EPA/530-SW-88-031N
FINAL
BEST DEMONSTRATED AVAILABLE TECHNOLOGY (BOAT)
BACKGROUND DOCUMENT FOR
K086 SOLVENT WASH
(Non CBI Version)
James R. Berlow, Chief
Treatment Technology Section
Jose Labiosa
Project Manager
U.S. Environmental Protection Agency
Office of Solid Waste
401 M Street, S.W.
Washington, D.C. 20460
August 1988
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TABLE OF CONTENTS
Section Page
EXECUTIVE SUMMARY vi i
1. INTRODUCTION 1-1
1.1 Legal Background 1-1
1.1.1 Requirements Under HSWA 1-1
1.1.2 Schedule for Developing Restrictions 1-4
1.2 Summary of Promulgated BOAT Methodology 1-5
1.2.1 Waste Treatability Groups 1-7
1.2.2 Demonstrated and Available Treatment
Technologies 1-7
1.2.3 Collection of Performance Data 1-11
1.2.4 Hazardous Constituents Considered and Selected
for 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-Prom"
and "Mixed" Wastes 1-36
1.2.8 Transfer of Treatment Standards 1-40
1.3 Variance from the BOAT Treatment Standard 1-41
2. INDUSTRIES AFFECTED AND WASTE CHARACTERIZATION 2-1
2.1 Industry Affected and Process Description 2-2
2.2 Waste Characterization 2-5
3. APPLICABLE/DEMONSTRATED TREATMENT TECHNOLOGIES 3-1
3.1 Applicable Treatment Technologies 3-1
3.2 Demonstrated Treatment Technologies 3-3
3.2.1 Incineration 3-5
3.2.2 Fuel Substitution 3-24
3.2.3 Stabilization 3-40
3.2.4 High Temperature Metals Recovery 3-47
3.2.5 Hexavalent Chromium Reduction 3-55
3.2.6 Chemical Precipitation 3-60
3.2.7 Polishing Filtration 3-72
3.2.8 Sludge Filtration 3-77
4. PERFORMANCE DATA 4-1
4.1 Organics Performance Data 4-1
4.2 Metals Treatment Data 4-2
4.2.1 Wastewater 4-2
4.2.2 Nonwastewater 4-3
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TABLE OF CONTENTS (Continued)
Section
5. IDENTIFICATION OF THE BEST DEMONSTRATED AVAILABLE
TECHNOLOGY (BOAT) 5-1
5.1 BOAT for Treatment of Organics 5-1
5.2 BOAT for Treatment of Metals 5-3
5.2.1 Wastewater 5-3
5.2.2 Nonwastewater 5-4
6. SELECTION OF REGULATED CONSTITUENTS 6-1
6.1 Identification of BOAT Li.st Constituents in K086
Solvent Waste 6-1
.6.2 Determination of Significant Treatment from BOAT 6-3
6.2.1 BOAT List Organic Constituents 6-4
6.2.2 BOAT List Metal Constituents 6-5
6.3 Rationale for Selection of Regulated Constituents 6-5
7. CALCULATION OF BOAT TREATMENT STANDARDS 7-1
7.1 Calculation of Treatment Standards for Nonwastewater
Forms of K086 Solvent Wash 7-1
7.1.1 Organic Treatment Standards 7-2
7.1.2 Metal Treatment Standards 7-3
7.2 Calculation of Treatment Standards for Wastewater Forms
of K086 Solvent Wash 7-4
7.2.1 Organic Treatment Standards 7-4
7.2.2 Metal Treatment Standards 7-5
8. ACKNOWLEDGMENTS 8-1
9. REFERENCES 9-1
APPENDIX A STATISTICAL METHODS A-l
APPENDIX B ANALYTICAL QA/QC B-l
APPENDIX C DETECTION LIMITS FOR THE K086 SCRUBBER WATER
SAMPLES C-l
APPENDIX D METHOD OF MEASUREMENT FOR THERMAL
CONDUCTIVITY . .• D-l
APPENDIX E ORGANIC DETECTION LIMITS FOR K086 SOLVENT
WASH NONWASTEWATERS E-l
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LIST OF TABLES
Table Page
1-1 BOAT Constituent List 1-18
2-1 Number of Ink Formulators by State and by EPA Region .. 2-4
2-2 Major Constituent Analysis of Untreated K086 Solvent
Wash 2-7
2-3 BOAT Constituent Composition and Other Data 2-8
4-1 Performance Data Collected by EPA for Incineration
of K086 Solvent Wash 4-5
4-2 Performance Data Collected by EPA for Chromium
Reduction, Chemical Precipitation, and Vacuum
Filtration of Metal-Bearing Wastewater at Envirite .... 4-6
6-1 Status of BOAT List Constituent Presence in
Untreated K086 Solvent Wash 6-8
6-2 BOAT Constituent Concentrations in Untreated K086
Solvent Wash and Scrubber Water Residual from
Test Burn 6-15
6-3 Calculated Bond Energy for the Candidate Organic
Constituents 6-16
6-4 Candidate Constituents for Regulation of K086 Solvent
Wash 6-17
7-1 . Calculation of K086 Solvent Wash Nonwastewater
Treatment Standards 7-6
7-2 Calculation of K086 Solvent Wash Wastewater Treatment
Standards 7-7
A-l 95th Percentile Values for the F Distribution
B-l Analytical Methods for K086 Solvent Waste Regulated
Constituents B-3
B-2 Specific Procedures or Equipment Used in Extraction
of Organic Compounds When Alternatives or Equivalents
Are Allowed in the SW-846 Methods B-5
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LIST OF TABLES (Continued)
Table Page
B-3 Specific Procedures or Equipment Used for Analysis
of Organic and Metal Compounds When Alternatives
or Equivalents Are Allowed in SW-846 B-7
B-4 Matrix Spike Recoveries Used to Calculate Correction
Factors for K086 Solvent Wash Scrubber Water Organic
Concentrations B-9
B-5 Matrix Spike Recoveries Used to Calculate Correction
Factors for the'Envirite Wastewater and TCLP Extract
Metal Concentrations B-10
B-6 Matrix Spike Recoveries Used to Calculate Correction
Factors for the Envirite Filter Cake Organic Detection
Limits B-ll
B-7 Accuracy-Corrected Envirite Metals Data for Treated
Wastewater from Chromium Reduction, Lime Precipitation,
and Sludge Filtration B-12
B-8 Accuracy-Corrected Envirite Metals Data for Filter
Cake Residuals from Lime Stabilization and Sludge
Filtration B-13
B-9 Accuracy-Corrected Organic Concentrations for Envirite
Filter Cake and K086 Solvent Wash Scrubber Water B-14
C-l Detection Limits for the K086 (Solvent Washes) Untreated
Waste Samples C-2
C-2 Detection Limits for the Scrubber Effluent Water
Samples C-9
E-l Organic Detection Limits for Envirite Filter Cake
Residuals from Lime Stabilization and Sludge
Filtration E-2
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LIST OF FIGURES
Figure Page
2-1 Geographical Distribution of Ink Manufacturing Sites .. 2-3
2-2 Ink Formulation and K086 Waste Generation 2-6
3-1 Liquid Injection Incinerator 3-9
3-2 Rotary Kiln Incinerator 3-10
3-3 Fluidized Bed Incinerator 3-12
3-4 Fixed Hearth Incinerator 3-13
3-5 Example High Temperature Metals Recovery System 3-51
3-6 Continuous Hexavalent Chromium Reduction System 3-57
3-7 Continuous Chemical Precipitation 3-63
3-8 Circular Clarifiers 3-66
3-9 Inclined Plate Settler 3-67
D-l Schematic Diagram of the Comparative Method D-2
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EXECUTIVE SUMMARY
BOAT Treatment Standards for K086 Solvent Wash
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 one
subcategory, solvent wash, of the listed waste identified in
40 CFR 261.32 as K086. Compliance with these BOAT treatment standards is
a prerequisite for placement of the waste in units designated as land
disposal units according to 40 CFR Part 268. These treatment standards
become effective as of August ,8, 1988.
This background document provides the Agency's rationale and
technical support for selecting the constituents to be regulated in K086
solvent wash 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.
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the treatment standards. The remainder of the document presents
waste-specific information—the number and locations of facilities
affected by the land disposal restrictions for K086 waste, the
waste-generating process, characterization data, the technologies used to
treat the waste (or similar wastes), and available performance data,
including data on which the treatment standards are based. The document
also explains EPA's determination of BOAT, selection of constituents to
be regulated, and calculation of treatment standards.
According to 40 CFR 261.32, waste code K086 is defined as "solvent
washes and sludges, caustic washes and sludges, or water washes and
sludges, from cleaning tubs and equipment used in the formulation of ink
from pigments, driers, soaps, and stabilizers containing chromium and
lead." The Agency has determined that K086 can be divided into three
treatability groups based on physical and chemical composition:
(1) solvent wash, (2) solvent sludge, and (3) the caustic/water wash and
sludge. This background document pertains to the development of
treatment standards for K086 solvent wash. Treatment standards for the
other groups are to be developed prior to promulgation of land disposal
restrictions for the Second or Final Thirds wastes.
The Agency estimates that approximately 460 facilities formulate ink
and thus may generate K086 solvent wash. These facilities fall under
Standard Industrial Classification (SIC) Code 2893.
The Agency is regulating 17 organic and 2 metal constituents in both
nonwastewater and wastewater forms of K086 solvent wash. (For the
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purpose of determining the applicability of the BOAT treatment standards,
wastewaters are defined as wastes containing less than 1 percent (weight
basis) total suspended solids* and less than 1 percent (weight basis)
total organic carbon (TOC). Wastes not meeting this definition must
comply with the treatment standards for nonwastewaters.) The treatment
standards for the organic constituents in both nonwastewater and
wastewater are based on performance data from incineration with liquid
injection capabilities. For the metal constituents, the treatment
standards for wastewater are based on performance data from chromium
reduction followed by precipitation and vacuum sludge filtration, while
the treatment standards for nonwastewater are based on performance data
from lime stabilization.
The following table lists the specific BOAT treatment standards for
K086 solvent wash nonwastewater and wastewater. For the BOAT list
organic constituents, treatment standards reflect the total constituent
concentration. For the BOAT list metal constituents, treatment standards
in the nonwastewater reflect the concentration of constituents in the
leachate from the Toxicity Characteristic Leaching Procedure (TCLP) and
*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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treatment standards in the wastewater reflect the total constituent
concentration. The units for the total constituent concentration are
mg/kg (parts per million on a weight-by-weight basis) for the
nonwastewater and mg/1 (parts per million on a weight-by-volume basis)
for the wastewater. The units for the leachate concentration are mg/1.
Note that if the concentrations of the regulated constituents in the
waste, as generated, are lower than or equal to the treatment standards,
then treatment is not required prior to land disposal.
Testing procedures for all sample analyses performed for the
regulated constituents are specifically identified in Appendix B of this
background document.
EPA wishes to point out that because of facility claims of
confidentiality, this document does not contain all of the data that EPA
usually discloses in the documents supporting its decision-making
process. In this document, the data restricted from public scrutiny
pertain to data used for selecting constituents to regulate, data used
for determining substantial treatment, and data used for developing BOAT
treatment standards. -Under 40 CFR Part 2, Subpart B, facilities may
claim any or all of the data that are submitted to EPA as confidential
business information (CBI). These confidentiality rules outline
procedures that EPA must follow when using these data for rulemaking.
Since EPA has not yet made a determination regarding the validity of the
data being claimed as CBI, the data will be treated as CBI until a
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determination is made. The Agency would like to emphasize, however, that
all the data have been evaluated according to the methodology presented
in Section 1 of this document. All deletions of CBI are noted in the
appropriate places.
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BOAT- Treatment Standards for K086 Solvent Wash
Constituent
Maximum for any single grab sample
Nonwastewater
Total
concentration
(mg/kg)
TCLP leachate
concentration
(mg/1)
Wastewater
Total
concentration
(mg/1)
Volatile Orqanics
Acetone
n-Butyl alcohol
Ethyl acetate
Ethyl benzene
Methanol
Methyl isobutyl ketone
Methyl ethyl ketone
Methylene chloride
To!uene
1,1,1-Trichloroethane
Trichloroethylene
Xylenes (total)
Semivolatile Orqanics
Bis(2-ethylhexyl)phthalate
Cyclohexanone
1,2-Dichlorobenzene
Napthalene
Nitrobenzene
Metals
Chromium
Lead
(total)
0.37
0.37
0.37
0.031
0.37
0.37
0.37
0.037
0.031
0.044
0.031
0.015
0.49
0.49
0.49
0.49
0.49
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.015
0.031
0.031
0.015
0.031
0.031
0.031
0.031
0.029
0.031
0.029
0.015
0.044
0.022
.044
.044
0.
0.
0.094
0.37
0.044
0.32
0.037
NA = Not applicable.
XI 1
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1. INTRODUCTION
This section of the background document presents a summary of the
legal authority pursuant to which the best demonstrated available
technology (BOAT) treatment standards were developed, a summary of EPA's
promulgated methodology for developing the BOAT treatment standards, and,
finally, a discussion of the petition process that should be followed to
request a variance from the BOAT treatment standards.
1.1 Legal Background
1.1.1 Requirements Under HSWA
The Hazardous and Solid Waste Amendments of 1984 (HSWA), which were
enacted on November 8, 1984, and which amended the Resource Conservation
and Recovery Act of 1976 (RCRA), impose substantial new responsibilities
on those who handle hazardous waste. In particular, the amendments
require the Agency to promulgate regulations that restrict the land
disposal of untreated hazardous wastes. In its enactment of HSWA,
Congress stated explicitly that "reliance on land disposal should be
minimized or eliminated, and land disposal, particularly landfill and
surface impoundment, should be the least favored method for managing
hazardous wastes" (RCRA section 1002(b)(7), 42 U.S.C. 6901(b)(7)).
One part of the amendments specifies dates on which particular groups
of untreated hazardous wastes will be prohibited from land disposal
unless "it has been demonstrated to the Administrator, to a reasonable
degree of certainty, that there will be no migration of hazardous
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constituents from the disposal unit or injection zone for as "long as the
wastes remain hazardous" (RCRA section 3004(d)(l), (e)(l), (g)(5),
42 U.S.C. 6924 (d)(l), (e)(l), (g)(5)).
For the purpose of the restrictions, HSWA defines land disposal "to
include, but not be limited to, any placement of ... hazardous waste in
a landfill, surface impoundment, waste pile, injection well, land
treatment facility, salt dome formation, salt bed formation, or
underground mine or cave" (RCRA section 3004(k), 42 U.S.C. 6924(k)).
Although HSWA defines land disposal to include injection wells, such
disposal of solvents, dioxins, and certain other wastes, known as the
California List wastes, is covered on a separate schedule (RCRA section
3004(f)(2), 42 U.S.C. 6924 (0(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 Ma.y 8, 1990, the waste is automatically prohibited from land
disposal unless the waste is placed in a land disposal unit that is the
subject of a successful "no migration" demonstration (RCRA section
3004(g), 42 U.S.C. 6924(g)). "No migration" demonstrations are based on
case-specific petitions that show there will be no migration of hazardous
constituents from the unit for as long as the waste remains hazardous.
1.1.2 Schedule for Developing Restrictions
Under section 3004(g) of RCRA, EPA was required to establish a
schedule for developing treatment standards for all wastes that the
Agency had listed as hazardous by November 8, 1984. Section 3004(g)
required that this schedule consider the intrinsic hazards and volumes
associated with each of these wastes. The statute required EPA to set
treatment standards according to the following schedule:
1. Solvent and dioxin wastes by November 8, 1986;
2. The "California List" wastes by July 8, 1987;
3. At least one-third of all listed hazardous wastes by
August 8, 1988 (First Third);
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4. At least two-thirds of all listed hazardous wastes by
June 8, 1989 (Second Third); and
5. All remaining listed hazardous wastes and all hazardous wastes
identified as of November 8, 1984, by one or more of the
characteristics defined in 40 CFR Part 261 by May 8, 1990 (Third
Third).
The statute specifically identified the solvent wastes as those
covered under waste codes F001, F002, F003, F004, and F005; it identified
the dioxin-containing hazardous wastes as those covered under waste codes
F020, F021, F022, and F023.
Wastes collectively known as the California List wastes, defined
under section 3004(d) of HSWA, are liquid hazardous wastes containing
metals, free cyanides, PCBs, corrosives (i.e., a pH less than or equal to
2.0), and any liquid or nonliquid hazardous waste containing halogenated
organic compounds (HOCs) above 0.1 percent by weight. Rules for the
California List were proposed on December 11, 1986, and final rules for
PCBs, corrosives, and HOC-containing wastes were established
August 12, 1987. In that rule, EPA elected not to establish treatment
standards for metals. Therefore, the statutory limits became effective.
On May 28, 1986, EPA published a final rule (51 FR 19300) that
delineated the specific waste codes that would be addressed by the First
Third, Second Third, and Third Third land disposal restriction rules.
This schedule is incorporated into 40 CFR 268.10, 268.11, and 268.12.
1.2 Summary of Promulgated BOAT Methodology
In a November 7, 1986, rulemaking, EPA promulgated a technology-based
approach to establishing treatment standards under section 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., avail able) 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 ;onstituents. 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
1-12
-------
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, EPA selects sites for visits strictly on the basis of which
facility could most expeditiously be visited and later sampled if
justified by the engineering visit.
(2) Engineering site visit. Once a treatment facility -has been
selected, an engineering site visit is. made to confirm that a candidate
for sampling meets EPA's criteria for a well-designed facility and to
1-13
-------
ensure that the necessary sampling points can be accessed to determine
operating parameters and treatment effectiveness. During the visit, EPA
also confirms that the facility appears to be well operated, although the
actual operation of the treatment system during sampling is the basis for
EPA's decisions regarding proper operation of the treatment unit. In
general, the Agency considers a well-designed facility to be one that
contains the unit operations necessary to treat the various hazardous
constituents of the waste, as well as to control other nonhazardous
materials in the waste that may affect treatment performance.
In addition to ensuring that a system is reasonably well designed,
the engineering visit examines whether the facility has a way to measure
the operating parameters that affect performance of the treatment system
during the waste treatment period. For example, EPA may choose not to
sample a treatment system that operates in a continuous mode, for which
an important operating parameter cannot be continuously recorded. In
such systems, instrumentation is important in determining whether the
treatment system is operating at design values during the waste treatment
period.
(3) Sampling and analysis plan. If after the engineering site visit
the Agency decides to sample a particular plant, the Agency will then
develop a site-specific sampling and analysis plan (SAP) according to the
Generic Quality Assurance Project Plan for the Land Disposal Restrictions
Program ("BOAT"). EPA/530-SW-87-011. In brief, the SAP discusses where
the Agency plans to sample, how the samples will be taken, the frequency
1-14
-------
of sampling, the constituents to be analyzed and the method of analysis,
operational parameters to be obtained, and specific laboratory quality
control checks on the analytical results.
The Agency will generally produce a draft of the site-specific SAP
within 2 to 3 weeks of the engineering visit. The draft of the SAP is
then sent to the plant for review and comment. With few exceptions, the
draft SAP should be a confirmation of data collection activities
discussed with the plant personnel during the engineering site visit.
EPA encourages plant personnel to recommend any modifications to the SAP
that they believe will improve the quality of the data.
It is important to note that sampling of a plant by EPA does not mean
that the data will be used in the development of BOAT treatment
standards. EPA's final decision on whether to use data from a sampled
plant depends on the actual analysis of the waste being treated and on
the operating conditions at the time of sampling. Although EPA would not
plan to sample a facility that was not ostensibly well designed and well
operated, there is no way to ensure that at the time of the sampling the
facility will not experience operating problems. Additionally, EPA
statistically compares its test data to suitable industry-provided data,
where available, in its determination of what data to use in developing
treatment standards. The methodology for comparing data is presented
later in this section.
1-15
-------
(Note: Facilities wishing to submit data for consideration in the
development of BOAT standards should, to the extent possible, provide
sampling information similar to that acquired by EPA. Such facilities
should review the Generic Quality Assurance Project Plan for the Land
Disposal Restrictions Program ("BOAT"), which delineates all of the
quality control and quality assurance measures associated with sampling
and analysis. Quality assurance and quality control procedures are
summarized in Section 1.2.6 of this document.)
(4) Sampling visit. The purpose of the sampling visit is to collect
samples that characterize the performance of the treatment system and to
document the operating conditions that existed during the waste treatment
period. At a minimum, the Agency attempts to collect sufficient samples
of the untreated waste and solid and liquid treatment residuals so that
variability in the treatment process can be accounted for in the
development of the treatment standards. To the extent practicable, and
within safety constraints, EPA or its contractors collect all samples and
ensure that chain-of-custody procedures are conducted so that the
integrity of the data is maintained.
In general, the samples collected during the sampling visit will have
already been specified in the SAP. In some instances, however, EPA will
not be able to collect all planned samples because of changes in the
facility operation or plant upsets; EPA will explain any such deviations
from the SAP in its follow-up onsite engineering report.
1-16
-------
(5) Onsite engineering report. EPA summarizes all its data
collection activities and associated analytical results for testing at a
facility in a report referred to as the onsite engineering report (OER).
This report characterizes the waste(s) treated, the treated residual
concentrations, the design and operating data, and all analytical results
including methods used and accuracy results. This report also describes
any deviations from EPA's suggested analytical methods for hazardous
wastes that appear in Test Methods for Evaluating Solid Waste, SW-846,
Third Edition, November 1986.
After the OER is completed, the report is submitted to the waste
generator and/or treater for review. This review provides a final
opportunity for claiming any information contained in the report as
confidential. Following the review and incorporation of comments, as
appropriate, the report is made available to the public with the
exception of any material claimed as confidential.
1.2.4 Hazardous Constituents Considered and Selected for Regulation
(1) Development of BDAT list. The list of hazardous constituents
within the waste codes that are targeted for treatment is referred to by
the Agency as the BDAT constituent list. This list, provided as
Table 1-1, is derived from the constituents presented in 40 CFR Part 261,
Appendices VII and VIII, as well as several ignitable constituents used
as the basis of listing wastes as F003 and F005. These sources provide a
1-17
-------
1521g
Table 1-1 UDAI Constituent List
BOAT
reference
no
222.
1 .
2.
3.
4.
5.
6.
223.
/.
8.
9.
10.
11.
12.
13.
14.
Ib.
16.
1.7.
18.
19.
20.
21.
22.
?3.
24.
25.
26.
27.
28.
29.
224.
225.
226.
30.
227.
31.
214.
32.
33.
228.
34.
Constituent
Volat i 1e orqanics
Acetone
Acetonitri le
Acrolein
Acrylonitrile
Benzene
Bromodichlorome thane
Bromomethane
n-Butyl alcohol
Carbon tetrach lor idu
Carbon disu If ide
Chlorobenzene
2-Chloro-l,3-butddiene
Chlorodibromomethane
Chloroethane
2-Chloroethyl vinyl ether
Chloroform
Chlorotnethane
3-Chloropropene
1 ,2-Dibromo-3-chloropropane
1.2-Dibromoethane
0 ibromome thane
trans-1 ,4-Dichloro-2-butene
Oichlorodif luoromethane
1 , 1-Oichloroethane
1 ,2-Dichloroethane
1.1-Dichloroethylene
trans-1 ,2-Oichloroethene
1 ,2-Dichloropropane
trans-1 ,3-Dichloropropene
cis-l,3-Dichloropropene
1.4-Dioxane
2-Ethoxyethanol
Ethyl acetate
Ethyl benzene
Ethyl cyanide
Ethyl ether
Ethyl methacrylate
Ethylene oxide
lodomethane
Isobutyl alcohol '
Hethano 1
Methyl ethyl ketone
CAS no.
67-64-1
75-05-8
107-02-8
107-13-1
71-43-2
75-27-4
74-83-9
71-36-3
56-23-5
75-15-0
108-90-7
12G-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
-------
IbZlg
table 1-1 (Continued)
UDAI
reference
no.
2?!).
35.
37.
38.
230.
39.
40.
41.
4?.
43.
44.
45.
46.
47.
48.
49.
231 .
50.
215.
216.
217.
51.
52.
53.
54.
55.
56.
57.
SB.
59.
Z18.
l>0.
61.
62.
63.
64.
55.
66.
Constituent
Volatile orqanics (continued)
Methyl isobutyl ketone
Methyl methacrylate
Methacrylonitri le
Methylene chloride
2-Nitropropane
Pyridine
1.1. 1 ,2-letrachloroethane
1 , 1 ,2,2-Tetrachloroethane
Tetrachloroethene
Toluene
Tribromomethane
1 . 1 , 1 - 1 r ich loroethane
1 ,1 ,2-Trichloroethane
Trichloroethene
Trichloromonof luoromethane
1 ,2,3-Trichloropropane
l,1.2-Trichloro-l,2,2-trif luoro-
ethane
Vinyl chloride
1.2-Xylene
1.3-Xylene
1.4 Xylene
Semivolat i le orqanics
Acenaphthalene
Acenaphthene
Acetophenone
2-Acety lam inof luorene
4-Aminobiphenyl
Aniline
Anthracene
Aratnite
Benz(a)anthracene
Benzal chloride
Benzenethiol
Deleted
Benzo(a)pyrene
Benzol 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
120-12-7
140-57-8
56-55-3
98-87-3
108-98-5
50-32-8
205-99-2
191-24-2
207-08-9
106-51-4
1-19
-------
fable 1-1 (Continued)
BUAI
reference
no.
67.
68.
uy.
70.
71.
72.
73.
74.
75.
76.
II .
78.
79.
80.
Bl .
«?.
232.
83.
84.
85.
86.
87.
8H.
89.
90.
91 .
92.
93.
94.
95.
96.
97.
98.
99.
100.
101.
102.
103.
104.
105.
106.
;;i9.
Const ituent
Semwolat i le orqanics (continued)
Bis(2-chloroethoxy)methane
Bis(2-chloroethyl (ether
Bis(2-chloroi sopropy 1 ) ether
Bis(2-ethylhexyl)phthalate
4- Bromophenyl phenyl ether
Butyl benzyl phthalate
2-sec-Buty 1-4 , 6-d in t tropheno 1
p-Chloroani 1 ine
Chlorobenz\ late
p-Chloro-m-cresol
2-Ch loronaphtha lene
2-Chlorophenol
3-Chloropropionitri le
Chrysene
ortho-Cresol
para-Cresol
Cyclohexanone
D ibenzl a. h) anthracene
0 i benzo ( a . e ) py rene
Dibenzo(a, i)pyrene
m D i ch lorobenzene
o-Dichlorobenzene
p-D ich lorobenzene
3,3'-Oichlorobenz id ine
2.4-Dichlorophenol
2,6-Dichlorophenol
Diethyl phthalate
3,3'-Dimethoxyben/ idine
p Dimethylaminoazobenzene
3,3'-D)tnethylbenzidine
2.4-Dimethylphenol
Dimethyl phthalate
Di-n-butyl phthalate
1 ,4-Oinitrobenzene
4 , 6-D in i tro-o-creso \
2,4-Dinitrophenol
2,4-Dinitrotoluene
2.6-Dinitrotoluene
Di-n-octyl phthalate
D i -n-propy In i trosam ine
Diphenylamine
Diphenylnitrosamin'e
CAS no.
111-91-1
111-44-4
39638-32-9
117-81-7
101-55-3
85-68-7
88-85-7
10B-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
192-6b-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
-------
15?)g
Table 1-1 (Continued)
«UA1
reference
no.
107.
lOb.
109.
110.
111.
112.
113.
114.
11!>.
116.
\\l.
113.
119.
120.
36.
121.
122.
123.
124.
125.
1?6.
127.
1?8.
129.
130.
131.
132.
133.
134.
135.
136.
137.
138.
139.
140.
141.
142.
<70.
143.
144.
145.
146.
Const ituent
Semivolat i le orqan ics (continued)
1 ,2-Diphenylhydrazine
F luoranthene
F luorene
Hexach lorobenzene
Hexach lorobutadiene
Hexachlorocyclopentadiene
Hexach loroethane
Hexach lorophene
Hexach loropropene
1 ndeno ( 1 , 2 , 3-cd ) py rene
Isosafrole
Methapyri lene
3-Methylcholanthrene
4.4' -Methylenebis
(2-chloroani 1 ine)
Methyl methanesulfonate
Naphthalene
1.4-Naphthoquinone
1-Naphthylamine
2-Naphthylamine
p-Nitroaniline
Nitrobenzene
4-Nitrophenol
N-Nitrosodi-n-butylamine
N-Nitrosodiethylamine
N-Nitrosodimethylamine
N-N i trosomethy lethy lamine
N-N itrosomorphol ine
N-Nitrosopiperidine
N-Nitrosopyrrolidine
5-NHro-o-toluidine
Pcntachlorobenzene
Pentach loroethane
Pen tach loron i t robenzene
Pentach loropheno 1
Phenacetin
Phenanthrene
Phenol
Phthal ic anhydride
2-Picoline
Pronamide
Pyrene
Resorcinol
CAS no.
122-66-7
206-44-0
86-73-7
118-74-1
87-68-3
77-47-4
67-72-1
70-30-4
1888-71-7
193-39-5
120-58-1
91-80-5
56-49-5
101-14-4
66-27-3
91-20 3
130-15-4
134-32-7
91-59-8
100-01-6
98-95-3
100-02-7
924-16-3
55-18-5
62-75-9
10595-95-6
59-89-2
100-75-4
930-55-2
99-65-8
608-93-5
76-01-7
82-68-8
87-86-5
62-44-2
85-01-8
108-95-2
85-44-9
109-06-8
23950-58-5
129-00-0
108-46-3
1-21
-------
1521q
Table 1 1 (Continued)
BDAr
reference
no.
147.
U8.
149.
150.
151.
152.
is:,.
154.
15b.
lb'5.
157.
158.
159.
221.
160.
161.
162.
163.
164.
165.
166.
!(>/.
1158.
169.
170.
171.
172.
1/3.
174.
1.75.
Constituent
Semivolat I le organ ics (continued)
Safrole
1,2,4, 5-Tetrach lorobenzene
2 , 3 , 4 , 6- Tet rach loropheno 1
1 ,2,4-Trichlorobenzene
2, 4. 5-T rich loropheno 1
2, 4, 6-Trich loropheno 1
T r i s ( 2 . 3-d i bromopropy 1 )
phosphate
Metals
Antimony
Arsenic
Ba r i urn
Beryll ium
Cadmium
Chromium (total)
Chromium (hexavalent)
Copper
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Inorganics other than metals
Cyanide
fluoride
Sulf ide
Organochlorine pesticides
Aldrin
a Ipha-BHC
beta-BHC
delta -BHC
CAS no.
94-59-7
95-94-3
58-90-2
120-82-1
95-95-4
88-06-2
126-72-7
7440-3B-0
7440-38-2
7440-39-3
7440-41-7
7440-43-9
7440-47-3
-
7440-50-8
7439-92-1
7439-97-6
7440-02-0
7782-49-2
7440-22 4
7440-28-0
7440-62-2
7440-66-6
57-12-5
16964-48-8
8496-25-8
309-00-2
319-84-6
319-85-7
319-86-8
1-22
-------
1521g
Table 1-1 (Continued)
BOAT
reference
no.
176.
177.
178.
179.
180.
181.
182.
183.
184.
18b.
186.
187.
18H.
IBS.
190.
191.
19;!.
193.
194.
195.
196.
197.
198.
199.
200.
201.
202.
203.
204.
205.
206.
Constituent
Orqanochlorine pesticides (continued)
gdimva-BHC
Chlordane
ODD
DOE
D01
Dieldrin
Endosulfan I
Endosulfan 11
Endr in
Enunn a Idehyde
Heptachlor
Meptachlor epoxide
Isodr in
Kepone
Methoxyclor
Toxaphene
Phenoxyacet ic acid herbicides
2,4-Dichlorophenoxyacetic acid
S i Ivex
2.4,5-T
Orqanophosphorous insecticides
Oisulfoton
Famphur
Methyl parathion
Parathion
Phorate
PCBs
Aroclor 1016
Aroclor 1221
Aroclor 1232
Aroclor 1242
Aroclor 1248
Aroclor 1254
Aroclor 1260
CAS no.
58-89-9
57-74-9
72-54-8
72-55-9
50-29-3
60-57-1
939-98-8
33213-6-5
72-20-8
7421-93-4
76-44-8
1024-57-3
465-73-6
143-50-0
72-43-5
8001-35-2
94-75-7
93-72-1
93-76-5
298-04-4
52-85-7
298-00-0
56-38-2
298-02-2
12674-11-2
11104-28-2
11141-16-5
53469-21-9
12672-29-6
11097-69-1
11096-82-5
1-23
-------
152!.g
Table 1-1 (Continued)
BOAT
reference Constituent CAS no.
no.
Dioxms and furans
207. Hexachlorodibenzo-p-dioxins
2015. Hexachlorodibenzofurans
209. Pentachlorodibenzo-p-dioxins
210. Pentachlorodibenzofurans
211. Tetrachlorodibenzo-p-dioxins
212. Tetrachlorodibenzofurans
213. 2.3.7.8-Ietrachlorodibenzo-p-dioxin 1746-01-6
1-24
-------
comprehensive list of hazardous constituents specifically regulated under
RCRA. The BOAT list consists of those constituents that can be analyzed
using methods published in SW-846, Third Edition.
The initial BOAT constituent list was published in EPA's Generic
Quality Assurance Project Plan for Land Disposal Restrictions Program
("BOAT") in March 1987. Additional constituents are added to the BOAT
constituent list as more key constituents are identified for specific
waste codes or as new analytical methods are developed for hazardous
constituents. For example, since the list was published in March 1987,
18 additional constituents (hexavalent chromium, xylenes (all three
isomers), benzal chloride, phthalic anhydride, ethylene oxide, acetone,
n-butyl alcohol, 2-ethoxyethanol, ethyl acetate, ethyl benzene, ethyl
ether, methanol, methyl isobutyl ketone, 2-nitropropane,
l,l,2-trichloro-l,2,2-trifluoroethane, and cyclohexanone) have been added
to the list.
Chemicals are listed in Appendix VIII if they are shown in scientific
studies to have toxic, carcinogenic, mutagenic, or teratogenic effects on
humans or other life-forms, and they include such substances as those
identified by the Agency's Carcinogen Assessment Group as being
carcinogenic. A waste can be listed as a toxic waste on the basis that
it contains a constituent in Appendix VIII.
Although Appendix VII, Appendix VIII, and the F003 and F005
ignitables provide a comprehensive list of RCRA-regulated hazardous
constituents, not all of the constituents can be analyzed in a complex
1-25
-------
waste matrix. Therefore, constituents that could not be readily analyzed
in an unknown waste matrix were not included on the initial BOAT
constituent list. As mentioned above, however, the BOAT constituent list
is a continuously growing list that does not preclude the addition of new
constituents when analytical methods are developed.
There are five major reasons that constituents were not included on
the BOAT constituent list:
1. Constituents are unstable. Based on their chemical structure,
some constituents will either decompose in water or will
ionize. For example, maleic anhydride will form maleic acid
when it comes in contact with water, and copper cyanide will
ionize to form copper and cyanide ions. However, EPA may choose
to regulate the decomposition or ionization products.
2. EPA-approved or verified analytical methods are not available.
Many constituents, such as 1,3,5-trinitrobenzene, are not
measured adequately or even detected using any of EPA's
analytical methods published in SW-846 Third Edition.
