vvEPA
United States
Environmental Protection
Agency
Office of
Solid Waste
Washington, D.C 20460
EPA/530-SW-88-0009-f
April 1988
Solid Waste
Best
Demonstrated
Available Technology
(BOAT) Background
Document for
K071
Proposed
Volume 6
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EPA/530-SW-88-009F
; PROPOSED
:5
BEST DEMONSTRATED AVAILABLE TECHNOLOGY (BOAT)
BACKGROUND DOCUMENT FOR K071
Volume 6
U.S. Environmental Protection Agency
Office of Solid Waste
401 M Street, S.W.
Washington, D.C. 20460
James R. Berlow, Chief John Keenan
Treatment Technology Section Project Manager
April 1988
u$ Environmental Protect^ Agency
Region 5, library (PL-12J) -
7 I Vst Jackson Boulevard, I2th Flo*
Chicago. U. 60604-3590
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BOAT BACKGROUND DOCUMENT FOR K071
TABLE OF CONTENTS
VOLUME 6
Executi ve Summary
BOAT Treatment Standards for K071
SECTION 1. Introduction 1
1.1 Legal Background 1
1.1.1 Authority 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) Proprietary or Patented Processes 10
(2) Substantial Treatment 10
1.2.3 Collection of Performance Data 11
(1) Identification of Facilities for Site Visits .. 12
(2) Engineering Site Visit 13
(3) Sampling and Analysis Plan 14
(4) Sampling Visit 16
(5) Onsite Engineering Report 17
1.2.4 Hazardous Constituents Considered and Selected for
Regulation 17
(1) Development of BOAT List 17
(2) Constituent Selection Analysis 27
(3) Calculation of Standards 29
1.2.5 Compliance with Performance Standards 30
1.2.6 Identification of BOAT 32
(1) Screening of Treatment Data 32
(2) Comparison of Treatment Data 33
(3) Quality Assurance/Quality Control 34
1.2.7 BOAT Treatment Standards for "Derived-From" and
"Mixed" Wastes 36
(1) Wastes from Treatment Trains Generating
Multiple Residues 36
(2) Mixtures and Other Derived-From JResidues 37
(3) Residues from Managing Listed Wastes or that
Contain Listed Wastes 38
1.2.8 Transfer of Treatment Standards 40
1.3 Variance from the BOAT Treatment Standard 41
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SECTION 2. Industries Affected and Waste Characterization 46
2.1 Industries Affected and Process Description 47
2.2 Waste Characterization 51
SECTIONS. Applicable/Demonstrated Treatment Technologies 55
3.1 Applicable Treatment Technologies 55
3.2 Demonstrated Treatment Technologies 56
3.2.1 Acid Leaching Treatment System 57
3.2.1.1 Acid Leaching 59
3.2.1.2 Sludge Filtration 65
3.2.2 Stabilization of Metals 69
3.2.3 Chemical Precipitation Treatment System 77
3.2.3.1 Chemical Precipitation 77
3.3 Performance Data for Nonwastewater 89
3.4 Performance Data for Wastewater 90
SECTION 4. Selection of Best Demonstrated Available Technology
(BOAT) 103
4.1 Data Screening 104
4.2 Data Accuracy 105
4.3 Analysis of Variance 106
4.4 Determination of Availability of Best Technology 106
SECTIONS. Selection of Regulated Constituents 110
SECTION 6. Calculation of Treatment Standards 120
SECTION 7. Conclusions 124
APPENDIX A Analytical Data Submitted by Industry for Treatment
of K071 129
APPENDIX B Analytical QA/QC 172
APPENDIX C Statistical Analysis 186
C.I F Value Determination for ANOVA Test 187
C.2 Variability Factor 197
APPENDIX D Other Agency Characterization Data 198
REFERENCES * 201
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LIST OF TABLES
Page No.
Table 1-1 BOAT Constituent List 19
Table 2-1 Number of Producers of Chlorine Using the Mercury
Cel 1 Process Listed by State 48
Table 2-2 Number of Producers of Chlorine Using the Mercury
Cell Process Listed by EPA Region 49
Table 2-3 Major Constituent Analysis of Untreated Brine
Purification Muds 52
Table 2-4 Major Constituent Analysis of Untreated Saturator
Insolubles 53
Table 2-5 BOAT Constituent Composition of Untreated K071
Waste 54
Table 3-1 EPA-Collected Data for Treatment of K071 Waste 91
Table 3-2 EPA-Collected Data for Treatment of K071 Waste 92
Table 3-3 EPA-Collected Data for Treatment of K071 Waste 93
Table 3-4 EPA-Collected Data for Treatment of K071 Waste 94
Table 3-5 EPA-Collected Data for Treatment of K071 Waste 95
Table 3-6 EPA-Collected Data for Treatment of K071 Waste 96
Table 3-7 EPA-Collected Data for Treatment of K071 Waste 97
Table 3-8 EPA-Collected Data for Acid Leaching (Percolation) .. 98
Table 3-9 Waste Characteristics Affecting Performance for
Acid Leaching 99
Table 3-10 Sulfide Precipitation - EPA-Collected Data 100
Table 3-11 Sulfide Precipitation - EPA-Collected'Data 101
Table 3-12 Sulfide Precipitation - EPA-Collected Data 102
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LIST OF TABLES (continued)
Page No.
Table 4-1 Treatment Data Used for Regulation of K071
Nonwastewater 108
Table 4-2 Treatment Data Used for Regulation of K071
Wastewater 109
Table 5-1 BOAT List of Constituents 113
Table 6-1 Calculation of Treatment Standards for K071
Acid Leaching, EPA-Collected Data 123
Table 7-1 BOAT Treatment Standards for K071 125
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LIST OF FIGURES
Figure 3-1 Schematic of K071 Waste Treatment Process 58
Figure 3-2 Continuous Extractor 62
Figure 3-3 Continuous Chemical Precipitation 80
Figure 3-4 Circular Clarifiers 83
Figure 3-5 Inclined Plate Settler 84
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EXECUTIVE SUMMARY
Pursuant to the Hazardous and Solid Waste Amendments (HSWA) enacted
on November 8, 1984, and in accordance with the procedures for
establishing treatment standards under Section 3004(m) of the Resource
Conservation and Recovery Act (RCRA), the following treatment standards
have been proposed as Best Demonstrated Available Technology (BOAT) for
the listed waste identified in 40 CFR Section 261.32 as K071 (brine
purification muds from the mercury cell process in chlorine production,
where separately prepurified brine is not used) as a prerequisite for
disposal of the waste in units designated as land disposal units
according to 40 CFR Part 268.
Standards are established for one metal (mercury). These standards
are established based on total constituent and leachate analyses
conducted on the waste. The leachate was obtained using the Toxicity
Characteristic Leaching Procedure (TCLP) as outlined in later sections of
this background document.
BOAT standards have been established based on performance data
obtained from a treatment train consisting of acid leaching followed by
chemical oxidation followed by a dewatering/washing step, designed to
remove mercury as soluble mercuric chloride. These treatment steps are
followed by a treatment train consisting of sulfitfe precipitation and
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filtration for treatment of the wastewater produced in the dewatering
step. This treatment is designed to precipitate dissolved mercury from
the wastewater as mercuric sulfide. The Agency has examined additional
data submitted by industry obtained using an alternative treatment of
water washing/dewatering. These additional data indicate that this
alternative treatment technology provides less effective treatment of
K071 waste.
These standards become effective as of the date established in the
final rule for the land disposal restrictions for K071 (40 CFR Section
268.10).
The following table lists the specific BOAT treatment standards for
wastes identified as K071. The units for the total waste concentration
analysis are mg/kg (parts per million on a weight by weight basis) for
nonwastewater and mg/1 (parts per million on a weight by volume basis)
for wastewater. The leachate standards are based on analysis of a TCLP
leachate and are in units of mg/1. Testing procedures for all sample
analyses performed are specifically identified in Appendix B of this
background document.
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BOAT TREATMENT STANDARDS FOR K071
Constituent Value
Mercury
Wastewater (total concentration) 0.030 mg/1
<$ a
Nonwastewater (total concentration) 4./mg/kg
Nonwastewater (TCLP) 0.0025 mg/1
a Facilities that land dispose of K071 nonwastewater must meet both the
total concentration and the TCLP standards.
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1. INTRODUCTION
This section of the background document presents a summary of the
legal authority pursuant to which the BOAT treatment standards were
developed, a summary of EPA's promulgated methodology for developing
BOAT, and finally a discussion of the petition process that should be
followed to request a variance from the BOAT treatment standards.
1.1 Legal Background
1.1.1 Requirements Under HSWA
The Hazardous and Solid Waste Amendments of 1984 (HSWA), enacted on
November 8, 1984, and which amended the Resource Conservation and
Recovery Act of 1976 (RCRA), impose substantial new responsibilities on
those who handle hazardous waste. In particular, the amendments require
the Agency to promulgate regulations that restrict the land disposal of
untreated hazardous wastes. In its enactment of HSWA, Congress stated
explicitly that "reliance on land disposal should be minimized or
eliminated, and land disposal, particularly landfill and surface
impoundment, should be the least favored method for managing hazardous
wastes" (RCRA section 1002(b)(7), 42 U.S.C. 6901(b)(7)).
One part of the amendments specifies dates on which particular groups
of untreated hazardous wastes will be prohibited from land disposal
unless "it has been demonstrated to the Administrator, to a reasonable
degree of certainty, that there will be no migration of hazardous
constituents from the disposal unit or injection zone for as long as the
wastes remain hazardous" (RCRA section 3004(d)(l), (e)(l), (g)(5), 42
U.S.C. 6924 (d)(l), (e)(l), (g)(5)).
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For the purpose of the restrictions, HSWA defines land disposal "to
include, but not be limited to, any placement of ... hazardous waste in
a landfill, surface impoundment, waste pile, injection well, land
treatment facility, salt dome formation, salt bed formation, or
underground mine or cave" (RCRA section 3004(k), 42 U.S.C. 6924(k)).
Although HSWA defines land disposal to include injection wells, such
disposal of solvents, dioxins, and certain other wastes, known as the
California List wastes, is covered on a separate schedule (RCRA section
3004(f)(2), 42 U.S.C. 6924 (f)(2)). This schedule requires that EPA
develop land disposal restrictions for deep well injection by
August 8, 1988.
The amendments also require the Agency to set "levels or methods of
treatment, if any, which substantially diminish the toxicity of the waste
or substantially reduce the likelihood of migration of hazardous
constituents from the waste so that short-term and long-term threats to
human health and the environment are minimized" (RCRA section 3004(m)(l),
42 U.S.C. 6924 (m)(l)). Wastes that meet treatment standards established
by EPA are not prohibited and may be land disposed. In setting treatment
standards for listed or characteristic wastes, EPA may establish
different standards for particular wastes within a single waste code with
differing treatability characteristics. One such characteristic is the
physical form of the waste. This frequently leads to different standards
for wastewaters and nonwastewaters.
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alternatively, EPA can establish a treatment standard that is applicable
to more than one waste code when, in EPA's judgment, all the waste can be
treated to the same concentration. In those instances where a generator
can demonstrate that the standard promulgated for the generator's waste
cannot be achieved, the Agency also can grant a variance from a treatment
standard by revising the treatment standard for that particular waste
through rulemaking procedures. (A further discussion of treatment
variances is provided in Section 1.3.)
The land disposal restrictions are effective when promulgated unless
the Administrator grants a national variance and establishes a different
date (not to exceed 2 years beyond the statutory deadline) based on "the
earliest date on which adequate alternative treatment, recovery, or
disposal capacity which protects human health and the environment will be
available" (RCRA section 3004(h)(2), 42 U.S.C. 6924 (h)(2)).
If EPA fails to set a treatment standard by the statutory deadline
for any hazardous waste in the First Third or Second Third of the
schedule (see section 1.1.2), the waste may not be disposed in a landfill
or surface impoundment unless the facility is in compliance with the
minimum technological requirements specified in section 3004(o) of RCRA.
In addition, prior to disposal, the generator must certify to the
Administrator that the availability of treatment capacity has been
investigated and it has been determined that disposal in a landfill or
surface impoundment is the only practical alternative to treatment
currently available to the generator. This restriction on the use of
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landfills and surface impoundments applies until EPA sets a treatment
standard for the waste or until May 8, 1990, whichever is sooner. If the
Agency fails to set a treatment standard for any ranked hazardous waste
by May 8, 1990, the waste is automatically prohibited from land disposal
unless the waste is placed in a land disposal unit that is the subject of
a successful "no migration" demonstration (RCRA section 3004(g), 42
U.S.C. 6924(g)). "No migration" demonstrations are based on case-
specific petitions that show there will be no migration of hazardous
constituents from the unit for as long as the waste remains hazardous.
1.1.2 Schedule for Developing Restrictions
Under Section 3004(g) of RCRA, EPA was required to establish a
schedule for developing treatment standards for all wastes that the
Agency had listed as hazardous by November 8, 1984. Section 3004(g)
required that this schedule consider the intrinsic hazards and volumes
associated with each of these wastes. The statute required EPA to set
treatment standards according to the following schedule:
(a) Solvents and dioxins standards must be promulgated by
November 8, 1986;
(b) The "California List" must be promulgated by July 8, 1987;
(c) At least one-third of all listed hazardous wastes must be
promulgated by August 8, 1988 (First Third);
(d) At least two-thirds of all listed hazardous wastes must be
promulgated by June 8, 1989 (Second Third); and
(e) All remaining listed hazardous wastes and all hazardous wastes
identified as of November 8, 1984, by one or more of the
characteristics defined in 40 CFR Part 261 must be promulgated
by May 8, 1990 (Third Third).
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The statute specifically identified the solvent wastes as those
covered under waste codes F001, F002, F003, F004, and F005; it identified
the dioxin-containing hazardous wastes as those covered under waste codes
F020, F021, F022, and F023.
Wastes collectively known as the California List wastes, defined
under Section 3004(d) of HSWA, are liquid hazardous wastes containing
metals, free cyanides, PCBs, corrosives (i.e., a pH less than or equal to
2.0), and any liquid or nonliquid hazardous waste containing halogenated
organic compounds (HOCs) above 0.1 percent by weight. Rules for the
California List were proposed on December 11, 1986, and final rules for
PCBs, corrosives, and HOC-containing wastes were established
August 12, 1987. In that rule, EPA elected not to establish standards
for metals. Therefore, the statutory limits became effective.
On May 28, 1986, EPA published a final rule (51 FR 19300) that
delineated the specific waste codes that would be addressed by the First
Third, Second Third, and Third Third. This schedule is incorporated into
40 CFR 268.10, .11, and .12.
1.2 Summary of Promulgated BOAT Methodology
In a November 7, 1986, rulemaking, EPA promulgated a technology-based
approach to establishing treatment standards under section 3004(m).
Section 3004(m) also specifies that treatment standards must "minimize"
long- and short-term threats to human health and the environment arising
from land disposal of hazardous wastes.
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Congress indicated in the legislative history accompanying the HSWA
that "[t]he requisite levels of [sic] methods of treatment established by
the Agency should be the best that has been demonstrated to be
achievable," noting that the intent is "to require utilization of
available technology" and not a "process which contemplates
technology-forcing standards" (Vol. 130 Cong. Rec. S9178 (daily ed.,
July 25, 1984)). EPA has interpreted this legislative history as
suggesting that Congress considered the requirement under 3004(m) to be
met by application of the best demonstrated and achievable (i.e.,
available) technology prior to land disposal of wastes or treatment
residuals. Accordingly, EPA's treatment standards are generally based on
the performance of the best demonstrated available technology (BOAT)
identified for treatment of the hazardous constituents. This approach
involves the identification of potential treatment systems, the
determination of whether they are demonstrated and available, and the
collection of treatment data from well-designed and well-operated systems.
The treatment standards, according to the statute, can represent
levels or methods of treatment, if any, that substantially diminish the
toxicity of the waste or substantially reduce the likelihood of migration
of hazardous constituents. Wherever possible, the Agency prefers to
establish BOAT treatment standards as "levels" of treatment
(i.e., performance standards) rather than adopting an approach that would
require the use of specific treatment "methods." EPA believes that
concentration-based treatment levels offer the regulated community greater
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flexibility to develop and implement compliance strategies as well as an
incentive to develop innovative technologies.
1.2.1 Waste Treatability Group
In developing the treatment standards, EPA first characterizes the
waste(s). As necessary, EPA may establish treatability groups for wastes
having similar physical and chemical properties. That is, if EPA
believes that wastes represented by different waste codes could be
treated to similar concentrations using identical technologies, the
Agency combines the codes into one treatability group. EPA generally
considers wastes to be similar when they are both generated from the same
industry and from similar processing stages. In addition, EPA may
combine two or more separate wastes into the same treatability group when
data are available showing that the waste characteristics affecting
performance are similar or that one waste would be expected to be less
difficult to treat.
Once the treatability groups have been established, EPA collects and
analyzes data on identified technologies used to treat the wastes in each
treatability group. The technologies evaluated must be demonstrated on
the waste or a similar waste and must be available for use.
1.2.2 Demonstrated and Available Treatment Technologies
Consistent with legislative history, EPA considers demonstrated
technologies to be those that are used to treat the waste of interest or
a similar waste with regard to parameters that affect treatment selection
(see November 7, 1986, 51 FR 40588). EPA also will consider as treatment
those technologies used to separate or otherwise process chemicals and
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other materials. Some of these technologies clearly are applicable to
waste treatment, since the wastes are similar to raw materials processed
in industrial applications.
For most of the waste treatability groups for which EPA will
promulgate treatment standards, EPA will identify demonstrated
technologies either through review of literature related to current waste
treatment practices or on the basis of information provided by specific
facilities currently treating the waste or similar wastes.
In cases where the Agency does not identify any facilities treating
wastes represented by a particular waste treatability group, EPA may
transfer a finding of demonstrated treatment. To do this, EPA will
compare the parameters affecting treatment selection for the waste
treatability group of interest to other wastes for which demonstrated
technologies already have been determined. The parameters affecting
treatment selection and their use for this waste are described in
Section 3.2 of this document. If the parameters affecting treatment
selection are similar, then the Agency will consider the treatment
technology also to be demonstrated for the waste of interest. For
example, EPA considers rotary kiln incineration a demonstrated technology
for many waste codes containing hazardous organic constituents, high
total organic content, and high filterable solids content, regardless of
whether any facility is currently treating these^wastes. The basis for
this determination is data found in literature and data generated by EPA
confirming the use of rotary kiln incineration on wastes having the above
characteristics.
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If no commercial treatment or recovery operations are identified for
a waste or wastes with similar physical or chemical characteristics that
affect treatment selection, the Agency will be unable to identify any
demonstrated treatment technologies for the waste, and, accordingly, the
waste will be prohibited from land disposal (unless handled in accordance
with the exemption and variance provisions of the rule). The Agency is,
however, committed to establishing treatment standards as soon as new or
improved treatment processes are demonstrated (and available).
Operations only available at research facilities, pilot- and bench-
scale operations will not be considered in identifying demonstrated
treatment technologies for a waste because these technologies would not
necessarily be "demonstrated." Nevertheless, EPA may use data generated
at research facilities in assessing the performance of demonstrated
technologies.
As discussed earlier, Congress intended that technologies used to
establish treatment standards under Section 3004(m) be not only
"demonstrated," but also available. To decide whether demonstrated
technologies may be considered "available," the Agency determines whether
they (1) are commercially available and (2) substantially diminish the
toxicity of the waste or substantially reduce the likelihood of migration
of hazardous constituents from the waste.
EPA will only set treatment standards based on a technology that
meets the above criteria. Thus, the decision to classify a technology as
"unavailable" will have a direct impact on the treatment standard. If
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the best technology is unavailable, the treatment standard will be based
on the next best treatment technology determined to be available. To the
extent that the resulting treatment standards are less stringent, greater
concentrations of hazardous constituents in the treatment residuals could
be placed in land disposal units.
There also may be circumstances in which EPA concludes that for a
given waste none of the demonstrated treatment technologies are
"available" for purposes of establishing the 3004(m) treatment
performance standards. Subsequently, these wastes will be prohibited
from continued placement in or on the land unless managed in accordance
with applicable exemptions and variance provisions. The Agency is,
however, committed to establishing new treatment standards as soon as new
or improved treatment processes become "available."
(1) Proprietary or Patented Processes. If the demonstrated
treatment technology is a proprietary or patented process that is not
generally available, EPA will not consider the technology in its
determination of the treatment standards. EPA will consider proprietary
or patented processes available if it determines that the treatment
method can be purchased or licensed from the proprietor or is
commercially available treatment. The services of the commercial
facility offering this technology often can be purchased even if the
technology itself cannot be purchased.
(2) Substantial Treatment. To be considered "available," a
demonstrated treatment technology must "substantially diminish the
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toxicity" of the waste or "substantially reduce the likelihood of
migration of hazardous constituents" from the waste in accordance with
section 3004(m). By requiring that substantial treatment be achieved in
order to set a treatment standard, the statute ensures that all wastes
are adequately treated before being placed in or on the land and ensures
that the Agency does not require a treatment method that provides little
or no environmental benefit. Treatment will always be deemed substantial
if it results in nondetectable levels of the hazardous constituents of
concern. If nondetectable levels are not achieved, then a determination
of substantial treatment will be made on a case-by-case basis. This
approach is necessary because of the difficulty of establishing a
meaningful guideline that can be applied broadly to the many wastes and
technologies to be considered. EPA will consider the following factors
in an effort to evaluate whether a technology provides substantial
treatment on a case-by-case basis:
(a) Number and types of constituents treated;
(b) Performance (concentration of the constituents in the
treatment residuals); and
(c) Percent of constituents removed.
If none of the demonstrated treatment technologies achieve
substantial treatment of a waste, the Agency cannot establish treatment
standards for the constituents of concern in that waste.
1.2.3 Collection of Performance Data
Performance data on the demonstrated available technologies are
evaluated by the Agency to determine whether the data are representative
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of well-designed and well-operated treatment systems. Only data from
well-designed and well-operated systems are included in determining
BOAT. The data evaluation includes data already collected directly by
EPA and/or data provided by industry. In those instances where
additional data are needed to supplement existing information, EPA
collects additional data through a sampling and analysis program. The
principal elements of this data collection program are: (a) identifi-
cation of facilities for site visits, (b) engineering site visit,
(c) Sampling and Analysis Plan, (d) sampling visit, and (e) Onsite
Engineering Report.
(1) Identification of Facilities for Site Visits. To identify
facilities that generate and/or treat the waste of concern, EPA uses a
number of information sources. These include Stanford Research
Institute's Directory of Chemical Producers, EPA's Hazardous Waste Data
Management System (HWDMS), the 1986 Treatment, Storage, Disposal Facility
(TSDF) National Screening Survey, and EPA's Industry Studies Data Base.
In addition, EPA contacts trade associations to inform them that the
Agency is considering visits to facilities in their industry and to
solicit assistance in identifying facilities for EPA to consider in its
treatment sampling program.
After identifying facilities that treat the waste, EPA uses this
hierarchy to select sites for engineering visits:,(1) generators treating
single wastes on site; (2) generators treating multiple wastes together
on site; (3) commercial treatment, storage, and disposal facilities
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(TSDFs); and (4) EPA in-house treatment. This hierarchy is based on two
concepts: (1) to the extent possible, EPA should develop treatment
standards from data produced by treatment facilities handling only a
single waste, and (2) facilities that routinely treat a specific waste
have had the best opportunity to optimize design parameters. Although
excellent treatment can occur at many facilities that are not high in
this hierarchy, EPA has adopted this approach to avoid, when possible,
ambiguities related to the mixing of wastes before and during treatment.
When possible, the Agency will evaluate treatment technologies using
commercially operated systems. If performance data from properly
designed and operated commercial treatment methods for a particular waste
or a waste judged to be similar are not available, EPA may use data from
research facilities operations. Whenever research facility data are
used, EPA will explain why such data were used in the preamble and
background document and will request comments on the use of such data.
Although EPA's data bases provide information on treatment for
individual wastes, the data bases rarely provide data that support the
selection of one facility for sampling over another. In cases where
several treatment sites appear to fall into the same level of the
hierarchy, EPA selects sites for visits strictly on the basis of which
facility could most expeditiously be visited and later sampled if
justified by the engineering visit.
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(2) Engineering Site Visit. Once a treatment facility has been
selected, an engineering site visit is made to confirm that a candidate
for sampling meets EPA's criteria for a well-designed facility and to
ensure that the necessary sampling points can be accessed to determine
operating parameters and treatment effectiveness. During the visit, EPA
also confirms that the facility appears to be well operated, although the
actual operation of the treatment system during sampling is the basis for
EPA's decisions regarding proper operation of the treatment unit. In
general, the Agency considers a well-designed facility to be one that
contains the unit operations necessary to treat the various hazardous
constituents of the waste as well as to control other nonhazardous
materials in the waste that may affect treatment performance.
