BEST DEMONSTRATED AVAILABLE TECHNOLOGY (BDAT)
BACKGROUND DOCUMENT FOR CYANIDE WASTES
Robert April, Chief
Treatment Technology Section
Monica Chatmon-McEaddy
Project Manager
U.S. Environmental Protection Agency
Office of Solid Waste
401 M Street, S.W.
Washington, D.C. 20460
June 1989
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ACKNOWLEDGMENTS
This document was prepared by the U.S. Environmental Protection
Agency, Office of Solid Waste, with the assistance of Versar Inc. under
Contract No. 68-01-7053. Mr. Robert April, Chief, Treatment Technology
Section, Waste Treatment Branch, served as the EPA Program Manager during
the preparation of this document and the development of treatment
standards for the metal finishing wastes. The Technical Project Officer
for these wastes was Ms. Monica Chatmon-McEaddy. Mr. Steven Silverman
served as legal advisor.
Versar personnel involved in the preparation of this document
included Mr. Jerome Strauss, Program Manager; Mr. Stephen Schwartz, Task
Manager; Mr. Mark Donnelly, Staff Engineer; Ms. Martha Martin, Technical
Editor; and Ms. Sally Gravely, Project Secretary. Mr. Alan Corson of
Jacobs Engineering Group and Mr. Mark Hereth of Radian Corporation
assisted in the review of this document.
We greatly appreciate the cooperation of the individual companies
that permitted their plants to be sampled and that submitted detailed
information to the U.S. EPA on treatment of these wastes.
ii
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TABLE OF CONTENTS
Section Page
1. INTRODUCTION 1-1
2. INDUSTRIES AFFECTED AND WASTE CHARACTERIZATION 2-1
2.1 Industries Affected 2-2
2.2 Process Description 2-3
2.3 Waste Characterization 2-9
3. APPLICABLE AND DEMONSTRATED TREATMENT TECHNOLOGIES 3-1
3.1 Applicable Treatment Technologies 3-1
3.2 Demonstrated Treatment Technologies 3-5
3.3 Descriptions of Cyanide Treatment Technologies 3-6
3.4 Descriptions of BDAT List Metals Treatment Technologies . 3-52
4. TREATMENT PERFORMANCE DATA BASE 4-1
4.1 Electrolytic Oxidation/Alkaline Chlorination Data 4-2
4.2 Wet Air Oxidation Data 4-2
4.3 Alkaline Chlorination Data 4-3
4.4 Electrolytic Oxidation Data 4-6
4.5 High Temperature Cyanide Hydrolysis Data 4-6
4.6 SOp/Air Oxidation Data 4-6
4.7 UV/Ozonolysis Data 4-7
4.8 Chemical Precipitation Data 4-7
4.9 Stabilization Data 4-7
4.10 Incineration Data 4-8
4.11 Other Agency Data on Cyanide Treatment 4-8
5. IDENTIFICATION OF BEST DEMONSTRATED AVAILABLE
TECHNOLOGY (BDAT) 5-1
5.1 Wastes from Electroplating Operations: F006, F007,
F008, and F009 5-2
5.2 Metal Heat Treating Wastes: F0I1 and F012 5-12
5.3 F010 Wastes 5-17
5.4 Wastes from Aluminum Conversion Coating: F019 5-18
6. SELECTION OF REGULATED CONSTITUENTS 6-1
6.1 Identification of BDAT List Constituents 6-1
6.2 Determination of Regulated Constituents 6-2
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TABLE OF CONTENTS
(Continued)
Section Page
7. CALCULATION OF PROMULGATED BDAT TREATMENT STANDARDS 7-1
7.1 Cyanide 7-2
7.2 BDAT List Metals 7-3
8. P WASTE CODES 8-1
8.1 Industries Affected 8-1
8.2 Applicable and Demonstrated Treatment Technologies 8-1
8.3 Identification of Best Demonstrated Available Technology. 8-2
8.4 Selection of Regulated Constituents 8-3
8.5 Promulgated Treatment Standards 8-4
9. REFERENCES 9-1
Appendix A - Analytical Methods and QA/QC A-l
Appendix B - Summary of Waste Composition Data B-l
Appendix C - Analytical Method for Measurement of Thermal
Conductivity C-l
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LIST OF TABLES
Page
Table 1-1 Summary of Promulgated BOAT for Cyanide Wastes 1-9
Table 1-2 BDAT Treatment Standards for F006 1-10
