixture rule (40 CFR
261.3(a)(2)(iii) and (iv)) or because the listed waste is contained in
the matrix (see, for example, 40 CFR 261.33(d)). The prohibition for the
particular listed waste consequently applies to this type of waste.
The Agency believes that the majority of these types of residues can
meet the treatment standards for the underlying listed wastes (with the
possible exception of contaminated soil and debris for which the Agency
is currently investigating whether it is appropriate to establish a
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separate treatability subcategorization). For the most part, these
residues will be less concentrated than the original listed waste. The
Agency's treatment standards also make a generous allowance for process
variability by assuming that all treatability values used to establish
the standard are lognormally distributed. The waste also might be
amenable to a relatively nonvariable form of treatment technology such as
incineration. Finally, and perhaps most important, the rules contain a
treatability variance that allows a petitioner to demonstrate that its
waste cannot be treated to the level specified in the rule (40 CFR Part
268.44(a)). This provision provides a safety valve that allows persons
with unusual waste matrices to demonstrate the appropriateness of a
different standard. The Agency, to date, has not received any petitions
under this provision (for example, for residues contaminated with a
prohibited solvent waste), indicating, in the Agency's view, that the
existing standards are generally achievable.
/
(3) Residues from managing listed wastes or that contain listed
wastes. The Agency has been asked if and when residues from managing
hazardous wastes, such as leachate and contaminated ground water, become
subject to the land disposal prohibitions. Although the Agency believes
this question to be settled by existing rules and interpretative
statements, to avoid any possible confusion the Agency will address the
question again.
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Residues from managing First Third wastes, listed California List
wastes, and spent solvent and dioxin wastes are all considered to be
subject to the prohibitions for the listed hazardous waste as originally
generated. Residues from managing California List wastes likewise are
subject to the California List prohibitions when the residues themselves
exhibit a characteristic of hazardous waste. This determination stems
directly from the derived-from rule in 40 CFR 261.3(c)(2) or, in some
cases, from the fact that the waste is mixed with or otherwise contains
the listed waste. The underlying principle stated in all of these
provisions is that listed wastes remain listed until delisted.
The Agency's historic practice in processing delisting petitions that
address mixing residuals has been to consider them to be the listed waste
and to require that delisting petitioners address all constituents for
which the derived-from waste (or other mixed waste) was listed. The
language in 40 CFR 260.22(b) states that mixtures or derived-from
residues can be delisted provided a delisting petitioner makes a
demonstration identical to that which a delisting petitioner would make
for the original listed waste. Consequently, these residues are treated
as the original listed waste for delisting purposes. The statute
likewise takes this position, indicating that soil and debris that are
contaminated with listed spent solvents or dioxin wastes are subject to
the prohibition for these wastes even though these wastes are not the
originally generated waste, but rather are a residual from management
(RCRA section 3004(e)(3)). It is EPA's view that all such residues are
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covered by the existing prohibitions and treatment standards for the
listed hazardous waste that these residues contain or from which they are
derived.
1.2.8 Transfer of Treatment Standards
EPA is proposing some treatment standards that are not based on
testing of the treatment technology on the specific waste subject to the
treatment standard. The Agency has determined that the constituents
present in the untested waste can be treated to the same performance
levels as those observed in other wastes for which EPA has previously
developed treatment data. EPA believes that transferring treatment
performance data for use in establishing treatment standards for untested
wastes is technically valid in cases where the untested wastes are
generated f^om similar industries or processing steps, or have similar
waste characteristics affecting performance and treatment selection.
Transfer of treatment standards to similar wastes or wastes from similar
processing steps requires little formal analysis. However, in a case
where only the industry is similar, EPA more closely examines the waste
characteristics prior to deciding whether the untested waste constituents
can be treated to levels associated with tested wastes.
EPA undertakes a two-step analysis when determining whether
constituent:; in the untested wastes can be treated to the same level of
performance as in the tested waste. First, EPA reviews the available
waste characterization data to identify those parameters that are
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expected to affect treatment selection. EPA has identified some of the
most important constituents and other parameters needed to select the
treatment technology appropriate for the given waste(s) in Section 3.
Second, when analysis suggests that an untested waste can be treated
with the same technology as a waste for which treatment performance data
are already available, EPA analyzes a more detailed list of
characteristics that the Agency believes will affect the performance of
the technology. By examining and comparing these characteristics, the
Agency determines whether the untested wastes will achieve the same level
of treatment as the tested waste. Where the Agency determines that the
untested waste can be treated as well or better than the tested waste,
the treatment standards can be transferred.
1.3 Variance from the BOAT Treatment Standard
The Agency recognizes that there may exist unique wastes that cannot
be treated to the level specified as the treatment standard. In such a
case, a generator or owner/operator may submit a petition to the
Administrator requesting a variance from the treatment standard. A
particular waste may be significantly different from the wastes on which
the treatment standards are based because the subject waste contains a
more complex matrix that makes it more difficult to treat. For example,
complex mixtures may Li formed when a restricted waste is mixed with
other waste streams by spills or other forms of inadvertent mixing. As a
result, the treatability of the restricted waste may be altered such that
it cannot meet the applicable treatment standard.
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Variance petitions must demonstrate that the treatment standard
established for a given waste cannot be met. This demonstration can be
made by showing that attempts to treat the waste by available
technologies were not successful or by performing appropriate analyses of
the waste, including waste characteristics affecting performance, which
demonstrate that the waste cannot be treated to the specified levels.
Variances will not be granted based solely on a showing that adequate
BOAT treatment capacity is unavailable. (Such demonstrations can be made
according to the provisions in Part 268.5 of RCRA for case-by-case
extensions of the effective date.) The Agency will consider granting
generic petitions provided that representative data are submitted to
support a variance for each facility covered by the petition.
Petitioners should submit at least one copy to:
The Administrator
U.S. Environmental Protection Agency
401 M Street, S.W.
Washington, DC 20460
An additional copy marked "Treatability Variance" should be submitted
to:
Chief, Waste Treatment Branch
Office of Solid Waste (WH-565)
U.S. Environmental Protection Agency
401 M Street, S.W.
Washington, DC 20460
Petitions containing confidential information should be sent with
only the inner envelope marked "Treatability Variance" and "Confidential
Business Information" and with the contents marked in accordance with the
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requirements of 40 CFR Part 2 (41 FR 36902, September 1, 1976, amended by
43 FR 4000).
The petition should contain the following information:
1. The petitioner's name and address.
2. A statement of the petitioner's interest in the proposed action.
3. The name, address, and EPA identification number of the facility
generating the waste, and the name and telephone number of the
plant contact.
4. The process(es) and feed materials generating the waste and an
assessment of whether such process(es) or feed materials may
produce a waste that is not covered by the demonstration.
5. A description of the waste sufficient for comparison with the
waste considered by the Agency in developing BOAT, and an
estimate of the average and maximum monthly and annual
quantities of waste covered by the demonstration. (Note: The
petitioner should consult the appropriate BOAT background
document for determining the characteristics of the wastes
considered in developing treatment standards.)
6. If the waste has been treated, a description of the system used
for treating the waste, including the process design and
operating conditions. The petition should include the reasons
the treatment standards are not achievable and/or why the
petitioner believes the standards are based on inappropriate
technology for treating the waste. (Note: The petitioner should
refer to the BOAT background document as guidance for
determining the design and operating parameters that the Agency
used in developing treatment standards.)
7. A description of the alternative treatment systems examined by
the petitioner (if any); a description of the treatment system
deemed appropriate by the petitioner for the waste in question;
and, as appropriate, the concentrations in the treatment
residual or extract of the treatment residual (i.e., using the
TCLP, where appropriate, for stabilized metals) that can be
achieved by applying such treatment to the waste.
8. A description of those parameters affecting treatment selection
and waste characteristics that affect performance, including
results of all analyses. (See Section 3 for a discussion of
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waste characteristics affecting performance that the Agency has
identified for the technology representing BOAT.)
9. The dates of the sampling and testing.
10. A description of the methodologies and equipment used to obtain
representative samples.
11. A description of the sample handling and preparation techniques,
including techniques used for extraction, containerization, and
preservation of the samples.
12. A description of analytical procedures used, including QA/QC
methods.
After receiving a petition for a variance, the Administrator may
request any additional information or waste samples that may be required
to evaluate and process the petition. Additionally, all petitioners must
certify that the information provided to the Agency is accurate under
40 CFR 268.4(b).
In determining whether a variance will be granted, the Agency will
first look at the design and operation of the treatment system being
used. If EPA determines that the technology and operation are consistent
with BOAT, the Agency will evaluate the waste to determine if the waste
matrix and/or physical parameters are such that the BOAT treatment
standards reflect treatment of this waste. Essentially, this latter
analysis will concern the parameters affecting treatment selection and
waste characteristics affecting performance parameters.
In cases where BOAT is based on more than one technology, the
petitioner will need to demonstrate that the treatment standard cannot be
met using any of the technologies, or that none of the technologies are
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appropriate for treatment of the waste. After the Agency has made a
determination on the petition, the Agency's findings will be published in
the Federal Register, followed by a 30-day period for public comment.
After review of the public comments, EPA will publish its final
determination in the Federal Register as an amendment to the treatment
standards in 40 CFR Part 268, Subpart D.
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2. INDUSTRY AFFECTED AND WASTE CHARACTERIZATION
According to 40 CFR 261.32, the waste identified as K099 is listed as
follows:
K099: Untreated wastewater from the production of 2,4-D.