In addition to ensuring that a system is reasonably well designed,
the engineering visit examines whether the facility has a way to measure
the operating parameters that affect performance of the treatment system
during the waste treatment period. For example, EPA may choose not to
sample a treatment 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
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Program ("BOAT"), EPA/530-SW-87-011. In brief, the SAP discusses where
the Agency plans to sample, how the samples will be taken, the frequency
of sampling, the constituents to be analyzed and the method of analysis,
operational parameters to be obtained, and specific laboratory quality
control checks on the analytical results.
The Agency will generally produce a draft of the site-specific
Sampling and Analysis Plan within 2 to 3 weeks of the engineering visit.
The draft of the SAP is then sent to the plant for review and comment.
With few exceptions, the draft SAP should be a confirmation of data
collection activities discussed with the plant personnel during the
engineering site visit. EPA encourages plant personnel to recommend any
modifications to the SAP that they believe will improve the quality of
the data.
It is important to note that sampling of a plant by EPA does not mean
that the data will be used in the development of treatment standards for
BOAT. EPA's final decision on whether to use data from a sampled plant
depends on the actual analysis of the waste being treated and on the
operating conditions at the time of sampling. Although EPA would not
plan to sample a facility that was not ostensibly well-designed and
well-operated, there is no way to ensure that at the time of the sampling
the facility will not experience operating problems. Additionally, EPA
statistically compares its test data to suitable industry-provided data,
where available, in its determination of what data to use in developing
treatment standards. The methodology for comparing data is presented
later in this section.
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(Note: Facilities wishing to submit data for consideration in the
development of BOAT standards should, to the extent possible, provide
sampling information similar to that acquired by EPA. Such facilities
should review the Generic Quality Assurance Project Plan for the Land
Disposal Restriction Program ("BOAT"), which delineates all of the
quality control and quality assurance measures associated with sampling
and analysis. Quality assurance and quality control procedures are
summarized in Section 1.2.6 of this document.)
(4) Sampling Visit. The purpose of the sampling visit is to collect
samples that characterize the performance of the treatment system and to
document the operating conditions that existed during the waste treatment
period. At a minimum, the Agency attempts to collect sufficient samples
of the untreated waste and solid and liquid treatment residuals so that
variability in the treatment process can be accounted for in the
development of the treatment standards. To the extent practicable, and
within safety constraints, EPA or its contractors collect all samples and
ensure that chain-of-custody procedures are conducted so that the
integrity of the data is maintained.
In general, the samples collected during the sampling visit will have
already been specified in the SAP. In some instances, however, EPA will
not be able to collect all planned samples because of changes in the
facility operation or plant upsets; EPA will explain any such deviations
from the SAP in its follow-up Onsite Engineering Report.
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(5) Onsite Engineering Report. EPA summarizes all its data
collection activities and associated analytical results for testing at a
facility in a report referred to as the Onsite Engineering Report (OER).
This report characterizes the waste(s) treated, the treated residual
concentrations, the design and operating data, and all analytical results
including methods used and accuracy results. This report also describes
any deviations from EPA's suggested analytical methods for hazardous
wastes (Test Methods for Evaluating Solid Waste, SW-846, Third Edition,
November 1986).
After the Onsite Engineering Report is completed, the report is
submitted to the plant for review. This review provides the plant with a
final opportunity to claim any information contained in the report as
confidential. Following the review and incorporation of comments, as
appropriate, the report is made available to the public with the
exception of any material claimed as confidential by the plant.
1.2.4 Hazardous Constituents Considered and Selected for Regulation
(1) Development of BOAT List. The list of hazardous constituents
within the waste codes that are targeted for treatment is referred to by
the Agency as the BOAT constituent list. This list, provided as Table
1-1, is derived from the constituents presented in 40 CFR Part 261,
Appendix VII and Appendix VIII, as well as several ignitable constituents
used as the basis of listing wastes as F003 and F005. These sources
provide a comprehensive list of hazardous constituents specifically
regulated under RCRA. The BOAT list consists of those constituents that
can be analyzed using methods published in SW-846, Third Edition.
17
-------
1521a
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
IB
19
20.
21
90
C (.
23
24
25
26
27
28.
29
224
225
226
30.
227
31
214
32
Parameter
Volatiles
Acetone
Acetomtrile
Acrolein
Acrylomtri le
Benzene
Bromodichloromethane
Bromomethane
n-Butyl alcohol
CarDon tetrachloride
Carnon disulfide
Chlorobenzene
2-Chloro-l,3-butadiene
Ch iorod i bromomethane
Chloroethane
2-Chloroethyl vinyl ether
Chloroform
Chloromethane
3-Chloropropene
l,2-Dibromo-3-ch loropropane
1 ,2-Oibromoethane
Oibromomethane
Trans- 1,4-Dich loro-2-butene
Dichlorodif luoromethane
1 , 1-Dichloroethane
1 ,2-Oichloroethane
1 . 1-Dicnloroethylene
Trans-1 , 2-Dichloroethene
1 ,2 -3 ich loropropane
Trans -1 ,3-Dichloropropene
cis-1 .3-Dicnloropropene
1 ,4-0 loxane
2-Etnoxyethanol
Etnv'i acetate
Etn>"i Denzene
Etnyl cyanide
Eti>i ether
Eth> 1 metnacrylate
Ethylene oxide
lojjcmethjne
Cas no.
67-64-1
75-05-8
107-02-8
107-13-1
71-43-2
75-27-4
74-83-9
71-36-3
56-23-5
75-15-0
108-90-7
126-99-8
124-48-1
75-00-3
110-75-8
67-66-3
74-87-3
107-05-1
96-12-8
106-93-4
74-95-3
110-57-6
75-71-6
75-34-3
107-06-2
75-35-4
156-60-5
76-87-5
10061-02-6
10061-01-5
123-91-1
110-60-5
141-78-6
100-41-4
107-12-0
60-29"- 7
97-63-2
75-21-6
7-3-86-4
18
-------
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
Volatiles (continued)
Isobutyl alcohol
Methanol
Methyl ethyl ketone
Methyl isobutyl ketone
Methyl methacrylate
Methacrylonitrlle
Methylene chloride
2-Nitropropane
Pyrtdine
1,1,1 , 2-Tetrach loroethane
1,1,2, 2-Tetrach loroethane
Tetrachloroethene
Toluene
Tribromomethane
1,1, 1-Tr ichloroethane
1 , 1 , 2-Trichloroethane
Trichloroethene
Tr ich loromonof luorometnane
1,2,3-Trich loropropane
l,1.2-Trichloro-l,2,2-tnf luoro-
ethane
Vinyl chloride
1,2-Xylene
1,3-Xylene
1,4-Xylene
Semivolatiles
Acenaphthalene
Acenaphthene
Acetophenone
2-Acetylaminof luorene
4-Aminobiphenyl
Ant 1 me
Anthracene
Aramite
Benz ( a ) anthracene
Benzal chloride
Benzenethiol
Deleted
Benzo(a)pyrene
Cas no.
78-83-1
67-56-1
78-93-3
108-10-1
80-62-6
126-98-7
75-09-2
79-46-9
110-86-1
630-20-6
79-34-6
127-18-4
108-88-3
75-25-2
71-55-6
79-00-5
79-01-6
75-69-4
96-18-4
76-13-1
75-01-4
97-47-6
108-38-3
106-44-5
208-96-6
83-32-9
96-86-2
53-96-3
92-67-1
62-53-3
120-12-7
140-57-8
56-55-3
98-87-3
108-98-5
50-32-8
19
-------
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.
86.'
87.
88.
89.
90.
91.
92.
93.
94.
95.
96.
97.
98.
99.
100.
101
Parameter
Semi volat iles (continued)
8enzo( b ) f luoranthene
Benzofghi jperylene
Benzo(k)f luoranthene
p-Benzoquinone
8 i s ( 2-ch loroethoxy Jmethane
8is(2-chloroethyl)ether
Bis(2-chloroisopropyl)ether
Bis(2-ethylhexyl)phthalate
4-Bromophenyl phenyl ether
Butyl benzyl phthalate
2-sec-Butyl-4,6-dinitrophenol
p-Chloroani line
Chlorobenzilate
p-Chloro-m-cresol
2-Chloronaphthalene
2-Chlorophenol
3-Chloropropionitn le
Chrysene
ortho-Cresol
para-Cresol
Cyclohexanone
D i benz ( a , h ) ant hracene
Dibenzo(a,e)pyrene
Dibenzofa, i Jpyrene
m-Dichlorobenzene
o-Dichlorobenzene
p-Oichlorobenzene
3.3'-Dichlorobenzidine
2 , 4-0 i ch loropheno 1
2,6-Oichlorophenol
Oiethyl phthalate
3.3'-Dimethoxybenzidme
p-0 imethy lam i noazobenzene
3,3'-Dimethylbenzidine
2,4-Dimethylphenol
Dimethyl phthalate
Oi-n-butyl phthalate
1,4-Dinitrobenzene
4,6-Dimtro-o-cresol
2,4-Dinitrophenol
CAS no.
205-99-2
191-24-2
207-08-9
106-51-4
111-91-1
111-44-4
39638-32-9
117-81-7
101-55-3
85-68-7
88-85-7
106-47-8
510-15-6
59-50-7
91-58-7
95-57-8
542-76-7
218-01-9
95-48-7
106-44-5
108-94-1
53-70-3
192-65-4
189-55-9
541-73-1
95-50-1
106-46-7
91-94-1
120-83-2
87-65-0
84-66-2
119-90-4
60-11-7
119-93-7
105-67-9
131-11-3
84-74-2
100-25-4
534-52-1
51-28-5
20
-------
ISZlg
Table 1-1 (continued)
BOAT
reference
no
102.
103.
104.
105.
106.
219.
107.
108.
109.
110.
111.
112.
113.
114.
115.
116.
117.
118.
119.
120.
36.
121.
122.
123.
124.
125.
126.
127.
128.
129.
130.
131.
132.
133.
134.
135.
136.
137.
138.
Parameter
Semi volat lies (continued)
2,4-Dinitrotoluene
2,6-Dmitrotoluene
Di-n-octyl phthalate
Di-n-propylnitrosamine
Diphenylamine
D i pheny 1 n 1 1 rosam i ne
1,2-Diphenyl hydraz i ne
Fluoranthene
Fluorene
Hexach lorobenzene
Hexach lorobutad lene
Hexachlorocyc lopentadiene
Hexach loroethane
Hexach lorophene
Hexach loropropene
lndeno(l,2,3-cd)pyrene
Isosafrole
Methapyrilene
3-Methylcholanthrene
4,4'-Methylenebis
(2-chloroaniline)
Methyl methanesulfonate
Naphthalene
1 ,4-Naphthoqinnone
1-Naphthylamine
2-Naphthylamine
p-Nitroani line
Nitrobenzene
4-Nitrophenol
N-Nitrosodi-n-butylamine
N-Nitrosodiethylamine
N-Nitrosodimethylamine
N-N it rosomet hy let hylamine
N-Nitrosomorphol ine
N-Nitrosopipendine
n-Nitrosopyrrol idine
5-Nitro-o-toluidine
Pent ach lorobenzene
Pentach loroethane
Pentachloronltrobenzene
CAS no.
121-14-2
606-20-2
117-84-0
621-64-7
122-39-4
66-30-6
122-66-7
206-44-0
86-73-7
118-74-1
87-68-3
77-47-4
67-72-1
70-30-4
1888-71-7
193-39-5
120-58-1
91-80-5
56-49-5
101-14-4
66-27-3
91-20-3
130-15-4
134-32-7
91-59-8
100-01-6
98-95-3
100-02-7
924-16-3
55-18-5
62-75-9
10595-95-6
59-89-2
100-75-4
930-55-2
99-65-8
608-93-5
76-01-7
82-68-8
21
-------
1521g
Table 1-1 (continued)
BOAT
reference
no.
139.
140.
141.
142.
220.
143.
144.
145.
146.
147.
148.
149.
150.
151.
152.
153.
154.
155.
156.
157.
158.
159.
221.
160.
161.
162.
163.
164.
165.
166.
167.
168.
169.
170.
171.
Parameter
Semivolatiles (continued)
Pentach loropheno 1
Phenacetin
Phenanthrene
Phenol
Phthalic anhydride
2-Picoline
Pronamide
Pyrene
Resorcinol
Safrole
1 , 2 , 4 , 5-Tetrach lorobenzene
2,3,4, 6-Tet rach loropheno 1
1, 2. 4-Tnch lorobenzene
2, 4, 5-Trich loropheno 1
2,4,6-Trichlorophenol
Tr i s ( 2 , 3-d i bromopropy 1 )
phosphate
Metals
Antimony
Arsenic
Barium
Beryl hum
Cadmium
Chromium (total)
Chromium (hexavalent)
Copper
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Inorganics
Cyanide
Fluoride
Sulfide
CAS no.
87-86-5
62-44-2
85-01-8
108-95-2
85-44-9
109-06-8
23950-58-5
129-00-0
108-46-3
94-59-7
95-94-3
58-90-2
120-82-1
95-95-4
88-06-2
126-72-7
7440-36-0
7440-38-2
7440-39-3
7440-41-7
7440-43-9
7440-47-32
-
7440-50-8
7439-92-1
7439-97-6
7440-02-0
7782-49-2
7440-22-4
7440-28-0
7440-62-2
7440-66-6
57-12-5
16964-48-8
8496-25-8
-------
1521g
Table 1-1 (continued)
BOAT
reference
no
172.
173.
174.
175.
176.
177.
178.
179.
180.
181.
182.
183.
184.
185.
186.
187.
188.
189.
190.
191.
192.
193.
194.
195.
196.
197.
196.
199.
200.
201.
202.
Parameter
Oraanochlorine pesticides
Aldrin
alpha-BHC
beta-BHC
delta-BHC
ganroa-BHC
Chlordane
ODD
DDE
DDT
Dieldnn
Endosulfan I
Endosulfan II
Endrin
Endnn aldehyde
Heptachlor
Heptachlor epoxide
Isodrin
Kepone
Methoxyclor
Toxaphene
Phenoxvacet ic acid herbicides
2,4-Dichlorophenoxyacetic acid
Silvex
2,4,5-T
Oroanoohosohorous insecticides
Disulfoton
Famphur
Methyl pa rat hi on
Parathion
Phorate
PCBs
Aroclor 1016
Aroclor 1221
Aroclor 1232
CAS no.
309-00-2
319-84-6
319-85-7
319-86-8
58-89-9
57-74-9
72-54-8
72-55-9
50-29-3
60-57-1
939-98-8
33213-6-5
72-20-8
7421-93-4
76-44-8
1024-57-3
465-73-6
143-50-0
72-43-5
8001-35-2
94-75-7
93-72-1
93-76-5
298-04-4
52-85-7
298-00-0
56-38-2
298-02-2
12674-11-2
11104-28-2
11141-16-5
23
-------
1521g
Table 1-1 (continued)
BOAT
reference Parameter CAS no.
no.
PCBs (continued)
203. Aroclor 1242 53469-21-9
204. Aroclor 1248 12672-29-6
205. Aroclor 1254 11097-69-1
206. Aroclor 1260 11096-82-5
Dioxins and furans
207. Hexachlorodibenzo-p-dioxins
208. Hexachlorodibenzofurans
209. Pentachlorodibenzo-p-dioxins
210. Pentachlorodibenzofurans
211. Tetrachlorodibenzo-p-dioxins
212. Tetrachlorodlbenzofurans
213. 2,3,7,8-Tetrachlorodibenzo-p-dioxm 1746-01-6
24
-------
The initial BOAT constituent list was published in EPA's Generic
Quality Assurance Project Plan, March 1987 (EPA/530-SW-87-011).
Additional constituents will be added to the BOAT constituent list as
additional key constituents are identified for specific waste codes or as
new analytical methods are developed for hazardous constituents. For
example, since the list was published in March 1987, eighteen additional
constituents (hexavalent chromium, xylene (all three isomers), benzal
chloride, phthalic anhydride, ethylene oxide, acetone, n-butyl alcohol,
2-ethoxyethanol, ethyl acetate, ethyl benzene, ethyl ether, methanol,
methyl isobutyl ketone, 2-nitropropane, l,l,2-trichloro-l,2,2-
trifluoroethane, and cyclohexanone) have been added to the list.
Chemicals are listed in Appendix VIII if they are shown in scientific
studies to have toxic, carcinogenic, mutagenic, or teratogenic effects on
humans or other life-forms, and they include such substances as those
identified by the Agency's Carcinogen Assessment Group as being
carcinogenic. Including a constituent in Appendix VIII means that the
constituent can be cited as a basis for listing toxic wastes.
Although Appendix VII, Appendix VIII, and the F003 and F005
ignitables provide a comprehensive list of RCRA-regulated hazardous
constituents, not all of the constituents can be analyzed in a complex
waste matrix. Therefore, constituents that could not be readily analyzed
in an unknown waste matrix were not included on the initial BOAT list.
As mentioned above, however, the BOAT constituent list is a continuously
growing list that does not preclude the addition of new constituents when
analytical methods are developed.
25
-------
There are 5 major reasons that constituents were not included on the
BOAT constituent list:
(a) Constituents are unstable. Based on their chemical structure,
some constituents will either decompose in water or will
ionize. For example, maleic anhydride will form maleic acid
when it comes in contact with water and copper cyanide will
ionize to form copper and cyanide ions. However, EPA may choose
to regulate the decomposition or ionization products.
(b) EPA-approved or verified analytical methods are not available.
Many constituents, such as 1,3,5-trinitrobenzene, are not
measured adequately or even detected using any of EPA's
analytical methods published in SW-846 Third Edition.
(c) The constituent is a member of a chemical group designated in
Appendix VIII as not otherwise specified (N.O.S.). Constituents
listed as N.O.S., such as chlorinated phenols, are a generic
group of some types of chemicals for which a single analytical
procedure is not available. The individual members of each such
group need to be listed to determine whether the constituents
can be analyzed. For each N.O.S. group, all those constituents
that can be readily analyzed are included in the BOAT
constituents list.
(d) Available analytical procedures are not appropriate for a
complex waste matrix. Some compounds, such as auramine, can be
analyzed as a pure constituent. However, in the presence of
other constituents, the recommended analytical method does not
positively identify the constituent. The use of high pressure
liquid chromotography (HPLC) presupposes a high expectation of
finding the specific constituents of interest. In using this
procedure to screen samples, protocols would have to be
developed on a case-specific basis to verify the identity of
constituents present in the samples. Therefore, HPLC is not an
appropriate analytical procedure for complex samples containing
unkown constituents.
(e) Standards for analytical instrument calibration are not
commercially available. For several constituents, such as
benz(c)acridine, commercially available standards of a
"reasonably" pure grade are not available. The unavailability
of a standard was determined by a review of catalogs from
specialty chemical manufacturers.
26
-------
Two constituents (fluoride and sulfide) are not specifically included
in Appendices VII and VIII; however, these compounds are included on the
BOAT list as indicator constituents for compounds from Appendices VII and
VIII such as hydrogen fluoride and hydrogen sulfide, which ionize in
water.
The BOAT constituent list presented in Table 1-1 is divided into the
following nine groups:
Volatile organics
Semivolatile organics
Metals
Other inorganics
Organochlorine pesticides
Phenoxyacetic acid herbicides
Organophosphorous insecticides
PCBs
Dioxins and furans
The constituents were placed in these categories based on their chemical
properties. The constituents in each group are expected to behave
similarily during treatment and are also analyzed, with the exception of
the metals and inorganics, by using the same analytical methods.
(2) Constituent Selection Analysis. The constituents that the
Agency selects for regulation in each treatability group are, in general,
those found in the untreated wastes at treatable concentrations. For
certain waste codes, the target list for the untreated waste may have
been shortened (relative to analyses performed to test treatment
technologies) because of the extreme unlikelihood of the constituent
being present.
27
-------
In selecting constituents for regulation, the first step is to
summarize all the constituents that were found in the untreated waste at
treatable concentrations. This process involves the use of the
statistical analysis of variance (ANOVA) test, described in Section
1.2.6, to determine if constituent reductions were significant. The
Agency interprets a significant reduction in concentration as evidence
that the technology actually "treats" the waste.
There are some instances where EPA may regulate constituents that are
not found in the untreated waste but are detected in the treated
residual. This is generally the case where presence of the constituents
in the untreated waste interferes with the quantification of the
constituent of concern. In such instances, the detection levels of the
constituent are relatively high, resulting in a finding of "not detected"
when, in fact, the constituent is present in the waste.
After determining which of the constituents in the untreated waste
are present at treatable concentrations, EPA develops a list of potential
constituents for regulation. The Agency then reviews this list to
determine if any of these constituents can be excluded from regulation
because they would be controlled by regulation of other constituents in
the list.
EPA performs this indicator analysis for two reasons: (1) it reduces
the analytical cost burdens on the treater and (2) it facilitates
implementation of the compliance and enforcement program. EPA's
rationale for selection of regulated constituents for this waste code is
presented in Section 5 of this background document.
28
-------
(3) Calculation of Standards. The final step in the calculation of
the BOAT treatment standard is the multiplication of the average
treatment value by a factor referred to by the Agency as the variability
factor. This calculation takes into account that even well-designed and
well-operated treatment systems will experience some fluctuations in
performance. EPA expects that fluctuations will result from inherent
mechanical limitations in treatment control systems, collection of
treated samples, and analysis of these samples. All of the above
fluctuations can be expected to occur at well-designed and well-operated
treatment facilities. Therefore, setting treatment standards utilizing a
variability factor should be viewed not as a relaxing of 3004(m)
requirements, but rather as a function of the normal variability of the
treatment processes. A treatment facility will have to be designed to
meet the mean achievable treatment performance level to ensure that the
performance levels remain within the limits of the treatment standard.
The Agency calculates a variability factor for each constituent of
concern within a waste treatability group using the statistical
calculation presented in Appendix A. The equation for calculating the
variability factor is the same as that used by EPA for the development of
numerous regulations in the Effluent Guidelines Program under the Clean
Water Act. The variability factor establishes the instantaneous maximum
based on the 99th percentile value.
There is an additional step in the calculation of the treatment
standards in those instances where the ANOVA analysis shows that more
29
-------
than one technology achieves a level of performance that represents
BOAT. In such instances, the BOAT treatment standard is calculated by
first averaging the mean performance value for each technology for each
constituent of concern and then multiplying that value by the highest
variability factor among the technologies considered. This procedure
ensures that all the BOAT technologies used as the basis for the
standards will achieve full compliance.
1.2.5 Compliance with Performance Standards
All the treatment standards reflect performance achieved by the Best
Demonstrated Available Technology (BOAT). As such, compliance with these
standards only requires that the treatment level be achieved prior to
land disposal. It does not require the use of any particular treatment
technology. While dilution of the waste as a means to comply with the
standard is prohibited, wastes that are generated in such a way as to
naturally meet the standard can be land disposed without treatment. With
the exception of treatment standards that prohibit land disposal, all
treatment standards proposed are expressed as a concentration level.
EPA has used both total constituent concentration and TCLP analyses
of the treated waste as a measure of technology performance. EPA's
rationale for when each of these analytical tests is used is explained in
the following discussion.
For all organic constituents, EPA is basing the treatment standards
on the total constituent concentration found in the treated waste. EPA
based its decision on the fact that technologies exist to destroy the
30
-------
various organics compounds. Accordingly, the best measure of performance
would be the extent to which the various organic compounds have been
destroyed or the total amount of constituent remaining after treatment.
(NOTE: EPA's land disposal restrictions for solvent waste codes
F001-F005 (51 FR 40572) uses the TCLP value as a measure of performance.
At the time that EPA promulgated the treatment standards for F001-F005,
useful data were not available on total constituent concentrations in
treated residuals and, as a result, the TCLP data were considered to be
the best measure of performance.)
For all metal constituents, EPA is using both total constituent
concentration and/or the TCLP as the basis for treatment standards. The
total constituent concentration is being used when the technology basis
includes a metal recovery operation. The underlying principle of metal
recovery is the reduction of the amount of metal in a waste by separating
the metal for recovery; therefore, total constituent concentration in the
treated residual is an important measure of performance for this
technology. Additionally, EPA also believes that it is important that
any remaining metal in a treated residual waste not be in a state that is
easily Teachable; accordingly, EPA is also using the TCLP as a measure of
performance. It is important to note that for wastes for which treatment
standards are based on a metal recovery process, the facility has to
comply with both the total constituent concentration and the TCLP prior
to land disposal.