Table 1-3 BDAT Treatment Standards for F007, F008, and F009 .... 1-11
Table 1-4 BDAT Treatment Standards for F010 1-12
Table 1-5 BDAT Treatment Standards for F011 and F012 1-13
Table 1-6 BDAT Treatment Standards for P013, P021, P029, P030,
P063, P074, P098, P099, P104, P106, and P121 1-14
Table 2-1 Chemical Compositions of Typical Electroplating
Baths 2-6
Table 2-2 Summary of Waste Composition Data for F006-F012 Wastes 2-10
Table 2-3 Composition of Wastewaters Generated in Electroplating
Operations 2-11
Table 4-1 Electrolytic Oxidation, Alkaline Chlorination,
Chemical Precipitation, and Sludge Dewatering Data
Collected by EPA at Plant A for Treatment of F011 and
Heat Treating Quenching Wastewaters 4-9
Table 4-2 Wet Air Oxidation Data Collected by EPA at Plant B for
F007 Waste 4-11
Table 4-3 Alkaline Chlorination Data Submitted by Plant C
During the Public Comment Period 4-17
Table 4-4 Electrolytic Oxidation Treatment Data from Literature
Source A for Treatment of FQ07 and F009 Wastes 4-31
Table 4-5 H1gh-Temperature Cyanide Hydrolysis Data from
Literature Source B for Treatment of F007, F008, and
F009 Wastes 4-32
Table 4-6 Incineration Data Submitted by Plant D for Treatment
of F010 and D003 4-33
Table 4-7 Alkaline Chlorination Data Submitted by Plant C for
Various Wastes 4-34
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LIST OF TABLES
(Continued)
Page
Table 4-8 Alkaline Chlorination Data Collected by EPA at
Plant E 4-42
Table 4-9 SC^/Air Oxidation Treatment Data Submitted by Plant F 4-43
Table 4-10 UV/Ozonolysis Treatment Data from Pilot Tests
Submitted by Plant C 4-50
Table 4-11 Stabilization Treatment Data for Aluminum Coil Plating
Sludge Collected by EPA 4-52
Table 4-12 Treatment of Cyanide-Containing Wastewaters by
Chemical Precipitation 4-65
Table 4-13 Treatment of Cyanide-Containing Wastewaters by
Ozonation 4-66
Table 4-14 Treatment of Cyanide-Containing Wastewaters by
A1kaline Chlorination 4-67
Table 5-1 Summary of Accuracy Adjustment of Treatment Data for
Total Cyanide in Electroplating Wastewaters 5-20
Table 5-2 Summary of Accuracy Adjustment of Treatment Data for
Amenable Cyanide in Electroplating Wastewaters 5-21
Table 5-3 Summary of Accuracy Adjustment of Cyanide Data in
F006 Waste as generated 5-22
Table 5-4 Summary of Accuracy Adjustment of Treatment Data for
Cyanide in Electroplating and Metal Heat Treating
Wastewaters 5-23
Table 5-5 Summary of Accuracy Adjustment of Treatment Data for
Amenable Cyanide in Electroplating and Metal Heat
Treating Wastewaters 5-24
Table 5-6 Summary of Accuracy Adjustment of Cyanide Data
in F012 Waste as Generated 5-25
Table 5-7 Summary of Accuracy Adjustment of Treatment
Data for Total Cyanide in F010 Waste 5-26
Table 6-1 Status of BDAT List Constituent Presence in Untreated
Tested Wastes 6-6
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LIST OF TABLES
(Continued)
Page
Table 7-1 Calculation of Wastewater Treatment Standards for
Total Cyanide for Waste Codes F007, F008, F009, F010,
F011, and F012 Based on Alkaline Chlorination 7-4
Table 7-2 Calculation of Nonwastewater Treatment Standards for
Total and Amenable Cyanide for F006, F007, F008, and
F009 Wastes Based on Generation of F006 Waste by a
Wei 1-Operated Treatment Process Consisting of Alkaline
Chlorination, Chemical Precipitation, Filtration, and
Sludge Dewatering 7-5
Table 7-3 Calculation of Nonwastewater Treatment Standards for
Total and Amenable Cyanide for F011 and F012 Wastes
Based on Generation of F012 Waste by a Wei 1-Operated
Treatment Process Consisting of Electrolytic Oxidation,
Alkaline Chlorination, Chemical Precipitation,