The chemical 2,4-D is 2,4-dichlorophenoxyacetic acid.
This section provides a complete characterization of K099 waste by
describing the industry that generates the waste, the process generating
the waste, and waste characterization data.
2.1 Industry Affected and Process Description
K099 waste is generated by the manufactures of 2,4-D. The Agency has
identified only one facility that produces 2,4-D - Dow Chemical USA,
Midland, Michigan (EPA Region V).
The manufacturing process for 2,4-D involves the reaction of
2,4-dichlorophenol with chloroacetic acid in the presence of sodium
hydroxide, hydrochloric acid, and a catalyst in a batch reactor to form
2,4-D. The 2,4-D is recovered using a proprietary solvent and is then
water-washed to form the final product. The solvent is recovered by
distillation and recycled. The solvent recovery still bottoms are sent
to incineration. The recovery and water-wash processes generate
wastewater, which is listed as K099. The K099 waste is treated by
chemical oxidation using chlorine. A flow diagram of the process is
presented in Figure 2-1.
2.2 Waste Characterization
This section presents the waste characterization data available to
the Agency for K099 waste. Based on engineering judgment and analytical
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[THIS FIGURE CONTAINS RCRA CONFIDENTIAL BUSINESS INFORMATION (CBI).]
Figure 2-1 Schematic Diagram of 2,4-Dichlorophenoxyacetic Acid
(2,4-D) Process
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results, it was concluded that the major constituents composing K099
waste are water and dissolved solids (approximately 95 percent) and
sodium salts (approximately 5 percent). These data are presented in
Table 2-1. The analytical data available for K099 waste further indicate
that BOAT constituents are present in concentrations of less than 0.01
percent, with 2,4-D present at the greatest concentration (26.9 ppm).
The ranges of BOAT constituents present in the waste are shown in
Table 2-2.
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1854g
Table 2-1 Major Constituent Composition of K099 Waste
Constituent Concentration (percent)
Water and dissolved solids < 95a
Sodium salts > 5
BOAT constituents < 0.01
100
Engineering estimate.
Reference: USEPA 1987a.
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1854g
Table 2-2 BOAT Constituent Composition and Other Data
Parameter
Untreated waste concentration
BOAT volatile organics (mg/1)
Chloroform
Tetrachloroetnene
BOAT semivolatile organics (rnq/1)
Phenol
2-Chlorophenol
2.4-Dichlorophenol
2,6-0 ichloropheno1
2.4.6-Trichlorophenol
Phenoxvacetic acid herbicides (mg/1)
2.4-0
BOAT chlorinated dibenzo-p-dioxins
and chlorinated dibenzofurans (ug/1)
Tetrachlorodibenzo-p-dioxins
Hexachlorodibenzo-p-dioxins
BOAT metals (mg/1)
Zinc
Non-BDAT metals (mg/1)
Calcium
Iron
Magnesium
Manganese
Sodium
Strontium
Non-BDAT chlorinated dibenzo-p-dioxins
and chlorinated dibenzofurans (uq/1)
Total octachlorodibenzofurans
[UNTREATED WASTE CONCENTRATIONS
ARE RCRA CBI.]
Reference: USEPA 1987a.
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3. APPLICABLE AND DEMONSTRATED TREATMENT TECHNOLOGIES
This section describes the applicable and demonstrated treatment
technologies for K099 waste. The demonstrated technology is discussed in
detail in Section 3.2.1.
3.1 Applicable Treatment Technologies
The waste characterization data in Section 2 indicate that untreated
K099 waste contains low concentrations of BOAT organic constituents, high
water content, and significant dissolved solids (as indicated by the
sodium content of the waste).
The Agency has identified the following treatment technologies as
applicable for such waste: chemical oxidation, wet air oxidation (a
specialized form of chemical oxidation), biological treatment followed by
incineration of the biological sludge, and carbon adsorption followed by
incineration of the carbon. The oxidation technologies are designed to
chemically destroy the organic constituents in the waste by reacting them
with an oxidizing agent such as oxygen, chlorine, or hydrogen peroxide.
Biological treatment uses naturally occurring, acclimated microorganisms
to degrade the organic contaminants in the waste. Carbon adsorption is
designed to adsorb hazardous constituents from the waste by surface
attraction within the internal pores of the carbon granules.
Incineration technologies are designed to destroy the toxic organics that
would be present in the biological sludge generated during biological
treatment or the spent carbon from the carbon adsorption system.
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3.2 Demonstrated Treatment Technologies
Of the applicable treatment technologies, only chemical oxidation
using chlorine has been identified as demonstrated. This technology is
used by the one facility that generates this waste. EPA has not
identified other applicable technologies as demonstrated either on this
waste or on a similar waste. Therefore, the Agency does not believe that
wet air oxidation, biological treatment followed by incineration of the
sludge, or carbon adsorption followed by incineration of the spent carbon
are demonstrated for K099 waste.
A detailed discussion of chemical oxidation is presented below.
3.2.1 Chemical Oxidation
(1) Applicability and use of chemical oxidation. Chemical oxidation
processes are used to oxidize a number of BOAT list organic compounds
including phenol and some substituted phenols. In addition, this process
is used to treat sulfide wastes by converting the sulfide to the
essentially insoluble sulfate form. The parameters that affect selection
of this technology include water content, filterable solids, and total
organic carbon content. The term chemical oxidation, as used in this
report, refers to the technology that is applicable only when treatment
can be conducted at ambient or near ambient pressure and temperature
conditions. When chemical oxidation is conducted at higher temperatures
and pressures, the process is referred to as wet air oxidation. This
latter technology is discussed separately. The processes described in
this section also do not include the oxidation of cyanides by similar
chemicals, which is also discussed separately.
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(2) Underlying principles of operation. Some dissolved organic
compounds or sulfides can be chemically oxidized to yield carbon dioxide,
water, salts, or acids, and, in the case of sulfides, sulfates. The
principal oxidants are hypochlorate or free chlorine, hydrogen peroxide,
and chlorine dioxide. The reaction chemistry for each of these oxidants
is discussed below.
(a) Oxidation with hypochlorite or free chlorine. This type of
oxidation is carried out using either sodium hypochlorite or free
chlorine. The reaction is normally conducted under slightly alkaline
conditions. Example reactions for the oxidation of phenol and sulfide
are shown below.
C6H5OH + HNaOCl -* 6C02 + 3H20 + 14NaCl
S= + 4NaOCl - S04= + 4NaCl.
(b) Peroxide oxidation. Peroxide also oxidizes the same
constituents (intermediate) under similar conditions. The relevant
reactions are:
S= + 4H202 - S04= + 4H20
C6H5OH + 14H202 - 6C02 + 17H20.
(c) Chlorine dioxide oxidation. Chlorine dioxide also oxidizes
the same pollutants under identical conditions. Chlorine dioxide first
hydrolyzes to form a mixture of chlorous (HC10 ) and chloric acids
(HC10 ). These acids act as the oxidants, as shown in the equations
below.
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2C102 + H20 - HC102 + HC103
C6H5OH + 7HC102 - 6C02 + 3H20 + 7HC1
3C5H5OH + 14HC103 - 8C02 + 9H20 + 14HC1.
*
(3) Technology description. Chemical oxidation can be accomplished
by either a batch or a continuous process. For batch treatment, the
wastewater is transferred to a reaction tank where the pH is adjusted and
the oxidizing agent is added. In some cases, the tank may be heated to
increase the reaction rate. For most operations, a slightly alkaline pH
is used. It. is important that the wastewater in the tank be well mixed
for effective treatment to occur. After treatment, the wastewater is
either directly discharged or transferred to another process for further
treatment.
In the continuous process, automatic instrumentation may be used to
control pH "levels, reagent oxidation, and temperature. In both types of
processes, typical retention times are in the 60- to 120-minute range.
(4) Waste characteristics affecting performance. In determining
whether performance standards can be transferred from a previously tested
waste to an untested waste, EPA will examine the following waste
characteristics: (1) the concentration of other oxidizable contaminants
and (2) the presence of metal salts.
(a) Concentration of organic oxidizable compounds. The presence
of other oxidizable compounds in addition to the BOAT constituents of
concern will increase the demand for oxidizing agents and hence will
potentially reduce the effectiveness of the treatment process. As a
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surrogate for the amount of oxidizable organics present, EPA will analyze
for total organic carbon (TOC).
(b) Concentrations of metal salts (oxidizable compounds). Metal
salts, especially lead and silver salts, will react with the oxidizing
agent(s) to form metal peroxides, chlorides, hypochlorites, and/or
chlorates. Formation of these compounds can cause excessive consumption
of oxidizing agents and potentially interfere with the effectiveness of
treatment. Lead and silver salts can be analyzed by EPA Method 3050.
(5) Design and operating parameters. In assessing the effectiveness
of the design and operation of a chemical oxidation system, the
parameters that the Agency will examine are:
1. Retention time;
2. Type of oxidizing agent;
3. Mixing;
4. pH; and
5. Temperature.
(a) Retention time. The system must be designed to provide
enough retention time to ensure complete oxidation. For a batch system,
adequate retention time is provided by holding the treated batch until
the reaction nears completion prior to discharge. The reaction typically
requires from 1 to 2 hours to approach completion. The rate may be
increased somewhat by increasing the temperature if the reaction tank is
equipped with heating units. The tank size is determined by the amount
of waste treated per batch and the amount of oxidizing agent added. For
continuous systems, retention time is determined by the size of the tank
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and the process flow rates of the waste treated. To ensure that the
system is operated at the design retention time, EPA will monitor the
waste feed rate.