31
-------
In cases where treatment standards for metals are not based on
recovery techniques but rather on stabilization, EPA is using only the
TCLP as a measure of performance. The Agency's rationale is that
stabilization is not meant to reduce the concentration of metal in a
waste but only to chemically minimize the ability of the metal to leach.
1.2.6 Identification of BOAT
(1) Screening of Treatment Data. This section explains how the
Agency determines which of the treatment technologies represent treatment
by BOAT. The first activity is to screen the treatment performance data
from each of the demonstrated and available technologies according to the
following criteria:
(a) Design and operating data associated with the treatment data
must reflect a well-designed, well-operated system for each
treatment data point. (The specific design and operating
parameters for each demonstrated technology for this waste code
are discussed in Section 3.2 of this document.)
(b) Sufficient QA/QC data must be available to determine the true
values of the data from the treated waste. This screening
criterion involves adjustment of treated data to take into
account that the type value may be different from the measured
value. This discrepancy generally is caused by other
constituents in the waste that can mask results or otherwise
interfere with the analysis of the constituent of concern.
(c) The measure of performance must be consistent with EPA's
approach to evaluating treatment by type of constituents (e.g.,
total concentration data for organics, and total concentration
and TCLP for metals in the leachate from the residual).
In the absence of data needed to perform the screening analysis, EPA
will make decisions on a case-by-case basis of wKether 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 are provided in Section 4 of this background document.
(2) Comparison of Treatment Data. In cases in which EPA has
treatment data from more than one technology following the screening
activity, EPA uses the statistical method known as analysis of variance
(ANOVA) to determine if one technology performs significantly better.
This statistical method (summarized in Appendix A) provides a measure of
the differences between two data sets. If EPA finds that one technology
performs significantly better (i.e., the data sets are not homogeneous),
BOAT treatment standards are the level of performance achieved by the
best technology multiplied by the corresponding variability factor for
each regulated constituent.
If the differences in the data sets are not statistically
significant, the data sets are said to be homogeneous. Specifically, EPA
uses the analysis of variance to determine whether BOAT represents a
level of performance achieved by only one technology or represents a
level of performance achieved by more than one (or all) of the
technologies. If the Agency finds that the levels of performance for one
or more technologies are not statistically different, EPA averages the
performance values achieved by each technology and then multiplies this
value by the largest variability factor associated with any of the
33
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acceptable technologies. A detailed discussion of the treatment
selection method and an example of how EPA chooses BOAT from multiple
treatment systems is provided in Section A-l.
(3) Quality Assurance/Quality Control. This section presents the
principal quality assurance/quality control (QA/QC) procedures employed
in screening and adjusting the data to be used in the calculation of
treatment standards. Additional QA/QC procedures used in collecting and
screening data for the BOAT program are presented in EPA's Generic
Quality Assurance Project Plan for Land Disposal Restrictions Program
("BOAT") (EPA/530-SW-87-001, March 1987).
To calculate the treatment standards for the Land Disposal
Restriction Rules, it is first necessary to determine the recovery value
for each constituent (the amount of constituent recovered after spiking,
which is the addition of a known amount of the constituent, minus the
initial concentration in the samples divided by the amount added) for a
spike of the treated residual. Once the recovery value is determined,
the following procedures are used to select the appropriate percent
recovery value to adjust the analytical data:
(a) If duplicate spike recovery values are available for the
constituent of interest, the data are adjusted by the lowest
available percent recovery value (i.e., the value that will
yield the most conservative estimate of treatment achieved).
However, if a spike recovery value of less than 20 percent is
reported for a specific constituent, the data are not used to
set treatment standards because the Agency does not have
sufficient confidence in the reported value to set a national
standard.
34
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(b) If data are not available for a specific constituent but are
available for an isomer, then the spike recovery data are
transferred from the isomer and the data are adjusted using the
percent recovery selected according to the procedure described
in (a) above.
(c) If data are not available for a specific constituent but are
available for a similar class of constituents (e.g., volatile
organics, acid-extractable semivolatiles), then spike recovery
data available for this class of constituents are transferred.
All spike recovery values greater than or equal to 20 percent
for a spiked sample are averaged and the constituent
concentration is adjusted by the average recovery value. If
spiked recovery data are available for more than one sample, the
average is calculated for each sample and the data are adjusted
by the lowest average value.
(d) If matrix spike recovery data are not available for a set of
data to be used to calculate treatment standards, then matrix
spike recovery data are transferred from a waste that the Agency
believes is a similar matrix (e.g., if the data are for an ash
from incineration, then data from other incinerator ashes could
be used). While EPA recognizes that transfer of matrix spike
recovery data from a similar waste is not an exact analysis,
this is considered the best approach for adjusting the data to
account for the fact that most analyses do not result in
extraction of 100 percent of the constituent. In assessing the
recovery data to be transferred, the procedures outlined in (a),
(b), and (c) above are followed.
The analytical procedures employed to generate the data used to
calculate the treatment standards are listed in Appendix B of this
document. In cases where alternatives or equivalent procedures and/or
equipment are allowed in EPA's SW-846, Third Edition (November 1986)
methods, the specific procedures and equipment used are also documented
in this Appendix. In addition, any deviations from the SW-846, Third
Edition, methods used to analyze the specific waste matrices are
documented. It is important to note that the Agency will use the methods
and procedures delineated in Appendix B to enforce the treatment
35
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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:
(a) All of the residues from treating the original listed wastes are
likewise considered to be the listed waste by virtue of the
derived-from rule contained in 40 CFR Part 261.3(c)(2). (This
point is discussed more fully in (2) below.) Consequently, all
of the wastes generated in the course of treatment would be
prohibited from land disposal unless they satisfy the treatment
standard or meet one of the exceptions to the prohibition.
(b) The Agency's proposed treatment standards generally contain a
concentration level for wastewaters and a concentration level
for nonwastewaters. The treatment standards apply to all of the
wastes generated in treating the original prohibited waste.
Thus, all solids generated from treating these wastes would have
36
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to meet the treatment standard for nonwastewaters. All
derived-from wastes meeting the Agency definition of wastewater
(less than 1 percent TOC and less than 1 percent total
filterable solids) would have to meet the treatment standard for
wastewaters. EPA wishes to make clear that this approach is not
meant to allow partial treatment in order to comply with the
applicable standard.
(c) The Agency has not performed tests, in all cases, on every waste
that can result from every part of the treatment train.
However, the Agency's treatment standards are based on treatment
of the most concentrated form of the waste. Consequently, the
Agency believes that the less concentrated wastes generated in
the course of treatment will also be able to be treated to meet
this value.
(2) Mixtures and Other Derived-From Residues. There is a further
question as to the applicability of the BOAT treatment standards to
residues generated not from treating the waste (as discussed above), but
from other types of management. Examples are contaminated soil or
leachate that is derived from managing the waste. In these cases, the
mixture is still deemed to be the listed waste, either because of the
derived-from rule (40 CFR Part 261.3(c)(2)(i)) or the mixture rule
(40 CFR Part 261.3(a)(2)(iii) and (iv) or because the listed waste is
contained in the matrix (see, for example, 40 CFR Part 261.33(d)). The
prohibition for the particular listed waste consequently applies to this
type of waste.
The Agency believes that the majority of these types of residues can
meet the treatment standards for the underlying listed wastes (with the
possible exception of contaminated soil and debris for which the Agency
is currently investigating whether it is appropriate to establish a
separate treatability subcategorization). For the most part, these
37
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residues will be less concentrated than the original listed waste. The
Agency's treatment standards also make a generous allowance for process
variability by assuming that all treatability values used to establish
the standard are lognormally distributed. The waste also might be
amenable to a relatively nonvariable form of treatment technology such as
incineration. Finally, and perhaps most important, the rules contain a
treatability variance that allows a petitioner to demonstrate that its
waste cannot be treated to the level specified in the rule (40 CFR Part
268.44(a). This provision provides a safety valve that allows persons
with unusual waste matrices to demonstrate the appropriateness of a
different standard. The Agency, to date, has not received any petitions
under this provision (for example, for residues contaminated with a
prohibited solvent waste), indicating, in the Agency's view, that the
existing standards are generally achievable.
(3) Residues from Managing Listed Wastes or that Contain Listed
Wastes. The Agency has been asked if and when residues from
managing hazardous wastes, such as leachate and contaminated ground
water, become subject to the land disposal prohibitions. Although the
Agency believes this question to be settled by existing rules and
interpretative statements, to avoid any possible confusion the Agency
will address the question again.
Residues from managing First Third wastes, li§ted California List
wastes, and spent solvent and dioxin wastes are all considered to be
subject to the prohibitions for the underlying hazardous waste. Residues
38
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from managing California List wastes likewise are subject to the
California List prohibitions when the residues themselves exhibit a
characteristic of hazardous waste. This determination stems directly
from the derived-from rule in 40 CFR Part 261.3(c)(2) or in some cases
from the fact that the waste is mixed with or otherwise contains the
listed waste. The underlying principle stated in all of these provisions
is that listed wastes remain listed until delisted.
The Agency's historic practice in processing delisting petitions
addressing mixing residuals has been to consider them to be the listed
waste and to require that delisting petitioners address all constituents
for which the derived-from waste (or other mixed waste) was listed. The
language in 40 CFR Part 260.22(b) states that mixtures or derived-from
residues can be delisted provided a delisting petitioner makes a
demonstration identical to that which a delisting petitioner would make
for the underlying waste. These residues consequently are treated as the
underlying listed waste for delisting purposes. The statute likewise
takes this position, indicating that soil and debris that are
contaminated with listed spent solvents or dioxin wastes are subject to
the prohibition for these wastes even though these wastes are not the
originally generated waste, but rather are a residual from management
(RCRA section 3004(e)(3)). It is EPA's view that all such residues are
covered by the existing prohibitions and treatment standards for the
listed hazardous waste that these residues contain and from which they
are derived.
39
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1.2.8 Transfer of Treatment Standards
EPA is proposing some treatment standards that are not based on
testing of the treatment technology of the specific waste subject to the
treatment standard. Instead, the Agency has determined that the
constituents present in the subject waste can be treated to the same
performance levels as those observed in other wastes for which EPA has
previously developed treatment data. EPA believes that transferring
treatment performance for use in establishing treatment standards for
untested wastes is valid technically in cases where the untested wastes
are generated from similar industries, similar processing steps, or have
similar waste characteristics affecting performance and treatment
selection. Transfer of treatment standards to similar wastes or wastes
from similar processing steps requires little formal analysis. However,
in the case where only the industry is similar, EPA more closely examines
the waste characteristics prior to concluding that the untested waste
constituents can be treated to levels associated with tested wastes.
EPA undertakes a two-step analysis when determining whether wastes
generated by different processes within a single industry can be treated
to the same level of performance. First, EPA reviews the available waste
characteristic data to identify those parameters that are expected to
affect treatment selection. EPA has identified some of the most
important constituents and other parameters needed to select the
treatment technology appropriate for a given waste. A detailed
discussion of each analysis, including how each parameter was selected
for each waste, can be found in the background document for each waste.
40
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Second, when an individual analysis suggests that an untested waste
can be treated with the same technology as a waste for which treatment
performance data are already available, EPA analyzes a more detailed list
of constituents that represent some of the most important waste
characteristics that the Agency believes will affect the performance of
the technology. By examining and comparing these characteristics, the
Agency determines whether the untested wastes will achieve the same level
of treatment as the tested waste. Where the Agency determines that the
untested waste is easier to treat than the tested waste, the treatment
standards can be transferred. A detailed discussion of this transfer
process for each waste can be found in later sections of this document.
1.3 Variance from the BOAT Treatment Standard
The Agency recognizes that there may exist unique wastes that cannot
be treated to the level specified as the treatment standard. In such a
case, a generator or owner/operator may submit a petition to the
Administrator requesting a variance from the treatment standard. A
particular waste may be significantly different from the wastes
considered in establishing treatability groups because the waste contains
a more complex matrix that makes it more difficult to treat. For
example, complex mixtures may be formed when a restricted waste is mixed
with other waste streams by spills or other forms of inadvertent mixing.
As a result, the treatability of the restricted waste may be altered such
that it cannot meet the applicable treatment standard.
Variance petitions must demonstrate that the treatment standard
established for a given waste cannot be met. This demonstration can be
41
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made by showing that attempts to treat the waste by available
technologies were not successful or by performing appropriate analyses of
the waste, including waste characteristics affecting performance, which
demonstrate that the waste cannot be treated to the specified levels.
Variances will not be granted based solely on a showing that adequate
BOAT treatment capacity is unavailable. (Such demonstrations can be made
according to the provisions in Part 268.5 of RCRA for case-by-case
extensions of the effective date.) The Agency will consider granting
generic petitions provided that representative data are submitted to
support a variance for each facility covered by the petition.
Petitioners should submit at least one copy to:
The Administrator
U.S. Environmental Protection Agency
401 M Street, S.W.
Washington, DC 20460
An additional copy marked "Treatability Variance" should be submitted
to:
Chief, Waste Treatment Branch
Office of Solid Waste (WH-565)
U.S. Environmental Protection Agency
401 M Street, S.W.
Washington, DC 20460
Petitions containing confidential information should be sent with
only the inner envelope marked "Treatability Variance" and "Confidential
Business Information" and with the contents marked in accordance with the
requirements of 40 CFR Part 2 (41 FR 36902, September 1, 1976, amended by
43 FR 4000).
The petition should contain the following information:
42
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(1) The petitioner's name and address.
(2) A statement of the petitioner's interest in the proposed action.
(3) The name, address, and EPA identification number of the facility
generating the waste, and the name and telephone number of the
plant contact.
(4) The process(es) and feed materials generating the waste and an
assessment of whether such process(es) or feed materials may
produce a waste that is not covered by the demonstration.
(5) A description of the waste sufficient for comparison with the
waste considered by the Agency in developing BOAT, and an
estimate of the average and maximum monthly and annual
quantities of waste covered by the demonstration. (Note: The
petitioner should consult the appropriate BOAT background
document for determining the characteristics of the wastes
considered in developing treatment standards.)
(6) If the waste has been treated, a description of the system used
for treating the waste, including the process design and
operating conditions. The petition should include the reasons
the treatment standards are not achievable and/or why the
petitioner believes the standards are based on inappropriate
technology for treating the waste. (Note: The petitioner should
refer to the BOAT background document as guidance for
determining the design and operating parameters that the Agency
used in developing treatment standards.)
(7) A description of the alternative treatment systems examined by
the petitioner (if any); a description of the treatment system
deemed appropriate by the petitioner for the waste in question;
and, as appropriate, the concentrations in the treatment
residual or extract of the treatment residual (i.e., using the
TCLP where appropriate for stabilized metals) that can be
achieved by applying such treatment to the waste.
(8) A description of those parameters affecting treatment selection
and waste characteristics that affect performance, including
results of all analyses. (See Section 3.0 for a discussion of
waste characteristics affecting performance that the Agency has
identified for the technology representing BOAT.)
(9) The dates of the sampling and testing.
(10) A description of the methodologies and equipment used to obtain
representative samples.
43
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(11) A description of the sample handling and preparation techniques,
including techniques used for extraction, containerization, and
preservation of the samples.
(12) A description of analytical procedures used including QA/QC
methods.
After receiving a petition for a variance, the Administrator may
request any additional information or waste samples that may be required
to evaluate and process the petition. Additionally, all petitioners must
certify that the information provided to the Agency is accurate under
40 CFR Part 268.4(b).
In determining whether a variance will be granted, the Agency will
first look at the design and operation of the treatment system being
used. If EPA determines that the technology and operation are consistent
with BOAT, the Agency will evaluate the waste to determine if the waste
matrix and/or physical parameters are such that the BOAT treatment
standards reflect treatment of this waste. Essentially, this latter
analysis will concern the parameters affecting treatment selection and
waste characteristics affecting performance parameters.
In cases where BOAT is based on more than one technology, the
petitioner will need to demonstrate that the treatment standard cannot be
met using any of the technologies, or that none of the technologies are
appropriate for treatment of the waste. After the Agency has made a
determination on the petition, the Agency's findings will be published in
the Federal Register, followed by a 30-day period for public comment.
44
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After review of the public comments, EPA will publish its final
determination in the Federal Register as an amendment to the treatment
standards in 40 CFR Part 268, Subpart D.
45
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2. INDUSTRIES AFFECTED .AND WASTE CHARACTERIZATION
This section presents a description of the industries affected by
land disposal restrictions for this waste, the process generating the
waste, and a summary of available waste characterization data for the
waste. As discussed in Section 1, those wastes listed in 40 CFR
Section 261.32 are subject to the land disposal restriction provisions of
HSWA. Within that industry-specific listing of hazardous wastes are the
following three wastes generated by the chlorine industry:
K071: Brine purification muds from the mercury cell process in
chlorine production, where separately prepurified brine is not
used.
K073: Chlorinated hydrocarbon waste from the purification step of
the diaphragm cell process using graphite anodes in chlorine
production.
K106: Wastewater treatment sludge from the mercury cell process in
chlorine production.
The Agency has determined that the listed waste K071 represents a
separate waste treatability group based on the physical and chemical
characteristics of the waste (see Section 1 for a discussion of waste
treatability groups). As a result, EPA has examined for this waste alone
the source of the waste, applicable technologies, and treatment
performance attainable.
The listed waste K106 represents a separate waste treatability group
and will be discussed in a separate background document. The listed
waste K073 is no longer generated in chlorine production.
46
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2.1 Industries Affected and Process Description
Chlorine is produced primarily from the electrolytic decomposition of
either sodium chloride or potassium chloride, from which the coproducts
are sodium hydroxide (caustic soda) or potassium hydroxide. All of the
caustic soda and potassium hydroxide and over 90 percent of the chlorine
produced in the U.S. are made by the electrolytic decomposition of sodium
chloride or potassium chloride. Chlorine is also produced from the
nonelectrolytic oxidation of hydrochloric acid (HC1), from the production
of sodium metal, and from the electrolytic production of magnesium metal
from molten magnesium chloride.
Three types of electrolytic cells are in commercial use for the
production of alkalies and chlorine: the mercury cell, the diaphragm
cell, and the membrane cell. The listed waste K071 is generated in
chlorine production by the mercury cell process. The Agency estimates
that there are 20 facilities that produce chlorine by the mercury cell
process and may generate K071 waste. The locations of these facilities
are provided in Table 2-1, listed by State, and in Table 2-2, listed by
EPA Region. Chlorine producers fall under SIC Code 2812, Alkalies and
Chlorine. Six of these facilities are believed to use prepurified salt
in the brine makeup step; therefore, while they do not generate K071
waste now, they may do so in the future. The number of these facilities,
by State and by EPA Region, are identified in the tables by the numbers
in parentheses.
47
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0341g
Table 2-1 Number of Producers of Chlorine Using the
Mercury Cell Process Listed by State
Number of
State producers3
Alabama (IV)
Delaware (III)
Georgia (IV)
Kentucky (IV)
Louisiana (VI)
Maine (I)
New York (II)
North Carolina (IV)
Ohio (V)
Tennessee (IV)
Texas (VI)
Washington (X)
West Virginia (III)
Wisconsin (V)
3
1
1 (1)
1
1 (1)
1
1 (1)
1
1
1
0 (1)
1
0 (2)
1
Total 14(6)
a Numbers in parentheses are numbers of additional facilities that use
prepunfied salt in the process, and therefore do not currently
generate K.071 waste.
Reference: SRI 1987.
48
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034 Ig
Table 2-2 Number of Producers of Chlorine Using
the Mercury Cell Process Listed by EPA Region
Number of
EPA Region producers3
1
II
III
IV
V
VI
X
1
1 (1)
1 (2)
7 (1)
2
1 (2)
1
Total 14 (6)
a Numbers in parentheses are numbers of additional facilities
that use prepurified salt in the process and therefore do
not currently generate K071 waste.
Reference: SRI 1987.
49
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In chlorine production by the mercury cell process, a saturated salt
brine solution is prepared by dissolving sodium chloride, usually in the
form of rock salt, in the depleted brine solution recycled from the
mercury cells. Brine purification removes impurities present in the raw
salt dissolved in the brine saturation step. In brine purification,
hydroxide and carbonate are added to remove calcium, magnesium, and iron
impurities by precipitation. In a separate treatment step, calcium
chloride is sometimes used to remove sulfate, also by precipitation.
After clarification and filtration, the purified saturated brine is fed
to the mercury cells, where electrolytic decomposition into sodium and
chlorine occurs. The solids removed in the clarifier and by the brine
filters are brine purification muds (a K071 nonwastewater).
A second source of K071 waste (nonwastewater) from this process is
insoluble materials present in the salt used in the brine saturation
step. These solids settle at the bottom of the brine saturator tank and
must be removed periodically. Solids removed from the saturator are also
brine purification muds, but are more commonly referred to as saturator
insolubles. This waste is significantly different in particle size,
water content, and mercury content from the brine purification muds
generated in the brine purification clarifier, and thus requires the use
of a different treatment system for acid leaching treatment.
50
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2.2 Haste Characterization
This section includes all waste characterization data available to
the Agency for K071 waste. The major constituents that comprise the two
waste forms of brine purification muds and their approximate
concentrations are presented in Tables 2-3 and 2-4. The ranges of
concentration of BOAT constituents detected in the wastes are presented
in Table 2-5. Appendix D presents other EPA data on K071 waste that in
the Agency's judgment represent the characterization of waste that has
been mixed with another listed waste and/or has undergone some treatment
before land disposal.
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0341g
Table 2-3 Major Constituent Analysis of Untreated Brine Purification Muds
Concentration (wt.
Major constituent (1) (2) (2) (2) (3)a
Brine purification muds
Calcium 17
Calcium carbonate 7.4 - 19.2-24.8 20 . 30-40
Calcium sulfate 9.5 - - - 50-60
Chloride - 9.4 - -
Graphite - - 1.1-5.5
Iron and aluminum hydroxides <0.1 - 1.1-3.3 0.3
Iron - 2800 ppm -
Magnesium - 1700 ppm - -
Magnesium carbonate 0.3 - 11-16.5
Magnesium hydroxide <0.1 - - 3.0
Sodium chloride 19.0 - 5.5-11 - 5-15
Sodium hydroxide 0.1
Sodium sulfate 0.2
Sulfate - 3.2 - -
Other solids - - - 30 -
Water 63.4 41 45 46.7
BOAT metals <0.1 <0.1
a Reported on a dry basis.
References:
(1) USEPA 1988a. Section 1.2.
(2) USEPA 1986.
(3) Bennett 1986.
52
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0341g
Table 2-4 Major Constituent Analysis of Untreated Saturator Insolubles
Major constituent Concentration (wt. %)
(1)
Saturator insolubles
Calcium carbonate 8.0
Calcium chloride 2.0
Calcium sulfate 1.8
Magnesium carbonate 1.2
Sodium chloride 67.1
Other solids 17.8
Water 2.1
References:
(1) USEPA 1988a. Section 1.2
53
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1533g
Table 2-5 BOAT Constituent Composition of Untreated K071 Waste
Data source
Volatile Organic Compounds
Bromod i ch loromethane
Bromoform (tribromomethane)
Chlorodibromomethane
Chloroform
Metals:
Antimony
Arsenic
Barium
Beryllium
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
ug/1
ug/1
ug/1
ug/1
mg/1
mg/1
mg/1
mg/1
mg/1
mg/1
mg/1
mg/1
mg/1
mg/1
mg/1
mg/1
mg/1
mg/1
mg/1
U)a
62
550
170
200
ND
ND
0.57-1.1
ND
ND
ND
ND
ND
17.0-22.1
3.15-<6.
NO
NO
7.74-<43
ND
(Db
<25
<25
<25
<25
ND
ND
1.4
ND
ND
ND
ND
ND
1.12
5 7.9
NO
NO
ND
ND
2.29-3.18 2.5
(2)a (2)a (3)a (3)b
.
-
-
- - - -
10.0
-
- - -
-
3.8 -
5.9 -
184.7
47.8
73.8 - 14 2.2
90.3
- - - -
-
- - - -
.
128.0
a Data specified for brine purification muds.
Data specified for saturator insolubles.
- = Not analyzed.
ND = Not detected
References:
(1) USEPA 1988a. Tables 5-2 through 5-8, 5-12, and 5-14.
(2) USEPA 1986.
(3) Bennett 1986.
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3. APPLICABLE/DEMONSTRATED TREATMENT TECHNOLOGIES
This section describes the applicable treatment technologies and
performance data for treatment of K071 waste. The technologies that are
considered to be applicable to the treatment of K071 waste are those that
treat toxic metals (especially mercury, the constituent for which the
waste was listed) by reducing their concentration and/or their
Teachability in the waste. Included in this section are discussions of
those applicable treatment technologies that have been demonstrated on a
commercial basis. The treatment technologies tested by the Agency and
the performance data obtained from the tests are also presented.