Filtration, and Sludge Dewatering 7-6
Table 7-4 Calculation of Nonwastewater Treatment Standards for
Incineration of F010 7-7
Table 7-5 BDAT Treatment Standards for F007, F008, and F009 7-8
Table 7-6 BDAT Treatment Standards for F006 (Cyanide) 7-9
Table 7-7 BDAT Treatment Standards for F011 and F012 7-10
Table 7-8 BDAT Treatment Standards for F010 7-11
Table 8-1 P Waste Codes Proposed for Regulation 8-6
Table 8-2 Promulgated Treatment Standards for P-Code Cyanide
Wastes 8-7
Table A-l Analytical Methods - Plant A A-2
Table A-2 Specific Procedures or Equipment Used for Analysis of
Cyanide When Alternatives or Equivalents Are Allowed
in SW-846 Methods - Plant A A-3
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LIST OF TABLES
(Continued)
Page
Table A-3 Matrix Spike Recoveries for Cyanide - Plant A A-4
Table A-4 Analytical Methods - Plant B A-5
Table A-5 Specific Procedures or Equipment Used for Analysis of
Cyanide When Alternatives or Equivalents Are Allowed
in SW-846 Methods - Plant B A-6
Table A-6 Matrix Spike/Matrix Spike Duplicate Results for
Cyanide - Plant B A-7
Table A-7 Analytical Methods - Plant C A-8
Table A-8 Matrix Spike/Matrix Spike Duplicate Results for
Total Cyanide Untreated F006 Nonwastewater A-9
Table A-9 Matrix Spike Results for Total Cyanide in Aqueous
Effluent - Plant C A-10
Table B-l F006 Waste Composition Data B-2
Table B-2 F007 Waste Composition Data B-5
Table B-3 F008 Waste Composition Data B-7
Table B-4 F009 Waste Composition Data B-8
Table B-5 F010 Waste Composition Data B-10
Table B-6 F011 Waste Composition Data B-ll
Table B-7 F012 Waste Composition Data B-12
Table B-8 F006 Waste Characterization Data - Composite
Samples B-14
Table B-9 F006 Waste Characterization Data Submitted
by Plant F B-17
Table B-10 F006 Waste Characterization Data Submitted by
Plant G B-18
Table B-ll F006 Waste Composition Data Submitted by
Waste Management, Inc B-19
vi i i
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LIST OF TABLES
(Continued)
Page
Table B-12 F006 Waste Composition from 1986 National
Survey of Hazardous Waste Generators B-20
Table B-13 F006 Waste Composition Data Submitted by
National Association of Metal Finishers B-29
ix
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LIST OF FIGURES
Page
Figure 3-1 Wet Air Oxidation Process Flow Diagram 3-28
Figure 3-2 Liquid Injection Incinerator 3-37
Figure 3-3 Rotary Kiln Incinerator 3-38
Figure 3-4 Fluidized Bed Incinerator 3-39
Figure 3-5 Fixed Hearth Incinerator 3-41
Figure 3-6 Continuous Hexavalent Chromium Reduction System 3-55
Figure 3-7 Continuous Chemical Precipitation 3-62
Figure 3-8 Inclined Plate Settler 3-64
Figure 3-9 Circular Clarifiers 3-65
Figure 3-10 High Temperature Metals Recovery System 3-95
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1. INTRODUCTION
Pursuant to section 3004(m) of the Resource Conservation and Recovery
Act (RCRA), enacted as a part of the Hazardous and Solid Waste Amendments
(HSWA) on November 8, 1984, the Environmental Protection Agency (EPA) is
promulgating treatment standards based on best demonstrated available
technology (BDAT) for the cyanide-containing electroplating and metal heat
treating wastes identified in 40 CFR 261.31 as F006, F007, F008, F009,
F010, F011, and F012 and for the commercial chemical product wastes
identified in 40 CFR 261.33 as P013, P021, P029, P030, P063, P074, P098,
P099, P104, P106, and P121. The Agency previously established treat-
ment standards for metals in F006 nonwastewaters with the First Third
listed hazardous wastes (53 FR 31137, August 17, 1988). The Agency
reserved the nonwastewater cyanide treatment standard for F006 waste.