(b) Type of oxidizing agent. Several factors govern the choice
of oxidizing agents. The amount of oxidizing agent required to treat a
given amount of reducing compound will vary with the agent chosen.
Enough oxidant must be added to ensure complete oxidation; the specific
amount will depend on the type and chemistry of the reducing compounds in
the waste. Theoretically, the amount of oxidizing agent to be added can
be computed from process stoichiometry; in practice, a small excess of
oxidant should be used. In assessing the effectiveness of any chemical
oxidation system, EPA would want to know how a facility determines the
amount of oxidant to be added, as well as how the facility ensures that
the particular addition rate is maintained.
(c) Mixing. Process tanks must be equipped with mixers to ensure
that there is maximum contact between the reducing solution and the
oxidizing agent. Proper mixing also limits the production of any solid
precipitates from side reactions that may resist oxidation. In addition,
mixing provides an even distribution of the tank contents and a
homogeneous pH throughout the waste, thereby improving oxidation of
wastewater constituents. The quantifiable degree of mixing is a complex
assessment that includes, the energy supplied, the time the material is
mixed, and the related turbulence effects of the specific size and shape
of the tank. EPA will, however, evaluate the degree of mixing
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qualitatively by considering whether mixing is provided and whether the
type of mixing device is one that could be expected to achieve uniform
mixing.
(d) pH. Operation at the optimal pH will maximize the chemical
oxidation by keeping the ions in solution and limiting the formation of
undesirable precipitates. The pH in batch processes should be monitored
at regular intervals during the reaction. The pH is controlled by the
addition of caustic, lime, or acid to the solution. In most cases, a
slightly alkaline pH is used. In a few cases involving the use of free
chlorine, slightly acidic pH values may be selected. In order to ensure
that the proper pH is maintained during treatment, EPA will continuously
monitor the pH.
(e) Temperature. Temperature is important because it affects the
rate of reaction and the solubility of the oxidizing agent. As the
temperature is increased, the required reaction time is reduced and the
solubility of the oxidizing agent will, in most instances, be increased.
EPA will monitor temperature during the treatment period to ensure that
the design value is achieved.
3-7
-------
4. PERFORMANCE DATA BASE
This section discusses the available performance data associated with
the demonstrated technology for K099 waste. Performance data include the
constituent concentrations in untreated and treated waste samples, the
operating data collected during treatment of the sampled waste, design
values for the treatment technology, and data on waste characteristics
that affect performance. EPA has presented all such data to the extent
that they are available.
EPA's use of these data in determining the technology that represents
BOAT, and for developing treatment standards, is described in Sections 5
and 7, respectively.
The Agency collected two untreated and treated waste samples at Dow
Chemical's Midland Plant in order to characterize the treatment of K099
waste by chemical oxidation using chlorine. While design and operating
data for the treatment system were not collected at the time of
treatment, data were subsequently obtained from the facility for the
nominal operating ranges. Table 4-1 presents the untreated and treated
data and the limited data available for the nominal operation of t-he
treatment system.
Dow Chemical submitted data showing 2,4-D concentrations for 31
additional treated samples from its Midland Plant. These analytical data
are presented in Table 4-2. Dow did not provide data on the untreated
waste or information on design and operation of the system at the time of
treatment.
4-1
-------
1854g
Table 4-1 Performance Data Collected by EPA for Treatment of K099 Waste
by Chemical Oxidation Using Chlorine
Parameter
Concentration (/ig/1)
Untreated K099
Sample 1 Sample 2
Treated K099
Sample 1 Sample 2
BOAT volatiles
Choloroform
Tetrachloroethene
Bromodichloromethane
BOAT semivolatiles
Phenol
2-chlorophenol
2,4-d ichloropheno1
2,6-dichlorophenol
2,4.6-trichlorophenol
BOAT phenoxyacetic acid herbicides
2,4-Dichlorophenoxyacetic acid (2.4-D)
BOAT dioxins and furans
[UNTREATED CONCENTRATIONS
ARE RCRA CBI.]
1560
<2
9
34
<20
80
61
2190
33
<20
73
Hexachlorod i benzo-p-d iox i ns
Hexachlorodibenzofurans
Pentach lorodibenzo-p-dioxins
Pentachlorodi benzofurans
Tetrachlorodibenzo-p-dioxins
Tetrachlorodibenzofurans
BOAT metals
Zinc
Other parameters
Non-BDAT dioxins and furans
0.007
0.068
0.004
0.041
0.008
0.035
285
0.007
0.053
0.005
0.065
0.009
0.045
330
Octachlorodibenzo-p-dioxins
Octachlorodi benzofurans
Heptach1orodi benzo-p-d i ox i ns
Heptachlorod i benzofurans
0.022
0.782
<0.002
0.013
0.021
0.826
0.004
0.014
4-2
-------
1854g
Table 4-1 (Continued)
Concentration (uq/11
Untreated K099 Treated K099
Parameter Sample 1 Sample 2 Sample 1 Sample 2
Non-BDAT metals
Calcium 3.320 7.380
Iron 1.710 3.350
Magnesium 945 1.950
Manganese . < 100 < 100
Sodium 31.000.000 49.800.000
Strontium 295 655
Nominal operating parameters for the chlorinator at the DOM 2,4-0 Plant were as follows:
1. pH in the chlorinator:
control 6.0 - 6.2
acceptable range 5.3 - 6.5
2. Chlorine feed quantity:
4 Ib/hr chlorine per gallon/minute of water to be treated
The chlorine feed is typically varied to maintain approximately 450 ppm of chlorine in
the chlorinator.
3. Reaction time:
Reaction time is 40 minutes per vessel or approximately 80 minutes total.
References: USEPA 1987a and letter from W. I. Delaney. Dow Chemical, to J. Carra, USEPA, 1987, concerning operating
information for treatment of 2,4-D wastewater.
4-3
-------
1854g
Table 4-2 Chemical Oxidation Performance Data
Submitted by Dow Chemical USA Showing
2,4-0 Concentrations in the Treated Wastewater
Sample no.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
Wastewater
2,4-D concentration
(ppb)
81.94
40.89
103.14
117.10
36.19
116.35
244.62
141.76
68.28
530.83
1031.46
8.39
4.42
41
31.31
393.66
302.79
54.04
157.44
55.74
1638.45
93.07
25.61
59.08
105.29
<4
152.38
18.87
32.89
33.65
272.98
Sampling date
05/11/87
05/26/87
06/09/87
06/22/87
07/07/87
07/27/87
08/10/87
08/24/87
09/08/87
09/21/87
10/05/87
10/12/87
10/14/87
10/26/87
10/19/87
12/03/07
12/06/87
12/13/87
12/25/87
12/28/87
01/21/88
01/25/88
01/31/88
02/02/88
02/03/88
02/25/88
02/29/88
03/24/88
03/28/88
04/24/88
04/26/88
Reference: Dow Chemical Company 1988 (LDR8-00036) and personal
communications with Reid Tait. Dow Chemical, on July 20, 1988.
4-4
-------
5. IDENTIFICATION OF BEST DEMONSTRATED AVAILABLE TECHNOLOGY (BOAT)
This section explains EPA's determination of the best demonstrated
available technology (BOAT) for K099 waste. As discussed in Section 1,
the BOAT for a waste must be the "best" of the "demonstrated"
technologies; the BOAT must also be "available." In general, the
technology that constitutes "best" is determined after screening the
available data from each demonstrated technology, adjusting these data
for accuracy, and comparing the performance of each technology to that of
the others. If only one technology is identified as demonstrated, this
technology is considered "best." To be "available," a technology
(1) must be commercially available and (2) must provide substantial
treatment.
Chemical oxidation using chlorine is the only technology identified
as being demonstrated for K099 waste. Accordingly, EPA considers this
technology "best."
EPA believes that chemical oxidation using chlorine represents BOAT
because it is commercially available and provides substantial treatment.
Having screened the data and eliminated four data points, EPA determined
that substantial treatment is provided, based on the observation that
untreated concentrations of 2,4-D as high as [CBI] ug/1 were reduced to
64 and 44 ug/1 in samples collected by the Agency, and moreover, in the
data submitted by Dow, expectedly similar untreated concentrations of
2,4-D were reduced to less than 4 to 456 ug/1. The treated residual
concentrations reported here have been corrected for accuracy using the
associated QA/QC information on recoveries.
5-1
-------
The analytical data recoveries and accuracy-corrected 2,4-D
concentrations are presented in Table 5-1. (Accuracy correction is
discussed in Appendix B.) Table 5-1 also indicates which data points
were eliminated during screening. The data point from sample number 26
in the Dow-submitted data was discarded because the recovery was less
than 20 percent, the minimum requirement for usable data. Three more
data points from the Dow-submitted data were discarded because they were
statistical outliers, an indication of poor operation. In cases where no
associated design and operating data are available, the Agency uses a
statistical outlier analysis to determine whether the data meet the
well-designed and well-operated criteria (51 FR 40590, November 7, 1986).
5-2
-------
1854g
Table 5-1 Accuracy-Corrected Performance Data for 2.4-0 in Treated IC099 Wastewater
Sample
no.