In the previous section, a discussion of the industry generating K071
waste and a major constituent analysis of K071 were presented.
3.1 Applicable Treatment Technologies
The Agency has identified the following treatment technologies,
either alone or in combination, as being applicable for treatment of K071
waste: (1) acid leaching, chemical oxidation, sludge dewatering combined
with either acid or water washing, stabilization, and retorting for
nonwastewaters, and (2) sulfide precipitation and filtration for the
wastewaters produced in the dewatering treatment step.
The Agency has identified treatment technologies that may be
applicable to K071 because the technologies are designed to treat toxic
metal constituents in high water content matrices with significant
filterable solids. The technologies applicable to K071 are those that
reduce the concentration of BDAT list metals in the treated residual
55
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and/or reduce the Teachability of BOAT list metals in the treated
residual from the total and/or leachate concentrations of BOAT list
metals in the untreated waste. The selection of treatment technologies
applicable for treating BOAT list metals in K071 waste is based on
information obtained from literature sources, information obtained from
engineering site visits, and information submitted by industry.
3.2 Demonstrated Treatment Technologies
i. Nonwastewater
The demonstrated technologies that the Agency has identified for
treatment of K071 nonwastewater are: (1) acid leaching followed by
chemical oxidation followed by dewatering/acid washing, (2) dewatering/
water washing, and (3) stabilization. Stabilization has not been
demonstrated on K071 waste, but has been demonstrated for treatment of
wastes containing similar concentrations of BOAT list metals and water.
Retorting has not been demonstrated on a waste containing free liquids
and low ppm levels of mercury; however, it has been demonstrated for
wastes containing greater than approximately one percent mercury and no
free 1iquids.
ii. Wastewater
The only demonstrated treatment train that the Agency has identified
for treatment of K071 wastewaters is chemical precipitation followed by
filtration.
The demonstrated technologies for both nonwastewater and wastewater
are described in this section, and performance data are presented that
indicate the relative effectiveness of these technologies in treating the
BOAT list constituents found in K071 waste.
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3.2.1 Acid Leaching Treatment System
The acid leaching, chemical oxidation, and dewatering/acid washing
treatment system used for treatment of K071 nonwastewaters involves
several individual process steps. This treatment is used to remove
mercury from the waste as soluble mercuric chloride, generating a solid
residual with reduced concentrations of hazardous metal constituents and
a wastewater containing the metals removed by acid leaching that requires
further treatment. A schematic diagram of this treatment system is
provided in Figure 3-1. In the acidification step, sulfuric acid is
added to the waste to reduce the pH and solubilize mercury present in the
waste as mercuric oxide (HgO), by reacting it to form soluble mercuric
chloride, HgCl . In a simultaneous reaction, the calcium in the waste
is precipitated as calcium sulfate, CaSO . In the next process step,
chemical oxidation, any elemental mercury present in the waste is
solubilized by reaction with sodium hypochlorite, NaOCl, to form
HgCl . After chemical oxidation, the waste is fed to a vacuum rotary
drum filter equipped with one hydrochloric acid and two water wash
sprays, where the solids are washed and dewatered. The filtrate is a
K071 wastewater.
The acid leaching treatment train described above removes
acid-soluble metals from the solid portion of the nonwastewater and
produces a wastewater containing the metals removed. Sulfide
precipitation and filtration treatment of the wastewater concentrates the
metals in a sulfide residual (K106) in which the Teachability of the
metals is reduced.
57
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BRINE PURIFICATION MUDS TREATMENT SYSTEM
ANIONIC
FLOCCULANT
in
CO
SULFURIC
BRINE PURIFICATION
MUDS ^
ACID
1
SODIUM
HYPOCHLORITE
ACID
LEACHING
1
CHEMICAL
OXIDATION
l
HYDROCHLORIC ACID
AND
WATER WASH SPRAYS
1
VAC
\
UUM
ATION
AND WASHING
\
\
FILTRATE
TREATED
K071
NONWASTEWATER
WASTEWATER TREATMENT SYSTEM
«
TREATED ^
WASTEWATER
PRESSURE
FILTRATION
SODIUM
SULFIDE
I
I
SULFIDE
PRECIPITATION
0
WAST
THER
OCESS
EWATERS
FILTER CAKE:
K106
FIGURE 3-1 SCHEMATIC OF K071 WASTE TREATMENT PROCESS
-------
This overall process results in the formation of a treated solid
residual from the rotary drum sludge dewatering step and both a treated
wastewater and a solid residual from the sulfide precipitation/filtration
step. The treated residual from the rotary drum sludge dewatering step
was analyzed to determine the performance of the acid leaching treatment
technology. The treated wastewater from the sulfide precipitation/
filtration step was analyzed to determine the performance of the sulfide
precipitation technology. The solid residual from the second filtration
step is the listed waste K106.
The second demonstrated technology, dewatering/water washing, used
alone to treat K071, removes most hazardous constituents present in the
liquid portion of the nonwastewater by separating these liquids from the
solid portion of the nonwastewater. The liquids removed are a K071
wastewater.
The third demonstrated technology, stabilization of metals, reduces
the Teachability of metals in the K071 nonwastewater.
The following demonstrated technologies or treatment steps are
discussed in detail below: acid leaching, sludge filtration
(dewatering), stabilization of metals, and chemical precipitation.
3.2.1.1 Acid Leaching
Acid leaching is a process that removes a soluble constituent or
constituents from a relatively insoluble solid phase by contacting the
solids with an acidic solution. The spent acid will concentrate the
leached constituent or constituents, and will then be subject to further
59
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treatment. A treatment system for acid leaching usually consists of some
type of solid/liquid contacting system followed by equipment for x
solid/liquid separation.
(1) Applicability and Use of Acid Leaching
Acid leaching can be applied to treatment of wastes in solid or
slurry form when the hazardous constituents of the waste are soluble in a
strong acid solution or can be converted by reaction with a strong acid
to a soluble form. It frequently is used to remove metals from sludges.
(2) Underlying Principles of Operation
The underlying principle of operation for acid leaching is that by
lowering the pH of the waste, metals can be concentrated in a solution
passing through the waste because of the higher solubility associated
with acidic pH values.
In order to assure effective removal of metals, strong acids, such as
sulfuric (H SO ), hydrochloric (HC1), nitric (HNO ), and
hydrofluoric (HF), frequently are used. Separation of the liquids from
the treated solids can be accomplished either by designing solid/liquid
contacting equipment used in the leaching step to retain solids and
release liquids, or by additional separation steps such as filtration.
(3) Physical Description of the Process
Acid leaching processes can be categorized into two major types:
(a) treatment by percolation of the acid through ihe solids, and
(b) treatment by dispersion of the solids in the acid and then subsequent
separation of the solids from the liquid.
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(a) Percolation processes. Percolation is carried out in batch
tanks and in several designs of continuous percolation equipment. Batch
percolators are large tanks. The solids are placed in the tank and the
acid is fed onto the solids. The acid percolates through the solid and
drains out through screens or porous media in the tank bottom. The acid
may flow countercurrently through a series of tanks, with fresh acid
being added to the tank containing the most nearly exhausted solids.
Following treatment, the solids are removed.
Continuous percolation is carried out in moving-bed equipment, where
the acid normally flows countercurrently to the solids (see Figure 3-2).
The acid drains from each solids bed to the solids bed beneath.
(b) Dispersed-solids processes. Leaching by dispersion of fine
solids into the acid is performed in batch tanks or in a variety of
continuous devices. In the batch and continuous system, the untreated
waste and the acid are mixed in the reaction tank. Following mixing, the
treated solids are separated from the acid; separation can be
accomplished either by settling or filtration, depending on the type and
concentration of solids involved. In both systems, sufficient acid must
be supplied to keep the pH at a level necessary to effectively leach the
metals from the waste.
(4) Waste Characteristics Affecting Performance
In determining whether an untested waste can be treated to the same
level of performance as a previously tested waste, the waste
characteristics EPA will examine for the acid leaching process are:
61
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SOLIDS
FEED
SPENT ACID
TO
TREATMENT
TREATED
SOLIDS
FIGURE 3-2
CONTINUOUS EXTRACTOR
62
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(a) the solid particle size, (b) the neutralizing capacity (or
alkalinity) of the solids being treated, and (c) the type and chemical
form of the hazardous metal constituent(s) in the waste.
(a) Particle size. The reaction rate of the acid with the hazardous
constituent(s) of the waste, and the rate of transport of acid to and
from the site of the hazardous constituent, are both affected by the size
of the solid particles. The smaller the particles, the more rapidly they
will leach because of the increased surface area that is exposed to acid.
(b) Neutralizing capacity. The neutralizing capacity, or
alkalinity, of the solid affects the amount of acid that must be added to
the waste in order to achieve and/or maintain the desired reactor pH. In
addition to dissolving the waste contaminants, the acid also will
dissolve some of the alkali bulk solids. Therefore, highly alkaline
wastes require more acid or a stronger acid in order to maintain the pH
during treatment.
(c) Type and chemical form of hazardous metal constituent(s). The
type of metal(s) present will affect the degree to which acid leaching
will be effective. Different metals will have different solubilities and
thus impact the removal that can be achieved.
The chemical form of each of the hazardous metal constituents is also
important in determining the reactivity and/or solubility of the
constituent. For example, mercury may exist in waste as mercuric oxide
(HgO) or metallic mercury (Hg). Reaction with a strong acid and a source
of chloride will transform the less soluble HgO into the more soluble
63
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mercuric chloride form (HgO + 2HC1 -* HgCl + HO). This will
allow removal of mercury present as HgO. Conversely, metallic mercury
(Hg) will not react with acid to form HgCl and will not leach.
(5) Design and Operating Parameters
The design and operating parameters of an acid leaching system that
affect performance are: (a) contact time between the solid and the acid,
(b) choice of acid used, (c) pH, and (d) type of contactor used.
(a) Contact time. In continuous percolation systems, contact time
is usually specified by the design volume of the equipment or the speed
of the moving bed. For a given contact time, the performance of either a
continuous or a batch percolation system can be increased by using a
countercurrent flow of acid. In all acid leaching systems, the extent of
reaction and dissolution of the contaminant are directly related to the
contact time.
(b) Choice and concentration of acid used. If the hazardous
constituents to be removed in the acid leaching system are already
present in the waste in a soluble form, or are solubilized by pH
reduction, then any acid that will reduce the pH to the desired value may
be used. However, if chemical reaction is necessary to form the soluble
species, then the appropriate acid must be used at the proper
concentration. If selection of the acid will have an effect on the
nonhazardous constituents of the waste (i.e., the. acid may precipitate an
alkali metal salt such as calcium sulfate), then an acid that produces a
waste that can be more effectively separated by a solid/liquid separation
device (such as a filter or a centrifuge) should be used.
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(c) £H. For dispersed-solids systems, the feed of acid to the
treatment reactor should be based on pH monitoring and control, since the
reaction rate is likely to be highly pH dependent. Because reaction rate
in acid leaching depends on pH, a pH should be selected, based on the
contact time and amount of the hazardous constituent(s) in the waste as
determined by laboratory testing, that provides for complete reaction in
the contact time provided. Also, the effect that the pH may have on the
composition or characteristics of the nonhazardous constituents of the
waste should be considered. For example, if maintenance of a certain pH
value leads to formation of solids that will allow the most efficient
solid/liquid separation after leaching is completed, then pH should be
maintained at this value.
For percolation systems, pH monitoring of the acid percolating
through the tank bottom should ensure that enough acid is being added.
If the pH is not low enough, additional acid may be added.
(d) Type of contactor used. The performance of an acid leaching
systems depends on the type of contacting system used. Additionally,
acid leaching processes are affected by the number of contacting stages
and the type of flow pattern of the acid (countercurrent or cocurrent).
3.2.1.2 Sludge Filtration
(1) Applicability
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.
65
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The remainder of the waste is essentially water. Sludge filtration is
applied to sludges, typically those that have settled to the bottom of
clarifiers, for dewatering. After filtration, these sludges can be
dewatered to 20 to 50 percent solids.
(2) Underlying Principles 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 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. 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) Physical Description of the Process
For sludge filtration, settled sludge is either pumped through a
cloth-type filter media (such as in a plate and frame filter that allows
66
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solid "cake" to build up on the media) or the sludge is drawn by vacuum
through the cloth media (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, cake is removed continuously. For a specific sludge, the
plate and frame type filter will usually produce a drier cake than 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 performance of
a sludge filtration unit: (a) size of particles and (b) 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 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,
67
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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, such
as lime or diatomaceous earth, to a gelatinous sludge will help
significantly. Finally, precoating the filter with diatomaceous earth
prior to sludge filtration will assist in dewatering gelatinous sludges.
(5) Design and Operating Parameters
For sludge filtration, the following design and operating variables
affect performance: (a) type of filter selected, (b) size of filter
selected, (c) feed pressure, and (d) 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 a vacuum type filter and
will also be more tolerant of variations in influent sludge
characteristics. Pressure type filters, however, are batch operations,
so that when cake is built up to the maximum depth physically possible
(constrained by filter geometry), or to the maximum design 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.
68
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(c) Feed pressure. This parameter impacts both the design pore size
of the filter and the design flow rate. It is important that in treating
waste 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 in that it may make the difference in a
vacuum filter 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.
However, polyelectrolyte coagulant usage usually does not increase sludge
volume significantly because the dosage is low.
3.2.2 Stabilization of Metals
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
69
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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 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 leached when water or a mild acid solution comes
into contact with the waste material.
There are two principal stabilization processes used; these are
cement based and lime based. A brief discussion of each is provided
below. In both cement-based or lime/pozzolan-based techniques, the
stabilizing process can be modified through the use of additives, such as
70
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silicates, that control curing rates or enhance the properties of the
sol id 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). When the anhydrous cement powder is
mixed with water, hydration occurs and the cement begins to set. The
chemistry involved is complex because many different reactions occur
depending on the composition of the cement mixture.
As the cement begins to set, a colloidal gel of indefinite
composition and structure is formed. Over a period of time, the gel
swells and forms a matrix composed of interlacing, thin, densely-packed
silicate fibrils. Constituents present in the waste slurry (e.g.,
hydroxides and carbonates of various heavy metals) are incorporated into
the interstices of the cement matrix. The high pH of the cement mixture
tends to keep metals in the form of insoluble hydroxide and carbonate
salts. It has been hypothesized that metal ions may also be incorporated
into the crystal structure of the cement matrix, but this hypothesis has
not been verified.
(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
71
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silicates or hydroxides, which inhibit leaching. Additives, again, can
be used to reduce permeability and thereby further decrease leaching
potential.
(3) Description of Stabilization Processes
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
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
72
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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 (a) fine particulates, (b) oil and
grease, (c) organic compounds, and (d) certain inorganic compounds.
(a) Fine particulates. For both cement-based and lime/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
decreases the resistance of the material to leaching.
(b) Oil and grease. The presence of oil and grease in both
cement-based and lime/pozzolan-based systems results in the coating of
waste particles and the weakening of the bonding between the particle and
the stabilizing agent. This coating can inhibit chemical bond formation
and thereby decrease the resistance of the material to leaching.
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(c) Organic compounds. The presence of organic compounds in the
waste interferes with the chemical reactions and bond formation that
occur during the curing of the stabilized material. This results in a
stabilized waste having decreased resistance to leaching.
(d) Sulfates 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 (a) selection of stabilizing agents and
other additives, (b) ratio of waste to stabilizing agents and other
additives, (c) degree of mixing, and (d) curing conditions.
(a) Selection of stabilizing agents and other additives. The
stabilizing agent and additives used will determine the chemistry and
structure of the stabilized material and, therefore, will affect the
Teachability of the solid material. Stabilizing agents and additives
must be carefully selected based on the chemical and physical
74
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characteristics of the waste to be stabilized. For example, the amount
of sulfates in a waste must be considered when a choice is being made
between a 1ime/pozzolan and a Portland cement-based system.
In order 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 important,
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 and overmixing are
undesirable. The first condition results in a nonhomogeneous mixture;
75
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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. However, if temperatures are too high, the
evaporation rate can be excessive and could result in too little water
being available for completion of the stabilization reaction. The
duration of the curing process should also be determined during the
design stage and typically will be between 7 and 28 days.
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3.2.3 Chemical Precipitation Treatment System
The K071 wastewater, containing the dissolved mercury as HgCl , is
treated by sulfide precipitation and filtration to remove the mercury as
the sulfide, HgS, in the wastewater treatment sludge. The wastewater
treatment sludge is the listed waste K106.
3.2.3.1 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 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
77
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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. This term 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 treatment chemical addition for
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 chemical is 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
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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, increasing the importance of the empirical tests.
(3) Description of the Technology
The equipment and instrumentation required for chemical precipitation
varies depending on whether the system is batch or continuous. Both
operations are discussed below; a schematic of the continuous system is
shown in Figure 3-3.
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 usually 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.
In a continuous system, additional tanks are necessary, as well as
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 can be mixed in order to
provide more uniformity, minimizing 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
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WASTEWATER
FEED
00
o
EQUALIZATION
TANK
ELECTRICAL' CONTROLS
WASTEWATER FLOW
MIXER
TREATMENT
CHEMICAL
FEED
SYSTEM
COAGULANT OR
FLOCCULANT FEED SYSTEM
EFFLUENT TO
DISCHARGE OR
SUBSEQUENT
TREATMENT
SLUDGE TO
OEWATERING
FIGURE 3-3 CONTINUOUS CHEMICAL PRECIPITATION
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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 both
dispersed throughout the tank, in order to ensure comingling 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
subsequently be removed. Settling can be chemically assisted through the
use of flocculating compounds. Flocculants increase the particle size
and density of the precipitated solids, both of which increase the rate
of settling. The particular flocculating agent that will best improve
settling characteristics will vary depending on the particular waste;
selection of the flocculating agent is generally accomplished by
performing laboratory bench tests. Settling can be conducted in a large
81
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tank by relying solely on gravity or can be mechanically assisted through
the use of a circular clarifier or an inclined separator. Schematics of
the latter two separators are shown in Figures 3-4 and 3-5.
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:
(a) the concentration and type of the metal(s) in the waste, (b) the
concentration of suspended solids (TSS), (c) the concentration of
dissolved solids (IDS), (d) whether the metal exists in the wastewater as
a complex, and (e) the oil and grease content. These parameters affect
the chemical reaction of the metal compound, the solubility of the metal
precipitate, or the ability of the precipitated compound to settle.
(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 affects treatment depends on the
particular metals to be removed, and their
82
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SLUDGE
INFLUENT
CENTER FEED CLARIRER WITH SCRAPER SLUDGE REMOVAL SUSTEM
INFLUENT
SLUDGE
RIM FEED - CENTER TAKEOFF CLARIFIES WITH
HYDRAULIC SUCTION SLUDGE REMOVAL SYSTEM
INFLUENT
EFFLUENT
SLUDGE
RIM FEED - RIM TAKEOFF CLARIRER
FIGURE 3-4
CIRCULAR CLARIFIERS
83
-------
INFLUENT
EFFLUENT
FIGURE 3-5
INCLINED PLATE SETTLER
84
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concentrations. An alternative can be 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 either their
particle size or shape. Accordingly, EPA will evaluate this
characteristic in assessing 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
(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
85
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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: (a) design value for
treated metal concentrations, as well as other characteristics of the
waste used for design purposes (e.g., total suspended solids), (b) pH,
(c) residence time, (d) choice of treatment chemical, and (e) choice of
coagulant/f1occulant. Below is an explanation of why EPA believes these
parameters are important to a design analysis; in addition, EPA explains
why other design criteria are not included in EPA's analysis.
(a) Treated and untreated design concentrations. EPA pays close
attention to the treated concentration the system is designed to achieve
when determining whether to sample a particular facility. Since the
86
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system will seldom out-perform 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) £H. The pH is important, because it can indicate that
sufficient treatment chemical (e.g., lime) is added to convert the metal
constituents in the untreated waste to forms that will precipitate. The
pH also affects the solubility of metal hydroxides and sulfides, and
therefore 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 in that 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
continuous data on the pH and periodic temperature conditions throughout
the treatment period.
(c) Residence time. The 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
87
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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 is important because these
compounds improve the settling rate of the precipitated metals and allows
for smaller systems (i.e., lower retention time) to achieve the same
degree of settling as a much larger system. 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, among other things, the energy supplied, the time the material
is mixed, and the related turbulence effects of the specific size and
shape of the tank. EPA will, however, consider whether mixing is
provided and whether the type of mixing device is one that could be
expected to achieve uniform mixing. For example, EPA may not use data
from a chemical precipitation treatment system where an air hose was
placed in a large tank to achieve mixing.
88
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3.3 Performance Data for Nonwastewater
The Agency collected seven data sets of untreated and treated data
for treatment of brine purification muds (nonwastewater) in a treatment
system that consisted of acid leaching, chemical oxidation, and sludge
dewatering/acid washing (as described in Section 3.2.1} and one data set
for treatment of saturator insolubles (nonwastewater) by a one-step acid
leaching (percolation) treatment process (see Section 3.2.1.1(4)). These
data are presented in Tables 3-1 to 3-8. These data show that the acid
leaching treatment system for which data on treatment of brine
purification muds were collected is effective in reducing the total and
leachate concentrations for mercury in K071 waste. The data in Table 3-8
show that the one step acid leaching (percolation) treatment of the
saturator insolubles did not effectively reduce either total or leachate
concentration of mercury. Table 3-9 presents the waste characteristics
affecting performance for the K071 nonwastewater for acid leaching and
chemical oxidation. Additional data were submitted by industry for
treatment of K071 nonwastewaters by dewatering/water washing. Appendix A
contains 12 data sets of total waste concentration and EP leachate
analyses and two TCLP leachate analyses of the treated solids for
dewatering/water washing treatment submitted by one plant, designated
Plant A. Appendix A also includes 24 data sets of total waste
concentration and EP leachate analyses of the treated solids for
dewatering/water washing submitted by another plant, designated Plant B,
and 232 data values for EP leachate analysis of the treated waste for
89
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dewatering/water washing treatment submitted by a third plant, designated
Plant C. These data show that these treatment systems are effective in
reducing the total and leachate concentrations for mercury in K071 waste.
3.4 Performance Data for Wastewater
The Agency collected three data sets of untreated and treated data
for treatment of K071 wastewater in a sulfide precipitation and
filtration treatment system. The data for K071 wastewater are presented
in Tables 3-10 to 3-12. These data show that K071 wastewater can be
treated effectively for removal of mercury and other BOAT metals by
sulfide precipitation and filtration.
90
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0341g
Table 3-1 EPA-Collected Data for Treatment of K071 Waste
Sample Set #la
ANALYTICAL DATA:
Untreated waste
DESIGN AND OPERATING PARAMETERS:
Parameter
Design value
aBrine purification muds.
Reference: USEPA 1988. Tables 3-1 and 5-2.
Treated waste
BOAT list constituent
Barium
Cadmium
Copper
Lead
Mercury
Nickel
Thallium
Zinc
(total)
(mg/1)
0.57
<0.3
<0.8
<6.6
17.0
4.87
12.2
2.29
(TCLP)
(mg/1)
0.31
<0.06
<0.16
<1.3
0.44
0.54
<1.7
0.11
(total)
(mg/kg)
3.3
<1.5
<4.0
<33
2.7
24
62
5.4
(TCLP)
(mg/1)
0.12
0.006
0.06
2.0
0.0003
0.08
0.25
0.21
Operating value
pH of acid leaching
pH of oxidation
Residence time of oxidation
Filter vacuum
2.5 - 3.0
6.5
> 0.05 hr
> 5.0 in Hg
2.94
6.4
0.25
5.0
hr
in Hg
91
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034 Ig
Table 3-2 EPA-Collected Data for Treatment of K071 Waste
Sample Set #2a
ANALYTICAL DATA.
Untreated waste
DESIGN AND OPERATING PARAMETERS
Parameter
Design value
Brine purification muds.
Reference- USEPA 1988. Tables 3-1 and 5-3.
