c/EPA
United States
Environmental Protection
Agency
Office of
Solid Waste
Washington, D.C. 20460
EPA/530-SW-88-0009-n
May 1988
Solid Waste
Best
Demonstrated
Available Technology
(BOAT) Background
Document for
K086
Proposed
Volume 15
Non Confidential Business Information
(CBI) Version
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PROPOSED
BEST DEMONSTRATED AVAILABLE TECHNOLOGY (BOAT)
BACKGROUND DOCUMENT FOR K086
SOLVENT WASH
U.S. Environmental Protection Agency
Office of Solid Waste
401 M Street, S.W.
Washington, D.C. 20460
James R. Berlow, Chief Jose Labiosa
Treatment Technology Section Project Manager
May 1988
Eb'-jT'onmsntal Protection -l^-^
' \ Library (5PL-16)
:- —born Street, Room I6?0
-j, iL 60604
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BOAT BACKGROUND DOCUMENT FOR K086 SOLVENT WASH
TABLE OF CONTENTS
VOLUME 15 Page
EXECUTIVE SUMMARY vi
1. INTRODUCTION 1
1.1 Legal Background 1
1.1.1 Requirements Under HSWA 1
1.1.2 Schedule for Developing Restrictions 4
1.2 Summary of Promulgated BOAT Methodology 5
1.2.1 Waste Treatability Groups 7
1.2.2 Demonstrated and Available Treatment
Technologies 7
1.2.3 Collection of Performance Data 11
1.2.4 Hazardous Constituents Considered and Selected
for Regulation 17
1.2.5 Compliance with Performance Standards 30
1.2.6 Identification of BOAT 32
1.2.7 BOAT Treatment Standards for "Derived-From"
and "Mixed" Wastes 36
1.2.8 Transfer of Treatment Standards 40
1.3 Variance from the BOAT Treatment Standard 41
2. INDUSTRIES AFFECTED AND WASTE CHARACTERIZATION 46
2.1 Industry Affected and Process Description 47
2.2 Waste Characterization 50
3. APPLICABLE/DEMONSTRATED TREATMENT TECHNOLOGIES 54
3.1 Applicable Treatment Technologies 54
3.2 Demonstrated Treatment Technologies 56
3.2.1 Incineration 58
3.2.2 Fuel Substitution 77
3.2.3 Stabilization 93
3.2.4 High Temperature Metals Recovery 100
3.2.5 Chromium Reduction 108
3.2.6 Chemical Precipitation 113
3.2.7 Polishing Filtration 125
3.2.8 Sludge Filtration 130
3.3 Performance Data 134
3.3.1 Organics Performance Data 134
3.3.2 Metals Treatment Data 136
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4. IDENTIFICATION OF THE BEST DEMONSTRATED AVAILABLE
TECHNOLOGY FOR K086 SOLVENT WASH
4.1 BOAT for Treatment of Organics
4.2 BOAT for Treatment of Metals
4.2.1 Wastewater
4.2.2 Nonwastewater
5. SELECTION OF REGULATED CONSTITUENTS
5.1 Identification of Constituents in the Untreated Waste
and Waste Residuals
5.2 Evaluation of the Process Generating the K086 Solvent
Wash Wastes
5.3 Determination of Significant Treatment from BOAT
5.3.1 BOAT List Organic Constituents
5.3.2 BOAT List Metal Constituents
5.4 Rationale for Selection of Regulated Constituents
6. CALCULATION OF BOAT TREATMENT STANDARDS
6.1 Calculation of Treatment Standards for Nonwastewater
Forms of K086 Solvent Wash
6.1.1 Organic Treatment Standards
6.1.2 Metal Treatment Standards
6.2 Calculation of Treatment Standards for Wastewater forms
of K086 Sol vent Wash
6.2.1 Organic Treatment Standards
6.2.2 Metal Treatment Standards
Appendix A Statistical Methods
Appendix B Analytical QA/QC
Appendix C Detection Limits for the K086 Scrubber Water
Samples
Appendix D Method of Measurement for Thermal
Conductivity
Appendix E Organic Detection Limits for K086 Solvent
Wash Nonwastewaters
References
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150
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152
154
157
158
159
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LIST OF TABLES
Page
Table 1-1 BOAT Constituent List 19
Table 2-1 Number of Ink Formulators by State and by EPA Region .. 49
Table 2-2 Major Constituent Analysis of Untreated K086 Solvent
Wash 52
Table 2-3 BOAT Constituent Composition and Other Data 53
Table 3-1 Incineration - EPA Collected Data for K086 Solvent Wash 135
Table 3-2 Chromium Reduction Chemical Precipitation Followed by
Vacuum Filtration - EPA Collected Data from Envirite .. 139
Table 5-1 BOAT Constituents Detected or Not Detected in the K086
Solvent Wash and Scrubber Water Samples 164
Table 5-2 BOAT Constituent Concentrations in Untreated K086
Solvent Wash Waste and Scrubber Water Residual 172
Table 5-3 Calculated Bond Energy for the Candidate Organic
Constituents 173
Table 5-4 Candidate Constituents for Regulation of K086 Solvent
Wash 174
Table 6-1 Calculation of K086 Solvent Wash Nonwastewater
Treatment Standards 179
Table 6-2 Calculation of K086 Solvent Wash Wastewater Treatment
Standards 181
Table A-l 95th Percentile Values for the F Distribution 185
Table B-l Analytical Methods for K086 Solvent Waste Regulated
Constituents 200
Table B-2 Specific Procedures or Equipment Used in Extraction
of Organic Compounds When Alternatives or Equivalents
Are Allowed in the SW-846 Method 202
m
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LIST OF TABLES
(continued)
Page
Table B-3 Specific Procedures or Equipment Used for Analysis
of Organic and Metal Compounds When Alternatives
or Equivalents Are Allowed in SW-846 204
Table B-4 Matrix Spike Recoveries Used to Calculate Correction
Factors for K086 Solvent Wash Scrubber Water Organic
Concentrations 206
Table B-5 Matrix Spike Recoveries Used to Calculate Correction
Factor for the Envirite Wastewater and TCLP Extract
Metal Concentrations 207
Table B-6 Matrix Spike Recoveries Used to Calculate Correction
Factors for the Envirite Filter Cake Organic Detection
Limits 208
Table B-7 Accuracy-Corrected Envirite Metals Data for Treated
Wastewater from Chromium Reduction, Lime Precipitation
and Sludge Filtration 209
Table B-8 Accuracy-Corrected Envirite Metals Data for Filter
Cake Residuals from Lime Stabilization and Sludge
Filtration 210
Table B-9 Accuracy-Corrected Organic Concentrations for Envirite
Filter Cake and K086 Solvent Wash Scrubber Water 211
Table C-l Detection Limits for the Scrubber Effluent Water
Samples 214
Table E-l Organic Detection Limits for Envirite Filter Cake
Residuals from Chromium Reduction, Chemical
Precipitation, and Sludge Filtration 227
IV
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LIST OF FIGURES
Page
Figure 2-1 Geographical Distribution of Ink Manufacturing Sites .. 48
Figure 2-2 Ink Formulation and K086 Waste Generation 51
Figure 3-1 Liquid Injection Incinerator 62
Figure 3-2 Rotary Kiln Incinerator 63
Figure 3-3 Fluidized Bed Incinerator 65
Figure 3-4 Fixed Hearth Incinerator 66
Figure 3-5 Example of High Temperature Metals Recovery System .... 104
Figure 3-6 Continuous Hexavalent Chromium Reduction System 110
Figure 3-7 Continuous Chemical Precipitation 116
Figure 3-8 Circular Clarifiers 119
Figure 3-9 Inclined Plate Settler 120
Figure D-l Schematic of the Comparative Method 223
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EXECUTIVE SUMMARY
BOAT Treatment Standards
K086 Solvent Wash
Pursuant to the Hazardous and Solid Waste Amendments (HSWA) enacted
on November 8, 1984, and in accordance with the procedures for
establishing treatment standards under section 3004 (m) of the Resource
Conservation and Recovery Act (RCRA), the Environmental Protection Agency
(EPA) is proposing treatment standards for one subcategory of the K086
listed waste. According to 40 CFR Part 261.32, waste code K086 is
defined as "solvent washes and sludges, caustic washes and sludges, or
waterwashes and sludges, from cleaning tubs and equipment used in
formulation of ink from pigments, driers, soaps and stabilizers
containing chromium and lead."
The Agency has determined that K086 represents three treatability
groups based on physical and chemical composition: the solvent wash
group, the solvent sludge group, and the caustic/water wash and sludge
group. This background document pertains to the development of treatment
standards for the K086 solvent wash treatability group. Treatment
standards for the K086 solvent sludge treatability group and the K086
caustic/water wash and sludge treatability group have been deferred
because there is insufficient characterization data and no treatment
performance data available to the Agency such that treatment standards
can be developed.
Treatment standards for organics are based on the performance of
incineration. The treatment of K086 solvent wash using incineration
generates a scrubber water residual which may contain metals and require
further treatment. Treatment of the scrubber water generates a
precipitated solids residual which may also need further treatment.
Treatment standards for metals in the scrubber water are based on
chromium reduction followed by lime precipitation and vacuum sludge
filtration; for metals in the lime-precipitated residuals, treatment
standards are based on the TCLP leachate values following vacuum
filtration (i.e., based on lime stabilization). These technologies were
determined by the Agency to represent the Best Demonstrated Available
Technology (BOAT) for organics and metals present in the K086 solvent
wash wastes.
The Agency has chosen to set treatment levels for these wastes rather
than designating the use of a specific technology. These levels are
established as a prerequisite for disposal of these wastes in units
designated as land disposal units according to 40 CFR part 268. Wastes
that, as generated, contain the regulated constituents at concentrations
that do not exceed the treatment standards are not restricted from land
disposal units. The proposed effective date for these standards is
August 8, 1988.
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Treatment standards have been proposed for a total of 2 metals and
17 organics that the Agency believes are indicators of effective
treatment for all of the BOAT list hazardous constituents identified as
typically present in K086 solvent wash. The regulated metals are total
chromium and lead. The regulated organics include the organics found in
the tested waste, as well as all BOAT listed organics which Agency data
indicate are organic solvents used in the ink formulation process and/or
in cleaning ink formulating equipment. The regulated organics include
acetone, n-butyl alcohol, ethyl acetate, ethylbenzene, methanol, methyl
isobutyl ketone, methyl ethyl ketone, methylene chloride, toluene,
1,1,1-trichloroethane, trichloroethylene, xylenes, bis(2-ethylhexyl)
phthalate, cyclohexanone, 1,2-dichlorobenzene, napthalene, and
nitrobenzene.
The table at the end of this summary lists the specific BOAT
standards for wastes identified as K086 solvent wash. For the purpose of
determining the applicability of the BOAT treatment standards,
wastewaters are defined as wastes containing less than 1 percent (weight
basis) solids and less than 1 percent (weight basis) total organic carbon
(TOC). Wastes not meeting this definition must comply with treatment
standards for nonwastewaters.
The Agency is setting standards for wastewaters based on analysis of
total constituent concentration for BOAT list organics and BOAT list
metals. For K086 solvent waste nonwastewaters, the standards are based
on total constituent concentration for BOAT list organics and analysis of
leachate for BOAT list metals. The leachate is obtained by use of the
Toxicity Characteristic Leaching Procedure (TCLP).
The units for total constituent concentration in the nonwastewaters
are in parts per million (mg/kg) on a weight-by-weight basis. The units
for total constituent concentration in the wastewaters and the leachate
are in parts per million (mg/1) on a weight-by-volume basis. Testing
procedures are specifically identified in the quality assurance sections
of this document.
EPA wishes to point out that, because of facility claims of
confidentiality, this document does not contain all of the data that EPA
used in its regulatory decision-making process, including selection of
constituents to regulate, determination of substantial treatment, and
development of 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. Any determinations regarding the validity of the
facility's claim of confidential business information (CBI) will be done
by EPA according to 40 CFR Part 2, Subpart B. In the meantime, the
Agency will treat the data as CBI. Additionally, the Agency would like
to emphasize that all the data evaluated for the development of BOAT
treatment standards for K086 solvent washes have been done according to
our methodology presented in Section 1 of this document. All deletions
of confidential business information (CBI) are noted in the appropriate
place in this background document.
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1844g
BOAT TREATMENT STANDARDS
K086 Solvent Wash
BOAT
reference
no
222
223
225
226
228
229
34
38
43
45
47
215-217
70
232
87
121
126
159
161
BOAT list
const ituents
Organ ics
Volat i le Organics
Acetone
n-Butyl alcohol
Ethyl acetate
Ethylbenzene
Methanol
Methyl isobutyl ketone
Methyl ethyl ketone
Methylene chloride
Toluene
1,1, J-Trichlo roe thane
Tnchloroethylene
Xylene (total)
Setiwo la 1 1 le Organics
8is(2-ethylhexyl)phtna
Cyc lohexanone
1 ,2-OichloroDenzene
Naphthalene
Nitrobenzene
Met.ils
Chromium ( Tola i )
Lead
Total compos
Nonwastewater
(mg/kg)
0 37
0 37
0 37
0 031
0 37
0 37
0 37
0 037
0 031
0 044
0 031
0 015
late 0 49
0.49
0 49
0 49
0 49
NA
NA
1 1 ion
Wastewater
(mg/1)
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
0 044
0 044
0 044
0 32
0 037
TCLP Extract
Nonwastewater
(rag/1)
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0 094
0 37
NA = Not appl icable
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1. INTRODUCTION
This section of the background document presents a summary of the
legal authority pursuant to which the BOAT treatment standards were
developed, a summary of EPA's promulgated methodology for developing
BOAT, and finally a discussion of the petition process that should be
followed to request a variance from the BOAT treatment standards.
1.1 Legal Background
1.1.1 Requirements Under HSWA
The Hazardous and Solid Waste Amendments of 1984 (HSWA), 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
constituents from the disposal unit or injection zone for as long as the
wastes remain hazardous" (RCRA section 3004(d)(l), (e)(l), (g)(5),
42 U.S.C. 6924 (d)(l), (e)(l), (g)(5)).
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For the purpose of the restrictions, HSWA defines land disposal "to
include, but not be limited to, any placement of ... hazardous waste in
a landfill, surface impoundment, waste pile, injection well, land
treatment facility, salt dome formation, salt bed formation, or
underground mine or cave" (RCRA section 3004(k), 42 U.S.C. 6924(k)).
Although HSWA defines land disposal to include injection wells, such
disposal of solvents, dioxins, and certain other wastes, known as the
California List wastes, is covered on a separate schedule (RCRA section
3004(f)(2), 42 U.S.C. 6924 (f)(2)). This schedule requires that EPA
develop land disposal restrictions for deep well injection by
August 8, 1988.
The amendments also require the Agency to set "levels or methods of
treatment, if any, which substantially diminish the toxicity of the waste
or substantially reduce the likelihood of migration of hazardous
constituents from the waste so that short-term and long-term threats to
human health and the environment are minimized" (RCRA section 3004(m)(l),
42 U.S.C. 6924 (m)(l)). Wastes that meet treatment standards established
by EPA are not prohibited and may be land disposed. In setting treatment
standards for listed or characteristic wastes, EPA may establish
different standards for particular wastes within a single waste code with
differing treatability characteristics. One such characteristic is the
physical form of the waste. This frequently leads to different standards
for wastewaters and nonwastewaters.
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Alternatively, EPA can establish a treatment standard that is
applicable to more than one waste code when, in EPA's judgment, all the
waste can be treated to the same concentration. In those instances where
a generator can demonstrate that the standard promulgated for the
generator's waste cannot be achieved, the Agency also can grant a
variance from a treatment standard by revising the treatment standard for
that particular waste through rulemaking procedures. (A further
discussion of treatment variances is provided in Section 1.3.)
The land disposal restrictions are effective when promulgated unless
the Administrator grants a national variance and establishes a different
date (not to exceed 2 years beyond the statutory deadline) based on "the
earliest date on which adequate alternative treatment, recovery, or
disposal capacity which protects human health and the environment will be
available" (RCRA section 3004(h)(2), 42 U.S.C. 6924 (h)(2)).
If EPA fails to set a treatment standard by the statutory deadline
for any hazardous waste in the First Third or Second Third of the
schedule (see Section 1.1.2), the waste may not be disposed in a landfill
or surface impoundment unless the facility is in compliance with the
minimum technological requirements specified in section 3004(o) of RCRA.
In addition, prior to disposal, the generator must certify to the
Administrator that the availability of treatment capacity has been
investigated, and it has been determined that disposal in a landfill or
surface impoundment is the only practical alternative to treatment
currently available to the generator. This restriction on the use of
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landfills and surface impoundments applies until EPA sets a treatment
standard for the waste or until May 8, 1990, whichever is sooner. If the
Agency fails to set a treatment standard for any ranked hazardous waste
by May 8, 1990, the waste is automatically prohibited from land disposal
unless the waste is placed in a land disposal unit that is the subject of
a successful "no migration" demonstration (RCRA section 3004(g),
42 U.S.C. 6924(g)). "No migration" demonstrations are based on case-
specific petitions that show there will be no migration of hazardous
constituents from the unit for as long as the waste remains hazardous.
1.1.2 Schedule for Developing Restrictions
Under section 3004(g) of RCRA, EPA was required to establish a
schedule for developing treatment standards for all wastes that the
Agency had listed as hazardous by November 8, 1984. Section 3004(g)
required that this schedule consider the intrinsic hazards and volumes
associated with each of these wastes. The statute required EPA to set
treatment standards according to the following schedule:
1. Solvents and dioxins standards must be promulgated by
November 8, 1986;
2. The "California List" must be promulgated by July 8, 1987;
3. At least one-third of all listed hazardous wastes must be
promulgated by August 8, 1988 (First Third);
4. At least two-thirds of all listed hazardous wastes must be
promulgated 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 must be promulgated
by May 8, 1990 (Third Third).
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The statute specifically identified the solvent wastes as those
covered under waste codes F001, F002, F003, F004, and F005; it identified
the dioxin-containing hazardous wastes as those covered under waste codes
F020, F021, F022, and F023.
Wastes collectively known as the California List wastes, defined
under section 3004(d) of HSWA, are liquid hazardous wastes containing
metals, free cyanides, PCBs, corrosives (i.e., a pH less than or equal to
2.0), and any liquid or nonliquid hazardous waste containing halogenated
organic compounds (HOCs) above 0.1 percent by weight. Rules for the
California List were proposed on December 11, 1986, and final rules for
PCBs, corrosives, and HOC-containing wastes were established
August 12, 1987. In that rule, EPA elected not to establish standards
for metals. Therefore, the statutory limits became effective.
On May 28, 1986, EPA published a final rule (51 FR 19300) that
delineated the specific waste codes that would be addressed by the First
Third, Second Third, and Third Third. This schedule is incorporated into
40 CFR 268.10, 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).
Section 3004(m) also specifies that treatment standards must "minimize"
long- and short-term threats to human health and the environment arising
from land disposal of hazardous wastes.
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Congress indicated in the legislative history accompanying the HSWA
that "[t]he requisite levels of [sic] methods of treatment established by
the Agency should be the best that has been demonstrated to be
achievable," noting that the intent is "to require utilization of
available technology" and not a "process which contemplates
technology-forcing standards" (Vol. 130 Cong. Rec. S9178 (daily ed.,
July 25, 1984)). EPA has interpreted this legislative history as
suggesting that Congress considered the requirement under section 3004(m)
to be met by application of the best demonstrated and achievable (i.e.,
available) technology prior to land disposal of wastes or treatment
residuals. Accordingly, EPA's treatment standards are generally based on
the performance of the best demonstrated available technology (BOAT)
identified for treatment of the hazardous constituents. This approach
involves the identification of potential treatment systems, the
determination of whether they are demonstrated and available, and the
collection of treatment data from wel1-designed and we!1-operated systems.
The treatment standards, according to the statute, can represent
levels or methods of treatment, if any, that substantially diminish the
toxicity of the waste or substantially reduce the likelihood of migration
of hazardous constituents. Wherever possible, the Agency prefers to
establish BOAT treatment standards as "levels" of treatment
(i.e., performance standards), rather than adopting an approach that
would require the use of specific treatment "methods." EPA believes that
concentration-based treatment levels offer the regulated community greater
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flexibility to develop and implement compliance strategies, as well as an
incentive to develop innovative technologies.
1.2.1 Waste Treatability Group
In developing the treatment standards, EPA first characterizes the
waste(s). As necessary, EPA may establish treatability groups for wastes
having similar physical and chemical properties. That is, if EPA
believes that wastes represented by different waste codes could be
treated to similar concentrations using identical technologies, the
Agency combines the codes into one treatability group. EPA generally
considers wastes to be similar when they are both generated from the same
industry and from similar processing stages. In addition, EPA may
combine two or more separate wastes into the same treatability group when
data are available showing that the waste characteristics affecting
performance are similar or that one waste would be expected to be less
difficult to treat.
Once the treatability groups have been established, EPA collects and
analyzes data on identified technologies used to treat the wastes in each
treatability group. The technologies evaluated must be demonstrated on
the waste or a similar waste and must be available for use.
1.2.2 Demonstrated and Available Treatment Technologies
Consistent with legislative history, EPA considers demonstrated
technologies to be those that are used to treat the waste of interest or
a similar waste with regard to parameters that affect treatment selection
(see November 7, 1986, 51 FR 40588). EPA also will consider as treatment
those technologies used to separate or otherwise process chemicals and
7
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other materials. Some of these technologies clearly are applicable to
waste treatment, since the wastes are similar to raw materials processed
in industrial applications.
For most of the waste treatability groups for which EPA will
promulgate treatment standards, EPA will identify demonstrated
technologies either through review of literature related to current waste
treatment practices or on the basis of information provided by specific
facilities currently treating the waste or similar wastes.
In cases where the Agency does not identify any facilities treating
wastes represented by a particular waste treatability group, EPA may
transfer a finding of demonstrated treatment. To do this, EPA will
compare the parameters affecting treatment selection for the waste
treatability group of interest to other wastes for which demonstrated
technologies already have been determined. The parameters affecting
treatment selection and their use for this waste are described in
Section 3.2 of this document. If the parameters affecting treatment
selection are similar, then the Agency will consider the treatment
technology also to be demonstrated for the waste of interest. For
example, EPA considers rotary kiln incineration to be a demonstrated
technology for many waste codes containing hazardous organic
constituents, high total organic content, and high filterable solids
content, regardless of whether any facility is currently treating these
wastes. The basis for this determination is data found in literature and
data generated by EPA confirming the use of rotary kiln incineration on
wastes having the above characteristics.
8
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If no commercial treatment or recovery operations are identified for
a waste or wastes with similar physical or chemical characteristics that
affect treatment selection, the Agency will be unable to identify any
demonstrated treatment technologies for the waste, and, accordingly, the
waste will be prohibited from land disposal (unless handled in accordance
with the exemption and variance provisions of the rule). The Agency is,
however, committed to establishing treatment standards as soon as new or
improved treatment processes are demonstrated (and available).
Operations only available at research facilities, pilot- and bench-
scale operations, will not be considered in identifying demonstrated
treatment technologies for a waste because these technologies would not
necessarily be "demonstrated." Nevertheless, EPA may use data generated
at research facilities in assessing the performance of demonstrated
technologies.
As discussed earlier, Congress intended that technologies used to
establish treatment standards under section 3004(m) be not only
"demonstrated," but also available. To decide whether demonstrated
technologies may be considered "available," the Agency determines whether
they (1) are commercially available and (2) substantially diminish the
toxicity of the waste or substantially reduce the likelihood of migration
of hazardous constituents from the waste.
EPA will only set treatment standards based on a technology that
meets the above criteria. Thus, the decision to classify a technology as
"unavailable" will have a direct impact on the treatment standard. If
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the best technology is unavailable, the treatment standard will be based
on the next best treatment technology determined to be available. To the
extent that the resulting treatment standards are less stringent, greater
concentrations of hazardous constituents in the treatment residuals could
be placed in land disposal units.
There also may be circumstances in which EPA concludes that for a
given waste none of the demonstrated treatment technologies are
"available" for purposes of establishing the 3004(m) treatment
performance standards. Subsequently, these wastes will be prohibited
from continued placement in or on the land unless managed in accordance
with applicable exemptions and variance provisions. The Agency is,
however, committed to establishing new treatment standards as soon as new
or improved treatment processes become "available."
(1) Proprietary or patented processes. If the demonstrated
treatment technology is a proprietary or patented process that is not
generally available, EPA will not consider the technology in its
determination of the treatment standards. EPA will consider proprietary
or patented processes available if it determines that the treatment
method can be purchased or licensed from the proprietor or is 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
10
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toxicity" of the waste or "substantially reduce the likelihood of
migration of hazardous constituents" from the waste in accordance with
section 3004(m). By requiring that substantial treatment be achieved in
order to set a treatment standard, the statute ensures that all wastes
are adequately treated before being placed in or on the land and ensures
that the Agency does not require a treatment method that provides little
or no environmental benefit. Treatment will always be deemed substantial
if it results in nondetectable levels of the hazardous constituents of
concern. If nondetectable levels are not achieved, then a determination
of substantial treatment will be made on a case-by-case basis. This
approach is necessary because of the difficulty of establishing a
meaningful guideline that can be applied broadly to the many wastes and
technologies to be considered. EPA will consider the following factors
in an effort to evaluate whether a technology provides substantial
treatment on a case-by-case basis:
• Number and types of constituents treated;
• Performance (concentration of the constituents in the
treatment residuals); and
• Percent of constituents removed.