Today, the Agency is promulgating amenable and total cyanide treatment
standards for F006 nonwastewaters. Also, the Agency is promulgating
cyanide and metal standards for F007, F008, F009, F010, F011, F012
wastewaters and nonwastewaters. Compliance with the final BDAT treatment
standards is a prerequisite for the placement of these wastes in units
designated as land disposal units according to 40 CFR Part 268. The
effective date of the treatment standards for F006 nonwastewaters and for
F007, F008, and F009 wastes is July 8, 1989. The effective date of the
treatment standards for F011 and F012 wastes is July 8, 1989, except that
the cyanide standards for electroplating nonwastewaters (F007-F009) shall
apply until December 8, 1989. The more rigorous cyanide standard
2343g
1-1
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(110 mg/kg total cyanide and 9.1 mg/kg amenable cyanide) is effective
December 8, 1989, for F011 and F012 nonwastewaters. The effective date
of the treatment standards for F010, P013, P021, P029, P030, P063, P074,
P098, P099, P104, P106, and P121 wastes is June 8, 1989.
This background document provides the Agency's technical support for
selecting and developing proposed treatment standards for the constituents
to be regulated for the electroplating and metal heat treating wastes.
Sections 2 through 7 present information for the F-code wastes. Section 2
describes the industries affected by regulation of these wastes, explains
the processes generating these wastes, and presents available waste char-
acterization data. Section 3 specifies the applicable and demonstrated
treatment technologies for these wastes and presents descriptions of those
technologies. Section 4 contains performance data for the demonstrated
technologies, and Section 5 analyzes these performance data to determine
BDAT for each waste. Section 6 presents the rationale for selection of
regulated constituents, and Section 7 presents the promulgated BDAT
treatment standards for the regulated constituents. Section 8 discusses
associated inorganic cyanide P-code wastes and details the development of
the proposed treatment standards for these wastes.
EPA's promulgated methodology for developing BDAT treatment standards
is described in two separate documents: Generic Quality Assurance Project
Plan for Land Disposal Restrictions Program ("BDAT") (USEPA 1987) and the
Methodology for Developing BDAT Treatment Standards (USEPA 1988d). The
second document also discusses the petition process to be followed in
requesting a variance from the BDAT treatment standards.
1-2
2343g
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For the purpose of determining the applicability of the proposed
treatment standards, wastewaters are defined as wastes containing less
than 1 percent (weight basis) total suspended solids* and less than
1 percent (weight basis) total organic carbon (TOC). Waste not meeting
this definition must comply with the proposed treatment standards for
nonwastewaters.
Cyanide-containing wastes generated in metal finishing operations
contain cyanide and BDAT list metals. The following paragraph details
the promulgated BDAT for nonwastewaters and wastewaters for each waste.
Table 1-1, at the end of this section, presents this information in
tabular form. In the January 11, 1989, proposed rule, EPA defined three
subcategories of cyanide wastes from the metal finishing industry: Metal
Finishing Aqueous Liquids, Metal Finishing Organic Liquids, and Metal
Finishing Sludges. The Agency has reexamined the need for categorizing
these wastes into these subcategories and believes that they are
unnecessary for the establishment of these treatment standards. Rather,
the Agency has decided that presentation of the treatment standards on a
waste code basis (according to the wastewater and nonwastewater forms of
* The term "total suspended solids" (TSS) clarifies EPA's previously
used terminology of "total solids" and "filterable solids."
Specifically, total suspended solids is measured by Method 209c (Total
Suspended Solids Dried at 103 to 105°C) in Standard Methods for the
Examination of Water and Wastewater, 16th Edition (APHA, AWWA, and WPCF
1985).
?343g
1-3
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the waste) provides a sufficient distinction of the treatability groups.