Treated waste
BOAT list constituent
Barium
Cadmium
Copper
Lead
Mercury
Nickel
Thai! lum
Zinc
(total)
(mg/1)
0.57
<0.3
<0.8
<6.6
17.0
4 87
12.2
2.29
(TCLP)
(mg/1)
0.31
<0.06
<0.16
<1.32
0.44
0.54
<1.7
0.11
(total)
(mg/kg)
3.2
<1.5
<4.0
<33
4.8
23
51
4.7
(TCLP)
(mg/1)
0.13
0.04
<0.08
0.84
<0.0002
<0.13
<0.86
0.18
Operating value
pH of acid leaching
pH of oxidation
Residence time of oxidation
Fi Iter vacuum
2.5 - 3.0
6.5
> 0.05 hr
> 5.0 in Hg
2.95
6.4
0.25
5.0
hr
in Hg
92
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0341g
Table 3-3 EPA-Collected Data for Treatment of k071 Waste
Sample Set #3
ANALYTICAL DATA:
Untreated waste
BOAT list constituent
Barium
Cadmium
Copper
Lead
Mercury
Nickel
Thallium
Zinc
DESIGN AND OPERATING
Parameter
pH of acid leaching
pH of oxidation
(total)
(rog/1)
0.814
<0.15
1.19
<3.3
22.1
3.15
7.74
3.18
PARAMETERS-
Residence time of oxidation
Fi Her vacuum
(TCLP)
(mg/1)
0.2Z
<0.3
<0.8
<6.6
20
<1.3
<8.6
0.92
Design value
2.5 - 3.0
6.5
> 0.05 hr
> 5.0 in Hg
Treated waste
(total) (TCLP)
(mg/kg) (mg/1)
2.7 0.18
<1.5 0.13
<4.0 <0.16
<33 <1.3
1.8 2.0
21 <0.26
51 <1.7
3.9 0.25
Operating value
2.93
6.4
0.38 hr
7.0 in Hg
Brine purification muds.
Reference: USEPA 1988. Tables 3-1 and 5-4.
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0341g
Table 3-4 EPA-Collected Data for Treatment of M)71 Waste
Sample Set #4a
ANALYTICAL DATA-
Untreated waste
BOAT list constituent
Barium
Cadmium
Copper
Lead
Mercury
Nickel
Thai 1 lum
Zinc
(total)
(mg/1)
0.814
<0.15
1.19
<3.3
22.1
3.15
7.74
3.18
DESIGN AND OPERATING PARAMETERS:
Parameter
pH of acid leaching
pH of oxidation
Residence time of oxidation
Filter vacuum
(TCLP)
(mg/1)
0.22
<0.3
<0.8
<6.6
20
<1.3
<8.6
0.92
Design value
2.5 - 3.0
6.5
> 0.05 hr
> 5.0 in Hg
Treated waste
(total) (TCLP)
(mg/kg) (mg/1)
2.7 0.16
<3.0 <0.01
<4.0 0.05
<33 0.33
1.7 0.0002
20 0.13
<43 <0.43
3.1 0 . 28
Operating value
2.93
6.4
0.36 hr
7.0 in Hg
Brine purification muds.
Reference. USEPA 1988. Tables 3-1 and 5-5.
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0341g
Table 3-5 EPA-Collected Data for Treatment of K.071 Waste
Sample Set #5a
ANALYTICAL DATA-
Untreated waste
DESIGN AND OPERATING PARAMETERS:
Parameter
• Design value
Brine purification muds.
Reference: USEPA 1988. Tables 3-1 and 5-6.
Treated waste
BOAT list constituent
Barium
Cadmium
Copper
Lead
Mercury
Nickel
Thallium
Zinc
(total)
(mg/1)
0.814
<0.15
1.19
<3.3
22.1
3.15
7.74
3.18
(TCLP)
(mg/1)
0.22
<0.3
<0.8
<6.6
20
<1.3
<8.6
0.92
(total)
(rag/kg)
2.4
<1.5
<4.0
<33
1.2
21
43
5.0
(TCLP)
(rag/1)
0.16
0.003
0.05
0.16
0.0005
0.07
0.26
0.23
Operating value
pH of acid leaching
pH of oxidation
Residence time of oxidation
Fi Her vacuum
2.5 - 3.0
6.5
> 0.05 hr
> 5.0 in Hg
2.94
6.4
0.46 hr
7.0 in Hg
95
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0341g
Table 3-6 EPA-Collected Data for Treatment of K071 Waste
Sample Set #6a
ANALYTICAL DATA
BOAT list constituent
Barium
Cadmium
Copper
Lead
Mercury
Nickel
Thallium
Zinc
Untreated
(total)
(mg/1)
1.1
<1.5
<4.0
<33
20.6
<6.5
<43
3.05
waste
(TCLP)
(mg/1)
0.34
<0.06
«0.16
<1.3
2.1
0.31
<1.7
0.37
Treated
(total)
(mg/kg)
2.4
<1.5
<4.0
<33
1.8
22
<43
5.3
waste
(TCLP)
(mg/1)
0.14
<0.01
0.05
<0.33
0.0016
0.11
<0.43
0.41
DESIGN AND OPERATING PARAMETERS:
Parameter
Design value
Brine purification muds
Reference: USEPA 1988. Tables 3-1 and 5-7.
Operating value
pH of acid leaching
pH of oxidation
Residence time of oxidation
Filter vacuum
2.5 - 3.0
6.5
> 0.05 hr
> 5.0 in Hg
2.92
6.4
0.30 hr
11 in Hg
96
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0341g
Table 3-7 EPA-Collected Data for Treatment of K071 Waste
Sample Set #7a
ANALYTICAL DATA.
Untreated waste
DESIGN AND OPERATING PARAMETERS:
Parameter
Design value
aBnne purification muds
Reference: USEPA 1988. Tables 3-1 and 5-8.
Treated waste
BOAT list constituent
Barium
Cadmium
Copper
Lead
Mercury
Nickel
Thallium
Zinc
(total)
(mg/1)
1.1
<1.5
<4.0
<33
20.6
<6.5
<43
3.05
(TCLP)
(mg/1)
0.34
<0.06
<0.16
<1.3
2.1
0.31
<1.7
0.37
(total)
(mg/kg)
3.1
<1.5
<4.0
<33
1.7
24
<43
5.3
(TCLP)
(mg/1)
0.16
<0.003
0.05
0.07
<0.0002
0.09
0.18
0.34
Operating value
pH of acid leaching
pH of oxidation
Residence time of oxidation
Filter vacuum
2.5 - 3.0
6.5
> 0.05 hr
> 5.0 in Hg
2.91
6.4
0.31 hr
11 in Hg
S7
-------
0341g
Table 3-6 EPA-Collected Data for Acid Leaching (Percolation)
Sample Set #8b
ANALYTICAL
DATA
Untreated waste
BOAT list constituent (total) (TCLP)
Barium
Cadmium
Copper
Lead
Mercury
Nickel
Si Iver
Thallium
Zinc
DESIGN AND
Parameter
pH of acid
Retention
(mg/1) (mg/1)
1.4 0.2
<1.5 0.09
<4.0 <0.16
<33 <1.3
1.1 0.0006
7.9 <0.26
<2.5 0.45
<43 <1.7
2.5 0.42
OPERATING PARAMETERS:
Design value
leaching 3.0
time for acid leaching >3.0 hrs
Treated
(total)
(mg/kg)
2.2
<1.5
<4.0
<33
1.6
<6.5
<2.5
<43
1.8
Operating value
3.0
1.0 hr
waste
(TCLP)
(mg/1)
0.18
<0.06
0.16
1.3
0.0006
0.46
<0.25
<1.7
0.18
Saturator insolubles.
Reference: USEPA 1988. Tables 3-3 and 5-12.
98
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0341g
Table 3-9 Waste Characteristics Affecting Performance
for Acid Leaching
WASTE CHARACTERISTICS AFFECTING PERFORMANCE:
Parameter
Value
Chemical form of hazardous constituents
The mercury content of the waste may be
present as HgCl.,, HgO, or Hg.
Reference: USEPA 1988.
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1412g
DRAFT MARCH 4, 1988
Table 3-10 Sulfide Precipitation - EPA-Collected Data
Sample Set #1
ANALYTICAL DATA.
BOAT list constituent
Arsenic
Barium
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Si Iver
Vanadium
Zinc
Untreated
wastewater
(mg/1)
<0.2
0.248
<0.03
<0.06
0.097
<0.66
23.7
0.157
0.148
<0.04
0.615
Fi Her cake
(total)
(mg/kg)
1.1
74
2.3
6.3
133
50
25,900
14
131
0.46
443
(K106)a
(TCLP)
(mg/1)
<0.01
0.74
0.02
<0.01
<0.02
0.13
0.01
0.15
<0.02
<0.01
1.7
Treated
wastewater
(mg/1)
<0.2
0.103
<0.06
0.553
<0.16
<1.32
0.028
0.275
<0.1
<0.08
0.047
DESIGN AND OPERATING PARAMETERS.
Parameter
Design value
Operating value
Excess sulfide
>40 mg/1
85 rug/1
a Only one sample was collected of the filter cake (K106)
Reference: USEPA 1988. Tables 3-2 and 5-9.
100
-------
1412g
DRAFT MARCH 4, 1986
Table 3-11 Sulfide Precipitation - EPA-Collected Data
Sample Set #2
ANALYTICAL DATA.
BOAT list constituent
Arsenic
Barium
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Silver
Vanadium
Zinc
Untreated
wastewater
(mg/1)
<0.1
0.226
<0.06
0.189
<0.16
<1.32
9.25
<0.26
0.1
<0.08
0.88
Filter cake
(total)
(mg/kg)
1.1
74
2.3
6.3
133
50
25,900
14
131
0.46
443
(K106)a
(TCLP)
(mg/1)
<0.01
0.74
0.02
<0.01
<0.02
0.13
0.01
0.15
<0.02
<0.01
1 7
Treated
wastewater
(mg/1)
<0.1
0.158
<0.06
<0 12
<0.16
<1.32
0.027
<0.26
<0.1
<0.08
<0.04
DESIGN AND OPERATING PARAMETERS:
Parameter
Design value
Operating value
Excess sulfide
>40 mg/1
101 mg/1
a Only one sample was collected of the filter cake (K.106).
Reference: USEPA 1988. Tables 3-2 and 5-10
101
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1412g
DRAFT MARCH 4, 1988
Table 3-12 Sulfide Precipitation - EPA-Collected Data
Sample Set #3
ANALYTICAL DATA
BOAT list constituent
Arsenic
Barium
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Si Iver
Vanadium
Zinc
Untreated
wastewater
(mg/1)
<0.1
0.293
<0.06
<0.12
<0.16
<1.32
77.2
<0.26
0.12
<0 08
0 535
Fi Iter cake
(total)
(mg/kg)
1.1
74
2.3
6.3
133
50
25.900
14
131
0.46
443
(K106)a
(TCLP)
(mg/1)
<0.01
0.74
0.02
<0.01
<0.02
0.13
0 01
0.15
<0 02
<0.01
1.7
Treated
wastewater
(mg/1).
<0.1
0.144
<0.06
<0.12
<0.16
<1.32
0.028
<0.26
<0.1
<0.08
0.064
DESIGN AND OPERATING PARAMETERS
Parameter
Design value
Operating value
Excess sulfide
>40 mg/ 1
96 mg/1
a Only one sample was collected of the filter cake (K106).
Reference: USEPA 1988. Tables 3-2 and 5-11.
102
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4. IDENTIFICATION OF BEST DEMONSTRATED AVAILABLE TECHNOLOGY (BOAT)
FOR K071
This section presents the rationale for selection of the best
technology of those that have been demonstrated for treatment of K071
waste. In Section 3, the technologies demonstrated for treatment of this
waste were identified. These are: (1) a treatment system consisting of
acid leaching followed by chemical oxidation followed by dewatering/acid
washing followed by sulfide precipitation and filtration treatment of the
filtrate from the dewatering step, (2) dewatering/water washing followed
by chemical precipitation and filtration treatment of the filtrate, and
(3) stabilization.
There are three primary differences between the dewatering/water
washing treatment system (technology (2) above) and the acid leaching
treatment train (technology (1) above). The first difference is that in
the acid leaching treatment step some of the metal constituents
(including mercury) are more fully solubilized from the solid portion of
the nonwastewater. The second is that the acid leaching treatment step
produces solids of different characteristics than the untreated waste
(calcium sulfate instead of calcium carbonate) and allows a more
efficient washing of the solids as they are being filtered. The third
difference is that the chemical oxidation step in the acid leaching
system solubilizes any mercury present in the elemental form in the
untreated waste. The combination of these three factors, along with the
use of an acid washing step during filtration, allows more metals to be
removed from the waste than by filtration/washing alone.
103
-------
The data presented for those technologies (in Section 3 and
Appendices A and B) will be evaluated based on the following screening
procedure. First, only leachate data obtained using the TCLP leaching
procedure will be considered. (The reason that EP leachate data are not
considered is discussed in Section 1 of this report.) If design and
operating data are reported for a data point or data set (paired influent
and effluent data), then these will be considered. Data points or data
sets that reflect the operation of poorly designed treatment systems or
systems that were not well operated at the time of treatment data
collection will not be used in development of treatment standards. Once
these data have been deleted, all remaining data will be adjusted based
on the analytical recovery values obtained from laboratory quality
assurance/quality control (QA/QC) analyses to take into account
analytical interferences associated with the sample. Finally, treatment
values for each technology for which the Agency has treatment data will
be compared by the analysis of variance (ANOVA) test, as presented in
Appendix C. This test will indicate if one technology performs
significantly better than another.
4.1 Data Screening
The available treatment data for K071 were reviewed and assessed in
order to determine whether they contained information on design and
operation of the system, quality assurance/quality control analysis of
the data, and the proper chemical analyses to indicate the performance of
the treatment system. Data collected by the Agency for acid leaching
104
-------
treatment of K071 nonwastewaters are presented in Table 4-1. Data
collected for treatment of K071 wastewaters are presented in Table 4-2.
EP leachate results submitted by plants A, B, and C, presented in
Appendix A, were not considered in developing the treatment standards
because TCLP data were available.
One data point collected by the Agency, for TCLP analysis of mercury
in the treated waste for sample set 3, was not used because the leachate
result indicated a laboratory error in either sampling or analysis (the
leachate concentration was higher than the corresponding total waste
concentration).
4.2 Data Accuracy
After data were eliminated from consideration for analysis of BOAT
based on the screening tests discussed above, EPA adjusted the data
values remaining 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. These adjusted values for the acid leaching treatment
105
-------
system described in Section 3.2.1 and for a single step dewatering/water
washing process were then used to determine BOAT for K071.
4.3 Analysis of Variance
In cases where the Agency has data on treatment of the same or
similar wastes using more than one technology, we performed an analysis
of variance (ANOVA) test to determine if one of the technologies performs
significantly better than another. In cases where a particular treatment
technology performs better, the treatment standard will be based on this
best technology.
In order to determine BOAT for K071, both acid leaching and
dewatering/water washing data were considered. In order to perform the
ANOVA test to compare the two technologies, the accuracy-corrected data
were used.
The ANOVA test was used to compare each set of data submitted for
dewatering/water washing to the acid leaching data. In all cases, for
both total constituent concentration and TCLP, the ANOVA indicated that
the acid leaching treatment system performs significantly better than the
dewatering/water washing system based on the mercury concentration in the
treated waste.
4.4 Determination of Availability of Best Technology
Acid leaching followed by chemical oxidation followed by sludge
dewatering/acid washing for nonwastewater and sulfide precipitation
followed by filtration for wastewater were determined to be available to
treat K071 wastes because: (1) these technologies are commercially
106
-------
available, and (2) these technologies provide substantial reduction of
hazardous constituent concentrations.
107
-------
1563g
Table 4-1 Treatment Data Used For Regulation of K071 Nonwastewater
BOAT constituent
Barium
Cadmium
Copper
Lead
Mercury
Nickel
Thai 1 lum
Zinc
* Data point eliminated
i — »
0
00
Sample
(total)
(mg/kg)
3.3
<1.5
<4.0
<33
2 7
24
62
5.4
because of
Set #1
(TCLP)
(mg/1)
0.12
0.006
0.06
2.0
0.0003
0.08
0.25
0.21
laboratory
Sample
(total)
(mg/kg)
3.2
<1.5
<4.0
<33
4 8
23
51
4.7
error.
Set #2
(TCLP)
(mg/1)
0.13
0.04
<0.08
0.84
<0 0002
<0 13
<0.86
0.18
Sample
(total)
(mg/kg)
2 7
<1.5
<4 0
<33
1.8
21
51
3 9
Set #3
(TCLP)
(mg/1)
0.18
0.13
<0 16
<1 3
*
<0.26
<1 7
0.25
Sample
(total)
(mg/kg)
2 7
<3.0
<4.0
<33
1.7
20
<43
3.1
Set #4
(TCLP)
(mg/1)
0.16
<0 01
0.05
0.33
0.0002
0.13
<0 43
0.28
Sample
(total)
(mg/kg)
2 4
<1.5
<4.0
<33
1 2
21
43
5.0
Set #5
(TCLP)
(mg/1)
0.16
0.003
0.05
0.16
0.0005
0.07
0.26
0.23
Sample Set #6
(total) (TCLP)
(mg/kg) (mg/1)
24 0 14
<1.5 <0 01
<4 0 0 05
<33 <0 33
1 8 0 0016
22 0 11
<43 <0 43
5 3 0.41
Sample
(total)
(mg/kg)
3 1
<] 5
<4 0
<33
1 7
24
<43
5 3
Set #7
(TCLP)
(mg/1)
0 16
<0 003
0 05
0 07
'0 0002
0 09
0 18
0 34
-------
1563g
Table 4-2 Treatment Data Used for Regulation of K07J Wastewater
Sample Set #1 Sample Set #2 Sample Set #3
BOAT constituent (mg/1) (mg/1) (mg/1)
Barium 0.103 0.158 0.144
Chromium 0 553 <0.12 <0.12
Mercury 0.028 0.027 0.028
Nickel 0.275 <0.26 <0.26
Silver <0.1 <0.1 <0.1
Zinc 0.047 <0.04 0.064
109
-------
5. SELECTION OF REGULATED CONSTITUENTS
This section describes, step by step, the process used to select the
constituents to be regulated for K071. The selected constituents must be
present in the untreated waste at concentrations that are treatable by
the chosen BOAT discussed in Section 4.
As discussed in Section 1, the Agency has developed a list of
hazardous constituents (Table 1-1) from which the constituents to be
regulated are selected. The list is a "growing list" that does not
preclude the addition of new constituents as additional key parameters
are identified. The list is divided into the following categories:
volatile organics, semivolatile organics, metals, inorganics other than
metals, organochlorine pesticides, phenoxyacetic acid herbicides,
organophosphorous insecticides, PCBs, and dioxins and furans. The
constituents in each category have similar chemical properties and are
analyzed for by the same analytical methods, with the exception of the
inorganics.
Table 5-1 presents the BOAT constituent list as discussed in
Section 1 and indicates which of the BOAT list constituents were analyzed
for in the untreated waste and which of those that were analyzed for were
detected.
One sample of the K071 waste was analyzed for volatile organics,
semivolatile organics, and total organic carbon. This waste is produced
from the treatment of a brine solution with inorganic chemicals, and thus
is not expected to contain BOAT list organic compounds other than at
110
-------
levels normally found in the process makeup water. Analysis of this
waste for volatile organic compounds showed only low concentrations of
chlorinated and brominated methanes that are below treatable levels. Of
the 170 volatile and semivolatile organic constituents on the list, we
analyzed for 80. Of the 80 analyzed for, 4 volatiles and no
semivolatiles were detected. The BOAT list volatile and semivolatile
organic compounds not analyzed for were not listed on the BOAT list of
constituents at the time that this treatment system was sampled. Of the
16 metals on the BOAT list of constituents, we analyzed for 15.
Hexavalent chromium was not analyzed for because it was not on the BOAT
list of constituents at the time this treatment system was sampled. Of
the 15 metals analyzed for, 6 were detected in both the total
concentration and TCLP analyses and 2 were detected only in the TCLP.
The untreated waste samples were not analyzed for other classes of
organics (organochlorine pesticides, phenoxyacetic acid herbicides,
orga.nophosphorus insecticides, PCBs, and dioxins and furans) because
there is no in-process source of these contaminants and because of the
extreme unlikelihood of finding these contaminants at treatable levels in
the waste. The three inorganics were not analyzed for because they were
not included on the BOAT list at the time of sampling.
In Section 4, acid leaching followed by chemical oxidation followed
by dewatering/acid washing was determined to be BOAT for K071
nonwastewaters. The acid leaching treatment train is designed to remove
mercury and other BOAT list metals that are solubilized under treatment
111
-------
conditions that maximize mercury removal. Mercury is the only
constituent detected in the untreated waste at treatable concentrations.
No other constituents were detected in the treated waste that were not
detected in the untreated waste. Therefore, mercury was selected as the
regulated constituent for this waste. BOAT list metals for which the
chloride or sulfate salts are not soluble (e.g., thallium) will not be
removed by this treatment system, but will be concentrated in the treated
solids. These metals will not be regulated here. The data on
characterization of the treated K071 nonwastewater do not indicate that
further significant reductions in the Teachability of these metals could
be obtained by stabilization treatment of the residual from the BOAT
treatment system.
112
-------
1543g
Table 5-1 BOAT List of Constituents
BOAT
reference Parameter
no
CAS no. Detection status
Volatiles
222.
1.
2.
3.
4.
5.
6.
223.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
25.
26.
27.
28.
29.
224.
225.
226.
30.
227.
31.
214.
32.
33.
228.
34.
Acetone
Acetonitri le
Acrolein
Acrylonitrile
Benzene
Bromodichloromethane
Bromome thane
n-Butyl alcohol
Carbon tetrachloride
Carbon disulfide
Chlorobenzene
2-Chloro-l,3-butadiene
Chlorodibromomethane
Chloroethane
2-Chloroethyl vinyl ether
Chloroform
Chloromethane
3-Chloropropene
1 ,2-Dibromo-3-chloropropane
1,2-Dibromoethane
Dibromomethane
trans-1 ,4-Dichloro-2-butene
Dichlorodif luoromethane
1,1-Dichloroethane
1,2-Dichloroethane
1 , 1-Dichloroethy lene
trans- 1 , 2-Dichloroethene
1,2-Dichloropropane
trans-1, 3-Dichloropropene
cis-l,3-Dichloropropene
1,4-Dioxane
2-Ethoxyethanol
Ethyl acetate
Ethylbenzene
Ethyl cyanide
Ethyl ether
Ethyl methacrylate
Ethylene oxide
lodomethane
Isobutyl alcohol
Methanol
Methyl ethyl ketone
67-64-1
75-05-8
107-02-8
107-13-1
71-43-2
75-27-4
74-83-9
71-36-3
56-23-5
75-15-0
108-90-7
126-99-8
124-48-1
75-00-3
110-75-8
67-66-3
74-87-3
107-05-1
96-12-8
106-93-4
74-95-3
110-57-6
75-71-8
75-34-3
107-06-2
75-35-4
156-60-5
78-87-5
10061-02-6
10061-01-5
123-91-1
110-80-5
141-78-6
100-41-4
107-12-0
60-29-7
97-63-2
75-21-8
74-88-4
78-83-1
67-56-1
78-93-3
NA
NA
NA
NA
ND
D
NO
NA
ND
ND
ND
NA
D
ND
ND
D
ND
NA
NA
NA
NA
NA
NA
ND
ND
ND
ND
ND
ND
ND
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
113
-------
1543g
Table 5-1 (continued)
BOAT
reference Parameter
no.
Volatiles
229.
35.
37.
38.
230.
39.
40.
41.
42.
43.
44.
45.
46.
47.
48.
49.
231.
50.
215.
216.
217.
(continued)
Methyl isobutyl ketone
Methyl methacrylate
Methacrylonitri le
Methylene chloride
2-Nitropropane
Pyridine
1,1,1 , 2-Tetrachloroethane
1,1.2, 2-Tetrachloroethane
Tetrachloroethene
Toluene
Tribromomethane
1 , 1 , 1-Tnchloroethane
1,1, 2-Trichloroethane
Trichloroethene
Trichloromonof luoromethane
1,2, 3-Tr ichloropropane
l,l,2-Trichloro-l,2,2-tnfluoro-
ethane
Vinyl chloride
1,2-Xylene
1,3-Xylene
1,4-Xylene
CAS no. Detection status
108-10-1
80-62-6
126-98-7
75-09-2
79-46-9
110-86-1
630-20-6
79-34-6
127-18-4
108-88-3
75-25-2
71-55-6
79-00-5
79-01-6
75-69-4
96-18-4
76-13-1
75-01-4
97-47-6
108-38-3
106-44-5
NA
NA
NA
ND
NA
NA
NA
ND
ND
ND
D
ND
ND
ND
NA
NA
NA
ND
ND
ND
NO
Sennvolatiles
51.
52.
53.
54.
55.
56.
57.
58.
218.
59.
60.
61.
63.
65.
64.
62.
66.