If none of the demonstrated treatment technologies achieve
substantial treatment of a waste, the Agency cannot establish treatment
standards for the constituents of concern in that waste.
1.2.3 Collection of Performance Data
Performance data on the demonstrated available technologies are
evaluated by the Agency to determine whether the data are representative
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of well-designed and well-operated treatment systems. Only data from
well-designed and well-operated systems are included in determining
BOAT. The data evaluation includes data already collected directly by
EPA and/or data provided by industry. In those instances where
additional data are needed to supplement existing information, EPA
collects additional data through a sampling and analysis program. The
principal elements of this data collection program are: (1) identifi-
cation of facilities for site visits, (2) an engineering site visit,
(3) a Sampling and Analysis Plan, (4) a sampling visit, and (5) an 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
12
-------
(TSDFs); and (4) EPA in-house treatment. This hierarchy is based on two
concepts: (1) to the extent possible, EPA should develop treatment
standards from data produced by treatment facilities handling only a
single waste, and (2) facilities that routinely treat a specific waste
have had the best opportunity to optimize design parameters. Although
excellent treatment can occur at many facilities that are not high in
this hierarchy, EPA has adopted this approach to avoid, when possible,
ambiguities related to the mixing of wastes before and during treatment.
When possible, the Agency will evaluate treatment technologies using
commercially operated systems. If performance data from properly
designed and operated commercial treatment methods for a particular waste
or a waste judged to be similar are not available, EPA may use data from
research facilities operations. Whenever research facility data are
used, EPA will explain 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.
13
-------
(2) Engineering site visit. Once a treatment facility has been
selected, an engineering site visit is made to confirm that a candidate
for sampling meets EPA's criteria for a well-designed facility and to
ensure that the necessary sampling points can be accessed to determine
operating parameters and treatment effectiveness. During the visit, EPA
also confirms that the facility appears to be well operated, although the
actual operation of the treatment system during sampling is the basis for
EPA's decisions regarding proper operation of the treatment unit. In
general, the Agency considers a well-designed facility to be one that
contains the unit operations necessary to treat the various hazardous
constituents of the waste, as well as to control other nonhazardous
materials in the waste that may affect treatment performance.
In addition to ensuring that a system is reasonably well designed,
the engineering visit examines whether the facility has a way to measure
the operating parameters that affect performance of the treatment system
during the waste treatment period. For example, EPA may choose not to
sample a treatment system that operates in a continuous mode, for which
an important operating parameter cannot be continuously recorded. In
such systems, instrumentation is important in determining whether the
treatment system is operating at design values during the waste treatment
period.
(3) Sampling and Analysis Plan. If after the engineering site visit
the Agency decides to sample a particular plant, the Agency will then
develop a site-specific Sampling and Analysis Plan (SAP) according to the
Generic Quality Assurance Project Plan for the Land Disposal Restriction
14
-------
Program ("BOAT"), EPA/530-SW-87-011. In brief, the SAP discusses where
the Agency plans to sample, how the samples will be taken, the frequency
of sampling, the constituents to be analyzed and the method of analysis,
operational parameters to be obtained, and specific laboratory quality
control checks on the analytical results.
The Agency will generally produce a draft of the site-specific
Sampling and Analysis Plan within 2 to 3 weeks of the engineering visit.
The draft of the SAP is then sent to the plant for review and comment.
With few exceptions, the draft SAP should be a confirmation of data
collection activities discussed with the plant personnel during the
engineering site visit. EPA encourages plant personnel to recommend any
modifications to the SAP that they believe will improve the quality of
the data.
It is important to note that sampling of a plant by EPA does not mean
that the data will be used in the development of treatment standards for
BOAT. EPA's final decision on whether to use data from a sampled plant
depends on the actual analysis of the waste being treated and on the
operating conditions at the time of sampling. Although EPA would not
plan to sample a facility that was not ostensibly well designed and well
operated, there is no way to ensure that at the time of the sampling the
facility will not experience operating problems. Additionally, EPA
statistically compares its test data to suitable industry-provided data,
where available, in its determination of what data to use in developing
treatment standards. The methodology for comparing data is presented
later in this section.
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 Restriction Program ("BOAT"), which delineates all of the
quality control and quality assurance measures associated with sampling
and analysis. (Quality assurance and quality control procedures are
summarized in Section 1.2.6 of this document.)
(4) Sampling visit. The purpose of the sampling visit is to collect
samples that characterize the performance of the treatment system and to
document the operating conditions that existed during the waste treatment
period. At a minimum, the Agency attempts to collect sufficient samples
of the untreated waste and solid and liquid treatment residuals so that
variability in the treatment process can be accounted for in the
development of the treatment standards. To the extent practicable, and
within safety constraints, EPA or its contractors collect all samples and
ensure that chain-of-custody procedures are conducted so that the
integrity of the data is maintained.
In general, the samples collected during the sampling visit will have
already been specified in the SAP. In some instances, however, EPA will
not be able to collect all planned samples because of changes in the
facility operation or plant upsets; EPA will explain any such deviations
from the SAP in its follow-up Onsite Engineering Report.
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 (see Test Methods for Evaluating Solid Waste. SW-846, Third
Edition, November 1986).
After the Onsite Engineering Report is completed, the report is
submitted to the plant for review. This review provides the plant with a
final opportunity to claim any information contained in the report as
confidential. Following the review and incorporation of comments, as
appropriate, the report is made available to the public with the
exception of any material claimed as confidential by the plant.
1.2.4 Hazardous Constituents Considered and Selected for Regulation
(1) Development of BDAT list. The list of hazardous constituents
within the waste codes that are targeted for treatment is referred to by
the Agency as the BDAT constituent list. This list, provided as
Table 1-1, is derived from the constituents presented in 40 CFR Part 261,
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
comprehensive list of hazardous constituents specifically regulated under
RCRA. The BDAT list consists of those constituents that can be analyzed
using methods published in SW-846, Third Edition.
17
-------
1521g
Table 1-1 BOAT Constituent List
BOAT
reference
no
222
1.
2
3
4
5
6.
223
7.
8.
9
10
11
12
13
14
15.
16.
17
18
19
20
21
22
L J
24
2^
L. O
27
28
29
224.
225.
226.
30
227
31.
214
32
Parameter
Volat i les
Acetone
Acetoni tn le
Aero le in
Aery Ion itn le
Benzene
Bromod ichloromethane
Bromomethane
n-Butyl alcohol
Carbon tetrachlor ide
Carbon bisulfide
Chlorobenzene
2-Chloro-l,3-butadiene
Ch lorodibromomethane
Chloroethane
2-Chloroethyl vinyl ether
Chloroform
Chloromethane
3-Chloropropene
1 , 2-Dibromo-3-chloropropane
1 ,2-Oibromoethane
Oibromomethane
Trans-l,4-Dichloro-2-butene
0 ichlorod i f luo route thane
1 , 1 -D ich Icroetrnne
i , 2-Q '.on icrcetn.ine
1 , 1 -D icn 'orcet h\ 'ene
Tr.ins 1.2 D i< nloroet nene
; . i' D icn ' jroprcpjre
Irans 1 .JOi^h loropropene
cis-l.j-Dichloropi'cpene
1 ,4-Oioxane
2-£tho\yethanol
tthyl acetate
Ethyl benzene
Ethyl cyanide
Ethyl ether
Ethyl methacrylate
Ethylene oxide
lodomethane
CAS no
67-64-1
75-05-8
107-02-8
107-13-1
71-43-2
/5-27-4
74-o3-9
71-36-3
5o-23-5
75-15-0
iOd-90-7
12o-99-8
124-48-1
7S-00-3
>i>75-8
C7-C.6-3
74-B7-3
i:7-05-l
95 -12- 6
1G6-9J-4
74-95-3
11C-57-6
7C 71 b
/ -.43
i o / '^ o - 2
/' -, - j c, - 4
1 ' ; ."0 c
1 , ; c
Ii>Lbi 02-15
10C61-01-5
123-91-1
110-aO-5
141-7b-6
100-41-4
107-12-0
60-29-7
97-63-2
75-21-8
7-1-08 4
19
-------
1521g
Table 1-1 (continued)
BOAT
reference
no
33.
228.
34.
229.
35
37
38.
230
39
40.
41.
42
43.
44.
45.
46.
47.
48.
49
231
50
215
216
217
51
52
53
54
55
56
57.
58
59
218.
60
61
62
Parameter
Volat i les (cont inued)
Isobutyl alcohol
Methanol
Methyl ethyl ketone
Methyl isobutyl ketone
Methyl methacrylate
Methacry lonitri le
Methylene chloride
2-Nitropropane
Pyndine
1,1,1 ,2-Tetrachloroethane
1 , 1 ,2,2-Tetrachloroethane
Tetrachloroethene
Toluene
Tribromomethane
1,1, 1-Tnchloroe thane
1 , 1 ,2-Trichloroethane
Tr ichloroethene
Trichloromonof luoromethane
1 , 2, 3-Tr ichloropropane
l,l,2-Tnchloro-l,2,2-trifluoro-
ethane
Vinyl chloride
1 ,2-Xy lene
1 ,3-Xylene
1.4-Xylene
Semivol it i les
Acenapnthd lene
Acenaphthene
Acetophenone
2-Acety lam inof luorene
4-Aminob ipheny 1
Am 1 me
Anthracene
Arami te
Benz(a)anthracene
Benzal chloride
Benzenethiol
Deleted
Benzo(a)pyrene
CAS no
78-83-1
67-56-1
78-93-3
108-10-1
30 62-6
12b-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
7:i-00-5
73-01-6
75-69-4
96-18-4
76-13-1
75-01-4
97-47-6
1C8-38-3
1CL-44-5
Jj.i .16 -o
83-32-9
96-86-2
53-96-3
92-67-1
62-53-3
120-12-7
140-57-8
56-55-3
9B-87-3
108-98-5
50-32^8
20
-------
1521g
Table 1-1 (continued)
BOAT
reference
no
63.
64.
65
66
67
68.
69.
70.
71
72
73
74.
75
76
77
78
79
80.
81.
82
232
83
84
85
a6
67
aa
o9
90
91
92
93
94
95.
96.
97
98
99
100
101
Parameter
Semivolat i les (continued)
Benzo(b)f luoranthene
Benzofghi )perylene
Benzo(k)f luoranthene
p-Benzoquinone
Bis(2-chloroethoxy)methane
Bis(2-chloroethyl )ether
Bis(2-chloro isopropy 1) ether
Bis(2-ethylhexy 1) phthalate
4-Bromophenyl phenyl ether
Butyl benzyl phthalate
2-sec -Butyl--]. 6-din i trophenol
p-Chloroan i 1 me
Chlorobenzi late
p-Chloro-m-cresol
2-Chloronaphtha lene
2-Chlorophenol
3-Chloropropion itn le
Chrysene
ortho-Cresol
para-Cresol
Cyc lohexanone
Oibenz(a,h)anthracene
D ibenzo(d,e)pyrene
0 ibenzo(a, i )pyrene
•n Oicr 'crcr.ervene
c- 'J icn loroue^-'erie
p-Q ich loroneruene
" , 3 ' -D ich lot oOL-tv ui me
L,4 D i c^ lorcpncnc I
i , 6-0 icn loropneno 1
Diethyl phthalate
3,3' -Dimethoxybenz id me
p-D i me thy lammoazobenzene
3,3'-Dimethylbenzidme
2 , 4-0 ime thy Ipheno 1
Dimethyl phthalate
Oi-n-butyl phthalate
1 ,4-Dmitrobenzene
4,6-Omitro-o-cresol
2 , 4-D in i tr opheno 1
CAb no
205-99-2
191^24-2
207-08-9
lCo-51-4
111-91-1
1.1--.4-4
:'-GJ6-32-9
117-81-7
lOi-55-3
d5-63-7
bB-d5-7
106-47-6
510-15-6
59-50-7
'.'1-58-7
95-57-8
542-76-7
218-01-9
95-48-7
1G6-44-5
103-94-1
53-70-3
19^-65-4
i -9-55-9
-4: 73-1
1 '01
'j - 1 lj - /
i.-94-l
. J j_ <:
o7-oL-0
o4-b6-2
119-90-4
^ 11-7
lla-93-7
1C5-67-9
Hl-11-3
K4-74-2
100-25-4
534-52-1
r-l-?8-5
21
-------
1521g
Table 1-1 (continued)
BOAT
reference
no.
102
103.
104.
105
106
219.
107.
108.
109.
110.
111.
112
113.
114.
115
116
117.
118.
119
120
36
121
122
123
124.
125
126
127
12B
129
130
131
132.
133.
134
135.
136.
137.
138.
Parameter
Seinivolat i les (continued)
2,4-Dinitrotoluene
2, 6-Oimtrotoluene
Oi-n-octyl phthdlate
Di -n-propylnitrosamine
Oiphenylamine
Oipheny In i trosamme
1 , 2-Diphenylhydraz me
Fluoranthene
Fluorene
Hexach lorobenzene
Hexach lorobutadlene
Hexachlorocyc lopentadiene
Hexachloroethane
Hexach lorophene
Hexach loropropene
indeno( 1 , 2,3-cd)pyrene
Isosaf role
Methapyr i lene
3-Methylcholanthrene
4,4' -Methy leneb is
(2-chloroani 1 me)
Methyl methanesu Ifonate
Naphtha lene
1 , 4-Napnthcqu inone
1 - Napft n^ ! dm i re
2-Napnthy lam me
p- N 1 1 roan i 1 me
Ni trotien.'tne
4-N i t re;,rc-'~o 1
H-Mitrosocn-n-uuty lam me
N-N i trosodiethy lam me
N-N 1 1 rosod line thy lam me
N-N 1 t rosomethy lethy lam me
N-N 1 1 rosomorpho 1 me
N-Ni trosopipendme
n-Nitrosopyrrol idme
5-Nitro-o-toluidme
Pen tach lorobenzene
Pentachloroethane
Pentachloron it robenzene
CAS no
121-14-2
6G6-20-2
117-84-0
621-64-7
122-39-4
S6-jO-6
122-66-7
206-44-0
86-73-7
lld-74-1
b7-Ca-3
77-47-4
67-72-1
70-30-4
Hoo-71-7
ljS-39-5
120-58-1
91-80-5
r,e-49-5
101-14-4
6t-27-3
91-20-3
1 -j-15-4
ii4 3^-7
'-.-C.9-B
r.L-Ql-6
':i : ''- 5 - 3
i 2 w C i.' - 7
'.' i i - 1 o - 3
5^-io-S
62-75-9
1C505-95-6
bJ-59-2
100-75-4
930-55-2
99 65-8
608-93-5
76-01-7
6?-(A-8
22
-------
1521g
Table 1-1 (continued)
BOAT
reference
no.
139.
140
141
142.
220
143
144
145.
146
147
148
149
150.
151
152
153
154
155
156
157
:5<3
159
22!
!60
161
162
163
164
165
166.
167
168.
169
170
171.
Parameter
Semi vo lat i les (continued)
Pentachlorophenol
Phenacet in
Phenanthrene
Phenol
Phtha 1 ic anhydr ide
2-Picol me
Pronamide
Pyrene
Resorcmol
Saf role
1,2,4,5-Tetrach lorobenzene
2,3,4,6-Tetrach loropheno I
1 ,2,4-Tnchlorobenzene
2,4, 5- T rich loropheno 1
2,4,6-Trichlorophenol
Tr is(2,3-dibromopropyl )
phosphate
Metals
Ant imony
Arsen ic
8a r i urn
Ber/ 1 1 ium
Cci.-in _,m
Chroin !uin ( told 1 )
Chro:i'i urn ( hex.iva ieM )
Copper
Lead
Mercury
Nickel
Selen lum
S i Iver
Ihd 1 1 lum
Vanadium
Zinc
Inorganics
Cyanide
F luor ide
Sulf ide
CAS no
B7-86-5
b2-44-2
85-01-8
108-95-2
85-44-9
109-06-8
23^50-58-5
12:1-00-0
10a-46-3
94-59-7
9c-94-3
5o-30-2
12o-d?-l
95-J5-4
Ho 05-2
126-72-7
/•J-iG-36-0
7440-36-2
744C-39-3
/4,u 41 7
7 , ;; 43-9
;'-i;C-47-32
-
74-:j 50-8
/ . > 5J-1
/4j!j-j7-6
7440-02-0
77d2-49-2
7-; 1C 22-4
/440-23-0
7440-62-2
7440-66-6
57-12-5
ie.'u4 48-8
B-l'jG-25-8
23
-------
1521g
Table 1-1 (continued)
BOAT
reference
no.
172.
173
174.
175.
176.
177
173
179
180.
181
182
183
184.
185
186
187
188.
189.
190.
191.
192
I'd 3
195
196
197
198
199
200
201
202
Parameter
Orqanochlorine pesticides
Aldrm
alpha-BHC
beta-BHC
delta-BHC
gamma -BHC
Chlordane
ODD
ODE
DOT
Dieldnn
Endosulfan I
Endosu If an II
Endr in
Endrin aldehyde
Heptachlor
Heptachlor epoxide
Isodr in
Kepone
Methoxyclor
Toxaphene
Phenoxvacet ic acid herbicides
2, 4-Oichloropnenoxyacet ic acid
-;i Ive*
2 , 4 , <. - 1
Disu Irotcn
Famphur
Methyl parathion
Parath ion
Phorate
PCBs
Aroclor 1016
Aroclor 1221
Aroclor 1232
CAS no.
309-00-2
319-84-6
319-85-7
319-86-8
58-89-9
57-74-9
72-54-8
72-55-9
50-29-3
60-57-1
939-98-8
33213-6-5
72-20-8
7421-93-4
76-44-3
1024-57-3
465-73-6
143-50-0
72-43-5
8001-35-2
94-75-7
93-72-1
'.13-76-5
296-04-4
52-85-7
298-00-0
56-38-2
298-02-2
12674-11-2
11104-28-2
11141-16-5
24
-------
1521g
Table 1-1 (continued)
BOAT
reference Parameter CAS no
no
PCBs (continued)
203. Aroclor 1242 53469-21-9
204 Aroclor 124a 12672-29-6
205. Aroclor 1254 11097-69-1
206 Aroclor 1260 11096-82-5
Dioxins and fur.ins
207 Hexachlorodibenzo-p-dioxins
208 Hexachlorodibenzofurans
209 Pentachlorodibenzo-p-dioxins
210 Pentachlorodlbenzofurans
211 Tetrachlorodibenzo-p-dioxins
212 Tetrachlorodibenzofurans
213 2,3,7,8-Tetrachlorodibenzo-p-dioxin 1746-01-6
-------
The initial BOAT constituent list was published in EPA's Generic
Quality Assurance Project Plan, March 1987 (EPA/530-SW-87-011).
Additional constituents will be added to the BOAT constituent list as
more key constituents are identified for specific waste codes or as new
analytical methods are developed for hazardous constituents. For
example, since the list was published in March 1987, 18 additional
constituents (hexavalent chromium, xylenes (all three isomers), benzal
chloride, phthalic anhydride, ethylene oxide, acetone, n-butyl alcohol,
2-ethoxyethanol, ethyl acetate, ethyl benzene, ethyl ether, methanol,
methyl isobutyl ketone, 2-nitropropane, 1, l,2-trichloro-l,2,2-
trifluoroethane, and cyclohexanone) have been added to the list.
Chemicals are listed in Appendix VIII if they are shown in scientific
studies to have toxic, carcinogenic, mutagenic, or teratogenic effects on
humans or other life-forms, and they include such substances as those
identified by the Agency's Carcinogen Assessment Group as being
carcinogenic. Including a constituent in Appendix VIII means that the
constituent can be cited as a basis for listing toxic wastes.
Although Appendix VII, Appendix VIII, and the F003 and F005
ignitables provide a comprehensive list of RCRA-regulated hazardous
constituents, not all of the constituents can be analyzed in a complex
waste matrix. Therefore, constituents that could not be readily analyzed
in an unknown waste matrix were not included on the initial BOAT list.
As mentioned above, however, the BOAT constituent list is a continuously
growing list that does not preclude the addition of new constituents when
analytical methods are developed.
25
-------
There are 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 1ist.
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 pressure
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 not an
appropriate analytical procedure for complex samples containing
unknown constituents.
5. Standards for analytical instrument calibration are not
commercially available. For several constituents, such as
benz(c)acridine, commercially available standards of a
"reasonably" pure grade are not available. The unavailability
of a standard was determined by a review of catalogs from
specialty chemical manufacturers.
26
-------
Two constituents (fluoride and sulfide) are not specifically included
in Appendices VII and VIII; however, these compounds are included on the
BOAT list as indicator constituents for compounds from Appendices VII and
VIII such as hydrogen fluoride and hydrogen sulfide, which ionize in
water.
The BOAT constituent list presented in Table 1-1 is divided into the
following nine groups:
• Volatile organics;
• Semivolatile organics;
. Metals;
• Other inorganics;
• Organochlorine pesticides;
• Phenoxyacetic acid herbicides;
• Organophosphorous insecticides;
• PCBs; 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 inorganics, by using the same analytical methods.
(2) Constituent selection analysis. The constituents that the
Agency selects for regulation in each treatability group are, in general,
those found in the untreated wastes at treatable concentrations. For
certain waste codes, the target list for the untreated waste may have
been shortened (relative to analyses performed to test treatment
technologies) because of the extreme unlikelihood that the constituent
will be present.
27
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In selecting constituents for regulation, the first step is to
summarize all the constituents that were found in the untreated waste at
treatable concentrations. This process involves the use of the
statistical analysis of variance (ANOVA) test, described in Section
1.2.6, to determine if constituent reductions were significant. The
Agency interprets a significant reduction in concentration as evidence
that the technology actually "treats" the waste.
There are some instances where EPA may regulate constituents that are
not found in the untreated waste but are detected in the treated
residual. This is generally the case where presence of the constituents
in the untreated waste interferes with the quantification of the
constituent of concern. In such instances, the detection levels of the
constituent are relatively high, resulting in a finding of "not detected"
when, in fact, the constituent is present in the waste.
After determining which of the constituents in the untreated waste
are present at treatable concentrations, EPA develops a list of potential
constituents for regulation. The Agency then reviews this list to
determine if any of these constituents can be excluded from regulation
because they would be controlled by regulation of other constituents in
the list.
EPA performs this indicator analysis for two reasons: (1) it reduces
the analytical cost burdens on the treater and (2) it facilitates
implementation of the compliance and enforcement program. EPA's
rationale for selection of regulated constituents for this waste code is
presented in Section 5 of this background document.
28
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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
treatment value by a factor referred to by the Agency as the variability
factor. This calculation takes into account that even well-designed and
well-operated treatment systems will experience some fluctuations in
performance. EPA expects that fluctuations will result from inherent
mechanical limitations in treatment control systems, collection of
treated samples, and analysis of these samples. All of the above
fluctuations can be expected to occur at well-designed and well-operated
treatment facilities. Therefore, setting treatment standards utilizing a
variability factor should be viewed not as a relaxing of section 3004(m)
requirements, but rather as a function of the normal variability of the
treatment processes. A treatment facility will have to be designed to
meet the mean achievable treatment performance level to ensure that the
performance levels remain within the limits of the treatment standard.
The Agency calculates a variability factor for each constituent of
concern within a waste treatability group using the statistical
calculation presented in Appendix A. The equation for calculating the
variability factor is the same as that used by EPA for the development of
numerous regulations in the Effluent Guidelines Program under the Clean
Water Act. The variability factor establishes the instantaneous maximum
based on the 99th percentile value.
There is an additional step in the calculation of the treatment
standards in those instances where the ANOVA analysis shows that more
29
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than one technology achieves a level of performance that represents
BOAT. In such instances, the BOAT treatment standard is calculated by
first averaging the mean performance value for each technology for each
constituent of concern and then multiplying that value by the highest
variability factor among the technologies considered. This procedure
ensures that all the BOAT technologies used as the basis for the
standards will achieve full compliance.
1.2.5 Compliance with Performance Standards
All the treatment standards reflect performance achieved by the best
demonstrated available technology (BOAT). As such, compliance with these
standards 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
standard is prohibited, wastes that are generated in such a way as to
naturally meet the standard can be land disposed without treatment. With
the exception of treatment standards that prohibit land disposal, all
treatment standards proposed are expressed as a concentration level.
EPA has used both total constituent concentration and TCLP analyses
of the treated waste as a measure of technology performance. EPA's
rationale for when each of these analytical tests is used is explained in
the following discussion.