Data source
EPA (Table 4-1) 1
2
Dow (Table 4-2) 1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
2.4-0
concentration
(ug/1)
61
42
81.94
40.89
103.14
117.10
36.19
116.35
244.62
141.76
68.28
530.83
1031.46
8.39
4.42
41.00
31.31
393.66
302.79
54.04
157.44
55.74
1638.45
93.07
25.61
59.08
105.29
<4
152.38
18.87
32.89
33.65
272.98
3,4-D spike
concentration
(ug/1)
_
-
29.37
16.24
53.18
35.90
15.32
43.85
35.68
41.11
23.14
17.20
38.93
43.89
67.75
26.46
48.58
43.19
49.64
25.88
60.61
44.14
27.01
35.91
45.39
53.68
' 45.29
0
40.86
56.20
40.04
48.14
47.14
Recovery3
0.96
0.96
0.59
0.32
1.06
0.72
0.31
0.88
0.71
0.82
0.46
0.34
0.78
0.88
1.36
0.53
0.97
0.86
0.99
0.52
1.21
0.88
0.54
0.72
0.91
1.07
0.91
0
0.82
1.12
0.80
0.96
0.94
Accuracy-corrected
2,4-0 concentration
(ug/1)
64
44
139.4961
125.8929
96.9725
163.0919
118.1136
132.6682
342.7971
172.4155
147.5367
1543.11
1324.26
9.5584
3.2618
77.4754
32.2252
455.7305
304.9859
104.4049
129.8796
63.1400
3033.04
129.5879
28.2111
55.0298
116.2398
-
186.4477
16.7883
41.0714
34.9501
289.5418
aRecovery = 3.4-0 spike concentration in ppb/50 ppb for Dow-submitted data. (Samples were
spiked with 50 ppb of 3,4-D.) See Appendix B for recovery information on EPA-collected
samples.
Accuracy-corrected 2,4-0 concentration = 2,4-D concentration/recovery.
5-3
-------
6. SELECTION OF REGULATED CONSTITUENTS
As discussed in Section 1, the Agency has developed a list of
hazardous constituents (Table 1-1) from which the constituents to be
regulated are selected. EPA may revise this list as additional data and
information become available. The list is divided into the following
categories: volatile organics, semivolatile organics, metals,
inorganics, organochlorine pesticides, phenoxyacetic acid herbicides,
organophosphorous pesticides, PCBs, and dioxins and furans.
This section describes the process used to select the constituents to
be regulated. The process involves developing a list of potential
regulated constituents and then eliminating those constituents that would
not be treated by the chosen BOAT or that would be controlled by
regulation of the remaining constituents.
6.1 Identification of BOAT List Constituents in the Untreated Waste
As discussed in Sections 2 and 4, the Agency has characterization
data as well as performance data from treatment of K099 waste by chemical
oxidation using chlorine. These data, along with information on the
waste generating process, have been used to determine which BOAT list
constituents may be present in the waste and thus which are potential
candidates for regulation in the nonwastewater and wastewater.
Table 6-1 indicates, for the untreated waste, which constituents were
analyzed, which constituents were detected, and which constituents the
Agency believes could be present though not detected. For those
constituents detected, concentrations are shown.
6-1
-------
Under the column "Believed to be present," constituents other than
those detected in the untreated waste are marked with X or Y if EPA
believes they are likely to be present in the untreated waste. For those
constituents marked with X, an engineering analysis of the waste
generating process indicates that they are likely to be present (e.g.,
the engineering analysis shows that a particular constituent is a major
raw material). Those constituents marked with Y have been detected in
the treated residual(s) and thus EPA believes they are present in the
untreated waste. Constituents may not have been detected in the
untreated waste for one of several reasons: (1) none of the untreated
waste samples were analyzed for those constituents, (2) masking or
interference by other constituents prevented detection, or (3) the
constituent indeed was not present. (With regard to Reason (3), it is
important to note that some wastes are defined as being generated from a
process. The process may utilize variable starting materials composed of
different constituents; therefore, all potentially regulated constituents
would not necessarily be present in any given sample.)
In samples collected by EPA at the Dow facility, EPA analyzed for 51
of the 231 BOAT list constituents. EPA believes that the compounds not
analyzed are unlikely to be present in the waste because there is no
in-process source for these compounds. Of the 45 analyzed constituents,
11 were detected in the untreated waste and an additional 5 were detected
in the treated residual wastewater. These 16 constituents are potential
candidates for regulation in K099 waste.
6-2
-------
6.2 Constituent Selection
EPA is regulating 7 of the 16 candidate constituents. These are
2,4-D, hexachlorodibenzo-p-dioxins, hexachlorodibenzofurans,
pentachlorodibenzo-p-dioxins, pentachlorodibenzofurans,
tetrachlorodibenzo-p-dioxins, and tetrachlorodibenzofurans. The 2,4-D is
clearly treated by the BOAT. Levels of the chlorinated dioxins and
dibenzofurans; in the untreated waste samples were relatively low (see
Table 4-1); thus, the data do not show treatment for these compounds.
The Agency believes, however, that in some cases these compounds may be
present in the waste at levels significantly higher.
The performance data presented in Table 4-1 indicate that the
tetrachloroethene concentration is reduced by treatment. It is unclear
to the Agency, however, how chemical oxidation using chlorine would
destroy this constituent; therefore, the Agency has chosen not to
regulate it.
The performance data also show that phenol, 2-chlorophenol,
2,4-dichlorophenol, 2,6-dichlorophenol, and 2,4,6-trichlorophenol
concentrations are reduced by the BOAT treatment. Because the recovery
data associated with these compounds show zero percent recoveries, the
analytical data are not reliable. Nevertheless, the Agency could
regulate these constituents if other data were available for transfer.
EPA is choosing not to regulate these constituents because it believes
they will be controlled by regulation of 2,4-D and the chlorinated
dioxins and furans.
6-3
-------
21«5g
Table 6-1 Status of BOAT List Constituent Presence
in Untreated K099 Waste
BOAT
reference
no.
222.
1.
2.
3.
4.
5.
6.
223.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
25.
26.
27.
28.
29.
224.
225.
226.
30.
227.
31.
214.
32.
33.
228.
34.
Constituent
Volatile organ ics
Acetone
Acetonitrile
Ac role in
Acrylonitrile
Benzene
Bromod ich loromethane
Bromome thane
n-Butyl alcohol
Carbon tetrachloride
Carbon disulfide
Chlorobenzene
2-Chloro-l,3-butadiene
Ch 1 orod i bromomet hane
Chloroethane
2-Chloroethyl vinyl ether
Chloroform
Chloromethane
3-Chloropropene
1 ,2-Oibromo-3-chloropropane
1 , 2 -0 i bromoethane
Oibromome thane
trans- 1 , 4-D ich loro-2-butene
Dich lorod i f luoromethane
1,1-Oichloroethane
1.2-Dichloroethane
1.1-Dichloroethylene
trans- 1.2-0 ich loroethene
1,2-Dichloropropane
trans- 1 . 3-D ich loropropene
c is- 1.3-0 ich loropropene
1.4-Dioxane
2-Ethoxyethanol
Ethyl acetate
Ethyl benzene
Ethyl cyanide
Ethyl ether
Ethyl methacrylate
Ethylene oxide
lodome thane
Isobutyl alcohol
Hethanol >
Methyl ethyl ketone
Detection Believed to
status3 be present
NA
NA
NA
NA
NO
NO
NA
NA
NO
NA
NA
NA
NO
NA
NA
D (CBI)
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA'
NA
NA
NA
NA
NO
NA
NA
NA
NA
NA
NA
NA
NA
6-4
-------
2185cj
Table 6-1 (Continued)
BOAT
reference
no.
229.
35.
37.
38.
230.
39.
40.
41.
42.
43.
44.
45.
46.
47.
48.
49.
231
50.
215.
216.
217.
51.
52.
53.
54.
55.
56.
57.
58.
59.
218.
60.
61.
62.
63.
64.
65.
66.
Constituent
Volatile organ ics (continued)
Methyl isobutyl ketone
Methyl methacrylate
Methacrylonitri le
Methylene chloride
2-Nitropropane
Pyridine
1.1.1. 2-Tetrach loroethane
1,1.2. 2-Tetrach loroethane
Tet rach loroethene
Toluene
Tribromomethane
1.1. 1-Trichloroethane
1,1. 2-Trich loroethane
Trich loroethene
Trichloromonof luorome thane
1 , 2 , 3-Tr ich loropropane
1.1.2-Trichloro-1.2.2-
trif luoroethane
Vinyl chloride
1,2-Xylene
1.3-Xylene
1.4-Xylene
Semivolat i le organ ics
Acenaphthalene
Acenaphthene
Acetophenone
2-Acetylaminof luorene
4-Aminobiphenyl
Ani line
Anthracene
Aramite
Benz ( a Janthracene
Benzal chloride
Benzene thiol
Deleted
Benzo(a)pyrene
Benzo(b)f luoranthene
Benzo( gh i ) pery lene
Benzo(k)f luoranthene
p-Benzoquinone
Detection Believed to
status3 be present
NA
NA
NA
NA
NA
NA
NA
NA
D (CBI)
ND
NA
NA
NA
ND
NA
NA
NA
NA
NO
ND
NO
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
6-5
-------
2185g
Table 6-1 (Continued)
BOAT
reference
no.
67.
68.
69.
70.
71.
72.
73.
74.
75.
76.
77.
78.
79.
80.
81.
82.
232.
83.
84.
85.
86.
87.
88.
89.
90.
91.
92.
93.
94.
95.
96.
97.
98.
99.
100.
101.
102.
103.
104.
10!i.
106.
219.