Acenaphthalene
Acenaphthene
Acetophenone
2-Acetylaminof luorene
4-Aminobiphenyl
Aniline
Anthracene
Aramite
Benzal chloride
Benz(a)anthracene
Benzenethiol
Deleted
Benzo(b)f luoranthene
Benzo(k)f luoranthene
Benzol ghijperylene
Benzo(a)pyrene
p-Benzoquinone
208-96-8
83-32-9
96-86-2
53-96-3
92-67-1
62-53-3
120-12-7
140-57-8
98-87-3
56-55-3
108-98-5
205-99-2
207-08-9
191-24-2
50-32-8
106-51-4
ND
ND
NA
NA
NA
NA
ND
NA
NA
ND
NA
ND
ND
ND
ND
NA
114
-------
1543g
Table 5-1 (continued)
BOAT
reference Parameter
no.
CAS no. Detection status
Semivolatiles (continued)
67.
68.
69.
70.
71.
72.
73.
74.
75.
76.
77.
78.
79.
80.
81.
82.
232.
83.
84.
85.
86.
87.
88.
89.
90.
91.
92.
93.
94.
95.
96.
97.
98.
99.
100.
101.
102.
103.
104.
105.
106.
219.
Bis(2-ch1oroethoxy)methane
Bis(2-chloroethyl) ether
Bis(2-chloroisopropyl) ether
Bis(2-ethylhexyl) phthalate
4-Bromophenyl phenyl ether
Butylbenzyl phthalate
2-sec-Butyl-4,6-dinitrophenol
p-Chloroaniline
Chlorobenzilate
p-Chloro-m-cresol
2-Chloronaphthalene
2-Chlorophenol
3-Chloropropionitri le
Chrysene
o-Cresol
p-Cresol
Cyclohexanone
Dibenz(a,h)anthracene
Di benzol a, e)pyrene
Dibenzo(a, i)pyrene
1,3-Dichlorobenzene
1 , 2-0 i ch lorobenzene
1,4-Dichlorobenzene
3,3'-Dichlorobenzidine
2,4-Dichlorophenol
2,6-Dichlorophenol
Oiethyl phthalate
3,3'-Dimethoxybenzidine
p-Dimethylaminoazobenzene
3,3'-Dimethylbenzidine
2,4-Dlmethylphenol
Dimethyl phthalate
Di-n-butyl phthalate
1 ,4-Dinitrobenzene
4 , 6-D i n 1 1 ro-o-creso 1
2,4-Dimtrophenol
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Di-n-octyl phthalate
D i -n-propy 1 n 1 1 rosam i ne
D i phenyl am ine
Diphenylnitrosamine
111-91-1
111-44-4
39638-32-9
117-81-7
101-55-3
85-68-7
88-85-7
106-47-8
510-15-6
59-50-7
91-58-7
95-57-8
542-76-7
218-01-9
95-48-7
106-44-5
108-94-1
53-70-3
192-65-4
189-55-9
541-73-1
95-50-1
106-46-7
91-94-1
120-83-2
87-65-0
84-66-2
119-90-4
60-11-7
119-93-7
105-67-9
131-11-3
84-74-2
100-25-4
534-52-1
51-28-5
121-14-2
606-20-2
117-84-0
621-64-7
122-39-4
86-30-6
ND
ND
ND
ND
NO
ND
NA
ND
NA
NA
ND
ND
NA
ND
NA
NA
NA
ND
NA
NA
ND
ND
ND
ND
ND
NA
ND
NA
NA
NA
ND
ND
ND
NA
NA
ND
ND
ND
ND
NA
NA
NA
115
-------
1543g
Table 5-1 (continued)
BOAT
reference Parameter
no.
CAS no. Detection status
Semivolat i les (continued)
107.
108.
109.
110.
111.
112.
113.
114.
115.
116.
117.
118.
119.
120.
36.
121.
122.
123.
124.
125.
126.
127.'
128.
129.
130.
131.
132.
133.
134.
135.
136.
137.
138.
139.
140.
141.
142.
220.
143.
144.
145.
146.
1 , 2-Diphenylhydrazine
Fluoranthene
Fluorene
Hexachlorobenzene
Hexach lorobutad iene
Hexachlorocyclopentadiene
Hexach loroethane
Hexach lorophene
Hexach loropropene
Indeno( 1,2, 3-cd)pyrene
Isosafrole
Methapyri Iene
3-Methylcholanthrene
4,4'-Methylenebis (2-chloroaniline)
Methyl methanesulfonate
Naphthalene
1,4-Naphthoquinone
l-Naphthylamine
2-Naphthylamine
p-Nitroani line
Nitrobenzene
4-Nitrophenol
N-Nitrosodi-n-butylamine
N-Nitrosodiethylamine
N-Nitrosodimethylamine
N-Nitrosomethylethylamine
N-N 1 1 rosomorpho 1 1 ne
N-Nitrosopi pen dine
N-Nitrosopyrrol idine
5-Nitro-o-toluidine
Pentachlorobenzene
Pent ach loroethane
Pentachloronitrobenzene
Pentachlorophenol
Phenacetin
Phenanthrene
Phenol
Phthalic anhydride
2-Picoline
Pronamide
Pyrene
Resorcinol
122-66-7
206-44-0
86-73-7
118-74-1
87-68-3
77-47-4
67-72-1
70-30-4
1888-71-7
193-39-5
120-58-1
91-80-5
56-49-5
101-14-4
66-27-3
91-20-3
130-15-4
134-32-7
91-59-8
100-01-6
98-95-3
100-02-7
924-16-3
55-18-5
62-75-9
10595-95-6
59-89-2
100-75-4
930-55-2
99-65-8
608-93-5
76-01-7
82-68-8
87-86-5
62-44-2
85-01-8
108-95-2
85-44-9
109-06-8
23950-58-5
129-00-0
108-46-3
NA
ND
ND
ND
ND
ND
ND
NA
NA
ND
NA
NA
NA
NA
NA
ND
NA
NA
NA
ND
ND
ND
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
ND
NA
ND
ND
NA
NA
NA
ND
. NA
116
-------
1543g
Table 5-1 (continued)
BOAT
reference Parameter
no.
Semivolati les (continued)
147. Safrole
148. 1,2,4,5-Tetrachlorobenzene
149. 2,3,4,6-Tetrachlorophenol
150. 1,2, 4-Trichlorobenzene
151. 2,4,5-Trichlorophenol
152. 2,4,6-Trichlorophenol
153. Tris(2,3-dibromopropyl)
phosphate
Metals
154. Antimony
155. Arsenic
156. Barium
157. Beryllium
158. Cadmium
159. Chromium (total)
221, Chromium (hexavalent)
160. Copper
161. Lead
162. Mercury
163. Nickel
164. Selenium
165. Silver
166. Thallium
167. Vanadium
168. Zinc
Inorganics
169. Cyanide
170. Fluoride
171. Sulfide
Orqanochlorine Pesticides
172. Aldrin
173. alpha-BHC
174. beta-BHC
175. delta-BHC
CAS no. Detection status
94-59-7
95-94-3
58-90-2
120-82-1
95-95-4
88-06-2
126-72-7
7440-36-0
7440-38-2
7440-39-3
7440-41-7
7440-43-9
7440-47-32
-
7440-50-8
7439-92-1
7439-97-6
7440-02-0
7782-49-2
7440-22-4
7440-28-0
7440-62-2
7440-66-6
57-12-5
16964-48-8
8496-25-8
309-00-2
319-84-6
319-85-7
319-86-8
NA
NA
NA
ND
ND
ND
NA
ND
ND
D
ND
D (TCLP only)
ND
NA
D
ND
D
D
ND
D (TCLP only)
D
ND
D
NA
NA
NA
NA
NA
NA
NA
117
-------
1543g
Table 5-1 (continued)
BOAT
reference Parameter
no.
Orqanochlorlne Pesticides (continued)
176. gamma-BHC
177. Chlordane
178. ODD
179. DOE
180. DOT
181. Dieldrin
182. Endosulfan I
183. Endosulfan II
184. Endnn
185. Endrin aldehyde
186. Heptachlor
187. Heptachlor epoxide
188. Isodnn
189. Kepone
190. Methoxychlor
191. Toxaphene
Phenoxvacetic Acid Herbicides
192. 2,4-Dichlorophenoxyacet ic acid
193. Silvex
194. 2,4,5-T
OraanoDhosDhorous Insecticides
195. Oisulfoton
196. Famphur
197. Methyl parathion
198. Parathion
199. Phorate
PCBs
200. Aroclor 1016
201. Aroclor 1221
202. Aroclor 1232
203. Aroclor 1242
204. Aroclor 1248
205. Aroclor 1254
206. Aroclor 1260
CAS no. Detection status
58-89-9
57-74-9
72-54-8
72-55-9
50-29-3
60-57-1
939-98-8
33213-6-5
72-20-8
7421-93-4
76-44-8
1024-57-3
465-73-6
143-50-0
72-43-5
8001-35-2
94-75-7
93-72-1
93-76-5
298-04-4
52-85-7
298-00-0
56-38-2
298-02-2
12674-11-2
11104-28-2
11141-16-5
53469-21-9
12672-29-6
11097-69-1
11096-82-5
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
118
-------
1543g
Table 5-1 (continued)
BOAT
reference Parameter CAS no. Detection status
no.
Dioxins and Furans
207.
208.
209.
210.
211.
212.
213.
Hexach lorod i benzo-p-d i ox i ns
Hexachlorodibenzofurans
Pentachlorodibenzo-p-dioxins
Pentachlorodibenzofurans
Tetrach lorod ibenzo-p-diox ins
Tetrach lorod i benzofurans
,3,7,8-Tetrachlorodibenzo-p-dioxin 1746-01-6
NA
NA
NA
NA
NA
NA
NA
D = Detected.
NO - Not detected.
NA = Not analyzed.
119
-------
6. CALCULATION OF TREATMENT STANDARDS
In this section, the performance level of the best technology for
treatment of K071 waste is calculated. For nonwastewater, this
calculation is based on the set of treatment data presented in Table 4-1
for a treatment system consisting of acid leaching followed by chemical
oxidation followed by dewatering/acid washing. For wastewater, this
calculation is based on the treatment data presented in Table 4-2, for a
treatment system consisting of sulfide precipitation followed by
filtration. In Section 5, mercury was selected as the regulated
constituent for this waste for both nonwastewater and wastewater.
EPA has data from four facilities for the treatment of K071
nonwastewater. These data include seven sets of influent and effluent
data collected from one facility using acid leaching followed by chemical
oxidation followed by dewatering/acid washing, and one set collected from
the same facility for a one-step acid leaching treatment. Seven of these
eight data sets for acid leaching are used for regulation of this waste.
The data on the one-step acid leaching process were not used because the
ANOVA analysis showed that significant reduction in the concentration of
hazardous constituents was not achieved by this treatment process. Three
facilities submitted data for dewatering/water washing treatment. One of
these three facilities submitted 12 data sets (total waste concentration
and EP leachate analyses) for only the treated waste, along with two data
points for TCLP leachate from the treated waste. The second of the three
facilities submitted 24 data sets (total waste concentration and EP
leachate analyses) for only the treated waste. The third plant submitted
120
-------
232 data values for EP leachate analysis of only the treated waste. The
first two of these facilities also submitted QA/QC data on matrix spike
recoveries for all metals analyses.
EPA also collected three sets of untreated and treated waste data
from one facility for the treatment of K071 wastewater. All three of
these data sets are used for regulation of this waste. No data were
submitted by industry for the treatment of K071 wastewater.
As discussed in Section 4, the technology upon which the treatment
standard for K071 nonwastewater is based is acid leaching followed by
chemical oxidation followed by dewatering/acid washing. The technology
upon which the treatment standard for K071 wastewater is based is sulfide
precipitation and filtration. Available data show that the treatment
systems on which the treatment standards are based were well designed and
well operated at the time of treatment data collection.
As discussed in Section 1, the following steps were taken to derive
the BOAT treatment standards for K071.
1. The Agency evaluated the data collected from the acid leaching and
sulfide precipitation treatment systems to determine whether any
of the data represented poor design or poor operation of the
treatment systems. The available data show that all seven data
sets collected from Agency testing for nonwastewater and all three
data sets collected from Agency testing for wastewater do not
represent poor design or poor operation. One data value from
Agency testing, for TCLP analysis for mercury in the treated
nonwastewater in sample set 3, was not used because the value for
leachate analysis was higher than the corresponding value for
total waste concentration.
2. Accuracy-corrected constituent concentrations were calculated for
all BOAT list constituents for both wastewater and nonwastewater.
An arithmetic average concentration level and a variability factor
were determined for each BOAT list constituent regulated in this
waste, as shown in Table 6-1.
121
-------
3. The analysis of variance method was used to compare the treatment
of K071 waste in the acid leaching treatment system to treatment
in a dewatering/water washing treatment system. All of the data
submitted by industry for dewatering/water washing treatment were
found by the analysis of variance method to represent
significantly worse treatment than treatment by acid leaching for
both compositional and leachate analyses.
4. The BOAT treatment standard for each constituent regulated in this
rulemaking was determined by multiplying the average
accuracy-corrected total composition or TCLP extract concentration
by the appropriate variability factor.
Table 6-1 summarizes the calculation of the treatment standards for
K071. EPA believes these constituent reductions substantially diminish
the toxicity of K071 and substantially reduce the likelihood of migration
of the hazardous constituents present in K071.
122
-------
1360g
Table 6-1 Calculation of Treatment Standards for K071
Acid Leaching. EPA-Collected Data
U>
Constituent
Wastewater
Mercury (mg/1)
Nonwastewater8
Mercury
(Total concen-
tration) (mg/kg)
(TLCP) (mg/1)
Average Treatment
Corrected Concentration
Sample Sample Sample Sample Sample Sample Sample Treated Waste Variability Level Untreated Treatment
Set 11 Set #2 Set #3 Set #4 Set *5 Set #6 Set #7 Concentration Factor Avg x VF K071 Range Standard
0.0295 - 0.0284 - - 0.0295 - 0.0288 1.05 0.030 - 0.030
2.16 3.84 1.44 1.36 0.96 1.44 1.36 1.79 2.57 4 6 17. 0-22. lb 4.6
0.0003 <0.0002 - 0.0002 0.0005 0.0017 <0.0002 0.00052 4.82 0 0025 0.46-20 0.0025
Facilities land-disposing of K071 nonwastewater must comply with both the total concentration and the TCLP standards.
Units are mg/1.
-------
7. CONCLUSIONS
The Agency has proposed treatment standards for the listed waste
K071. Standards for nonwastewater and wastewater forms of this waste are
presented in Table 7-1.
The treatment standards proposed for K071 have been developed
consistent with EPA's promulgated methodology for BOAT (November 7, 1986,
51 FR 40572). This waste is generated by brine purification in the
mercury cell process in chlorine production. Based on a careful review
of the industry processes that generate this waste and all available data
characterizing this waste, the Agency has determined that this waste
represents a separate waste treatability group.
Through available data bases, EPA's technology testing program, and
data submitted by industry, the Agency has identified the following three
demonstrated technologies for treatment of inorganic constituents present
in the K071 nonwastewater: (1) treatment train consisting of acid
leaching, chemical oxidation, and dewatering/acid washing treatment
steps, (2) dewatering/water washing, and (3) stabilization. For K071
wastewater, only one demonstrated treatment technology was identified,
consisting of chemical precipitation followed by filtration.
Regulated constituents were selected based on a careful evaluation of
the constituents found at treatable levels in the untreated waste and
constituents detected in the treated waste. All available waste
characterization data and applicable treatment data consistent with the
type and quality of data needed by the Agency on this program were used
to make this determination. If the performance data for the technology
124
-------
Table /-I BOAT Treatment Standards for k071
Constituent Value
Mercury
Wastewater (total concentration) 0.030mg/l
a
Nonwastewater (total concentration) 4.7 mg/kg
a
Nonwastewater (TCLP) 0.0025 mg/1
a Facilities land-disposing of K071 nonwastewater must meet both the
total waste concentration and the TCLP standards.
125
-------
selected as BOAT indicated that a constituent was not treated, then that
constituent was not regulated. Some constituents present at treatable
concentrations in the untreated waste were not regulated if it was
determined that they would be adequately controlled by regulation of
another constituent.
In the development of treatment standards for these wastes, the
Agency examined all available treatment data. The Agency conducted tests
on a full scale treatment system treating K071 waste, consisting of acid
leaching followed by chemical oxidation followed by dewatering/acid
washing followed by sulfide precipitation and filtration treatment of the
wastewater produced in the dewatering/washing step. Design and operating
data collected during the testing of this technology indicate that the
technology was properly operated during collection of each sample set;
accordingly, all of the treatment performance data collected during the
tests were used in the development of the BOAT treatment standards except
for one data point for TCLP analysis for mercury, which, because of
laboratory error, was higher than the corresponding total waste
concentration analysis. Additionally, the Agency considered performance
data for K071 nonwastewater submitted by industry for dewatering/water
washing.
Acid leaching followed by chemical oxidation followed by dewatering/
acid washing was determined to be BOAT for K071 nonwastewaters based on a
statistical comparison of performance data from this treatment train to
the other available treatment data. Other available treatment data
126
-------
either showed a lower level of performance than the acid leaching
treatment system or there was insufficient information to allow the
Agency to compare statistically the treatment performance (e.g., TCLP
leachate data were not submitted for the dewatering/water washing
treatment system except for two data points from one facility).
Chemical precipitation followed by filtration was determined to be
BOAT for K071 wastewaters. The Agency collected three sets of
untreated/treated data for this treatment system. No other data are
available for treatment of K071 wastewaters for this or any other
technologies.
Treatment standards for these wastes were derived after adjustment of
laboratory data to account for recovery. Subsequently, the mean of the
accuracy-corrected data was multiplied by a variability factor determined
for each constituent to derive the treatment standard. The variability
factor represents the variability inherent in the treatment process and
in sampling and analytical methods. Variability factors were determined
by statistically calculating the variability seen for a number of data
points for a given constituent.
Wastes determined to be K071 may be land disposed if they meet the
treatment standards specified in Table 7-1 at the point of disposal. The
BOAT technology upon which the treatment standards are based (acid
leaching followed by chemical oxidation followed by dewatering/acid
washing or precipitation followed by filtration) need not be specifically
utilized prior to land disposal, provided that the alternative treatment
127
-------
technology utilized achieves the standards and does not pose a greater
risk to human health and the environment than land disposal.
These standards become effective as of August 8, 1988, as per the
schedule set forth in 40 CFR 268.10. Due to the lack of nationwide
capacity at this time for the acid leaching treatment system determined
to be BOAT, the Agency has proposed to grant a 2-year nationwide variance
to the effective date of the land disposal ban for K071. A detailed
discussion of the Agency's determination that a lack of nationwide
capacity for the acid leaching treatment train determined to be BOAT
exists is presented in the Capacity Background Document, which is
available in the Administrative Record for the First Sixths Rule.
Consistent with Executive Order 12291, EPA prepared a regulatory
impact analysis (RIA) to assess the economic effect of compliance with
this proposed rule. The RIA prepared for this proposed rule is available
in the Administrative Record for the First Sixths Rule.
128
-------
APPENDIX A
ANALYTICAL DATA SUBMITTED BY INDUSTRY FOR
TREATMENT OF K071
129
-------
155«g
Table A-l Dewatenng/Washing Data Submitted by Plant A
Sample Set ttle
ANALYTICAL DATA-
BOAT Constituent
Arsenic
Barium
Cadmium
Chromium
Lead
Mercury
Nickel
Si Iver
Treated
(Total composition)
(mg/kg)
3.7
34
1.4
13
42
150
11
0.51
residual concentration
(EP Toxicity)
(mg/1)
<0.005
0.4
0.016
<0.005
0.08
0.013
0.06
<0.005
(TCLP)
(mg/1)
<0.005
<0.005
0.01
<0.005
0.09
0.014
<0.005
<0.005
Brine purification muds.
Reference: Occidental Chemical Corporation. 1987a.
130
-------
155ag
Table A-2 Dewatering/Washing Data Submitted by Plant A
Sample Set #2a
ANALYTICAL DATA-
BOAT Constituent
Arsenic
Barium
Cadmium
Chromium
Lead
Mercury
Nickel
Silver
Treated residual
(Total composition)
(nig/kg)
4.3
37
1.3
16
48
120
12
0.58
concentration
(EP Toxicity)
(rag/1)
<0.005
0.33
0.009
<0.005
0.06
0.014
0.05
<0.005
aBrine purification muds.
Reference: Occidental Chemical Corporation. 1987a.
131
-------
155Hg
Table A-3 Dewatering/Wash ing Data Submitted by Plant A
Sample Set #3a
ANALYTICAL DATA:
BOAT Constituent
Arsenic
Barium
Cadmium
Chromium
Lead
Mercury
Nickel
Si Iver
Treated residual
(Total composition)
(mg/kg)
0.82
6.3
1.1
3.9
10
78
2.0
0.89
concentration
(EP Toxicity)
(mg/D
<0.005
<0.30
0.008
<0.005
0.06
0.018
0.06
<0.005
Brine purification muds.
Reference: Occidental Chemical Corporation 1987a.
132
-------
1558g
Table A-4 Dewatering/Uashing Data Submitted by Plant A
Sample Set f4a
ANALYTICAL DATA:
BOAT Constituent
Arsenic
Barium
Cadmium
Chromium
Lead
Mercury
Nickel
Silver
Treated residual
(Total composition)
(mg/kg)
0.49
3.9
3.4
4.3
4.9
60
2.0
<0.5
concentration
(EP Toxicity)
(mg/1)
<0.005
0.30
0.009
<0.005
<0.03
0.013
0.02
<0.005
aBnne purification muds.
Reference. Occidental Chemical Corporation. 1987a.
133
-------
155Bg
Table A-5 Dewatenng/Washing Data Submitted by Plant A
Sample Set #5
ANALYTICAL DATA.
BOAT Constituent
Arsenic
Barium
Cadm i urn
Chromium
Lead
Mercury
Nickel
Si Iver
Treated residual
(Total composition)
(mg/kg)
1.1
16
3.0
15
25
82
8.4
<0.5
concentrat ion
(EP Toxicity)
(mg/1)
<0.005
<0.30
0.009
<0.005
0.31
<0.024
0.08
<0.005
Brine purification muds.
Reference: Occidental Chemical Corporation. 1987a.
134
-------
Table A-6 Dewatering/Washing Data Submitted by Plant A
Sample Set #6a
ANALYTICAL DATA:
BOAT Constituent
Arsenic
Barium
Cadmium
hromium
Lead
Mercury
Nickel
Silver
Treated residual
(Total composition)
(mg/kg)
1.4
15
2.0
26
32
95
12
<0.5
concentration
(EP Toxicity)
(rng/1)
<0.005
<0.30
<0.006
0.11
0.07
0.021
0.06
<0.005
aBrine purification muds.
Reference: Occidental Chemical Corporation. 1987a.
135
-------
Table A-7 Filtration/Washing Data Submitted by Plant A
Sample Set #7b
ANALYTICAL DATA.
BOAT Constituent
Arsenic
Barium
Cadmium
Chromium
Lead
Mercur>
Selenium
Si Iver
Treated residual concentration
(Total composition) (EP Toxicity)
(mg/kg) (mg/1)
7.7 <0.005
200 0.52
5.2 0.012
700 0.010
38 0.09
240 0.011
4.7 <0.005
100 0.40
Saturator insolubles
Reference. Occidental Chemical Corporation. 1987a.
136
-------
1562g
Table A-8 Filtration/Washing Data Submitted by Plant A
Sample Set »8
ANALYTICAL DATA.
BOAT Constituent
Arsenic
Barium
Cadm i urn
Chromium
Lead
Mercury
Selenium
Silver
Treated residual
(Total composition)
(mg/kg)
7.5
67
3.5
430
42
92
0.80
44
concentration
(EP Toxicity)
(mg/1)
<0.005
<0.30
0.012
0.019
0.08
0.003
<0.005
0.12
Saturator insolubles.
Reference: Occidental Chemical Corporation. 1987a.
137
-------
ISGZg
Table A-9 Filtration/Washing Data Submitted by Plant A
Sample Set #9b
ANALYTICAL DATA:
BOAT Constituent
Arsenic
Barium
Cadmium
Chromium
Lead
Mercury
Selenium
Si Iver
Treated residual
(Total composition)
(mg/kg)
25
71
3.9
390
62
78
<0.5
56
concentration
(EP Toxicity)
(mg/1)
<0.005
<0.30
0.009
<0.005
0.11 •
<0.0005
<0.005
1.2
Saturator insolubles.
Reference: Occidental Chemical Corporation. 1987a.