For all organic constituents, EPA is basing the treatment standards
on the total constituent concentration found in the treated waste. EPA
based its decision on the fact that technologies exist to destroy the
30
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various organics compounds. Accordingly, the best measure of performance
would be the extent to which the various organic compounds have been
destroyed or the total amount of constituent remaining after treatment.
(NOTE: EPA's land disposal restrictions for solvent waste codes
F001-F005 (51 FR 40572) use the TCLP value as a measure of performance.
At the time that EPA promulgated the treatment standards for F001-F005,
useful data were not available on total constituent concentrations in
treated residuals and, as a result, the TCLP data were considered to be
the best measure of performance.)
For all metal constituents, EPA is using both total constituent
concentration and/or the TCLP as the basis for treatment standards. The
total constituent concentration is being used when the technology basis
includes a metal recovery operation. The underlying principle of metal
recovery is the reduction of the amount of metal in a waste by separating
the metal for recovery; therefore, total constituent concentration in the
treated residual is an important measure of performance for this
technology. Additionally, EPA also believes that it is important that
any remaining metal in a treated residual waste not be in a state that is
easily leachable; accordingly, EPA is also using the TCLP as a measure of
performance. It is important to note that for wastes for which treatment
standards are based on a metal recovery process, the facility has to
comply with both the total constituent concentration and the TCLP prior
to land disposal.
31
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In cases where treatment standards for metals are not based on
recovery techniques but rather on stabilization, EPA is using only the
TCLP as a measure of performance. The Agency's rationale is that
stabilization is not meant to reduce the concentration of metal in a
waste but only to chemically minimize the ability of the metal to leach.
1.2.6 Identification of BOAT
(1) Screening of treatment data. This section explains how the
Agency determines which of the treatment technologies represent treatment
by BOAT. The first activity is to screen the treatment performance data
from each of the demonstrated and available technologies according to the
following criteria:
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 this waste code
are discussed in Section 3.2 of this document.)
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 type value may be different from the measured
value. This discrepancy generally is caused by other
constituents in the waste that can mask results or otherwise
interfere with the analysis of the constituent of concern.
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 for metals in the leachate from the residual).
In the absence of data needed to perform the screening analysis, EPA
will make decisions on a case-by-case basis as to whether to include the
data. The factors included in this case-by-case analysis will be the
32
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actual treatment levels achieved, the availability of the treatment data
and their completeness (with respect to the above criteria), and EPA's
assessment of whether the untreated waste represents the waste code of
concern. EPA's application of these screening criteria for this waste
code is provided in Section 4 of this background document.
(2) Comparison of treatment data. In cases in which EPA has
treatment data from more than one technology following the screening
activity, EPA uses the statistical method known as analysis of variance
(ANOVA) to determine if one technology performs significantly better than
the others. This statistical method (summarized in Appendix A) provides
a measure of the differences between two data sets. If EPA finds that
one technology performs significantly better (i.e., the data sets are not
homogeneous), BOAT treatment standards are the level of performance
achieved by the best technology multiplied by the corresponding
variability factor for each regulated constituent.
If the differences in the data sets are not statistically
significant, the data sets are said to be homogeneous. Specifically, EPA
uses the analysis of variance to determine whether BOAT represents a
level of performance achieved by only one technology or represents a
level of performance achieved by more than one (or all) of the
technologies. If the Agency finds that the levels of performance for one
or more technologies are not statistically different, EPA averages the
performance values achieved by each technology and then multiplies this
value by the largest variability factor associated with any of the
33
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acceptable technologies. A detailed discussion of the treatment
selection metho and an example of how EPA chooses BOAT from multiple
treatment systems is provided in Section A-l.
(3) Quality assurance/quality control. This section presents the
principal quality assurance/quality control (QA/QC) procedures employed
in screening and adjusting the data to be used in the calculation of
treatment standards. Additional QA/QC procedures used in collecting and
screening data for the BOAT program are presented in EPA's Generic
Quality Assurance Project Plan for Land Disposal Restrictions Program
("BOAT") (EPA/530-SW-87-011, March 1987).
To calculate the treatment standards for the Land Disposal
Restriction Rules, it is first necessary to determine the recovery value
for each constituent (the amount of constituent recovered after spiking,
which is the addition of a known amount of the constituent, minus the
initial concentration in the samples divided by the amount added) for a
spike of the treated residual. Once the recovery value is determined,
the following procedures are used to select the appropriate percent
recovery value to adjust the analytical data:
1. If duplicate spike recovery values are available for the
constituent of interest, the data are adjusted by the lowest
available percent recovery value (i.e., the value that will
yield the most conservative estimate of treatment achieved).
However, if a spike recovery value of less than 20 percent is
reported for a specific constituent, the data are not used to
set treatment standards because the Agency does not have
sufficient confidence in the reported value to set a national
standard.
34
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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 spiked sample are averaged and the constituent
concentration is adjusted by the average recovery value. If
spiked recovery data are available for more than one sample, the
average is calculated for each sample and the data are adjusted
by the lowest average value.
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 a similar matrix (e.g., if the data are for an ash
from incineration, then data from other incinerator ashes could
be used). While EPA recognizes that transfer of matrix spike
recovery data from a similar waste is not an exact analysis,
this is considered the best approach for adjusting the data to
account for the fact that most analyses do not result in
extraction of 100 percent of the constituent. In assessing the
recovery data to be transferred, the procedures outlined in (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 (November 1986)
methods, the specific procedures and equipment used are also documented
in this Appendix. In addition, any deviations from the SW-846, Third
Edition, methods used to analyze the specific waste matrices are
documented. It is important to note that the Agency will use the methods
and procedures delineated in Appendix B to enforce the treatment
35
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standards presented in Section 6 of this document. Accordingly,
facilities should use these procedures in assessing the performance of
their treatment systems.
1.2.7 BOAT Treatment Standards for "Derived-From" and "Mixed" Wastes
(1) Wastes from treatment trains generating multiple residues. In a
number of instances, the proposed BOAT consists of a series of
operations, each of which generates a waste residue. For example, the
proposed BOAT for a certain waste code is based on solvent extraction,
steam stripping, and activated carbon adsorption. Each of these
treatment steps generates a waste requiring treatment — a
solvent-containing stream from solvent extraction, a stripper overhead,
and spent activated carbon. Treatment of these wastes may generate
further residues; for instance, spent activated carbon (if not
regenerated) could be incinerated, generating an ash and possibly a
scrubber water waste. Ultimately, additional wastes are generated that
may require land disposal. With respect to these wastes, the Agency
wishes to emphasize the following points:
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 Part 261.3(c)(2). (This
point is discussed more fully in (2) below.) Consequently, all
of the wastes generated in the course of treatment would be
prohibited from land disposal unless they satisfy the treatment
standard or meet one of the exceptions to the prohibition.
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 solids generated from treating these wastes would have
36
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to meet the treatment standard for nonwastewaters. All
derived-from wastes meeting the Agency definition of wastewater
(less than 1 percent TOC and less than 1 percent total
filterable solids) would have to meet the treatment standard for
wastewaters. EPA wishes to make clear that this approach is not
meant to allow partial treatment in order to comply with the
applicable standard.
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 Part 261.3(c)(2)(i)) or the mixture rule
(40 CFR Part 261.3(a)(2)(iii) and (iv)) or because the listed waste is
contained in the matrix (see, for example, 40 CFR Part 261.33(d)). The
prohibition for the particular listed waste consequently applies to this
type of waste.
The Agency believes that the majority of these types of residues can
meet the treatment standards for the underlying listed wastes (with the
possible exception of contaminated soil and debris for which the Agency
is currently investigating whether it is appropriate to establish a
separate treatability subcategorization). For the most part, these
37
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residues will be less concentrated than the original listed waste. The
Agency's treatment standards also make a generous allowance for process
variability by assuming that all treatability values used to establish
the standard are lognormally distributed. The waste also might be
amenable to a relatively nonvariable form of treatment technology such as
incineration. Finally, and perhaps most important, the rules contain a
treatability variance that allows a petitioner to demonstrate that its
waste cannot be treated to the level specified in the rule (40 CFR Part
268.44(a)). This provision provides a safety valve that allows persons
with unusual waste matrices to demonstrate the appropriateness of a
different standard. The Agency, to date, has not received any petitions
under this provision (for example, for residues contaminated with a
prohibited solvent waste), indicating, in the Agency's view, that the
existing standards are generally achievable.
(3) Residues from managing listed wastes or that contain listed
wastes. The Agency has been asked if and when residues from managing
hazardous wastes, such as leachate and contaminated ground water, become
subject to the land disposal prohibitions. Although the Agency believes
this question to be settled by existing rules and interpretative
statements, to avoid any possible confusion the Agency will address the
question again.
Residues from managing First Third wastes, listed California List
wastes, and spent solvent and dioxin wastes are all considered to be
subject to the prohibitions for the underlying hazardous waste. Residues
38
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from managing California List wastes likewise are subject to the
California List prohibitions when the residues themselves exhibit a
characteristic of hazardous waste. This determination stems directly
from the derived-from rule in 40 CFR Part 261.3(c)(2) or, in some cases,
from the fact that the waste is mixed with or otherwise contains the
listed waste. The underlying principle stated in all of these provisions
is that listed wastes remain listed until delisted.
The Agency's historic practice in processing delisting petitions 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 Part 260.22(b) states that mixtures or derived-from
residues can be delisted provided a delisting petitioner makes a
demonstration identical to that which a delisting petitioner would make
for the underlying waste. Consequently, these residues are treated as
the underlying listed waste for delisting purposes. The statute likewise
takes this position, indicating that soil and debris that are
contaminated with listed spent solvents or dioxin wastes are subject to
the prohibition for these wastes even though these wastes are not the
originally generated waste, but rather are a residual from management
(RCRA section 3004(e)(3)). It is EPA's view that all such residues are
covered by the existing prohibitions and treatment standards for the
listed hazardous waste that these residues contain and from which they
are derived.
39
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1.2.8 Transfer of Treatment Standards
EPA is proposing some treatment standards that are not based on
testing of the treatment technology of the specific waste subject to the
treatment standard. Instead, the Agency has determined that the
constituents present in the subject waste can be treated to the same
performance levels as those observed in other wastes for which EPA has
previously developed treatment data. EPA believes that transferring
treatment performance for use in establishing treatment standards for
untested wastes is technically valid in cases where the untested wastes
are generated from similar industries, have similar processing steps, or
have similar waste characteristics affecting performance and treatment
selection. Transfer of treatment standards to similar wastes or wastes
from similar processing steps requires little formal analysis. However,
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 wastes
generated by different processes within a single industry can be treated
to the same level of performance. First, EPA reviews the .avai1 able waste
characteristic data to identify those parameters that are expected to
affect treatment selection. EPA has identified some of the most
important constituents and other parameters needed to select the
treatment technology appropriate for a given waste. A detailed
discussion of each analysis, including how each parameter was selected
for each waste, can be found in Section 5 of this document.
40
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Second, when an individual analysis suggests that an untested waste
can be treated with the same technology as a waste for which treatment
performance data are already available, EPA analyzes a more detailed list
of constituents that represent some of the most important waste
characteristics that the Agency believes will affect the performance of
the technology. By examining and comparing these characteristics, the
Agency determines whether the untested wastes will achieve the same level
of treatment as the tested waste. Where the Agency determines that the
untested waste is easier to treat than the tested waste, the treatment
standards can be transferred. A detailed discussion of this transfer
process for each waste can be found in later sections of this document.
1.3 Variance from the BOAT Treatment Standard
The Agency recognizes that there may exist unique wastes that cannot
be treated to the level specified as the treatment standard. In such a
case, a generator or owner/operator may submit a petition to the
Administrator requesting a variance from the treatment standard. A
particular waste may be significantly different from the wastes
considered in establishing treatability groups because the waste contains
a more complex matrix that makes it more difficult to treat. For
example, complex mixtures may be formed when a restricted waste is mixed
with other waste streams by spills or other forms of inadvertent mixing.
As a result, the treatability of the restricted waste may be altered such
that it cannot meet the applicable treatment standard.
Variance petitions must demonstrate that the treatment standard
established for a given waste cannot be met. This demonstration can be
41
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made by showing that attempts to treat the waste by available
technologies were not successful or by performing appropriate analyses of
the waste, including waste characteristics affecting performance, which
demonstrate that the waste cannot be treated to the specified levels.
Variances will not be granted based solely on a showing that adequate
BOAT treatment capacity is unavailable. (Such demonstrations can be made
according to the provisions in Part 268.5 of RCRA for case-by-case
extensions of the effective date.) The Agency will consider granting
generic petitions provided that representative data are submitted to
support a variance for each facility covered by the petition.
Petitioners should submit at least one copy to:
The Administrator
U.S. Environmental Protection Agency
401 M Street, S.W.
Washington, DC 20460
An additional copy marked "Treatability Variance" should be submitted
to:
Chief, Waste Treatment Branch
Office of Solid Waste (WH-565)
U.S. Environmental Protection Agency
401 M Street, S.W.
Washington, DC 20460
Petitions containing confidential information should be sent with
only the inner envelope marked "Treatability Variance" and "Confidential
Business Information" and with the contents marked in accordance with the
requirements of 40 CFR Part 2 (41 FR 36902, September 1, 1976, amended by
43 FR 4000).
The petition should contain the following information:
42
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1. The petitioner's name and address.
2. A statement of the petitioner's interest in the proposed action.
3. The name, address, and EPA identification number of the facility
generating the waste, and the name and telephone number of the
plant contact.
4. The process(es) and feed materials generating the waste and an
assessment of whether such process(es) or feed materials may
produce a waste that is not covered by the demonstration.
5. A description of the waste sufficient for comparison with the
waste considered by the Agency in developing BOAT, and an
estimate of the average and maximum monthly and annual
quantities of waste covered by the demonstration. (Note: The
petitioner should consult the appropriate BOAT background
document for determining the characteristics of the wastes
considered in developing treatment standards.)
6. If the waste has been treated, a description of the system used
for treating the waste, including the process design and
operating conditions. The petition should include the reasons
the treatment standards are not achievable and/or why the
petitioner believes the standards are based on inappropriate
technology for treating the waste. (Note: The petitioner should
refer to the BOAT background document as guidance for
determining the design and operating parameters that the Agency
used in developing treatment standards.)
7. A description of the alternative treatment systems examined by
the petitioner (if any); a description of the treatment system
deemed appropriate by the petitioner for the waste in question;
and, as appropriate, the concentrations in the treatment
residual or extract of the treatment residual (i.e., using the
TCLP, where appropriate, for stabilized metals) that can be
achieved by applying such treatment to the waste.
8. A description of those parameters affecting treatment selection
and waste characteristics that affect performance, including
results of all analyses. (See Section 3.0 for a discussion of
waste characteristics affecting performance that the Agency has
identified for the technology representing BOAT.)
9. The dates of the sampling and testing.
10. A description of the methodologies and equipment used to obtain
representative samples.
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11. A description of the sample handling and preparation techniques,
including techniques used for extraction, containerization, and
preservation of the samples.
12. A description of analytical procedures used, including QA/QC
methods.
After receiving a petition for a variance, the Administrator may
request any additional information or waste samples that may be required
to evaluate and process the petition. Additionally, all petitioners must
certify that the information provided to the Agency is accurate under
40 CFR Part 268.4(b).
In determining whether a variance will be granted, the Agency will
first look at the design and operation of the treatment system being
used. If EPA determines that the technology and operation are consistent
with BOAT, the Agency will evaluate the waste to determine if the waste
matrix and/or physical parameters are such that the BOAT treatment
standards reflect treatment of this waste. Essentially, this latter
analysis will concern the parameters affecting treatment selection and
waste characteristics affecting performance parameters.
In cases where BOAT is based on more than one technology, the
petitioner will need to demonstrate that the treatment standard cannot be
met using any of the technologies, or that none of the technologies are
appropriate for treatment of the waste. After the Agency has made a
determination on the petition, the Agency's findings will be published in
the Federal Register, followed by a 30-day period for public comment.
44
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After review of the public comments, EPA will publish its final
determination in the Federal Register as an amendment to the treatment
standards in 40 CFR Part 268, Subpart D.
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2. INDUSTRIES AFFECTED AND WASTE CHARACTERIZATION
The previous section presents the generic methodology for developing
BOAT standards. The purpose of this section is to discuss the rationale
for dividing the K086 listed waste into three treatability groups and
provide a complete characterization of the KQ86 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 Part 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. These
solvent washes, solvent sludges, and caustic/water cleaning wastes are
inherently different from a treatment perspective 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
46
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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 there are approximately 460 facilities that
formulate ink and 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 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. There are many types of pigments and dyes 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.
47
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1484g
Table 2-1 Number of Ink Formulators by
State and by EPA Region
EPA Region
I
II
III
IV
V
i
VI
VII
VIII
IX
X
State
Connect icut
Massachusetts
New Hampshire
Rhode Island
New Jersey
New York
0 C.
Maryland
Pennsy Ivan la
Virgin la
Alabama
F lor ida
Georgia
Kentucky
Mississippi
North Carol ina
South Carolina
Tennessee
1 1 1 inois
Indiana
Michigan
Minnesota
Ohio
Wiscons in
Arkansas
LOJ i j Idfia
Ok lanoma
Te
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Ink formulation consists of a batch mixing of the pigments, vehicles,
solvents, and other speciality additives (see Figure 2-2). The pigment
may be in a powder or in a paste form. The 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 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.
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SOLVENT
WASH
SOLVENT
WASH
SOLVENTS
PIGMENTS
VEHICLES
MIXING
MILLING
REDUCING
DUALITY
CONTROL
FILLING AND
SHIPPING
PRODUCT
KOB6
SOI VENT
WASH
K086
SOLVENT
WASH
Figure 2-2. INK FORMULATION AND K006 WASTE GENERATION
-------
1484g
Table 2-2 Major Constituent Analysis of
Untreated K086 Solvent Wash
Solvent wash
Major constituent concentration (wt %)
Water <0 5
BOAT list metal constituents (including lead and chromium) <0.1
Spent solvents (may be BOAT list organic constituents) 97 0
Total Solids* 2 4
* These are volatile and nonvolatile solids remaining after the waste
has been heated to 1Q3-105"C. The solids may be organic ink pigments
Reference USEPA 1985
-------
1599g
Table 2-3 BOAT Constituent Composition and Other Data
BOAT
Reference
No.
222
226
225
229
38
43
215-217
70
232
121
154
156
158
159
160
221
161
163
164
165
168
169
171
Analysis
BOAT Volat i 1e Organ ics
Acetone
Ethylbenzene
Ethyl acetate
Methyl isobutyl ketone
Methylene chloride
Toluene
Xylene (Total)
BOAT Semivolat i le Orqanics
bis (2-E thy Ihexyljphtha late
Cyclohexanone
Napthalene
BDAT Metals
Ant imony
Barium
Cadmium
Chromium
Copper
Hexavalent chromium
Lead
Nickel
Se lenium
S i Iver
Z me
Otrer bC-V ! i-yi nan !.:•,
Cyanide
Sulf ide
Otner Pai -ureters
pH
Total solids
Water content
Heating value (Btu/ Ib)
Total organic carbon
Ash content
Organic ink pigments
Ethyl alcohol
High flash point naptha
compounds
Untreated K086 solvent
waste charcterization
(a)
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
CBI
CBI
CBI
CBI
wash
(mq/kq)
(b)
-
-
256,000
-
-
-
-
-
-
-
-
0 54
4.3
116
17
-
1 06
2.4
0 05
0 32
1 I
-
-
6 3
5,700
-
13,600
-
-
77,000
667,000
-
CBI - Confidential Business Information
= No analysis performed
(a) Reference USCPA I9«7a
(b) Reference USEPA ly»5
-------
3. APPLICABLE/DEMONSTRATED TREATMENT TECHNOLOGIES
This section describes the applicable treatment technologies,
demonstrated treatment technologies, and any available performance data
pertinent to the treatment of K086 solvent wash. Since the waste
characterization data in Section 2 reveal that K086 solvent wash wastes
contain 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 BOAT list
metals present in the K086 solvent wash wastes.
3.1 Applicable Treatment Technologies
The methodology used to determine the applicable technologies is
called analysis of parameters affecting treatment selection. This
analysis involves the identification of applicable treatment technologies
based on the physical and chemical composition of the waste. The K086
solvent wash wastes primarily consist of the particular solvent(s) used
in the cleaning process; these wastes also contain water, BOAT list
metals, and solids with boiling points higher than 1053C. The waste
also 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 BOAT 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
54
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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
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.
55
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High temperature metals recovery provides for recovery of metals from
wastes primarily by volatilization of some of the metals, subsequent
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.
56
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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.
Sections 3.2.5 through 3.2.8 describe chromium reduction, chemical
precipitation, settling filtration, and the parameters affecting
selection of these treatment technologies. Performance data for chromium
reduction precipitation and sludge filtration of the metal bearing
wastewater are presented in Section 3.3. 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 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 3.3.
High temperature metals recovery has been identified as potentially
applicable for treatment of K086 precipitated solids. At this time, EPA
57
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does not have any treatment performance data for high temperature metals
recovery of wastewater treatment precipitated solids; however, the data
have been requested. When the data are received, EPA will continue to
investigate the application and demonstration of high temperature metals
recovery for treatment of the K086 solvent wash nonwastewaters such as
the precipitated solids residual from wastewater treatment.
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. Following the
technology discussions is the technology performance data base for
treatment of K086 solvent wash wastes.
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 this technology
(a) Liquid injection. Liquid injection is applicable to wastes
that have viscosity values sufficiently low so that the waste can be
atomized in the combustion chamber. A range of literature maximum
viscosity values are reported, with the low being 100 Saybolt seconds
58
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universal (SSU) and the high being 10,000 SSU. It is important to note
that viscosity is temperature dependent; while liquid injection may not
be applicable to a waste at ambient conditions, it may be applicable when
the waste is heated. Other factors that affect the use of liquid
injection are particle size and the presence of suspended solids. Both
of these waste parameters can cause plugging of the burner nozzle.
(b) Rotary kiln/fluidized bed/fixed hearth. These incineration
technologies are applicable to a wide range of hazardous wastes. They
can be used on wastes that contain high or low total organic content,
high or low filterable solids, various viscosity ranges, and a range of
other waste parameters. EPA has not found these technologies to be
demonstrated on wastes that are composed essentially of metals with low
organic concentrations. In addition, the Agency expects that some of the
high metal content wastes may not be compatible with existing and future
air emission limits without emission controls far more extensive than
those currently 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.
59
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(b) Rotary kiln and fixed hearth. There are two distinct
principles of operation for these incineration technologies, one for each
of the chambers involved. In the primary chamber, energy, in the form of
heat, is transferred to the waste to achieve volatilization of the
various organic waste constituents. During this volatilization process
some of the organic constituents 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
incinerator technology is somewhat different from that for rotary kiln
and fixed hearth incineration, in that there is only one chamber, which
contains the fluidizing sand and a freeboard section above the sand. The
purpose of the fluidized bed is to both volatilize and combust the
waste. Destruction of the waste organics can be accomplished to a better
degree in this chamber than in the primary chamber of the rotary kiln and
fixed hearth because of (1) improved heat transfer from the fluidization
of the waste using forced air and (2) the fact that the fluidization
process provides sufficient oxygen and turbulence to convert the organics
to carbon dioxide and water vapor. The freeboard generally does not have
an afterburner; however, additional time is provided for conversion of
60
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the organic constituents to carbon dioxide, water vapor, and hydrochloric
acid if chlorine is present in the waste.
(3) Description of incineration technologies
(a) Liquid injection. The liquid injection system is capable
of incinerating a wide range of gases and liquids. The 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.
61
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WATER
AUXILIARY FUEL
BURNER
AIR-
o-
LIQUID OR GASEOUS.
WASTE INJECTION
•»JBURNER
Tl
PRIMARY
COMBUSTION
CHAMBER
AFTERBURNER
(SECONDARY
COMBUSTION
CHAMBER)
SPRAY
CHAMBER
I
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
AFTERBURNER
SOLID
WASTE
INFLUENT
FEED
MECHANISM
COMBUSTION
GASES
LIQUID OR
GASEOUS
WASTE
INJECTION
ASH
FIGURE 3-2
ROTARY KILN INCINERATOR
b3
-------
(c) Fluidized bed. A fluidized bed incinerator consists of a
column containing inert particles such as sand, which is referred to as
the bed. Air, driven by a blower, enters the bottom of the bed to
fluidize the sand. Air passage through the bed promotes rapid and
uniform mixing of the injected waste material within the fluidized bed.
The fluidized bed has an extremely high heat capacity (approximately
three times that of flue gas at the same temperature), thereby providing
a large heat reservoir. The injected waste reaches ignition temperature
quickly and transfers the heat of combustion back to the bed. Continued
bed agitation by the fluidizing air allows larger particles to remain
suspended in the combustion zone (See Figure 3-3).