Constituent
Semi volatile orqanics (continued)
Bis(2-chloroethoxy)methane
Bis(2-chloroethyl)ether
Bis(2-chloroisopropyl)ether
Bis(2-ethylhexyl)phthalate
4-Bromophenyl phenyl ether
Butyl benzyl phthalate
2-sec-Buty 1 -4 . 6-d i n i tropheno 1
p-Chloroani line
Chlorobenzilate
p-Chloro-ro-cresol
2-Ch loronaphtha lene
2-Chlorophenol
3-Chloropropionitrile
Chrysene
ortho-Cresol
para-Cresol
Cyc lohexanone
0 i benz ( a , h ) anthracene
Dibenzo(a,e)pyrene
Dibenzo(a, ijpyrene
m-Dichlorobenzene
o-Oichlorobenzene
p-Oichlorobenzene
3,3'-Oichlorobenz idine
2.4-Oichlorophenol
2.6-Dichlorophenol
Diethyl phthalate
3 . 3 ' -D imethoxybenz id ine
p- D imet hy lam i noazobenzene
3,3'-Dimethylbenzidine
2.4-Oimethylphenol
Dimethyl phthalate
Oi-n-butyl phthalate
1.4-Oinitrobenzene
4.6-Oinitro-o-cresol
2,4-Dinitrophenol
2,4-Dinitrotoluene
2.6-Oinitrotoluene
Di-n-octyl phthalate
Oi-n-propylnitrosamine
Oipheny lamine
D i pheny 1 n i t rosam i ne
Detection Believed to
status be present
NA
NA
NA
NA
NA
NA
NA
NA
NA
NO
NA
D (CBI)
NA
NA
NO
NO
NA
NA
NA
NA
NA
NA
NA
NA
D (CBI)
D (CBI)
NA
NA
NA
NA
NO
NA
NA
NA
ND
NO
NA
NA
NA
NA
NA
NA
6-6
-------
2185c|
Table 6-1 (Continued)
BOAT
reference
no.
107.
108.
109.
110.
111.
112.
113.
114.
115.
116.
117.
118.
119.
120.
36.
121.
122.
123.
124.
125.
126.
127.
128.
129.
130.
131.
132.
133.
134.
135.
136.
137.
138.
139.
140.
141.
142.
220.
143.
144.
145.
146.
Constituent
Semi volatile orqanics (continued)
1.2-Oiphenylhydrazine
Fluoranthene
Fluorene
Hexach loro benzene
Hexachlorobutadiene
Hexachlorocyc lopentadiene
Hexach loroethane
Hexach lorophene
Hexach loropropene
lndeno(1.2.3-cd)pyrene
Isosafrole
Hethapyrilene
3-Methy Icho lanthrene
4.4'-Methylenebis
(2-chloroani 1 ine)
Methyl methanesulfonate
Naphthalene
1 , 4-Naphthoqu i none
1-Naphthylamine
2-Naphthylamine
p-Nitroani line
Nitrobenzene
4-Nitrophenol
N-Nitrosodi-n-butylamine
N-Nitrosodiethylamine
N-Nitrosodimethy lamine
N-Nitrosomethylethylamine
N - N i t rosomorpho 1 i ne
N-Nitrosopiperidine
n-N i trosopyrro 1 id ine
5-Nitro-o-toluidine
Pentachlorobenzene
Pentach loroethane
Pentach loron i trobenzene
Pentach loropheno 1
Phenacetin
Phenanthrene
Phenol
Phthalic anhydride
2-Picoline
Pronamide
Pyrene
Resorcinol
Detection Believed to
status3 be present
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NO
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NO
NA
NA
0 (CBI)
NA
NA
NA
NA
NA
6-7
-------
2185g
Table 6-1 (Continued)
BOAT
reference
no.
147.
148.
149.
150.
151.
152.
153.
154.
155.
156.
157.
158.
159.
221.
160.
161.
162.
163.
164.
165.
166.
167.
161).
169.
170.
171.
172.
173.
174.
175.
Constituent
Semivolatile organ ics (continued)
Safrole
1 ,2,4,5-Tetrachlorobenzene
2,3.4,6-Tetrachlorophenol
1,2. 4-Tr ich lorobenzene
2,4,5-Trichlorophenol
2,4.6-Trichlorophenol
Tr i s ( 2 . 3-d i bromopropy 1 )
phosphate
Metals
Antimony
Arsenic
Barium
Beryllium
Cadmium
Chromium (total)
Chromium (hexavalent)
Copper
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Inorganics other than metals
Cyanide
Fluoride
Sulfide
Orqanochlorine pesticides
Aldrin
alpha-BHC
beta-BHC
delta-BHC
Detection Believed to
status3 be present
NA
NA
NO
NA
NO
D (CBI)
NA
NA
NA
ND
ND
ND
ND
NA
ND
ND
NA
ND
NA
ND
NA
NO
0 (CBI)
NA
NA
NA
NA
NA
NA
NA
6-8
-------
2185g
Table 6-1 (Continued)
BOAT
reference
no.
Constituent
Detection Believed to
status6 be present
Organochlorlne pesticides (continued)
176.
177.
178.
179.
180.
181.
182.
183.
184.
185.
186.
187.
188.
189.
190.
191.
192.
193.
194.
195.
196.
197.
198;.
199.
200.
201.
20!.'.
203.
204.
205.
206.
gamna-BHC
Chlordane
ODD
DOE
DDT
Dieldrin
Endosulfan I
Endosulfan II
Endrin
Endrin aldehyde
Heptachlor
Heptachlor epoxide
Isodrin
Kepone
Methoxyc lor
Toxaphene
Phenoxyacetic acid herbicides
2,4-Dichlorophenoxyacetic acid
Silvex
2.4.5-T
OrqanoDhoschorous insecticides
Disulfoton
Famphur
Methyl parathion
Parathion
Phorate
PCBs
Aroclor 1016
Aroclor 1221
Aroclor 1232
Aroclor 1242
Aroclor 1248
Aroclor 1254
Aroclor 1260
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0 (CBI)
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
6-9
-------
2185g
Table 6-1 (Continued)
BOAT Detection Believed to
reference Constituent status3 be present
no.
Dioxins and furans
207. Hexachlorodibenzo-p-dioxins D (CBI)
208. Hexachlorodibenzofurans ND Y
209. Pentachlorodibenzo-p-dioxins NO Y
210. Pentachlorodibenzofurans ND Y
211. Tetrachlorodibenzo-p-dioxins D (CBI)
212. Tetrachlorodibenzofurans ND Y
213. 2.3.7.8-Tetrachlorodibenzo-
p-dioxin ND
CBI = Confidential Business Information
D = Detected
ND = Not detected.
NA = Not analyzed.
X = Believed to be present based on engineering analysis of waste generating
process.
Y = Believed to be present based on detection in treated residuals.
alf detected, concentration is shown, units are mg/1.
6-10
-------
7. CALCULATION OF THE BOAT TREATMENT STANDARDS
This section discusses the determination of the treatment standards
for the regulated constituents in K099 waste. EPA is establishing
treatment standards for 2,4-D based on performance data from chemical
oxidation using chlorine. The chlorinated dioxin and furan treatment
standards are being transferred from the promulgated rule for dioxin-
containing wastes (40 CFR 268.41).
As discussed in the introduction, the following steps are taken to
derive the BOAT treatment standards:
1. The Agency screens the available data to determine whether any of
the data fail to meet QA/QC requirements or represent poor design
or poor operation of the treatment system.
2. Accuracy-corrected constituent concentrations are calculated.
3. The mean (arithmetic average) and variability factor for the
accuracy-corrected data are calculated (See Appendix A for a
discussion on the variability factor).
4. The treatment standard is computed by multiplying the mean by the
variability factor.
For 2,4-D, EPA has 33 wastewater data points from one facility
(2 collected by EPA and 31 submitted by Dow) from the BOAT treatment of
K099 waste. In Section 5, EPA eliminated 4 data points (for reasons
given in Step 1) and corrected the remaining 29 data points for
accuracy. The 29 data points, their recoveries, and the accuracy-
corrected data are presented in Table 7-1, along with the variability
factor and the treatment standard.
The Agency cannot calculate wastewater treatment standards for the
chlorinated dioxins and furans using the available performance data
because these constituents were not present at treatable levels in the
7-1
-------
untreated waste sampled by EPA. The Agency, instead, is transferring
treatment standards established for the dioxin-containing wastes (see 51
FR 40615, November 7, 1986).
EPA has identified a nonwastewater waste that would be classified as
K099 under the "derived-from" rule. This waste could be generated from
the collection of clarification sludges from biological treatment or from
the spent carbon from carbon adsorption treatment. Because EPA has no
data on treatment of this waste, or on a waste believed to be similar,
the Agency is establishing standards for the nonwastewater that are equal
to the wastewater standards.
Table 7-2 summarizes the treatment standards established for K099
waste.
7-2
-------
Tab!
Ca
ion
Sample
no.
Data source
EPA (Table 4-1) 1
2
Dow (Table 4-2) 1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
2.4-D
concentration
(ug/1)
61
42
81.94
40.89
103.14
117.10
36.19
116.35
244.62
141.76
68.28
530.83
1031.46
8.39
4.42
41.00
31.31
393.66
302.79
54.04
157.44
55.74
1638.45
93.07
25.61
59.08
105.29
<4
152.38
18.87
32.89
33.65
272.98
3.4-D spike
concentration
(ug/1)
.