3. The constituent is a member of a chemical group .designated in
Appendix VIII as not otherwise specified (N.O.S.). Constituents
listed as N.O.S., such as chlorinated phenols, are a generic
group of some types of chemicals for which a single analytical
procedure is not available. The individual members of each such
group need to be listed to determine whether the constituents
can be analyzed. For each N.O.S. group, all those constituents
that can be readily analyzed are included in the BOAT
constituent list.
4. Available analytical procedures are not appropriate for a
complex waste matrix. Some compounds, such as auramine, can be
analyzed as a pure constituent. However, in the presence of
other constituents, the recommended analytical method does not
positively identify the constituent. The use of high
performance liquid chromatography (HPLC) presupposes a high
expectation of finding the specific constituents of interest.
In using this procedure to screen samples, protocols would have
to be developed on a case-specific basis to verify the identity
of constituents present in the samples. Therefore, HPLC is
usually not an appropriate analytical procedure for complex
samples containing unknown constituents.
1-26
-------
5. Standards for analytical instrument calibration are not
commercially available. For several constituents, such as
benz(c)acrid>ne, 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
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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 wonstituent 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.
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(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
wel1-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.
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There is an additional step in the calculation of the treatment
standards in those instances where the ANOVA analysis shows that more
than one technology achieves a level of performance that represents
BOAT. In such instances, the BOAT treatment standard for each
constituent of concern is calculated by first averaging the mean
performance value for each technology and then multiplying that value by
the highest variability factor among the technologies considered. This
procedure ensures that all the technologies used as the basis for the
BOAT treatment standards will achieve full compliance.
1.2.5 Compliance with Performance Standards
Usually the treatment standards reflect performance achieved by the
best demonstrated available technology (BOAT). As such, compliance with
these numerical standards requires only that the treatment level be
achieved prior to land disposal. It does not require the use of any
particular treatment technology. While dilution of the waste as a means
to comply with the standards is prohibited, wastes that are generated in
such a way as to naturally meet the standards can be land disposed
without treatment. With the exception of treatment standards that
prohibit land disposal, or that specify use of certain treatment methods,
all established treatment standards are expressed as concentration levels,
EPA is. using both the total constituent concentration and the
concentration of the constituent in the TCLP extract of the treated waste
as a measure of technology performance.
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For all organic constituents, EPA is basing the treatment standards
on the total constituent concentration found in the treated waste. EPA
is using this measurement because most technologies for treatment of
organics destroy or remove organics compounds. Accordingly, the best
measure of performance would be the total amount of constituent remaining
after treatment. (NOTE: EPA's land disposal restrictions for solvent
waste codes F001-F005 (51 FR 40572) use the TCLP extract value as a
measure of performance. At the time that EPA promulgated the treatment
standards for F001-F005, useful data were not available on total
constituent concentrations in treated residuals, and, as a result, the
TCLP data were considered to be the best measure of performance.)
For all metal constituents, EPA is using both total constituent
concentration and/or the TCLP extract concentration as the basis for
treatment standards. The total constituent concentration is being used
when the technology basis includes a metal recovery operation. The
underlying principle of metal recovery is that it reduces the amount of
metal in a waste by separating the metal for recovery; total constituent
concentration in the treated residual, therefore, is an important measure
of performance for this technology. Additionally, EPA also believes that
it is important that any remaining metal in a treated residual waste not
be in a state that is easily Teachable; accordingly, EPA is also using
the TCLP extract concentration as a measure of performance. It is
important to note that for wastes for which treatment standards are based
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on a metal recovery process, the facility has to comply with both the
total and the TCLP extract constituent concentrations prior to land
•
disposing the waste.
In cases where treatment standards for metals are not based on
recovery techniques but rather on stabilization, EPA is using only the
TCLP value as a measure of performance. The Agency's rationale is that
stabilization is not meant to reduce the concentration of metal in a
waste but only to chemically minimize the ability of the metal to leach.
1.2.6 Identification of BOAT
BOAT for a waste must be the "best" of the demonstrated available
technologies. EPA determines which technology constitutes "best" after
screening the available data from each demonstrated technology, adjusting
these data for accuracy, and comparing the performance of each
demonstrated technology to that of the others. If only one technology is
identified as demonstrated, it is considered "best"; if it is available,
the technology is BOAT.
(1) Screening of treatment data. The first activity in
determining which of the treatment technologies represent treatment by
BOAT is to screen the treatment performance data from each of the
demonstrated and available technologies according to the following
criteria:
1. Design and operating data associated with the treatment data
must reflect a well-designed, well-operated system for each
treatment data point. (The specific design and operating
parameters for each demonstrated technology for the waste
code(s) of interest are discussed in Section 3.2 of this
document.)
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2. Sufficient QA/QC data must be available to determine the true
values of the data from the treated waste. This screening
criterion involves adjustment of treated data to take into
account that the true value may be different from the measured
value. This discrepancy generally is caused by other
constituents in the waste that can mask results or otherwise
interfere with the analysis of the constituent of concern.
3. The measure of performance must be consistent with EPA's
approach to evaluating treatment by type of constituents (e.g.,
total concentration data for organics, and total concentration
and TCLP extract concentration for metals from the residual).
In the absence of data needed to perform the screening analysis, EPA
will make decisions on a case-by-case basis as to whether to use the data
as a basis for the treatment standards. The factors included in this
case-by-case analysis will be the actual treatment levels achieved, the
availability of the treatment data and their completeness (with respect
to the above criteria), and EPA's assessment of whether the untreated
waste represents the waste code of concern.
(2) Comparison of treatment data. In cases in which EPA has
treatment data from more than one demonstrated available technology
following the screening activity, EPA uses the statistical method known
as analysis of variance (ANOVA) to determine if one technology performs
significantly better than the others. This statistical method
(summarized in Appendix A) provides a measure of the differences between
two data sets. Specifically, EPA uses the analysis of variance to
determine whether BOAT represents a level of performance achieved by only
one technology or represents a level of performance achieved by more than
one (or all) of the technologies. If EPA finds that one technology
performs significantly better (i.e., is "best"), BOAT treatment standards
1-33
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are the level of performance achieved by that best technology multiplied
by the corresponding variability factor for each regulated constituent.
If the Agency finds that the levels of performance for one or more
technologies are not statistically different, EPA averages the
performance values achieved by each technology and then multiplies this
value by the largest variability factor associated with any of the
technologies.
(3) Quality assurance/quality control. ' This section presents the
principal quality assurance/quality control (QA/QC) procedures employed
in screening and adjusting the data to be used in the calculation of
treatment standards. Additional QA/QC procedures used in collecting and
screening data for the BOAT program are presented in EPA's Generic
Quality Assurance Pro.lect Plan for Land Disposal Restrictions Program
("BOAT"), EPA/530-SW-87-011.
To calculate the treatment standards for the land disposal restriction
rules, it is first necessary to determine the recovery value for each
constituent (the amount of constituent recovered after spiking—which is
the addition of a known amount of the constituent—minus the initial
concentration in the samples, all divided by the spike amount added) for
each spiked sample of the treated residual. Once the recovery values are
determined, the following procedures are used to select the appropriate
percent recovery value to adjust the analytical data:
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1. If duplicate spike recover" values are available for the
constituent of interest, tn= data are adjusted by the lowest
available percent recovery value (i.e., the value that will
yield the most conservative estimate of treatment achieved).
However, if a spike recovery value of less than 20 percent is
reported for a specific constituent, the data are not used to
set treatment standards because the Agency does not have
sufficient confidence in the reported value to set a national
standard.
2. If data are not available for a specific constituent but are
available for an isomer, then the spike recovery data are
transferred from the isomer and the data are adjusted using the
percent recovery selected according to the procedure described
in (1) above.
3. If data are not available for a specific constituent but are
available for a similar class of constituents (e.g., volatile
organics, acid-extractable semivolatiles), then spike recovery
data available for this class of constituents are transferred.
All spike recovery values greater than or equal to 20 percent
for a spike sample are averaged and the constituent
concentration is adjusted by the average recovery value. If
spiked recovery data are available for more than one sample, the
average is calculated for each sample and the data are adjusted
by using the lowest average value.
4. If matrix spike recovery data are not available for a set of
data to be used to calculate treatment standards, then matrix
spike recovery data are transferred from a waste that the Agency
believes is similar (e.g., if the data represent an ash from
incineration, then data from other incinerator ashes could be
used). While EPA recognizes that transfer of matrix spike
recovery data from a similar waste is not an exact analysis,
this is considered the best approach for adjusting the data to
account for the fact that most analyses do not result in
extraction of 100 percent of the constituent. In assessing the
recovery data to be transferred, the procedures outlined in (1),
(2), and (3) above are followed.
The analytical procedures employed to generate the data used to
calculate the treatment standards are listed in Appendix B of this
document, In cases where alternatives or equivalent procedures and/or
equipment are allowed in EPA's SW-846, Third Edition methods, the
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specific procedures and equipment used are documented. In addition, any
deviations from the SW-846, Third Edition methods used to analyze the
specific waste matrices are documented. It is important to note that the
Agency will use the methods and procedures delineated in Appendix B to
enforce the treatment standards presented in Section 7 of this document.
Accordingly, facilities should use these procedures in assessing the
performance of their treatment systems.
1.2.7 BOAT Treatment Standards for "Derived-From" and "Mixed" Wastes
(1) Wastes from treatment trains generating multiple residues. In a
number of instances, the proposed BOAT consists of a series of
operations, each of which generates a waste residue. For example, the
proposed BOAT for a certain waste code is based on solvent extraction,
steam stripping, and activated carbon adsorption. Each of these
treatment steps generates a waste requiring treatment — a
solvent-containing stream from solvent extraction, a stripper overhead,
and spent activated carbon. Treatment of these wastes may generate
further residues; for instance, spent activated carbon (if not
regenerated) could be incinerated, generating an ash and possibly a
scrubber water waste. Ultimately, additional wastes are generated that
may require land disposal. With respect to these wastes, the Agency
wishes to emphasize the following points:
1. All of the residues from treating the original listed wastes are
likewise considered to be the listed waste by virtue of the
derived-from rule contained in 40 CFR 261.3(c)(2). (This point
is discussed more fully in.(2) below.) Consequently, all of the
wastes generated in the course of treatment would be prohibited
from land disposal unless they satisfy the treatment standard or
meet one of the exceptions to the prohibition.
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2. The Agency's proposed treatment standards generally contain a
concentration level for wastewaters and a concentration level
for nonwastewaters. The treatment standards apply to all of the
wastes generated in treating the original prohibited waste.
Thus, all derived-from wastes meeting the Agency definition of
wastewater (less than 1 percent total organic carbon (TOC) and
less than 1 percent total suspended solids) would have to meet
the treatment standard for wastewaters. All residuals not
meeting this definition would have to meet the treatment
standard for nonwastewaters. EPA wishes to make clear that this
approach is not meant to allow partial treatment in order to
comply with the applicable standard.
3. The Agency has not performed tests, in all cases, on every waste
that can result from every part of the treatment train.
However, the Agency's treatment standards are based on treatment
of the most concentrated form of the waste. Consequently, the
Agency believes that the less concentrated wastes generated in
the course of treatment will also be able to be treated to meet
this value.
(2) Mixtures and other derived-from residues. There is a further
question as to the applicability of the BOAT treatment standards to
residues generated not from treating the waste (as discussed above), but
from other types of management. Examples are contaminated soil or
leachate that is'derived from managing the waste. In these cases, the
mixture is still deemed to be the listed waste, either because of the
derived-from rule (40 CFR 261.3(c)(2)(i)) or the mixture rule (40 CFR
261.3(a) (2}(iii) and (iv)) or because the listed waste is contained in
the matrix (see, for example, 40 CFR 261.33(d)). The prohibition for the
particular listed waste consequently applies to this type of waste.
The Agency believes that the majority of these types of residues can
meet the treatment standards for the underlying listed wastes (with the
possible exception of contaminated soil and debris for which the Agency
is currently investigating whether it is appropriate to establish a
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separate treatability subcategorization). For the most part, these
residues will be less concentrated than the original listed waste. The
Agency's treatment standards also make a generous allowance for process
variability by assuming that all treatability values used to establish
the standard are lognormally distributed. The waste also might be
amenable to a relatively nonvariable form of treatment technology such as
incineration. Finally, and perhaps most important, the rules contain a
treatability variance that allows a petitioner to demonstrate that its
waste cannot be treated to the level specified in the rule (40 CFR Part
268.44(a)). This provision provides a safety valve that allows persons
with unusual waste matrices to demonstrate the appropriateness of a
different standard. The Agency, to date, has not received any petitions
under this provision (for example, for residues contaminated with a
prohibited solvent waste), indicating, in the Agency's view, that the
existing standards are generally achievable.
(3) Residues from managing listed wastes or that contain listed
wastes. The Agency has been asked if and when residues from managing
hazardous wastes, such as leachate and contaminated ground water, become
subject to the land disposal prohibitions. Although the Agency believes
this question to be settled by existing rules and interpretative
statements, to avoid any possible confusion the Agency will address the
question again.
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Residue;; from managing First Third wastes, listed California List
wastes, and spent solvent and dioxin wastes are all considered to be
subject to the prohibitions for the listed hazardous waste as originally
generated. Residues from managing California List wastes likewise are
subject to the California List prohibitions when the residues themselves
exhibit a characteristic of hazardous waste. This determination stems
directly from the derived-from rule in 40 CFR 261.3(c)(2) or, in some
cases, from the fact that the waste is mixed with or otherwise contains
the listed waste. The underlying principle stated in all of these
provisions is that listed wastes remain listed until delisted.
The Agency's historic practice in processing delisting petitions that
address mixing residuals has been to consider them to be the listed waste
and to require that delisting petitioners address all constituents for
which the derived-from waste (or other mixed waste) was listed. The
language in 40 CFR 260.22(b) states that mixtures or derived-from
residues can be delisted provided a delisting petitioner makes a
demonstration identical to that which a delisting petitioner would make
for the original listed waste. Consequently, these residues are treated
as the original listed waste for delisting purposes. The statute
likewise takes this position, indicating that soil and debris that are
contaminated with listed spent solvents or dioxin wastes are subject to
the prohibition for these wastes even though these wastes are not the
originally generated waste, but rather are a residual from management
(RCRA section 3004(e)(3)). It is EPA's view that all such residues are
1-39
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covered by the existing prohibitions and treatment standards for the
listed hazardous waste that these residues contain or from which they are
derived.
1.2.8 Transfer of Treatment Standards
EPA is proposing some treatment standards that are not based on
testing of the treatment technology on the specific waste subject to the
treatment standard. The Agency has determined that the constituents
present in the untested waste can be treated to the same performance
levels as those observed in other wastes for which EPA has previously
developed treatment data. EPA believes that transferring treatment
performance data for use in establishing treatment standards for untested
wastes is technically valid in cases where the untested wastes are
generated from similar industries or processing steps, or have similar
waste characteristics affecting performance and treatment selection.
Transfer of treatment standards to similar wastes or wastes from similar
processing steps requires little formal analysis. However, in a case
where only the industry is similar, EPA more closely examines the waste
characteristics prior to deciding whether the untested waste constituents
can be treated to levels associated with tested wastes.
EPA undertakes a two-step analysis when determining whether
constituents in the untested wastes can be treated to the same level of
performance as in the tested waste. First, EPA reviews the available
waste characterization data to identify those parameters that are
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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
c-;se, a generator or owner/operator may submit a petition to the
Administrator requesting a variance from the treatment standard. A
particular waste may be significantly different from the wastes on which
the treatment standards are based because the subject waste contains a
more complex matrix that makes it more difficult to treat. For example,
complex mixtures may be formed when a restricted waste is mixed with
other waste streams by spills or other forms of inadvertent mixing. As a
result, the treatability of the restricted waste may be altered such that
it cannot meet the applicable treatment standard.
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Variance petitions must demonstrate that the treatment standard
established for a given waste cannot be met. This demonstration can be
made by showing that attempts to treat the waste by available
technologies were not successful or by performing appropriate analyses of
the waste, including waste characteristics affecting performance, which
demonstrate that the waste cannot be treated to the specified levels.
Variances will not be granted based solely on a showing that adequate
BOAT treatment capacity is unavailable. (Such demonstrations can be made
according to the provisions in Part 268.5 of RCRA for case-by-case
extensions of the effective date.) The Agency will consider granting
generic petitions provided that representative data are submitted to
support a variance for each facility covered by the petition.
Petitioners should submit at least one copy to:
The Administrator
U.S. Environmental Protection Agency
401 M Street, S.W.
Washington, DC 20460
An additional copy marked "Treatability Variance" should be submitted
to:
Chief, Waste Treatment Branch
Office of Solid Waste (WH-565)
U.S. Environmental Protection Agency
401 M Street, S.W.
Washington, DC 20460
Petitions containing confidential information should be sent with
only the inner envelope marked "Treatability Variance" and "Confidential
Business Information" and with the contents marked in accordance with the
1-42
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requirements of 40 CFR Part 2 (41 FR 36902, September 1, 1976, amended by
43 FR 4000).
The 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. INDUSTRIES AFFECTED AND WASTE CHARACTERIZATION
The purpose of this section is to discuss the rationale for dividing
the K086 listed waste into three treatability groups and to provide a
complete characterization of the K086 solvent wash by describing the
industry that generates the waste, the process generating the waste, and
the available data characterizing the waste.
According to 40 CFR 261.32, the waste identified as K086 is
specifically generated by ink formulating facilities and includes washes
and sludges from both solvent cleaning and caustic/water cleaning. When
viewed from a treatment perspective, these solvent washes, solvent
sludges, and caustic/water cleaning wastes are inherently different
because of the chemical and physical properties of the wastes. These
treatability groups have been divided as follows:
1. K086 solvent wash treatability group - Solvent washes from
cleaning tubs and equipment used in formulation of ink from
pigments, driers, soaps, and stabilizers containing chromium and
lead.
2. K086 solvent sludge treatability group - Solvent sludges from
cleaning tubs and equipment used in formulation of ink from
pigment, driers, soaps, and stabilizers containing chromium and
lead.
3. K086 caustic/water treatability group - Caustic washes and
sludges, or water washes and sludges from cleaning tubs and
equipment used in formulation of ink from pigments, driers,
soaps, and stabilizers containing chromium and lead.
The solvent wash treatability group has high organics concentrations
and a low filterable solids concentration; as a consequence, liquid
injection incineration can be applied. The solvent sludge treatability
group also has a high organic content, but does not allow for the use of
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liquid injection incineration because of a high solids content. The
caustic/water treatability group is considered by EPA as a wastewater
containing organics and metals for which EPA would evaluate technologies
other than incineration.
2.1 Industry Affected and Process Description
The Agency estimates that approximately 460 facilities formulate ink
and thus may generate K086 solvent wash waste. The locations of these
facilities are provided on Figure 2-1 by State and in Table 2-1 by State
and by EPA Region. While this waste can be generated in almost all of
the listed facilities, a large percentage of the facilities generating
K086 solvent wash are located in California, New Jersey, and the States
surrounding the Great Lakes.
Ink production involves the formulation of a desired product from
various raw materials. The blending process takes place in mixing tubs
ranging in size from 5 gallons to over 1,000 gallons. Because of the
demand for various types of inks having different properties, the inks
are made in batch operations.
Inks are a complex mixture of pigments, solvents, resins, soaps,
plasticizers, and stabilizers, combined to give the desired properties
for application. Many types of pigments and dyes are available to
produce any color ink, but certain inorganic pigments are the primary
source of lead and chromium. Chrome yellow is a compound consisting of
lead and hexavalent chromium. Molybdate orange contains lead, chromium,
and molybdenum.
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MARYLAND
1
HAWAII
FIGURE 2-1 GEOGRAPHICAL DISTRIBUTION OF INK MANUFACTURING SITES
REFERENCE: USEPA1979
-------
Table 2-1 Number of ink Fornvj'iators oy
State and by EPA Region
EPA Reci on State
1 Connecticut
Massachusetts
New Hampshire
Rhode Island
II New Jersey
New York
II! D.C.
Maryland
Pennsylvania
Virginia
IV Alabama
Florida
Georgia
Kentucky
Mississippi
North Carolina
South Carolina
Tennessee
V Illinois
Indiana
Michigan
Minnesota
. Ohio
Wisconsin
VI Arkansas
Louisiana
Oklahoma
Texas
VII Iowa
Kansas
Missouri
Nebraska
VIII Colorado
Utah
IX Arizona
California
Hawa i i
X Oregon
Washington
Number of
oroaucers
6
21
2
1
39
34
1
9
24
9
2
14
20
4
1
10
3
13
46
7
13
g
28
14
2
9
1
22
3
1
16
2
5
3
4
47
2
7
6
TOTAL :
Total number
of oroducers
30
73
43
67
117
34
22
6
53
13
_
460
Reference: UiEPA 1979 and U.S. Department of Commerce 1964.
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Ink formulation consists of batch mixing of the pigments, vehicles,
solvents, and other specialty additives (see Figure 2-2). The pigment
may be in either a powder or a paste form. Even dispersion is
accomplished by the use of ball mills, sand mills, or high speed mixers.
The wetted form of pigment does not require as much dispersion as the
powdered form. After each batch, the mills, mixers, and tubs must be
washed clean of all residuals in preparation for the next batch. The
method of equipment cleaning depends upon the type of ink produced.
In tubs used to formulate solvent-based or oil-based ink, solvent
washes are needed to remove the residuals. The solvent wash can be used
numerous times until the solvent becomes spent. The spent solvent can
then be used in the next batch of ink as part of the vehicle if the color
desired is compatible with that of the previous batches; otherwise, it
is disposed of as K086 solvent wash waste.
2.2 Waste Characterization
This section includes all waste characterization data available to
the Agency for the untreated K086 solvent wash waste. The approximate
percent concentrations of major constituents making up K086 solvent wash
are listed in Table 2-2. The percent concentration in the waste was
determined from the analyses of K086 solvent wash wastes presented in
Table 2-3. It is important to realize that the composition of the waste
can vary depending upon which solvent or solvents are used to clean the
ink formulating equipment.
2-5
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SOLVENT
WASH
PIGMENTS
VEHICLES
ro
MIXING
i
i
K086
SOLVENT
WASH
SOLVENT
WASH
MILLING
KOB6
SOLVENT
WASH
SOLVENTS
REDUCING
QUALITY
CONTROL
FILLING AND
SHIPPING
-»• PRODUCT
FIGURE 2-2 INK FORMULATION AND K086 WASTE GENERATION
-------
Table 2-2 Major Constituent Analysis of
Untreated IC086 Solvent Wash
Solvent wash
Major constituent concentration (wt. X)
Witer ent solvents (may be BOAT list organic constituents) 57.0
Total solids,3 2.4
a'These are volatile and nonvolatile solids remaining after the waste
has been heated to 103 to 105"C. The solids may be organic ink
pigments.
2-7
-------
1599g
Table 2-3 K086 Solvent Wash Characterization Data
BOAT
reference
no.
222
226
225
229
38
43
215-217
70
232
121
154
156
158
1S9
160
221
161
163
164
165
168
169
171
Untreated K086 solvent wash
waste concentration (mq/kq)
Analysis
BOAT Volatile Organics
Acetone
Ethylbenzene
Ethyl acetate
Methyl isobutyl ketone
Methylene chloride
Toluene
Xylene (Total)
BOAT Semivolati le Orqanics
bis(2-E thy lhexyl)phtha late
Cyclohexanone
Naphthalene
BOAT Metals
Antimony
Barium
Cadm i urn
Chromium
Copper
llexavalent chromium
Lead
Nickel
Selenium
Silver
Zinc
Other BOAT Inorganics
Cyanide
Sulfide
Other Parameters
pH
Total solids
Water content
Heating value (Btu/lb)
Total organic carbon
Ash content
Organic ink pigments
Ethyl alcohol
High flash point naphtha
compounds
(1)
CB1
CBI
-
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
-
-
CBI
(2)
-
-
256,000
-
-
-
-
-
-
-
-
0.54
4.3
116
17
-
1.06
2.4
0.05
0.32
1.1
-
-
6.3
5.700
-
13,600
-
-
77.000
667.000
~
CBI = Confidential Business Information.
= No analysis performed.
Reference sources:
(1) USEPA 1987a.
(2) USCPA 1985.
2-8
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3. APPLICABLE/DEMONSTRATED TREATMENT TECHNOLOGIES
This section identifies the applicable and demonstrated treatment
technologies for K086 solvent wash. Detailed discussions are provided
for those technologies that are demonstrated. Information on the
applicable and demonstrated treatment technologies comes from literature
sources, engineering site visits, and industry submittals.
3.1 Applicable Treatment Technologies
K086 solvent wash waste contains both BOAT list organics and BOAT
list metals; the technologies considered applicable are those that
destroy or recover the various BOAT list organic compounds and stabilize
or remove the various BDAT list metals.
K086 solvent wash waste primarily consists of the particular
solvent(s) used in the cleaning process; the waste also contains water,
metals, and solids, and has a high heating value, a high total organic
carbon (TOC) content, and a nondetectable ash content.
The applicable technologies that the Agency has identified for
treatment of BDAT list organics are incineration, batch distillation,
fractional distillation, and fuel substitution systems with air pollution
control devices. Incineration is a technology that destroys the organic
components in the waste. Batch distillation and fractional distillation
can be used to separate and recover components having different boiling
points. The distillation technologies reduce the amount of material to
be treated; nevertheless, residues from these processes still contain
3-1
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BOAT list organic concentrations and would still require further
treatment prior to land disposal. Fuel substitution, like incineration,
destroys the organic constituents in the waste. In fuel substitution,
however, fuel value is also derived from the waste. The fuel
substitution unit should be equipped with an air pollution control device
to eliminate potential emissions of lead and chromium in the stack gas.
Incineration of K086 solvent wash results in the formation of a
scrubber water treatment residual that may need metals treatment. For
the BOAT list metals present in the wastewater residual (i.e., scrubber
water), the applicable treatment technologies are chromium reduction
followed by chemical precipitation and removal of precipitated solids,
using settling or sludge filtration. Polishing filtration may also be
applicable if the solids formed are difficult to settle or remove by the
sludge filtration process. The chromium reduction process converts
hexavalent chromium to trivalent chromium. Chemical precipitation
removes dissolved metals from solution and settling/sludge filtration
removes suspended solids.
Treatment of the scrubber water generates a precipitated solids
residual that may also require treatment. For the BOAT list metals
present in these solid residuals, potentially applicable treatment
technologies are stabilization and high temperature metals recovery.
Stabilization immobilizes the metal constituents to minimize leaching.
High temperature metals recovery provides for recovery of metals from
wastes primarily by volatilization of some of the metals, subsequent
3-2
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condensation, and collection. The process yields a metal product for
reuse and reduces the amount of waste that needs to be land disposed.
It is important to mention that stabilization can be incorporated as
part of the chemical precipitation process by the addition of excess lime
in concentrations significantly greater than the stoichiometric amount;
this treatment is sometimes referred to as lime stabilization. In some
instances, when lime stabilization of the precipitated residual is
performed as part of the chemical precipitation process, sludge
filtration is the only additional treatment step necessary to minimize
the Teachability of the metals in the precipitated/stabilized waste. EPA
considers the combined process to be effectively the same as
stabilization of the precipitated residuals, and will refer to the
combination process as stabilization in the context of treatment for
nonwastewaters. Relative to wastewaters, this treatment is chemical
precipitation, as already discussed.
3.2 Demonstrated Treatment Technologies
The Agency believes that all the applicable technologies for organics
treatment are demonstrated to treat K086 solvent wash since they are
currently used to treat such wastes. The Agency has identified at least
one facility using incineration, one facility using batch distillation,
one facility using fractional distillation, and one facility using fuel
substitution.
3-3
-------
The Agency has not identified any facilities using chromium reduction
followed by chemical precipitation and settling or sludge filtration on
the scrubber water generated by incineration of K086 solvent wash. This
treatment, however, is demonstrated on a metal-bearing wastewater that
has similar parameters affecting treatment selection, and thus the Agency
considers the treatment to be demonstrated for the K086 scrubber water.
Performance data for chromium reduction, precipitation, and sludge
filtration of the metal-bearing wastewater are presented in Section 4. A
comparison of these data to those of the K086 scrubber water shows that
the parameters affecting treatment selection are similar.
The Agency has not identified any facilities using stabilization on
the precipitate that would be generated by treatment of K086 scrubber
water generated during incineration of K086 solvent wash. Stabilization,
however, is used on a full-scale basis to treat metals in wastes (e.g.,
Envirite wastewater treatment precipitates) that have similar parameters
affecting treatment selection. Thus, the Agency considers stabilization
to be demonstrated for K086 wastewater treatment precipitates.
Stabilization is described in Section 3.2.3. Performance data for
stabilization of waste are presented in Section 4.
High temperature metals recovery has been identified as potentially
applicable for treatment of K086 precipitated solids. At this time, EPA
does not have any treatment performance data for high temperature metals
recovery of wastewater treatment precipitated solids that would be
3-4
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similar to the K086 precipitated solids. EPA will continue to
investigate the application and demonstration of high temperature metals
recovery for such treated residual wastes.
Detailed discussions of the high temperature metals recovery and the
demonstrated technologies, including incineration, fuel substitution,
stabilization, chromium reduction, chemical precipitation, polishing
filtration, and sludge filtration, are presented below.
3.2.1 Incineration
This section addresses the commonly used incineration technologies:
liquid injection, rotary kiln, fluidized bed, and fixed hearth. A
discussion is provided regarding the applicability of these technologies,
the underlying principles of operation, a technology description, waste
characteristics that affect performance, and, finally, important design
and operating parameters. As appropriate, the subsections are divided by
type of incineration unit.
(1) Applicability and use of incineration.
(a) Liquid injection. Liquid injection is applicable to wastes
that have viscosity values low enough that the waste can be atomized in
the combustion chamber. A range of literature maximum viscosity values
is reported, with the low being 100 Saybolt seconds universal (SSU) and
the high being 10,000 SSU. It is important to note that viscosity is
temperature dependent so that while liquid injection may not be
applicable to a waste at ambient conditions, it may be applicable when
3-5
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the waste is heated. Other factors that affect the use of liquid
injection are particle size and the presence of suspended solids. Both
of these waste parameters can cause plugging of the burner nozzle.
(b) Rotary kiln/fluidized bed/fixed hearth. These incineration
technologies are applicable to a wide range of hazardous wastes. They
can be used on wastes that contain high or low total organic content,
high or low filterable solids, various viscosity ranges, and a range of
other waste parameters. EPA has not found these technologies to be
demonstrated on wastes that are composed essentially of metals with low
organic concentrations. In addition, the Agency expects that air
emissions from incinerating some of the high metal content wastes may not
be compatible with existing and future air emission limits without
emission controls far more extensive than those currently in use.
(2) Underlying principles of operation.
(a) Liquid injection. The basic operating principle of this
incineration technology is that incoming liquid wastes are volatilized
and then additional heat is supplied to the waste to destabilize the
chemical bonds. Once the chemical bonds are broken, these constituents
react with oxygen to form carbon dioxide and water vapor. The energy
needed to destabilize the bonds is referred to as the energy of
activation.
(b) Rotary kiln and fixed hearth. There are two distinct
principles of operation for these incineration technologies, one for each
of the chambers involved. In the primary chamber, energy, in the form of
3-6
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heat, is transferred to the waste to achieve volatilization of the
various organic waste constituents. During this volatilization process
some of the organic constituents will oxidize to carbon dioxide and water
vapor. In the secondary chamber, additional heat is supplied to overcome
the energy requirements needed to destabilize the chemical bonds and
allow the constituents to react with excess oxygen to form carbon dioxide
and water vapor. The principle of operation for the secondary chamber is
similar to that of liquid injection.
(c) Fluidized bed. The principle of operation for this
incineration technology is somewhat different from that for rotary kiln
and fixed hearth incineration relative to the functions of the primary
and secondary chambers. In fluidized bed incineration, the purpose of
the primary chamber is not only to volatilize the wastes but also to
combust the waste. Destruction of the waste organics can be accomplished
to a better degree in the primary chamber of a fluidized bed incinerator
than in that of a rotary kiln or a fixed hearth incinerator because of
(1) improved heat transfer from fluidization of the waste using forced
air and (2) the fact that the fluidization process provides sufficient
oxygen and turbulence to convert the organics to carbon dioxide and water
vapor. The secondary chamber (referred to as the freeboard) generally
does not have an afterburner; however, additional time is provided for
conversion of the organic constituents to carbon dioxide, water vapor,
and hydrochloric acid if chlorine is present in the waste.
3-7
-------
(3) Description of the incineration process.
(a) Liquid injection. The liquid injection system is capable
of incinerating a wide range of gases and liquids. The combustion system
has a simple design with virtually no moving parts. A burner or nozzle
atomizes the liquid waste and injects it into the combustion chamber,
where it burns in the presence of air or oxygen. A forced draft system
supplies the combustion chamber with air to provide oxygen for combustion
and turbulence for mixing. The combustion chamber is usually a cylinder
lined with refractory (i.e., heat-resistant) brick and can be fired
horizontally, vertically upward, or vertically downward. Figure 3-1
illustrates a liquid injection incineration system.
(b) Rotary kiln. A rotary kiln is a slowly rotating,
refractory-lined cylinder that is mounted at a slight incline from the
horizontal (see Figure 3-2). Solid wastes enter at the high end of the
kiln, and liquid or gaseous wastes enter through atomizing nozzles in the
kiln or afterburner section. Rotation of the kiln exposes the solids to
the heat, vaporizes them, and allows them to combust by mixing with air.
The rotation also causes the ash to move to the lower end of the kiln,
where it can be removed. Rotary kiln systems usually have a secondary
combustion chamber or afterburner following the kiln for further
combustion of the volatilized components of solid wastes.
(c) Fluidized bed. A fluidized bed incinerator consists of a
column containing inert particles such as sand, which is referred to as
the bed. Air, driven by a blower, enters the bottom of the bed to
3-8
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WATER
AUXILIARY FUEL
BURNER
AIR-
i
vo
LIQUID OR GASEOUS.
WASTE INJECTION
'{BURNER
PRIMARY
COMBUSTION
CHAMBER
AFTERBURNER
(SECONDARY
COMBUSTION
CHAMBER)
SPRAY
CHAMBER
J
I
GAS TO AIR
POLLUTION
CONTROL
HORIZONTALLY FIRED
LIQUID INJECTION
INCINERATOR
ASH
WATER
FIGURE 3-1
LIQUID INJECTION INCINERATOR
-------
GAS TO
AIR POLLUTION
CONTROL
AUXILIARY
FUEL
SOLID
WASTE
INFLUENT
FEED
MECHANISM
COMBUSTION
GASES
LIQUID OR
GASEOUS
WASTE
INJECTION
ASH
FIGURE 3-2
ROTARY KILN INCINERATOR
3-10
-------
fluidize the sand. Air passage through the bed promotes rapid and
uniform mixing of the injected waste material within the fluidized bed.
The fluidized bed has an extremely high heat capacity (approximately
three times that of flue gas at the same temperature), thereby providing
a large heat reservoir. The injected waste reaches ignition temperature
quickly and transfers the heat of combustion back to the bed. Continued
bed agitation by the fluidizing air allows larger particles to remain
suspended in the combustion zone (See Figure 3-3).