(d) Fixed hearth. Fixed hearth incinerators, also called
controlled air or starved air incinerators, are another major technology
used for hazardous waste incineration. Fixed hearth incineration is a
two-stage combustion process (see Figure 3-4). Waste is ram-fed into the
first stage, or primary chamber, and burned at less than stoichiometric
conditions. The resultant smoke and pyrolysis products, consisting
primarily of volatile hydrocarbons and carbon monoxide, along with the
normal products of combustion, pass to the secondary chamber. Here,
additional air is injected to complete the combustion. This two-stage
process generally yields low stack particulate and carbon monoxide
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.
64
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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
65
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AIR
GAS TO AIR
POLLUTION
CONTROL
1
AIR
WASTE
INJECTION
BURNER
PRIMARY
COMBUSTION
CHAMBER
GRATE
SECONDARY
COMBUSTION
CHAMBER
AUXILIARY
FUEL
2-STAGE FIXED HEARTH
INCINERATOR
ASH
FIGURE 3-4
FIXED HEARTH INCINERATOR
-------
(e) Air pollution controls. Following incineration of
hazardous wastes, combustion gases are generally further treated in an
air pollution control system. The presence of chlorine or other halogens
in the waste requires a scrubbing or absorption step to remover
hydrochloric acid and other halo-acids from the combustion gases. Ash in
the waste is not destroyed in the combustion process. Depending on its
composition, ash will either exit as bottom ash, at the discharge end of
a kiln or hearth, for example, or as particulate matter (fly ash)
suspended in the combustion gas stream. Particulate emissions from most
hazardous waste combustion systems generally have particle diameters of
less than one micron and require high-efficiency collection devices to
minimize air emissions. In addition, scrubber systems provide an
additional buffer against accidental releases of incompletely destroyed
waste products as a result of poor combustion efficiency or combustion
upsets, such as flameouts.
(4) Waste characteristics affecting performance (WCAP)
(a) Liquid injection. In determining whether liquid injection
is likely to achieve the same level of performance on an untested waste
as on a previously tested waste, the Agency will compare dissociation
bond energies of the constituents in the untested and tested waste. 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;
67
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however, in practice this is not always the case. Other energy effects
(e.g., vibrational effects, the formation of intermediates, and
interactions between different molecular bonds) may have a significant
influence on activation energy.
Because of the shortcomings of bond energies in estimating activation
energy, EPA analyzed other waste characteristic parameters to determine
if these parameters would provide a better basis for transferring
treatment standards from an untested waste to a tested waste. These
parameters include heat of combustion, heat of formation, use of
available kinetic data to predict activation energies, and general
structural class. All of these were rejected for reasons provided below.
The heat of combustion measures only the difference in energy of the
products and reactants; it does not provide information on the transition
state (i.e., the energy input needed to initiate the reaction). Heat of
formation is used as a predictive tool for whether reactions are likely
to proceed; however, these data are not available for a significant
number of hazardous constituents. 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.
68
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(b) Rotary kiln/fluidized bed/fixed hearth. Unlike liquid
injection, these incineration technologies also generate a residual ash.
Accordingly, in determining whether these technologies are likely to
achieve the same level of performance on an untested waste as on a
previously tested waste, EPA would need to examine the waste
characteristics that affect volatilization of organics from the waste, as
well as destruction of the organics, once volatilized. Relative to
volatilization, EPA will examine thermal conductivity of the entire waste
and boiling point of the various constituents. As with liquid injection,
EPA will examine bond energies in determining whether treatment standards
for scrubber water residuals can be transferred from a tested waste to an
untested waste. Below is a discussion of how EPA arrived at thermal
conductivity and boiling point as the best 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
69
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amount of heat transferred by radiation. With regard to convection, EPA
also believes that the type of heat transfer will generally be more a
function of the type and design of incinerator than of the waste itself.
However, EPA is examining particle size as a waste characteristic that
may significantly impact the amount of heat transferred to a waste by
convection and thus impact volatilization of the various organic
compounds. EPA believes that the final type of heat transfer,
conduction, 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, which 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 heat
transfer characteristics of a waste. Below is a discussion of both the
70
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limitations associated with thermal conductivity, as well as other
parameters considered.
Thermal conductivity measurements, as part of a treatability
comparison for two different wastes through a single incinerator, are
most meaningful when applied to wastes that are homogeneous (i.e., major
constituents are essentially the same). As wastes exhibit greater
degrees of nonhomogeneity (e.g., significant concentration of metals in
soil), thermal conductivity becomes less accurate in predicting
treatability because the measurement essentially reflects heat flow
through regions having the greatest conductivity (i.e., the path of least
resistance) and not heat flow through all parts of the waste.
Btu value, specific heat, and ash content were also considered for
predicting heat transfer characteristics. These parameters can no better
account for nonhomogeneity than 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) Boi1 ing point. Once heat is transferred to a constituent
within a waste, then removal of this constituent from the waste will
depend on its volatility. As a surrogate for volatility, EPA is using
boiling point of the constituent. Compounds with lower boiling points
have higher vapor pressures and, therefore, would be more likely to
vaporize. The Agency recognizes that this parameter does not take into
consideration the impact of other compounds in the waste on the boiling
71
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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) Incineration 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.
72
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(i) Temperature. Temperature is important in that it provides
an indirect measure of the energy available (i.e., Btu/hr) to overcome
the activation energy of waste constituents. As the design temperature
increases, the more likely it is that the molecular bonds will be
destabilized and the reaction completed.
The temperature is normally controlled automatically through the use
of instrumentation that senses the temperature and automatically adjusts
the amount of fuel and/or waste being fed. The temperature signal
transmitted to the controller can be simultaneously transmitted to a
recording device, referred to as a strip chart, and thereby continuously
recorded. To fully assess the operation of the unit, it is important to
know not only the exact location in the incinerator at which the
temperature is being monitored but also the location of the design
temperature.
(ii) Excess oxygen. It is important that the incinerator
contain oxygen in excess of the stiochiometric amount necessary to
convert the organic compounds to carbon dioxide and water vapor. If
insufficient oxygen is present, then destabilized waste constituents
could recombine to the same or other BOAT list organic compounds and
potentially cause the scrubber water to contain higher concentrations of
BOAT list constituents than would be the case for a wel1-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, thereby
73
-------
increasing 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 this analysis plus the
total amount of air added, the volume of combustion gas can be
calculated. After both the Btu content and the expected combustion gas
74
-------
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 it is likely that sufficient
energy will 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.
75
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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 for volatilization to occur. As the time that the waste is
in the kiln is increased, a greater quantity of heat is transferred to
the hazardous waste constituents. The residence time will be a function
of the specific configuration of the rotary kiln, including the length
and diameter of the kiln, the waste feed rate, and the rate of rotation.
(iii) Revolutions per minute (RPM). This parameter provides an
indication of the turbulence that occurs in the primary chamber of a
rotary kiln. As the turbulence increases, the quantity of heat
transferred to the waste 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 on
"Underlying principles of operation," the primary chamber accounts for
almost all of the conversion of organic wastes to carbon dioxide, water
vapor, and acid gas (if halogens are present). The secondary chamber
will generally provide additional residence time for thermal oxidation of
the waste constituents. Relative to the primary chamber, the parameters
that the Agency will examine in assessing the effectiveness of the design
76
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are temperature, residence time, and bed pressure differential. The
first two were discussed under "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 technology. Fuel substitution has been
used with industrial waste solvents, refinery wastes, synthetic
fibers/petrochemical wastes, and waste oils. It can also be used when
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combusting other waste types produced during the manufacturing of
Pharmaceuticals, pulp and paper, and pesticides. These wastes can be
handled in a solid, liquid, or gaseous form.
The most common types of units in which waste fuels are burned are
industrial furnaces and industrial boilers. Industrial furnaces include
a 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 are:
• 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 a boiler unless the boiler has 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 so that it can be atomized in the
combustion chamber. If viscosity is too high, heating of storage tanks
may be required prior to combustion. For atomization of liquids, a
viscosity of 165 centistokes (750 SSU) or less is typically required.
If filterable material suspended in the liquid fuel prevents or
hinders pumping or atomization, unacceptable combustion conditions may
result.
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) Physical description of the process. As stated, a number of
industrial applications can use fuel substitution. Therefore, there is
no one process description that will fit all of these applications.
However, the following section provides a general description of
industrial kilns (one form of industrial furnace) and industrial
boi1ers.
(a) Kilns. Combustible wastes have the potential to be used as
fuel in kilns and, for waste liquids, are often used with oil to co-fire
kilns. Coal-fired kilns are capable of handling some solid wastes. In
the case of cement kilns, there are usually no residuals requiring land
disposal since any ash formed becomes part of the product or is removed
by particulate collection systems and recycled back to the kiln. The
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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°C and 1,540°C (2,500°F 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
rotary kiln, typically to temperatures of 980°C to 1,260°C
(1,800°F to 2,300°F). Lime kilns are less likely to burn
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hazardous wastes than 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°C to 1,150°C (2,000°F 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 BOAT 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 kilns 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; however, in practice 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 waste to a tested waste. These
parameters included heat of combustion, heat of formation, use of
available kinetic data to predict activation energies, and general
structural class. All of these 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 predictive tool for 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 three parameters is
given below.
(i) Design temperature. Industrial boilers are generally
designed based on their steam generation potential (Btu output). This
factor is related to the design combustion temperature, which in turn
depends on the amount of fuel burned and its Btu value. The fuel feed
rates and combustion temperatures of industrial boilers are generally
fixed based on the Btu values of fuels normally handled (e.g., No. 2
versus No. 6 fuel oils). When wastes are to be blended with fossil fuels
for combustion, the blending, based on Btu values, must be such that the
resulting Btu value of the mixture is close to that of the fuel value
used in 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) Retention time. A sufficient retention time of combustion
products is normally necessary to ensure that the hazardous substances
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being combusted (or formed during combustion) are completely oxidized.
Retention times on the order of a few seconds are normally 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 flow rate, (2) fuel feed rate, (3) steam pressure or rate of
production, and (4) temperature. EPA believes that these four parameters
will be used to determine 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 below.
(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 flow rate
can be increased or decreased to maintain proper fuel-to-oxygen ratios.
Some industrial furnaces do not completely combust fuels (e.g., coke
ovens and blast furnaces); hence, oxygen concentration in the flue gas is
a meaningless variable.
(ii) Fuel feed rate. The rate at which fuel is injected into
the boiler or industrial furnace will determine the thermal output of the
system per unit of time (Btu/hr). If steam is produced, steam pressure
monitoring will indirectly determine if the fuel feed rate is adequate.
However, various velocity and mass measurement devices can be used to
monitor fuel flow directly.
(iii) Steam pressure or rate of production. Steam pressure in
boilers provides a direct measure of the thermal output of the system and
is directly monitored by use of in-system pressure gauges. Increases or
decreases in steam pressure can be 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 rate.
Wastes should not be added to primary fuels until the boiler
temperature reaches the minimum needed for destruction of the wastes.
Temperature instrumentation and control should be designed to stop waste
addition in the event of process upsets.
Monitoring and control of temperature in industrial furnaces are also
critical to the product quality; e.g., lime, cement, or aggregate kilns,
which require minimum operating temperatures. Kilns have very high
thermal inertia in the refractory and in-process product, high residence
times, and high air flow rates, so that even in the case of a momentary
stoppage of fuel flow to the kiln, organic constituents are likely to
continue to be destroyed. The main operational control required for
wastes burned in kilns is to stop waste flow in the event of low kiln
temperature, loss of the electrical power to the combustion air fan, and
loss of primary fuel flow.
(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 were also
considered. However, 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 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 in order 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
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leached when water or a mild acid solution comes into contact with the
waste material.
There are two principal stabilization processes 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°C to 1500°C or 2550°F to 2730°F). 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
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into the crystal structure of the cement matrix, but this hypothesis has
not been verified.
(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 quantity of the 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 be first 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
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wastes to the mixing pits and pumpable uncured wastes to the curing
site. Stabilized wastes are then removed to a final disposal site.
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
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waste particles and the weakening of the bonding between the particle and
the stabilizing agent. This coating can inhibit chemical bond formation,
thereby decreasing the resistance of the material to leaching.
(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 having decreased resistance to leaching.
(d) Sulfate and chlorides. The presence of certain inorganic
compounds will interfere 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 leachable metal constituents is minimized are (1) selection
of stabilizing agents and other 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
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Teachability of the solid material. Stabilizing agents and additives
must be carefully selected based on the chemical and physical
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 port!and 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 bind the
waste constituents of concern properly, 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
importantly, may not allow the chemical reactions that bind the hazardous
constituents to be fully completed.
(c) Mixing. The conditions of mixing include the type and
duration of mixing. Mixing is necessary to ensure homogeneous
distribution of the waste and the stabilizing agents. Both undermixing
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and overtaxing 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. The 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 and result
in too little water being available for completion of the stabilization
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reaction. The duration of the curing process should also be determined
during the design stage and typically will be 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 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 treated
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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 in order 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 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
condenser and baghouse. As noted earlier, the particular system 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 on the final disposition of
the material. If further recovery is performed, then the waste would be
treated in another furnace. If the material were to be land disposed,
the final process step would generally consist of quenching.
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K061
CARBON
FLUXES
(ADDITIVES)
FEED
BLENDING
HIGH
TEMPERATURE
PROCESSING
PRODUCT
COLLECTION
REUSE
RESIDUAL
COLLECTION
I
REUSE OR
LAND DISPOSAL
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. There is no conventional direct
measurement of the heat transfer characteristics of a waste. 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 named "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. For the
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 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 ions) from the valence state of six (+6) to the
trivalent (+3) state. "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 + 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 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 acid and base 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-
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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 other metals in the waste 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 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 metals 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
sulfide (FeS).
The solubility of a particular compound will depend on the extent to
which the electrostatic forces holding the ions of the compound together
can be overcome. The solubility will change significantly with
temperature; most metal compounds are more soluble as the temperature
increases. Additionally, the solubility will be 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. In general, pH provides a measure of the extent to
which a solution contains either an excess of 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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FIGURE 3-7 CONTINUOUS CHEMICAL PRECIPITATION
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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, thereby 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 it be well
mixed so that the waste and the treatment chemicals are dispersed
throughout the tank, in order 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 the density of the precipitated solids, both of which increase the
rate of settling. The 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 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, we will
examine the following waste characteristics: (1) the concentration and
type of the metal(s) in the waste, (2) the concentration of suspended
solids (TSS), (3) the concentration of 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.
lib
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SLUDGE
INFLUENT
CENTER FEED CLARIFIER WITH SCRAPER SLUDGE REMOVAL SUSTEM
INFLUENT
SLUDGE
RIM FEED - CENTER TAKEOFF CLARIFIER WITH
HYDRAULIC SUCTION SLUDGE REMOVAL SYSTEM
INFLUENT
SLUDGE
RIM FEED - RIM TAKEOFF CLARIFIER
FIGURE 3-8
CIRCULAR CLARsFIERS
-------
INFLUENT
EFFLUENT
FIGURE 3-9
INCLINED PLATE SETTLER
120
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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. 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 in order 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., 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
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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 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.
125
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(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.
126
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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
clari fi er.
(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.
127
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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) waste feed
pressure, 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
128
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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 on 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 in order 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
129
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filtration performance, it is important to know both the type of filter
aid used and the basis for 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
sol ids.
(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.
130
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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 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,
removal of the solids is accomplished 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 media. This is especially
true for a vacuum filter. For a pressure filter (like a plate and
131
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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. Also, the addition of filter aids to a
gelatinous sludge, such as lime or diatomaceous earth, 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; they 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
132
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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 discharge.
(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 through 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
significantly increases the amount of sludge solids to be disposed of.
133
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However, polyelectrolyte coagulant usage usually does not increase sludge
volume significantly because the dosage is low.
3.3 Performance Data Base
3.3.1 Organics Treatment Data
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. To help develop organic
treatment standards, 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 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, located 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 3-1. Although a
rotary kiln incinerator was used to treat the K086 solvent wash, the data
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
134
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Table 3-1 Incineration
EPA Collected Data
K066 Solvent Wash
A"jl,t iral Dote,
BDAT Oraanic Constituent Concent
Sample Set »1 Sample °,
k086
solvent
wash
BOAT List Constituents (mg/kg)
Vo1?! ' le Orga^ >rs
Acetcr.e CBI
Ethylbenzene CBI
Methyl isobutyi ketone CBI
Me thy 'ene chlo- u:e CBI
lolue-e CBI
Xylene (total) CBI
^PTIIVC Vt i le Or games
i is(2-ethylhe/, Ijphthalate CBI
f vc Ic'iexanone CBI
t^phtidlene CBI
kObt
Scrubber solvent
water wash
(mg/1) (mg/kq)
<0 005 CBI
<0 005 CBI
<0 010 CBI
<0 010 Cbl
<0 010 CBI
<0 005 CBI
-0 010 CBI
•0 OCci CB1
-0 010 Cfl
ft «2 Sample Set #3 Sample
KOB6
Scrubber solvent
water wash
(mg/1) (mg/kg)
<0 005 CBI
•-0 005 CBI
•-0 010 CBI
-------
concentration found in the scrubber water. EPA's analyses of these data
for the development of organic treatment standards for K086 solvent wash
can be found in Sections 4 and 6.
3.3.2 Metals Treatment Data
(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, EPA does have data
from EPA's testing of Envirite Corporation that the Agency believes
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.
EPA believes that the Envirite treatment process could be used to
treat K086 scrubber water because the treatment system consists of
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 3-2.
EPA reviewed the characterization data for K086 scrubber water, also
presented in Table 3-2, as well as data on parameters that would affect
the performance of the Envirite treatment system (i.e., sulfide
136
-------
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.
(2) Nonwastewater. The Agency does not have performance data on
treatment of the BOAT metals in the precipitate from treatment of K086
scrubber water. However, EPA does have data from EPA's testing of
Envirite Corporation that the Agency believes represent a level of
treatment performance that can be achieved for the K086 precipitate by
using lime stabilization followed by sludge filtration.
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.
137
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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.
138
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IcbSg
Idble 3-2 Chromium Reduction Chemical Precipitation,
Followed by Vacuum Filtration
EPA Collected Data from Envirite
Const i tuent
•30AT Met.i's
Ant imony
Arsen ic
Barium
Beryl 1 ium
Cadmium
Chromium (nexavalent)
Chrom ium (total)
Copper
_ecid
Me re i. ry
N icr. carl, or.
Tota 1 en iOr icies
totd ' org-.n ic n3 1 ides
::•".••:
->
ph
P(_M|,.L irg itjent
Rut'C ct reducing agent
Lre'rr:. a1 r'rec ip i tat ion
pH
Prec ipit.it ing agents
Fi ltr,t '0''
fype (jl t :ter
Sample Set »1
KOSF solvent wash Untreated Envirite Filter cake
scrubber water wastewater Filtrate Total TCLP
(nig/1) (mg/1) (mg/1) (ing/kg) (mg/1)
0 Oo3-0 107 -.10 <1 <10
0 059-0 093 -1 <0 1 <1 <0 010
0 226-0 287 -.10 <1 25 0 23
<0 001 <2
-------
Ioo3g
Table 3-2 (continued)
Const i tuent
bDA! Metals
Ant imony
Arser. ic
Bar ium
ber> 1 1 ium
Cadmium
Cnromium ( r.exava lent )
Chromium (total)
Lopper
Lend
Mercury
"iickel
;e len i urn
c, i tver
Tna 1 1 ium
Zinc
0-r.(,r p ,,, .,,,ter-,
"otil orgaric c.jrbc.i
Tota 1 SOl 1'JS
rot j 1 chloi ides
Tct 1 1 orcjnri ic na 1 idps
C/dn ide
_ u "i f Kie
-
-vr • '. '•" t L"i ";•• ."
Re ' u c ui'j n.jert
Ratio of reducing agent
' rr IDK... 1 ?• ci i [y 1 1.: t ion
pH
Precipi tat ing agents
f , 1 1 r.it ion
T/pe of f i Her
I Cu leu i n t ur t er encti
- ,'iOt r ' 1 /ZC'.'I
KOB6 solvent wash
scrubber water
(ing/ U
0 Ob3-0 107
0 059 0 0~<3
0 ^'C-0 267
•0 001
'0 004
<0 010-0 014
0 099-0 193
0 il-j-0. 1 jO
0 d27-l 52
=0 0002
= 0 Oil
• 0 00 j
•;0 006-0 007
0 022-0 027
0 laO-0 216
1 97-S 36
y:oC-4iuO
1 2-101
0 Olc-0 072
'-0 OlO
-0 5
to he/ovalent chromium
Sample Set »2
Untreated Envinte Filter cake
wdstewdter Filtrdte Total TCLP
(mg/1) (mg/1) (mg/kg) (mg/1)
=10 <1 '10
-1 ^01 1 -0 010
10
-------
lB83g
Table 3-2 (continued)
Const i tuent
BOAT Met i !-,
Ant nnony
Arsenic
Barium
Bery 1 1 ium
Cadmium
Chromium (nexavalent)
Chromium (total)
Copper
Lead
Mercury
'( icke 1
-,e ' en i L..II
:. i Iver
Tha 1 1 ium
Zinc
0; npr P ir ,i';oter~
Total organic carbon
Tota 1 sol ids
I old i en I'ji ides
'ota'i organic ha 1 ules
C ,-an ine
^ LJ i i de
DC' :- 'T, ] " r-r:,' - -; !\v
,
Reaucirig 3gent
Ratio of reducing agent
Cnpmir.il Proripu.iMon
ph
Precipitating agents
F i ltr.it ion
Type of f i Iter
K0»6 solvent wash
scrubber water
(mg/1)
0 0&3-0 107
0 059-0 093
0 226-0 2b7
•0 001
-------
lB83g
3-2 (conl inued)
Const i tuent
BOAT Metals
Ant imony
Arsen ic
Bdl 1UI11
Beryl 1 mm
Cadmium
Chromium (hexavalent)
Chromium (total)
Cooper
Lead
Mercury
N icke 1
5e ien lum
S i Ker
T ha 1 1 lum
Z IMC
Qtner P;. r-j^eters
Total organic carbon
fctd 1 ^0 i 'ClS
Total chlorides
~otai organic haliaes
I/on ide
.jit ,ile
_.f . IT" -" 1 jC=r~ t "'I ' • '
'•
KeJjC'rg aCi&Pt
"it 10 of reducing dyerit
CreiiTical Precipitation
pH
Prec ip i tdt ing agents
f i It rat 'on
Type of f i Iter
K066 solvent wash
scrubber water
(mq/1)
0 OB3-0 107
0 OC9-0 093
0 ^26-0 2b7
<0 001
<0 004
--0 010-0 014
0 093-0 193
0 11S-0 130
0 627-1 52
-0 OOOd
*0.011
<0 005
<0 006-0 007
0. 022-0. Q27
0 1BO-0 216
i ii -a 3C
;-,oO-41t,Q
: 2-101
j 015-C 072
--0 010
• 0 5
to hexaVdleit chromium
Sample Set »4
Untreated Envirite Filter
wastewater Filtrate Total
(mq/1) (mq/1) (mg/kq)
•'10 - =10
-' 1 < 1 2
-10 -10
-------
Table 3-2 (continued)
Const i tuent
FDAT Met ill
Ant imon>
r\i sen ic
Bar lum
Ber-y 1 1 mm
Cadmium
Chromium (hexavalent)
Chromium ( tot j 1 )
Copper
Lead
Mercury
:, iCKel
~,e- i en i .nil
•^ i Iver
T ha 1 1 lum
L me
Otr.er Parameters
Total organic Caroon
Tola ! so 1 ids
Total cnlcrices
Tota 1 organ ic na 1 ides
Cyanide
••"''•'"
' < . \, • • ' Crr -,,-1 ' /:•
r^educ , ng jger.t
•^-ilio of r eduL i ny ayeril
L neTi •-_-;' P rec i P i T 1 1 ion
fl
Pi eL ip ' td t mg dgents
F i it r it ion
Type of f i Iter
KOH6 solvent wash
scrubher water
(mg/1)
0 Os3 0 107
0 059-0 09j
0 226-0 2b7
-0 001
<0 004
-0.010-0 014
0 099-0 193
0 115-0 130
0 d27-l 52
<0 0002
• 0 Oil
^0 005
ron
n ,2-10
d-10
1 line
vacuum f i Iter
interference
^tPA TiHoa
L43
-------
1883g
Table 3-2 (continued)
Const ituent
BOAT Men Is
Ant imony
Arsen ic
Barium
Ber_v 1 1 mm
Cadmium
Chromium (hexavd lent )
Chromium ( tota 1 )
Copper
Lead
Mercury
Nickel
Se len i uiVi
S i Iver
Tha 1 1 lum
1 me
Otier Parameters
fold 1 organic Carbon
Tot d 1 '^o 1 ids
Total en 'or ides
Total orqanic ha"; ides
Cyan ide
Suit me
Ofc . ' J' v J Ouc • - ' \ 'iu r -. :
_,...,,,, fp!S,..,
Stl
•'educ. fig =yent
H.itio of reducing .iyent
Chemical Precipitation
pH
Preu ip i td t my dyents
F i Itrat ion
lype of f i Her
K086 solvent wash
scrubber water
(mg/1)
0 Obj-0 107
0 Ob'd-0 093
0 226-0 287
<0 001
< 0.004
-------
Iaa3g
Table 3-2 (continued)
Const i tuent
BOAT Metals
Ant imony
Arsen ic
Bar ium
beryl 1 ium
Cadmium
Chromium (hexava l(?nt )
Chromium (total)
Copper
Lead
Mercury
Nickel
Se ien ium
S i Iver
Tha 1 1 ium
Zinc
Other Parameters
Tot j 1 org,in ic carhon
Tcta 1 so i icis
Total cnlorides
Iota 1 organic hd 1 ides
Cydn ide
-3ulf ide
1 - - "
, _ _^
^
ReuuL my ,iyent
Ritio of Deducing agent
LhemiLdl Pr ec ip i tdt ion
pH
Precipitat ing agents
F i Itrat ion
Type of f i Her
K036 solvent wash
scrubber water
(ing/ I)
0 OH3-0 107
0 059-0 093
0 226-0 2a7
<0.001
<0 004
<0 OlO-O 014
0 099-0 193
0 115-0 130
0 «27-l 52
••0 0002
2-1 0
8-10
1 ime
vacuum f i Her
i - Color interference
Reference UiEPA 19b6a
i4b
-------
iaa3g
Table 3-2 (continued)
Coribt i tuent
BOA I Metals
Ant imony
Arsen ic
Barium
Bery 1 1 lum
Cadmium
Chromium (hexavalent)
Chromium (total)
Cooper
Lea.:
Mercury
II icke 1
ie len ium
Silver
Tha 1 1 ium
Zinc
Other P-inmeters
Tcti' orjinic carbon
Total so lias
Tota 1 ch lorides
Tot -, } or y-in ic hd 1 ides
Cy..n ine
iu'f icie
- __, , '. ^ , ' , 1 . r. ,, P •
(
' r^
Ratio cf reducing agent
( iM'iu ii.,, i Pr cc i u . ' it ion
pH
Prec ipi tat ing agents
P i 1 1 r at ion
Type of f i Iter
K086 solvent wash
scrubber water
(mg/ I )
0 OH3-0 107
0 050-0 013
0 226-0 2e7
<0.001
«0 004
<0 010-0 014
0 099-0 193
0 115-0.130
0 627-1 52
-.0 0002
<0 Oil
^0.005
<0 006-0 007
0 022-0 027
0 180-0.216
1 :<7-
-------
l«83g
Table 3-2 (continued)
Const itucnt
BOAT Met ,1-,
Ant imony
Arsenic
Barium
Bery 1 1 lum
Cadmium
Chromium (hexavalent)
Chromium (total)
Cooper
Leju
Mercury-
Nickel
Selenium
S i 1 ver
Tha 1 1 lum
Zinc
Other Parameters
Tcta 1 orqanic carbon
Tota 1 sol ids
7c, t j 1 cr: lor ides
Tcta 1 organ ic ha 1 ides
L ,-iniae
^u if icie
3-:-; 'an r,.; Zr*' it irn P -,
"• • ' , , ,C' 1 L!" „!!"..•!