-
29.37
16.24
53.18
35.90
15.32
43.85
35.68
41.11
23.14
17.20
38.93
43.89
67.75
26.46
48.58
43.19
49.64
25.88
60.61
44.14
27.01
35.91
45.39
53.68
45.29
0
40.86
56.20
40.04
48.14
47.14
Recovery3
0.96
0.96
0.59
0.32
1.06
0.72
0.31
0.88
0.71
0.82
0.46
0.34
0.78
0.88
1.36
0.53
0.97
0.86
0.99
0.52
1.21
0.88
0.54
0.72
0.91
1.07
0.91
0
0.82
1.12
0.80
0.96
0.94
Accuracy-corrected Variability
2.4-D concentration'' Mean factor
(ug/1) (ug/1)
64 125 8.27
44
139.4961
125.8929
96.9725
163.0919
118.1136
132.6682
342.7971
172.4155
147.5367
1543.11
1324.26
9.5584
3.2618
77.4754
32.2252
455.7305
304.9859
104.4049
129.8796
63.1400
3033.04
129.5879
28.2111
55.0298
116.2398
-
186.4477
16.7883
41.0714
34.9501
289.5418
Treatment
standard
(mg/D
1.0
Recovery = (3.4-D spike concentration in ppb)/50 ppb for Dow-submitted data.
recovery information on EPA collected data.
Accuracy-corrected 2.4-D concentration = 2.4-D concentration/recovery.
(Samples were spiked with 50 ppb of 3.4-D.). See Appendix B for
-------
1854g
Table 7-2 BOAT Treatment Standards for K099
Const ituent
Total concentration
Nonwastewater
(mg/kg)
Wastewater
(mg/1)
2,4-Oichlorophenoxyacetic acid
Hexachlorodibenzo-p-dioxins
Hexachlorod ibenzofurans
Pentach lorodibenzo-p-diox ins
Pentachlorodibenzofurans
Tetrachlorodibenzo-p-diox ins
Tetrachlorodibenzofurans
1.0
0.001
0.001
0.001
0.001
0.001
0.001
1.0
0.001
0.001
0.001
0.001
0.001
0.001
7-4
-------
8. ACKNOWLEDGMENTS
This document was prepared for the U.S. Environmental Protection
Agency, Office of solid Waste, by Versar Inc. under Contract
No. 68-01-7053. Mr. James Berlow, Chief, Treatment Technology Section,
Waste Treatment Branch, served as the EPA Program Manager during the
preparation of this document and the development of treatment standards
for K099 waste. The technical project officer for K099 waste was
Mr. Jerry Vorbach. Mr. Steven Silverman served as legal advisor.
Versar personnel involved in the preparation of this document
included Mr. Jerome Strauss, Program Manager; Mr. David Pepson, Senior
Technical Reviewer; Ms. Justine Alchowiak, Quality Assurance Officer;
Ms. Olenna Truskett, Technical Reviewer; Ms. Barbara Malczak, Technical
Editor; and the Versar secretarial staff, Ms. Linda Gardiner and Ms. Mary
Burton.
Data were collected on treatment of K099 at Dow Chemical, Midland,
Michigan, by Midwest Research Institute, contractor to the Office of
Solid Waste under Contract No. 68-01-7287.
We greatly appreciated the cooperation of Dow Chemical USA whose
plant was sampled and who submitted additional data and information to
the U.S. EPA.
8-1
-------
9. REFERENCES
Dow Chemical. 1987. Letter concerning operating information for
treatment of 2,4-D wastewater. Letter from W.I. Delaney, Dow Chemical,
to J. Carra, U.S. Environmental Protection Agency.
Dow Chemical. 1988. Comments on the proposed land disposal restrictions
for First Thirds wastes. Submitted to EPA RCRA Docket F-88-LDR8-FFFFF.
Comment No. LDR8-00036. Washington, D.C.: U.S. Environmental
Protection Agency.
Encyclopedia of science and technology. 1982. McGraw-Hill Book Co.
Vol. 3, p 825.
Gurnham, C.F. 1985. Principles of industrial waste treatment. John
Wiley and Sons.
Metcalf & Eddy, Inc. 1986. Briefing, Technologies Applicable to
Hazardous Waste Prepared for USEPA, HWERL.
Patterson, J.W. 1985. Industrial wastewater treatment technology.
2nd ed., Butterworth Publishers.
USEPA. 1986. U.S. Environmental Protection Agency, Office of Solid Waste
and Emergency Response. Test methods for evaluating solid waste;
physical/chemical methods. SW-846. Washington, D.C. U.S.
Environmental Protection Agency November 1986.
USEPA. 1986. U.S. Environmental Protection Agency, Office of Solid
Waste. Hazardous waste management system; land disposal restrictions;
final rule. 51 FR 40615-40643, November 7, 1986.
USEPA. 1987a. U.S. Environmental Protection Agency. Sampling and
analysis of the 2,4-D production process at the Dow Chemical USA,
Midland, Michigan, Plant. Midwest Research Institute. Contract
No. 68-01-7287 Draft final report for Office of Solid Waste.
Washington, D.C. U.S. Environmental Protection Agency.
USEPA. 1987b. U.S. Environmental Protection Agency. Memorandum
concerning relisting issues regarding wastes K043 and K099 from 2,4-D
production. Memorandum from Y.M. Garbe, EPA, to M.A. Strauss, EPA.
USEPA. 1987c. U.S. Environmental Protection Agency. RCRA Section 3007
questionnaire for organic pesticides industry. Submitted to EPA by Dow
Chemical U..S.A.
9-1
-------
USEPA. 1987d. U.S. Environmental Protection Agency. Final sampling and
analysis plan for the 2,4-D production
process at the Dow Chemical USA, Midland, Michigan Plant. EPA Contract
No. 68-01-7287. Prepared by Midwest Research Institute. Kansas City,
Mo.
Weast, R.C., ed. 1978. Handbook of chemistry and physics. 58th
Edition, CRC Press.
9-2
-------
APPENDIX A
STATISTICAL METHODS
A.I F Value Determination for ANOVA Test
As noted in Section 1.2, EPA is using the statistical method known as
analysis of variance (ANOVA) to determine the level of performance that
represents "best" treatment where more than one technology is
demonstrated. This method provides a measure of the differences between
data sets.
If the Agency found that the levels of performance for one or more
technologies are not statistically different (i.e., the data sets are
homogeneous), EPA would average the long-term performance values achieved
by each technology and then multiply this value by the largest
variability factor associated with any of the acceptable technologies.
If EPA found that one technology performs significantly better (i.e., the
data sets are not homogeneous), the "best" technology would be the
technology that achieves the best level of performance, i.e., the
technology with the lowest mean value.
To determine whether any or all of the treatment performance data
sets are homogeneous using the analysis of variance method, it is
necessary to compare a calculated "F value" to what is known as a
"critical value." (See Table A-l.) These critical values are available
in most statistics texts (see, for example, Statistical Concepts and
Methods by Bhattacharyya and Johnson, 1977, John Wiley Publications,
New York).
A-l
-------
Table A-l
95th PERCENTILE VALUES FOR
THE F DISTRIBUTION
ni degrees of freedom for numerator
nj = degrees of freedom for denominator
(shaded area = .95)
jjjj^
FM
«t\
!
i
;
.
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
00
24
26
28
30
40
50
60
70
80
100
150
200
400
"
1
^
161.4
16.51
10.13
7.71
6.61
5.99
5.59
5.32
5.12
4.96
4.84
4.75
4.67
4.60
4.54
4.49
4.45
4.41
4.38
4.35
4.30
4.26
4.23
4.20
4.17
4.08
4.03
4.00
3.98
3.96
3.94
3.91
3.89
3.86
3.84
2
199.5
19.00
9.55
6.94
5.79
5.14
4.74
4.46
4.26
4.10
3.98
3.89
3.31
3.74
3.68
3.63
3.59
3.55
3.52
3.49
3.4,',
3.40
3.37
3.3,1
3.32
3.23
3.18
3.15
3.13
3.22
3.09
3.06
3.04
3.02
2.9»
3
215.7
19.16
9.28
6.59
5.41
4.76
4.35
4.07
3.86
3.71
3.59
3.49
3.41
3.34
3.29
3.24
3.20
3.16
3.13
3.10
3.05
3.01
2.98
2.95
2.92
2.84
2.79
2.76
2.74
2.72
2.70
2.67
2.65
2.62
2.60
4
224.6
19.25
9.12
6.39
5.19
4.53
4.12
3.84
3.63
3.48
3.36
3.26
3.18
3.11
3.06
3.01
2.96
2.93
2.90
2.87
2.82
2.78
2.74
2.71
2.69
2.61
2.56
2.53
2.50
2.48
2.46
2.43
2.41
2.39
2.37
5
230.2
19.30
9.01
6.26
5.05
4.39
3.97
3.69
3.48
3.33
3.20
3.11
3.03
2.96
2.90
2.85
2.81
2.77
2.74
2.71
2.66
2.62
2.59
2.56
2.53
2.45
2.40
2.37
2.35
2.33
2.30
2J27
2.26
2^3
ISl
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
2JZ5
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
229
2J27
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
2J29
2J25
2JJ1
2.18
2.13
2.09
2.05
2.02
1.99
1.90
1.85
1.81
1.79
1.77
1.75
1.71
1.69
1.67
1.64
20
248.0
19.45
8.66
5.80
4.56
3.87
3.44
3.15
2.93
2.77
2.65
2.54
2.46
2,39
2,33
2.28
2^3
2,19
2.15
2.12
2,07
2.03
1.99
1.96
1.93
1.84
2.78
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.CO
5.71
4.46
3.77
3.34
3.05
2.82
2.67
2.53
2.42
2.34
2.27
2.21
2.16
2.11
2.07
2.02
1.99
1.93
1.89
1.85
1.81
1.79
1.69
1.63
1.59
1.56
1.54
1.51
1.47
1.45
1.42
1.40
50
252JI
19.47
8.58
5.70
4.44
3.75
3.32
3.03
2.80
2.64
2.50
2.40
2.32
2^4
2.18
2.13
2.08
2.04
2.00
1.96
1.91
1.86
1.82
1.78
1.76
1.66
1.60
1.56
1.53
1.51
1.48
1.44
1.42
1.38
1.32
100
253.0
19.49
8.56
5.66
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
25;.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
1.88
1.84
1.78
1.73
1.69
1.65
1.62
1.51
1.44
1.39
1.35
1.32
1.28
1.22
1.19
1.13
1.00
A-2
-------
Where the F value is less than the critical value, all treatment data
sets are homogeneous. If the F value exceeds the critical value, it is
necessary to perform a "pair wise F" test to determine if any of the sets
are homogeneous. The "pair wise F" test.must be done for all of the
various combinations of data sets using the same method and equation as
the general F test.