(d) Fixed hearth. Fixed hearth incineration, also called
controlled air or starved air incineration, is another major technology
used for hazardous waste incineration. Fixed hearth incineration is a
two-stage combustion process (see Figure 3-4). Waste is ram-fed into the
first stage, or primary chamber, and burned at less than stoichiometric
conditions. The resultant smoke and pyrolysis products, consisting
primarily of volatile hydrocarbons and carbon monoxide, along with the
normal products of combustion, pass to the secondary chamber. Here,
additional air is injected to complete the combustion. This two-stage
process generally yields low stack particulate and carbon monoxide (CO)
emissions. The primary chamber combustion reactions and combustion gas
are maintained at low levels by the starved air conditions so that
particulate entrainment and carryover are minimized.
(e) Air pollution controls. Following incineration of
hazardous wastes, combustion gases are generally further treated in an
air pollution control system. The presence of chlorine or other halogens
3-11
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WASTE
INJECTION
BURNER
FREEBOARD
SAND BED
GAS TO
AIR POLLUTION
CONTROL
MAKE-UP
SAND
AIR
ASH
FIGURE 3-3
FLUIDIZED BED INCINERATOR
3-12
-------
AIR
GAS TO AIR
POLLUTION
CONTROL
AIR
co
H-*
CO
WASTE
INJECTION
BURNER
1
PRIMARY
COMBUSTION
CHAMBER
GRATE
SECONDARY
COMBUSTION
CHAMBER
I
AUXILIARY
FUEL
2-STAGE FIXED HEARTH
INCINERATOR
ASH
FIGURE 3-4
FIXED HEARTH INCINERATOR
-------
in the waste requires a scrubbing or absorption step to remove
hydrochloric acid and other halo-acids from the combustion gases. Ash in
the waste is not destroyed in the combustion process. Depending on its
composition, ash will exit either as bottom ash, at the discharge end of
a kiln or hearth, for example, or as particulate matter (fly ash)
suspended in the combustion gas stream. Particulate emissions from most
hazardous waste combustion systems generally have particle diameters of
less than 1 micron and require high-efficiency collection devices to
minimize air emissions. In addition, scrubber systems provide an
additional buffer against accidental releases of incompletely destroyed
waste products, which result from poor combustion efficiency or
combustion upsets, such as flameouts.
(4) Waste characteristics affecting performance.
(a) Liquid injection. In determining whether liquid injection
is likely to achieve the same level of performance on an untested waste
as on a previously tested waste, the Agency will compare dissociation
bond energies of the constituents in the untested and tested wastes.
This parameter is being used as a surrogate indicator of activation
energy, which, as discussed previously, destabilizes molecular bonds. In
theory, the bond dissociation energy would be equal to the activation
energy; in practice, however, this is not always the case. Other energy
effects (e.g., vibrational effects, the formation of intermediates, and
interactions between different molecular bonds) may have a significant
influence on activation energy.
3-14
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Because of the shortcomings of bond energies in estimating activation
energy, EPA analyzed other waste characteristic parameters to determine
whether these parameters would provide a better basis for transferring
treatment standards from an untested waste to a tested waste. These
parameters include heat of combustion, heat of formation, use of
available kinetic data to predict activation energies, and general
structural class. All of these parameters were rejected for the reasons
provided below.
The heat of combustion measures only the difference in energy of the
products and reactants; it does not provide information on the transition
state (i.e., the energy input needed to initiate the reaction). Heat of
formation is used as a tool to predict whether reactions are likely to
proceed; however, there are a significant number of hazardous
constituents for which these data are not available. Use of kinetic data
was rejected because these data are limited and could not be used to
calculate free energy values (AG) for the wide range of hazardous
constituents to be addressed by this rule. Finally, EPA decided not to
use structural classes because the Agency believes that evaluation of
bond dissociation energies allows for a more direct determination of
whether a constituent will be destabilized.
(b) Rotary kiln/fluidized bed/fixed hearth. Unlike liquid
injection, these incineration technologies also generate a residual ash.
Accordingly, in determining whether these technologies are likely to
3-15
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achieve the same level of performance on an untested waste as on a
previously tested waste, EPA would need to examine the waste
characteristics that affect volatilization of organics from the waste, as
well as destruction of the organics once volatilized. Relative to
volatilization, EPA will examine thermal conductivity of the entire waste
and boiling point of the various constituents. As with liquid injection,
EPA will examine bond energies in determining whether treatment standards
for scrubber water residuals can be transferred from a tested waste to an.
untested waste. Below is a discussion of how EPA arrived at thermal
conductivity and boiling point as the best methods to assess
volatilization of organics from the waste; the discussion relative to
bond energies is the same for these technologies as for liquid injection
and will not be repeated here.
(i) Thermal conductivity. Consistent with the underlying
principles of incineration, a major factor with regard to whether a
particular constituent will volatilize is the transfer of heat through
the waste. In the case of rotary kiln, fluidized bed, and fixed hearth
incineration, heat is transferred through the waste by three mechanisms:
radiation, convection, and conduction. For a given incinerator, heat
transferred through various wastes by radiation is more a function of the
design and type of incinerator than of the waste being treated.
Accordingly, the type of waste treated will have a minimal impact on the
amount of heat transferred by radiation. With regard to convection, EPA
3-16
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also believes that the type of heat transfer will generally be more a
function of the type and design of the incinerator than of the waste
itself. However, EPA is examining particle size as a waste
characteristic that may significantly impact the amount of heat
transferred to a waste by convection and thus impact volatilization of
the various organic compounds. The final type of heat transfer,
conduction, is the one that EPA believes will have the greatest impact on
volatilization of organic constituents. To measure this characteristic,
EPA will use thermal conductivity; an explanation of this parameter, as
well as how it can be measured, is provided below.
Heat flow by conduction is proportional to the temperature gradient
across the material. The proportionality constant is a property of the
material is referred to as the thermal conductivity. (Note: The
analytical method that EPA has identified for measurement of thermal
conductivity is named "Guarded, Comparative, Longitudinal Heat Flow
Technique"; it is described in Appendix D.) In theory, thermal
conductivity would always provide a good indication of whether a
constituent in an untested waste would be treated to the same extent in
the primary incinerator chamber as the same constituent in a previously
tested waste.
In practice, thermal conductivity has some limitations in assessing
the transferability of treatment standards; however, EPA has not
identified a parameter that can provide a better indication of the heat
transfer characteristics of a waste. Below is a discussion of both the
3-17
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limitations associated with thermal conductivity and the other parameters
considered.
Thermal conductivity measurements, as part of a treatability
comparison for two different wastes through a single incinerator, are
most meaningful when applied to wastes that are homogeneous (i.e., major
constituents are essentially the same). As wastes exhibit greater
degrees of nonhomogeneity (e.g., significant concentration of metals in
soil), then thermal conductivity becomes less accurate in predicting
treatability because the measurement essentially reflects heat flow
through regions having the greatest conductivity (i.e., the path of least
resistance) and not heat flow through all parts of the waste.
Btu value, specific heat, and ash content were also considered for
predicting heat transfer characteristics. These parameters can no better
account for nonhomogeneity than can thermal conductivity; additionally,
they are not directly related to heat transfer characteristics.
Therefore, these parameters do not provide a better indication of the
heat transfer that will occur in any specific waste.
(ii) Boil ing point. Once heat is transferred to a constituent
within a waste, removal of this constituent from the waste will depend on
its volatility. EPA is using boiling point as a surrogate for volatility
of the constituent. Compounds with lower boiling points have higher
vapor pressures and therefore would be more likely to vaporize. The
Agency recognizes that this parameter does not take into consideration
3-18
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the impact of other compounds in the waste on the boiling point of a
constituent in a mixture; -however, the Agency is not aware of a better
measure of volatility that can easily be determined.
(5) Design and operating parameters.
(a) Liquid injection. For a liquid injection unit, EPA's
analysis of whether the unit is well designed will focus on (1) the
likelihood that sufficient energy is provided to the waste to overcome
the activation level for breaking molecular bonds and (2) whether
sufficient oxygen is present to convert the waste constituents to carbon
dioxide and water vapor. The specific design parameters that the Agency
will evaluate to assess whether these conditions are met are temperature,
excess oxygen, and residence time. Below is a discussion of why EPA
believes these parameters to be important, as well as a discussion of how
these parameters will be monitored during operation.
It is important to point out that, relative to the development of
land disposal restriction standards, EPA is concerned with these design
parameters only when a quench water or scrubber water residual is
generated from treatment of a particular waste. If treatment of a
particular waste in a liquid injection unit would not generate a
wastewater stream, then the Agency, for purposes of land disposal
treatment standards, would be concerned only with the waste
characteristics that affect selection of the unit, not with the
above-mentioned design parameters.
3-19
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(i) Temperature. Temperature is important in that it provides
an indirect measure of the energy available (i.e., Btu/hr) to overcome
the activation energy of waste constituents. As the design temperature
increases, it is more likely that the molecular bonds will be
destabilized and the reaction completed.
The temperature is normally controlled automatically through the use
of instrumentation that senses the temperature and automatically adjusts
the amount of fuel and/or waste being fed. The temperature signal
transmitted to the controller can be simultaneously transmitted to a
recording device, referred to as a strip chart, and thereby continuously
recorded. To fully assess the operation of the unit, it is important to
know not only the exact location in the incinerator at which the
temperature is being monitored but also the location of the design
temperature.
(ii) Excess oxygen. It is important that the incinerator
contain oxygen in excess of the stoiochiometric amount necessary to
convert the organic compounds to carbon dioxide and water vapor. If
insufficient oxygen is present, then destabilized waste constituents
could recombine to the same or other BOAT list organic compounds and
potentially cause the scrubber water to contain higher concentrations of
BOAT list constituents than would be the case for a well-operated unit.
In practice, the amount of oxygen fed to the incinerator is
controlled by continuous sampling and analysis of the stack gas. If the
amount of oxygen drops below the design value, then the analyzer
transmits a signal to the valve controlling the air supply and thereby
3-20
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increases the flow of oxygen to the afterburner. The analyzer
simultaneously transmits a signal to a recording device so that the
amount of excess oxygen can be continuously recorded. Again, as with
temperature, it is important to know the location from which the
combustion gas is being sampled.
(iii) Carbon monoxide. Carbon monoxide is an important
operating parameter because it provides an indication of the extent to
which the waste organic constituents are being converted to carbon
dioxide and water vapor. An increase in the carbon monoxide level
indicates that greater amounts of organic waste constituents are
unreacted or partially reacted. Increased carbon monoxide levels can
result from insufficient excess oxygen, insufficient turbulence in the
combustion zone, or insufficient residence time.
(iv) Waste feed rate. The waste feed rate is important to
monitor because it is correlated to the residence time. The residence
time is associated with a specific Btu energy value of the feed and a
specific volume of combustion gas generated. Prior to incineration, the
Btu value of the waste is determined through the use of a laboratory
device known as a bomb calorimeter. The volume of combustion gas
generated from the waste to be incinerated is determined from an analysis
referred to as an ultimate analysis. This analysis determines the amount
of elemental constituents present, which include carbon, hydrogen,
sulfur, oxygen, nitrogen, and halogens. Using results from this analysis
plus considering the total amount of air added, one can calculate the
volume of combustion gas. After both the Btu content and the expected
3-21
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combustion gas volume have been determined, the feed rate can be fixed at
the desired residence time. Continuous monitoring of the feed rate will
determine whether the unit was operated at a rate corresponding to the
designed residence time.
(b) Rotary kiln. For this incineration, EPA will examine both
the primary and secondary chamber in evaluating the design of a
particular incinerator. Relative to the primary chamber, EPA's
assessment of design will focus on whether sufficient energy is likely to
be provided to the waste to volatilize the waste constituents. For the
secondary chamber, analogous to the sole liquid injection incineration
chamber, EPA will examine the same parameters discussed previously under
liquid injection incineration. These parameters will not be discussed
again here.
The particular design parameters to be evaluated for the primary
chamber are kiln temperature, residence time, and revolutions per
minute. Below is a discussion of why EPA believes these parameters to be
important, as well as a discussion of how these parameters will be
monitored during operation.
(i) Temperature. The primary chamber temperature is important,
in that it provides an indirect measure of the energy input (i.e.,
Btu/hr) available for heating the waste. The higher the temperature is
designed to be in a given kiln, the more likely it is that the
constituents will volatilize. As discussed earlier under "Liquid
Injection," temperature should be continuously monitored and recorded.
3-22
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Additionally, it is important to know the location of the
temperature-sensing device in the kiln.
(ii) Residence time. This parameter is important in that it
affects whether sufficient heat is transferred to a particular
constituent in order for volatilization to occur. As the time that the
waste in the kiln is increased, a greater quantity of heat is transferred
to the hazardous waste constituents. The residence time will be a
function of the specific configuration of the rotary kiln, including the
length and diameter of the kiln, the waste feed rate, and the rate of
rotation.
(iii) Revolutions per minute (RPM). This parameter provides an
indication of the turbulence that occurs in the primary chamber of a
rotary kiln. As the turbulence increases, the quantity of heat
transferred to the waste is also be expected to increase. However, as
the RPM value increases, the residence time decreases, resulting in a
reduction of the quantity of heat transferred to the waste. This
parameter needs to be carefully evaluated because it provides a balance
between turbulence and residence time.
(c) Fluidized bed. As discussed previously in the section
"Underlying principles of operation," the primary chamber accounts for
almost all of the conversion of organic wastes to carbon dioxide, water
vapor, and acid gas (if halogens are present). The secondary chamber
will generally provide additional residence time for thermal oxidation of
the waste constituents. Relative to the primary chamber, the parameters
that the Agency will examine in assessing the effectiveness of the design
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are temperature, residence time, and bed pressure differential. The
first two were included in the discussion of the rotary kiln and will not
be discussed here. The last, bed pressure differential, is important in
that it provides an indication of the amount of turbulence and therefore
indirectly the amount of heat supplied to the waste. In general, as the
pressure drop increases, both the turbulence and heat supplied increase.
The pressure drop through the bed should be continuously monitored and
recorded to ensure that the design value is achieved.
(d) Fixed hearth. The design considerations for this
incineration unit are similar to those for a rotary kiln with the
exception that rate of rotation (i.e., RPM) is not an applicable design
parameter. For the primary chamber of this unit, the parameters that the
Agency will examine in assessing how well the unit is designed are the
same as those discussed under "Rotary kiln"; for the secondary chamber
(i.e., afterburner), the design and operating parameters of concern are
the same as those previously discussed under "Liquid injection."
3.2.2 Fuel Substitution
Fuel substitution involves using hazardous waste as a fuel in
industrial furnaces or in boilers for generation of steam. The hazardous
waste may be blended with nonhazardous wastes (e.g., municipal sludge)
and/or fossil fuels.
(1) Applicability and use of fuel substitution. Fuel substitution
has been used with industrial waste solvents, refinery wastes, synthetic
fibers/petrochemical wastes, and waste oils. It can also be used when
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combusting other waste types produced during the manufacture of
Pharmaceuticals, pulp and paper, and pesticides. These wastes can be
handled in a solid, liquid, or gaseous form.
The most common types of units in which waste fuels are burned are
industrial furnaces and industrial boilers. Industrial furnaces include
a diverse variety of industrial processes that produce heat and/or
products by burning fuels. They include blast furnaces, smelters, and
coke ovens. Industrial boilers are units wherein fuel is used to produce
steam for process and plant use. Industrial boilers typically use coal,
oil, or gas as the primary fuel source.
A number of parameters affect the selection of fuel substitution.
These parameters are as follows:
• Halogen content of the waste;
• Inorganic solids content (ash content) of the waste,
particularly heavy metals;
• Heating value of the waste;
• Viscosity of the waste (for liquids);
• Filterable solids concentration (for liquids); and
• Sulfur content.
If halogenated organics are burned, halogenated acids and free
halogen are among the products of combustion. These released corrosive
gases may require subsequent treatment prior to venting to the
atmosphere. Also, halogens and halogenated acids formed during
combustion are likely to severely corrode boiler tubes and other process
equipment. For this reason, halogenated wastes are blended into fuels
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only at very low concentrations to minimize such problems. High chlorine
content can also lead to the incidental production (at very low
concentrations) of other hazardous compounds such as polychlorinated
biphenyls (PCBs), polychlorinated dibenzo-p-dioxins (PCDDs), chlorinated
dibenzofurans (PCDFs), and polychlorinated phenols.
High inorganic solids content (i.e., ash content) of wastes may cause
two problems: (1) scaling in the boiler and (2) particulate air
emissions.' Scaling results from deposition of inorganic solids on the
walls of the boiler. Particulate emissions are produced by
noncombustible inorganic constituents that flow out of the boiler with
the gaseous combustion products. Because of these problems, wastes with
significant concentrations of inorganic materials are not usually handled
in boilers unless the boilers have an air pollution control system.
Industrial furnaces vary in their tolerance to inorganic
constituents. Heavy metal concentrations, found in both halogenated and
nonhalogenated wastes used as fuel, can cause environmental concern
because they may be emitted in the gaseous emissions from the combustion
process, in the ash residues, or in any produced solids. The
partitioning of the heavy metals to these residual streams primarily
depends on the volatility of the metal, waste matrix, and furnace design.
The heating value of the waste must be sufficiently high (either
alone or in combination with other fuels) to maintain combustion
temperatures consistent with efficient waste destruction and operation of
the boiler or furnace. For many applications, only supplemental fuels
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having minimum heating values of 4,400 to 5,600 kcal/kg (8,000 to 10,000
Btu/lb) are considered to be feasible. Below this value, the unblended
fuel would not be likely to maintain a stable flame and its combustion
would release insufficient energy to provide needed steam generation
potential in the boiler or the necessary heat for an industrial furnace.
Some wastes with heating values of less than 4,400 kcal/kg (8,000 Btu/lb)
can be used if sufficient auxiliary fuel is employed to support
combustion or if special designs are incorporated into the combustion
device. Occasionally, for wastes with heating values higher than those
of virgin fuels, blending with auxiliary fuel may be required to prevent
overheating or overcharging the combustion device.
In combustion devices designed to burn liquid fuels, the viscosity of
liquid waste must be low enough that the liquid can be atomized in the
combustion chamber. If viscosity is too high, heating of storage tanks
may be required prior to combustion. For atomization of liquids, a
viscosity of 165 centistokes (750 Saybolt Seconds Universal (SSU))) or
less is typically required.
Filterable material suspended in the liquid fuel may prevent or
hinder pumping or atomization.
Sulfur content in the waste may prevent burning of the waste because
of potential atmospheric emissions of sulfur oxides. For instance, there
are proposed Federal sulfur oxide emission regulations for certain new
source industrial boilers (51 FR 22385). Air pollution control devices
are available to remove, sulfur oxides from the stack gases.
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(2) Underlying principles of operation. For a boiler and most
industrial furnaces, there -are two distinct principles of operation.
Initially, energy in the form of heat is transferred to the waste to
achieve volatilization of the various waste constituents. For liquids,
volatilization energy may also be supplied by using pressurized
atomization. The energy used to pressurize the liquid waste allows the
atomized waste to break into smaller particles, thus enhancing its rate
of volatilization. The volatilized constituents then require additional
energy to destabilize the chemical bonds and allow the constituents to
react with oxygen to form carbon dioxide and water vapor. The energy
needed to destabilize the chemical bonds is referred to as the energy of
activation.
(3) Description of the fuel substitution process. As stated, a
number of industrial applications can use fuel substitution. Therefore,
there is no one process description that will fit all of these
applications. However, the following section provides a general
description of industrial kilns (one form of industrial furnace) and
industrial boilers.
(a) Kilns. Combustible wastes have the potential to be used as
fuel in kilns and, for waste liquids, are often used with oil to co-fire
kilns. Goal-fired kilns are capable of handling some solid wastes. In
the case of cement kilns, there are usually no residuals requiring land
disposal since any ash formed becomes part of the product or is removed
by participate collection systems and recycled back to the kiln. The
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only residuals may be low levels of unburned gases escaping with
combustion products. If this is the case, air pollution control devices
may be required.
Three types of kilns are particularly applicable: cement kilns, lime
kilns, and lightweight aggregate kilns.
(i) Cement kilns. The cement kiln is a rotary furnace, which
is a refractory-lined steel shell used to calcine a mixture of calcium,
silicon, aluminum, iron, and magnesium-containing minerals. The kiln is
normally fired by coal or oil. Liquid and solid combustible wastes may
then serve as auxiliary fuel. Temperatures within the kiln are typically
between 1,380 and 1,540°C (2,500 to 2,800°F). To date, only
liquid hazardous wastes have been burned in cement kilns.
Most cement kilns have a dry particulate collection device (i.e.,
either an electrostatic precipitator or a baghouse), with the collected
fly ash recycled back to the kiln. Buildup of metals or other
noncombustibles is prevented through their incorporation in the product
cement. Since many types of cement require a source of chloride, most
halogenated liquid hazardous wastes currently can be burned in cement
kilns. Available information shows that scrubbers are not used.
(ii) Lime kilns. Quick-lime (CaO) is manufactured in a
calcination process using limestone (CaCO ) or dolomite (CaCO and
MgCO ). These raw materials are also heated in a refractory-lined
«3
rotary kiln, typically to temperatures of 980 to 1,260°C (1,800 to
2,300CF). Lime kilns are less likely to burn hazardous wastes than
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are cement kilns because product lime is often added to potable water
systems. Only one lime kiln currently burns hazardous waste in the U.S.
That particular facility sells its product lime for use as flux or as
refractory in blast furnaces.
As with cement kilns, any collected fly ash is recycled back to the
lime kiln, resulting in no residual streams from the kiln. Available
information shows that scrubbers are not used.
(iii) Lightweight aggregate kilns. Lightweight aggregate kilns
heat clay to produce an expanded lightweight inorganic material used in
Portland cement formulations and other applications. The kiln has a
normal temperature range of 1,100 to 1,150°C (2,000 to 2,100°F).
Lightweight aggregate kilns are less amenable to combustion of hazardous
wastes as fuels than the other kilns described above because of the lack
of material in the kiln to adsorb halogens. As a result, burning of
halogenated organics in these kilns would likely require afterburners to
ensure complete destruction of the halogenated organics and scrubbers to
control acid gas production. Such controls would produce a wastewater
residual stream subject to treatment standards.
(b) Industrial boilers. A boiler is a closed vessel in which
water is transformed into steam by the application of heat. Normally,
heat is supplied by the combustion of pulverized coal, fuel oil, or gas.
These fuels are fired into a combustion chamber with nozzles and burners
that provide mixing with air. Liquid wastes, and granulated solid wastes
in the case of grate-fired boilers, can be burned as auxiliary fuel in a
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boiler. Few grate-fired boilers burn hazardous wastes, however. For
liquid-fired boilers, residuals requiring land disposal are generated
only when the boiler is shut down and cleaned. This is generally done
once or twice per year. Other residuals from liquid-fired boilers would
be the gas emission stream, which would consist of any products of
incomplete combustion, along with the normal combustion products. For
example, chlorinated wastes would produce acid gases. In this case, air
pollution control devices may be required. For solid-fired boilers, an
ash normally is generated. This ash may contain residual amounts of
organics from the blended waste/fuels, as well as noncombustible
materials. Land disposal of this ash would require compliance with
applicable BDAT treatment standards.
(4) Waste characteristics affecting performance. For cement kilns
and lime kilns and for lightweight aggregate kilns burning nonhalogenated
wastes (i.e., no scrubber is needed to control acid gases), no residual
waste streams would be produced. Any noncombustible material in the
waste would leave the kiln in the product stream. As a result, in
transferring standards EPA would not examine waste characteristics
affecting performance but rather would determine the applicability of
fuel substitution. That is, EPA would investigate the parameters
affecting treatment selection. As mentioned previously, for k-ilns these
parameters are Btu content, percent filterable solids, halogenated
organics content, viscosity, and sulfur content.
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Lightweight aggregate kilns burning halogenated organics and boilers
burning wastes containing any noncombustibles will produce residual
streams subject to treatment standards. In determining whether fuel
substitution is likely to achieve the same level of performance on an
untreated waste as on a previously treated waste, EPA will examine
(1) relative volatility of the waste constituents, (2) the heat transfer
characteristics (for solids), and (3) the activation energy for
combustion.
(a) Relative volatility. The term relative volatility (a)
refers to the ease with which a substance present in a solid or liquid
waste will vaporize from that waste upon application of heat from an-
external source. Hence, it bears a relationship to the equilibrium vapor
pressure of the substance.
EPA recognizes that the relative volatilities cannot be measured or
calculated directly for the types of wastes generally treated in an
industrial boiler or furnace. The Agency believes that the best measure
of relative volatility is the boiling point of the various hazardous
constituents and will, therefore, use this parameter in assessing
volatility of the organic constituents.
(b) Heat transfer characteristics. Consistent with the
underlying principles of combustion in aggregate kilns or boilers, a
major factor with regard to whether a particular constituent will
volatilize is the transfer of heat through the waste. In the case of
industrial boilers burning solid fuels, heat is transferred through the
waste by three mechanisms: radiation, convection, and conduction. For a
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given boiler, it can be assumed that the type of waste will have a
minimal impact on the heat transferred from radiation. With regard to
convection, EPA believes that the range of wastes treated would exhibit
similar properties with regard to the amount of heat transferred by
convection. Therefore, EPA will not evaluate radiation convection heat
transfer properties of wastes in determining similar treatability. For
solids, the third heat transfer mechanism, conductivity, is the one
principally operative or most likely to change between wastes.
Using thermal conductivity measurements as part of a treatability
comparison for two different wastes through a given boiler or furnace is
most meaningful when applied to wastes that are homogeneous. As wastes
exhibit greater degrees of nonhomogeneity, thermal conductivity becomes
less accurate in predicting treatability because the measurement
essentially reflects heat flow through regions having the greatest
conductivity (i.e., the path of least resistance and not heat flow
through all parts of the waste). Nevertheless, EPA has not identified a
better alternative to thermal conductivity, even for wastes that are
nonhomogeneous.
Other parameters considered for predicting heat transfer
characteristics were Btu value, specific heat, and ash content. These
parameters can neither better account for nonhomogeneity nor better
predict heat transferability through the waste.
(c) Activation energy. Given an excess of oxygen, an organic
waste in an industrial furnace or boiler would be expected to convert to
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carbon dioxide and water vapor, provided that the activation energy is
achieved. Activation energy is the quantity of heat (energy) needed to
destabilize molecular bonds and create reactive intermediates so that the
oxidation (combustion) reaction will proceed to completion. As a measure
of activation energy, EPA is using bond dissociation energies. In
theory, the bond dissociation energy would be equal to the activation
energy; in practice, however, this is not always the case.
In some instances, bond energies will not be available and will have
to be estimated, or other energy effects (e.g., vibrational effects) and
other reactions will have a significant influence on activation energy.
Because of the shortcomings of bond energies in estimating activation
energy, EPA analyzed other waste characteristic parameters to determine
whether these parameters would provide a better basis for transferring
treatment standards from an untested to a tested waste. These parameters
included heat of combustion, heat of formation, use of available kinetic
data to predict activation energies, and general structural class. All
of these parameters were rejected for the reasons provided below.
The heat of combustion measures only the difference in energy of the
products and reactants; it does not provide information on the transition
state (i.e., the energy input needed to initiate the reaction). Heat of
formation is used as a tool to predict whether reactions are likely to
proceed; however, there are a significant number of hazardous
constituents for which these data are not available. Use of available
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kinetic data was rejected because while such data could be used to
calculate some free energy values (AG), they could not be used for
the wide range of hazardous constituents. Finally, EPA decided not to
use structural classes because the Agency believes that evaluation of
bond dissociation energies allows for a more direct comparison.
(5) Design and operating parameters.
(a) Design parameters. Cement kilns and lime kilns, along with
aggregate 'kilns burning nonhalogenated wastes, produce no residual
streams. Their design and operation are such that any wastes that are
incompletely destroyed will be contained in the product. As a result,
the Agency will not look at design and operating values for such devices
since treatment, per se, cannot be measured through detection of
constituents in residual streams. In this instance, it is important
merely to ensure that the waste is appropriate for combustion in the
kilns and that the kiln is operated in a manner that will produce a
usable product.
Specifically, cement, lime, and aggregate kilns are only demonstrated
on liquid hazardous wastes. Such wastes must be sufficiently free of
filterable solids to avoid plugging the burners at the hot end of the
kiln. Viscosity also must be low enough to inject 'the waste into the
kiln through the burners. The sulfur content is not a concern unless the
concentration in the waste is high enough to exceed Federal, State, or
local air pollution standards promulgated for industrial boilers.
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The design parameters that normally affect the operation of an
industrial boiler (and aggregate kilns with residual streams) with
respect to hazardous waste treatment are (1) the design temperature,
(2) the design retention time of the waste in the combustion chamber, and
(3) the turbulence in the combustion chamber. Evaluation of these
parameters would be important in determining whether an industrial boiler
or industrial furnace is adequately designed for effective treatment of
hazardous wastes. The rationale for selection of these three parameters
is given below.
(\) Design temperature. Industrial boilers are generally
designed based on their steam generation potential (Btu output). This
factor is related to the design combustion temperature, which in turn
depends on the amount of fuel burned and its Btu value. The fuel feed
rates and combustion temperatures of industrial boilers are generally
fixed based on the Btu values of fuels normally handled (e.g., No. 2
versus No. 6 fuel oils). When wastes are to be blended with fossil fuels
for combustion, the blending, based on Btu values, must be such that the
resulting Btu value of the mixture is close to that of the fuel value
used in design of the boiler. Industrial furnaces also are designed to
operate at specific ranges of temperature to produce the desired product
(e.g., lightweight aggregate). The blended waste/fuel mixture should be
capable of maintaining the design temperature range.
(ii) Design retention time. A sufficient retention time of
combustion products is normally necessary to ensure that the hazardous
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substances being combusted (or formed during combustion) are completely
oxidized. Retention times on the order of a few seconds are generally
needed at normal operating conditions. For industrial furnaces as well
as boilers, the retention time is a function of the size of the furnace
and the fuel feed rates. For most boilers and furnaces, the retention
time usually exceeds a few seconds.
(iii) Turbulence. Boilers are designed so that fuel and air
are intimately mixed. This helps ensure that complete combustion takes
place. The shape of the boiler and the method of fuel and air feed
influence the turbulence required for good mixing. Industrial furnaces
also are designed for turbulent mixing where fuel and air are mixed.
(b) Operating parameters. The operating parameters that
normally affect the performance of an industrial boiler and many
industrial furnaces with respect to treatment of hazardous wastes are
(1) air feed rate, (2) fuel feed rate, (3) steam pressure or rate of
production, and (4) temperature. EPA believes that these four parameters
will be used to determine whether an industrial boiler burning blended
fuels containing hazardous waste constituents is properly operated. The
rationale for selection of these four operating parameters is given
below. Most industrial furnaces will monitor similar parameters, but
some exceptions are noted.
(i) Air feed rate. An important operating parameter in boilers
and many industrial furnaces is the oxygen content in the flue gas, which
is a function of the air feed rate. Stable combustion of a fuel
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generally occurs within a specific range of air-to-fuel ratios. An
oxygen analyzer in the combustion gases can be used to control the feed
ratio of air to fuel to ensure complete thermal destruction of the waste
and efficient operation of the boiler. When necessary, the air feed rate
can be increased or decreased to maintain proper fuel-to-oxygen ratios.
Some industrial furnaces do not completely combust fuels (e.g., coke
ovens and blast furnaces); hence, oxygen concentration in the flue gas is
a meaningless variable.
(ii) Fuel feed rate. The rate at which fuel is injected into
the boiler or industrial furnace will determine the thermal output of the
system per unit of time (Btu/hr). If steam is produced, steam pressure
monitoring will indirectly determine if the fuel feed rate is adequate.
However, various velocity and mass measurement devices can be used to
monitor fuel flow directly.
(iii) Steam pressure or rate of production. Steam pressure in
boilers provides a direct measure of the thermal output of the system and
is directly monitored-by use of in-system pressure gauges. Increases or
decreases in steam pressure can be effected by increasing or decreasing
the fuel and air feed rates within certain operating design limits. Most
industrial furnaces do not produce steam, but instead produce a product
(e.g., cement, aggregate) and monitor the rate of production.
(iv) Temperature. Temperatures are monitored and controlled in
industrial boilers to ensure the quality and flow rate of steam.
Therefore, complex monitoring systems are frequently installed in the
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combustion unit to provide a direct reading of temperature. The
efficiency of combustion in industrial boilers is dependent on combustion
temperatures. Temperature may be adjusted to design settings by
increasing or decreasing air and fuel feed rates.
Wastes should not be added to primary fuels until the boiler
temperature reaches the minimum needed for destruction of the wastes.
Temperature instrumentation and control should be designed to stop waste
addition in the event of process upsets.
Monitoring and control of temperature in industrial furnaces are also
critical to the product quality. For example, lime, cement, and
aggregate kilns require minimum operating temperatures. Kilns have very
high thermal inertia in the refractory and in-process product, high
residence times, and high air feed rates, so that even in the case of a
momentary stoppage of fuel flow to the kiln, organic constituents are
likely to continue to be destroyed. The main operational control
required for wastes burned in kilns is to stop waste flow in the event of
low kiln temperature, loss of the electrical power to the combustion air
fan, and loss of primary fuel flow.
(v) Other Operating Parameters. In addition to the four
operating parameters discussed above, EPA considered and then discarded
one additional parameter--fuel-to-waste blending ratios. While the
blending is done to yield a uniform Btu content fuel, blending ratios
will vary widely depending on the Btu content of the wastes and the fuels
being used.
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3.2.3 Stabilization
Stabilization refers to a broad class of treatment processes that
chemically reduce the mobility of hazardous constituents in a waste.
Solidification and fixation are other terms that are sometimes used
synonymously for stabilization or to describe specific variations within
the broader class of stabilization. Related technologies are
encapsulation and thermoplastic binding; however, EPA considers these
technologies to be distinct from stabilization in that the operational
principles are significantly different.
(1) Applicability and use of stabilization. Stabilization is used
when a waste contains metals that will leach from the waste when it is
contacted by water. In general, this technology is applicable to wastes
containing BOAT list metals and having a high filterable solids content,
low TOC content, and low oil and grease content. This technology is
commonly used to treat residuals generated from treatment of
electroplating wastewaters. For some wastes, an alternative to
stabilization is metal recovery.
(2) Underlying principles of operation. The basic principle
underlying this technology is that stabilizing agents and other chemicals
are added to a waste to minimize the amount of metal that leaches. The
reduced Teachability is accomplished by the formation of a lattice
structure and/or chemical bonds that bind the metals to the solid matrix
and thereby limit the amount of metal constituents that can be leached
when water or a mild acid solution comes into contact with the waste
material.
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Two principal stabilization processes are used--cement-based and
lime-based. A brief discussion of each is provided below. In both
cement-based and 1ime/pozzolan-based techniques, the stabilizing process
can be modified through the use of additives, such as silicates, that
control curing rates or enhance the properties of the solid material.
(a) Portland cement-based process. Portland cement is a
mixture of powdered oxides of calcium, silica, aluminum, and iron,
produced by kiln burning of materials rich in calcium and silica at high
temperatures (i.e., 1400 to 1500=C). When the anhydrous cement
powder is mixed with water, hydration occurs and the cement begins to
set. The chemistry involved is complex because many different reactions
occur depending on the composition of the cement mixture.