pn
Peciucinn aqent
Katio of reducing agent
f"einirni Precipitation
pri
Prec ip i tat ing agents
F i 1 1 rvit ion
Type of f i Iter
KOU6 solvent wash
scrubber water
(mg/1)
0 083-0 107
0 059-0.093
0 226-0 287
<0 001
<0 004
<0 010-0 014
0 099-0.193
0 115-0 130
0 o27-l 52
<0 0002
--o on
• 0 005
<0 006-0 007
0 022-0 027
0 180-0 216
1 97-8 36
35oO-41CO
1 2-101
0 015-0 072
<0 010
•0 5
r.,,:^
to hexavalent chromium
Sample Set »9
Untreated Envinte Filter cake
wastewater Filtrate Total TCLP
(mg/1) (mg/D (mg/kg) (mg/1)
'-10 <1 <10
<1 <0 1 3 0 Oil
--10 <1 <10 0 20
•2 <0 2 -2
'5 <0 5 6 <0 020
0 07 0 041 I
939 0 10 3400 <0 050
225 0 03 775
•-10 <0.01 85 ^0 10
<1 <0 1 <1 <0 0002
940 0 33 3500
• 1 0 - 1 -10 • 0 j 1 0
--2 --0 2 <2
-------
18«3g
Table j-Z (continued)
Const i tuent
H)AT Met 1 Is
Ant unony
Arsen ic
Barium
Beryl I ium
Cadmium
Chromium (hexavalent)
Chromium (tota I )
Copper
Lead
Mercury
NiCKel
3e leri i uin
5 i Iver
Tha I I ium
line
Other Parameters
Total organic carbon
Tota I so I ids
'ota I Lh ior idfc^
Totul organic nalides
C/aniae
^u 'f ide
^ ^ r _ , , , ^ r n -
pH
Reducing agent
Ratio of reducing agent
Chemical Prrr i n i tat ion
pH
Precipitating agents
F i It rat ion
T/pe of f i Iter
K0a6 solvent wash
scrubber water
(mg/l)
0 083-0 107
0 059-0 093
0 226-0 28/
-Q 001
<0 004
<0 010-0 014
0 099-0 193
0 115-0 130
0 627-1 52
<0 0002
-------
Table 3-2 (continued)
Const i tuent
PDAT Met.^s
Ant imony
Arsen ic
Bar ium
Beryl 1 ium
Cadmium
Chromium (hexavalent)
Chromium (total)
Cooper
Lt^U
Mercurv
N i c < e 1
* 6 SI 1 ulTl
i i vei
Thd i 1 ium
Z;nc
Other fit ameters
"ot 1 I or ._: in ic carbon
Tot 3 "' cr 'or :06S
fold1. jrgdfilC hdlldtt,
C/rin ine
- jlf irie
i- - ' '!',,('* ' '!'; r 1 '
CM
SL-LIUL , ng -igent
R.itio -f reducing agent
Lnem ' Cd ^rec imitation
Precipitating agents
(• i It i at ion
Type of f i Her
K0b6 solvent wash
scrubber water
(rug/ I)
0 03J-0 107
0 059-0 093
0 226-0 2H7
<0 001
-0 004
<0 010-0.014
0 099-0 193
0 115-0 130
0 o27-1.62
'-0 0002
<0 Oil
-------
4. IDENTIFICATION OF THE BEST DEMONSTRATED AVAILABLE
TECHNOLOGY FOR K086 SOLVENT WASH
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 another. Next, the "best" performing treatment technology is
evaluated to determine whether the resulting treatment is substantial.
If the "best" technology provides substantial treatment and it has been
determined that the technology is also available to the affected
industry, then the technology represents BOAT.
4.1 BOAT for Treatment of Orqanics
The only demonstrated technology for treatment of K086 solvent wash
that the Agency has data for is liquid injection incinerator where the
liquid was injected in the nozzle on the rotary kiln unit. Nevertheless,
the Agency believes that the other demonstrated treatment technologies,
including liquid injection on other incinerators, would not improve the
level of performance for K086; therefore EPA believes that incineration
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
150
-------
process leaves behind still bottoms that need additional treatment for
organics. EPA believes that well-designed and well-operated fuel
substitution systems would not achieve better results because such
systems operate at approximately the same temperature with similar
residence times and turbulence patterns as incineration systems.
Consistent with EPA's methodology for determining BOAT, the Agency
evaluated the incineration performance data to determine whether
incineration provides substantial treatment for K086 solvent wash. As a
first step, EPA examined the data to determine whether any data
represented treatment by a poorly designed or poorly operated system.
EPA did not find any such data and, therefore, used all the data in its
determination of substantial treatment.
Next, EPA adjusted the data values based on the analytical recovery
values in order to take into account analytical interferences associated
with the chemical makeup of the treated sample. In developing recovery
data (also referred to as accuracy data), EPA first analyzed a waste for
a constituent and then added a known amount of the same constituent
(i.e., spike) to the waste material. The total amount recovered after
spiking minus the initial concentration in the sample divided by the
amount added is the recovery value. Percent recovery values for BOAT
list metals used in adjustment of the performance data are presented in
Appendix B. The analytical data were adjusted for accuracy using the
lowest recovery value for each constituent.
151
-------
EPA's determination of substantial 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.
The Agency believes that the reduction of hazardous organic constituents
is substantial and that incineration is available to treat organics
present in K086 solvent wash wastes because it is commercially
available. Therefore, incineration represents BOAT for the organics
present in K086 solvent wash.
4.2 BOAT for Treatment of Metals
Treatment of the organics present in K086 solvent wash using
incineration generates a scrubber water (i.e., wastewater residual) that
may need treatment for metals. Treatment of the scrubber water may
generate a precipitate (i.e., nonwastewater residual) that also needs
treatment for metals.
4.2.1 Wastewater
The only demonstrated technology identified for treatment of metals
in K086 scrubber water that the Agency has data for chromium reduction
followed by lime precipitation and sludge filtration. The Agency has no
reason to expect that the other chemical precipitation processes could
improve the level of performance; therefore, chromium reduction followed
by lime precipitation and sludge filtration is the "best" performing
technology. As discussed earlier, EPA does not have treatment data for
K086 solvent wash wastewaters generated from incineration; however, EPA
does have treatment data for metal-containing wastewaters (Envirite)
believed to be similar to K086 solvent wash scrubber waters.
152
-------
Data collected by the Agency on treatment of the Envirite wastewater
by chromium reduction lime precipitation and vacuum sludge filtration are
shown in Table 3-2. Operating data collected during treatment of this
waste show that these data represent the performance of a well-designed,
well-operated treatment system; therefore, all data were used to
determine substantial treatment.
EPA adjusted the data values based on the analytical recovery values
in order to take into account analytical interferences associated with
the chemical makeup of the treated sample. In developing recovery data
(also referred to as accuracy data), EPA first analyzed a waste for a
constituent and then added a known amount of the same constituent (i.e.,
spike) to the waste material. The total amount recovered after spiking
minus the initial concentration in the sample divided by the amount added
is the recovery value. Percent recovery values for BOAT list metals used
in adjustment of the performance data are presented in Appendix B. The
analytical data were adjusted for accuracy using the lowest recovery
value for each constituent.
EPA's determination of substantial wastewater treatment for the
Envirite treatment system is based on the reductions of hexavalent
chromium from 917 mg/1 to 0.058 mg/1, chromium from 2,581 mg/1 to
0.12 mg/1, lead from 212 mg/1 to 0.01 mg/1, copper from 225 mg/1 to
0.08 mg/1, nickel from 16,330 mg/1 to 0.33 mg/1, and zinc from 171 mg/1
to 0.115 mg/1.
153
-------
The Agency believes that these reductions of hazardous constituents
are substantial and that chromium reduction followed by lime
precipitation and sludge filtration is available to treat K086 scrubber
waters because it is commercially available; therefore, chromium
reduction followed by lime precipitation and sludge filtration represents
BOAT for K086 scrubber waters.
4,2.2 Nonwastewaters
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
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" performing technology for treatment of
the precipitate generated during treatment of the K086 scrubber water.
The Agency does not have treatment data for the precipitate specifically
generated during treatment of the K086 scrubber waters; however, EPA
does have treatment data for a metal-containing precipitate (Envirite)
believed to be similar to the K086 wastewater treatment precipitate.
Data collected by the Agency on treatment of the Envirite precipitate
by lime stabilization and sludge filtration are shown in Table 3-2.
Operating data collected during treatment of this waste show that these
data represent the performance of a well-designed, well-operated
treatment system; therefore, all these data were used to determine
substantial treatment.
154
-------
EPA adjusted the data values based on the analytical recovery values
in order to take into account analytical interferences associated with
the chemical makeup of the treated sample. In developing recovery data
(also referred to as accuracy data), EPA first analyzed a waste for a
constituent and then added a known amount of the same constituent (i.e.,
spike) to the waste material. The total amount recovered after spiking
minus the initial concentration in the sample divided by the amount added
is the recovery value. Percent recovery values for BOAT list metals used
in adjustment of the performance data are presented in Appendix B. The
analytical data were adjusted for accuracy using the lowest recovery
value for each constituent.
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."
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
155
-------
stabilization followed by sludge filtration provides substantial
treatment.
The Agency believes that these reductions of hazardous constituents
are substantial and that lime stabilization followed by sludge filtration
is available to treat K086 precipitated wastes because it is commercially
available; therefore, lime stabilization followed by sludge filtration
represents BOAT for K086 precipitated wastes.
156
-------
5. SELECTION OF REGULATED CONSTITUENTS
This section presents the rationale for selection of the regulated
constituents, from the BOAT list of constituents, for the K086 solvent
wash treatability group. In the previous section, incineration was
determined to achieve a level of performance that represents BOAT for
treatment of organics present in K086 solvent wash. Chromium reduction
followed by chemical precipitation and filtration was determined to
achieve a level of performance that represents BOAT for treatment of
metals present in K086 scrubber waters, and lime stabilization followed
by sludge filtration was determined to achieve a level of performance
that represents BOAT for treatment of metals present in the precipitate
from treatment of the K086 scrubber water. Therefore, performance data
from the determined BOAT for organics treatment and BOAT for metals
treatment will be used to help select the regulated constituents.
When developing performance data for treatment technologies, the
Agency analyzes untreated and treated wastes for the constituents
presented in Table 1-1. The list is referred to by EPA as the BOAT list
of constituents and is an expanding list that does not preclude the
addition of new constituents as additional key parameters are
identified. The list is divided into the following categories: volatile
organics, semivolatile organics, metals, inorganics other than metals,
pesticides, PCBs, and dioxins and furans.
157
-------
5.1 Identification of Constituents in the Untreated Waste
and Waste Residuals
The first step in selecting candidate constituents to be regulated is
to identify the BOAT list constituents present in the untreated K086
solvent wash wastes (i.e., the waste as generated, the scrubber water).
The regulated constituent must demonstrate one of two criteria:
1. The constituent is detected in the untreated waste above its
detection limit. (A detection limit is defined as the practical
quantification limit, PQL, that is the method detection limit
achievable when using an EPA-approved analytical method
specified for a particular analysis in SW-846, 3rd Edition.)
2. The constituent could not be detected in the untreated waste due
to high detection limits caused by analytical interference, but
is detected in any of the treatment residuals and is likely to
be present in the untreated waste.
Table 5-1 (at the end of this section) shows which of the 231 BOAT
list constituents were detected, not detected, and not analyzed in the
K086 solvent wash and scrubber water incineration residual. Of the 231
BOAT constituents, the Agency analyzed for 193. None of the 28 pesticide
constituents were analyzed because of the extreme unlikelihood of their
presence. Another 10 volatile and semivolatile organic constituents were
analyzed for because at the time the analysis was performed, these
constituents were not on the BOAT pollutant list. Of the
193 constituents analyzed 19 were detected in the K086 solvent wash.
These 19 constituents concentrations are given in Table 5-2 (at the end
of this section).
For those constituents not detected (NO) in the untreated waste, but
detected in the scrubber water (i.e., arsenic, silver, vanadium), it was
assumed that such constituents may very well be present in the K086
158
-------
solvent wash, but were undetected because of masking or interference by
other constituents in the K086 solvent wash. These three constituent
concentrations are also given in Table 5-2. Detection limits for the
analytical methods used to analyze K086 solvent wash have been classified
as confidential information by the generator. The analytical detection
limits for the scrubber water are given in Appendix C.
5.2 Evaluation of the Process Generating the K086 Solvent Wash Wastes
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 8 BOAT list organic solvents are used in
the ink formulation process and/or in cleaning ink formulating
equipment: n-butyl alcohol, 1,2-dichlorobenzene, ethyl acetate,
methanol, methyl ethyl ketone, nitrobenzene, 1,1,1-trichloroethane, and
trichloroethylene. EPA is concerned that by not considering these other
solvents not found in the tested waste, 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.
5.3 Determination of Significant Treatment from BOAT
The next step in selecting the constituents to be regulated is to
eliminate those identified constituents in the waste that were not
significantly treated by the technologies designated as BOAT.
159
-------
5.3.1 BOAT List Organic Constituents
Table 5-2 presents the concentrations of constituents in the organics
treatment residual from incineration, i.e., scrubber water. The data
demonstrate that all the organic constituents detected in the K086
solvent wash are reduced signficantly, 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 combustiblity. 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 be treated to nondetectable
levels. (Table 5-3, at the end of this section, shows the calculated
bond energies for the candidate organic constituents.)
160
-------
5.3.2 BOAT List Metal Constituents
The data show a scrubber water with no treatable levels of organics,
but 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 has
treatment data using chromium reduction, followed by chemical
precipitation incorporated with lime stabilization and sludge filtration,
of a waste similar (i.e., Envirite wastewaters). Treatment of the metals
present in the Envirite wastewaters 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 wastewaters do 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.
5.4 Rationale for Selection of Regulated Constituents
Table 5-4 (at the end of this section) presents all of the candidate
constituents that were detected in the untreated waste, used in the waste
generating process, and treated with the identified BOAT. 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.
161
-------
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
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.
162
-------
An incinerator is not specifically designed to treat metals.
Accordingly, the concentration of metals found 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 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.
163
-------
1599g
Table 5-1 BOAT Constituents Detected or Not Detected in the
K086 Solvent Wash and Scrubber Water Samples
BOAT
reference
no
222
I
2
3
4
5
6
223
7
a
9
10
11
12
13
14
15
16
17
Ib
I'J
20
<- 1
22
L 3
24
25
26
27
28
29
224
225
226
Parameter
Volat i le Orqanics
Acetone
Aceton i tr t le
Acrolein
Acrylonitr i le
Benzene
Bromodichlorome thane
Bromomethane
n-Butyl alcohol
Carbon tetrachlor ide
Carbon disulfide
Chlorobenzene
2-Chloro-l ,3- butadiene
Ch lorodibromomethane
Chloroethane
2-Chloroethyl vinyl ether
Chloroform
Chloromethane
3-Chtoropropene
1 , 2-Dibromo-3-chloropropane
1 . 2-Oibromoethdine
D; Dromometndne
Trin--, - ! ,4-3;c:h loro-r1 r/utenp
Dichlorod f iuoromern.ine
I . 1 -D'chloroethane
1 . 2-D-ch loroetrMne
1 , 1 -D icn lo roe thy lent
Trans-l,2-Dicnloroethent
1 , 2-Dichloropropane
Trans-l,3-Dichloropropene
cis-l,3-0ichloropropene
1 ,4-Dioxane
2-Ethoxyethanol
Ethyl acetate
Ethyl benzene
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
103-90-7
108-90-7
75-00-3
110-75-d
67-66-3
74-87-3
107-05-1
96-12-8
1C6-95-4
/4-.-5-J
i 10-57-h
75-71 o
7 •; - _. 5 - j
105 Ob-.-
/-. -,S-4
1-.6 60 -5
73-a7-5
10061-02-6
10061-01-5
123-91-1
110-HO-5
141-78-6
100-41-4
K086
solvent
wash
(mg/kg)
D
ND
NO
ND
ND
ND
NO
ML
NO
ND
NO
ND
NO
ND
NO
ND
NO
ND
ND
ND
ND
NO
ND
ND
ND
HO
ND
NO
NO
ND
ND
NL
HI
D
Scrubber
water
Ug/D
ND
NO
ND
NO
ND
NO
ND
NL
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NO
ND
ND
NL
NL
ND
lb4
-------
1599g
Table 5-1. (Continued)
BOAT
reference
no
30
227
31
214
32
33
228
34
229
35
36
37
38
230
39
40
41
42
43
44
45
46
47
4«
49
23!
50
215
216
217
51
52
Parameter
Volatile Orqanics (continued)
Ethyl cyanide
Ethyl ether
Ethyl methacrylate
Ethylene oxide
loaoinethane
Isobutyl alcohol
Methano 1
Methyl ethyl ketone
Methyl isobutyl ketone
Methyl methacrylate
Methyl methaneiu If ana te
Methy lacry Ion i tn le
Methylene chloride
2-N i tropropane
Pyr idine
1,1,1 , 2-Tetrachloroethane
1 , 1 ,2, 2-Tetrachloroethane
Tetrachloroethene
loluene
Tr ibromomethane
1 , 1 , 1-Trichloroethane
1 , 1 , 2-Tr ichloroethane
Tr ich loroethene
T r >Lh loromonot Vi'jrc.T'i t n me
1 ,2,3-TricnlorsproO'jne
1 , 1 , 2-Tr ich loro- 1.2,2-
t ; . t !^ci rju thane
Vinyl c n 1 o r : de
1 ,2-Xy lene
1 ,3-Xylene
1 ,4-Xylene
Semi volat i les
Acenaphtha lene
Acenaphthene
CAS no
10712-0
60-29-7
97-63-2
75-21-8
74-88-4
78-83-1
b/-56-l
7H-93-3
108-10-1
80-62-6
66-27-3
126-98-7
75-09-2
79-46-9
110-86-1
630-20-6
79-34-5
127-18-4
108-88-3
75-25-2
71-55-6
79-00-5
7--01-6
7 5 r, i - 4
": i a - -i
; • i i - 1
7 ' C ! 4
>i7 47 -c
lGd--S-3
106-44-5
208-96-8
83-32-9
K086
solvent
wash
(mg/kg)
NO
NL
NO
NL
ND
ND
NL
ND
D
ND
NO
ND
D
NL
NO
ND
ND
NO
D
ND
ND
ND
ND
ND
ND
NL
ND
D
D
D
ND
ND
Scrubber
water
Ug/D
ND
NL
ND
NL
NO
ND
NL
ND
ND
ND
ND
NO
ND
NL
ND
NO
NO
ND
ND
NO
NO
ND
NO
ND
ND
NL
NO
ND
NO
NO
ND
ND
165
-------
1599g
Table 5-1. (Continued)
BOAT
reference
no.
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
76
79
oO
81
82
232
83
S4
85
86
87
Parameter
Semivolat i les (continued)
Acetophenone
2-Acetylaminof luorene
4-Aminobipheny 1
Am 1 me
Anthracene
Arami te
Benz(a)anthracene
Benzal chloride
Benzal chloride
Benzenethiol
8enzo(a)pyrene
Benzo(b)f luoranthene
Benzofghi )perylene
Benzo(k)f luoranthene
p-8enzoquinone
Bis (2-chloroethoxy) me thane
Bis(2-chloroethyl)ether
Bis(2-chloroisopropyl)ether
Bis(2-ethylhexyl)phthalate
4-Bromopheny 1 phenyl ether
Butyl benzyl phthalate
2-sec-Butyl-4,6-dimtrophenol
p-Ch loroan i 1 me
Ch lorobenz i Kite
p-Ch ioro-m-c-esol
2-Cn loronapnthd iene
2-Ch loropheno 1
3-Chloroprop ion 1 1 r i le
Cnr>sene
ortho-Cresol
para-Creso 1
Cyc lohexanone
Oibenz(a ,h)anthracene
Dibenzo(a,e)pyrene
Oibenzofa, i Jpyrene
m-Oichlorobenzene
o-Dichlorobenzene
CAS no.
96-86-2
53-96-3
92-67-1
62-53-3
120-12-7
140-57-a
56-55-3
98-87-3
98-87-3
108-98-1;
50-32-8
205-99-?
191-24-2
207-08-9
106-51-4
111-91-1
111-44-4
39638-32-9
117-81-7
101-55-3
85-68-7
«8-a5-7
106-47-b
510-15-6
r'-50-7
'jl-5o-7
95-57-8
M?-76-7
J 1 6 0 i - :•
95-4H-7
106-44-5
108-94-1
53-70-3
192-65-4
189-55-9
541-73-1
95-50-1
K086
solvent
wash
(mg/kg)
NO
NO
NO
NO
NO
NO
NO
NL
NO
NO
NO
ND
NO
ND
NO
ND
ND
ND
D
ND
NO
ND
ND
ND
NO
NO
ND
ND
ND
ND
NO
D
NO
ND
ND
NO
NO
Scrubber
water
(M9/1)
ND
NO
ND
ND
NO
ND
ND
NL
ND
ND
ND
ND
NO
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NO
ND
ND
ND
ND
NO
ND
ND
ND
ND
ND
NO
166
-------
1599g
Table 5-1. (Continued)
BOAT
reference
no
88
89
90
91
92
93
94
95
96
97
98
99
100
101
102
103
104
105
106
219
107
108
109
110
11!