138
-------
Table A-10 Filtration/Washing Data Submitted by Plant A
Sample Set #10b
ANALYTICAL DATA-
BOAT Constituent
Arsenic
Barium
Cadmium
Chromium
Lead
Mercury
Selenium
Si Iver
Treated residual concentration
(Total composition) (EP Toxicity)
(nig/kg) (mg/1)
6.8 <0.005
110 <0.30
1.3 <0.006
760 0.018
110 0.08
72 0.0082
<0.5 <0.005
260 0.44
Saturator insolubles.
Reference: Occidental Chemical Corporation. 1987a.
139
-------
1562q
Table A-ll Filtration/Washing Data Submitted by Plant A
Sample Set #llb
ANALYTICAL DATA
BOAT Constituent
Arsenic
Barium
Cadmium
Chromium
Lead
Mercury
Selenium
Si Iver
Treated residual
(Total composition)
(mg/kg)
53
57
<0.5
590
41
53
<0.5
50
concentration
(EP Toxicity)
(mg/1)
<0.005
<0.30
<0.006
<0.001
0.10
<0.005
<0.005
0.10
Saturator insolubles.
Reference. Occidental Chemical Corporation. 1987a.
140
-------
1562g
Table A-12 Filtration/Washing Data Submitted by Plant A
Sample Set »12b
ANALYTICAL DATA:
BOAT Constituent
Arsenic
Barium
Cadmium
Chromium
Lead
Mercury
Selenium
Silver
Treated
(Total composition)
(mg/kg)
5.0
120
0.53
820
30
150
<0.5
48
residual concentration
(EP Toxicity)
(mg/1)
<0.005
<0.30
0.014
<0.005
0.10
<0.0005
<0.005
0.23
(TCLP)
(mg/1)
<0.005
0.40
0.017
<0.005
0.06
<0.0005
<0.005
0.08
Saturator insolubles.
Reference: Occidental Chemical Corporation. 1987a.
141
-------
155t>g
Table A-13 Dewatering/Wash ing Data Submitted by Plant
Sample Set #la
ANALYTICAL DATA.
BOAT Constituent
Arsenic
Barium
Cadmium
Chromium
Lead
Mercury
S i Iver
Treated residual
(Total composition)
(mg/kg)
0.46
35
0.92
7.5
82
5.7
14
concentration
(EP Toxicity)
(mg/1)
<0.005
0.11
<0.008
<0.005
0.10
<0.002
0.10
aBnne purification muds.
Reference: Occidental Chemical Corporation. 1987b
142
-------
Table A-14 Dewatenng/Washing Data Submitted by Plant B
Sample Set )C2a
ANALYTICAL DATA.
BOAT Constituent
Arsenic
Barium
Cadmium
Chromium
Lead
Mercury
Si Iver
Treated residual
(Total composition)
(mg/kg)
0.73
45
<0.73
6.7
86
6.2
11
concentration
(EP Toxicity)
(mg/1)
<0.005
0.19
<0.008
<0.005
0.11
<0.002
0.12
aBnne purification muds.
Reference. Occidental Chemical Corporation. 1987b
143
-------
1558g
Table A-15 Dewatenng/Washing Data Submitted by Plant B
Sample Set »<3a
ANALYTICAL DATA
BOAT Constituent
Arsenic
Barium
Cadmium
Chromium
Lead
Mercury
Si Iver
Treated residual
(Total composition)
(mg/kg)
<0.52
86
<0.73
6.6
97
6.5
13
concentration
(EP Toxicity)
(mg/D
<0.005
0.24
<0.008
<0.005
0.12
<0.005
0.15
Brine purification muds.
Reference: Occidental Chemical Corporation. 1987b
144
-------
1558q
Table A-16 Dewatering/Uashing Data Submitted by Plant B
Sample Set *4a
ANALVTICAL DATA-
BOAT Constituent
Arsenic
Barium
Cadmium
Chromium
Lead
Mercury
Si Iver
Treated residual
(Total composition)
(mg/kg)
0.70
81
0.71
6.3
89
5.9
12
concentration
(EP Toxicity)
(mg/1)
<0.005
<0.20
<0.008
<0.006
0.14
<0.005
0.13
Brine purification muds.
Reference Occidental Chemical Corporation. 1987b
145
-------
1369g
Table A-17 Filtration/Washing Data Submitted by Plant. B
Sample Set #5a
ANALYTICAL DATA.
BOAT Constituent
Arsen ic
Barium
Cadmium
Chromium
Lead
Mercury
Si Iver
Treated residual
(Total composition)
(nig/kg)
0.63
15
<0.63
7.0
41
3.9
4.4
concentration
(EP Toxicity)
(mg/1)
<0.005
0.05
<0.008
<0.005
0.12
<0.005
<0.07
aBnne purification muds.
Reference: Occidental Chemical Corporation. 1987b.
146
-------
1369g
Table A-18 Filtration/Washing Data Submitted by Plant B
Sample Set #6a
ANALYTICAL DATA.
BOAT Constituent
Arsenic
Barium
Cadmium
Chromium
Lead
Mercury
Si Iver
Treated residual
(Total composition)
(mg/kg)
0.54
97
<0.76
6.8
86
3.3
11
concentration
(EP Toxicity)
(mg/1)
cO.005
0.02
- <0.008
<0.005
0.10
<0.005
0.12
Brine purification muds.
Reference: Occidental Chemical Corporation. 1987b.
147
-------
136Sg
Table A-19 Filtration/Washing Data Submitted by Plant B
Sample Set #7a
ANALYTICAL DATA.
BOAT Constituent
Arsenic
Barium
Cadmium
Chromium
Lead
Mercury
Si Iver
Treated residual
(Total composition)
(mg/kg)
<0.58
180
<0.81
7.6
110
4.2
13
concentration
(EP Toxicity)
(mg/1)
<0.005
0.30
<0.008
0.006
0.10
<0.005
0.17
Brine purification muds.
Reference: Occidental Chemical Corporation. 1987b.
148
-------
1369g
Table A-20 Filtration/Washing Data Submitted by Plant B
Sample Set #8d
ANALYTICAL DATA:
BOAT Constituent
Arsenic
Bar lum
Cadmium
Chromium
Lead
Mercury
Si Iver
Treated residual
(Total composition)
(mg/kg)
0.61
82
<0.71
6.8
72
4.9
7.1
concentration
(EP Toxicity)
(mg/D
<0.005
0.43
<0.008
<0.005
0.06
<0.005
0.09
Brine purification muds.
Reference: Occidental Chemical Corporation. 1987b.
149
-------
136c
-------
1369g
Table A-22 Filtration/Washing Data Submitted by Plant B
Sample Set #10a
ANALYTICAL DATA.
BOAT Constituent
Arsenic
Barium
Cadmium
Chromium
Lead
Mercury
Si Iver
Treated residual
(Total composition)
(mg/kg)
0.96
39
0.74
6.6
110
3.6
21
concentration
(EP Toxicity)
(mg/1)
<0.005
<0.02
<0 . 008
<0.005
0.10
<0.005
0.28
Brine purification muds.
Reference- Occidental Chemical Corporation. 1987b.
151
-------
1369g
Table A-23 Filtration/Washing Data Submitted by Plant B
Sample Set *llc
ANALYTICAL DATA:
BOAT Constituent
Arsenic
Barium
Cadmium
Chromium
Lead
Mercury
Si Iver
Treated residual
(Total composition)
(mg/kg)
0.89
29
1.3
6.7
85
4.0
15
concentration
(EP Toxicity)
(tng/1)
<0.005
<0.02
<0.008
<0.005
0.11
<0.005
0.12
dBnne purification muds.
Reference: Occidental Chemical Corporation. 1987b.
152
-------
Table A-24 Filtration/Washing Data Submitted by Plant B
Sample Set #12a
ANALYTICAL DATA
BOAT Constituent
Arsenic
Barium
Cadmium
Chromium
Lead
Mercury
Silver
Treated residual
(Total composition)
(mg/kg)
1.1
22
0.84
6.6
94
2.9
16
concentration
(EP Toxicity)
(mg/1)
<0.005
0.11
<0.008
<0.005
0.09
<0.005
0.19
aBrine purification muds.
Reference: Occidental Chemical Corporation. 1987b.
153
-------
1369g
Table A-25 Filtration/Washing Data Submitted by Plant B
Sample Set #13d
ANALYTICAL DATA-
BOAT Constituent
Arsenic
Barium
Cadmium
Chromium
Lead
Mercury
Si Iver
Treated residual
(Total composition)
(mg/kg)
6.0
70
<0.63
17
330
3.5
92
concentration
(EP Toxiclty)
(nig/1)
<0.005
0.05
<0.008
<0.005
0.35
0.0080
0.66
Brine purification muds.
Reference- Occidental Chemical Corporation. 1987b.
154
-------
1369g
Table A-26 Filtration/Washing Data Submitted by Plant B
Sample Set #14a
ANALYTICAL DATA:
BOAT Constituent
Arsenic
Barium
Cadmium
Chromium
Lead
Mercury
Silver
Treated residual
(Total composition)
(mg/kg)
7.7
56
<0.71
16
340
3.7
76
concentration
(EP Toxicity)
(mg/1)
<0.005
0.11
<0.008
<0.005
0.77
0.0063
0.63
Brine purification muds.
Reference: Occidental Chemical Corporation. 1987b.
155
-------
1369g
Table A-27 Filtration/Washing Data Submitted by Plant B
Sample Set #15
ANALYTICAL DATA:
BOAT Constituent
Arsenic
Barium
Cadmium
Chromium
Learl
Mercury
Si Iver
Treated residual
(Total composition)
(mg/kg)
15
60
<0.78
17
340
4.8
81
concentration
(EP Toxicity)
(mg/1)
<0.005
0.27
<0.008
<0.005
0.40
0.032
0.79
Brine purification muds.
Reference. Occidental Chemical Corporation. 1987b.
156
-------
1369g
Table A-28 Filtration/Washing Data Submitted by Plant B
Sample Set #16a
ANALYTICAL DATA:
BOAT Constituent
Arsenic
Barium
Cadm i urn
Chromium
Lead
Mercury
Selenium
Si Iver
Treated residual
(Total composition)
(mg/kg)
<0.51
24
<0.71
11
170
2.3
1.6
69
concentration
(EP Toxicity)
(mg/1)
<0.005
0.21
<0.008
<0.005
0.08
0.0080
<0.005
0.22
Brine purification muds.
Reference: Occidental Chemical Corporation. 1987b.
157
-------
Table A-29 Filtration/Washing Data Submitted by Plant B
Sample Set #17a
ANALYTICAL DATA
BOAT Constituent
Arsenic
Barium
Cadmium
Chromium
Lead
Mercury
Si Iver
Treated residual
(Total composition)
(mg/kg)
2.5
7.9
<0 69
5.7
100
6.9
30
concentration
(EP Toxicity)
(mg/D
<0.005
0.11
<0.008
<0.005
0.11
<0.002
0.14
aBrine purification muds.
Reference: Occidental Chemical Corporation. 1987b.
158
-------
Table A-30 Filtration/Washing Data Submitted by Plant B
Sample Set *18a
ANALYTICAL DATA
BOAT Constituent
Arsenic
Barium
Cadmium
Chromium
Lead
Mercury
Silver
Treated residual
(Total composition)
(mg/kg)
7.3
42
<0.77
16
200
11
95
concentration
(EP Toxicity)
(rog/1)
<0.005
<0.04
<0.008
<0.005
0.10
0.0093
0.16
]
aBrine purification muds.
Reference. Occidental Chemical Corporation. 1987b.
159
-------
1369g
Table A-31 Filtration/Washing Data Submitted by Plant B
Sample Set f!9
ANALYTICAL DATA-
BOAT Constituent
Arsen ic
Barium
Cadm i urn
Chromium
Lead
Mercury
Si Iver
Treated residual
(Total composition)
(mg/kg)
6.1
98
<0.70
19
310
2.0
77
concentration
(EP Toxicity)
(mg/D
<0.005
<0.02
<0.008
<0.005
0.36
0.013
0.46
Brine purification muds.
Reference: Occidental Chemical Corporation. 1987b.
160
-------
1369g
Table A-32 Filtration/Washing Data Submitted by Plant B
Sample Set #20a
ANALYTICAL DATA-
BOAT Constituent
Arsenic
Barium
Cadmium
Chromium
Lead
Mercury
Si Iver
Treated residual concentration
(Total composition) (EP Toxicity)
(nig/kg) (mg/1)
7.9 <0.005
79 0.38
<0 70 <0.008
20 <0.005
430 0.33
9.6 0.014
220 1.22
Brine purification muds.
Reference: Occidental Chemical Corporation. 1987b.
161
-------
1369g
Table A-33 Filtration/Washing Data Submitted by Plant B
Sample Set #21b
ANALYTICAL DATA.
BOAT Constituent
Arsenic
Barium
Cadmium
Chromium
Lead
Mercury
Si Iver
Treated residual
(Total composition)
(mg/kg)
<0.6
<3.0
0.73
0.10
79
5.5
1.3
concentration
(EP Toxicity)
(mg/1)
<0.005
<0.03
<0.005
0.007
0.15
0.0008
<0.005
Saturator insolubles.
Reference: Occidental Chemical Corporation. 1987b.
162
-------
1369g
Table A-34 Filtration/Washing Data Submitted by Plant B
Sample Set #22b
ANALYTICAL DATA:
BOAT Constituent
Arsenic
Barium
Cadmium
Chromium
Lead
Mercury
Si Iver
Treated residual
(Total composition)
(mg/kg)
<0.6
<3.0
<0.70
0.78
42
1.8
<0.6
concentration
(EP Toxicity)
(mg/1)
<0.005
<0.03
0.005
<0.005
0.17
<0.0005
<0.005
Saturator insolubles.
Reference: Occidental Chemical Corporation. 1987b.
163
-------
1369q
Table A-35 Filtration/Washing Data Submitted by Plant B
Sample Set *23b
ANALYTICAL DATA.
BOAT Constituent
Arsenic
Barium
Cadmium
Chroinium
Lead
Mercury
Nickel
Si Iver
Treated residual
(Total composition)
(mg/kg)
<0.6
<3 0
0.73
0.62
34
3.0
6.2
0 83
concentration
(EP Toxicity)
(mg/1)
<0.005
<0.03
<0.005
0.007
0.11
<0.0005
<0.03
<0.005
Saturator insolubles.
Reference: Occidental Chemical Corporation. 1987b.
164
-------
1369g
Table A-36 Filtration/Washing Data Submitted by Plant B
Sample Set #24b
ANALYTICAL DAI A
BOAT Constituent
Arsen ic
Barium
Cadmium
Chromium
Lead
Mercury
Nickel
Silver
Treated residual concentration
(Total composition) (EP Toxicity)
(rug/kg) (mg/1)
<0.6 <0.005
50 0.06
0.50 <0.005
0.10 0.006
42 0.12
3.4 <0.0005
3.0 <0.03
<0.6 <0.005
Saturator insolubles.
Reference- Occidental Chemical Corporation. 1987b.
165
-------
1558g
Table A-37 Dewatering/Washing Data Submitted by Plant C
ANALYTICAL DATA:
Quarter EP Toxicity - Mercury
3rd '87 0.013
0.005
0.017
0.020
0.048
0.070
0.002
0.008
0.013
2nd '87 0.010
0.009
0.004
<0.002
0.008
0.004
0.003
0.012
0.007
0.011
0.006
0.001
0.009
0.002
0.001
0.003
0.004
<0.001
0.009
0.003
0.015
0.006
0.009
0.008
0.005
0.011
0.014
0.010
0.002
0.005
0.012
0.002
166
-------
1558g
Table A-37 (continued)
ANALYTICAL DATA:
Quarter
EP Toxicity - Mercury
1st '87
0.010
<0.001
0.010
<0.001
0.001
<0.001
0.003
0.004
0.003
0.022
0.006
0.005
0.015
0.030
0.013
0.018
0.024
0.010
<0.001
0.012
0.017
0.009
0.006
0.001
0.001
0.011
0.012
0.007
0.006
0.016
0.040
0.010
0.016
0.040
0.024
0.021
0.010
0.013
<0.001
0.014
0.012
167
-------
1558g
Table A-37 (continued)
ANALYTICAL DATA:
Quarter
EP Toxicity - Mercury
4th '86
3rd '86
0.027
0.020
0.010
0.023
0.046
0.005
0.025
0.036
0.024
0.009
0.012
0.030
0.039
0.036
0.033
0.049
0.035
0.037
0.030
0.009
0.006
0.009
0.006
0.016
0.009
0.014
0.010
0.008
0.007
0.006
0.006
<0.001
0.003
0.009
0.021
0.006
0.027
0.035
0.028
0.029
0.034
168
-------
1558g
Table A-37 (continued)
ANALYTICAL DATA:
Quarter EP Toxicity - Mercury
<0.001
0.013
0.007
0.014
0.056
0.037
0.026
0.016
0.023
0.037
0.037
0.039
0.001
0.039
0.002
0.041
0.072
0.005
0.107
0.036
0.008
0.039
2nd '86 0.014
0.005
0.034
0.004
0.002
0.004
0.008
0.066
0.001
0.004
<0.001
0.002
0.007
0.005
0.018
0.022
0.031
0.014
0.091
169
-------
1558g
Table A-37 (continued)
ANALYTICAL DATA:
Quarter
EP Toxicity - Mercury
1st '86
4th '85
0.037
0.164
0.005
0.008
0.004
0.005
0.091
0.011
0.038
0.090
0.065
0.007
0.012
0.020
0.016
0.030
0.114
0.169
0.051
0.012
0.045
0.037
0.027
0.029
0.055
0.115
0.041
0.030
0.033
0.025
0.022
0.040
0.001
0.038
0.016
0.020
0.021
0.038
0.039
0.027
0.023
170
-------
1558g
Table A-37 (continued)
ANALYTICAL DATA:
Quarter
EP Toxicity - Mercury
0.015
0.026
0.023
0.029
0.010
0.023
0.023
0.027
0.032
0.028
0.035
0.027
0.031
0.064
0.031
0.022
0.025
0.035
0.050
0.031
0.026
0.042
0.063
0.044
0.043
0.053
0.022
0.017
Reference: B.L. Bennett. 1986.
171
-------
APPENDIX B
ANALYTICAL QA/QC
172
-------
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 Evaluating 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 PR 40643, November 7, 1986.
SW-846 allows for the use of alternative or equivalent procedures or
equipment; these are noted in Table B-2. These alternatives or
equivalents included use of alternative sample preparation methods and/or
use of different extraction techniques to reduce sample matrix
interferences.
The accuracy determination for a constituent is based on the matrix
spike recovery values. Tables B-3 and B-4 present the matrix spike
recoveries for mercury for both total composition and TCLP analyses for
K071 residuals for the EPA-collected data. Matrix spike recoveries for
total composition, TCLP, and EP toxicity analyses for data submitted by
Plants A and B are presented in Tables B-5 through B-8.
The accuracy correction factors for mercury for each treatment
residual are summarized in Tables B-3 through B-8. The accuracy
correction factors were determined in accordance with the general
methodology presented in the Introduction. For example, for mercury,
173
-------
034ig
Table B-l Analytical Methods for Regulated Constituents
Regulated Constituent
Extraction Method
Analytical Method
Reference
TOTAL COMPOSITION
Mercury
TCLP EXTRACT
Mercury
Specified in analytical method
Specified in analytical method
Specified in analytical method
Mercury in Liquid Waste
(Manual Cold-Vapor Technique)
7470
Mercury in Solid or Semi-Solid 7471
Waste (Manual Cold-Vapor Technique)
Toxicity Characteristic Leaching 51 FR 40643
Procedure (TCLP)
Mercury in Liquid Waste 7470
(Manual Cold-Vapor Technique)
References:
1. Environmental Protection Agency. 1986b. Test Methods for Evaluating Solid Waste. Third Edition. U.S. EPA. Office of Solid Waste
and Emergency Response. November 1986.
2. Environmental Protection Agency. 19B6c. Hazardous Waste Management Systems; Land Disposal Restrictions; Final Rule; Appendix I to
Part 268 - Toxicity Leaching Procedure (TCLP). Federal Register. Vol. 51. No. 216. November 7. 1986. pp. 40643-40654.
-------
Table 6-2 Specific Procedures or Equipment Used in Mercury Analysis
When Alternatives or Equivalents are Allowed in the SW-846 Methods
Analysis Method Equipment
Alternatives or Equivalents
Allowed by SW-&46 Method
Specific Procedures
or Equipment Used
Mercury 7470 Perkin Elmer 50A • Operate equipment following instructions
7471 by instrument manufacturer.
• Equipment operated using procedures
specified in Perkin Elmer 50A
Instructions Manual.
• Cold vapor apparatus as described in
SW-846 or an equivalent apparatus may
be used.
Mercury was analyzed by cold vapor
method using the apparatus as
specified in SW-846, except that there
was no scrubber.
Samples may be prepared using the water
bath method or the autoclave method,
both described in SW-846
• Samples were prepared using the water
bath method.
Reference USEPA. 1988a Table 6-7
175
-------
0341g
Table B-3 Matrix Spike Recoveries for Solid Waste Matrix - EPA-Collected Data
BOAT
constituent
Original amount
found (mg/kg)
Spike added
(mg/kg)
Sample Result
Spike result Percent
(mg/kg) recovery*
DUD! icate Result
Spike added
(mg/kg)
Spike result Percent
(mg/kg) recovery*
Accuracy
correct ion
factor"
Mercury
1.1
2.0
3.6
125
2.0
3.7
130
1.0
NC = Not calculable.
'Percent Recovery = [(Spike Result - Original Amount)/Spike Added].
"Accuracy Correction Factor = 100/Percent Recovery (using the lowest percent recovery value).
Note: Matrix spike data obtained from untreated K071(b) waste (Sample Set #8).
-------
034 Ig
Table B-4 Matrix Spike Recoveries for TCLP Extracts for Treated Waste - EPA-Collected Data
BOAT
constituent
Original amount
found (ug/1)
Spike added
(ug/1)
Sample Set #6
Spike result
(ug/1)
Sample Set #6 Duplicate
Percent
recovery*
Spike added
(ug/1)
Spike result
(ug/1)
Percent
recovery*
Accuracy
correct ion
factor**
Mercury
1.6
4.0
5.4
95
4.0
5.5
98
1.05
NC = Not calculable.
'Percent Recovery = [(Spike Result - Or-iginal Amount)/Spike Added].
**Accuracy Correction Factor = 100/Percent Recovery (using the lowest percent recovery value).
Reference: USEPA. 1988a. Table 6-16.
-------
Table B-5 Matrix Spike Recoveries for Treated Residual - Plant A
Sample Result Accuracy
BDA1 Original amount Spike added Spike result Percent correction
constituent found (mg/kg) (mg/kg) (mg/kg) recovery* factor**
Sample "3.
Mercury 78 0.4 NR 106 1.0
Sample *8:
Mercury 92 0.4 NR 88 1.14
NR = Not reported
'Percent Recovery = [(Spike Result - Original Amount)/Spike Added].
'"Accuracy Correction Factor = 100/Percent Recovery (using the lowest percent recovery value).
Reference Occidental Chemical Corporation. 1987a.
178
-------
0341g
Table B-6 Matrix Spike Recoveries for TCLP and EP Toxicity Extracts for Treated Waste - Plant A
BOAT Original amount
constituent found (ug/1)
Sample #1 - EP Toxicity
Mercury 13
Sample #1 - TCLP-
Mercury 14
Sample #2 - EP Toxicity:
Mercury 14
Sample 13 - EP Toxicity:
Mercury 18
Sample #4 - EP Toxicity.
Mercury 13
Sample #5 - EP Toxicity
Mercury 24
Sample #6 - EP Toxicity
Mercury 21
Sample #7 - EP Toxicity:
Mercury 11
Sample #8 - EP Toxicity:
Mercury 3.0
Sample #9 - EP Toxicity:
Mercury <0.5
Sample #10 - EP Toxicity.
Sample Result Duplicate Result
Spike added Spike result Percent Spike added Spike result Percent
(ug/1) (ug/1) recovery* (ug/1) (ug/1) recove-y*
0.2 NR 124 0.4 NR 112
0.2 NR 95 0.4 NR 97
0.2 NR 117 0.4 NR 121
0.2 NR 104 0.4 NR 115
0.2 NR 120 0.4 NR 112
0.2 NR 81 0.4 NR 84
0.2 NR 94 0.4 NR 79
0.2 NR 76 0.4 NR 105
0.2 NR 105 0.4 NR 122
0.2 NR 125 0.4 NR 119
Accuracy
correct ion
factor**
1 0
1.05
1 0
1.0
1 0
1.23
1.27
1 32
1.0
1.0
0.2
NR
80
0.4
NR
90
1.25
-------
0341g
Table B-6 (continued)
BOAT Original amount
constituent found (ug/1)
Sample #11 - EP Toxicity:
Mercury 0.7
Sample #12 - EP Toxicity:
Mercury <0.5
Sample #12 - TCLP:
Mercury <0.5
Sample Result Duplicate Result
Spike added Spike result Percent Spike added Spike result Percent
(ug/1) (ug/1) recovery* (ug/1) (ug/1) recovery'
0.2 NR 106 0 4 NR 98
0.2 NR 99 04 NR 101
0.2 NR 90 0.4 NR 99
Accuracy
correct ion
factor'"
1 02
1 01
1 11
NR = Not reported.