As the cement begins to set, a colloidal gel of indefinite
composition and structure is formed. Over a period of time, the gel
swells and forms a matrix composed of interlacing, thin, densely packed
silicate fibrils. Constituents present in the waste slurry (e.g.,
hydroxides and carbonates of various heavy metals) are incorporated into
the interstices of the cement matrix. The high pH of the cement mixture
tends to keep metals in the form of insoluble hydroxide and carbonate
salts. It has been hypothesized that metal ions may also be incorporated
into the crystal structure of the cement matrix, but this hypothesis has
not been verified.
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(b) Lime/pozzolan-based process. Pozzolan, which contains
finely divided, noncrystalline silica (e.g., fly ash or components of
cement kiln dust), is a material that is not cementitious in itself but
becomes so upon the addition of lime. Metals in the waste are converted
to silicates or hydroxides, which inhibit leaching. Additives, again,
can be used to reduce permeability and thereby further decrease leaching
potential.
(3) Description of the stabilization process. In most stabilization
processes, the waste, stabilizing agent, and other additives, if used,
are mixed and then pumped to a curing vessel or area and allowed to
cure. The actual operation (equipment requirements and process
sequencing) will depend on several factors such as the nature of the
waste, the amount of waste, the location of the waste in relation to the
disposal site, the particular stabilization formulation to be used, and
the curing rate. After curing, the solid formed is recovered from the
processing equipment and shipped for final disposal.
In instances where waste contained in a lagoon is to be treated, the
material should first be transferred to mixing vessels where stabilizing
agents are added. The mixed material is then fed to a curing pad or
vessel. After curing, the solid formed is removed for disposal.
Equipment commonly used also includes facilities to store waste and
chemical additives. Pumps can be used to transfer liquid or light sludge
wastes to the mixing pits and pumpable uncured wastes to the curing
site. Stabilized wastes are then removed to a final disposal site.
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Commercial concrete mixing and handling equipment generally can be
used with wastes. Weighing conveyors, metering cement hoppers, and
mixers similar to concrete batching plants have been adapted in some
operations. Where extremely dangerous materials are being treated,
remote-control and in-drum mixing equipment, such as that used with
nuclear waste, can be employed.
(4) Waste characteristics affecting performance. In determining
whether stabilization is likely to achieve the same level of performance
on an untested waste as on a previously tested waste, the Agency will
focus on the characteristics that inhibit the formation of either the
chemical bonds or the lattice structure. The four characteristics EPA
has identified as affecting treatment performance are the presence of
(1) fine particulates, (2) oil and grease, (3) organic compounds, and
(4) certain inorganic compounds.
(a) Fine particulates. For both cement-based and
1ime/pozzolan-based processes, the literature states that very fine solid
materials (i.e., those that pass through a No. 200 mesh sieve, 74 urn
particle size) can weaken the bonding between waste particles and cement
by coating the particles. This coating can inhibit chemical bond
formation and decrease the resistance of the material to leaching.
(b) Oil and grease. The presence of oil and grease in both
cement-based and 1ime/pozzolan-based systems results in the coating of
waste particles and the weakening of the bonding between the particle and
the stabilizing agent. This coating can inhibit chemical bond formation
and thereby decrease the resistance of the material to leaching.
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(c) Organic compounds. The presence of organic compounds in
the waste interferes with the chemical reactions and bond formation,
which inhibits curing of the stabilized material. This results in a
stabilized waste that has decreased resistance to leaching.
(d) Sulfate and chlorides. The presence of certain inorganic
compounds interferes with the chemical reactions, weakening bond strength
and prolonging setting and curing time. Sulfate and chloride compounds
may reduce -the dimensional stability of the cured matrix, thereby
increasing Teachability potential.
Accordingly, EPA will examine these constituents when making
decisions regarding transfer of treatment standards based on
stabilization.
(5) Design and operating parameters. In designing a stabilization
system, the principal parameters that are important to optimize so that
the amount of Teachable metal constituents is minimized are (!) selection
of stabilizing agents and additives, (2) ratio of waste to stabilizing
agents and other additives, (3) degree of mixing, and (4) curing
'conditions.
(a) Selection of stabilizing agents and other additives. The
stabilizing agent and additives used will determine the chemistry and
structure of the stabilized material and therefore will affect the
Teachability of the solid material. Stabilizing agents and additives
must be carefully selected based on the chemical and physical
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characteristics of the waste to be stabilized. For example, the amount
of sulfates in a waste must be considered when a choice is being made
between a 1ime/pozzolan-based system and a portland cement-based system.
To select the type of stabilizing agents and additives, the waste
should be tested in the laboratory with a variety of materials to
determine the best combination.
(b) Amount of stabilizing agents and additives. The amount of
stabilizing agents and additives is a critical parameter in that
sufficient stabilizing materials are necessary in the mixture to properly
bind the waste constituents of concern, thereby making them less
susceptible to leaching. The appropriate weight ratios of waste to
stabilizing agent and other additives are established empirically by
setting up a series of laboratory tests that allow separate leachate
testing of different mix ratios. The ratio of water to stabilizing agent
(including water in waste) will also impact the strength and leaching
characteristics of the stabilized material. Too much water will cause
low strength; too little will make mixing difficult and, more important,
may not allow the chemical reactions that bind the hazardous constituents
to be fully completed.
(c) Mixing. This parameter includes both the type and the
duration of mixing. Mixing is necessary to ensure homogeneous
distribution of the waste and the stabilizing agents. Both undermixing
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and overmixing are undesirable. The first condition results in a
nonhomogeneous mixture; therefore, areas will exist within the waste
where waste particles are neither chemically bonded to the stabilizing
agent nor physically held within the lattice structure. Overmixing, on
the other hand, may inhibit gel formation and ion adsorption in some
stabilization systems. As with the relative amounts of waste,
stabilizing agent, and additives within the system, optimal mixing
conditions generally are determined through laboratory tests. During
treatment it is important to monitor the degree (i.e., type and duration)
of mixing to ensure that it reflects design conditions.
(d) Curing conditions. Curing conditions include the duration
of curing and the ambient curing conditions (temperature and humidity).
The duration of curing is a critical parameter to ensure that the waste
particles have had sufficient time in which to form stable chemical bonds
and/or lattice structures. The time necessary for complete stabilization
depends upon the waste type and the stabilization used. The performance
of the stabilized waste (i.e., the levels of constituents in the
leachate) will be highly dependent upon whether complete stabilization
has occurred. Higher temperatures and lower humidity increase the rate
of curing by increasing the rate of evaporation of water from the
solidification mixtures. If temperatures are too high, however, the
evaporation rate can be excessive, resulting in too little water being
available for completion of the stabilization reaction. The duration of
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the curing process, which should also be determined during the design
stage, typically will range between 7 and 28 days.
3.2.4 High Temperature Metals Recovery
High temperature metals recovery (HTMR) provides for recovery of
metals from wastes primarily by volatilization and collection. The
process yields a metal product or products for reuse and reduces the
concentration of metals in the residual. This process also significantly
reduces the amount of treated waste that needs to be land disposed.
There are a number of different types of high temperature metals
recovery systems. These systems generally differ from one another
relative to the source of energy and the method of recovery. Such HTMR
systems include the rotary kiln process, plasma arc reactor, rotary
hearth/electric furnace system, molten slag reactor, and flame reactor.
This technology is different from retorting in that HTMR is conducted in
a carbon reducing atmosphere, while the retorting process simply
vaporizes the untreated metal. Retorting is discussed in a separate
technology section.
(1) Applicability and use of high temperature metals recovery. This
process is applicable to wastes containing BOAT list metals, low water
content (or a water content that can be either blended to the required
level or lowered by dewatering), and low concentration of organics. This
technology is applicable to a wide range of metal salts including
cadmium, chromium, lead, mercury, nickel, and zinc.
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HTMR is generally not used for mercury-containing wastes even though
mercury will volatilize readily at the process temperatures present in
high temperature units. The rotary kiln recovery process is one example
of this technology; it has been applied to zinc-bearing wastes as an
upgrading step that yields a zinc oxide product for further refinement
and subsequent reuse. Although this technology was originally developed
in the 1920s for upgrading zinc from ores, it has recently been applied
to electric furnace dust from the steel-making industry.
(2) Underlying principles of operation. The basic principle of
operation for this technology is that metals are separated from a waste
through volatilization in a reducing atmosphere in which carbon is the
reducing compound. An example chemical reaction would be:
2ZnO + C - 2Zn + CO .
In some cases, the waste contains not only BOAT list metal
constituents that can be volatilized but also nonvolatile BOAT list
metals as well. In such cases, the HTMR process can yield two
recoverable product streams. Whether such recovery can be accomplished,
however, depends on the type and concentration of metals in the original
waste stream. Below is a discussion of the recovery techniques for the
volatile stream, as well as for the waste material that is not
volatilized.
(a) Recovery of volatilized metals. The volatilized metals can
be recovered in the metallic form or as an oxide. In the case of the
metallic form, recovery is accomplished by condensation alone, while in
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the case of an oxide, it is accomplished by reoxidation, condensation,
and the subsequent collection of the metal oxide particulates in a
baghouse. There is no difference between these two types of metal
product recovery systems relative to the kinds of waste that can be
treated; the difference is simply reflected in a facility's preference
relative to product purity. In the former case, the direct condensation
of metals, while more costly, allows for the separation and collection of
metals in a relatively uncontaminated form; in the latter case, the
metals are collected as a combination of several metal oxides. If
necessary, this combination of metal oxides could be further processed to
produce individual metal products of increased purity.
(b) Less volatile treatment residual. The fraction of the
waste that is not originally.volatilized has three possible
dispositions: (1) the material can be used directly as a product (e.g.,
a waste residual containing mostly metallic iron can be reused directly
in steel making); (2) the material can be reused after further processing
(e.g., a waste residual containing oxides of iron, chromium, and nickel
can be reduced to the metallic form and then recovered for use in the
manufacture of stainless steel); and (3) the material has no recoverable
value and is land disposed as a slag.
(3) Description of the high temperature metals recovery process.
The process essentially consists of four operations: (1) a blending
operation to control feed parameters, (2) high temperature processing,
(3) a product collection system, and (4) handling of the less volatile
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treated residual. A generic schematic diagram for high temperature
metals recovery is shown in Figure 3-5.
(a) Blending. For the system shown, variations in feeds are
minimized by blending wastes from different sources. Prior to feeding
the kiln, fluxing agents are added to the waste. Carbon is also added to
the waste as required.. The fluxes (limestone or sand) are added to react
with certain waste components to prevent their volatilization and thus
improve the purity of the desired metals recovered. In addition, the
moisture content is adjusted by either adding water or blending various
wastes.
(b) High temperature processing. These materials are fed to
the furnace where they are heated and the chemical reactions take place.
The combination of residence time and turbulence helps to ensure maximum
volatilization of metal constituents.
(c) Product collecting. As discussed previously, the product
collection system can consist of either a condenser or a combination of
condenser and baghouse. The particular system used depends on whether
the metal is to be collected in the metallic form or as an oxide.
(d) Handling of residual. The equipment needed to handle the
less volatile metal-treated residual depends upon the final disposition
of the material. If further recovery is to be performed, then the waste
would be treated in another,furnace. If the material is to be land
disposed, the final process step would generally consist of quenching.
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K061
CARBON
FLUXES
(ADDITIVES)
FEED
BLENDING
I
en
HIGH
TEMPERATURE
PROCESSING
RESIDUAL
COLLECTION
I
REUSE OR
LAND DISPOSAL
PRODUCT
COLLECTION
REUSE
FIGURE 3-5 EXAMPLE HIGH TEMPERATURE METALS RECOVERY SYSTEM
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(4) Waste characteristics affecting performance. In determining
whether high temperature metals recovery technologies are likely to
achieve the same level of performance on an untested waste as on a
previously tested waste, EPA will examine the following three waste
characteristics that have an impact on treatability: (1) type and
concentrations of metals in the waste, (2) relative volatility of the
metals, and (3) heat transfer characteristics of the waste.
(a) Type and concentrations of metals in the waste. Because
this is a metals recovery process, the product must meet certain
requirements for recovery. If the waste contains other volatile metals
that are difficult to separate and whose presence may affect the ability
to refine the product for subsequent reuse, high temperature metals
recovery may provide less effective treatment. Analytical methods for
metals can be found in SW-846.
(b) Boiling point. The relative volatilities of the metals in
the waste also affect the ability to separate various metals. There is
no conventional measurement technique for determining the relative
volatility of a particular constituent in a given waste. EPA believes
that the best measure of volatility of a specific metal constituent is
the boiling point. EPA recognizes that the boiling point has certain
shortcomings; in particular, boiling points are given for pure
components, even though the other constituents in the waste will affect
partial pressures and thus the boiling point of the mixture. EPA has not
identified a parameter that can better assess relative volatility.
Boiling points of metals can be determined from the literature.
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(c) Heat transfer characteristics. The ability to heat
constituents within a waste matrix is a function of the heat transfer
characteristics of a heterogeneous waste material. The constituents
being recovered from the waste must be heated near or above their boiling
points in order for them to be volatilized and recovered. Whether
sufficient heat will be transferred to the particular constituent to
cause the metal to volatilize will depend on the heat transfer
characteristics of the waste. Since there is no conventional direct
measurement of these characteristics, EPA believes that the best measure
of the heat transfer characteristics of the waste is thermal
conductivity. The analytical method that EPA has identified for
measurement of thermal conductivity is the "Guarded, Comparative,
Longitudinal Heat Flow Technique"; it is described in Appendix D.
(5) Design and operating parameters. The parameters that EPA will
evaluate when determining whether a high temperature metals recovery
system is well designed and well operated are (1) the furnace
temperature, (2) the furnace residence time, (3) the amount and ratio of
the feed blending materials, and.(4) mixing. Below is an explanation of
why EPA believes these parameters are important to an analysis of the
design and operation of the system.
(a) Furnace temperature. In order for sufficient heat to be
transferred to the waste for volatilization, high temperatures must be
provided. The higher the temperature in the furnace, the more likely it
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is that the constituents will react with carbon to form free metals and
volatilize. The temperature must be approximately equal to or greater
than the boiling point of the metals being volatilized. Excessive
temperatures could volatilize unwanted metals into the product, possibly
inhibiting the potential for reuse of the volatilized product. In
assessing performance during the treatment period, EPA would want
continuous temperature data.
(b) Furnace residence time. Furnaces must be designed to
ensure that the waste has sufficient time to be heated to the boiling
point of the metals to be volatilized. The time necessary for complete
volatilization of these constituents is dependent on the furnace
temperature and the heat transfer characteristics of the waste. The
residence time is a function of the physical dimensions of the furnace
(i.e., length, diameter, and slope (for rotary kilns)), the rate of
rotation (if applicable), and the feed rate.
(c) Amount and ratio of feed blending materials. To achieve
maximum volatilization of the metals being recovered, the following feed
parameters must be controlled by the addition of carbon, fluxes, and
other agents, if necessary. Blending of these feed components is also
needed to adjust the following feed parameters to the required volume:
carbon content, moisture content, calcium-to-silica ratio, and the
initial concentration of the metals to be recovered. These parameters
all affect the rate of the reduction reaction and volatilization. EPA
will examine blending ratios during treatment to ensure that they comply
with design conditions.
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(d) Mixing. Effective mixing of the total components is
necessary to ensure that a uniform waste is being treated. Turbulence in
the furnace also ensures that no "pockets" of waste go untreated.
Accordingly, EPA will examine the type and degree of mixing involved when
assessing treatment design and performance.
3.2.5 Hexavalent Chromium Reduction
(1) Applicability and use of hexavalent chromium reduction. The
6+
process of hexavalent chromium (Cr ) reduction involves its conversion
from the hexavalent form to the trivalent form of chromium. This
technology has wide application to hexavalent chromium wastes, including
plating solutions, stainless steel acid baths and rinses, "chrome
conversion" coating process rinses, and chromium pigment manufacturing
wastes. Because this technology requires the pH to be in the acidic
range, it would not be applicable to a waste that contains significant
amounts of cyanide or sulfide. In such cases, lowering of the pH can
generate toxic gases such as hydrogen cyanide or hydrogen sulfide. It is
important to note that additional treatment is required to remove
trivalent chromium from solution.
(2) Underlying principles of operation. The basic principle of
treatment is to reduce the valence of chromium in solution (in the form
of chromate or dichromate i'ons) from the valence state of six (+6) to the
trivalent state (+3). "Reducing agents" used to effect the reduction
include sodium bisulfite, sodium metabisulfite, sulfur dioxide, sodium
hydrosulfide, or the ferrous form of iron.
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A typical reduction equation, using sodium sulfite as the reducing
agent, is:
H2Cr207 + 3Na2S03 + (S04)3 - Cr2(S04)3 + 3Na2S04 -t- 4H20.
The reaction is usually accomplished at pH values in the range of 2 to 3.
At the completion of the chromium reduction step, the trivalent
chromium compounds are precipitated from solution by raising the pH to a
value exceeding about 8. The less soluble trivalent chromium (in the
form of chromium hydroxide) is then allowed to settle from solution. The
precipitation reaction is as follows:
Cr2(S04)3 + 3Ca(OH)2 - 2Cr(OH)3 + CaS04.
(3) Description of the .chromium reduction process. The chromium
reduction treatment process can be operated in a batch or a continuous
mode. A batch system will consist of a reaction tank, a mixer to
homogenize the contents of the tank, a supply of reducing agent, and a
source of acids and bases for pH control.
A continuous chromium reduction treatment system, as shown in
Figure 3-6, will usually include a holding tank upstream of the reaction
tank for flow and concentration equalization. It will also include
instrumentation to automatically control the amount of reducing agent
added and the pH of the reaction tank. The amount of reducing agent is
controlled by the use of a sensor called an oxidation-reduction potential
(ORP) cell. The ORP sensor electronically measures, in millivolts, the
level to which the redox reaction has proceeded at any given time. It
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REDUCING
AGENT
FEED
SYSTEM
ACID
FEED
SYSTEM
L-^
HEXAVALENT-
CHROMIUM
CONTAINING
WASTEWATER
OJ
en
o
®-^
ALKALI
FEED
SYSTEM
r
D
ORP pH
SENSORS
TO SETTLING
REDUCTION
PRECIPITATION
ELECTRICAL CONTROLS
MIXER
FIGURE 3-6
CONTINUOUS HEXAVALENT
CHROMIUM REDUCTION SYSTEM
-------
must be noted, though, that the ORP reading is very pH dependent.
Consequently, if the pH is not maintained at a steady value, the ORP will
vary somewhat, regardless of the level of chromate reduction.
(4) Waste characteristics affecting performance. In determining
whether chromium reduction can treat an untested waste to the same level
of performance as a previously tested waste, EPA will examine waste
characteristics that affect the reaction involved with either lowering
the pH or reducing the hexavalent chromium. EPA believes that such
characteristics include the oil and grease content of the waste, total
dissolved solids, and the presence of other compounds that would undergo
reduction reaction.
(a) Oil and grease. EPA believes that these compounds could
potentially interfere with the oxidation-reduction reactions, as well as
cause monitoring problems by fouling the instrumentation (e.g.,
electrodes). Oil and grease concentrations can be measured by EPA
Methods 9070 and 9071.
(b) Total dissolved solids. These compounds can interfere with
the addition of treatment chemicals into solution and can possibly cause
monitoring problems.
(c) Other reducible compounds. These compounds would generally
consist of other metals in the waste. Accordingly, EPA will evaluate the
type and concentration of th'ese other metals when evaluating transfer of
treatment performances.
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(5) Design and operating parameters. The parameters that EPA will
examine in assessing the design and operation of a chromium reduction
treatment system are discussed below.
(a) Treated and untreated design concentration. EPA will need
to know the level of performance that the facility is designed to achieve
in order to ensure that the design is consistent with best demonstrated
practices. This parameter is important because a system will not usually
perform better than its design. Along with knowledge of the treated
design concentration, it is also important to know the characteristics of
the untreated waste that the system is designed to handle. Thus, EPA
will obtain data on the untreated wastes to ensure that the waste
characteristics fall within the design specifications.
(b) Reducing agent. The choice of a reducing agent establishes
the chemical reaction upon which the chromium reduction system is based.
The amount of reducing agent needs to be monitored and controlled in both
batch and continuous systems. In batch systems, the reducing agent is
usually controlled by an analysis of the hexavalent chromium remaining in
solution. For continuous systems, the ORP reading is used to monitor and
control the addition of the reducing agent.
The ORP reading will change slowly until the correct amount of
reducing agent has been added, at which point the ORP will change
rapidly, indicating that the reaction has been completed. The set point
for the ORP monitor is generally the reading just after the rapid change
has begun. The reduction system must then be monitored periodically to
determine whether the selected set point needs further adjustment.
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(c) pH. For batch and continuous systems, pH is an important
parameter because of its effect on the reduction reaction. For a batch
system, pH can be monitored intermittently during treatment. For a
continuous system, it should be monitored continuously because of its
effect on the ORP reading. In evaluating the design and operation of a
continuous chromium reduction system, it is important to know the pH on
which the design ORP value is based, as well as the designed ORP value.
(d) Retention time. Retention time should be adequate to
ensure that the hexavalent chromium reduction reaction goes to
completion. In the case of the batch reactor, the retention time is
varied by adjusting the treatment time in the reaction tank. If the
process is continuous, it is important to monitor the feed rate to ensure
that the designed residence time is achieved.
3.2.6 Chemical Precipitation
(1) Applicability and use of chemical precipitation. Chemical
precipitation is used when dissolved metals are to be removed from
solution. This technology can be applied to a wide range of wastewaters
containing dissolved BOAT list metals and other metals as well. This
treatment process has been practiced widely by industrial facilities
since the 1940s.
(2) Underlying principles of operation. The underlying principle of
chemical precipitation is that meta.ls in wastewater are removed by the
addition of a treatment chemical that converts the dissolved metal to a
metal precipitate. This precipitate is less soluble than the original
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metal compound and therefore settles out of solution, leaving a lower
concentration of the metal present in the solution. The principal
chemicals used to convert soluble metal compounds to the less soluble
forms include: lime (Ca(OH) ), caustic (NaOH), sodium sulfide (Na S),
and, to a lesser extent, soda ash (Na CO ), phosphate, and ferrous
L. «J
sulfide (FeS).
The solubility of a particular compound depends on the extent to
which the electrostatic forces holding the ions of the compound together
can be overcome. The solubility changes significantly with temperature;
most metal compounds are more soluble as the temperature increases.
Additionally, the solubility is affected by the other constituents
•
present in a waste. As a general rule, nitrates, chlorides, and sulfates
are more soluble than hydroxides, sulfides, carbonates, and phosphates.
An important concept related to treatment of the soluble metal
compounds is pH. This term provides a measure of the extent to which a
solution contains an excess of either hydrogen or hydroxide ions. The pH
scale ranges from 0 to 14; with 0 being the most acidic, 14 representing
the highest alkalinity or hydroxide ion (OH ) content, and 7.0 being
neutral.
When hydroxide is used, as is often the case, to precipitate the
soluble metal compounds, the pH is frequently monitored to ensure that
sufficient treatment chemicals are added. It is important to point out
that pH is not a good measure of the addition of treatment chemicals for
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compounds other than hydroxides; when sulfide is used, for example,
facilities might use an oxidation-reduction potential meter (ORP)
correlation to ensure that sufficient treatment chemicals are used.
Following conversion of the relatively soluble metal compounds to
metal precipitates, the effectiveness of chemical precipitation is a
function of the physical removal, which usually relies on a settling
process. A particle of a specific size, shape, and composition will
settle at a specific velocity, as described by Stokes' Law. For a batch
system, Stokes' Law is a good predictor of settling time because the
pertinent particle parameters remain essentially constant. Nevertheless,
in practice, settling time for a batch system is normally determined by
empirical testing. For a continuous system, the theory of settling is
complicated by factors such as turbulence, short-circuiting, and velocity
gradients, thereby increasing the importance of the empirical tests.
(3) Description of the chemical precipitation process. The
equipment and instrumentation required for chemical precipitation vary
depending on whether the system is batch or continuous. Both operations
are discussed below; a schematic of the continuous system is shown in
Figure 3-7.
For a batch system, chemical precipitation requires only a feed
system for the treatment chemicals and a second tank where the waste can
be treated and allowed to settle. When lime is used, it is generally
added to the reaction tank in a slurry form. In a batch system, the
supernate is usually analyzed before discharge, thus minimizing the need
for instrumentation.
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WASTEWATER
FEED
ATHENT
EMICAL
= EED
fSTEM
COAGULANT OR
FLOCCULANT FEED SYSTEM
CO
I
EQUALIZATION
TANK
ELECTRICAL CONTROLS
WASTEWATER FLOW
MIXER
EFFLUENT TO
DISCHARGE OR
SUBSEQUENT
TREATMENT
SLUDGE TO
DEWATERING
FIGURE 3-7 CONTINUOUS CHEMICAL PRECIPITATION
-------
In a continuous system, additional tanks are necessary, as well as
the instrumentation to ensure that the system is operating properly. In
this system, the first tank that the wastewater enters is referred to as
an equalization tank. This is where the waste is mixed in order to
provide more uniformity, minimizing the wide swings in the type and
concentration of constituents being sent to the reaction tank. It is
important to reduce the variability of the waste sent to the reaction
tank because control systems inherently are limited with regard to the
maximum fluctuations that can be managed.
Following equalization, the waste is pumped to a reaction tank where
treatment chemicals are added; this is done automatically by using
instrumentation that senses the pH of the system and then pneumatically
adjusts the position of the,treatment chemical feed valve such that the
design pH value is achieved. Both the complexity and the effectiveness
of the automatic control system will vary depending on the variation in
the waste and the pH range that is needed to properly treat the waste.
An important aspect of the reaction tank design is that the tank's
contents be well mixed so that the waste and the treatment chemicals are
dispersed throughout the tank to ensure commingling of the reactant and
the treatment chemicals. In addition, effective dispersion of the
treatment chemicals throughout the tank is necessary to properly monitor
and thereby control the amount of treatment chemicals added.
After the waste is reacted with the treatment chemical, it flows to a
quiescent tank where the precipitate is allowed to settle and then be
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subsequently removed. Settling can be chemically assisted through the
use of flocculating compounds. Flocculants increase the particle size
and density of the precipitated solids, both of which increase the rate
i
of settling. The particular flocculating agent that will best improve
settling characteristics will vary depending on the particular waste;
selection of the flocculating agent is generally accomplished by
performing laboratory bench tests. Settling can be conducted in a large
tank by relying solely on gravity or can be mechanically assisted through
the use of a circular clarifier or an inclined separator. Schematics of
the latter two separators are shown in Figures 3-8 and 3-9.
Filtration can be used for further removal of precipitated residuals
both in cases where the settling system is underdesigned and in cases
where the particles are difficult to settle. Polishing filtration is
discussed in a separate technology section.
(4) Waste characteristics affecting performance. In determining
whether chemical precipitation is likely to achieve the same level of
performance on an untested waste as on a previously tested waste, EPA
will examine the following waste characteristics: (1) the concentration
and type of the metal(s) in the waste, (2) the concentration of total
suspended solids (TSS), (3) the concentration of total dissolved solids
(IDS), (4) whether the metal exists in the wastewater as a complex, and
(5) the oil and grease content. These parameters may affect the chemical
reaction of the metal compound, the solubility of the metal precipitate,
or the ability of the precipitated compound to settle.
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EFFLUENT
SLUDGE
INFLUENT
CENTER FEED CLAR1FIER WITH SCRAPER SLUDGE REMOVAL SYSTEM
SLUDGE
RIM FEED - CENTER TAKEOFF CLARIFIER WITH
HYDRAULIC SUCTION SLUDGE REMOVAL SYSTEM
SLUDGE
RIM FEED - RIM TAKEOFF CLARIFIER
EFFLUENT
INFLUENT
EFFLUENT
FIGURE 3-8 CIRCULAR CLARIFIERS
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INFLUENT
EFFLUENT
FIGURE 3-9
INCLINED PLATE SETTLER
3-67
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(a) Concentration and type of metals. For most metals, there
is a specific pH at which the metal hydroxide is least soluble. As a
result, when a waste contains a mixture of many metals, it is not
possible to operate a treatment system at a single pH that is optimal for
the removal of all metals. The extent to which this situation affects
treatment depends on the particular metals to be removed and their
concentrations. One approach is to operate multiple precipitations, with
intermediate settling, when the optimum pH occurs at markedly different
levels for the metals present. The individual metals and their
concentrations can be measured using EPA Method 6010.
(b) Concentration and type of total suspended solids (TSS).
Certain suspended solid compounds are difficult to settle because of
their particle size or shape. Accordingly, EPA will evaluate this
characteristic in assessing the transfer of treatment performance. Total
suspended solids can be measured by EPA Wastewater Test Method 160.2.
(c) Concentration of total dissolved solids (TDS). Available
information shows that total dissolved solids can inhibit settling. The
literature states that poor flocculation is a consequence of high TDS and
shows that higher concentrations of total suspended solids are found in
treated residuals. Poor flocculation can adversely affect the degree to
which precipitated particles are removed. Total dissolved solids can be
measured by EPA Wastewater Test Method 160.1.
(d) Complexed metals. Metal complexes consist of a metal ion
surrounded by a group of other inorganic or organic ions or molecules
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(often called ligands). In the complexed form, the metals have a greater
solubility and therefore may not be as effectively removed from solution
by chemical precipitation. EPA does not have an analytical method to
determine the amount of complexed metals in the waste. The Agency
believes that the best measure of complexed metals is to analyze for some
common complexing compounds (or complexing agents) generally found in
wastewater for which analytical methods are available. These complexing
agents include ammonia, cyanide, and EDTA. The analytical method for
cyanide is EPA Method 9010, while the method for EDTA is ASTM
Method D3113. Ammonia can be analyzed using EPA Wastewater Test
Method 350.
(e) Oil and grease content. The oil and grease content of a
particular waste directly inhibits the settling of the precipitate.
Suspended oil droplets float in water and tend to suspend particles such
as chemical precipitates that would otherwise settle out of the
solution. Even with the use of coagulants or flocculants, the separation
of the precipitate is less effective. Oil and grease content can be
measured by EPA Method 9071.
(5) Design and operating parameters. The parameters that EPA will
evaluate when determining whether a chemical precipitation system is well
designed are: (1) design value for treated metal concentrations, as well
as other characteristics of the waste used for design purposes (e.g.,
total suspended solids); (2) pH; (3) residence time; (4) choice of
treatment chemical; (5) choice of coagulant/flocculant; and (6) mixing.
The reasons why EPA believes these parameters are important to a design
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analysis are cited below, along with an explanation of why other design
criteria are not included in this analysis.
(a) Treated and untreated design concentrations. When
determining whether to sample a particular facility, EPA pays close
attention to the treated concentration the system is designed to
achieve. Since the system will seldom outperform its design, EPA must
evaluate whether the design is consistent with best demonstrated practice.
The untreated concentrations that the system is designed to treat are
important in evaluating any treatment system. Operation of a chemical
precipitation treatment system with untreated waste concentrations in
excess of design values can easily result in poor performance.
(b) pH. The pH is important because it can indicate whether
sufficient treatment chemical (e.g., lime) has been added to convert the
metal constituents in the untreated waste to forms that will
precipitate. The pH also affects the solubility of metal hydroxides and
sulfides and thus directly impacts the effectiveness of removal. In
practice, the design pH is determined by empirical bench testing, often
referred to as "jar" testing. The temperature at which the "jar" testing
is conducted is important since it also affects the solubility of the
metal precipitates. Operation of a treatment system at temperatures
above the design temperature can result in poor performance. In
assessing the operation of a chemical precipitation system, EPA. prefers
to use continuous data on the pH and periodic temperature conditions
throughout the treatment period.
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(c) Residence time. Residence time is important because it
impacts the completeness of the chemical reaction to form the metal
precipitate and, to a greater extent, the amount of precipitate that
settles out of solution. In practice, it is determined by "jar"
testing. For continuous systems, EPA will monitor the feed rate to
ensure that the system is operated at design conditions. For batch
systems, EPA will want information on the design parameter used to
determine sufficient settling time (e.g., total suspended solids).
(d) Choice of treatment chemical. A choice must be made as to
what type of precipitating agent (i.e., treatment chemical) will be
used. The factor that most affects this choice is the type of metal
constituents to be treated. Other design parameters, such as pH,
residence time, and choice of coagulant/flocculant agents, are based on
the selection of the treatment chemical.
(e) Choice of coagulant/flocculant. This parameter is
important because these compounds improve the settling rate of the
precipitated metals and allow smaller systems (i.e., those with a lower
retention time) to achieve the same degree of settling as much larger
systems. In practice, the choice of the best agent and the required
amount is determined by "jar" testing.
(f) Mixing. The degree of mixing is a complex assessment that
includes the energy supplied, the time the material is mixed, and the
related turbulence effects of the specific size and shape of the tank.
In its analysis, EPA will consider whether mixing is provided and whether
3-71
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the type of mixing device used is one that could be expected to achieve
uniform mixing. For example, EPA may not use data from a chemical
precipitation treatment system in which an air hose was placed in a large
tank to achieve mixing.
3.2.7 Polishing Filtration
Filtration is the removal of solids from wastes by a medium that
permits the flow of the fluid but retains the particles. When filtration
is conducted on wastewaters with low concentrations of solid particles
(generally below 1,000 ppm), the term "polishing" filtration is applied;
when conducted on wastes with higher concentrations of solids, the term
"sludge" filtration is applied. This section discusses "polishing"
filtration; sludge filtration is discussed separately.
(1) Applicability and use of polishing filtration. Polishing
filtration is used to treat wastewaters containing relatively low
concentrations of solids. Multimedia filtration, pressure or gravity
sand filtration, and cartridge filtration are some of the types of
equipment used for polishing filtration. This type of filtration is
typically used as a polishing step for the supernatant after
precipitation and settling (clarification) of wastewaters containing
metal precipitates. In general, filtration is used either to remove
particles that are difficult to settle because of shape and/or density or
to assist in removal of precipitated particles from an underdesigned
settling device.
3-72
-------
(2) Underlying principle of operation. The basic principle of
filtration is the separation of particles from a mixture of fluids and
particles by a medium that permits the flow of the fluid but retains the
particles. As would be expected, larger particles are easier to separate
from the fluid than are smaller particles.
Extremely small particles in the colloidal range may not be filtered
effectively in a polishing filter and may appear in the treated
wastewater. To mitigate this problem, the wastewater should be treated
prior to filtration in order to modify the particle size distribution in
favor of the larger particles, by the use of appropriate precipitants,
coagulants, flocculants, and filter aids. The selection of the
appropriate precipitant or coagulant is important because it affects the
particles formed. For example, lime neutralization usually produces
larger, less gelatinous particles than does caustic soda precipitation.
For larger particles that become too small to filter effectively because
of poor resistance to shearing, shear resistance can be improved by the
use of coagulants and flocculants. Also, if pumps are used to feed the
filter, shear can be minimized by designing for a lower pump speed, or by
use of a pump with an impeller design that minimizes shearing.
Filter aids such as diatomaceous earth are used to precoat the
cloth-type filter material and provide an initial filter cake onto which
additional solids will be deposited during the filtration process. The
presence of the precoat allows for removal of small particles from the
solution being filtered. Smaller particles will mechanically adhere to
the precoat solids during the filtration process.