112
113
114
115
116
117
118
119
120
121
122
123
Parameter
Semivolat i les (continued)
p-Oichlorobenzene
3,3 ' -Dichlorobenz id me
2,4-Dichlorophenol
2,6-Dichlorophenol
Diethyl phthalate
3,3' -Dimethoxybenz id me
p-Dimethy lammoazobenzene
3,3' -Dime thy Ibenz id me
2 ,4-Oimethy Iphenol
Dimethyl phthalate
Di-n-butyl phthalate
1 ,4-Dmitrobenzene
4,6-Dmitro-o-cresol
2,4-Dmitrophenol
2,4-Dmitrotoluene
2,6-Dmitrotoluene
Di-n-octyl phthalate
Di-n-propy Initrosarame
Dipheny lamine
Diphenylnitrosamme
1 , 2-0 iphenyl hydra z me
F luoranthene
F luorene
Hexacn lorobenzene
Hexachlorobutadiere
nexacn lorocyc lope»t'id lene
Hexachloroethdne
Hexacn ioropnene
lndeno( 1 , i , ;-ol)p/rvi e
Isosat ro le
Methapyr i lene
3-Methylcholanthrene
4,4' -Methy lenebis
(2-chloroani 1 me)
Naphthalene
1 ,4-Naphthoqinnone
1-Maphthy lamine
CAS no
106-46-7
91-94-1
120-63-2
87-65-0
84-66-2
119-90-4
60-11-7
119-93-7
105-67-9
131-11-j
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
122-66-7
206-44-0
B6-73-/
lla-74-1
87-68-3
77-47 -1
F.7-72-1
70 jC-4
1 :" _ ~ ' -
120-r,a-l
C'l-BO-5
56-49-5
101-14-4
91-20-3
130-15-4
1J4-32-7
K086
solvent
wash
(mg/kg)
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
ND
ND
NO
ND
NO
ND
NO
ND
NO
ND
NO
ND
NO
ND
ND
ND
ND
ND
ND
ND
ND
NO
D
ND
ND
Scrubber
water
Ug/D
ND
ND
NO
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NO
ND
NO
ND
NO
ND
ND
ND
NO
ND
NO
ND
ND
ND
ND
NO
ND
ND
NO
ND
ND
ND
ND
Ib7
-------
1599g
Table 5-1. (Continued)
BOAT
reference
no.
124
125
126
127
128
129
130
131
132
133
134
135
136
137
138
139
140
141
142
220
143
144
145
146
147
.46
149
,r,0
151
152
153
154
155
Parameter
Seinivo Idt i Iris (continued)
2-Naphthy lamme
p-N i troani 1 me
N i trobenzene
4-Nitrophenol
N-Nitrosodi-n-butylamme
N-N itrosodiethy lamme
N-N i trosod line thy lamme
N-Ni trosomethy let hy lamme
N-Nitrosomorphol me
N-N i trosop i per id me
n-N i trosopyrro 1 id me
5-Nitro-o-toluidme
Pentachlorobenzene
Pentachloroethane
Pentach loron 1 1 robenzene
Pentachlorophenol
Phenacet m
Phenanthrene
Phenol
Phtha 1 ic anhydride
2-Picol me
Pronamide
Pyrene
Resorc mo 1
Suf ro le
! ,2 , 4 . 'j-Tetrach loi cijeruene
2 , 3 . 4 , t-Tet i'dch loropneno 1
, , ? , 4 Tr icr; iorohen.-ene
2 . 4 . 5- fr icn'oropheriOl
2,4,6-Tnunlorophenol
Tr is(2,3-dibromopropy 1 )
phosphate
Metals
Ant imony
Arsenic
CAS no
91-59-8
100-01-6
98-95-3
100-02-;
924-16-3
55-18-5
62-75-9
10595-95-6
59-69-2
100-/5-4
930-55-2
99-65-a
608-93-5
76-01-7
82-68-8
87-86-5
62-44-2
85-01-8
108-95-2
rf5-44-9
109-06-B
23950-56-5
129-00-0
108-46-3
"i4 '.:< !
>5-y4-j
5b-yo-2
120 ,V 1
1 ' '.' *. ^
oo-Cb-2
126-72-7
7440-36-0
7440-38-2
K086
solvent
wash
(mg/kg)
NO
NO
NO
NO
NO
NO
NO
NO
ND
NO
NO
NO
ND
ND
ND
NO
NO
NO
ND
NL
NO
NO
ND
ND
NO
NO
ND
ND
ND
ND
ND
D
ND
Scrubber
water
Ug/D
ND
NO
ND
ND
ND
ND
ND
ND
ND
ND
ND
NO
ND
ND
ND
ND
ND
ND
ND
NL
ND
NO
ND
ND
ND
ND
ND
ND
ND
ND
ND
D
D
Iba
-------
1599g
Table 5-1. (Continued)
BOAT
reference
no.
156
157
158
159
160
221
161
162
163
164
165
166
157
168
169
170
171
Jt
' 7"
174
175
17o
:??
17d
179
1«0
1S1
182
1S3
184
185
Parameter
Metals (continued)
Barium
Beryl 1 lum
Cadmium
Chromium
Copper
Hexavalent Chromium
Lead
Mercury
Nickel
Selen lum
Si Tver
T ha 1 1 lum
Vanad lum
Zinc
Inorqan ics
Cyanide
F luor ide
Su If itie
Orqanoch lor me Pesticides
Alarm
I'rih <-RHC
netd-EHC
aelt 3-BrtC
gdinnd-Bnl
Cnloraane
ODD
DDE
DDT
Dieldr in
Endosulfan I
Endosulfan II
Endr in
Endrin aldehyde
CAS no
7440-39-3
7440-41-7
7440-43-9
7440-47-32
7440-50-8
NA
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
3496-25-b
:0'.i-CO-^
-, l°i-*4 c.
^ 1 ' ' ', ' '
' - C 'j ' ~
• - . f j - :-.
' . / - / \ '
72-54-3
7 2 - rj ^ - J
SO-2'-«-j
r.O ^7-1
939-98-ci
33213-6-5
72-20-8
7421-93-4
K086
solvent
wash
(mg/kg)
D
NO
NO
0
D
D
0
NO
D
NO
ND
NO
ND
0
D
ND
D
-
-
-
-
-
-
-
-
-
-
-
Scrubber
water
Ug/D
D
ND
ND
D
0
0
D
ND
ND
ND
D
ND
D
0
NO
ND
ND
-
-
-
-
-
-
-
-
-
-
-
-
169
-------
1599g
Table 5-1. (Continued)
BOAT
reference
no
186
la?
188
189
190
191
192
193
194
195
196
197
198
199
200
:01
232
t_ 0 J
2C4
205
206
207
208
209
210
Parameter
Orqanochlor me Pesticides (continued)
Heptachlor
Heptacnlor epoxide
Isodrin
Kepone
Methoxyc lor
Toxaphene
Phenoxvacet ic Acid Herbicides
2.4-0 ich lorophenoxyacet ic ac id
S i Ivex
2,4,5-T
Orqanophosphorous Insecticides
Disulfoton
Fainphur
Methyl parathion
Parathion
Phorate
PCBs
A roc lor 1C 10
trader I,-'?!
A r oc 1 o r 1232
Aroclor 1242
Aroclor 1-M8
ArOLlor 1254
Aroclor 1260
Oioxins and Furans
Hexachlorodibenzo-p-dioxins
Hexachlorodibenzofuran
Pentachlorodibenzo-p-diox ins
Pentachlorodlbenzofuran
CAS no
76-44-8
1024-57-3
465-73-6
143-SO-O
72-43-5
bOOl-35-2
94-75-7
93-72-1
yj-76-0
298-04-4
52-85-7
298-00-0
56-38-2
298-02-2
12o/4-ll-2
: 1104-2^-?
! 1 1 4 1 >, - 5
c: JtO-21 9
; 'o/J-.^-L.
1 1: .7-1'- i
HC'jt.-o2-5
NA
NA
NA
NA
K086
solvent Scrubber
wash water
(mg/kg) Ug/1)
_
-
-
-
-
-
.
-
-
.
-
-
-
-
NO ND
ND ND
ND ND
ND ND
ND ND
ND ND
ND ND
ND ND
ND ND
ND ND
ND ND
170
-------
1599g
Table 5-1. (Continued)
BOAT
reference
no
211
212
213
Parameter CAS no
Oioxins and Fur-ans (continued)
Tetrachlorodibenzo-p-dioxins NA
Tetrachlorodibenzofuran NA
2,3,7 ,8-Tetrachlorodibenzo-p-dioxin NA
K086
solvent
wash
(mg/kg)
NO
NO
NO
Scrubber
water
Ug/D
ND
ND
ND
NL - Not on list at the time of analysis
ND = Not detected
D = Detected
= No analysis performed because of the low likelihood of its presence.
NA = Not appl icable
Reference- USEPA 1987a
171
-------
1599g
Table 5-2 BOAT Constituent Concentrations in Untreated K086
Solvent Wash Waste and Scrubber Water Residual
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
Volat i le orqanics
Acetone
Ethy 1 benzene
Methyl isobutyl ketone
Methylene Chloride
Toluene
Xylene (total)
Semivolat i le orqanics
Bis(2-ethylhexyl)phthalate
Cyc lohexanone
Naphthalene
Metals
Antimony
Arsenic
Barium
Chromium (total)
Chromium (hexavalent)
Copper
Lead
Nickel
Si Iver
Vanadium
Z me
! norqan ics
Cyanide
Sulf ide
K086 solvent wash
Untreated waste
(mg/1)
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
Scrubber water
(mg/1)
<0.010
<0.005
<0.010
<0.010
<0.010
<0.005
•=0.010
<0.005
<0.010
0.083-0
0 059-0
0.226-0.
0.099-0,
<0. 010-0,
0 115-0
0.827-1
<0.011
<0. 006-0.
0.022-0.
0.180-0.
^0 010
<0 5
.107
.093
.287
,193
,014
130
52
007
027
216
CBI = Confidential Business Information
Reference: USEPA 1987a
17 Z
-------
1599g
Table 5-3 Calculated Bond Energy for the Candidate
Organic Constituents
Calculated bond energy
Constituent (kcal/mol)
BOAT Volati 1e Orqanics
Acetone 945
n-Butyl alcohol 1350
Ethyl acetate 1655
Ethyl benzene 1900
Methanol 495
Methyl isobutyl ketone IbOO
Methyl ethyl ketone 1230
Methylene chloride 355
Toluene 1615
1,1,1-Trichloroethane 625
Trichloroethylene 485
Xylenes (total) 1900
BOAT Semivol.Uile Organ ics
Bis(2-eth>Ihexyljphthalate 6620
Cyc lohexanone 1685
1,2-Oichlorobenzene 1320
Naphthalene 2140
Nitrobenzene 1430
Reference Sanderson 1971
173
-------
159yq
Table 5-4 Candidate Constituents for Regulation of kOdt jolvent Woih
BOAT reference no
Constituent
Volat i le
jb
43
45
47
215-217
tiennvolat i le Organics
70
232
B7
121
126
Ai-L'tcriL1
n but,1 d Icohci
Crn,1 acetate
Ltny li^en^erit
Mel t-Ki'.u I
Mftn, ' i -,or.u; » i Ketone
Metny etn/1 ketone
Mttth., lurie th lor ide
Toluene
1,1,1-Trichloroethane
Trichloroethylene
Xylene (total)
Bis(2-ethy1hexyl)pnthalate
Cyclohexanone
1,2-Dichlorobenzene
Naphthalene
Nitrobenzene
Metals
159
221
160
161
163
168
Chromium (total)
Chromium (hexavalent)
Copper
Lead
Nickel
2 me
Inorganics
169
171
Cyanide
Sulf ide
174
-------
6. 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 5. 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
operation of the treatment systems.
2. Next, averages for accuracy-corrected constituent concentrations
are calculated and a variability factor are 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 the 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.
6.1 Calculation of Treatment Standards for Nonwastewater Forms of
K086 Solvent Wash
For purposes of describing the applicability of the BOAT treatment
standards, EPA has defined nonwastewaters as wastes that contain greater
than 1 percent filterable solids or greater than 1 percent total organic
175
-------
carbon (TOC). 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 one
percent) and to the precipitated residual generated from treatment of
K086 incinerator scrubber waters (a nonwastewater based on the filterable
solids content). Below is a description of how the BOAT treatment
standards were calculated for BOAT list organics and metals in K086
nonwastewaers.
6.1.1 Organic Treatment Standards
Section 5.4 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. In order
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 5 show that organic levels in the
176
-------
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
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 where 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.
No data were deleted because of poor design or operation of the
treatment system. The corrected average concentrations, determined
variability factors, and calculated organic standards for K086
nonwastewaters are present in Table 6-1.
177
-------
6.1.2 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.
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 3-2. None of the data were deleted
because of poor design or operation of the treatment system. Hence, all
11 data points are used for regulation of 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
standard for lead and chromium were determined by multiplying the average
accuracy-corrected total composition by the appropriate variability
factor as shown in Table 6-1.
178
-------
Ib44g
Table 6-1 Calculation of kOtiG Solvent Wash NonwdStewdter Treatment Standard:,
BOAT
reference
no
Approx irnate
BOAT list accuracy-corrected
constituents average concentration"
Approx imate
vanabi 1 ity
factor**
Treatment
standard***
Volati1e Orqanics
222 Acetone 0 13
223 n-Butyl alcohol 0 13
225 Ethyl acetate 0 13
226 Ethylbenzene 0 Oil
228 Methanol 0 13
229 Methyl tsobutyl ketone 0 13
34 Methyl ethyl ketone 0 13
38 Methylene chloride 0 313
43 Toluene 0 01 ]
45 1,1,1-Tr ichloroethdne 0 OIL
4/ Tr ich loroetru lurit- 0 Oil
215-217 Xjlene (total) C 0055
Semivolatile Orqanics
70 Bis(2-ethylhex>Ijphthalate 0 IB
232 Cyclohexanone 0 18
87 1,2-Dichlorobenzene 0 18
121 Naphthalene 0.18
126 Nitrobenzene 0 18
Metals
159 Chromium (Total) 0 076
161 Lead 0 013
2 8
2 8
2 8
2 8
2 8
2 8
2 8
? B
2 b
L d
i o
2 b
2 8
2 8
2 3
2 8
2 b
1.24
2 8
0 37
0 37
0 37
0 031
0 37
0 37
0 37
C 037
: 031
0 49
0 49
0 49
0.49
0.49
0.094
0 37
'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
""Treatment 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
179
-------
6.2 Calculation of Treatment Standards for Wastewater Forms of K086
Solvent Mash
As defined in Section 1.0, wastewater forms of K086 solvent wash are
those wastes that contain less than one percent filterable solids and
less than one percent total organic carbon. The only data available to
the Agency characterizing wastewater forms of K086 solvent wash is the
scrubber water data generated during incineration of the K086 solvent
wash.
6.2.1 Organic Treatment Standards
The data characterizing K086 solvent wash scrubber waters show
nondetectable levels of the regulated organic constituents that were
detected in the untreated K086 solvent wash. Therefore, the organic
treatment standard's will be based on the analytical detection levels.
All six data points were used in development of the treatment standards.
The Agency has detection levels for 10 volatiles and all 5 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
6-2.
6.2.2 Metal Treatment Standards
The Agency does not have any treatment performance data on treatment
of K086 solvent wash scrubber waters. Therefore, the Agency is
180
-------
lB44g
Table 6-2 Calculation of K086 Solvent Wash Wastewater Treatment Standards
BOAT
reference
no.
BOAT list
constituents
Approximate
accuracy-corrected
average concentration*
Approximate
variabi1ity
factor**
Treatment
standard***
Volat i1e Orqanics
222 Acetone 0 0055
223 n-Butyl alcohol 0.011
225 Ethyl acetate 0.011
226 Ethylbenzene 0 0055
228 Methanol 0 Oil
229 Methyl isobutyl ketone 0 Oil
34 Methyl ethyl ketone 0 Oil
38 Methylene chloride 0 Oil
43 Toluene 0 010
45 1,1.1-Tnchloroethone 0011
47 Trichloroethyiene 0 010
215-217 Xylene (total) 0 0055
Semivolatile Orqanics
70 Bis(2-ethylhexyl)phthalate 0 016
232 Cyclohexanone 0 007&
87 1,2-Dichlorobenzene 0.016
121 Naphthalene 0.016
126 Nitrobenzene 0.016
159
161
Metals
Chromium (Total)
Lead
0 19
0.013
2.8
2 8
2.8
2 8
2 8
2 8
2 B
2 b
2 8
2 6
2 B
2 6
2.8
2 8
2 8
2.6
2.8
1 69
2 8
0 015
0 031
0 031
0 015
0 031
0 031
C 031
0 031
0 025
0 031
0 029
0 015
0 044
0 022
0 044
0 044
0 044
0 32
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.
'"Treatment. 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
181
-------
transferring treatment data from a similar wastewater treated at
Envirite. The Agency expects that the Envirite wastewaters are at least
as difficult to treat as the K086 solvent wash scrubber waters 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 wastewaters. 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 6-2.
182
-------
APPENDIX A
183
-------
APPENDIX A
STATISTICAL METHODS
A.I F Value Determination for ANOVA Test
As noted earlier in Section 1.0, EPA is using the statistical method
known as analysis of variance in the determination of the level of
performance that represents "best" treatment where more than one
technology is demonstrated. This method provides a measure of the
differences between data sets. If the differences are not statistically
significant, the data sets are said to be homogeneous.
If the Agency found that the levels of performance for one or more
technologies are not statistically different (i.e., the data sets are
homogeneous), EPA would average the long term performance values achieved
by each technology and then multiply this value by the largest
variability factor associated with any of the acceptable technologies.
If EPA found that one technology performs significantly better (i.e., the
data sets are not homogeneous), BOAT would be the level of performance
achieved by the best technology multiplied by its variability factor.
To determine whether any or all of the treatment performance data
sets are homogeneous using the analysis of variance method, it is
necessary to compare a calculated "F value" to what is known as a
"critical value." (See Table A-l.) These critical values are available
in most statistics texts (see, for example, Statistical Concepts and
Methods by Bhattacharyya and Johnson, 1977, John Wiley Publications, New
York).
Where the F value is less than the critical value, all treatment data
sets are homogeneous. If the F value exceeds the critical value, it is
184
-------
Table A-l
95th PERCENTILE VALUES FOR
• THE F DISTRIBUTION
ni = degrees of freedom for numerator
«2 = degrees of freedom for denominator
(shaded area = .95)
/~\
*is
A'! i
1 101.4
2 IS. 51
3 , 10.13
4
5
G
•"
S
Q
10
11
12
1C
14
15
16
17
IS
19
20
fjn
O '
-.1
26
2S
30
40
50
60
70
80
100
150
200
400
CO
*~ ~ 1
6.51
5. 99
5.59
5.32
"to
4.96
4.S4
4.75
4.57
4. GO
4.54
4.49
4.45
4.41
4.38
4.25
4.30
4.25
< rt ^
•»._O
4.20
4.17
4.08
4.03
4.00
3.93
3.96
3.94
3.91
3.S9
3.S6
3.S4
o
199.5
19.00
9.55
6.94
5.79
5.14
1. i -»
4.4G
4.2G
4.10
3.9S
3.S9
3.S1
O *. 1
O. ;4
o — ^
•3.00
3.53
3.59
3— —
.00
3.52
3.49
3.44
3.40
3.37
3-t »
-w*
•? ->o
3.23
3.1S
3.15
3.13
3.11
3.09
3.06
3.04
3.02
2.99
3
215.7
19.16
O 1C
*• ...G
6.59
5.41
4.76
4.25
4.07
3.86
3.71
3.59
3.49
3.41
3.34
O OQ
U.-.y
0 O 4
O.-.1
3.20
3.16
3.13
3.10
3.05
3.01
2.98
2.95
2 92
2.S4
2.79
2.76
2.74
O »7O
2.70
2.G7
2.G5
2.G2
2.GO
4
224.6
19.25
9.12
6.29
5.19
4.53
4.12
3.34
3.G3
3.4S
3.36
' °fi
U._U
3.18
3.11
3.06
3.01
2.96
2.03
2.90
2.S7
o po
*».*J«
2. 78 '
2.74
2.71
2.69
2.61
2.55
2.53
2.50
2.48
2.46
2.43
2.41
2.39
2.37
E
220.2
19.30
9.01
6.25
5.05
4.29
3.27
n ~ o
o.ua
3. 48
3.33
3.20
3.11
3.03
2.96
2.90
2.S5
2.S1
2.77
2.74
2.71
2.66
2.62
2.59
2.56
2.53
2.45
2.40
2.37
0 1Z
4_.ot?
2.33
2.30
2.27
2.26
r> nn
tf.^tj
2.21
6
234.0
19.23
8.94
6.16
4.95
4.28
3.S7
3.58
3.37
3.22
3.09
3.00
2.92
2.S5
2.79
2.74
2.70
2.66
2.53
2.60
2.55
2.51
2.47
2.45
2.42
2.34
o no
o or
*..«3
O TJ
O Ot
O 1 Q
2.16
2.14
2.12
2.09
8
OOQ Q
19.37
8.S5
6.04
4.S2
4.15
3.73
ft 4 4
a,44
3O»*
. — «J
3.07
2.95
2.S5
O — »*
2.70
2.64
2.59
2.55
2.51
2.4S
2.45
2.40
2.26
O *?1
O OQ
2.27
2.1S
2.: 3
2.10
2.07
2.05
2.03
2.00
1.2S
1.96
1.94
12
O * O Q
19.41
8.74
5.91
4. Go
4.00
3.57
•7 no
u.~3
rt n*"
o.U i
2.91
2.79
2.69
2.60
2.53
2.4S
O «O
o r>o
•..OO
O 0 *
•..1^1
2.31
O 00
o._O
O 0«J
mfrf^tj
2.18
2.15
O 1 O
2.09
2.00
1.95
1 °2
1.89
l.SS
1.85
1.82
1.80
1.78
1.75
16
24G.3
19.43
8.59
5.S4
4. GO
3.92
3.49
3.20
2.98
O QO
2.70
2.60
2.51
2.44
O ^Q
*..o J
O «0
«.i_f 0>
0 OQ
2.25
O O^
2.18
2.13
2.09
2.05
2 02
1.99
1.90
1.35
1.31
1.79
1.77
1.75
1.71
1.59
1.67
1.64
20
248.0
19.45
8.66
5. SO
4.56
3.S7
3.44
3.15
2.93
2.77
2.65
2.54
2.46
2.39
o •?•?
*>.oo
O OO
*>.HiD
o 03
2.19
2.15
O 10
2.07
2.03
1.99
1.96
1.93
1.S4
1.78
1.75
1.72
1.70
1.68
1.64
1.62
1.60
1.57
30
250.1
19.46
S.62
5.75
4.50
2.S1
2.38
3.08
2. 36
2.70
2.57
2.46
0 TO
— ..-•O
2.21
2.25
2.20
2.15
2.11
2.07
2.04
1.98
1.94
1.90
1.87
1.84
1.74
1.69
1.65
1.62
1.60
1.57
1.54
1.52
1.49
1.46
40
251.1
19.46
8. GO
5.71
4.4G
3.77
*) O 4
W.01
2.05
O CO
2.67
2.53
2.42
0 0 i
~.bl t
O OT
O 15
2.16
2.11
2.07
O ,"| O
1.99
1.93
1.S9
1.85
1.81
1.79
1.69
1.53
1.59
1.56
1.54
1.51
1.47
1.45
1.42
1.40
50
oro n
19.47
8. 53
5.70
4.44
3.75
3.22
3.03
2.80
2.64
2.50
2.40
O OO
O o *
2.18
2.13
2.08
2.04
2.00
1.96
1.91
1.86
1 22
1.78
1.76
1.66
1.50
1.56
1.53
1.51
1.48
1.44
1.42
1.38
1.22
100
252.0
19.4P
8.56
5.6C
4.40
2.71
3.2S
2.98
2.76
2.59
2.45
2.25
2.26
2 19
2 •» o
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
1.29
1.24
T oo
1.28
1.24
•T
or • ->
_ i>-i .0
19.30
S.53
5.C2
4.25
3.67
•5 o-
2.93
2.71
2.54
2.40
2.30
*> OT
2.13
2.07
2.01
1.25
1 o'*
l.SS
1.34
1.78
1.73
1.59
1.65
1.52
1.51
1.44
1.29
1.35
1.22
1.2S
^ no
1.19
1.13
1.00
185
-------
necessary to perform a "pair wise F" test to determine if any of the sets
are homogeneous. The "pair wise F" test must be done for all of the
various combinations of data sets using the same method and equation as
the general F test.
The F value is calculated as follows:
(i) All data are natural logtransformed.
(ii) The sum of the data points for each data set is computed (T.).
(iii) The statistical parameter known as the sum of the squares
between data sets (SSB) is computed:
SSB =
where:
k = number of treatment technologies
n^ = number of data points for technology i
N = number of data points for all technologies
T.J = sum of natural logtransformed data points for each technology.
(iv) The sum of the squares within data sets (SSW) is computed:
k n^
k
f T-2 1
. >
—
" k
.1 Ti
N
t. -
SSW =
where:
k
- I
n.
x-j j = the natural logtransformed observations (j) for treatment
technology (i).
(v) The degrees of freedom corresponding to SSB and SSW are
calculated. For SSB, the degree of freedom is given by k-1. For SSW,
the degree of freedom is given by N-k.
186
-------
(vi) Using the above parameters, the F value is calculated as
follows:
MSB
F = MSW
where:
MSB = SSB/(k-l) and
MSW = SSW/(N-k).
A computational table summarizing the above parameters is shown below.