The F value is calculated as follows:
(i) All data are natural logtransformed.
(ii) The sum of the data points for each data set is computed (T.).
(iii) The statistical parameter known as the sum of the squares
between data sets (SSB) is computed:
SSB - [ A
where:
k = number of treatment technologies
nj = number of data points for technology i
N = number of data points for all technologies
T^ = sum of natural logtransformed data points for each technology.
(iv) The sum of the squares within data sets (SSW) is computed:
SSW =
' k
z
1=1
where:
ni
y x2-
_L * i , j
k f V 1
- y
^
1-1 n<
= the natural logtransformed observations (j) for treatment
technology (i).
A-3
-------
(v) The degrees of freedom corresponding to SSB and SSW are
calculated. For SSB, the degree of freedom is given by k-1. For SSW,
the degree of freedom is given by N-k.
(vi) Using the above parameters, the F value is calculated as
follows:
MSB
F = MSW
where:
MSB = SSB/(k-1) and
MSW = SSW/(N-k).
A computational table summarizing the above parameters is shown below.
Computational Table for the F Value
Source
Between
Within
Degrees of
freedom
k-1
N-k
Sum of
squares
SSB
SSW
Mean square
MSB = SSB/k-1
MSW = SSW/N-k
F value
MSB/MSW
Below are three examples of the ANOVA calculation. The first two
represent treatment by different technologies that achieve statistically
similar treatment; the last example represents a case in which one
technology achieves significantly better treatment than the other
technology.
A-4
-------
1790g
Example 1
Methylene Chloride
jiteam stripping
Influent
1/19/1 '
1550.00
1290.00
1640.00
5100.00
1450.00
4600.00
1760.00
2400.00
4800.00
12100.00
Effluent
(M9/D
10.00
10.00
10.00
12.00
10.00
10.00
. 10.00
10.00
10.00
10.00
ln(ef fluent)
2.30
2.30
2.30
2.48
2.30
2.30
2.30
2.30
2.30
2.30
[In(effluent)]2 Influent
(rt/U
5.29 1960.00
5.29 2568.00
5.29 1817.00
6.15 1640.00
5.29 3907.00
5.29
5.29
5.29
5.29
5.29
Biological treatment
Effluent In(effluent) [ln(eff luent)]2
(M9/D
10.00 2.30 5.29
10.00 2.30 5.29
10.00 2.30 5.29
26.00 3.26 10.63
10.00 2.30 5.29
Sum:
23.18
53.76
12.46
31.79
Sample Si/e:
10 10
10
Mean:
3669
10.2
2.32
2378
13.2
2.49
Standard Deviation:
3328.67 .63
Variability Factor:
1.15
.06
923.04
7.15
2.48
.43
ANOVA Calculations:
SS8 =
ssw = [ 1 .2;
I i=l J=l
MSB = SSB/(k-l)
MSW = SSW/(N-k)
U"]
1=1
N
A-5
-------
1790g
Example 1 (Continued)
F = MSB/HSU
where:
k = number of treatment technologies
n = number of data points for technology i
i
N - number of natural logtransformed data points for all technologies
T = sum of logtransformed data points for each technology
i
X = the nat. logtransformed observations (j) for treatment technology (i)
n = 10. n = 5. N = 15. k = 2. T = 23.18. T = 12.46. T = 35.64. T = 1270.21
I2 = 537.31 T = 155.25
SSB -
10
1270.21
15
0.10
SSW = (53.76 * 31.79) -
MSB = 0.10/1 = 0.10
MSW - 0.77/13 i 0.06
0.10
10
= 1.67
0.06
0.77
ANOVA Table
Source
Between(B)
Uithin(W)
Degrees of
freedom
1
13
SS HS F value
0.10 0.10 1.67
0.77 0.06
The critical value of the F test at the 0.05 significance level is 4.67. Since
the F vd lue is less than the critical value, the means are not significantly
different (i.e.. they are homogeneous).
Note: All calculations Mere 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
Steam stripping
Influent
(M9/D
1650.00
5200.00
5000.00
1720.00
1560.00
10300.00
210.00
1600.00
204.00
160.00
Sum:
Sample Size:
10
Mean :
2760
Effluent
(«/!)
10.00
10.00
10.00
10.00
10.00
10.00
10.00
27.00
85.00
10.00
-
10
19.2
ln(eff luent)
2.30
2.30
2.30
2.30
2.30
2.30
2.30
3.30
4.44
2.30
26.14
10
2.61
[In(effluent)]2
5.29
5.29
5.29
5.29
5.29
5.29
5.29
10.89
19.71
5.29
72.92
-
-
Influent
Ug/1)
200.00
224.00
134.00
150.00
484.00
163.00
182.00
-
7
220
Biological treatment
Effluent
Ug/1)
10.00
10.00
10.00
10.00
16.25
10.00
10.00
-
7
10.89
In(effluent)
2.30
2.30
2.30
2.30
2.79
2.30
2.30
16.59
7
2.37
[In(effluent)]2
5.29
5.29
5.29
5.29
7.78
5.29
5.29
39.52
-
-
Standard Deviation:
3209.6 23.7
Varidbi I ity Factor:
3.70
.71
120.5
2.36
1.53
.19
ANOVA Calculations:
SSB =
2 1
Ti
1
f\ ~ j
-
f k 12
1 Z Til
1 i = l I
N
k nj
MSB = SSB/(k-l)
MSW =- SSW/(N-k)
A-7
-------
1790q
Example 2 (Continued)
F = MSB/MSV
where:
k = number of treatment technologies
n = number of data points for technology i
i
N = number of data points for all technologies
T = sum of natural logtransformed data points for each technology
i
X = the natural logtransformed observations (j) for treatment technology (i)
ij
N = 10. N = 7. N = 17. k = 2. T = 26.14, T - 16.59. T - 42.73. T - 1825.85. T = 683.30.
T = 275.23
SSB =
683.30 275.23
+ _
10' 7
1825.85
17
= 0.25
SSU = (72.92 + 39.52) -
MSB - 0.25/1 = 0.25
MSW = 4.1'9/lS = 0.32
F = °'2 = 0.78
0.32
10
= 4.79
ANOVA Table
Degrees of
Source freedom
Between(B) 1
Uithin(W) 15
SS HS F value
0.25 0.25 0.78
4.79 0.32
The critical value of the F test at the 0.05 significance level is 4.54. Since
the F value is less than the critical value, the means are not significantly
different .(i.e.. they are homogeneous).
Note: All calculations were rounded to two decimal places. Results may differ
depending upon the number of decimal places used in each step of the calculations.
A-8
-------
1790g
Example 3
Chlorobenzene
Activated sludge followed by carbon adsorption
Biologic.i I treatment
Influent
Ug/D
Effluent
Ug/1)
In(effluent) [ln(eff luent)r Influent
Effluent
Ug/D
In(effluent)
ln[(effluent)]'
7200.00
6500.00
6075.00
3040.00
80.00
70.00
35.00
10.00
4.38
4.25
3.56
2.30
19.18
18.06
12.67
5.29
9206.00
16646.00
49775.00
14731.00
3159.00
6756.00
3040.00
1083.00
709.50
460.00
142.00
603.00
153.00
17.00
6.99
6.56
6.13
4.96
6.40
5.03
2.83
48.86
43.03
37.58
24.60
40.96
25.30
8.01
Sum:
Sample Size:
4 4
Mean:
5703
49
Standard Deviation:
1835.4 32.24
Variabi I ity Factor:
7.00
14.49
3.62
.95
55.20
14759
16311.86
452.5
379.04
15.79
38.90
5.56
1.42
228.34
ANOVA Calculations:
2
SSB =
Ti
F k nj ^
SSW
MSB = SSB/(k-l)
MSW = SSU/(N-k)
F = MSB/MSW
I,")
A-9
-------
1790g
where.
Example 3 (Continued)
k = number of treatment technologies
n - number of data points for technology i
i
N - number of data points for all technologies
T = sum of natural logtransformed data points for each technology
i
X.. - the natural logtransformed observations (j) for treatment technology (i)
2 2
N = 4. N7= 7. N = 11. k = 2. T = 14.49. T = 38.90. T = 53.39, T = 2850.49. T = 209.96
T? = 1513.21
'209.96 + 1513.21
4 7
SSW = (55.20 + 228.34)
= 9.52
14.88
MSB = 9.52/1 = 9.52
MSW ^ 14.88/9 - 1.65
F = 9.52/1.65 = 5.77
ANOVA Table
Degrees of
Source freedom
SS
MS
F value
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 5.1?. Since
the F value is larger than the critical value, the means are significantly
different (i.e.. they are heterogeneous). Activated sludge followed by carbon
adsorption is "best" in this example because the mean of the long-term performance
value, i.e., the effluent concentration, is lower.