*Percent Recovery = [(Spike Result - Original Amount)/Spike Added].
**Accuracy Correction Factor = 100/Percent Recovery (using the lowest percent recovery value).
oo
0
Reference Occidental Chemical Corporation. 1987a
-------
034Ig
Table B-7 Matrix Spike Recoveries for Treated Residual - Plant B
BDA1 Original amount
constituent found (mg/kg)
Sample fll:
Mercury 4 0
Sampje *19.
Mercury 2.0
Sample §22-
Mercury 1 8
Sample Result
Spike added Spike result Percent
(mg/kg) (mg/kg) recovery*
0.4 NR 83
0.4 NR 99
0.4 NR 99
Accuracy
correction
factor**
1.20
1.01
1.01
NR = Not reported
''Percent Recovery = [(Spike Result - Original Amount)/Spike Added].
"Accuracy Correction Factor = 100/Percent Recovery (using the lowest percent recovery value).
Reference Occidental Chemical Corporation. 1987b
181
-------
0341g
Table B-8 Matrix Spike Recoveries for EP Toxicity Extracts for Treated Waste - Plant B
03
BOAT
constituent
Sample Set #1
Mercury
Sample Set #2 .
Mercury
Sample Set #3
Mercury
Sample Set 14
Mercury
Sample Set #5
Mercury
Sample Set #6-
Mercury
Sample Set #7:
Mercury
Sample Set #8:
Mercury
Sample Set #9:
Mercury
Sample Set #10:
Mercury
Sample Set 111:
Mercury
Sample Result
Original amount Spike added Spike result Percent
found (ug/1) (ug/1) (ug/1) recovery*
<2.0 0.2 NR 99
<2.0 0.2 NR 106
<5.0 0.2 NR 96
<5.0 0.2 NR 115
<5.0 0.2 NR 112
<5.0 0.2 NR 101
<5.0 0.2 NR 109
<5.0 0.2 NR 110
<5.0 0.2 NR 113
<5 0 0.2 NR 109
<5.0 0.2 NR 108
Duplicate Result
Spike added Spike result Percent
(ug/1) (ug/1) recove'y4
0.4 NR 93
0.4 NR 93
0.4 NR 100
0.4 NR 98
04 NR 104
0.4 NR 102
0.4 NR 103
0.4 NR 101
0.4 NR 101
0.4 NR 103
0.4 NR 101
Accuracy
correct 'or
factor"
1 06
1 08
1 04
1 02
1 0
1.0
1.0
1.0
1.0
1 0
1 0
-------
0341g
Table B-8 (continued)
OJ
Sample Result
BOAT Original amount Spike added Spike result Percent
constituent found (ug/1) (ug/1) (ug/1) recovery*
Sample Set #12:
Mercury '5.0 0.2 NR 108
Sample Set #13:
Mercury 8.0 0.2 NR 93
Sample Set #14:
Mercury 6.3 0.2 NR 94
Sample Set #15:
Mercury 32 0.2 NR 92
Sample Set #16:
Mercury 8.0 02 NR 89
Sample Set #17:
Mercury <2.0 0.2 NR 92
Sample Set #16:
Mercury 9.3 0.2 NR 94
Sample Set #19:
Mercury 13 0.2 NR 80
Sample Set #20:
Mercury 14 0.2 NR 83
Sample Set #21:
Mercury 0.8 0.2 NR 107
Sample Set #22.
Mercury <0.5 0.2 NR 102
Duplicate Result
Spike added Spike result Percent
(ug/1) (ug/1) recovery*
0.4 NR 102
0.4 NR 94
0.4 NR 97
0.4 NR 82
0.4 NR 87
0.4 NR 97
0.4 NR 82
0.4 NR 81
0.4 NR 83
0.4 NR 109
0.4 NR 102
Accuracy
correction
factor'*
1 0
1 06
1 06
1 22
1 15
1 09
1.22
1.25
1.20
1.0
1.0
-------
0341g
Table B-6 (continued)
BOAT
constituent
Original amount
found (ug/1)
Spike added
Sample Result
Spike result
(ug/1)
Percent
recovery*
Duplicate Result
Spike added
(ug/1)
Spike result
(ug/1)
Percent
recovery*
Accuracy
correction
factor'*
Sample Set f23-
Mercury
Sample Set 024.
Mercury
<0.5
<0.5
0.2
0.2
NR
NR
102
104
0.4
0.4
NR
NR
104
108
1.0
1 0
NR = Not reported.
*Percent Recovery = [(Spike Result - Original Amount)/Spike Added].
"Accuracy Correction Factor = 100/Percent Recovery (using the lowest percent recovery value).
Reference: Occidental Chemical Corporation. 1987b.
co
-------
actual spike recovery data were obtained for analysis of both solid and
liquid matrices and the lowest percent recovery value was used to
calculate the accuracy correction factor. An example of the calculation
of a corrected constituent concentration value is shown below.
Analytical Correction Corrected
Value % Recovery Factor Value
0.0016 mg/1 95 100 - 1 05 1.05 x 0.0016 = 0.0017 mg/1
95 "
185
-------
APPENDIX C
STATISTICAL ANALYSIS
186
-------
APPENDIX C - STATISTICAL ANALYSIS
C.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
different, 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 C-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
187
-------
Table C-l
95th PERCENTILE VALUES FOR
THE F DISTRIBUTION
MI = degrees of freedom for numerator
«2 = degrees of freedom for denominator
(shaded area — .95}
y^V
FM
^
1
2
3
4
5
G
t
8
p
10
11
12
13
14
15
16
17
18
19
20
2°
24
26
28
30
40
50
60
70
80
100
150
200
400
eo
i
1G1.4
18.51
10.13
7.71
6.61
5.99
5.59
5.32
5.12
4.96
4.84
4.75
4.G7
4.60
4.54
4.49
4.45
4.41
4.38
4.35
4.30
4.26
4.23
4.20
4.17
4.08
4.03
4.00
3.98
3.96
3.94
3.91
3.89
3.86
3.84
2
199.5
19.00
9.55
6.94
5.79
5.14
4.74
4.46
4.26
4.10
3.98
3.89
3.S1
3.74
3.68
3.63
3.59
3.55
3.52
3.49
3.44
3.40
3.37
3.34
3.32
3.23
3.18
3.15
3.13
3.11
3.09
3.06
3.04
3.02
2.99
3
215.7
19.16
9.28
6.59
5.41
4.76
4.35
4.07
3.86
3.71
3.59
3.49
3.41
3.34
3.29
. 3.24
3.20
3.16
3.13
3.10
3.05
3.01
2.98
2.95
2.92
2.84
2.79
2.76
2.74
2.72
2.70
2.67
2.65
2.62
2.60
4
224.6
19.25
9.12
6.39
5.19
4.53
4.12
3.84
3.G3
3.48
3.36
3.26
3.18
3.11
3.06
3.01
2.96
2.93
2.90
2.87
2.82
2.78
2.74
2.71
2.69
2.61
2.56
2.53
2.50
2.48
2.46
2.43
2.41
2.39
2.37
5
230.2
19.30
9.01
6.26
5.05
4.39
3.97
3.69
3.48
3.33
3.20
3.11
3.03
2.96
2.90
2.85
2.81
2.77
2.74
2.71
2.66
2.62
2.59
2.56
2.53
2.45
2.40
2.37
2.35
2.33
2.30
2.27
2.26
2.23
2.21
6
234.0
19.33
8.94
6.16
4.95
4.28
3.87
3.58
3.37
3.22
3.09
3.00
2.92
2.85
2.79
2.74
2.70
2.66
2.63
2.60
2.55
2.51
2.47
2.45
2.42
2.34
2.29
2.25
2.23
2.21
2.19
2.16
2.14
2.12
2.09
8
238.9
19.37
8.85
6.04
4.82
4.15
3.73
3.44
3.23
3.07
2.95
2.85
2.77
2.70
2.64
2.59
2.55
2.51
2.48
2.45
2.40
2.36
2.32
2.29
2.27
2.18
2.13
2.10
2.07
2.05
2.03
2.00
1.98
1.96
1.94
12
243.9
19.41
8.74
5.91
4.68
4.00
3.57
3.28
3.07
2.91
2.79
2.69
2.60
2.53
2.48
2.42
2.38
2.34
2.31
2.28
2.23
2.18
2.15
2.12
2.09
2.00
1.95
1.92
1.89
1.88
1.85
1.82
1.80
1.78
1.75
16
24G.3
19.43
8.69
5.84
4.60
3.92
3.49
3.20
2.98
2.82
2.70
2.60
2.51
2.44
2.39
2.33
2.29
2.25
2.21
2.18
2.13
2.09
2.05
2.02
1.99
1.90
1.85
1.81
1.79
1.77
1.75
1.71
1.69
1.67
1.64
20
248.0
19.45
8.66
5.80
4.56
3.87
3.44
3.15
2.93
2.77
2.65
2.54
2.46
2.39
2.33
2.28
2.23
2.19
2.15
2.12
2.07
2.03
1.99
1.96
1.93
1.84
1.78
1.75
1.72
1.70
1.68
1.64
1.62
1.60
1.57
30
250.1
19.46
8.62
5.75
4.50
3.81
3.38
3.08
2.86
2.70
2.57
2.46
2.38
2.31
2.25
2.20
2.15
2.11
2.07
2.04
1.98
1.94
1.90
1.87
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.CO
5.71
4.46
3.77
3.34
3.05
2.82
2.67
2.53
2.42
2.34
2.27
2.21
2.16
2.11
2.07
2.02
1.99
1.93
1.89
1.85
1.81
1.79
1.69
1.63
1.59
1.56
1.54
1.51
1.47
1.45
1.42
1.40
50
252.2
19.47
8.58
5.70
4.44
3.75
3.32
3.03
2.80
2.64
2.50
2.40
2.32
2.24
2.18
2.13
2.08
2.04
2.00
1.96
1.91
1.86
1.82
1.78
1.76
1.66
1.60
1.56
1.53
1.51
1.48
1.44
1.42
1.38
1.32
100
253.0
19.49
8.56
5.66
4.40
3.71
3.28
2.98
2.76
2.59
2.45
2.35
2.26
2.19
2.12
2.07
2.02
1.98
1.94
1.90
1.84
1.80
1.76
1.72
1.69
1.59
1.52
1.48
1.45
1.42
1.39
1.34
1.32
1.28
1.24
C
254.3
19.50
8.53
5.63
4.35
3.67
3.23
2.93
2.71
2.54
2.40
2.30
2.21
2.13
2.07
2.01
1.96
1.92
l.SS
1.84
1.78
1.73
1.69
1.65
1.62
1.51
1.44
1.39
1.35
1.32
1.28
1.22
1.19
1.13
1.00
188
-------
necessary to perform a "pair wise F" test to determine if any of the sets
are homogeneous. The "pair wise F" test must be done for all of the
various combinations of data sets using the same method and equation as
the general F test.
The F value is calculated as follows:
(i) All data are natural logtransformed.
(ii) The sum of the data points for each data set is computed (T.).
(iii) The statistical parameter known as the sum of the squares
between data sets (SSB) is computed:
SSB
where:
k = number of treatment technologies
n^ = number of data points for technology i
N = number of data points for all technologies
T^ = sum of natural logtransformed data points for each technology.
(iv) The sum of the squares within data sets (SSW) is computed:
k
I
i = l
rVi
Ni
" k
•Z! ^
1=1
N
f. -
SSW =
k ni
r- t-' ?
£ £ x iJ
1-1 j-1
k
- I
i-1
where:
fTi2
—
I
x-j i = 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.
189
-------
(vi) Using the above parameters, the F value is calculated as
follows:
MSB
F = MSW
where:
. MSB = SSB (k-1) and
MSW . SSW (N-k).
A computational table summarizing the above parameters is shown below.
Computational Table for the F Value
Source
Between
Within
Degrees of
freedom
k-1
N-k
Sum of
squares
SSB
SSW
Mean square
MSB = SSB/k-1
MSW = SSW/N-k
F
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.
190
-------
1 790g
Example 1
Methylene Chloride
Steam stripping
Influent Effluent
Ug/D
1550 00
1290 00
1640.00
5100 00
1-150 00
4600.00
1760 00
2400.00
4800 00
12100.00
Ug/D
10 00
10.00
10 00
12 00
10 00
10.00
10 00
10.00
10.00
10 00
Biological treatment
In(effluent) [ln(eff luent )]2 Influent Effluent In(effluent)
2 30
2 30
2.30
2.48
2.30
2.30
2 30
2 30
2.30
2.30
Ug/i) Ug/D
5.29 1960 00 10.00 2.30
5.29 2568.00 10.00 2.30
5.29 1817.00 10.00 2.30
6.15 1640.00 26.00 3.26
5.29 3907.00 10.00 2.30
5.29
5.29
5.29
5.29
5.29
[In(effluent)]2
5.29
5.29
5.29
10.63
5.29
Sum
23.18
53.76
12.46
31.79
Sample Size.
10 10
Mean
3669 10 2
Standard Deviation:
3328.67 .6;
Vdr labi1ity Factor.
10
2.32
.06
2378
923.04
1.15
13.2
7.15
2.48
2.49
.43
ANOVA Calculations.
"i
k ni
SSW = - -
MSB = SSB/(k-l)
MSW = SSW/(N-k)
V
nT"
191
-------
1790g
Example 1 (continued)
F = MSB/MSW
where
k = number of treatment technologies
n = number of data points for technology i
N = number of natural log transformed data points for all technologies
T = sum of log transformed data points for each technology
X = the nat. log transformed observations (j) for treatment technology (i)
n = 10, n = 5, N = 15, k = 2, T = 23 18, T = 12.46, T = 35.64, T = 1270.21
T2 = 537.31 T2 = 155.25
SSB =
537.31 155.25
10
1270.21
15
= 0.10
SSW = (53.76 + 31.79) -
537.31 155.25'
10
= 0.77
MSB = 0 10/1 = 0.10
MSW = 0.77/13 = 0.06
0.10
F = =1.67
0.06
ANOVA Table
Source
Degrees of
freedom
SS
MS
Between(B)
Uithin(W)
1
13
0.10
0.77
0.10
0.06
1.67
The critical value of the F test at the 0 05 significance level is 4.67. Since
the F value is less than the critical value, the means are not significantly
different (i e., they are homogeneous).
Note: All calculations were rounded to two decimal places. Results may differ
depending upon the number of decimal places used in each step of the calculations.
192
-------
1790cj
Example 2
Trichloroethylene
Steam st r iup inq
Influent
U9/1)
1650 00
5200.00
5000 00
1720 00
1560 00
10300.00
210 00
1600.00
204.00
160.00
Effluent
Ug/l)
10 00
10.00
10.00
10 00
10.00
10.00
10.00
27 00
85 00
10.00
ln(eff luent)
2 30
2.30
2.30
2.30
2.30
2.30
2 30
3.30
4 44
2.30
[In(effluent)]2
5 29
5.29
5.29
5.29
5.29
5.29
5.29
10.89
19.71
5.29
Influent
Ug/1!
200 00
224.00
134.00
150.00
484.00
163.00
182.00
Biological treatment
Effluent
Ug/l)
10.00
10.00
10.00
10.00
16.25
10.00
10.00
ln(eff luent)
2.30
2.30
2.30
2.30
2.79
2.30
2.30
[In(effluent)]2
5.29
5.29
5.29
5.29
7.78
5.29
5.29
26.14
72.92
16.59
39.52
Sample Size:
10 10
10
Meanj
2760
19 2
2 61
220
10.89
2.37
Standard Deviation.
3209.6 23 7
.71
120.5
2.36
.19
Variability Factor:
70
1.53
ANOVA Calculations:
SSB =
SSW =
-
n.
k n,
2
i=l J=l
MSB = SSB/(k-l)
r k
tt
* n>2
"1=1
MSW = SSW/(N-k)
193
-------
17ciQg
Example 2 (continued)
F = MSB/MSW
where'
k = number of treatment technologies
n = number of data points for technology i
N = number ot data points for all technologies
T = sum of natural log transformed data points for each technology
X = the natural log transformed observations (j) for treatment technology (i)
N, = 10, N = 7, N = 17, k = 2, T = 26.14, T = 16.59, T = 42.73, T2- 1825.85, T2 = 683.30,
T? = 275.23
SSB =
683 30
275.23
10
1825.85
SSW = (72.92 + 39 52) -
MSB = 0 25/1 = 0.25
MSW = 4.79/15 = 0.32
0 25
F = = 0 78
0 32
f 683.30 275.23
10
7
= 0.25
= 4.79
ANOVA Table
Degrees of
Source freedom
Between (B) 1
Withm(W) 15
SS MS F
0.25 0.25 0.78
4.79 0.32
The critical value of the F test at the 0.05 significance level is 4.54. Since
the F value is less than the critical value, the means are not significantly
different (i e., they are homogeneous).
Note: All calculations were rounded to two decimal places. Results may differ
depending upon the number of decimal places used in each step of the calculations.
194
-------
1790g
Example 3
Chlorobenzene
Activated sludge followed by carbon adsorption
Biological treatment
hit luent
Effluent
(fig/1)
ln(eftluent) [ln(eff luent)] Influent
Effluent
(fig/1)
ln(effluent)
ln[(ef fluent)]'
7200.00
6500 00
6075 00
.3040.00
HO 00
70 00
35.00
10 00
4.38
4 25
3.56
2.30
19.18
18.06
12.67
5.29
9206 00
16646.00
49775.00
14731.00
3159.00
6756 00
3040.00
1083.00
709.50
460.00
142.00
603.00
153.00
17.00
6.99
6.56
6.13
4.96
6.40
5.03
2.83
48.86
43.03
37.58
24.60
40.96
25.30
8.01
Sample Size.
4 4
14.49
55.20
38.90
228.34
Mean
5703
49
3 62
14759
452.5
5.56
Standard Deviation.
1835.4 32.24
Variability Factor:
7.00
95
16311.86
379.04
15.79
1.42
ANOVA Calculations:
SSB
1=1
n,
2 1
SSW =
MSB = SSB/(k-l)
MSW = SSW/(N-k)
F = MSB/MSW
195
-------
1790g
Example 3 (continued)
where,
k = number of treatment technologies
n = number of data points for technology i
i
N - number of data points for all technologies
T = sum of natural log transformed data points for each technology
X = the natural log transformed observations (j) for treatment technology (i)
ij
N = 4. N = 7, N = 11, k = 2. T - 14.49, T = 38.90, T = 53.39, T?= 2850.49, T = 209.96
T* = 1513.21
20996 1513.21 2850.49
7 I 11
SSW - (55.20 + 228.34) - I_ + _ =14.88
MSB = 9.52/1 =9.52
MSW = 14.88/9 = 1.65
F = 9 52/1.65 = 5.77
ANOVA Table
Degrees of
Source freedom SS MS
Between(B)
Within(W)
1
9
9.53
14.89
9.53
1.65
5.77
The critical value of the F test at the 0.05 significance level is 5.12. Since
the F value is larger than the critical value, the means are significantly
different (i.e., they are heterogeneous).
Note: All calculations were rounded to two decimal places. Results may differ depending
upon the number of decimal places used in each step of the calculations.
196
-------
C.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.
197
-------
APPENDIX D
OTHER AGENCY CHARACTERIZATION DATA
198
-------
APPENDIX D - OTHER AGENCY CHARACTERIZATION DATA
The following table presents data collected by the characterization
and assessment division of the Office of Solid Waste. These data were
collected with the intent to characterize K071 wastes as land disposed.
These data represent K071 wastes that were either mixed with other listed
wastes or treated by simple dewatering which the Agency does not consider
to be BOAT. The data presented in this Appendix do not represent
sampling of K071 waste as generated.
199
-------
1356g
Table D-l Other Agency-Collected Characterization Data
ro
o
o
BOAT Metals
Antimony
Arsenic
Barium
Beryllium
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Silver
Vanadium
Zinc
Mixed
K071/K106
Plant D
<3.8
2.6
7.5
<0.1
<0.3
2.3
10
12
337
9.5
<0.5
<0.5
1.4
42
Mixed
dewatered
K071/K106
Plant D
<3 8
7.5
20
0.15
0.52
8.1
36
44
4400
19
<0.8
<0.5
7.0
97
Dewatered
K071
Plant E
<15.2
<7.4
4.2
<0.4
1.8
<2.4
7.5
29
40
18
<5.0
<2.0
28
Dewatered
K071
Plant E
13'-
64
9.8
0.9
7.6
29
25
270
12
38
5.0
32
20
14
Dewatered
K071
Plant E
<15.2
<7.4
15
<0.4
<1.2
<2.4
50
106
9.8
12
<2.5
<2.0
130
Dewatered
K071
Plant F
<15.2
<7.4
6.5
<0.4
<1.2
4.0
47
72
8.6
29
<0.5
<2.0
2.5
50
Dewatered
K071
Plant F
<15.2
<7 4
10
<0.4
<1.2
<2.4
5.6
<26
8.3
21
<2.5
<2.0
17
Dewatered
K071
Plant F
<15.2
18
33
<0.4
<1.2
16
190
360
36
140
<0.5
<2.0
12
206
Dewatered
K071
Plant G
<15 2
<7.4
11.5
<0.4
<1.2
<2.4
4.3
34
62
21
<2.5
<2.0
45
Dewatered
KG71
Plart H
3i
31
135
0.56
1.5
22
89
380
91
140
<0.5
12
11
320
-------
REFERENCES
Bennett. 1986. Memorandum from B.L. Bennett, Plant Manager, Stauffer
Chemical Company, St. Gabriel, LA to Jim Berlow, USEPA, Office of
Solid Waste. Mercury analysis values for treatment of K071 waste by
a dewatering/water washing treatment system, November 12, 1986.
Occidental Chemical Corporation. 1987b. Delisting petition for inorganic
waste stream K071: brine purification muds. Submitted by Occidental
Chemical Corporation, Muscle Shoals plant, Sheffield, Alabama. Office
of Solid Waste. Washington, D.C.: U.S. Environmental Protection
Agency.
Occidental Chemical Corporation. 1987a. Delisting petition for NaCl brine
purification muds (K071). Submitted by Occidental Chemical
Corporation, Delaware City, Delaware. Office of Solid Waste.
Washington, D.C.: U.S. Environmental Protection Agency.
SRI. 1987. Stanford Research Institute. 1987 Directory of chemical
producers - United States of America. Menlo Park, Calif.: Stanford
Research Institute.
USEPA. 1986a. U.S. Environmental Protection Agency, Office of Solid
Waste. Summary of available waste composition data from review of
literature and data bases for use in treatment technology application
and evaluation for "California list" waste streams. Final Report.
Washington, D.C.: U.S. Environmental Protection Agency.
USEPA. 1986b. U.S. Environmental Protection Agency. Test methods for
evaluating solid waste. 3rd ed. U.S. Environmental Protection
Agency. Office of Solid Waste and Emergency Response. November 1986.
USEPA. 1986c. U.S. Environmental Protection Agency. Hazardous waste
management systems; land disposal restrictions; Final Rule; Appendix
I to Part 268 - Toxicity Leaching Procedure (TCLP). Federal
Register. Vol. 51, No. 216. November 7, 1986. pp. 40643-40654.
USEPA. 1987a. Office of Solid Waste. Computer printout: Data on
management of K071 wastes from HWDMS data base. Retrieved January
16, 1987. Washington, D.C.: U.S. Environmental Protection Agency.
USEPA. 1987b. U.S. Environmental Protection Agency, Office of Solid
Waste. Engineering analysis for production of chlorine and sodium or
potassium hydroxide by the mercury cell process. Final Report.
Washington, D.C.: U.S. Environmental Protection Agency.
201
-------
REFERENCES (continued)
USEPA. 1988a. U.S. Environmental Protection Agency, Office of Solid
Waste. Onsite engineering report of treatment technology performance
and operation for Vulcan Materials Company, Port Edwards, Wisconsin.
Final Report. Washington, D.C.: U.S. Environmental Protection
Agency. (See 2.6.5.1(a)).
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