Computational Table for the F Value
Source
Between
Within
Degrees of
freedom
K-l
N-k
Sum of
squares
SSB
SSW
Mean
MSB =
MSW =
square
SSB/k-1
SSW/N-k
F
MSB/MSW
Below are three examples of the ANOVA calculation. The first two
represent treatment by different technologies that achieve statistically
similar treatment; the last example represents a case where one
technology achieves significantly better treatment than the other
technology.
187
-------
1790g
Example 1
Methylene Chloride
Steam Stripping
Influent Effluent
Ug/l)
1550.00
1290.00
1640 00
5100 00
1-550 00
4600 00
176C Co
2400 00
• c An A A
•* 0 u w U U
•?-nr. QO
Ug/ 1 )
10.00
10.00
10 00
12 00
10 00
10 00
10 CO
10 00
10 00
10 00
Biological Treatment
In(effluent) [In(effluent)]2 Influent Effluent In(effluent)
2.30
2.30
2 30
2 48
2.30
2 30
2.30
2.30
2.30
2.30
Ug/l) Ug/l)
5.29 1960.00 10.00 2.30
5.29 2568.00 10.00 2.30
5.29 1817.00 10.00 2.30
6.15 1640 00 26.00 3.26
5.29 3907.00 10.00 2.30
5 29
5 29
5 29
5.29
5.29
[In(effluent)]2
5.29
5.29
5.29
1C 6
S 29
Sum
23 18
53 8
12 46
r.P '6 2 1Z6
10
10
10
Mean
3669
10.2
2.32
2378
13.2
2.49
Stanaara Deviation
3328 67 63
06
923.04
7.15
.43
laoi 1 i ty factor
1 14
2.48
ANOVA Calculations.
SSB =
. n
N
SSW r
HSU = SSU/(M-k.)
188
-------
1790g
Example 1 (continued)
F = MSB/MSU
Where.
k * number of treatment technologies
n * numoer of data points for technology i
N = number of natural log transformed data points for all technologies
T = sum of log transformed data points for each technology
T = Total sum of all the natural log transformed data points for all technologies
X = the nat log transformed observations (j) for treatment technology (i)
- 10. n = 5. N = 15. k = 2. T = 23 18, T = 12 46. T = 35.64. T = 1270.
= 537 3, T j 155.2.
537 3 155.2
10 5
1270
15
= 0 1233
Si. - !53 6 - 31 8) -
537.3 155 3
10
= 0 7600
MSB = 0.1233/1 = 0.1233
MSW * 0 76/13 = 0.0584
F .
. 2 109
0.0584
ANOVA Table
Source
Between! B)
Within(W)
Degrees of
freedom
1
13
SS MS F
0.1233 0.1233 2.109
0 7600 0.0584
The critical value of the F test at 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)
189
-------
1790g
Example 2
Tnchloroethy lene
Steam Stripping
Influent
Ug/D
1650.00
5200.00
5000 00
172C 00
1560 00
1030C 00
21C 00
160C OC
20-* 00
16C 00
Effluent
U9/1)
10.00
10.00
10 00
10 00
10 00
10 00
10 00
27 00
85 00
10 OC
In(effluent)
2.30
2.30
2.30
2.30
2 30
2.30
2 30
3 30
4 44
2.30
[In(effluent)]2
5.Z9
5.29
5.29
5.29
5.29
5.29
5.29
10.9
19 7
5.29
Influent
Ug/D
200.00
224.00
134.00
150.00
484.00
163.00
182.00
Biological Treatment
Effluent In(effluent)
l«/U
10.00
10.00
10.00
10.00
16.25
10.00
10.00
2.30
2.30
2.30
2.30
2.79
2.30
2.30
(In(effluent)]2
5.29
5.29
5.29
5.29
7 78
5.29
5.29
26 14
72.9
16 5S
3S
idnc ie b ne
10
10
Mean
2760 19 2
Stsnaaro Deviation
3209 6 23 7
Var ;ac i ! i ty ractor
10
2.61
71
220
120.5
3 76
10.89
2.36
1.51
2.37
.18
ANOVA Calculations
SSB =
G?)
ssw -
MSB -- SiS/lk-i)
MiW = $SW/(N-k.)
190
-------
1790g
Example 2 (continued)
F = MSB/HSU
Where,
k. = numoer of treatment technologies
n = number of data points for technology i
i
N = number of data points for all technologies
T = sum of natural log transformed data points for each technology
i
T = total sum of all the natural log transformed data points for all technologies
X = the natural log transformed ooservations (j) for treatment technology (i)
.IT;
N = iO. N = 7. N = 17, k = 2, T = 26.14. T = 16 59. T » 42.73. T = 1826, T = 665.3
T = 275.2.
2
683 3
SSE =
_____ »
10
275 2
_____
7
1826
~ ^_^^^_
17
0.2325
SS'w = ! 72 9 •> 39 5)
683 3 275 2
10
7
4 856
MSB = 0 2325/1 = 0 2325
MSW = 4 856/15 = 0.3237
. 0 2325
= 0 7163
0 3237
Degrees of
Source freedom
ANOVA Table
SS
MS
Between(B)
Withm(W)
1
15
0 2325
4 856
0.2325
0.3237
0.7183
The critical value of the F test at 0.05 significance level is 4 54 Since f
value is less than the critical value, the means are not significantly different
(i e . thev are homogeneous)
191
-------
1790g
Example 3
Chlorobenzene
Activated Sludge Followed bv Carbon
Influent Effluent In(effluent)
Ug/1) Ug/1)
[ln(effluent)]'
Influent
Ug/1)
iological Treatment
Effluent In(effluent)
[In (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
19.2
18.1
12.7
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
48.9
43.0
37.6
24 6
41 0
25.3
8 01
49
55.
38 90
226 4
Sams ie 5ize
Mean
4S
14759
452.5
5.56
Standard Oev lation
i£35 4 32.24
Var iat) i 1 i ty factor
7 00
.95
16311.86
379.04
15.79
1.42
ANDVA Calculations
SS5 =
G?)
ssw -
^i£ = SS5/(K-i)
MSw = SSU/(S-k)
F = MSB/MSW
Where.
192
-------
1790g
Example 3 (continued)
k = numoer of treatment technologies
n = numoer of data points for technology i
N * number of data points for all technologies
T * sum of natural log transformed data points for each technology •
T = total sum of all the natural log transformed data points for all technologies «
X = the natural log transformed observations (j) for treatment technology (i)
N = 4, N = 7. N • 11. k • 2. T « 14.49, T * 38.90. T » 53.39. T?« 2850, T2
210.0
T" = 1513.
1513
2850
9 552
SSW = (55 3 » 228 4)
210.0 1513
•f
4 7
14 96
MSB = 9.552/1 = 9 552
MSw = 14 96/9 = 1 662
' = 9 552/1 662 = 5 75
ANOVA Table
Degrees of
Source freedom
SS
MS
Between(B)
Within(U)
1
9
9 552
14 96
9.552
1.662
5.75
The critical value of the F test at 0 OS significance level is 5.12. Since f
value is larger than the critical value, the means are significantly different
(i e . they are heterogeneous)
193
-------
has been used routinely in the EPA development of numerous regulations in
the Effluent Guidelines program and in the BOAT program. The variability
factor (VF) was defined as the ratio of the 99th percentile (C ) of
the lognormal distribution to its arithmetic mean (Mean).
VF = C99 (])
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 (p) and standard deviation (a) of the normal distribution as
follows:
C99 = Exp („ + 2.33a) (2)
Mean = Exp U + -5a2) (3)
Substituting (2) and (3) in (1) the variability factor can then be
expressed in terms of a as follows:
VF = Exp (2.33 a • .So2) (4)
For residuals with concentrations that are not all below the
detection limit, the 99 percentile and the mean can be estimated from
the actual analytical data and accordingly, the variability factor (VF)
can be estimated using equation (1). For residuals with concentrations
that are below the detection limit the above equations can be used in
conjunction with the assumptions below to develop a variability factor.
194
-------
Step 1: The actual concentrations follow a lognormal distribution. The
upper limit (UL) is equal to the detection limit. The lower limit (LL)
is assumed to be equal to one tenth of the detection limit. This
assumption is based on the fact that data from well-designed and
well-operated treatment systems generally falls within one order of
magnitude.
Step 2: The natural logarithms of the concentrations have a normal
distribution with an upper limit equal to In (UL) and a lower limit equal
to In (LL).
Step 3: The standard deviation (a) of the normal distribution is
approximated by
a = [(In (UL) - In (LL)] / [(2)(2.33)] = [ln(UL/LL)] / 4.66
when LL = (0.1)(UL) then a = (InlO) / 4.66 = 0.494
Step 4: Substitution of the value from Step 3 in equation (4) yields the
variability factor, VF.
VF = 2.8
195
-------
A.2. Variability Factor
-£99-
VF = Mean
where:
VF = estimate of daily maximum variability factor determined from
a sample population of daily data.
Cgg = Estimate of performance values for which 99 percent of the
daily observations will be below. Cgg is calculated using
the following equation: Cgg = Exp(y + 2.33 Sy) where y and
Sy are the mean and standard deviation, respectively, of the
logtransformed data.
Mean = average of the individual performance values.
EPA is establishing this figure as an instantaneous maximum because
the Agency believes that on a day-to-day basis the waste should meet the
applicable treatment standards. In addition, establishing this
requirement makes it easier to check compliance on a single day. The
99th percentile is appropriate because it accounts for almost all process
variability.
In several cases, all the results from analysis of the residuals from
BOAT treatment are found at concentrations less than the detection
limit. In such cases, all the actual concentration values are considered
unknown and hence, cannot be used to estimate the variability factor of
the analytical results. Below is a description of EPA's approach for
calculating the variability factor for such cases with all concentrations
below the detection limit.
It has been postulated as a general rule that a lognormal
distribution adequately describes the variation among concentrations.
Agency data shows that the treatment residual concentrations are
distributed approximately lognormally. Therefore, the lognormal model
196
-------
APPENDIX B
197
-------
Appendix B
Analytical QA/QC
The analytical methods used for analysis of the regulated
constituents identified in Section 5 are listed in Table B-l. SW-846
methods, (EPA's Test Methods for Evaluation Solid Waste; Physical/Chemical
Methods, SW-846, Third Edition, November 1986) are used in most cases for
determining total constituent concentrations. 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 anlaysis 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 present 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.
Since no matrix spike recovery values were available for the Envirite
data, matrix spike recovery values for a similar wastewater (i.e., K061
198
-------
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.
199
-------
1900g
Table B-l Analytical Methods for K.08C 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
Regulated
const ituent
Volat i le Orqanics
Acetone
n-Butyl alcohol
Ethyl acetate
Ethyl benzene
Methanol
Methyl isobutyl ketone
Methyl ethyl ketone
Methylene chloride
Toluene
1,1,1-Tnchloroe thane
Tr ichloroethy lene
Xylene (total)
Semivolatile Organic
Bis(2-ethyl hexy 1 Jphtha late
Cyc lohexanone
1 ,2-Dichlorobenzene
Naphthalene
Nitrobenzene
Metals
Extraction
method
Purge and Trap
Purge and 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/
liquid extract ion
Continuous liquid/
1 iquid extraction
Continuous liquid/
1 iquid extract ion
Continuous liquid/
liquid extract ion
Method
number
5030
5030
5030
5030
5030
5030
5030
5030
5030
5030
5030
3520
3520
3520
3520
3520
Analytical method
Gas
Gas
Gas
Gas
Gas
Gas
Gas
fa-,
fa-,
Gas
Gas
Gas
fa".
fa-
fa:,
Gas
Gas
Chromatography/Mass
Chromatography/Mass
Chromatography/Mass
Chromatography/Mass
Chromatography/Mass
Chromatography/Mass
Chromatography/Mass
Chromatography/Mass
Chromatography/Mass
Chromatography/Mass
Chromatography/Mass
Chromatography/Mass
Chroma tography/M^ss
Chromatography/Mass
Chromatography/Mass
Chromatography/Mass
Chromatography/Mass
Spectrometry
Spectrometry
Spectrometry
Spect rometry
Spectrometry
E pect rometry
Spect romet r /
Spectrometry
Soect romet ry
Spectrometry
Spect romet ry
-pect rometry
'•pect ro^etry
pect rorrc-t i >
Spect romet r y
Spectrometry
: pect rometry
Method number
8240
8240
8240
8240
8240
8240
8240
8240
8240
8240
8240
8240
8270
8270
8270
8270
8270
Reference
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
159 Chromium (total composition) Specified in
analytical method
161 Lead (total composition) Specified in
analytical method
Chromium (atomic absorption, direct
aspirat ion method)
lead (atomic absorption, direct
aspiration method)
7190
7420
-------
1900g
Table B-l (continued)
BOAT
reference Regulated
number constituent
Extract ion
method
Method
number
Analytical method
Method number Reference
Metals (continued)
159 Chromium (TCLP extract)
161 Lead (TCLP extract)
Specified in
analytical method
Specified in
analytical method
Toxicity Characteristic Leaching
Procedure (TCLP)
Toxicity Characteristic Leaching
Procedure (TCLP)
51 FR 1750 2
51 FR 1750 2
References: 1 USEPA 1982
2. Federal Register 1986
rv>
-------
1900g
Table B-2 Specific Procedures or Equipment Used in Extraction of Organic Compounds When
Alternatives or Equivalents are Allowed in the SW-646 Methods
Analysis
SW-846 method
Sample al iquot
Alternatives or equivalents allowed
by SW-846 methods
Specific procedures or
equipment used
Purge and trap
5030 5 mi Hi liters of liquid
The purge and trap device to be
used is specified in the method in
Figure 1, the desorber to be used
is described in Figures 2 and 3,
and the packing materials are
described in Section 4 10 2 The
method allows equivalents of this
equipment or materials to be user!
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
ro
c
ro
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
toIuene-d8,4-bromofluorobenzene,
and 1 , 2-dichloroethane-cf" The
recommended concent rat icf level is
50 ug/1
The length of the trap was 30 cm
nd headiaraeter was 0.105 cm.
The surrogates were added as
specified in SW-846
Continuous liquid-
1iquid extraction
3520
1 liter of 1iquid
Acid and base/neutral extracts
are usually combined before
analysis by GC/MS However,
under some situations, they may
lie extracted and analyzed
separately.
Acid and base/neutral extracts
were combined.
The base/neutral surrogates
recommended are 2-fluorobipheny1,
M 11 roben?ene-d5. terphcnyl d!4
The acid surrogates recommended
are 2-fluorophenol,
".4,6-tribromopheno1. and
l>hrMol-d6 Add 11 londl c o^pouncl''
Surrogates were the same as those
recommended by SW-846. with the
exception that phenol-dS was
substituted for phenol-d6 The
concentrations used were tne
concentrations recommended >r> ,-W-Mf,
-------
1900g
Table B-2 (continued)
Analysis
SW-846 method
Sample aliquot
Alternatives or equivalents allowed
by SW-846 methods
Specific procedures or
equipment used
Continuous liquid-
1iquid extract ion
(Continued)
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
INJ
O
CO
The internal standards aie
prepared by dissolving them
in carbon disulfide and then
diluting to volume so thdt
the f inal solvent is 20
ca'iion disulfide and 8C
mp'hylene chloride
The preparation of the
internal standards was
changed to eliminate the
use of carbon disulfide
The internal standards
weie prepared in
methylene chloride only
Reference: USEPA 1987a
-------
J901g
Table B-3 Specific Procedures or Equipment IKed for Analysis of Or CMP
When Alternatives or Equivalents Allowed in SW-846
arid Metal Compounds
Analysis
SW-846
Method
Sample
preparation
method
Alternatives or equivalents
al lowed in SW-fc46 for
equipment or in procedure
Specific equipment or procedures used
Organic Compounds
Gas Chromatography/
Mass Spectrometry
for volatile
organics
8240
5030
re
cr
Recommended GC/MS operating conditions:
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
4S C
3 mm
8"C/min
200"C
I1) mm
200-225-C
According to manufacturer's
spec ification
?%-300'C
Hydrogen at 50 cm/sec or
hellum at 30 cm/sec
The column should be 6-ft x 0 1 in. I.D. glass.
packed with 1% SP-1000 on Carbopack B (60/80 mesh) or
an equivalent
Samples may be analyzed by purcie and trap technique
or by direct injection
Actual GC/MS operating conditions-
Electron energy.
Mass range
Scan time
70 ev
35 - 260 amu
2 5 sec/scar,
Initial column temperature: 38°C
Initial column holding time 2 mm
Column temperature program: 10'C/mm
Final column temperature:
Final column holding time:
In lector temperature:
Source temperature
Transfer line temperature:
Carrier gas
225X
30 mm or xylene elutes
225'C
manufacturer's recommended
va lue of IOC C
275'C
Hel lum (B 30 ml/mm
•Additional Information on Actual System Used
Equipment Finnegan model 5100 GC/MS/DS system
Data system: SUPERINCOS Autoquan
Mode. Electron impact
NBS library available
Interface to MS - Jet separator
•The column used was an 8-ft. x 0 1 in ID glass,
packed with 1% SP-1000 on Carbopack E (60 'yo mesh)
•The samples were analyzed using the purqe end trap technique
-------
1901g
Table B-3 (Continued)
Analysis
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
Actu.il GC/MS operating conditions
Gas Chromatography/
Mass Spectrometry
for semivolati le
organics: capillary
column technique
8270 3520-Liquids
rv
o
en
Mass range
Scan time
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 gas
35-500 amu
1 sec/scan
40"C
4 mm
40-270'C at
10'C/min
?70'C (until
benzofg.h, i ,]perylene has
fluted)
250-300*C
250-300°C
According to
"Mnuf ac t urer ' s
•-pec if icat ion
broh-type, splitless
1-2 uL
Hvdrogen at 50 cm/sec or
he 1 lum at 30 cm/sec
• The column should be 30 m by 0 ?5 mm I D , 1-um film
thickness s licon-ooated fused silica capillary column
(J&W Scientific DB-5 or equivalent)
35 - 5CO an-u
1 sec/scan
30'C
4 mm
8'C/mir to 275 '
and 10'C/m"i until
305'C
Final column temperature hold: 305 C
Mass range
Scan time
Initial column temperature
Initial column holding time
Column temperature program
injector temperature:
Transfer line temperature'
Source temperature
1 •' iec to1"
Sample volume
Carrier aas
240-2GC'C
300 C
Manufact jre' 's
recomTerid^t ion
(non-heate;')
Grch-1 ,v.-. -sit less
1 ul o' ' A~\ e extract
Hel urn k £C c'T'sec
Metals
cicitional Information on Actual Syste1" _;-r'
Fquipment Finnegan model 5100 GC''M> 3j system
Software Package SUPERINCOS AUTOQU^N
The column used was a 30 m x 0 32 rrm ] D
Rl. -5 (5/- phenyl methyl silicone) FSC',
Inductively coupled
6010
Operate equipment following instructions
provided by instrument's manufacturer
• Equipment operated using procedures spe.'fied
in the Jarrell Ash (JA) 1140 Operator's Manual
For operation with organic solvents,
auxilliary argon gas inlet i •. recommended
• Auxiliary argon gas was not required 'c" S
11' 11 r i x
-------
1900g
Table B-4 Matrix Spike Recoveries used to Calculate Correction lactori, for
K086 Solvent Wash Scrubber Water Organic Concentrations
Sample Qjplicate Ac<
BOAT List Original
Constituent amount found
Ug/i)
Volat i 1e Orqanics
1. 1-Dichloroethane
Trichloroethene
Chlorobenzene
Toluene
Benzene
Other volatile organics
Semivolat i 1e Orqanics
Base/Neutrals
1 ,2 , 4 -Tri chlorobenzene
Acenaphthene
2 , 4-0 in i trotoluene
Pyrene
N-Nitrosodi-n-propylamine
1 , 4 -Di chlorobenzene
Other base/neutral
semivolatile organics
Acids
Pentachlorophenol
Phenol
2-Chlorophenol
4-Chloro-3-methyl phenol
4-Nitrophenol
Other acid semivolatile
organics
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Amount
spiked
Ug/i)
50
50
50
50
50
100
100
100
100
100
100
200
200
200
200
200
Amount
recovered
Ug/l)
37
49
50
48
42
36
61
75
92
85
42
167
169
157
161
173
Percent Amount
Recovery" recovered
Uq/1)
74 36
98 53
100 53
96 49
84 42
90.4 (average)
36 -1
61 r7
75 r\
92 c-">
85 c'
42 ;i,
65 2 (averaae)
83 139
84 1 V-i
79 14«
81 169
87 165
82 8 (averaae)
Percent coi
recovery* 1
72
106
106
98
84
93 2 (average)
31
57
81
94
83
36
63 7 (average)
70
79
74
85
83
78 2 (averaae)
:uracy
rrect ic-
Factor' '
1 39
1 02
1 CD
1 C4
i r-
1 i!
3 21
1 7r
i :-:
1 C°
1 23
2 7r
1 C-'
1 "'
1 'll
1 '^
\ 7-
1 <~C
1 2t
*Percent Recovery = [(Spike Result - Original Amount)/Spike Added]
"Accuracy Correction Factor = 100/Percent Recovery (using the lowest percent recovery values)
Reference USEPA 1987a
-------
1900g
Table B-5 Matrix Spike Recoveries Use,I to Calculate Correction Factors for the
Envirite Wastewater and TCLP Extract Metal Concentrations
re
Sample
Constituent
Antimony
Arsenic
Barium
Beryl 1 lum
Cadmium
Chromium (hexavalent)
Chromium (total)
Copper
Lead
Mercury
Nickel
Selenium
Si Iver
Thai 1 lum
Zinc
Original
Ug/
<21
<10
1,420
1
4
<10
<4
<4
<5
'0
203
<25
<4
<10
sample
1)
4
2
0
0
0
2
0
2.640
Spike added
Ug/i)
300
50
5,000
25
25
50
50
125
25
1 0
1,000
25
50
50
10,000
Spike result
275
70
5.980
25
26
53
35
107
22
0 rj
1.140
12
42
51
12,600
Percent
recovery*
92
140
91
94
87
106
70
86
88
90
94
48
84
102
100
Dupl icate
Spike result
276
66
'..940
24
27
54
?-
104
19
1 1
1 , 12H
•?r>
-•<$
4K
12.400
Percent
recovery*
92
132
90
90
91
108
68
83
76
110
93
NC
76
96
98
Accuracy
Correct ion
factor"
1
0
1
1
1
0
1
1
1
1
1
2
1
1
1
09
76
11
11
IS
94
•"
20
31
11
Od
C6
32
G-
°'
*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
-------
1900g
Table B-6 Matrix Spike Recoveries Used to Calculate Correction Factors
for the Envirite Filter Cake Organic Detection Limits
Const ituent
Volat lies
Toluene-8
Bromof luorobenzene
1 ,2-Dichloroethane
Other volatile organics
Semwolat i les
Base/neutrals
Nitrobenzene-ri5
2-F luorobiphen> 1
Terpheny l-d!4
Other base/ neutral semi
volflt i le organ ics
Acids
Phenol-d5
2-Fluorophenol
2,4 , 6-Tr ibromophenol
Other acid semwolatile
organics
Original amount
found Ug/1)
NO
ND
ND
ND
ND
HD
-
ND
ND
ND
Spike added
(/«g/D
50
50
50
100
100
100
200
200
200
Spike result
(/
-------
1900g
Table B-7 Accuracy-Corrected Envir .te Metals Data for Treated Wa'tewater
from Chromium Reduction, Lime Precipitation and Sludge filtration
Constituent
Antimony
Arsenic
Barium
Beryl lium
Cadmium
Chromium (hexavalent)
Chromium (Total)
Copper
Lead
Mercury
Nickel
Selenium
Si Iver
Thai 1 lum
Zinc
Correct ion
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 0?