Note: All calculations were rounded to two decimal places. Results may differ depending
upon the number of decimal places used in each step of the calculations.
A-10
-------
A.2 Variabilitv Factor
C99
VF = Mean
where:
VF = estimate of daily maximum variability factor determined
from a sample population of daily data;
Cgg = estimate of performance values for which 99 percent of the
daily observations will be below. Cgq is calculated
using the following equation: Cgg = txp(y + 2.33 Sy)
where y and Sy are the mean and standard deviation,
respectively, of the logtransformed data; and
Mean = average of the individual performance values.
EPA is establishing this figure as an instantaneous maximum because
the Agency believes that on a day-to-day basis the waste should meet the
applicable treatment standards. In addition, establishing this
requirement makes it easier to check compliance on a single day. The
99th percentile is appropriate because it accounts for almost all process
variability.
In several cases, all the results from analysis of the residuals from
BOAT treatment are found at concentrations less than the detection
limit. In such cases, all the actual concentration values are considered
unknown and, hence, cannot be used to estimate the variability factor of
the analytical results. Below is a description of EPA's approach for
calculating the variability factor for such cases with all concentrations
below the detection limit.
It has been postulated as a general rule that a lognormal
distribution adequately describes the variation among concentrations.
Agency data show that the treatment residual concentrations are
A-I1
-------
distributed approximately lognormally. Therefore, the lognormal model
has been used routinely in the EPA development of numerous regulations in
the Effluent Guidelines program and is being used in the BOAT program.
The variability factor (VF) was defined as the ratio of the 99th
percentile (C ) of the lognormal distribution to its arithmetic mean
(Mean), as follows:
VF= Jsa. w
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 (») and standard deviation (a) of the normal distribution as
follows:
Cg9 = Exp (M + 2.33a) (2)
Mean = Exp (M + 0.5a2). (3)
By substituting (2) and (3) in (1), the variability factor can then
be expressed in terms of a as follows:
VF = Exp (2.33 o - 0.5a2). (4)
For residuals with concentrations that are not all below the
detection limit, the 99th percentile and the mean can be estimated from
the actual analytical data and, accordingly, the variability factor (VF)
can be estimated using equation (1). For residuals with concentrations
A-12
-------
that are below the detection limit, the above equations can be used in
conjunction with the following assumptions to develop a variability
factor.
Assumption 1: The actual concentrations follow a lognormal
distribution. The upper limit (UL) is equal to the detection
limit. The lower limit (LL) is assumed to be equal to one-tenth
of the detection limit. This assumption is based on the fact that
data from well-designed and well-operated treatment systems
generally fall within one order of magnitude.
Assumption 2: The natural logarithms of the concentrations have
a normal distribution with an upper limit equal to In (UL) and a
lower limit equal to In (LL).
Assumption 3: The standard deviation (a) of the normal
distribution is approximated by:
a = [In(UL) - ln(LL)] / [(2)(2.33)]
= [ln(UL/LL)] / 4.66. (5)
(Note that when LL = (0.1)(UL) as in Assumption 1, then
a = (InlO) / 4.66 = 0.494.)
Substitution of the a value from equation (5) into equation (4)
yields the variability factor, VF, as shown:
VF = 2.8. (6)
A-13
-------
APPENDIX B
ANALYTICAL QA/QC
The analytical methods used for analysis of the regulated constituents
identified in Section 6 are listed in Table B-l. SW-846 methods (EPA's
Test Methods for Evaluation Solid Waste: Physical/
Chemical Methods, SW-846, Third Edition, November 1986) are used in most
cases for determining total constituent concentrations.
The accuracy determination for a constituent is based on the matrix
spike recovery values. Table B-2 presents the matrix spike recoveries
for 2,4-dichlorophenoxyacetic acid total constituent analyses for K099
residuals for the EPA-collected data.
For the data collected by EPA, the accuracy correction factor for
2,4-dichlorophenoxyacetic acid was determined in accordance with the
general methodology discussed in the Introduction and is presented in
Table B-2. For 2,4-dichlorophenoxyacetic acid, actual spike recovery
data were obtained for analysis of wastewaters, and the lowest percent
recovery value was used to calculate the accuracy correction factor. The
calculation of a corrected concentration value for 2,4-D is shown below.
Analytical Correction Corrected
value % Recovery factor value
0.052 96 100 = i 04 1.04 x 0.052 = 0.054 ppm
96
B-l
-------
1854g
Table B-l Analytical Methods for Regulated Constituents
Regulated constituent
Extraction method
Analyt ical
method
Total Composition
2.4-Dichlorophenoxyacetic acid
Total Hexachlorodibenzo-p-dioxins
Total Hexachlorodibenzofurans
Total Pentachlorodibenzo-p-dioxins
Total Pentachlorodibenzofurans
Total Tetrachlorodibenzo-p-dioxins
Total Tetrachlorodibenzofurans
Specified in analytical method
Specified in analytical method
Specified in analytical method
Specified in analytical method
Specified in analytical method
Specified in analytical method
Specified in analytical method
8150a
8280
8280
8280
8280
8280
8280
aSamples analyzed by GC/MS rather than GC/ECD as specified in the method.
Source: USEPA 1986. U.S. Environmental Protection Agency. Test methods for
evaluating solid waste: Physical/chemical methods. SW-846. Washington, O.C.
U.S. Environmental Protection Agency, Office of Solid Waste and Emergency
Response, November 1986.
B-2
-------
Table B-2 Matrix Spike Recoveries for K099 Treated Wastewater-EPA-Collected Data
BOAT Original amount
constituent found (mg/1)
2,4-Dichlorophenoxy-
acetic acid
Bromodichloromethane
Chloroform
Tetrachloroethene
2-Chlorophenol
2,4-Dichlorophenol
Phenol
2,4.6-Trichlorophenol
Zinc
0.0516
0.009
1.83
1.3
ND
0.033
NO
0.08
0.308
Spike added
(mg/1)
0.050
10
1
10
0.05
0.05
0.05
0.15
2.0
Matrix spike
Spike result
(mg/1)
0.0549
10.4
2.80
9.5
ND
0.03
ND
0.096
2.3
Matrix spike duplicate
Percent
recovery3
6.6b
104
92
95
0
0
0
13
101
Spike added
(mg/1)
0.05
10
1
10
0.05
0.05
50
0.15
NA
Spike result
(mg/1)
0.148
10.8
2.84
9.88
ND
0.03
ND
0.08
NA
Percent
recovery3
193b
108
96
99
0
0
0
0
NA
Accuracy-
correction
factor0
1.04
0.96
1.09
1.05
0
0
0
0
0.99
NC = Not calculable because the only values available were the spike amount and the percent recovery.
Percent recovery = [(spike result - original amount)/spike added].
The OER documents that, for the matrix spike, the 2,4-dichlorophenoxyacetic acid (2,4-D) was apparently not added to the sample, and for the matrix
spike duplicate, the sample was accurately spiked with twice the amount. Based on a review of the data, EPA believes that the matrix spike duplicate
was spiked with 0.1 mg/1 of 2,4-D and the recovery value is 96 percent. Therefore, 96 percent is used to calculate the accuracy-correction factor.
°Accuracy-correction factor = 100/percent recovery (using the lowest percent recovery value).
Note: For the chlorinated dioxins and furans, the samples were spiked with 2,3,7,8-TCDD; however, because of the dilution required to quantify the other
chlorinated dioxin and furan values, the spike value was not measurable.
Reference: USEPA 1987a. U.S. Environmental Protection Agency, Office of Solid Waste. Draft final report, Sampling and analysis of the 2,4-D production
process at the Dow Chemical USA Midland, Michigan, Plant. May 29, 1987. EPA Contract No. 68-01-7287. Prepared by Midwest Research Institute,
Kansas City, Mo.
-------
APPENDIX C
DETECTION LIMITS FOR K099 WASTE SAMPLES
Table C-l presents detection limits for the analyzed constituents in
untreated and treated waste sample data.
C-l
-------
1854g
Table C-l Detection^imits for K099 Untreated
and Treated Samples
BOAT
reference
no.
5
14
42
78
90
91
142
152
160
192
207
208
209
210
211
212
BOAT Untreated
list waste
constituent (ug/1)
Bromodichloromethane [UNTREATED WASTE
Chloroform CONCENTRATIONS
Tetrachloroethene ARE RCRA CBI.]
2-Chlorophenol
2.4-Dichlorophenol
2.6-Dichlorophenol
Phenol
2.4.6-Trichlorophenol
Zinc
2.4-Dichlorophenoxyacetic
acid (2-4-0)
Total Hexachlorodibenzo-p-
dioxins
Total Hexachlorodibenzofurans
Total Pentachlorodibenzo-p-
dioxins
Total Pentachlorodibenzofurans
Total Tetrachlorodibenzo-p-
dioxins
Total Tetrachlorodibenzofurans
Treated
waste
(ug/1)
2
2
2
15
15
20
15
45
NA
20. 4a
0.002
0.002
0.002
0.002
0.002
0.002
NA - Not available
Reference: USEPA 1987a and Dow Chemical 1988 (LDR7-00036).
a Detection limit for 2,4-D is 20 jig/l in EPA-collected data and
4 «ig/l in Dow-submitted data.
C-2
------- |