3-73
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(3) Description of polishing filtration system. For relatively low
flows, a cartridge filter can be used. In this case a cylindrically
shaped cartridge, such as a matted cloth, is placed within a sealed metal
vessel. Wastewater is pumped through the cartridge until the flow drops
excessively because the filter media are plugged. The sealed vessel is
then opened and the plugged cartridge is removed and replaced with a new
cartridge. The plugged cartridge is then disposed of.
For relatively large volume flows, granulated media (such as sand or
anthracite coal) are used to trap suspended solids within the pore spaces
of the media. Wastewater is filtered until excessive pressure is
required to maintain the flow or until the flow drops to an unacceptable
level. Granular media filters are cleaned by backwashing with filtered
water that has been stored for that purpose. (Backwashing is always
upflow to loosen the media granules and resuspend the entrapped solids.)
The backwash water, which may be as much as 10 percent of the volume of
the filtered wastewater, is then returned to the treatment system, so
that the solids in the backwash water can be settled in the system
clarifier.
(4) Waste characteristics affecting performance. To determine
whether filtration would achieve a level of performance on an untested
waste similar to that on a tested waste, EPA will examine the following
waste characteristics: (1) size of suspended particles and (2) type of
particles.
3-74
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(a) Size of particles. Extremely small particles in the
colloidal range may not be filtered effectively in a polishing filter and
may appear in the filtrate. Accordingly, EPA would examine the particle
size in assessing transfer of performance. Particle size can be
determined using ASTM Method D422, Particle Size Distribution.
(b) Particle type. Some suspended solids are gelatinous in
nature and are difficult to filter. When assessing transfer of
performance, therefore, EPA will assess the type of suspended solids
particles present. EPA is not aware of any specific quantitative method
to measure the particle type; accordingly, such an assessment will be
based on a qualitative engineering analysis of the suspended solids
particles.
(5) Design and operating parameters. The design and operating
parameters that EPA will evaluate in assessing the performance of
polishing filtration are: (1) treated and untreated design
concentrations, (2) type of filter, (3) pore size, (4) pressure drop
across filter, and (5) use and type of filter aids. Each of these
parameters is discussed below.
(a) Treated and untreated design concentrations. As with other
technologies, it is important to know the level of performance that the
particular unit was designed to achieve in order to ensure that the
design value represents best demonstrated practice. Additionally, EPA
would want to evaluate feed characteristics to the filter during
treatment to ensure that the unit was operated within design
3-75
-------
specifications. Operation of the filter in excess of feed conditions
could easily lead to poor performance.
(b) Type of filter. There are several different types of
polishing filters, including granular media, cartridge filters, and
pressure filters such as plate and frame. Factors that affect filter
selection include the concentration of suspended solids, particle type
and size, process conditions (including flow rate and pressure), and
whether the treatment system is operated as a batch or a continuous
process. While more than one type of filter will generally work, it is
important to know which filter is used, as well as the basis for
selecting that filter.
(c) Pore size. The pore size determines the particle size that
will be effectively removed; accordingly, it is an important factor in
assessing filtration effectiveness on a particular waste. EPA will need
to know the pore size used, as well as the basis for its selection.
(d) Pressure drop across the filter. An important filter
design specification is the pressure drop across the filter. A pressure
drop that is higher than the filter design can force solid particles
through the filter and thus reduce the filter's effectiveness. During
treatment, EPA will periodically examine pressure readings to ensure that
the filter is.being operated within design specifications.
(e) Use and type of filter aids. As previously discussed,
filter aids improve the effectiveness of filtering gelatinous particles
and increase the time that the filter can stay on line. In assessing
3-76
-------
filtration performance, it is important to know both the type of filter
aid used and the basis for its selection.
3.2.8 Sludge Filtration
(1) Applicability and use of sludge filtration. Sludge filtration,
also known as sludge dewatering or cake-formation filtration, is a
technology used on wastes that contain high concentrations of suspended
solids, generally higher than 1 percent. The remainder of the waste is
essentially water. Sludge filtration is applied to sludges, typically
those that have settled to the bottom of clarifiers, for dewatering.
After filtration, these sludges can be dewatered to 20 to 50 percent
solids.
(2) Underlying principle of operation. The basic principle of
filtration is the separation of particles from a mixture of fluids and
particles by a medium that permits the flow of the fluid but retains the
particles. As would be expected, larger particles are easier to separate
from the fluid than are smaller particles. Extremely small particles, in
the colloidal range, may not be filtered effectively and may appear in
the treated waste. To mitigate this problem, the wastewater should be
treated prior to filtration to modify the particle size distribution in
favor of the larger particles, by the use of appropriate precipitants,
coagulants, flocculants, and filter aids. The selection of the
appropriate precipitant or coagulant is important because it affects the
particles formed. For example, lime neutralization usually produces
larger, less gelatinous particles than does caustic soda precipitation.
3-77
-------
For larger particles that become too small to filter effectively because
of poor resistance to shearing, shear resistance can be improved by the
use of coagulants and flocculants. Also, if pumps are used to feed the
filter, shear can be minimized by designing for a lower pump speed or by
using a low-shear type of pump.
(3) Description of the sludge filtration process. For sludge
filtration, settled sludge is either pumped through a cloth-type filter
medium (such as in a plate and frame filter that allows solid "cake" to
build up on the medium) or the sludge is drawn by vacuum through the
cloth medium (such as on a drum or vacuum filter, which also allows the
solids to build). In both cases the solids themselves act as a filter
for subsequent solids removal. For a plate and frame type filter, of the
solids are removed by taking the unit off line, opening the filter, and
scraping the solids off. For the vacuum type filter, the cake is removed
continuously. For a specific sludge, the plate and frame type filter
will usually produce a drier cake than will a vacuum filter. Other types
of sludge filters, such as belt filters, are also used for effective
sludge dewatering.
(4) Waste characteristics affecting performance. The following
characteristics of the waste will affect the performance of a sludge
filtration unit: (1) size of particles and (2) type of particles.
(a) Size of particles. The.smaller the particle size, the more
the particles tend to go through the filter medium. This is especially
true for a vacuum filter. For a pressure filter (like a plate and
3-78
-------
frame), smaller particles may require higher pressures for equivalent
throughput, since the smaller pore spaces between particles create
resistance to flow.
(b) Type of particles. Some solids formed during metal
precipitation are gelatinous in nature and cannot be dewatered well by
cake-formation filtration. In fact, for vacuum filtration a cake may not
form at all. In most cases, solids can be made less gelatinous by use of
the appropriate coagulants and coagulant dosage prior to clarification,
or after clarification but prior to filtration. In addition, the use of
lime instead of caustic soda in metal precipitation will reduce the
formation of gelatinous solids. The addition of filter aids, such as
lime or diatomaceous earth, to a gelatinous sludge will help
significantly. Finally, precoating the filter with diatomaceous earth
prior to sludge filtration will assist in dewatering gelatinous sludges.
(5) Design and operating parameters. For sludge filtration, the
following design and operating variables affect performance: (1) type of
filter selected, (2) size of filter selected, (3) feed pressure, and
(4) use of coagulants or filter aids.
(a) Type of filter. Typically, pressure type filters (such as
a plate and .frame) will yield a drier cake than will a vacuum type filter
and will also be more tolerant of variations in influent sludge
characteristics. Pressure type filters, however, are batch operations,
so that when the cake is built up to the maximum depth physically
possible (constrained by filter geometry), or to the maximum design
3-79
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pressure, the filter is turned off while the cake is removed. A vacuum
filter is a continuous device (i.e., cake discharges continuously), but
will usually be much larger than a pressure filter with the same
capacity. A hybrid device is a belt filter, which mechanically squeezes
sludge between two continuous fabric belts.
(b) Size of filter. As with in-depth filters, the larger the
filter, the greater its hydraulic capacity and the longer the filter runs
between cake discharges.
(c) Feed pressure. This parameter impacts both the design pore
size of the filter and the design flow rate. In treating waste, it is
important that the design feed pressure not be exceeded; otherwise,
particles may be forced thro.ugh the filter medium, resulting in
ineffective treatment.
(d) Use of coagulants. Coagulants and filter aids may be mixed
with filter feed prior to filtration. Their effect is particularly
significant for vacuum filtration since in this instance they may make
the difference between no cake and a relatively dry cake. In a pressure
filter, coagulants and filter aids will also significantly improve
hydraulic capacity and cake dryness. Filter aids, such as diatomaceous
earth, can be precoated on filters (vacuum or pressure) for sludges that
are particularly difficult to filter. The precoat layer acts somewhat
like an in-depth filter in that sludge solids are trapped in the precoat
pore spaces. Use of precoats and most coagulants or filter aids
3-80
-------
significantly increases the amount of sludge solids to be disposed of.
However, polyelectrolyte coagulant usage usually does not increase sludge
volume significantly because the dosage is low.
3-81
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4. PERFORMANCE DATA BASE
This section discusses performance data associated with the
demonstrated technologies for K086 solvent wash. Performance data
include the constituent concentrations in untreated and treated waste
samples, the operating data collected during treatment of the waste
samples, design values for the treatment technology, and data on waste
characteristics that affect treatment performance. EPA has presented all
such data, to the extent that they are available, in'tables found at the
end of this section.
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.
4.1 Organics Treatment Data
EPA tested incineration to demonstrate the actual performance
achievable by this technology for treatment of K086 solvent wash. Since
EPA is not aware of any generator or treatment, storage, and disposal
(TSD) facilities currently using incineration for treatment of wastes
containing high percentages of K086 solvent wash, the K086 solvent wash
was collected from a generator and incinerated at EPA's test facility.
The rationale for selecting the generator chosen for waste collection is
presented in a memorandum dated March 21, 1988, placed in the
Administrative Record for K086 solvent wash.
EPA has six untreated and treated data sets for K086 solvent wash
using incineration. These data are shown in Table 4-1. Although a
rotary kiln incinerator was used to treat the K086 solvent wash, the data
4-1.
-------
effectively represent liquid injection because the waste was fed through
the liquid injection nozzle on the rotary kiln unit. Each of the six
data sets provides performance for the nine BOAT list organics detected
in the untreated K086 solvent wash; therefore, the total number of
treated data points is 54. The treated data represent total waste
concentration found in the scrubber water.
The Agency does not have performance data for treatment of the
organics present in K086 solvent wash using batch distillation,
fractional distillation, or fuel substitution.
4.2 Metals...Jreatmerit. Data
4.2.1 Wastewater
The Agency does not have performance data on treatment of the BOAT
metals in the scrubber water generated specifically from the incineration
of K086 solvent wash; however, data are available from EPA's testing of a
metal-bearing wastewater at Envirite Corporation. The Agency believes
these data represent a level of treatment performance that can be
achieved for the K086 solvent wash scrubber water by using chromium
reduction, followed by lime precipitation and vacuum sludge filtration.
The data collected for the Envirite treatment system consist of 11
untreated and treated sample sets. The untreated waste is a
metal-containing wastewater that is a mixture of F006, D002, D003, and
K062 wastewaters. The two treated streams are the filtrate and the
filter cake generated from vacuum dewatering. The performance data for
the Envirite wastewater treatment system are shown in Table 4-2.
4-2
-------
EPA reviewed the characterization data for K086 scrubber water, also
presented in Table 4-2, as well as data on parameters that would affect
the performance of the Envirite treatment system (i.e., sulfide
concentration, oil and grease content, total solids content, complex
metal concentration, and type and concentration of metals). The only
data available for evaluation were type and concentration of metals and
oil and grease content (using total organic carbon as an indicator).
The concentrations of untreated metals in the Envirite wastewater are
greater than the metal concentrations in the K086 solvent wash scrubber
water. Specifically, the principal metals in the K086 scrubber water are
present at concentrations less than 0.193 mg/1 for chromium and 1.52 mg/1
for lead. In the Envirite metal-containing wastewater, the
concentrations for chromium range from 395 to 2,581 mg/1 and the
concentrations for lead range from 10 to 212 mg/1. Both the Envirite
wastewater and the K086 scrubber water have low oil and grease contents
(i.e., less than 0.3 percent total organic carbon). In conclusion, these
data show that the K086 scrubber water could be treated to the same
levels as the Envirite metal-containing wastewaters.
4.2.2 Nonwastewater
The Agency does not have performance data on treatment of the BOAT
metals in the precipitate from treatment of K086 scrubber water. Data
are available, however, from EPA's testing of a metal-bearing waste at
Envirite Corporation, and the Agency believes these data represent a
level of treatment performance that can be achieved for the K086
precipitate by using lime stabilization followed by sludge filtration.
4-3
-------
The Envirite treatment process incorporates the lime precipitation
process with lime stabilization before sludge dewatering to reduce the
Teachability of the metals in the precipitate.
Since the Agency has established that the Envirite wastewaters are
similar to K086 scrubber waters, it is reasonable to expect that the
Envirite filtered precipitate (i.e., filter cake) is similar to the K086
filtered precipitate.
4-4
-------
1 599g
Table 4-1 Performance Data Collected by EPA for Incinoralion of K08F> Solvent Wash
i
en
Analytical Data
BDA1 organic constituent concentrations
Sample Set 11 Sample Set 12 Sample Set 13
BOAT list constituents
Volatile Organ ics
Acetone
Ethylbenzene
Methyl isobutyl ketone
Hethylenc chloride
Toluene
Xylene (total)
Scmivolatile Organ ics
his(2-ethylhexyl)phthalate
Cyc lohexanone
Naphthalene
K086
solvent
wash
(mg/kg)
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
K086
Scrubber solvent
water wash
(mg/l) (mg/kg)
<0.005 CBI
<0.005 CBI
<0.010 CBI
<0.010 CBI
<0.010 CBI
<0.005 CBI
<0.010 CBI
<0.005 CBI
<0.010 CBI
K086
Scrubber solvent
water wash
(mg/l) (mg/kg)
<0.005 CBI
<0.005 CBI
<0.010 CBI
<0.005 CBI
<0.005 CBI
<0.005 CBI
<0.010 CBI
<0.005 CBI
<0 010 CBI
Scrubber
water
(mg/l)
<0.005
<0.005
<0.010
<0.005
<0.005
<0.005
<0.010
<0.005
<0.010
Sample Set 14
KOHG
solvent Scrubber
wash water
(mg/kq) (mg/l)
CHI
CBI <0.010
CHI <0.005
CHI <0.005
CBI <0.005
CBI <0.010
CBI <0.00'j
CBI <0.010
Samiile
Set JG
KOHG
solvent Scrubber
wash
(mg/kg)
CHI
CHI
CHI
cm
CBI
CHI
CBI
CHI
CBI
water
(mg/l)
<0.00!>
<0.00!>
<0.010
<0.00!>
<0.00!>
<0.00!>
<0.010
<0.00!>
<0.010
Design and Operating Data
Kiln Design Value
Temperature 1800
Revolutions per minute 0
Afterburner
Temperature 2200
•F
.2 rpm
•F
Excess oxygen 6-8%
Carbon monoxide <1000
ppm
Sample Set »1
1912-1919'F
0.2 rpm
2039-2051 -F
5.0-6.0%
4.0-5.0 ppm
Sample Set 12
1898-1929'F
0.2 rpm
2032-2051 -F
5.5%
4.0 ppm
Sample Set
1943-Z053T
0.2 rpm
2044- 2053 -F
5.5-6.?%
4.0 ppm
13 Sample Set 14
I892-195IT
0.2 rpm
2034- 2044 T
5.5-6.0%
4 . 0 ppm
Sample Set 15
1945-1954T
0.2 rpm
?037-2049T
5.7 6.0%
3.7-4.0 ppm
Sample Set If)
1830
0.
2041
5.0
4.0
1<)70M
2 rpm
20SG-I
5./%
pirn
CBI = Confidential Business Information.
Reference: USF.PA I987a.
-------
Fsrfo'ir.ance Oats CcMectec; by EPA for Cnroir.ium Reduction. Cnemici' 5recipitat 'O',
i!ic: VSLUJ:;I F lit :'-t :cr. of Kfeif. 1-ter.r i'ig Wac.tei-.aier at Envirite
Lor.s: ituent
K'JGO iClv
scruh.oer
Untreated Envinte
(mq. 1)
Filtrate
(mg/1)
Total
ED.AT
Ant imon>
Arsenic
be. u,;
Bfcry 1 1 ;um
Cacimium
Chromium (nexavalent)
Chromium (total)
Copper
Leac
Kercur,
li !L>.C !
0.063-0.107
0.059-0.093
G. 226-0. 2S7
<0. 001
<0.004
<0.01C-0.014
0.09S-0.193
O.m-0.130
0.627-l.SJ
-• 0.0002
-0.011
<0.005
;0. 005-0. 007
0. 022-0. Oe?
0.180-0.216
-1
•=10
<2
13
693
25B1
i38
£4
c\
•171
--10
116
-0.2
= 0.5
0.011
0.12
0.21
<0.01
20
1.43
7300.
3SO
2800
--0.01C
0.23
<0.020
<.0.050
'-0.010
0.125
Other Parameters
Total organic carbon
Total solids
Total chlorides
Total organic halides
Cyanide
Sulfide
1.97-8.36
3580-4160
1.2-101
0.015-0.072
<0.010
<0.5
2700
2500
Design and Operating Parameters:
it Chromium
PH
Reducing agent
Ratio of reducing agent to hexavalent chromium
ChemicaV Precipitat ion
pH
Precipitating agents
Fi Hrat ion
Type of f i Her
8.5-9.0
ferrous iron
3.2-1.0
8-10
lime and sulfide
vacuum f i Her
1 = Color interference.
- = Not analyzed.
Reference: USEPA 19&6a.
4-6
-------
Table
(Cent injed)
Con-.-.-.tufen-.
EDi.T Metals
Ant -.monv
Arsenic
5a".jm
berylr.un-
Cadmium
Cnromuim (hexavalent)
Chromium (total)
Copoer
Leod
Mercury
!, icke!
ieler.iiOT
i i Iver
I ha! !!u:n
Zinc
Other Parameters
Total organic carbon
Total solids
Total chlorides
Total organic halides
Cyanide
Sulf ide
Deiiun rind Ooerotinc Pa
Hexavalent Chromium
pH
Reducing agent
Ratio of reducing agent
Chemical Precipitation
PH
Precipitating agents
Fi Itrat ion
Type of f i Iter
ivOo?- solvent wasn
scrubDer water
(mg'l)
C. 063-0. 107
0.059-0.093
0. 226-0. 2S7
<0.001
-0.004
-.0.010-0.014
0.099-0. 193
0.115-0.130
0.b27-!.52
<0. 0002
=0.011
-0.005
-•0.006-0.007
0.022-0.027
0.180-0.216
1.97-8.36
3580-4160
1.2-101
0.015-0.072
<0.010
<0.5
rameters:
to hexavalent chromium
Concent -at 'or-:, •>,- -.«::•!,'& '-.'•.: -i
Untreated Envir-.te ri":ier r-.-'e
wastenater Filtrate Total TC.P
(mg/1) (mg.'l! (nig \c) (IK ',}
<\0 <1 <10
<1 <0 ! 1
-------
iContinued)
Lcicer.fjt IQ-.S
unireatea Envir;te
wai tender Filtrate
(mg ') (mg 1}
RD;I
An:imony
Arsenic
barium
bery 11 i uin
Caair.ium
Chromium (hexavalent)
Chromium (total)
Copper
Lead
Mercury
Silver
0.C&i-O.
0.059-0.
0.226-0.
<0.
<0.
<0.010-0.
0.099-0.
0.115-0.
O.S27-1.
<0.
<0.005-0
0.022-0
0.160-0
107
093
267
001
004
014
193
130
52
0002
Oil
DCS
007
GI-7
216
•-•10
775
1990
133
1E330
<2
3.9
3.5
<0.2
<0.5
I
0.20
0.21
<0.01
0.140
t
= 10
<2
4000
445
lib
3900
^10
<2
-•1C
112
0.45
•=0.020
<0.050
Otner Parameters
Total organic carbon
Total solids
Total chlorides
Total organic halides
Cyanide
Sulfide
1.97-6.36
3580-4160
1.2-101
0.015-0.072
<0.010
<0.5
500
Design and Operating Parameters:
Hexavtilent Chromium
pH
Reaucing agent
Ratio of reducing agent to hexavalent chromium
Chemical Precipitation
PH
Precipitating agents
FiItrat ion
Type of filter
6.5-5.0
ferrous iron
3.2-1.0
8-10
1ime and sulfide
vacuum filter
I = Color interference.
- = Not analyzed.
Reference: USEPA 1986a.
4-8
-------
Ta:;le 4-2 ;Continued)
Constituent
f.-.'ot so ivent
scrubber w.s;
Concent 'it 'o't. T
u:U reeled Envirite
wastewater Filtrate
(mg.'i) (mg/1)
Total
SPA7 Met..1 Is
Ant irriony
Arsenic
barlum
Ber', "iliurn
Cadmium
Cnromium (hexavalent)
Chromium (total)
Copper
Lean
Mercury
ii line';
0.063-0.107
0.059-0.093
0.226-0.267
<0.00l
<0.004
<0.0l0-0.0l4
0.099-0.193
O.H5-0.130
O.S27-1.52
'0.0002
-j.Oll
^0.005
«0.006-0.007
0.022-0.027
O.lc0-0.2i6
-I
••10
--2
<5
0.6
556
68
<10
6E!0
-------
Tsole ~-i (Cont inuecli
Lc/:,l,l^..l
PD-T M~cK
Ar.l iiliony
Arsenic
Ban urn
ter/ll luiP
CoUin i uin
Chromium (hexavalent)
Chromium (total)
Copper
Lead
Mercury
Nickel
Selenium
Si Ive'
Tnc: " ' u;:n
Zinc
Other Parameters
Total organic carbon
Total solids
Total chlorides
Total organic ha 1 ides
Cyanide
Sulf ide
Der-inn and Ooer.it i no Pa
Hexavalent Chromium
pH
Reducing agent
Ratio of reducing agent
Chemical Precipitation
PH
Precipitating agents
Fi It rat ion
Type of f i Her
rnrcpr,.,t,o,,^
M066 sci.en: •,-.»;.<- Jntreatec Envir-te
scruoDer water wistev.ater Filtriie
(ray 1) (:nu: "' ) Imu.' ! )
O.Obi-0.107 <10 •=!
0.059-0.093 --1 <0.1
0.226-0.267 =10 =1
-0.001 =2 =0.2
^0.004 <5 <0.5
<0. 010-0. 014 917 0.056
0.099-0.193 2236 0.11
0.115-0.130 91 0.14
0.627-1.52 16 <0.01
<0.0002 1 <0.1
<0.011 1414 0.310
-•0.005 <10 -'!
<0. 006-0. 007 <2 <0/2
0. 022-0. C2? "10 "• i
0.180-0.216 71 0.125
1.97-8.36 200
3580-4160
1.2-101
0.015-0.072 0
<0.010
<0.5
rameters :
6.5-9.0
ferrous iron
to hexavalent chromium 3.2-1.0
8-10
lime and sulfide
vacuum f i Iter
.-v-1- -• -
F-. ':&' :a--s
Tote ! T__-
(inc; ky) (ir,c ' )
,,
1 <0.010
=10 <0.75
<2
••-. -O.OiO
0.741
11500 <0.050
375
525 <0.10
-1 •= 0.0002
3300
-•10
-------
4-2 (Con: ir,uea)
Con:,; itjer,;
EDAT Metnli
An i. imony
Arsenic
Barium
Ber'y 1 1 ium
Ccidmium
Chromium (hexavalent)
Chromium (total)
Copper
Lead
Mercjr>
IncKcl
Stile:, vjm
:. i l-.er
Trie,: ;-,u-
Zinc
Other Parameters
Total organic carbon
Total solids
Total chlorides
Total organic ha 1 ides
Cyanide
Suit" ide
KjtC solvent vvasn
^C'-'jl;ber water
( m'j ' 1 )
0.01-3-0.107
0.059-0.093
0.226-0.267
-0.001
< 0.004
-0.010-0.014
0.099-0.193
0.115-0.130
0.627-1.52
<0.0002
-0.011
< 0.005
'•'j. 006-0. 007
0.022-0.027
0.160-0.216
1.S7-8.36
3580-4160
1.2-101
0.015-0.072
<0.010
--0.5
Concert rat ions re" •"5T"ie ie: -o
untreatea Envirue Filter ca*.e
KdOtewatfer Filtrate Toti'i TCLD
( tug • 1 ) ( mg ' 1 ) ( mg ''kg, ( ir.g ;' 1 )
^10 ^1 <1G
<1 <0.1 1 <0.010
«10 <2 <10 <0.10
<2 <0.2 '.2
<5 ' ^0.5 ' <5 <0.020
734 I 1.7i -
2546 0.10 10000 <0.050
149 0.12 432
<10 <0.01 42 -2 <0.2 >;2 '-O.C2;
4 0.095 6t
700
-
-
700
-
~
Desian and Operating Parameters:
Hexavalent Chromium
pH
Reducing agent
Ratio of reducing agent
Chemical Precipitation
pH
Precipitating agents
Fi Itrat ion
Type of f i Her
to hexavalent chromium
8.5-9.0
ferrous iron
3.2-1.0
8-10
1 ime and sulf ide
vacuum filter
I = Color interference.
- = Not analyzed.
Reference: USEPA 1966=.
4-11
-------
ISSSg
(Continued)
Const ituent
BOAT Metals
Ant imony
Arsenic
Ba r i urn
Beryl hum
Cadmium
Chromium (hexavalent)
Chromium (total)
Copper
Lead
Mercury
UlCKBl
ie lenium
Silver
The ' '> i utn
Zinc
Other Parameters
Total organic carbon
Total solids
Total chlorides
Total organic ha 1 ides
Cyanide
Sulf ide
Conce."t r-riT i Dnr. *'o-' '
KDoo solvent wash Untreated Envirite
scrubber witer wastewater Filtrate
(mg.'l) (mg/1) (mg.'l)
G. 063-0. 10? <10 '1
0.059-0.093 <\ '0.1
0.226-0. 287 <10 <1
-0.001 <2 <0.2
'0.004 10 .'0.5
--0.010-0.014 769 0.121
0.099-0.193 2314 0.12
0.115-0.130 72 0.16
O.BZ7-1.5Z 106 '0.01
<0.0002 <1 '0.01
<0.011 426 0.40
<0.00i"
-------
Ibcig
Table --2 (Con:inued)
Con^t itueiit
60- 7 Met el s
Ant imony
Arsenic
Ba r i urn
Beryll lum
Cadmium
Chromium (hexavalent)
Chromium (total)
Copper
Lfeoc;
Mercury
Ir.cnel
Selenium
i ' '. v e r
Tr-.rfll'.uiV.
Zinc
Other Parameters
Total organic carbon
Total solids
Total chlorides
Total organic ha 1 icies
Cyanide
Sulf ide
Concent rat ior.s fc' iiimnle ~.e: ?i
NOic solvent wasn untreated Envinte rilte' ca^e
scr-jaoer water wastewater Filtrate Total 1CLF
(mg'l) (my'T) (mg/1) (mg/kg) (mcj/1)
O.OKi-0.107 <10 <1 <10
0.059-0.093 <1 <0.1 4 0.011
0.226-0.267 <10 <1 '10 0.11
<0.001 <2 <0.2 <2
<0.004 <5 <0.5 52 <0.020
<0. 010-0. 014 0.13 <0.01 0.116
0.099-0.193 831 . 0.15 2800 <0.050
0.115-0.130 217 0.16 666
0.827-1.52 212 <0.01 300 --C.10
<0.0002 «i <0.1 «1 «O.OOG2
=0.011 669 0.36 2600
<0.005 --10 <1 --10 --0.0:0
^0.006-0.007 ^2 --0.2 -2 «0.02C
C. 022-0. 027 '10 <1 «1C
0.180-0.216 151 0.130 420
1.97-8.36 5900
3580-4160
1.2-101
0.015-0.072 SOO
<0.010
<0.5
De^ian and Ooerat ina Parameters:
Hexavalent Chromium
pH
Reducing agent
Ratio of reducing agent
Chemical Precioitat ion
pH
Precipitating agents
Fi Itrat ion
Type of filter
8.5-9.0
ferrous iron
to hexavalent chromium 3.2-1.0
8-10
lime and sulfide
vacuum f i Her
1 = Color interference.
- = Not analyzed.
Reference: USEPA 198Ca.
4-13
-------
(Com inued)
Const ituent
EDAT Herts Is
Ant imony
Arsenic
Ear HUH
Beryl 1-, urn
Cadmium
Chromium (hexava lent)
Chromium (total)
Copper
Lead
Mercery
Hi cue i
se len i u~
Silver
T ho Ilium
I inc
Other Parameters
Total organic carbon
Total solids
Total chlorides
Total organic halides
Cyanide
Sulfide
CoriCer t '.'-. I !0'V_ '2' inivcle ifc* --
Kuif. solvent wscn untreated Envirite Filter rsve
scrunoer water v.-astewater Filtrate Toto' TCL"'
(mg-"i) dug"!) (mg.'l) (ma'kg) (in; ",)
0.063-0.107 <10 <1 -10
0.05S-0.093 <1 <0.1 3 G.Oli
0.226-0.267 <10 <\ <=iu 0.20
<0.001 <2 <0.2 <2
<0.004 ^5 --0.5 6 <0.02Q
<0. 010-0. 014 0.07 0.041 1
0.099-0.193 939 0.10 3400 <0.050
0.115-0.130 225 0.08 775
0.627-1.52 <10 <0.01 65 -0.10
^0.0002 *- 1 ^0.1 < 1 "-O.OOG2
<0.011 940 0.33 3500
<0.005 <10
-------
Ibtoc:
(Co-: T.uecl)
Con^t u -ei-.t
EDA" Metals
Am iinuiiy
Arsenic
Ba r i urn
ber.> 1 1 luiii
Catiir lum
Chromium (hexavalent)
Chromium (total)
Copper
Leai:
Mercury
l.-CKel
ie'ier.i -.,!!•.
i: 've'
T n.'i "' '. •. urn
Zinc
Other Parameters
Total organic carbon
Total solids
Total chlorides
Total organic halicies
Cyanide
Sulf ide
Dei inn ^nd Oneratir.n PS
Hexavalent Chromium
pH
Reducing agent
Ratio of reducing agent
Chemical Precipitation
PH
Precipitating agents
F i Itrat ion
Type of f i Iter
C 0"ce"T rat i o'"-r ?zr i^ns'is ieT ?1C
'.C:? io'iven: w-3ir- O'tr&atec Envirue r-'- = - ::--e
scru&oer v;iter «=stef.ater FiUrate • Total KLP
(mg, 1} (ng.'lj (ing /I) 0"y kt) (mg''')
- . uc o - u . i 0 7 •- 1 u *- 1 • 1 0
0.059-0.093
-------
Tjo'ie --. (Cont injes!
Co^lH^t
BOAT Petals
Ant imony
Arsenic
Barium
beryl 1 lum
Cadmium
Chromium (hexavalent)
Chromium (total)
Copper
Lead
Mercury
!i '.CKcl
ieler ijr,
3i '-vei
T ho ' '. -, urn
Z i nc
Other Parameters
Total organic carbon
Total solids
Total chlorides
Total organic ha 1 ides,
Cyanide
Sulf ide
Cor.cent ri; :or'- *'cr iamsle ie: =:!
kjiJ solvent was* untreitec Envirue "liter ca-'e
scruboer water wastewater Filtrate Total TC_P
(mg/'l) (nvj.'l) (mg;i) (mg/'kg) (mg "! )
0.083-0.107 <10 <1 <1C
0.055-0.093 <1 <0.1 3 <0.010
0.226-0.267 <12 <1 40 0:26
<0.001 <2 <0.2 --2
<0.004 23 <5 50 <0.020
<0. 010-0. 014 0.30 <0.01 1.240
0. 099-0. 1S3 617 0.18 2100 '0.050
0.115-0.130 137 0.24 3»6
C. 627-1. 52 136 -=0.01 200 -'0.10
«0.0002 <1 '-0.1 <1 - 0.0002
'0.011 362 0.3;' 1500
<0.005 -'10 <1 -1C -G.G-C
-.0.006-0.007 -.2 --C.2 --2 -.0.020
0.022-0.027 '-JO ^\ '-10
0.160-0.216 135 0.1 323
1.97-8.36 52
3580-4160
1.2-101
0.015-0.072 300
<0.010
<0.5
Der. ;nn and Operating Parameters:
Hexavalent Chromium
pH
Reciutiny agent
Ratio of reducing agent
Chemical Precipitation
pH
Precipitat ing agents
F i Hrat ion
Type of filter
6.5-9.0
ferrous iron
to hexavalent chromium 3.2-1.0
8-10
lime and sulfide
vacuum f i Her
1 = Color interference.
- = Not analyzed.
Reference: UiEPA 156&6.
4-16
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5. IDENTIFICATION OF THE BEST DEMONSTRATED AVAILABLE TECHNOLOGY (BOAT)
This section presents the rationale for the determination of best
demonstrated available technology (BOAT) for K086 organics and metals
treatment. As discussed in Section 1 and summarized here, the Agency
examines all the available data for the demonstrated technologies to
determine whether one of the technologies performs significantly better
than the others. Next, the "best" performing treatment technology is
evaluated to determine whether the resulting treatment is substantial.
If the "best" technology is "available," that is, it provides substantial
treatment and EPA has determined that the technology is commercially
available to the affected industry, then the technology represents BOAT.
5.1 BOAT for Treatment of Orqanics
For treatment of organics in K086 solvent wash, the Agency has data
only from incineration. The data were collected during a treatment test
in which the solvent wash waste was injected through a nozzle on a rotary
kiln unit. Because data from the other demonstrated technologies are not
available, the Agency cannot compare performance to determine which
technology is "best." However, the Agency believes that liquid injection
incineration, using any type of incinerator with liquid injection
capabilities, is "best." EPA's rationale is provided below.
Although the Agency encourages recycling to minimize the amount of
waste that needs to be land disposed, batch and fractional distillation
could not improve the level of performance because the distillation
5-1
-------
process leaves behind still bottoms that require additional treatment for
organics. EPA believes that well-designed and well-operated fuel
substitution systems would not achieve better results since such systems
operate at approximately the same temperature as incineration systems and
have similar residence times and turbulence patterns.
Consistent with EPA's methodology for determining BOAT, the Agency
evaluated the incineration performance data to determine whether the
technology provides substantial treatment for K086 solvent wash.
As a first step in making this determination, EPA examined the data
to ascertain whether any data represented treatment by a poorly designed
or poorly operated system. Since such data were not found, EPA used all
the incineration data in its determination of substantial treatment.
Next, EPA adjusted the treated concentration values based on the
analytical recoveries to take into account analytical interferences
associated with the chemical makeup of the treated sample. In summary,
EPA first analyzes a waste for a constituent and then adds a known amount
of the same constituent (i.e., spike) to the waste material. The total
amount recovered after spiking minus the initial concentration in the
sample, all divided by the amount added, is the recovery value. The
reciprocal of the recovery (EPA uses the lower value of the matrix spike
and matrix duplicate recoveries, in general), multiplied by the treated
concentration, is the accuracy-corrected value used in comparing
treatment and calculating treatment standards. Percent recoveries for
the BOAT list constituents in the K086 solvent wash performance data are
5-2
-------
presented in Appendix B. (The methodology for adjusting the performance
data is discussed in Section 1.)