Accuracy -corrected
Accuracy-corrected concentration* (mg/1) average
Sample Set # concentration
123456789 10 11
(No substantial treatment)
(No substantial treatment)
<1.1 '11 <3 9 <11 <1 1 <1 1 '11 <1 1 '11 <1.1 <1.1
(No substantial treatment)
<0.57 '0.57 <0 57 <5.7 <0 57 '0 57 '0 57 --C 57 <0.57 <0.57 <5.7
0 010 0 179 ** 0 040 0 055 ** 0 114 -c 009 0 039 0 100 '0 009
0.176 0 176 0 294 0 147 0 162 0 147 P 176 C 221 0 147 0 176 0 265
0 253 0 181 0 253 0 084 0 169 0 145 0 193 C 193 0 096 0 169 0 289
'0013 <0.013 '0013 <0.013 '0013 '0013 '0013 -0013 '0.013 <0 013 <0 013
(No substantial treatment)
0.355 0 355 0 355 0 355 0 333 0 355 0 430 0 387 0 355 0 355 0.419
(No substantial treatment)
(No substantial treatment)
(No substantial treatment)
0 128 0 117 0 143 1.653 0 128 0 097 0 117 0 133 0 061 0.071 0 102
(mg/1)
'„
-5 7
0 56
0 19
0 18
-0 013
0 37
0 25
* Accuracy-corrected concentration = (uncorrected concentration presented in Table 3-2) x (roirp-tm-i 'ac
" fnnrpntrat inn rnuld not hp measured because of analytical interference
-------
1900g
Table B-8 Accuracy-Corrected Envirite Metals Data for Fillet Cake-
from Lime Stabilization and Sludge Filtration
BOAT list
constituent
Arsenic
Barium
Cadmium
Chromium (Total)
Lead
Mercury
Selen ium
ro
c
Silver
Correct ion
factor
0.76
1.11
1.15
1 47
1.31
1.11
2 08
1.33
Accuracy-corrected concentration"1 (mo/1)
Sample Set f
123456789 10
(No substantial treatment)
0.255 0 31 0.50 <0 11 <0 83 <0 11 0 20 0 12 0 22 0 33
<0.023 <0.023 <0.023 <0.023 <0 023 <0 023 '.0 023 <0 023 <0 023 <0.023
<0.074 0 074 <0 074 0 10 '0 074 <0.074 -0 074 --0 074 <0 074 <0 074
<0.13 <0 13 <0 13 <0 13 <0 13 <0 13 <0 13 -9 13 <0 13 <0 13
(No substantial treatment)
(No substantial treatment)
(No substantial treatment)
Accuracy-corrected
average
concept rat ion
11 (rog/1)
0 31 0 30
<0.023 <0 023
<0 074 0 076
-------
1900g
Table B-9 Accuracy-Corrected Organic Concentrations foi tn
Filter Cake and K086 Solvent Wash Scrubber Water
BOAT list
Const ituent
Volatile Orqamcs
Acetone
n-Butyl alcohol
Ethyl acetate
Ethyl benzene
Methanol
Methyl isobutyl ketone
Methyl ethyl ketone
Methylene chloride
Toluene
1 , 1 , 1-Trichloroethane
Trichloroethy lene
Xylene (total)
Semivoleti 1e Organic
Bis(2-ethyl hexy 1 )phtha late
Cyc lohexanone
1 ,2-Dichlorobenzene
Naphthalene
Nitrobenzene
K086 Solvent
Correction
factor
1.11
1.11
1.11
1.11
1 11
1 11
1.11
1 11
1 04
1.11
1.02
1 11
1 57
1 57
1 57
1.57
1.57
Wash Scrubber Water
Accuracy-corrected
Concentrat ion*
(mg/1)
0.0055
0 Oil
0.011
0 0055
0 Oil
0.011
0.011
0.011
0.010
0 Oil
0 010
0 Oil
0 016
0.0078
0 016
0 016
0.016
for rec t ion
factor
1 11
1 11
1 11
1 11
1 11
1 11
1 !1
1 1!
1 11
1 11
1 :1
1 11
1 4f
1 Ji
1 .46
1 46
1 1C
Fi Her Cake
Accuracy-corrected
concentrat ion**
(mg/1)
0.13
0.13
0 13
0.011
0.13
0 13
0.13
0.13
0.011
0 016
0.011
0 0055
0 Ib
0 16
0 18
0.18
0 18
'Accuracy-corrected concentration = (highest detection limit present in Table 3-1) y (correction 'ertor)
"Accuracy-corrected concentration = (highest detection limit present in Tab
tot )
-------
APPENDIX C
21?
-------
Appendix C
Detection Limits for the
K086 Scrubber Water Samples
The detection limits for the analyses of the K086 solvent wash
samples have been classified as confidential by the generator. The
detection limits for analyses of the scrubber effluent water samples are
1isted on Table C-l.
213
-------
1015g
Table C-l Detection Limit1-, tor tin SLT-UI.U" fffluent Wdter
BOAT
reference
no
222
1
2
3
4
5
6
• -> i
1
ti
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
229
35
Constituents (units)
BOAT Volatile Orqanics (mq/1)
Acetone
Acetomtr i le
Acrolein
Aery Ion it r i le
Benzene
bronioU ich loroinethdne
Bromometnane
n-But y 1 a Icohol
Carbon tetracn lor \cie
Carbon disulfiae
Chlorobenzene
2-Chloro-l ,3-butadiene
Chlorodibromomethane
Chloroethane
2-Chloroet hy 1 vinyl ether
Chloroform
Chloromethane
3-Chloropropene
1 , 2-Dibromo-3-chloropropane
1 , 2-Dibromoethane
Dibromomethane
Trans-1 ,4-dichloro-2-butene
Dichlorod if luoromethane
1 , 1-Dichloroethane
1 , 2-Dichloroethane
1 , 1-Dichloroethylene
Trans-1 ,2-dichloroethene
1 , 2-Dichloropropane
Trans-1 , 3 -dich loropropene
cis-1 , 3 -Dich loropropene
1 ,4-Dioxane
2-Ethoxyethanol
Ethyl acetate
Ethy Ibenzene
Ethyl cyanide
Ethyl ether
Ethyl methacrylate
Ethylene oxide
lodomethane
Isobutyl alcohol
Methanol
Methyl ethyl ketone
Methyl isobutyl ketone
Methyl methacrylate
Scrubber effluent
water sample #1
detect ion 1 imits
0 005
0 200
0 200
0 2CG
o o;:
G C1C
o cro
NL
G oic
0 010
0 010
0 200
0 010
0 020
0 0?0
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
NL
NL
0 005
0 200
NL
0.200
NL
0.100
0 400
NL
0.010
0.010
0.200
icrubber ef f luent
water sample 12,
*3, *4 #5, and 16
detection limits
0 005
0 100
0 100
0 ICO
0 Gj5
0 00 1
0 010
NL
0 OCfj
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
NL
NL
0 005
0.100
NL
0 100
NL
0.050
0 200
NL
0 010
0.010
0 100
214
-------
lG15g
T.ti.lc
(LOM!
BOAT
reference
no
Constituents (units)
Scrubber effluent
water sample *1
detect ion 1 units
Scrubber et t luent
water sample ttZ,
#3. «<4, ?5. and »
detection limits
BOAT Volatile Orqanics (mq/1) (continued)
36 Methyl methanesu Itonate 0 400
37 Metnylacrylonitrile 0 ,00
38 Methylene chloride 0 110
23C 2-Nitropropane NL
P> i id ;:ie C cJO
-1C 1,1,1,2-Tetrachloroethane 0
•ij 1, 1 ,2,2-Tetrachloroethane 0
4.' let rdcnloroethene C
4j Toluene 0
J-I Tr i oroinomethane 0
45 1,1,1-Trichloroethane 0010
47 1,1,2-Trichloroethane 0010
4b Trichloroetnene 0 010
4:i Tr ichloromonof Iuoromethane 0 010
231 1 , 1 ,2-tnchloro-l ,2,2-tnf luoroethane NL
r.C 1 , L , 3-Tr ich loropropane 0 210
Vinyl chloride 0 C20
215 l,2-X>lene 0 005
216 1,3-Xylene 0 005
217 1,4-Xylene 0 005
0 200
0 100
0 005
NL
0 400
0 005
0 005
0 OC1
0 00;,
0 005
0 005
0 005
0 005
0 005
NL
0 005
0 010
0 005
0 005
0 005
215
-------
1615g
C i (c^nt i
BOAT
reference
no
51
52
53
54
55
56
57
5b
59
216
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)
BOAT Semwolatile Orqanics (mq'l)
Acenaphtha lene
Acenaphthene
Acetophenone
2-Acety laminof luorene
4 - Am i nob i phen> 1
Am 1 me
Anthracene
Araii'ii te
Ben? (a) anthracene
Benzdl chloride
Benzenethiol
Benz idine
Benzo(a)pyrene
Benzo(b)f luoranthene
Benzo(ghi Jperylene
6en;o(k)fluoranthene
p-Benzoquinone
Bis(2-chloroethoxy)ethane
Bis(2-chloroethyl)ether
Bis(2-chloroisopropyl)ether
Bis(2-ethylhexyl)phthalate
4-Bromopheny 1 phenyl ether
Butyl benzyl phthalate
2-sec-Butyl-4,6-dinitrophenol
p-Chloroam 1 me
Chlorobenzi late
p-Chloro-m-cresol
2-Chloronaphtha lene
2-Cnlorophenol
3-Chloropropiomtri le
Chrysene
ortho-Cresol
para-Cresol
Cyclohexanone
Scrubber effluent
water (all samples)
detect ion 1 imits
0 010
0 010
0 010
1 000
0 200
0 020
0 010
NA
0 010
NL
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
NA = Not available
216
-------
1615g
IL- C -1 (i out irun .!)
BOAT
reference
no
83
84
85
tfb
b/
bH
89
90
Ql
92
93
94
95
96
97
9a
99
100
101
.102
103
104
105
106
219
107
108
109
"no
111
112
113
114
Constituents (units)
BOAT Semivolat i le Orqanics (mq/1) (continued)
Dibenz(a,h)anthracene
Dibenzo(a,e)pyrene
Dibenzo(a, i )pyrene
m-Dichlorobenzene
o-D icnloroneiiZene
p-Dichlorobenzene
3,3 ' -Dicnlorobenz idine
2 ,4-Dichloropnenol
2 , 6-D ichloropheno 1
Diethyl phthalate
3,3' -Dimethoxybenzidine
p- Dimethyl am inoazobenzene
3,3 '-Dimethylbenzidme
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
D i - n - propy 1 n i t rosam i ne
Diphenylamine
Diphenylnitrosamine
1 ,2-Diphenylhydrazme
Fluoranthene
Fluorene
Hexachlorobenzene
Hexachlorobutadiene
Hexachlorocyc lopentadiene
Hexachloroethane
Hexachlorophene
Scrubber effluent
water (all samples)
detection limits
0.010
NA
0 050
0 010
0 QIC
0 CIO
0 020
0 010
NA
0 01C
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
NA = Not avai Table
217
-------
1615Q
le C 1 (com iriuc;:)
BOAT
reference
no
115
116
117
116
119
120
in
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
Constituents (units)
BOAT Semivolat i le Orqanics (mq/1) (continued)
Hexach loropropene
Indeno( 1,2, 3-cd)pyrene
Isosaf role
Methapyr i lene
3-Methy Ichc iant hrene
4,4' -Met hy lenotiis
( 2 -chloroan i 1 me)
Naphtha lene
1 , 4-Naphthoqu mone
1 -Naphthy lamme
2-Naphthy lamme
p-Nitroani 1 me
N itrobenzene
4-Ni t rophenoi
N-Nitrosodi-n-butylamme
N-Nitrosodiethy lamme
N-N i trosod ime thy lam ine
N-Nitrosomethylethy lamme
N-Nitrosomorphol me
N-Nitrosopiperidme
n-Ni trosopyrrol id me
5-Nitro-o-toluidme
Pentachlorobenzene
Pentachloroethane
Pentachloronltrobenzene
Pentachlorophenol
Phenacet in
Phenanthrene
Phenol
Phthalic anhydride
2-Picol me
Pronamide
Pyrene
Resorcmol
Scrubber effluent
water (all samples)
detection limits
NA
0 010
0 100
NA
c i:c
0 200
0 GIG
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
NL
0 100
NA
0 010
NA
NA = Not ava i lable
218
-------
1615g
BOAT
reference
no.
147
148
149
150
151
152
155
154
155
156
157
15«
159
221
160
.161
162
163
164
165
166
167
168
169
170
171
Constituents (units)
BOAT Semwolatile Orqanics (mq/1) (continued)
Saf role
1,2,4, 5-Tetrachlorobenzene
2,3, 4,6-Tetrach lorophenol
1 , ?, 4-Tr ichlorobenzene
2 , 4 , 5-Tr ichloropheno 1
2,4, 6-Trich lorophenol
T r i s ( 2 , 3-d i bromopropy 1 )
phosphate
BOAT Metals (mq/1)
Ant imony
Arsenic
Barium
Bery 1 1 lum
Cadmium
Chromium (total)
Chromium (hexavalent)
Copper
Lead
Mercury
Nickel
Selenium
S i Iver
Tha 1 1 lum
Vanadium
Z me
BDAT Inorganics (mq/1)
Cyanide
F luor ide
Sulf ide
Scrubber effluent
water (all samples)
detection limits
0 100
0 010
NA
C 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 Oil
0 005
0 006
0 010
0 006
0 002
0 010
0 2
0 5
NA = Not available
219
-------
1615g
Idlj le C 1 (corit inuei.:)
BOAT Scrubber effluent
reference water (all samples)
no Constituents (units) detection limits
BOAT PCBs (rnq/1)
200 Aroclor 1016 0 0015
201 Aroclor 1221 0 0015
202 Aroclor 1232 0 0015
203 Aroclor 1242 0 0015
2C4 Aroclor 124o C Gui,
205 Aroclor 1254 0 0015
206 Aroclor 1260 0 0015
BOAT R'o.ins/Furans (mq'1)
207 hexachlorodibenzo-p-dioxins 0 1
208 Hexachlorodibenzofuran 0 04
209 Pentachlorodibenzo-p-dioxins 0 11
210' Pentachlorodibenzofuran 0 05
211 Tetrachlorodibenzo-p-dioxins 0 1
212 Tetrachlorodibenzofuran 0 04
213 2,3,7,8-Tetrachlorodibenzo-p-dioxin 0 13
Other Analyses (mq/1)
Iron 0 006
Magnesium 0.001
Manganese 0 003
Titanium 0 003
Chloride 1 000
Total solids 1 000
Total organic carbon 1.000
Total organic halides 0 010
Reference USEPA 1987a
220
-------
APPENDIX D
221
-------
Appendix D
METHOD OF MEASUREMENT FOR THERMAL CONDUCTIVITY
The comparative method of measuring thermal conductivity has been
proposed as an ASTM test method under the name "Guarded, Comparative,
Longitudinal Heat Flow Technique." A thermal heat flow circuit is used
which is the analog of an electrical circuit with resistances in series.
A reference material is chosen to have a thermal conductivity close to
that estimated for the sample. Reference standards (also known as heat
meters) having the same cross-sectional dimensions as the sample are
placed above and below the sample. An upper heater, a lower heater, and
a heat sink are added to the "stack" to complete the heat flow circuit.
See Figure 1.
The temperature gradients (analogous to potential differences) along
the stack are measured with type K (chromel/alumel) thermocouples placed
at known separations. The thermocouples are placed into holes or grooves
in the references and also in the sample whenever the sample is thick
enough to accommodate them.
For molten samples, pastes, greases, and other materials that must be
contained, the material is placed into a cell consisting of a top and
bottom of Pyrex 7740 and a containment ring of marinite. The sample is 2
inch in diameter and .5 inch thick. Thermocouples are not placed into
the sample but rather the temperatures measured in the Pyrex are
extrapolated to give the temperature at the top and bottom surfaces of
the sample material. The Pyrex disks also serve as the thermal
conductivity reference material.
222
-------
GUARD
GRADIENT.
STACK
GRADIENT-
o,
THERMOCOUPLE
CLAMP
UPPER STACK
HEATER
TOP REFERENCE
SAMPLE
J
TESTySAMPLE
BOTTOM
REFERENCE
SAMPLE
I
LOWER STACK
HEATER
LIQUID 'COOLED
HEAT SINK
HEAT FLOW
DIRECTION
Figure 1.
SCHEMATIC DIAGRAM OF THE COMPARATIVE METHOD
UPPER
GUARD
HEATER
LOWER
GUARD
HEATER
223
-------
The stack is clamped with a reproducible load to ensure intimate
contact between the components. In order to produce a linear flow of
heat down the stack and reduce the amount of heat that flows radially, a
guard tube is placed around the stack and the intervening space is filled
with insulating grains or powder. The temperature gradient in the guard
is matched to that in the stack to further reduce radial heat flow.
The comparative method is a steady state method of measuring thermal
conductivity. When equilibrium is reached the heat flux (analogous to
current flow) down the stack can be determined from the references. The
heat into the sample is given by
Q. = A (dT/dx)
in top top
and the heat out of the sample is given by
Q
out = AL (dT/dx)
bottom bottom
where
x - 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 just down the stack, then
Q and Q would be equal. If Q and Q are in reasonable
in out in out
agreement, the average heat flow is calculated from
Q = (Q. + Q J/2
in out
The sample thermal conductivity is then found from
\ = Q/(dT/dx) .
sample sample
224
-------
APPENDIX E
225
-------
APPENDIX E
Organic Detection Limits for K086 Solvent Wash 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 sufficiently similar 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, ethyl 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.
226
-------
1839g
Table E-l Organic Detection Limits for Envrite Filter Cake Rf, id.ji I1:
from Lime Stabilization and Sludge Filtration
ro
ro
—i
BOAT list
constituent
Volatile orqanics
Acetone
n-Butyl alcohol
Ethyl acetate
Ethyl benzene
Methanol
Methyl isobutyl ketone
Methyl ethyl ketone
Methylene chloride
Toluene
1 , 1 , 1-Tr ichloroethane
Tr ichloroethylene
Xylene (total)
Semivolatile orgamcs
Bis(2-ethylhexyl)phthalate
Cyclohexanone
1 ,2-Dichlorobenzene
Naphthalene
Nitrobenzene
Determined
Total concentration (ug/1) level of
Sample Set # ' detection
1 2 34 5 6 7 8 9 10 11 12 13 14 IS (uq/1)
79 84 - 120 120 120 12C
120
120
32- - - - - 10 34- 49 - 48 10
120
120
120
8.6 8 9 7 1 7 9 8 2 - - 798310 8 4 * ? 12 12 12 12
2 8 3 2 3 3 - - - 1C 3 4 - 49 - 46 10
14 3 2 - - - 1C -• 4 49 - - 14
3.4- 28323332- - - 1C - 49 49 40 10
32----- - 4r-t- - 49
120
120
120
120
120
- = No detection limit reported
Reference USEPA 1986a
-------
REFERENCES
Ackerman D.G., McGaughey J.F., Wagoner D.E., "At Sea Incineration of
PCB-Containing Wastes on Board the M/T Vulcanus," USEPA, 600/7-83-024,
April 1983.
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, James R. 1985. "Effects of pH and proportioning of ferrous and
sulfide reduction chemicals on electroplating waste treatment sludge
production." In Proceeding of the 39th Purdue Industrial Waste
Conference, May 8, 9, 10, 1984. Stoneham, MA: 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., Engineering Handbook for Hazardous Waste
Incineration. SW-889. Prepared by Monsanto Research Corporation for
U.S. EPA NTIS PB 81-248163. June 1981.
Castaldini C., et al., Disposal of Hazardous Wastes in Industrial Boilers
on Furnaces, Noyes Publications, New Jersey, 1986.
Center for Metals Production, Electric arc furnace dust-disposal, recycle
and recovery, Pittsburgh, PA; May 1985.
Cherry, Kenneth F. 1982. Plating Waste Treatment. Ann Arbor, MI; Ann
Arbor Science, Inc. pp 45-67.
Cushnie, George C., Jr. 1984. Removal of Metals from Wastewater:
Neutralization and Precipitation. Park Ridge, NJ; Noyes Publications.
pp 55-97.
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
Engineer Waterways Experiment Station. EPA report No. 540/2-86/001.
Cincinnati, Ohio: U.S. Environmental Protection Agency.
228
-------
Cushnie, George C., Jr. 1985. Electroplating Wastewater Pollution
Control Technology. Park Ridge, NJ; Noyes Publications, pp 48-62,
84-90.
Duby, Paul. 1980. Extractive Metallurgy, In Klrk-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, California: Electric Power Research Institute.
Federal Register. 1986. Hazardous Waste Management Systems; Land
Disposal Restrictions; Final Rule; Appendix I to Part 268 - Toxicity
Leaching Procedure (TCLP). Vol. 51, No. 216. November 7, 1986 pp.
40643-40654.
Grain, Richard W. 1981. Solids Removal and Concentration. In Third
Conference on Advanced Pollution Control for the Metal Finishing
Industry. Cincinnati, Ohio: U.S. Environmental Protection Agency.
pp. 56-62.
Gurnham, C.F. 1955. Principles of Industrial Waste Treatment. New York;
John Wiley and Sons, pp 224-234.
Kirk-Othmer. 1980. Encyclopedia of Chemical Technology, 3rd ed.,
Flocculation, Vol. 10. New York; John Wiley and Sons, pp 489-516.
Lanouette, Kenneth H. 1977. Heavy Metals Removal. Chemical Engineering,
October 17, 1977, pp. 73-80.
Lloyd, Thomas, and Showak, Walter, 1980. Zinc and Zinc Alloys. In
Kirk-Othmer encyclopedia of Chemical Technology, 3rd. ed. Vol. 24, p.
824.
Lloyd, Thomas. 1980. Zinc compounds. Kirk-Othmer Encyclopedia of
Chemical Technology, 3rd. ed. Vol. 24, p. 856.
Maczek, Helmut and Kola, Rolf, 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.
229
-------
Mitre Corp. Guidance Manual for Hazardous Waste Incinerator Permits
NTIS PB84-100577. July 1983.
Novak R.G., Troxler W.L., Dehnke T.H., "Recovering Energy from Hazardous
Waste
Incineration," Chemical Engineering Progress 91:146 (1984).
Oppelt ET. "Incineration of Hazardous Waste"; JAPCA; Volume 37, No. 5;
May 1987.
Patterson, James W. 1985. Industrial Wastewater Treatment Technology,
2nd Ed. Butterworth Publishers; Stoneham, MA.
Perry, Robert H. and Chilton, Cecil H. 1973. Chemical Engineers'
Handbook. Fifth Edition. New York: McGraw Hill, Inc., Section 19.
Pojasek RB. 1979. Sol id-Waste Disposal: Solidification, Chemical
Engineering 86(17): 141-145.
Price, Laurence. Tensions Mount in EAF dust Bowl. Metal Producing.
February 1986.
Rudolfs, William. 1953. Industrial Wastes. Their Disposal and
Treatment. L.E.C. Publishers Inc., Valley Stream, NY. p. 294
Sanderson. 1971. Chemical Bonds and Bond Energy. Vol. 21 in Physical
Chemistry. New York: Academic Press.
Santoleri J.J., Energy Recovery A By-Product of Hazardous Waste
Incineration Systems, in Proceedings of the 15th Mid-Atlantic
Industrial Waste Conference on Toxic and Hazardous Waste, 1983.
U.S. Department of Commerce, 1982 Census of Manufacturers - Miscellaneous
Chemical Products. December 1984.
USEPA. 1979. Effluent Guidelines Division. Development Document for
Proposed Effluent Limitations Guidelines and Standards for the Ink
Formulation Point Source Category. EPA No. 440/1-79/090-b.
USEPA. 1980. U.S. Environmental Protection Agency. RCRA Listing
Background Document Waste Code K086.
USEPA. 1980a. U.S. Environmental Protection Agency. U.S. Army Engineer
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.
230
-------
USEPA. 1983,
Control/Removal
pp 111.3.1.3-2.
Treatabllity Manual, Volume III, Technology for
EPA-600/2-82-001C, January 1983,
of Pollutants.
USEPA. 1985. Characterization of Waste Streams Listed in 40 CFR; Section
261, Waste Profiles. Prepared for the Waste Identification Branch,
Characterization and Assessment Division, U.S. EPA. Prepared by
Environ Corporation, Washington, D.C. 1985.
USEPA. 1986a. Onsite Engineering Report of Treatment Technology
Performance and Operation for Envirite Corporation. York, Pennsylvania.
Washington, D.C.: U.S. Environmental Protection Agency.
USEPA. 1986b. Test Methods for Evaluating Solid Waste; Physical/
Chemical Methods. Third Edition. U.S. EPA. Office of Solid Waste and
Emergency Response. November 1986.
USEPA, 1986c. Best Demonstrated Available Technology (BOAT) Background
Document for F001-F005 Spent Solvents, Volume 1, EPA/530-SW-86-056,
November 1986.
USEPA. 1987a. 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
USEPA. 1987b. 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
Aqency.
USEPA. 1987c. Onsite Engineering Report for Horsehead Resource
Development Co., Inc. Palmerton, Pennsylvania, for K061. Washington,
D.C.: U.S. Environmental Protection Agency.
USEPA. 1988a. Onsite Engineering Report for Waterways Experiment
Station, Vicksburg, Mississippi for K048 and K051.
USEPA. 1988b. Onsite Engineering Report for Waterways Experiment
Station, Vicksburg, Mississippi forK061.
USEPA. 1988c. Onsite Engineering Report of Treatment Technology
Performance and Operation for Shell Oil (Dear Park Manufacturing
Complex), Deer Park, Texas. Draft Report. November 18, 1987.
231
-------
Versar. 1984. Estimating PMN Incineration Results (Draft). U.S.
Environmental Protection Agency, Exposure Evaluation Division, Office
of Toxic Substances, Washington, DC. EPA Contract No. 68-01-6271, Task
No. 66.
Vogel G, et al. 1986. Incineration and Cement Kiln Capacity for
Hazardous
Waste Treatment," in Proceedings of. the 12th Annual Research
Symposium. Incineration and Treatment of Hazardous Wastes.
Cincinnati, Ohio. April 1986.
232
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