EPA's determination that substantial treatment occurs is based on the
reduction of BOAT list organic constituents from levels as high as (CBI)
ppm to nondetectable levels (i.e., 0.10 ppm) in the scrubber water
residual. Therefore, incineration with liquid injection capabilities
meets the second criterion for "availability." As "best,"
"demonstrated," and "available," the technology represents BOAT for the
organics present in the K086 solvent wash.
5.2 BOAT for Treatment of Metals
Incineration of K086 solvent wash generates a scrubber water (i.e.,
wastewater residual), which may require treatment for metals. No
nonwastewater residual is produced because of the waste's low ash
content. Treatment of the scrubber water, however, may generate a
precipitate (i.e., nonwastewater residual) that also may require
treatment for metals. The BDATs for metals in both the wastewater and
nonwastewater residuals are determined below.
5.2.1 Wastewater
The only demonstrated technology identified for treatment of metals
in K086 scrubber water for which the Agency has data is chromium
reduction followed by lime precipitation and sludge filtration. The
Agency has no reason to expect that the use of other chemical
precipitation processes could improve the level of performance;
therefore, chromium reduction followed by lime precipitation and sludge
filtration is "best."
5-3
-------
Chromium reduction, lime precipitation, and sludge filtration are
"available" (and therefore BOAT) because the three components of the
treatment are commercially available and provide substantial treatment.
As discussed earlier, EPA does not have treatment data for K086
solvent wash wastewater generated from incineration; however, EPA does
have treatment data specifically for metal-containing wastewater
(Envirite) that is believed to be similar to the K086 solvent wash
scrubber water.
EPA's determination of substantial wastewater treatment for the
Envirite treatment system is based on the reductions of hexavalent
chromium from 917 to 0.058 mg/1, chromium from 2,581 to 0.12 mg/1, lead
from 212 to 0.01 mg/1, copper from 225 to 0.08 mg/1, nickel from 16,330
to 0.33 mg/1, and zinc from 171 to 0.115 mg/1. The treated
concentrations are accuracy-corrected values adjusted in the same manner
as those described for the organic constituents. Since the operating
data collected during treatment of this waste show that these data
represent the performance of a well-designed, well-operated treatment
system, all data were used in determining substantial treatment.
5.2.2 Nonwastewater
For BOAT list metals in the K086 wastewater treatment precipitate,
the addition of excess lime (i.e., lime stabilization) during the
precipitation process followed by sludge filtration has been identified
as the only demonstrated technology for which the Agency has data. The
5-4
-------
Agency has no reason to believe that other stabilization processes could
improve the level of performance; therefore, lime stabilization followed
by sludge filtration is the "best" technology for treatment of the
precipitate generated during treatment of the K086 scrubber water.
EPA believes that lime stabilization provides substantial treatment,
as explained below. The Agency does not have treatment data for the
precipitate specifically generated during treatment of the K086 scrubber
water; however, EPA does have treatment data for a metal-containing
precipitate (Envirite) believed to be similar to the K086 wastewater
treatment precipitate. Operating data collected during treatment of this
waste show that these data represent the performance of a well-designed,
well-operated treatment system; therefore, these data were used to
determine substantial treatment.
EPA adjusted the data values as described earlier to take into
account analytical interferences associated with the chemical makeup of
the treated sample.
EPA does not have the TCLP leachate values of the untreated waste to
compare to the TCLP leachate values of the treated waste. The Agency
believes that theoretical TCLP leachate values for the treated waste can
be calculated by dividing the total metal concentrations of the treated
waste by a dilution factor of 20. This dilution factor accounts for the
amount of waste and extraction fluid used in the test. A discussion of
the dilution factor can be found in "Best Demonstrated Available
Technology (BOAT) Background Document for F001-F005 Spent Solvents."
5-5
-------
EPA compared the theoretical leachate value of 815 mg/1 to the actual
TCLP leachate value of 0.050 mg/1 for chromium and the theoretical
leachate value of 140 mg/1 to the actual leachate value of 0.10 mg/1 for
lead. Based on these comparisons, the Agency believes that lime
stabilization followed by sludge filtration provides substantial
treatment.
Because the Agency believes that substantial treatment is provided by
this treatment and because it is commercially available, lime
stabilization followed by sludge filtration represents BOAT for K086
precipitated wastes.
5-6
-------
6. SELECTION OF REGULATED CONSTITUENTS
As discussed in Section 1, the Agency has developed a list of
hazardous constituents (Table 1-1) from which the constituents to be
regulated are selected. EPA may revise this list as additional data and
information become available. The list is divided into the following
categories: volatile organics, semivolatile organics, metals, inorganics
other than metals, organochlorine pesticides, phenoxyacetic acid
herbicides, organophosphorous insecticides, PCBs, and dioxins and furans.
This section presents the rationale for selection of the regulated
constituents, from the BOAT list of constituents, for the K086 solvent
wash treatability group. 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 K086 Solvent Wash
As discussed in Sections 2 and 4, the Agency has characterization
data as well as performance data from treatment of K086 solvent wash.
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 K086
solvent wash n.onwastewater and wastewater.
Table 6-1, at the end of this section, indicates for the untreated
waste, which constituents were analyzed, which constituents were
detected, and which constituents the Agency believes could be present
6-1
-------
though not detected. For those constituents detected, concentrations are
indicated. (In the non CBI document, concentrations are given only for
constituents detected in the non CBI characterization data presented in
Table 2-3.)
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 would be present (e.g., the
engineering analysis shows that a particular constituent is present in 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; this process may utilize variable starting materials composed of
different constituents. Therefore, all potentially regulated
constituents would not necessarily be present in any given sample.)
Detection limits for the analytical methods used to analyze K086 solvent
wash have been classified as confidential information by the generator.
However, the analytical detection limits for the scrubber water are given
in Appendix C.
6-2
-------
The Agency analyzed for 193 of the 231 BOAT list constituents in
samples collected during the K086 solvent wash test burn. Of the 38
constituents not analyzed, EPA believes they were unlikely to be
present. Of the 193 constituents analyzed, 19 were detected in the
untreated K086 solvent wash. (Note that the xylene compounds were not
differentiated during analysis and therefore are being counted as one of
the 19 constituents.) The other available characterization data and the
scrubber water data from the test burn indicate that ethyl acetate,
cadmium, arsenic, silver, selenium, and vanadium also can be present.
EPA has examined the K086 waste generating process and believes that
solvents other than those found in the tested waste can be used to clean
ink formulating equipment or can be used in the formulation of inks
containing lead and chromium. Furthermore, the Agency has data
indicating that the following seven additional BOAT list organic solvents
are used in the ink formulation process and/or in cleaning ink
formulating equipment: n-butyl alcohol, o-dichlorobenzene, methanol,
methyl ethyl ketone, nitrobenzene, 1,1,1-trichloroethane, and
trichloroethylene. EPA is concerned that by not considering these other
solvents, the Agency would not only be presenting an incentive to switch
to these solvents, but would also be sending an erroneous signal that EPA
is not concerned about land disposal of these other constituents.
6.2 Determination of Significant Treatment from BOAT
The next step in selecting the constituents to be regulated is to
eliminate those constituents identified in the waste that cannot be
significantly treated by the technologies designated as BOAT.
6-3
-------
6.2.1 BOAT List Organic Constituents
Table 6-2, at the end of this section, presents the concentrations of
constituents in the untreated waste and the treatment residual from the
incineration test burn, i.e., scrubber water. The data demonstrate that
all the organic constituents detected in the K086 solvent wash are
reduced significantly, especially in the cases of acetone,
bis(2-ethylhexyl)phthalate, napthalene, cyclohexanone, and xylene. This
indicates that incineration, the BOAT identified for organics treatment,
is effective in reducing organic constituents to nondetectable levels in
the scrubber water. The performance data also show incineration as
treatment for the small quantities of cyanide and sulfide present in the
K086 solvent wash.
As discussed in Section 3.2.1, the Agency is using theoretical bond
energies as a surrogate for measuring combustibility. In general, the
higher the bond energy for a constituent, the more difficult it is to
combust that constituent. Out of all the BOAT list organics either
determined to be present in K086 solvent wash by examining the waste
generating process or actually detected in K086 solvent wash by
analytical analyses, bis(2-ethylhexyl)phthalate, napthalene, xylene, and
ethyl benzene rank as the most difficult to treat based on their high
bond energies. Since these four constituents were actually treated to
nondetectable concentrations in the K086 scrubber water, EPA believes
that the other organic constituents can also be treated to nondetectable
levels. (Table 6-3, at the end of this section, shows the calculated
bond energies for the candidate organic constituents.)
6-4
-------
6.2.2 BOAT List Metal Constituents
The data show a scrubber water with no treatable levels of organics
but with treatable amounts of metals. The detected metals in the K086
solvent wash scrubber water include antimony, arsenic, barium, chromium,
copper, hexavalent chromium, lead, silver, vanadium, and zinc. The
Agency does not have treatment data for K086 scrubber water; however,
EPA does have treatment data, using chromium reduction, followed by
chemical precipitation incorporated with lime stabilization and sludge
filtration, for a similar waste (i.e., Envirite wastewater). Treatment
of the metals present in the Envirite wastewater is demonstrated by the
significant reduction of cadmium, hexavalent chromium, chromium, copper,
lead, nickel, and zinc in the filtrate and in the filter cake leachate.
However, the untreated Envirite wastewater does not contain detectable
levels of antimony, arsenic, barium, silver, and vanadium. Therefore,
even though these metals may be present in quantities below the detection
levels, one cannot determine whether these metals were treated since the
amounts present cannot be measured.
6.3 Rationale for Selection of Regulated Constituents
Table 6-4, at the end of this section, presents all of the candidate
constituents. Note that all 25 could be regulated; however, the Agency
believes that regulation of fewer constituents will have the same desired
effect if the constituents are selected carefully.
6-5
-------
EPA is regulating all the organic constituents detected in K086
solvent wash and all the BOAT list organic constituents that were not
detected but could be present in other solvent washes generated in the
cleaning of ink formulating equipment. Since K086 solvent washes can
vary depending on the type of solvent or solvents used to clean ink
formulating equipment, the Agency has chosen to regulate all the
candidate organics, because regulation of a few may not control land
disposal of the others. Acetone, n-butyl alcohol, ethyl acetate,
ethylbenzene, methanol, methyl isobutyl ketone, methyl ethyl ketone,
methylene chloride, toluene, 1,1,1-trichloroethane, trichloroethylene,
xylene, bis(2-ethylhexyl)phthalate, cyclohexanone, 1,2-dichlorobenzene,
napthalene, and nitrobenzene are the 17 BOAT list organic constituents
selected as the regulated organic constituents for wastewater and
nonwastewater forms of K086 solvent wash. Cyanide and sulfide were not
chosen as regulated constituents because they are present in small
quantities and EPA believes that they will be controlled by regulation of
the other constituents.
In selecting metal constituents to regulate, EPA considered both the
concentration of the metal in the incinerator residual (i.e., scrubber
water) and the concentration of the metal in the K086 solvent wash. By
using metal concentrations in the K086 solvent wash as part of the basis
for selecting metal constituents to regulate, EPA has included some
metals that were not in the scrubber water at treatable concentrations.
EPA's rationale for this selection approach is discussed below.
6-6
-------
In general, an incinerator is not specifically designed to treat
metals. Accordingly, the concentration of metals in the scrubber water
and in the ash will depend on the specific design and operating
parameters selected for volatilization and destruction of the organic
constituents in the waste. For example, an incinerator that operates at
a higher temperature would be expected to have higher metal
concentrations in the scrubber water than an incinerator that operates at
a lower temperature. If EPA relied solely on the residual metal
concentrations in one, or even several, incinerator test(s) in making
decisions on which constituents to regulate, the Agency could easily
decide not to regulate metal constituents that would appear at
significant concentrations in another incinerator treating the same waste
under different design and operating parameters. In addition to metal
residual concentrations varying from one incinerator to the next because
of different operating temperatures, residence times, and turbulence
effects, residual metal concentrations will also vary because the K086
solvent wash can have different concentrations of a particular metal
constituent. In particular, lead and chromium concentrations can vary in
K086 solvent wash relative to the amounts added to a particular ink batch.
For the above reasons, EPA is selecting the constituents for lead and
chromium based on both the metal concentration in the K086 solvent wash
and scrubber water residual. Facilities are reminded that if the
incinerator scrubber water residual as generated already complies with
the BOAT treatment standards, the residual does not need to be treated.
6-7
-------
Table 6-1 Status of BOAT List Constituent Presence
. in Untreated K086 Solvent Wash
BOAT
reference
no.
222.
1.
2.
3.
4.
5.
6.
223.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
25.
26.
27.
28.
29.
224.
225.
226.
30.
227.
31.
214.
32.
33.
228.
34.
Constituent
Volatile orqanics
Acetone
Acetonitri le
Acrolein
Acrylonitrile
Benzene
Bromodichlorome thane
Bromomethane
n-Butyl alcohol
Carbon tetrachloride
Carbon disulfide
Chlorobenzene
2-Chloro-1.3-butadiene
Chlorodibromomethane
Chloroethane
2-Chloroethyl vinyl ether
Chloroform
Chloromethane
3-ChloTopropene
1.2-Dibromo-3-chloropropane
1 ,2-Dibromoethane
Dibromome thane
trans-1 ,4-Dichloro-2-butene
Dichlorodif luoromethane
1 , 1-Dichloroethane
1.2-Dichloroethane
1 . 1-Dichloroethy lene
trans-l,2-Dichloroethene
1.2-Dichloropropane
trans- 1 , 3-D ich loropropene
cis-1 ,3-Dichloropropene
1,4-Oioxane
2-Ethoxyethanol
Ethyl acetate
Ethyl benzene
Ethyl cyanide
Ethyl ether
Ethyl methacrylate
E thy lene oxide
lodomethane
Isobutyl alcohol
Hethanol
Methyl ethyl ketone
Detection Believed to
status9 be present
D (CB1)
ND
ND
ND
ND
ND
ND
NA X
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NA
256.000
D (CBI)
ND
NA
ND
NA
ND
ND
NA X
ND X
6-8
-------
Z164g
Table 6-1 (Continued)
BOAT
reference
no.
229.
35.
37.
38.
230.
39.
40.
41.
42.
43.
44.
45.
46.
47.
48.
49.
231.
50.
215.
216.
217.
51.
52.
53.
54.
55.
56.
57.
58.
59.
218.
60.
61.
62.
63.
64.
65.
66.
Constituent
Volati 1c organics (continued)
Methyl isobutyl ketone
Methyl methacrylate
Methacrylonitrile
Methylene chloride
2-Nitropropane
Pyridine
1.1.1. 2-Tetrachloroethane
1,1,2, 2-Tetrachloroethane
Tetrachloroethene
Toluene
Tribromomethane
1 , 1 . 1-Trichloroethane
1 , 1 ,2-Trichloroethane
Ir ichloroethene
T r i ch loromonof 1 uoromethane
1 ,2.3-Trichloropropane
1.1.2-Trichloro-1.2,2-
trif luoroethane
Vinyl chloride
1,2-Xylene
1,3-Xylene
1.4-Xylene
Semivolatile orqanics
Acenaphtha lene
Acenaphthene
Acetophenone
2 - Acet y 1 am i nof 1 uorene
4-Aminobiphenyl
Aniline
Anthracene
Aramite
Benz ( a ) an t hracene
Benzal chloride
Benzenethiol
.Deleted
Benzo(a)pyrene
Benzo(b)f luoranthene
Benzofghi Iperylene
Benzo(k)f luoranthene
p-Benzoquinone
Detection Believed to
status3 be present
D (CBI)
ND
ND
D (CBI)
NA
ND
ND
ND
ND
D (CBI)
ND
ND X
ND
ND X
ND
ND
NA
ND
D (CBI)
D (CBI)
D (CBI)
ND
ND
ND
ND
ND
ND
ND
ND
ND
NA
ND
ND
ND
ND
ND
ND
6-9
-------
2164g
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.
105.
106.
219.
Detection
Constituent status3
Semivolatile 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-Butyl-4,6-dinitrophenol
p-Chloroaniline
Chlorobenzilate
p-Chloro-m-cresol
2-Chloronaphthalene
2-Chlorophenol
3-Chloropropionitr i le
Chrysene
ortho-Cresol
para-Cresol
Cyclohexanone
Dibenz(a,h)anthracene
Oibenzo(a,e)pyrene
Dibenzo(a, i)pyrene
m-Dichlorobenzene
o-Dichlorobenzene
p-Dichlorobenzene
3,3'-Dichlorobenzidine
2 , 4 -D ich loropheno 1
2.6-Dichlorophenol
Diethyl phthalate
3 . 3 ' -0 imethoxybenz idine
p-D imct hy lam i noazobenzene
3.3'-Dimethylbenzidine
2.4-Dimethylphenol
Dimethyl phthalate
Di-n-butyl phthalate
1,4-Dinitrobenzene
4.6-Dinitro-o-cresol
2,4-Dinitrophenol
2,4-Dinitrotoluene
2.6-Dinitrotoluene
Di-n-octyl phthalate
Di-n-propylnitrosamine
Diphenylamine
D i pheny Initrosamine
Believed to
be present
ND
ND
ND
D (CB1)
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0 (CBI)
ND
ND
ND
ND
ND X
ND
ND
ND
ND
ND
NO
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
6-10
-------
2164g
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.
Detection
Constituent status3
Semivolati 1e organics (continued)
1.2-Diphenylhydrazine
Fluoranthcne
Fluorene
Hexach lorobenzene
Hexachlorobutadiene
Hexach lorocyc lopentad i ene
Hexach loroethane
Hexachlorophene
Hexach loropropene
I ndeno ( 1 , 2 , 3-cd ) py rene
Isosafrole
Methapyrilene
3-Methylcholanthrene
4,4'-Methylenebis
(2-chloroaniline)
Methyl methanesulfonate
Naphthalene
1 , 4 -Naphthoqu i none
1-Naphthylamine
2-Naphthylamine
p-Nitroaniline
Nitrobenzene
4-Nitrophenol
N-Nitrosodi-n-butylamine
N-Nitrosodiethylamine
N-Nitrosodimethylamine
N-Nitrosomethylethylamine
N-Nitrosomorphol ine
N-Nitrosopiperidine
n-Nitrosopyrrol idine
5-Nitro-o-toluldine
Pentachlorobenzene
Pentach loroethane
Pentach loron i t robenzene
Pentach lorophenol
Phenacetin
Phenanthrene
Phenol
Phthalic anhydride
2-Picoline
Pronamide
Pyrene
Resorcinol
Believed to
be present
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
D (CB1)
ND
ND
ND
ND
ND X
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NA
ND
ND
ND
ND
6-11
-------
2164g
Table 6-1 (Continued)
BDA1
reference
no.
147.
148.
149.
150.
151.
152.
153.
154.
155.
156.
157.
158.
159.
2Z1.
160.
161.
162.
163.
164.
165.
166.
167.
168.
169.
170.
171. •
172.
173.
174.
175.
Detection
Constituent status3
Semivolatile orqanics (continued)
Safrole
1 , 2 , 4 . 5-1 et rach lorobenzene
. 2,3,4,6-Tetrachlorophenol
1 ,2,4-Trichlorobenzene
2,4.5-Trichlorophenol
2,4,6-Trichlorophenol
Tris(2,3-dibromopropyl)
phosphate
Held Is
Ant imony
Arsenic
Barium
Beryllium
Cadmium
Chromium (total)
Chromium (hexavalent)
Copper
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Inorganics other than metals
Cyanide
Fluoride
Sulfide
Organochlorine pesticides
Aldrin
alpha-BHC
beta-BHC
delta-BHC
Bel ieved to
be present
ND
ND
ND
ND
ND
ND
ND
D (CB1)
ND Y
D (CB1, 0.54)
ND
4.3
D (CB1. 116)
D (CBI)
0 (CBI. 17)
D (CBI. 1.06)
ND
D (CBI. 2.4)
0.05
0.32
ND
ND Y
D (CBI. 1.1)
D (CBI)
ND
D (CBI)
NA
NA
NA
NA
6-12
-------
2164g
Table 6-1 (Continued)
BOA!
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.
Detection
Constituent status3
Orqanochlorine pesticides (continued)
ganroa-BHC
Chlordane
000
DDE
DDT
Oieldrin
Endosulfan 1
Endosulfan II
Endrin
Endrin aldehyde
Heptachlor
Heptachlor epoxide
Isodrin
Kepone
Hethoxyc lor
Toxaphene
Phenoxvacetic acid herbicides
2.4-Dichlorophenoxyacetic acid
Silvex
2,4.5-T
Orqanophosphorous insecticides
Disulfoton
Famphur
Methyl parathion
Parathion
Phorate
PCBs
Aroclor 1016
Aroclor 1221
Aroclor 1232
Aroclor 1242
Aroclor 1248
Aroclor 1254
Aroclor 1260
Believed to
be present
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
ND
ND
ND
ND
ND
ND
ND
6-13
-------
2164g
Table 6-1 (Continued)
BDA1
reference
no.
Constituent
Detection
status3
Believed to
be present
207.
208.
209.
210.
211.
212.
213.
Dioxins and furans
Hexachlorodibenzo-p-diox ins
Hexachlorod i benzofurans
Pentachlorodibenzo-p-dioxins
Pentachlorodibenzofurans
Tetrachlorodibenzo-p-dioxins
Tetrachlorod ibenzofurans
2.3.7,8-Tetrachlorodi benzo-
p-dioxin
NO
NO
NO
NO
ND
NO
ND
D = Detected in untreated waste samples.
ND = Not detected.
NA = Not analyzed.
CB1 = Confidential business information.
X = Believed to be present based on engineering analysis of the waste
generating process.
Y = Believed to be present based on detection in treated residuals.
alf detected, concentration is shown; units are mg/kg.
Xylene isomers were not differentiated during analysis.
6-14
-------
1599g
Table 6-2 BOAT Constituent Concentrations in Untreated K086 Solvent Wash
and Scrubber Uater Residual from Test Burn
BOAT
reference
no.
222
226
229
38
43
215-217
70
232
121
154
155
156
159
221
160
161
163
165
167
168
169
171
Constituent
Volatile orqanics
Acetone
Ethylbenzene
Methyl isobutyl ketone
Methylene Chloride
Toluene
Xylene (total)
Semivolat i 1e orqanics
Bis(2-ethylhexyl)phthalate
Cyclohexanone
Naphthalene
Metals
Antimony
Arsenic
Barium
Chromium (total)
Chromium (hexavalent)
Copper
Lead
Nickel
Silver
Vanadium
Zinc
Inorganics
Cyanide
Sulfide
K086 solvent wash
untreated waste
(mg/1)
CB1
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
Scrubber water
(mg/D
<0.010
<0.005
<0.010
<0.010
<0.010
<0.005
<0.010
<0.005
<0.010
0.083-0.107
0.059-0.093
0.226-0.287
0.099-0.193
<0. 010-0. 014
0.115-0.130
0.827-1.52
<0.011
<0. 006-0. 007
0.022-0.027
0.180-0.216
<0.010
<0.5
CBI = Confidential Business Information.
Reference: USEPA 1987a.
6-15
-------
1599g
Idble 6-3 Calculated Bond Energy for the Candidate
Organic Constituents
Calculated bond energy
Constituent (kcal/mol)
Volatile orqanics
Acetone 945
n-Butyl alcohol 1350
Ethyl acetate 1655
Ethyl benzene 1900
Hcthanol 495
Methyl isobutyl ketone 1800
Methyl ethyl ketone 1230
Methylene chloride 355
Toluene 1615
1,1.1-Trichloroethane 625
Trichloroethylene 485
Xylenes (total) 1900
Semivolatile orqanics
Bis(2-ethylhexyl)phthalate 6620
Cyclohexanone 1685
1.2-Dichlorobenzene 1320
Naphthalene 2140
Nitrobenzene 1430
Reference: Sanderson 1971.
6-16
-------
1599g
Table 6-4 Candidate Constituents for Regulation of K086 Solvent Wash
BOAT reference no. Constituent
222
223
225
226
228
229
34
38
43
45
47
215-217
70
232
87
121
126
159
221
160
161
163
168
169
171
Volatile orqanics
Acetone
n-Butyl alcohol
Ethyl acetate
Ethylbenzene
Methanol
Methyl isobutyl ketone
Methyl ethyl ketone
Methylene chloride
Toluene
1.1.1-lrichloroethane
Tricnloroethylene
Xylene (total)
Semivolati le orqanics
Bis(2-ethylhexyl)phthalate
Cyclohexanone
1 , 2-0 ich lorobenzene
Naphthalene
Nitrobenzene
Metals
Chromium (total)
Chromium (hexavalent)
Copper
Lead
Nickel
Zinc
Inorganics
Cyanide
Sulfide
6-17
-------
7. CALCULATION OF BOAT TREATMENT STANDARDS
The purpose of this section is to calculate the actual treatment
standards using analytical treatment data for the regulated constituents
selected in Section 6. As discussed in the Introduction, the following
steps are taken to derive the BOAT treatment standards:
1. The Agency evaluates the available data for the BOAT treatment
technologies and deletes any data representing poor design or
poor operation of the treatment systems.
2. Next, averages for accuracy-corrected constituent concentrations
are calculated and a variability factor is also determined for
each constituent selected for regulation.
3. The BOAT treatment standard for each constituent selected for
regulation is determined by multiplying the average
accuracy-corrected total composition by the appropriate
variability factor.
Using these three steps, the following sections discuss the
calculation of the BOAT list organic and metal treatment standards for
K086 solvent wash nonwastewaters and wastewaters. Appendix B presents
the calculation of the corrected average concentrations and the quality
assurance/quality control data used to calculate these corrected values.
The method for calculation of the variability factors is presented in
Appendix A, and the actual calculations can be found in the
Administrative Record for K086 solvent wash.
7.1 Calculation of Treatment Standards for Nonwastewater Forms of
K086 Solvent wash
. For K086 solvent wash,' EPA is proposing nonwastewater standards that
would apply to untreated K086 solvent wash (considered to be a
nonwastewater because the TOC value, would be greater than 1 percent) and
to the precipitated residual generated from treatment of K08.6 incinerator
7-1
-------
scrubber waters (a nonwastewater based on the total suspended solids
content). Below is a description of how the BOAT treatment standards
were calculated for BOAT list organics and metals in K086 nonwastewaters.
7.1.1 Organic Treatment Standards
Section 6.3 describes the specific organic constituents that EPA has
selected for regulation. In general, the BOAT list organic treatment
standards for nonwastewaters are derived from ash residual data when BOAT
represents incineration. In the case of K086 solvent wash, EPA could not
base nonwastewater standards on residual ash concentrations because
incineration of this waste did not result in an ash residual. To
establish standards for the BOAT list organics in nonwastewaters, EPA
related the treatment performance represented by the scrubber water
organic concentrations to the BOAT list organic concentrations that would
be expected in nonwastewater residuals generated from treatment of K086
scrubber water. This relationship is discussed in more detail below.
The Agency does not have data on the filtered precipitate generated
specifically from treatment of K086 solvent wash scrubber waters. The
incineration data presented in Section 4 show that organic levels in the
K086 solvent wash scrubber water are nondetectable. The Agency believes
that metals treatment of the K086 solvent wash scrubber waters can
generate a nonwastewater, the filtered precipitate, that will also have
nondetectable levels of organics. Therefore, K086 solvent wash treatment
standards for organic constituents in a nonwastewater matrix were
calculated based on the organic detection limits of a wastewater
7-2
-------
treatment filter cake (Envirite) determined to be similar to the K086
solvent wash filter cake.
In estimating the analytical detection levels of organics for the
precipitated residual waste, EPA examined available data on detection
levels for 15 chemically precipitated wastes believed to be most similar
to the waste that would be generated by metals treatment of K086 scrubber
water. These data are presented in Appendix E and consist of detection
levels for 7 of the 12 volatile constituents selected for regulation.
Detection levels were not available for the 5 semivolatile constituents
selected for regulation. For the 5 volatile constituents and the
5 semivolatile constituents for which EPA does not have detection levels,
the Agency is proposing the highest volatile detection level observed in
the similar wastes. EPA believes that this approach provides a
conservative estimate of the detection levels.
None of the Envirite data were deleted because of poor design or poor
operation of the treatment system. The corrected average concentrations,
determined variability factors, and calculated organic standards for K086
nonwastewaters are presented in Table 7-1 at the end of this section.
7.1.2 Metal Treatment Standards
As stated previously, the Agency does not have data for the filtered
precipitate generated specifically from treatment of K086 scrubber
water. Therefore, the Agency is transferring levels of performance from
a similar waste treated at Envirite.
7-3
-------
The best measure of metals in a nonwastewater matrix that may migrate
into the environment is the analysis of the toxicity characteristics
leaching procedure (TCLP) extract. Therefore, BOAT treatment standards
for metals were calculated based on TCLP data from the Envirite filter
cake determined to be similar to K086 solvent wash filter cake.
The data used for calculation of the K086 solvent wash nonwastewater
metal standards is presented in Table 4-2. None of the data were deleted
because of poor design or poor operation of the treatment system. Hence,
all 11 data sets are used for regulation of metals in K086 solvent wash
nonwastewater.
Next, the accuracy-corrected constituent concentrations were
calculated for all selected BOAT list constituents. The arithmetic
average concentration and a variability factor were determined for each
BOAT for the lead and chromium data. Finally, the BOAT performance
standards for lead and chromium were determined by multiplying the
average accuracy-corrected total composition by the appropriate
variability factor as shown in Table 7-1.
7.2 Calculation of Treatment Standards for Wastewater Forms of K086
Solvent Wash
The only data available to the Agency characterizing wastewater forms
of K086 solvent wash are the scrubber water data generated during
incineration of the K086 solvent wash.
7.2.1 Organic Treatment Standards
The data characterizing K086 solvent wash scrubber water show
nondetectable levels of the regulated organic constituents that were
7-4
-------
detected in the untreated K086 solvent wash. Therefore, the organic
treatment standards will be based on the analytical detection levels.
All six data sets were used in development of the treatment standards.
The Agency has detection levels for ten volatiles and all five
semivolatiles. Two volatiles, n-butyl alcohol and ethyl acetate, were
not analyzed for because they were not on the list at the time of the
analysis. For these volatile organics, EPA is proposing the highest
volatile detection observed in the K086 scrubber water. The calculations
of the wastewater organic treatment standards for K086 solvent wash are
presented in Table 7-2.
7.2.2 Metal Treatment Standards
The Agency does not have any treatment performance data on treatment
of K086 solvent wash scrubber water. Therefore, the Agency is
transferring treatment data from a similar wastewater treated at Envirite
(see Section 4). The Agency expects that the Envirite wastewater is at
least as difficult to treat as the K086 solvent wash scrubber water since
the Envirite untreated metal concentrations are higher. Accordingly, EPA
believes that the level of performance achieved for lead and chromium in
the wastes treated in the Envirite treatment system can be transferred
for lead and chromium levels in the K086 solvent wash wastewater. The
data consist of 11 influent and effluent sample sets. All .effluent data
were used in development of the treatment standards. The calculations of
the wastewater metal treatment standards for K086 solvent wash are
presented in Table 7-2.
7-5
-------
Ti:/!e 7-! Cilcjlition of i.Oc-'l solvent Wash tonwaitev.cter
B[;,-
reference
P.O.
Appro.-, unate Aoprox unite
EDAT liit accuracy-corrected variability
constituents average concentration8 factor3
Treatment
standard0
Vclat ! le organics (mg/kg)
222 Acetone 0.13 2.is 0.37
223 n-Butyl alcohol 0.13 2.8 0.37
225 Ethyl acetate 0.13 2.6 0.37
226. Ethylbenzene 0.011 2.8 0.031
228 Methanol 0.13 2.6 . 0.37
229 Methyl isobutyl ketone 0.13 2.6 0.37
34 Methyl ethyl ketone 0.13 2.6 0.37
36 Methylene chloride 0.013 2.6 0.037
43 Toluene 0.011 2.6 0.031
45 1,1'. l-Tricnloroethane 0.016 2.6 0.044
47 Trichloroethylene 0.01! 2.6 0.031
21S-217 Xylene (total) 0.0055 2.S 0.015
Semu'olati le oraanics (mg/kg)
70 Bis(2-ethylhexyl)phthalate 0.18 2.8 0.49
232 Cyclohexanone 0.18 2.8 0.49
87 1.2-Dichlorobenzene 0.18 2.8 0.49
121 Naphthalene 0.18 2.8 0.49
125 Nitrobenzene 0.18 2.8 0.49
Metals. TCLP leachate (mg/1)
15& Chromium (total) 0.076 1.24 0.094
161 Lead 0.013 2.8 0.37
aCalculation for the accuracy-corrected average concentration is shown in Appendix B.
Method used for calculation of the variability factor is shown in Appendix A.
cTreatment standard = (accuracy-corrected, average concentration) x (variability
factor). The value for the treatment standard was rounded to two significant
figures at the end of the calculation.
7-6
-------
7-i Cr.';•;•-U: 10:1. cf r.O'd'I iolvent Wcih WcStev.ater Treatment iianc
fcGAT Approximate Approximate
reference BDAT list accuracy-corrected variability Treatment
no constituents average concentration3 factor5 standard0
Volat ile oraanics (mg/1)
222 Acetone 0.0055 2.6 0.015
223 n-butyl alcohol 0.011 2.6 0.021
225 Ethyl acetate 0,011 2.6 0.031
226 Ethylbenzene 0.0055 2.8 0.015
226 Metnanol 0.011 2.8 0.031
2W Methyl isobutyl ketone 0.011 2.6 0.031
34 Methyl ethyl ketone 0.011 2.8 0.031
3S Methylene chloride 0.011 2.6 0.031
41 Toluene 0.010 2.6 0.029
45 1.1,1-Trichloroethane 0.011 2.6 0.031
47 Trichlcroetnylene 0.010 2.8 O.G29
215-217 Xylene (total) 0.0055 2.8 0.015
Semivolatile orqanics (mg/1)
70 Bis(2-ethylhexyl)phthalate 0.016 2.8 0.044
232 Cyclohexanone 0.0078 2.8 0.022
87 1,2-Dichlorpbenzene 0.016 2.8 0.044
121 Naphthalene 0.016 2.8 0.044
126 Nitrobenzene 0.016 2.8 0.044
Metals (mg/1)
155 Chromium (Total) 0.19 1.69 0.32
161 Lead 0.013 • 2.8 0.037
Calculation for the accuracy-corrected average concentration is shown in Appendix B.
Method used for calculation of the variability factor is shown in Appendix A.
cTreatment standard = (accuracy-corrected, average concentration) x (variability
factor). The value for the treatment standard was rounded to two significant
figures at the end of the calculation.
7-7
-------
8. ACKNOWLEDGMENTS
This document was prepared for the U.S. Environmental Protection
Agency, Office of Solid Waste, by Versar Inc. under Contract
No. 68-01-7053. Mr. James Berlow, Chief, Treatment Technology Section,
Waste Treatment Branch, served as the EPA Program Manager during the
preparation of this document and the development of treatment standards
for the K086 solvent washes waste. The technical project officer for the
waste was Mr. Jose Labiosa. Mr. Steven Silverman served as legal advisor.
Versar personnel involved in the preparation of this document
included Mr. Jerome Strauss, Program Manager; Ms. Laura Fargo,
Engineering Team Leader; Ms. Justine Alchowiak, Quality Assurance
Officer; Mr. David Pepson, Senior Technical Reviewer; Ms. Olenna
Truskett, Technical Reviewer; Ms. Barbara Malczak, Technical Editor; and
the Versar secretarial staff, Ms. Linda Gardiner and Ms. Mary Burton.
The K086 treatment test was executed at the U.S. EPA Combustion
Research Facility by Acurex Corporation, contractor to the Office of
Research and Development. Field sampling for the test was conducted
under the leadership of Mr. William Myers of Versar; laboratory
coordination was provided by Mr. Jay Bernarding, also of Versar.
We greatly appreciated the cooperation of the National Association of
Printing Ink Manufacturers and the individual companies whose plants were
sampled and who submitted detailed information to the U.S. EPA.
8-1
-------
9. REFERENCES
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incineration of PCB-containing wastes on board the M/T Vulcanus.
600/7-83-024. Washington, D.C.: U.S. Environmental Protection Agency.
Ajax Floor Products Corp. n.d. Product literature: technical data
sheets, hazardous waste disposal system. P.O. Box 161, Great Meadows,
N.J. 07838.
Aldrich, J. 1985. Effects of pH and proportioning of ferrous and
sulfide reduction chemicals on electroplating waste treatment sludge
production. In Proceedings of the 39th Purdue Industrial Waste
Conference, May 8, 9, 10, 1984. Stoneham, Mass.: Butterworth
Publishers.
Austin. G.T. 1984. Shreve's chemical process industries. 5th ed.
New York: McGraw-Hill.
Bishop, P.L., Ransom, S.B., and Grass, D.L. 1983. Fixation mechanisms
in solidification/stabilization of inorganic hazardous wastes. In
Proceedings of the 38th Industrial Waste Conference, 10-12 May 1983, at
Purdue University, West Lafayette, Indiana.
Bonner, T.A., et al. 1981. Engineering handbook for hazardous waste
incineration. SW-889. Prepared by Monsanto Research Corporation for
U.S. Environmental Protection Agency. NTIS PB 81-248163. June 1981.
Castaldini, C., et al. 1986. Disposal of hazardous wastes in industrial
boilers or furnaces. Park Ridge, N.J.: Noyes Publications.
Center for Metals Production. 1985. Electric arc furnace dust-disposal.
recycle and recovery. Pittsburgh, Pa.
Cherry, K.F. 1982. Plating waste treatment, pp. 45-67. Ann Arbor,
Mich.: Ann Arbor Science, Inc.
Conner, J.R. 1986. Fixation and solidification of wastes. Chemical
Engineering. Nov. 10, 1986.
Cullinane, M.J., Jr., Jones, L. W., and Malone, P.G. 1986. Handbook
for stabilization/solidification of hazardous waste. U.S. Army
Engineers Waterways Experiment Station. EPA Report no. 540/2-86/001.
Cincinnati, Ohio: U.S. Environmental Protection Agency.
Cushnie, G.C., Jr. 1984. Removal of metals from wastewater:
neutralization and precipitation, pp. 55-97. Park Ridge, N.J.: Noyes
Publications.
9-1
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Cushnie. G.C., Jr. 1985. Electroplating wastewater pollution
control technology, pp. 48-62, 84-90. Park Ridge, N.J.: Noyes
Publications.
Duby, P. 1980. Extractive metallurgy. In Kirk-Othmer encyclopedia of
chemical technology. Vol. 9, p. 741.
Eckenfelder, W.W. 1985. Wastewater treatment. Chemical Engineering
85:72. .
Electric Power Research Institute. 1980. FGD sludge disposal manual,
2nd ed. Prepared by Michael Baker, Jr., Inc. EPRI CS-1515 Project
1685-1. Palo Alto, Calif.: Electric Power Research Institute.
Grain, R.W. 1981. Solids removal and concentration. In Third
Conference on Advanced Pollution Control for the Metal Finishing
Industry, pp. 56-62. Cincinnati, Ohio: U.S. Environmental Protection
Agency.
Gurnham, C.F. 1955. Principles of industrial waste treatment.
pp. 224-234. New York: John Wiley and Sons..
Halverson, F., and Panzer, H.P. 1980. Flocculating agents. In
Kirk-Othmer encyclopedia of chemical technology. Vol. 10, pp. 489-516.
New York: John Wiley and Sons.
Lanouette, K.H. 1977. Heavy metals removal.. Chemical Engineering,
October 17, 1977, pp. 73-80.
Lloyd, T. 1980. Zinc compounds. In Kirk-Othmer encyclopedia of
chemical technology, 3rd ed., Vol. 24, p. 856. New York: John Wiley
and Sons.
Lloyd, T., and Showak, W. 1980. Zinc and zinc alloys. In
Kirk-Othmer encyclopedia of chemical technology, 3rd ed. Vol. 24,
p. 824. New York: John Wiley and Sons.
Maczek, H., and Kola, R. 1980. Recovery of zinc and lead from
electric furnace steelmaking dust at Berzelius. Journal of Metals
32:53-58.
Mishuck, E., Taylor, D.R., Telles R., and Lubowitz, H. 1984.
Encapsulation/fixation (E/F) mechanisms. Report no.
DRXTH-TE-CR-84298. Prepared by S-Cubed under Contract no.
DAAK11-81-C-0164.
9-2
-------
Mitre Corp. 1983. Guidance manual for hazardous waste incinerator
permits. NTIS PB84-100577.
Novak, R.G., Troxler, W.L., and Dehnke, T.H. 1984. Recovering energy
from hazardous waste incineration. Chemical Engineering Progress
91:146.
Oppelt, E.T. 1987. Incineration of hazardous waste. JAPCA 37(5),
May 1987.
Patterson, J.W. 1985. Industrial wastewater treatment technology
2nd ed. Stoneham, Mass.: Butterworth Publishers.
Perry, R.H., and Chilton, C.H. 1973. Chemical engineers' handbook.
5th ed. Sec. 19. New York: McGraw Hill Book Co.
Pojasek, P.B. 1979. Solid waste disposal: solidification. Chemical
Engineering 86(17):141-145.
Price. L. 1986. Tensions mount in EAF dust bowl. Metal Producing.
February 1986.
Rudolfs, W. 1953. Industrial wastes. Their disposal and
treatment, p. 294. Valley Stream, N.Y. L.E.C. Publishers Inc.
Sanderson. 1971. Chemical bonds and bond energy. In Physical
chemistry. Vol. 21. New York: Academic Press.
Santoleri, J.J. 1983. Energy recovery — a by-product of hazardous waste
incineration systems. In Proceedings of the 15th Mid-Atlantic
Industrial Waste Conference on Toxic and Hazardous Waste.
USDOC. 1984. U.S. Department of Commerce. Census of Manufacturers -
Miscellaneous Chemical Products. December 1984.
USEPA. 1979. U.S. Environmental Protection Agency, Effluent Guidelines
Division. Development document for proposed effluent limitations
guidelines and standards for the ink formulation point source
category. EPA Report Mo. 440/1-79/090-b.
USEPA. 1980a. U.S. Environmental Protection Agency. RCRA listing
background document waste code K086.
USEPA. 1980b. U.S. Environmental Protection Agency. U.S. Army Engineers
Waterways Experiment Station. Guide to the disposal of chemically
stabilized and solidified waste. Prepared for MERL/ORD under
Interagency Agreement no. EPA-IAG-D4-0569. PB81-181505. Cincinnati,
Ohio.
9-3
-------
USEPA. 1983. U.S. Environmental Protection Agency. Treatability manual.
Vol. III. Technology for control/removal of pollutants.
EPA-600/2-82-001C. pp. 111.3.1.3-2. January 1983.
USEPA. 1985. U.S. Environmental Protection Agency. Characterization of
waste streams listed in 40 CFR Section 261. waste profiles. Prepared
for the Waste Identification Branch, Characterization and Assessment
Division, U.S. Environmental Protection Agency. Prepared by Environ
Corporation, Washington, D.C.
USEPA. 1986a. U.S. Environmental Protection Agency. Onsite engineering
report of treatment technology performance and operation for Envirite
Corporation. York, Pennsylvania. Washington, D.C.: U.S.
Environmental Protection Agency.
USEPA. 1986b. U.S. Environmental Protection Agency. Test methods for
evaluating solid waste; physical/chemical methods. 3rd ed. U.S.
Environmental Protection Agency. Office of Solid Waste and Emergency
Response. November 1986.
USEPA. 1986c. U.S. Environmental Protection Agency. Best demonstrated
available technology (BOAT) background document for F001-F005 spent
solvents. Vol. 1. EPA/530-SW-86-056. November 1986.
USEPA. 1986d. U.S. Environmental Protection Agency, Office of Solid
Waste. Hazardous waste management systems; land disposal restrictions;
Final rule; Appendix I to Part 268 - Toxicity characteristic leaching
procedure (TCLP). 51 FR 40643, November 7, 1986.
USEPA. 1987a. U.S. Environmental Protection Agency. Onsite engineering
report of treatment technology performance and operation for
incineration of K086 solvent wash waste at the Combustion Research
Facility. CBI draft report. November 16, 1987. Washington, D.C.:
U.S. Environmental Protection Agency.
USEPA. 1987b. U.S. Environmental Protection Agency. Onsite engineering
report of treatment technology performance and operation for
Safety-Kleen Corporation, Hebron, Ohio. CBI draft report. Washington,
D.C.: U.S. Environmental Protection Agency.
USEPA. 1987c. U.S. Environmental Protection Agency. Onsite engineering
report for Horsehead Resource Development Co., Inc. Palmerton,
Pennsylvania, for K061. Washington, D.C.: U.S. Environmental
Protection Agency.
USEPA. 1988a. U.S. Environmental Protection Agency. Onsite engineering
report for Waterways Experiment Station, Vicksburg, Mississippi, for
K048 and K051. Washington, D.C.: U.S. Environmental Protection Agency.
9-4
-------
USEPA. 1988b. U.S. Environmental Protection Agency. Onsite engineering
report for Waterways Experiment Station, Vicksburg, Mississippi, for
K061. Washington, D.C.: U.S. Environmental Protection Agency.
USEPA. 1988c. U.S. Environmental Protection Agency. Onsite engineering
report of treatment technology performance and operation for Shell Oil
(Deer Park Manufacturing Complex), Deer Park, Texas. Draft report.
November 18, 1987. Washington, D.C.: U.S. Environmental Protection
Agency.
Versar. 1984. Estimating PMN incineration results. Draft report. EPA
Contract no. 68-01-6271, Task no. 66. Washington, D.C.: U.S.
Environmental Protection Agency, Exposure Evaluation Division, Office
of Toxic Substances.
Vogel, G., et al. 1986. Incineration and cement kiln capacity for
hazardous waste treatment. In Proceedings of the 12th Annual Research
Symposium. Incineration and Treatment of Hazardous Wastes.
Cincinnati, Ohio.
9-5
-------
APPENDIX A
STATISTICAL METHODS
A.1 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
«i = degrees of freedom for numerator
nj = degrees of freedom for denominator
(shaded area = .95)
V
"X
1
n
«
o
•t
5
C
7
8
Q
10
11
12
13
14
15
16
17
18
19
20
ftn
21
26
28
30
40
50
60
70
80
100
150
200
400
•0
1
^
161.4
18.51
10.13
7.71
6.61
5.99
5.59
5.22
5.12
4.9C
4.84
4.75
4.67
4.CO
4.54
4.49
4.45
4.41
4.38
4.35
4.30
4.26
4.23
4.20
4.17
4.08
4.03
4.00
3.98
3.96
3.94
3.91
3.89
3.86
3.84
2
199.5
19.00
9.55
6.94
5.79
5.14
4.74
4.4C
4.2C
4.10
3.98
3.89
3.S1
3.74
3.68
3.63
3.59
3.55
3.52
3.49
3.44
3.40
3.37
3.34
3.32
3.23
3.18
3.15
3.13
3.11
3.09
3.06
3.04
3.02
2.99
3
215.7
19.16
D.28
6.59
5.41
4.76
4.35
4.07
0.86
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.G5
2.62
2.60
4
224.6
19.25
9.12
6.39
5.19
4.53
4.12
3.84
3.C3
3.48
3.36
3.26
3.18
3.11
3.06
3.01
2.96
2.93
2.90
2.87
2.S2
2.78
2.74
2.71
2.69
2.61
2.56
2.53
2.50
2.48
2.46
2.43
2.41 '
2.39
2.37
6
230.2
19.30
9.01
6.26
5.05
4.39
3.97
3.69
3.48
3.33
3.20
3.11
3.03
2.96
2.90
2.85
2.81
2.77
2.74
2.71
2.66
2.62
2.59
2.56
2.53
2.45
2.40
2.37
2.35
2.33
2.30
2.27
2.26
2.23
2.21
6
234.0
19.33
8.94
6.16
4.95
4.28
3.87
3.58
3.37
3.22
3.09
3.00
2.92
2.85
•2.79
2.74
2.70
2.66
2.63
2.60
2.55
2,51
2.47
2.45
2.42
2.34
2.29
2JZ5
2JB
2.21
2.19
2.16
2.14
2.12
2.09
8
238.9
19.37
8.85
6.04
4.82
4.15
3.73
3.44
3.23
3.07
2.95
2.85
2.77
2.70
2.64
2.59
2.55
2.51
2.48
2.45
2.40
2.36
2.32
2-29
2JJ7
2.18
2.13
2JO
2.07
2.05
2.03
2.00
1.98
1.96
1.94
12
243.9
19.41
8.74
5.91
4.68
4.00
3.57
3.28
3.07
2.91
2,79
2.69
2.60
2.53
2.48
2.42
2.38
2.34
2.31
2.28
2.23
2.18
2.15
2.12
2.09
2.00
1.95
1.92
1.89
1.88
1.85
1.82
1.80
1.78
1.75
16
24C.3
19.43
8.69
5.84
4.GO
3.92
3.49
3.20
2.98
2.82
2.70
2.60
2.51
2.44
2.39
2.33
2.29
2.25
2.21
2.18
2.13
2.09
2.05
2.02
1.99
1.90
1.85
1.81
1.79
1.77
1.75
1.71
1.69
'1.67
1.64
20
248.0
19.45
8.66
5.80
4.56
3.87
3.44
3.15
2.93
2.77
2.65
2.54
2.46
2.39
2.33
2.28
2.23
2.19
2.15
2.12
2.07
2.03
1.99
1.96
1.93
1.84
1.78
1.75
1.72
1.70
1.68
1.64
1.62
1.60
1.57
30
250.1
19.46
8.62
5.75
4.50
3.81
3.38
3.08
2.86
2.70
2.57
2.46
2.38
2.31
2.25
2.20
2.15
2.11
2.07
2.04
1.98
1.94
1.90
1.B7
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
o 01
2.16
2.11
2.07
2.02
1.99
1.93
1.89
1.85
1.81
1.79
1.69
1.63
1.59
1.56
1.54
1.51
1.47
1.46
1.42
1.40
50
**5** °
19.47
8.58
5.70
4.44
3.75
3.32
3.03
2.80
2.64
2.50
2.40
2.32
2.24
2.18
2.13
2.08
2.04
2.00
1.96
1.91
1.86
1.82
1.78
1.76
1.66
1.60
1.56
1.53
1.51
1.48
1.44
1.42
1.38
1.32
100
253.0
19.49
8.56
5.6C
4.40
3.71
3.2S
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
•O
25-i.S
19.50
E.53
5.63
4.3G
3.67
3.23
2.93
2.71
2.5;
2.40
2.30
2.21
2.13
2.07
2.01
1.96
1.92
1.88
1.84
1.78
1.73
1.69
1.65
1.62
1.51
1.44
1.39
1.35
1.32
1.28
1.22
1.19
1.13
1.00
A-2
-------
Where the F value is less than the critical value, all treatment data
sets are homogeneous. If the F value exceeds the critical value, it is
necessary to perform a "pair wise F" test to determine if any of the sets
are homogeneous. The "pair wise F" test must be done for all of the
various combinations of data sets using the same method and equation as
the general F test.
The F value is calculated as follows:
(i) All data are natural logtransformed.
(ii) The sum of the data points for each data set is computed (T.).
(iii) The statistical parameter known as the sum of the squares
between data sets (SSB) is computed:
»• A(^
'-1 I n.
where:
k = number of treatment technologies
n^ = number of data points for technology i
N = number of data points for all technologies
T.J = sum of natural logtransformed data points for each technology.
(iv) The sum of the squares within data sets (SSW) is computed:
T.2
SSW =
where:
x
k n;
I I
,2
k
- i
.j j = the natural logtransformed observations (j) for treatment
technology (i).
A-3
-------
(v) The degrees of freedom corresponding to SSB and SSW are
calculated. For SSB, the degree of freedom is given by k-1. For SSW,
the degree of freedom is given by N-k.
(vi) Using the above parameters, the F value is calculated as
follows:
MSB
F = MSW
where:
MSB = SSB/(k-l) and
MSW = SSW/(N-k).
A computational table summarizing the above parameters is shown below.
Computational Table for the F Value
Source
Between
Within
Degrees of
freedom
k-1
N-k
Sum of
squares
SSB
SSW
Mean square
MSB = SSB/k-1
MSW = SSW/N-k
F value
MSB/MSW
Below are three examples of the ANOVA calculation. The first two
represent treatment by different technologies that achieve statistically
similar treatment; the last example represents a case in which one
technology achieves significantly better treatment than the other
technology.
A-4
-------
1790q
Example 1
Methylene Chloride
S_team stripping
Inf luent
(eg/1)
1550.00
1290.00
1640.00
5100.00
1450.00
4600.00
1760.00
2400.00
4«00.00
12100.00
til luent
(eg/1)
10.00
10.00
10.00
12.00
10.00
10.00
10.00
10.00
10.00
10.00
ln(ef f luenl)
2.30
2.30
2.30
2.48
2.30
2.30
2.30
2.30
2.30
2.30
[ln(eff luent)]2
5.29
5.29
5.29
6.15
5.29
5.29
5.29
5.29
5.29
5.29
Biological treatment
Influent tf fluent ln(ef fluent)
(eg/I) (eg/I)
1960.00 10.00 2.30
2568.00 10.00 2.30
1817.00 10.00 2.30
1640.00 26.00 3.26
3907.00 10.00 2.30
[In(effluent)]2
5.29
5.29
5.29
10.63
5.29
Sum:
23.18
53.76
12.46
31.79
Sample Si/e:
10 10
Mean:
3669
10.2
Standard Deviation:
3328.67 .63
Variabi1ity factor:
10
2.32
.06
2378
923.04
1.15
13.2
7.15
2.48
2.49
.43
ANOVA Calculations:
SSB =
k
T|T
n. j j
-
i «=i TI r
N
MSB = SSB/(k-l)
HSW = SSU/(N-k)
ssw-f 1 I'^J-jLflfl
I i'l J=l J '=1 I nj J
A-5
-------
1790g
Example 1 (Continued)
r * MSB/HSU
where:
k = number of treatment technologies
n = number of data points for technology i
N - number of natural logtranstormed data points for all technologies
T = sum of logtransformed data points for each technology
X - the nat. logtransformed observations (j) for treatment technology (i)
n = 10. n = 5. N = IS, k = 2. T = 23.18. T = 12.46. T = 35.64. T = 1270.21
T = 537.31 T = 155.25
SSB =
537.31 155.25
10
SSW - (53.7C + 31.79) -
MSB = 0.10/1 = 0.10
MSW = 0.77/13 - 0.06
F = =1.67
0.06
1270.21
15
537.31 155.25
= 0.10
10
- 0.77
ANOVA Table
Degrees of
Source freedon
Between! B) 1
Withm(W) 13
SS MS F value
0.10 0.10 1.67
0.77 0.06
The critical value of the F test at the 0.05 significance level is 4.67. Since
the F value is less than the critical value, the means are not significantly
different (i.e., they are homogeneous).
Note: All calculations were rounded to two decimal places. Results may differ
depending upon the number of decimal places used in each step of the calculations.
A-6
-------
1790g
Example 2
Irichloroethy lene
Steam stripping
Inf luent
Us/0
1650.00
5200.00
SOOO.OO
1720.00
IbbO.OO
10300.00
210.00
1600.00
204 . 00
160.00
Ef fluent
Ug/D
10.00
10.00
10.00
10.00
10.00
10.00
10.00
27.00
85.00
10.00
In(effluent)
2.30
2.30
2.30
2.30
2.30
2.30
2.30
3.30
4.44
2.30
[tn(effluent)]2
5.29
5.29
5.29
5.29
5.29
5.29
5.29
10.89
19.71
5.29
Influent
Ug/D
200.00
224.00
134.00
150.00
484.00
163.00
182.00
Biological treatment
Effluent
(/.g/D
10.00
10.00
10.00
10.00
16.25
10.00
10.00
Infeff luent)
2.30
2.30
2.30
2.30
2.79
2.30
2.30
[In(effluent)]2
5.29
5.29
5.29
5.29
7.78
5.29
5.29
Sum:
Sample Size:
10 10
Mean:
2760
19.2
Standard Deviation:
3209.6 23.7
Variabi I ity Factor:
3.70
26.14
10
2.61
.71
72.92
220
120.5
10.89
2.36
1.53
16.59
2.37
.19
39.5?
ANOVA Calculations:
2
SSH =
li
n.
SSU=[ I S'rf.
[ i = l j=l -J
MSB = SSB/(k-l)
MSU - SSW/(N-k)
A-7
-------
1790g
Example 2 (Continued)
r - MSB/HSU
where:
k = number of treatment technologies
n - number of data points for technology i
i
N = number of data points for all technologies
T - sum of natural logtransformed data points for each technology
X = the natural logtransformed observations (j) for treatment technology (i)
N = 10. N - /. N - I/, k - 2. T - 26.14, F - 1C.59. 1 - 42.73. (2= 1825.85. F = 683.30.
T = 275.23
SSB
275.23
SSW - (/2.92 + 39.52) -
MSB - 0.25/1 = 0.25
MSV = 4.79/15 = 0.32
F-°-25 .0.78
0.32
1825.B5
17
G«3.30 2/5.23
10
-- 0.25
= 4.79
ANOVA Table
Degrees of
Source freedom SS MS F value
Between(B) 1 0.25 0.25 0.78
Uithin(W) 15 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
Influent Effluent In(effluent) [ln(effluent)]
Ug/D Ug/D
Sum:
Sample Size:
4 4
14.49
Biological treatment
2 Influent Effluent
Ug/1) Ug/D
ln(effluent)
55.20
38.90
ln[(effluent)]2
7200.00
6500.00
6075.00
3040.00
80.00
70.00
35.00
10.00
4.38
4.25
3.56
2.30
19.18
18.06
12.67
5.29
9206.00
16646.00
49775.00
14731.00
3159.00
6756.00
3040.00
1083.00
709.50
460.00
142.00
603.00
153.00
17.00
6.99
6.56
6.13
4.96
6.40
5.03
2.83
48.86
43.03
37.58
24.60
40.96
25.30
8.01
228.34
Mean:
5703
49
Standard Deviation:
1835.4 32.24
Variabi1ity Factor:
3.62
.95
14759
16311.86
7.00
452.5
379.04
15.79
5.56
1.42
ANOVA Calculations:
SSB -
All
N
ss«= f 1 .£; xZj.j] -1 I — }
I i=l J=l J J i=l I "i J
MSB = SSB/(k-l)
MSU = SSU/(N-k)
F = MSB/MSU
A-9
-------
1790g
where,
txample 3 (Continued)
k - number of treatment technologies
n - number of data points for technology i
i
N = number of data points for all technologies
T = sum of natural logtransformed data points for each technology
i
X - the natural logtransformed observations (j) for treatment technology (i)
ij
N = 4. N = 7. N = 11. k = 2. T = 14.49. T = 38.90, T = 53.39. T = 2850.49, T = 209.96
T = 1513.71
SSD -
1513'21
SSW = (55.20 t 228.34)
- 9.52
= 14.88
MSB = 9.52/1 = 9.52
MSW - 14.88/9 - 1.65
K - 9.52/1.65 - 5.77
ANOVA Table
Degrees of
Source freedom
SS
MS
F value
Bctwecn(B)
Uithin(U)
1
9
9.53
14.89
9.53
1.65
5.77
The critical value of the F test at the 0.05 significance level is 5.12. Since
the F value is larger than the critical value, the means are significantly
different (i.e., they are heterogeneous). Activated sludge followed by carbon
adsorption is "best" in this example because the mean of the long-term performance
value, i.e., the effluent concentration, is lower.
Note: All calculations were rounded to two decimal places. Results may differ depending
upon the number of decimal places used in each step of the calculations.
A-10
-------
A.2 Variabilitv Factor
C99
VF = Mean
where:
VF = estimate of daily maximum variability factor determined
from a sample population of daily data;
Cgg = estimate of performance values for which 99 percent of the
daily observations will be below. Cgg is calculated
using the following equation: Cgg = Exp(y + 2.33 Sy)
where y and Sy are the mean and standard deviation,
respectively, of the logtransformed data; and
Mean = average -of the individual performance values.
EPA is establishing this figure as an instantaneous maximum because
the Agency believes that on a day-to-day basis the waste should meet the
applicable treatment standards. In addition, establishing this
requirement makes it easier'to check compliance on a single day. The
99th percentile is appropriate because it accounts for almost all process
variability.
In several cases, all the results from analysis of the residuals from
BOAT treatment are found at concentrations less than the detection
limit. In such cases, all the actual concentration values are considered
unknown and, hence, cannot be used to estimate the variability factor of
the analytical results. Below is a description of EPA's approach for
calculating the variability factor for such cases with all concentrations
below the detection limit.
It has been postulated as a general rule that a lognormal
distribution adequately describes the variation among concentrations.
Agency data show that the treatment residual concentrations are
A-ll
-------
distributed approximately lognormally. Therefore, the lognormal model
has been used routinely in the EPA development of numerous regulations in
the Effluent Guidelines program and is being used in the BOAT program.
The variability factor (VF) was defined as the ratio of the 99th
percentile (C ) of the lognormal distribution to its arithmetic mean
(Mean), as follows:
VF = C99. (1)
Mean
The relationship between the parameters of the lognormal distribution
and the parameters of the normal distribution created by taking the
natural logarithms of the lognormally distributed concentrations can be
found in most mathematical statistics texts (see, for example,
Distribution in Statistics-Volume 1 by Johnson and Kotz, 1970). The mean
of the lognormal distribution can be expressed in terms of the
mean (^) and standard deviation (a) of the normal distribution as
follows:
C9g = Exp („ + 2.33a) (2)
Mean = Exp (M + 0.5a2). (3)
By substituting (2) and (3) in (1), the variability factor can then
be expressed in terms of a as follows:
VF = Exp (2.33 a - 0.5a2). (4)
For residuals with concentrations that are not all below the
detection limit, the 99th percentile and the mean can be estimated from
the actual analytical data and, accordingly, the variability factor (VF)
can be estimated using equation (1). For residuals with concentrations
A-12
-------
that are below the detection limit, the above equations can be used in
conjunction with the following assumptions to develop a variability
factor.
• Assumption 1: The actual concentrations follow a lognormal
distribution. The upper limit (UL) is equal to the detection
limit. The lower limit (LL) is assumed to be equal to one-tenth
of the detection limit. This assumption is based on the fact that
data from well-designed and well-operated treatment systems
generally fall within one order of magnitude.
• Assumption 2: The natural logarithms of the concentrations have
a normal distribution with an upper limit equal to In (UL) and a
lower limit equal to In (LL).
• Assumption 3: The standard deviation (o) of the normal
distribution is approximated by:
a = [ln(UL) - ln(LL)] / [(2)(2.33)]
= [ln(UL/LL)j / 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 of Solid Waste; Physical/
Chemical Methods, SW-846, Third Edition, November 1986) are used in most
cases for determining total constituent concentrations. Leachate
concentrations were determined using the Toxicity Characteristic Leaching
Procedure (TCLP), published in 51 FR 1750, November 7, 1986.
In some instances, SW-846 allows for the use of alternative or
equivalent procedures or equipment. Table B-2 presents the specific
procedures or equipment used in extraction of organic compounds. The
specific procedures or equipment used for analysis of organic and metal
compounds are shown in Table B-3.
As stated in the introduction, all concentrations for the regulated
constituents will be corrected to account for analytical interference
associated with the chemical makeup of the waste matrix. The correction
factor for a constituent is based on the matrix spike recovery values.
Table B-4 presents the organic matrix spike recoveries used to determine
the correction factor for the EPA-collected organic data for the K086
scrubber water residual. Since spikes were not performed for every
organic compound, it was necessary to calculate an average recovery value
for volatile organics, base/neutral semivolatile organics, and acid
semivolatile organics.
B-l
-------
Since no matrix spike recovery values were available for the Envirite
data, matrix spike recovery values for a similar wastewater (i.e., K061
TCLP extract) and nonwastewater (i.e., K061) matrix have been used to
correct the Envirite data. The recoveries used to correct the Envirite
wastewaters and TCLP extract metal concentrations are shown in Table B-5.
Table B-6 presents the recoveries used to correct the Envirite filter
cake organic detection limits. It was necessary to calculate average
recovery values since spikes were not performed for every organic
constituent.
The accuracy-corrected, average concentrations for the Envirite
wastewater metal concentrations are calculated in Table B-7. Table B-8
presents the accuracy-corrected, average concentrations for the Envirite
filter cake metal TCLP concentrations. The accuracy-corrected, average
concentrations for the regulated organic constituents in the K086 solvent
wash wastewater and filter cake residual are presented in Table B-9. In
cases where all the concentrations reported are the detection limits, the
highest detection limit was selected as the average concentration.
B-2
-------
HlOOg
Table 6-1 Analytical Methods for K086 Solvent Waste Regulated Constituents
BOAT
reference
number
222
223
225
226
228
229
34
38
43
45
47
215-217
70
232
87
121
126
159
161
Regulated
const ituent
Volat i 1e Orqanics
Acetone
n-Butyl alcohol
Ethyl acetate
Ethyl benzene
Methanol
Methyl isobutyl ketone
Methyl ethyl ketone
Methylene chloride
Toluene
1,1, 1-Trichloroethane
Tr ichloroethylene
Xylene (total)
Semivolati 1e Orqanics
Bis(2-ethyl hexyl)phthalate
Cyclohexanone
1 ,2-Dichlorobenzene
Naphthalene
Nitrobenzene
Metals
Chromium (total composition)
Lead (total composition)
Extraction
method
Purge and Trap
Purge arid Trap
Purge and Trap
Purge and Trap
No extraction
Purge and Trap
Purge and Trap
Purge and Trap
Purge and Trap
Purge and Trap
Purge and Trap
Purge and Trap
Continuous liquid/
1 iquid extraction
Continuous liquid/
1 iquid extraction
Continuous liquid/
1 iquid extract ion
Continuous liquid/
1 iqu id extract ion
Continuous liquid/
1 iquid extract ion
Specified in
ana lyt ical method
Specified in
Method
number
5030
5030
5030
5030
5030
5030
5030
5030
5030
5030
5030
3520
3520
3520
3520
3520
Ana lyt ica 1 method
Gas Chromatography/Mass Spectrometry
Gas Chromatography/Mass Spectrometry
Gas Chromatography/Mass Spectrometry
Gas Chromatography/Mass Spectrometry
Gas Chromatography/Mass Spectrometry
Gas Chromatography/Mass Spectrometry
Gas Chromatography/Mass Spectrometry
Gas Chromatography/Mass Spectrometry
Gas Chromatography/Mass Spectrometry
Gas Chromatography/Mass Spectrometry
Gas Chromatography/Mass Spectrometry
Gas Chromatography/Mass Spectrometry
Gas Chromatography/Mass Spectrometry
Gas Chromatography/Mass Spectrometry
Gas Chromatography/Mass Spectrometry
Gas Chromatography/Mass Spectrometry
Gas Chroma) ography/Mtiss Spectrometry
Chromium (atomic .jhsorn* ion, direct
aspirat. ion method)
Lead (atomic: absorption, direct
Method number
S240
8240
8240
8240
8240
8240
8240
6240
8240
8240
8240
8240
8270
8270
8270
8270
8270
^7190
7420
Reference-
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
!
1
1
1
analytical method
aspirat ion met hni.1)
-------
I'lOOa
Table B-l (Continued)
BOAT
reference
number
159
161
Regulated
constituent
Metals (continued)
Chromium (TCLP extract)
Lead (TCLP extract)
Extraction Method
method number
Specified in
analytical method
Specified in
analytical method
Analytical mtithod Method number Reference'
Toxicity Characteristic Leaching 51 FR 1750 ?
Procedure (TCLP)
Toxicity Characteristic Leaching 51 FR 1750 ?
Procedure (TCLP)
References: 1. USEPA 1982.
2. USEPA 1986d.
-------
1900g
Table B-2 Specific Procedures or Equipment Used in Extraction of Organic Compounds When
Alternatives or Equivalents Are Allowed in the SW-846 Method:;
Analysis
SW-846 method
Sample aliquot
Alternatives or equivalents allowed
by SW-846 methods
Specific procedures cr
equipment used
Purge and trap
5030 5 milliliters of liquid
CO
in
Cont inuous 1 iquid-
1 iquid extract ion
3530 1 liter of liquid
The purge and trap device to he
used is specified in the method in
Figure 1; the desorber to he used
is described in Figures 2 and 3;
and the packing materials are
described in Section 4.10.2 of SW-846.
The method allows equivalents of this
equipment or materials to he used.
The method specifies that the
trap must be at least 25 cm long
and have an inside diameter of at
least 0.105 cm.
The surrogates recommended are
toluene-d8,4-bromofluorobenzene,
and 1,2-dichloroethane-d-J. The
recommended concentrat ion level is
50 ug/1.
Acid and base/neutral extracts
are usually combined before
analysis by GC/MS. However.
under some situations, they may
be extracted and analyzed
separately.
The base/neutral surrogates
recommended are 2-fluorobiphenyl.
nitrobenzene-d5. and terpnenyl-dl4.
The acid surrogates recommended
are 2-f luorophenol.
2,4,6-tribromopheno!. and
phenol-d6. Additionol compounds
The purge and trap equipment and
the desorber used were as specified
in SW-846. The purge and trap
equipment is a Teckmar LSC-2 with
standard purging chambers (Supelco
cat. 2-0293). The packing materials
for the traps were 1/3 silica gel
and 2/3 2,6-diphenylene.
The length of the trap was 30 cm
and the diameter was 0.105 cm.
The surrogates were added as
specif ied in SW-846.
Acid and base/neutral extract:
were combined.
Surrogates were the same as those
recommended by SW-846. with the.
exception that phenol-d5 was
substituted for phenol-dC. The;
concentrations used were the
concentrations recommended in ;>W• fi
-------
Ib'OOa
Table 6-2 (Continued)
ftnalvsis
SW-846 method
Sample aliquot
Alternatives or equivalents allowed
by SW-846 methods
Specific procedures or
equipment used
Continuous liquid-
liquid extract ion
(Cont inuecl)
may be used for surrogates. The
recommended concentrations for
low-medium concentration level
samples are 100 ppm for acid
surrogates and 200 ppm for
base/neutral surrogates. Volume
of surrogate may be adjusted.
Solvent Extraction 3540
The internal standards are
prepared by dissolving them
in carbon disulfide and then
diluting the volume so that
the final solvent is 20/
carbon disulfide and 80'/.
methylene chloride.
The preparation of the
internal standards was
changed to eliminate the
use of carbon disulfide.
The internal standards
were prepared in
methylene chloride only.
Reference: USEPA 1987a.
-------
inoig
Table 6-3 Specific Procedures or Equipment Used for Analysis ol Organic and Metal Compounds
When Alternatives or Equivalents Are Allowed in SW-MC
Analysis
SW-S46
Method
Sample
preparation
method
Alternatives or equivalents
allowed in SW-846 for
equipment or in procedure
Specific equipment or procedures user!
Organic Compounds
Gas Chromatography/
Mass Spectrometry
for volatile
organics
Recommended GC/MS operating conditions:
Actual GC/MS operating conditions:
8240 5030
Electron energy.
Mass range:
Scan time:
Initial column temperature:
Initial column holding time
Column temperature program:
Final column temperature:
Final column holding time:
Injector temperature:
Source temperature:
Transfer line temperature:
Carrier gas:
70 ev (nominal)
35-260 amu
To give 5 scans/peak but
not to exceed 7 sec/scan
45"C
3 min
8"C/min
ZOO'C
15 min
200-225'C
According to manufacturer's
specification
250-300"C
Hydrogen at 50 cm/sec or
helium at 30 cm/sec
The column should be 6-ft x 0.1 in l.D. glass.
packed with 17 SP-1000 on Carbopack B (60/60 mesh) or
an equivalent.
Samples may be analyzed by purge and trap technique
or by direct injection.
Electron energy:
Mass range:
Scan time:
Initial column temperature:
Initial column holding time:
Co-lumn temperature program:
Final column temperature:
Final column holding time:
Injector temperature:
Source temperature:
Transfer line temperature:
Carrier gas:
70 ev
35 - 260 amu
2.5 sec/scan
38 "C
2 min
10'C/min
225-C
30 min or xylene elules
225"C
manufacturer's recommended
value of 100'C
275T
Hel Him @ 30 ml,'inin
•Additional Information on Actual System Used:
Equipment: Finnegan model 5100 GC/MS/'DS system
Data system: SUPER I NCOS Autoquan
Mode: Electron impact.
NBS library available
Interface to MS - Jet separator
•The column used was an 8-ft x 0.1 in l.D glass.
packed with I'/ SP-1000 on Carbopack B (60/80 mesh).
•The samples were analyzed using the purge and trap. technique.
-------
Table B-3 (Continued)
Ana lysis
SW-846
method
Sample
preparation
method
Alternatives or equivalents
allowed in SW-846 for
equipment or in procedure
Specific equipment or procedures used
Recommended GC/'MS operating conditions:
Actual GC/MS operating conditions:
Gas Chromatography/
Mass Spectrometry
for semivolatile
orqanics: capillary
column technique
8270 3520-1(quids
03
i
oo
Mass range:
Scan t ime:
Initial column temperature:
Initial column holding time:
Column temperature program:
35-500 amu
1 sec/scan
40'C
4 min
40-270'C at
10"C/min
Final column temperature hold: 270"C (until
benzotg.h,i.]perylene has
e luted)
250-300*C
250-300'C
According to
manufacturer's
specification
Injector:
Sample volume:
Carrier gas:
Injector temperature:
Transfer line temperature:
Source temperature:
Grob-type. splitless
1-2 ul
Hydrogen at 50 cm/sec or
helium at 30 cm/sec
The column should be 30 m by 0.25 mm I.D.. 1-um film
thickness, silicon-coated fused silica capillary
column (J&W Scientific DB-5 or equivalent).
Mass range:
Scan t ime:
Initial column temperature:
Initial column holding time:
Column temperature program:
Final column temperature hold:
Injector temperature:
Transfer line temperature:
Source temperature:
Injector:
Sample volume:
Carrier aas:
35 - 500 amu
1 sec/scan
30"C
4 min
8"C/min to 2713"
and 10"C/min unt i1
305 T.
305'C
240-2GO"C
. 300"C
Manufacturer 's
recommendat ion
(non-heated)
Grob-type, spit less
1 ul of sample extract
Helium @ 40 cm/sec
•Additional Information on Actual System Used:
tquipmeni: F mutrucin mu^lc' ^»CC r.d
Software Package: SUPER I NCOS AUTOQIIAN
The column used was a 30 m x 0.32 inn 1.0.
Rl . -5 (57. phenyl methyl silicone) FSCC.
Metals
Inductively coupled
6010
Operate equipment following instructions
provided by instrument's manufacturer.
For operation with organic solvents,
auxiliary argon gas inlet is recommended.
• Equipment operated using procedures specified
in the Jarrell Ash (JA) 1140 Operator's Hiinun 1
• Auxiliary argon gas was not required for sample
m.T t r i x .
-------
I900g
Table B-4 Matrix Spike Recoveries Used to Calculate Correction factors for
K086 Solvent Wash Scrubber Water Organic Concentrations
Sample
BOAT list Original
constituent amount found
(/•g/D
Volat i le Orqanics
1 , 1-Dichloroethane
Tr ichloroethene
Chlorobenzene
Toluene
Benzene
Other volatile organics
Semivolatile Orqanics
Base/Neutrals
1 .2, 4- T rich lorobenzene
Acenaphthene
2.4-Dinitrotoluene
Pyrene
H-Nitrosodi-n-propylamine
1 .4 -Dich lorobenzene
Other base/neutral
Semivolatile organics
Acids
Pentachlorophenol
Phenol
?-Chloropheno)
4-Chloro-3-methyl phenol
4-N itrophenol
Other acid Semivolatile
organics
NO
NO
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Amount
spiked
lc.9/1)
50
50
50
50
50
100
100
100
100
100
100
200
200
200
200
200
Amount.
recovered
37
49
50
48
42
36
61
75
92
85
42
167
169
157
161
173
Duplicate Accuracy-
Percent Amount
recovery recovered
Uj/D
74
98
100
96
84
90.4 (average)
36
61
75
92
85
42
~r - . !
83
84
79
81
87
82.8 (average)
36
53
53
49
42
31
57
81
94
83
36
139
159
148
169
165
Percent correction
recovery factor
72
106
106
98
84
93.2 (average)
31
57
81
94
83
36
C1 7 1 ,.,nr,r,o\
70
79
74
85
83
78.2 (average)
1.39
1.02
1.00
1.04
1.19
1.11
3.23
1.75
1.33
1.09
1.20
2.78
i t;?
1.43
1.27
1.35
1.23
1.20
1.28
Percent recovery = [(spike result - original amount(/spike added].
'Accuracy-correction factor = 100/percent recovery (using the lowest percent recovery values).
b
Reference: USEPA 1987a.
-------
1900ci
Table B-5 Matrix Spike Recoveries Used to Calculate Correction Factors for the
Envirite Wastewater and TCLP Extract Metal Concentrations
Sample
Constituent
Ant imony
Arsenic
Barium
Beryl 1 ium
Cadmium
Chromium (hexavalent)
Chromium (total)
Copper
Lead
Mercury
Nickel
Selenium
Si Iver
T ha 1 1 i urn
Z inc
Original sample
<21
<10
1,420
1.4
4.2
<10
<4.0
<4.0
<5.0
<0.2
203
<25
<4.0
<10
2.640
Spike added
(..g/1)
300
50
5,000
25
25
50
50
125
25
1.0
1.000
25
50
50
10.000
Spike result
(/•g/D
275
70
5,980
25
26
53
35
107
22
0.9
1.140
12
42
51
12.600
Percent
recovery3
92
140
91
94
87
106
70
86
88
90
94
48
84
102
100
Duplicate
Spike result
27G
66
5.940
24
27
54
34
104
19
1.1
1.128
<25
38
48
12.400
Percent
a
recovery
92
132
90
90
91
108
68
83
76
110
93
NC
76
96
98
Accuracy-
correction
factor11
1.09
0.76
1.11
1.11
1.15
0.94
1.47
1.20
1.31
1.11
1.08
2.08
1.32
1.04
1 .02
Percent recovery = [(spike result - original amount)/spike amount] x 100.
'Accuracy-correction factor = 100/percent recovery (using the lowest percent recovery values).
Reference: USEPA 1987c.
-------
190CCJ
Table E-6 Matrix Spike Recoveries Used to Calculate Correction Factors
for the Envirite Filter Cake Organic Detecfor- Limits
Original amount
Constituent found (j
-------
1900q
Table B-7 Accuracy-Corrected Envirite Metals Data for Irc.itcil War.tewater
from Chromium Reduction. Lime Precipitation, and Sludciu Filtration
Const iluent
Antimony
Arsenic
Ba r i um
Beryl lium
Cadmium
Chromium (hexavalent)
Chromium (Total)
Copper
Lead
Mercury
Nickel
Selenium
S i Iver
1 ha 1 1 i um
Z inc
Correction
factor
1.09
0.76
1.11
1.11
1.15
0.94
1.47
1.20
1.31
1.11
1.08
2.08
1 .33
1 .04
1.02
Accurt'icy-i:orri'C Ifil
Accuracy-corrected concentral ion (inq/1) tivcrnije
Sample Set # concentration
123456789 10 11
(No substantial treatment)
(No substantial treatment)
<1.1 <1.1 <3.9 <11 <1.1
-------
1900q
Table B-6 Accuracy-Corrected Envirite Metals Data tor Tiller Cako Residuals
from Lime Stabilization and Sludtie F i 11 r,i I ion
BDAI list
const ituent
Arsenic '
Bar lum
Cadmium
Chromium (Total)
Lead
Mercury
CO
1
(^ Selenium
S i Iver
Correction
factor
0.76
1.11
1.15
1.47
1.31
1.11
2.08
1.33
Accuracy corrcrt e:
-------
1900g
Table P-9 Accuracy-Corrected Organic Concentrat IOIIL- for Envirite
Filter Cake and K086 Solvent Wash Scrubber Water
BOAT list
const ituent
Volat i 1e Oreianics
Acetone
n-Butyl alcohol
Ethyl acetate
Ethyl benzene
Methanol
Methyl isohutyl ketone
Methyl ethyl ketone
Methylene chloride
Toluene
1.1, 1-Trichloroethane
Trichloroethylene
Xylene (total)
Semivolat i 1e Orqanics
Bis(3-ethyl hexyl)phthalate
Cyclohexanone
1 ,?-Dichlorobenzene
Naphthalene
Nitrobenzene
K086 solvent
Correct ion
factor
1.11
1.11
1.11
1.11
1.11
1.11
1.11
1.11
1.04
1.11
\.Q2.
1.11
1.57
1.57
1.57
1.57
1.57
wash scrubber water
Accuracy- corrected
concentration3
(mg/1)
0.0055
0.011
0.011
0.0055
0.011
0.011
0.011
0.011
0.010
0.011
0.010
0.011
0.016
0.0078
0.016
0.016
0.016
Correct ion
factor
1.1)
1.11
1.11
1.11
1.11
1.11
1.11
1.11
1.11
1.11
1.11
1.11
1.46
1.46
1.46
1.46
1.46
r i Her c-ike
Accuracy- cor reeled
concent rat ion '
(my/l)
O.I
0.1
0.1
0.0 1
0.1
0.1
0.1
0.1
0.011
0.016
0.011
0.0055
0.18
0.18
0.18
0.18
0.18
'Accuracy-corrected concentration = (highest detection limit present in Table 4-1) x (correction factor).
'Accuracy-corrected concent rat ion '= (highest detection limit present in Table E-l) x (correction factor).
b
-------
APPENDIX C
DETECTION LIMITS FOR THE
K086 SCRUBBER WATER SAMPLES
The detection limits for the analyses of the K086 solvent wash
samples (see Table C-l) have been classified as confidential by the
generator. The detection limits for analyses of ".he scrubber effluent
water samples are listed on Table C-2.
C-l
-------
1977g
Table C-l Detection Limits for the K086 (Sol lent Washes) Untreated Waste Samples
BOAT
reference
no. Constituents (units)
Untreated waste
(all samples)
detection limits
Volatile BOAT Constituents (mq/1)
222 Acetone
1 Acetonitrile
2 Acrolein
3 Acrylonitrile
4 Benzene
5 Bromodichloromethane
6 Bromomethane
223 n-Butyl alcohol
7 Carbon tetrachloride
B Carbon distil fide
9 Chlorobenzene
10 2-Chloro-l,3-butadiene
11 Chlorodibromomethane
12 Chloroethane
13 2-Chloroethyl vinyl ether
14 Chloroform
15 Chloromethane
16 3-Chloropropene
17 l,2-Dibromo-3-chloropropane
18 1,2-Dibromomethane
19 Dibromotnethane
20 Trans-l,4-Dichloro-2-butene
21 Dichlorodifluoromethane
22 1.1-Dichloroethane
23 1.2-Dichloroethane
24 1.1-Dichloroethylene
25 Trans-1.2-Diocnloroethene
26 1,2-Dichloropropane
27 Trans-1.3-Dichloropropene
28 Cis-1,3-Dichloropropene
29 1.4-Dioxane
224 2-Ethoxyethanol
225 Ethyl acetate
226 Ethylbenzene
30 Ethyl cyanide
227 Ethyl ether
31 Ethyl methacrylate
214 Ethylene oxide
(Detection limits for analyzed
constituents are Confidential
Business Information.)
C-2
-------
1977g
Table C-l (Continued)
BOAT Untreated waste
reference (all samples)
no. Constituents (units) detection limits
Volatile BOAT Constituents (mq/1) (continued)
32 lodomethane
33 Isobutyl alcohol
228 Methanol
34 Methyl ethyl ketone
229 Methyl isobutyl ketone
35 Methyl methacrylate
36 Methyl methanesulfonate NA
37 Methylacrylonitrile
38 Methylene chloride
230 2-Nitropropane
39 Pyridine
40 1.1,1.2-Tetrachloroethane
41 1,1,2,2-letrachloroethane
42 Tetrachloroethene
43 Toluene
44 Tribromomethane
45 1,1.1-Trichloroethane
47 1,1.2-Trichloroethane •
48 Trichloroethene
49 Trichloromonofluoromethane
231 l,l,2-Trichloro-l,2.2-trifluoroethane
50 1,2,3-Trichloropropane
Vinyl chloride
215 1.2-Xylene
216 1.3-Xylene
217 1,4-Xylene
C-3
-------
1977g
Table C-l (Continued)
BOAT
reference
no.
Constituents (units)
Sample
Untreated waste samr1e detection limits
Sample #2 Samp'e #3 Sample #4
Sample #5
Sample ?6
BDAT Semivolati1e Orqanics (mq/1)
51 Acenaphthalene
52 Acenaphthene
53 Acetophenone
54 2-Acetylaminofluorene
55 4-AminobiphenyI
56 An i 1 i ne
57 Anthracene
58 Aramite NA
59 Benz(
-------
1977g
Table C-l (Continued)
BOAT
reference
no.
Constituents (units)
Sample #1
Untreated Haste sample detection limits
Sample #2 Saimle #3 Sample #4 Sample *5 Sample =6
BOAT Sranivolati1e Orqanics (mq/1) (continued)
85 Dibenzofa,iIpyrene
86 m-Oichlorobenzene
87 o-Dichlorobcnzcne
88 p-Oichlorobenzene
89 3.3'-Dichlorobenzidine
90 2,4-Dichlorophenol
91 2,6-Dichlorophenol
92 Diethyl phthalate
93 3,3'-Dimethoxybenzidine
9-1 p-Dimethylaminodzobenzene
9b 3,3'-Dimclhylbcnzidine
96 2,4 Dimethylphenol
97 Dimethyl phthalate
98 Di-n-butyl phthalatu
99 1,4-Dinitrobenzene
100 4,6-Dinitro-o-cresol
101 2.4-Dinitrophenol
102 2.4-Dinitrotoluene
103 2,6-Dinitrotoluene
104 Di-n-octyl phthalate
105 Di-n-octyl phthalate
106 Diphenylamine
219 Diphenylnitrosamine
107 1,2-Diphenylhydrazine
108 Tluoranthene
109 Fluorene
110 Hexachlorobenzene
111 Hexachlorobutadiene
112 Hexachlorocyclopentadiene
113 Hexachloroethane
114 Hcxachlorophene
115 Hexachloropropene
116 lndeno(1.2.3-cd)pyrene
117 Isosafrole
118 Hethapyrilene
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
^A
IIA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
C-5
-------
1977g
Table C-l (Continujd)
BDA1
reference
no.
Untreated waste sanple detection limits
Sample #1 Sample 12 Sam;>le #3 Sample #4 Sample #5 Sample £6
Constituents (units)
BOAT Scmivolatile Orqnnics (mci/1) (continued)
119 3-Methylcholanthrene
120 4,V-Melhylenebis(2-cnloro
ani1ine)
121 Naphthalene
122 1,4-Naphthoquinone
123 1-Naphthylamine
124 2-Naphthylamine
125 p-Nitroaniline
12G Nitrobenzene
127 4-Nitrophenol
1?8 N-Nitrosodi-n-butylamine
129 N Nitrosodiethylamine
130 N-Nitrosodimethylsmine
131 N-Nitrosomethylethylamine
132 N-Nitrosomorpholine
133 N-Nitrosopiperidine
134 N-Nitrosopyrrolidine
135 5-Nitro-o-toluidine
136 Pentachlorobenzene
137 Pentachloroethane
138 Pentachloronitrobenzene
139 Pentachlorophenol
140 Phenacetin
141 Phenanthrene
142 Phenol
220 Phthalic anhydride
143 2-Picoline
144 Pronamide
145 Pyrene
146 Resorcinol
147 Safrole
148 1.2.4.5-Tetrachlorobenzene
149 2.3.4.6-Tetrachlorophenol
150 1.2,4-Trichlorobenzene
151 2.4.5-Trichlorophenol
152 2.4.6-Trichlorophenol
153 Tris(2,3-dibromopropyl)
phosphate
NA
NA
NA
NA
NA
NA
NA
NA
NA
HA
IIA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
1A
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
C-6
-------
1977g
Table C-l (Cont nued)
bDAI Untreated waste
reference (all samples)
no. Constituents (units) detection limits
BOAT Metals (mq/1)
154 Antimony
155 Arsenic
156 Barium
157 Beryllium
158 Cadmium
159 Chromium (Total)
221 Chromium (Hexavalent)
160 Copper
161 Lead
162 Mercury
163 Nickel
164 Selenium
165 Silver
166 Thallium
167 Vanadium
168 Zinc
Inorganics (mq/11
169 Cyanide
170 Fluoride
171 Sulfide
BOAT PCBs (mq/1)
200 Aroclor 1016
201 Aroclor 1221
202 Aroclor 1232
203 Aroclor 1242
204 Aroclor 1248
205 Aroclor 1254
206 Aroclor 1260
C-7
-------
1977g
Table C-l (Continued)
BOAT
reference
no.
Constituents (units)
Untreated waste
(all samples)
detection limits
207
208
209
210
211
212
213
BDAT Dioxins/Furans (pom)
Hexachlorod i benzo-p-d i ox i ns
Hexachlorod i benzofuran
Pentachlorod i benzo-p-d iox ins
Pentach lorodibenzofuran
1etrachlorod ibenzo-p-d iox i ns
Tetrachlorodibenzofuran
2.3.7.8-Tetrachlorodibenzo-p-dioxin
Other Analyses (pom)
Iron
Magnesium
Manganese
Titanium
Total solids
Total organic carbon
Total organic ha 1 ides
Percent water
Ash content
- = No analysis performed.
NA = Not available. Detection limit studies havj not been completed.
Reference: UStPA 1987a.
C-8
-------
2022g
Table C-2 Detection Limits for the Scrubber El fluent Water Samples
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
Constituents (units)
BDAT Volatile Orqanics (mq/1)
Acetone
Acetonitrile
Acrolein
Acrylonitrile
Benzene
B romod i c h 1 o rome t ha ne
Bromometharie
n-Butyl alcohol
Carbon tetrachloride
Carbon bisulfide
Chlorobenzene
2-Chloro-l ,3-butadiene
Chlorodibromome thane
Chloroethane
2-Chloroethyl vinyl ether
Chloroform
Chloromethane
3-Chloropropene
1.2-Oibromo-3-chloropropane
1 ,2-Dibromoethane
Dibromomethane
Trans-1 ,4-dichloro-2-butene
Dichlorodif luoromethane
1 , 1 -D ich loroethane
1.2-Dichloroethane
1 . 1-Dichloroethylene
lrans-l,2-dichloroethene
1 ,2-Dichloropropane
Trans-1 ,3-dichloropropene
cis-1 ,3-Dichloropropene
1 , 4-Dioxane
2-Ethoxyethanol
Ethyl acetate
Ethylbenzene
Ethyl cyanide
Ethyl ether
Ethyl methacrylate
Ethylene oxide
Scrubber effluent
water sample 11
detection limits
0.005
0.200
0.200
0.200
0.010
0.010
0.020
-
0.010
0.010
0.010
0.200
0.010
0.020
0.020
0.010
0.020
0.200
0.020
0.010
0.010
0.200
0.020
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.400
-
-
0.005
0.200
-
0.200
-
Scrubber effluent
water sample 12.
#3, #4, *5. and #6
detection limits
0.005
0.100
0.100
0.100
0.005
0.005
0.010
-
0.005
0.005
0.005
0.100
0.005
0.010
0.010
0.005
0.010
0.100
0.010
0.005
0.005
0.100
0.010
0.005
0.005
0.005
0.005
0.005
0.005
0.005
0.200
-
-
0.005
0.100
-
0.100
-
C-9
-------
2022g
•lable C-2 (Continued)
BDA1 Scrubber effluent
reference water sample *1
no. Constituents (units) detection limits
32
33
228
34
229
3b
'36
37
38
230
39
40
41
42
43
44
45
47
48
49
231
50
215
216
217
BOAT Volatile Ornanics (mq/1) (continued)
lodomethane
Isobutyl alcohol
Hcthanol
Methyl ethyl ketone
Methyl isobutyl ketone
Methyl methacry Idle
Methyl methanesulfonate
Methylacrylonitrile
Methylene chloride
2-Nitropropane
Pyridinc
1.1.1 ,2-Tetrachloroethane
1.1.2. 2-Tetrachloroethane
1 et rach loroethene
Toluene
Tr i bromomethane
1 , 1 , 1-Trichloroethane
1.1. 2-Tr ichloroethane
Trich loroethene
Tr ichloromonof luoromethane
l,1.2-trichloro-l,2.2-trif luoroethane
1.2.3-Trichloropropane
Vinyl chloride
1.2-Xylene
1.3-Xylene
1,4-Xylene
0.100
0.400
-
0.010
0.010
0.200
0.400
0.200
0.010
-
0.800
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
-
0.010
0.020
0.005
0.005
0.005
Scrubber effluent
water sample 12,
i3. #4. 15, and *6
detection limits
0.050
0.200
-
0.010
0.010
0.100
0.200
0.100
0.005
-
0.400
0.005
0.005
0.005
0.005
0.005
0.005
0.005
0.005
0.005
-
0.005
0.010
0.005
0.005
0.005
C-10
-------
2022g
Table C-? (Continued)
BDAT
reference
no.
bl
52
53
54
55
56
57
58
59
218
60
61
62
63
64
65
66
67
68
69
70
71
72
73
74
75
76
77
78
79
80
81
82
232
Constituents (units)
BDAT Semivolatile Orqanics (mq/1)
Acenaphthalene
Acenaphthene
Acetophenone
2-Acetylaminof luorene
4 - Am i nob i pheny 1
Ani 1 ine
Anthracene
Aramite
Benz ( a ) anthracene
Benzal chloride
Benzenethiol
Benz id ine
Benzo(a)pyrene
Benzo(b)f luoranthene
Benzol ghi)perylene
Benzo(k)f luoranthene
p-Benzoqu i none
Bis(2-chloroethoxy)ethane
Bis(2-chloroethyl)ether
Bis(2-chloroisopropyl)ether
Bis(2-ethylhexyl)phthalate
4-Bromophenyl pheny 1 ether
Butyl benzyl phthalate
2-sec -Buty 1 -4 , 6-d i n i tropheno 1
p-Chloroani line
Chlorobenzilate
p-Chloro-nt-cresol
2-Chloronaphthalene
2-Chlorophenol
3-Chloropropionitri le
Chrysene
ortho-Cresol
para-Cresol
Cyclohexanone
Scrubber effluent
water (all samples)
detection limits
0.010
0.010
0.010
1.000
0.200
0.020
0.010
NA
0.010
-
NA
1.000
0.010
0.010
0.010
0.010
NA
0.010
0.010
0.010
0.010
0.010
0.010
0.100
0.100
NA
0.010
0.010
0.010
NA
0.010
0.010
0.010
0.005
C-ll
-------
2022g
Table C-2 (Continued)
BOAT
reference
no.
83
84
85
86
87
88
89
90
91
92
93
94
95
96
97
98
99
100
101
102
103
104
105
106
219
107
108
109
110
111
112
113
114
Constituents (units)
BDAT Semivolat ile Orqanics (mq/1) (continued)
Dibenz (a ,h (anthracene
Dibenzo(a.e)pyrene
0 i benzo ( a . i ) py rene
m-D ich lorobenzene
o- D ich lorobenzene
p-D ich lorobenzene
3,3'-Oichlorobenzidine
2,4-Dich lorophenol
2,6-Dichlorophenol
Diethyl phthalate
3 . 3 ' -D imethoxybenz id i ne
p-D i me thy laminoazobenzene
3,3'-Dimethylbenzidine
2. 4 -Dimethyl phenol
Dimethyl phthalate
Di-n-butyl phthalate
1,4-Dinitrobenzene
4.6-Dinitro-o-cresol
2,4-Dinitrophenol
2,4-Oinitrotoluene
2.6-Dinitrotoluene
Di-n-octyl phthalate
Di-n-propylnitrosamine
Diphenylamine
D i pheny 1 n i t rosam i ne
1 . 2-D i pheny Ihydraz ine
Huoranthene
Fluorene
Hexach lorobenzene
Hexach lorobutad i ene
Hexach lorocyclopentadiene
Hexach loroethane
Hexach lorophene
Scrubber effluent
water (all samples)
detection limits
0.010
NA
0.050
0.010
0.010
0.010
0.020
0.010
NA
0.010
10.000
0.200
NA
0.010
0.010
0.010
0.100
0.050
0.050
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
NA
C-12
-------
2022g
.Table C-2 (Continued)
BDA1
reference
no.
115
116
117
118
119
120
121
122
123
121
1?5
126
127
128
129
130
131
132
133
134
135
136
137
138
139
140
141
142
220
143
144
145
146
Constituents (units)
BOAT Semivolat i le Orqanics (mq/1) (continued)
Hexach loropropene
1 ndenof 1.2. 3-cd )pyrene
Isosafrole
Methapyrilene
3-Methylcholanthrene
4,4'-Methylenebis
(2-chloroani 1 ine)
Naphthalene
1 ,4-Naphthoquinone
1-Naphthylamine
2-Ndphthy laminu
p-Nitroaniline
Nitrobenzene
4-Nitrophenol
N-Nitrosodi-n-butylatnine
N-Nitrosodiethylamine
N-Nitrosodimethylamine
N-Nitrosomethylethylamine
N-N i trosomorpho 1 ine
N-Nitrosopipertdine
n-Nitrosopyrrolidine
5-Nitro-o-toluidine
Pentachlorobenzene
Pentachloroethane
Pentachloronitrobenzene
Pentachlorophenol
Phenacet in
Phenanthrene
Phenol
Phthalic anhydride
2-Picoline
Pronamide
Pyrene
Resorcinol
Scrubber effluent
water (all samples)
detection limits
NA
0.010
0.100
NA
0.100
0.200
0.010
NA
0.100
0.100
0.050
0.010
0.050
NA
NA
0.100
0.100
0.200
0.200
0.200
0.200
NA
NA
0.100
0.050
0.100
0.010
0.010
-
0.100
NA
0.010
NA
C-13
-------
2022g
Table C-2 (Continued)
BDA1
reference
no.
147
148
149
150
151
152
153
154
155
156
157
158
159
?21
160
161
162
163
164
165
166
167
168
169
170
171
Constituents (units)
BDAT Semivolat i le Orqanics (mq/1) (continued)
Safrole
1 ,2,4.5-Tetrachlorobenzene
2,3,4. 6-Tetrachlorophenol
1.2,4-Trichlorobenzene
2,4, 5-1 r ich lorophenol
2,4.6-Trich loropheno 1
Tris(2,3 -dibromopropyl)
phosphate
BDAT Metals (mq/1)
Antimony
Arsenic
Ba r i um
Beryllium
Cadmium
Chromium (total)
Chromium (hexavalent)
Copper
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
BDAT Inorganics (mq/1)
Cyanide
Fluoride
Sulfide
Scrubber effluent
water (all samples)
detection limits
0.100
0.010
NA
0.010
0.050
0.010
NA
0.032
0.010
0.001
0.001
0.004
0.007
0.010
0.006
0.005
0.0002
0.011
0.005
0.006
0.010
0.006
0.002
0.010
0.2
0.5
C-14
-------
2022g
Table C-2 (Continued)
UDAI
reference
no.
200
201
202
203
204
205
?06
207
208
209
210
211
212
213
Constituents (units)
BOAT PCBs (mq/1)
Aroclor 1016
Aroclor 1221
Aroclor 1232
Aroclor 1242
Aroclor 1248
Aroclor 1254
Aroclor 1260
BOAT Dioxins/Turans (mq/1)
Hexach lorod ibenzo-p-d iox ins
Hexachlorodibenzofuran
Pentach lorod i benzo-p-d i ox i ns
Pentach lorod ibenzof uran
Tetrachlorodibenzo-p-dioxins ,
Tet rach 1 orod i benzof uran
2. 3. 7. 8-Tetrach lorod ibenzo-p-d iox in
Other Analyses (mq/1)
Iron
Magnesium
Manganese
Titanium
Chloride
Total solids
Total organic carbon
Total organic halides
Scrubber effluent
water (all samples)
detection limits
0.0015
0.0015
0.0015
0.0015
0.0015
0.0015
0.0015
0.1
0.04
0.11
0.05
0.1
0.04
0.13
0.006
0.001
0.003
0.003
1.000
1.000
1.000
0.010
- = No analysis performed.
NA = Not available. Detection limit studies have not been completed.
Reference: USEPA 1987a.
C-15
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APPENDIX D
METHOD OF MEASUREMENT FOR THERMAL CONDUCTIVITY
The comparative method for measuring thermal conductivity has been
proposed as an ASTM test method under the name "Guarded, Comparative,
Longitudinal Heat Flow Technique." The thermal heat flow circuit used is
the analog of an electrical circuit with resistances in series. A
reference material is chosen to have a thermal conductivity close to that
estimated for the sample. Reference standards (also known as heat
meters) having the same cross-sectional dimensions as the sample are
placed above and below the sample. An upper heater, a lower heater, and
a heat sink are added to the "stack" to complete the heat flow circuit.
See Figure D-l.
The temperature gradients (analogous to potertial differences) along
the stack are measured with type K (chromel/alumel) thermocouples placed
at known separations. The thermocouples are placed into holes or grooves
in the references and also in the sample whenever the sample is thick
enough to accommodate them.
For molten samples, pastes, greases, and othtir materials that must be
contained, the material is placed into a cell consisting of a top and
bottom of Pyrex 7740 and a containment ring of marinite. The sample is
2 inches in diameter and 0.5.inch thick. Thermocouples are not placed
into the sample; rather, the temperatures measured in the Pyrex are
extrapolated to give the temperature at the top and bottom surfaces of
the sample material. The Pyrex disks also serve as the thermal
conductivity reference material.
D-l
-------
GUARD
GRADIENT X
STACK
GRADIENT
X
THERMOCOUPLE
CLAMP
i
UPPER STACK
HEATER
i
i
TOP
REFERENCE
SAMPLE
BOTTOM
REFERENCE
SAMPLE
i
i
LOWER STACK
HEATER
i
i
LIQUID COOLED
HEAT SINK
i
HEAT FLOW
DIRECTION
UPPER
GUARD
HEATER
LOWER
GUARD
HEATER
FIGURE D-l
SCHEMATIC DIAGRAM OF THE COMPARATIVE METHOD
D-2
-------
The stack is clamped with a reproducible load to ensure intimate
contact between the components. To produce a linear flow of heat down
the stack and to reduce the amount of heat that flows radially, a guard
tube is placed around the stack, and the interven-ng space is filled with
insulating grains or powder. The temperature gradient in the guard is
matched to that in the stack to further reduce radial heat flow.
The comparative method is a steady-state method of measuring thermal
conductivity. When equilibrium is reached, the huat flux (analogous to
current flow) down the stack can be determined from the references. The
heat into the sample is given by
Q = A (dT/dx)
in top top
and the heat out of the sample is given by
Q = A (dT/dx)
out bottom bottom
where
A = thermal conductivity
dT/dx = temperature gradient
and top refers to the upper reference, while bottom refers to the lower
reference. If the heat were confined to flow dovn the stack, then Q
in
and Q would be equal. If Q. and Q are in reasonable
out in out
agreement, the average heat flow is calculated from
Q = (Q + Q )/2.
in out
The sample thermal conductivity is then found from
A = Q/(dT/dx)
sample sample.
D-3
-------
APPENDIX E
ORGANIC DETECTION LIMITS FOR K086 SOLVENT rfASH NONWASTEWATERS
Since the Agency does not have treatment data for K086 solvent wash
scrubber waters, organic detection limits for the filter cake generated
specifically from chromium reduction followed by chemical precipitation
and sludge filtration of the K086 solvent wash scrubber waters are not
available. However, EPA does have organic detection limits for wastes
that the Agency believes are similar enough to K086 solvent wash filtered
precipitate.
The data consist of organic detection limits for 15 chemically
precipitated wastes. These data are shown in Table E-l. The highest
detection limit has been selected as the level for each regulated organic
constituent. In the cases of n-butyl alcohol, e:hyl acetate, methanol,
methyl isobutyl ketone, methyl ethyl ketone, bis(2-ethylhexyl)phthalate,
cyclohexanone, 1,2-dichlorobenzene, naphthalene, and nitrobenzene where
no detection limits were reported, the overall highest level of detection
(i.e., 120 ug/1) has been selected as the detection limit for those
constituents.
E-l
-------
1839g
Table E-l Organic Detection Limits for Envirite Filter Cake Residuals
from Lime Stabilization and Sludge Filtration
BOAT list
constituent
Volati 1e orqanics
Acetone
n-Butyl alcohol
Ethyl acetate
Ethyl benzene
Methanol
Methyl isobutyl ketone
Methyl ethyl ketone
Methylene chloride
Toluene
1,1, 1-Trichloroethane
Trichloroethylene
Xylene (total)
Bis(2-ethylhexyT)phthalate
Cyclohexanone
1 ,2-Dichlorobenzene
Naphthalene
Nitrobenzene
Determined
Total concentration (ug/1) level of
Sample Set f detection
123456 7 8 9 10 11 12 13 14 15 (ug/1)
79 - 84 - 120 120 120 120
120
120
3.2 - - - 10 3.4 - 4.9 - 4.8 10
120
120
120
8.6 8.9 7.1 7.9 8.2 - - 7.9 8.3 10 8.4 8.3 12 12 12 12
2.8 3.2 3.3 - - - - 10 3.4 - 4.9 - 4.8 10
14 3.2 - - - - - 10 3.4 - 4.9 - - 14
3.4 - 2.8 3.2 3.3 3.2 - - - 10 - - 4.9 4.9 4.8 10
3.2 -------- 4.9 - 4.9
120
120
120
120
120
- = No detection limit reported.
Reference: USEPA 1986a.
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