The revised treatment standards are promulgated based on the difference
in the processes generating these wastes (e.g., electroplating, metal
heat treating) rather than on the difference in physical form of the
waste. Upon reexamination of the characteristics of the metal finishing
cyanide wastes, the Agency believes that the process generating the
wastes influences the treatability of the waste to a greater extent than
the physical form of the waste, based on the variability in complexed
cyanide, iron, and other metals concentrations among these metal
finishing processes.
Alkaline chlorination is determined to be BDAT for cyanide in
wastewaters for waste codes F007, F008, and F009, generated in
electroplating operations. For BDAT list metals in F007, F008, and F009
wastes in wastewaters, BDAT is determined to be chemical precipitation
followed by filtration. The Agency is not promulgating treatment
standards for F006 wastewaters at this time. For cyanide in F006, F007,
F008, and F009 nonwastewaters, BDAT treatment standards are based on
generation of these wastes from an alkaline chlorination treatment
system. For metals in F007, F008, and F009 nonwastewaters, stabilization
is determined to be BDAT. Stabilization was the basis of the F006
nonwastewater BDAT treatment standards for metals, promulgated with the
First Third land disposal restrictions.
For F011 and F012, generated in metal heat treating operations, BDAT
for cyanide in wastewaters is determined to be alkaline chlorination.
2343g
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For BDAT list metals for these waste codes in wastewaters, chemical
precipitation followed by filtration is determined to be BDAT. For
cyanide in F011 and F012 nonwastewaters, BDAT treatment standards are
based on generation of the waste from a treatment system consisting of
electrolytic oxidation followed by alkaline chlorination. For metals in
F011 and F012 nonwastewaters, stabilization is determined to be BDAT.
For cyanide in F010 wastes, incineration is determined to be BDAT for
nonwastewaters. Alkaline chlorination is determined to be BDAT for F010
wastewaters, such as scrubber water produced in incineration treatment of
these wastes. EPA expects that such scrubber waters would meet the BDAT
treatment standards without treatment in a wel1-operated incineration
system. EPA believes that F010 waste may exist as a bilayered waste
(i.e., as an oil layer and a water layer) and the generator of this waste
may choose to treat the aqueous layer of the waste separately by alkaline
chlorination. The Agency would like to note that treatment residuals
from treating F010 wastewaters are listed as the F012 waste code
(wastewater treatment sludges from metal heat treating operations) and
would thus be subject to the cyanide standards for F012 nonwastewaters.
Such sludges would thus not be subject to the standards based on
performance of incineration. Because the Agency believes that these
aqueous F010 wastewaters have waste characteristics similar to those of
F011 and F012 wastewaters, the Agency is transferring the performance of
the treatment system of alkaline chlorination for cyanide. The Agency
notes that if a generator or treater of an F010 waste does not separate
2343g
1-5
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the waste into the two layers, that facility would have to meet the 1.5
mg/kg treatment standard for total cyanide in the nonwastewater residuals
(based on incineration).
The promulgated treatment standards for total and amenable cyanide
for F007, F008, F009, F010, F011, and F012 wastewaters and F006, F007,
F008, and F009 nonwastewaters were developed based on data on alkaline
chlorination followed by chemical precipitation, filtration, and sludge
dewatering that were received during the public comment period. These
data, which were collected from treatment of mixed metal finishing waste-
waters and sludges, were noticed for further public comment and are part
of the Administrative Record for this rule.
The promulgated treatment standard for amenable cyanide for F011 and
F012 nonwastewaters has been recalculated from the proposed rule from the
same data upon which the proposed standard was based. The proposed
standard was derived from an incorrect detection limit for amenable
cyanide. Also, one of the percent recovery factors used to adjust these
data for accuracy was reported in error in the proposed background
document. The calculation of the revised standard is clarified in
Appendix D.
For cyanide, the promulgated treatment standards reflect total waste
concentration. The units for the total waste concentration are mg/kg
(parts per million on a weight-by-weight basis) for nonwastewaters and
mg/1 (parts per million on a weight-by-volume basis) for wastewaters.
For 6DAT list metals in nonwastewaters, the promulgated treatment
2343g
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standards reflect the leachate concentration from the Toxicity
Characteristic Leaching Procedure (TCLP). The units for the leachate
concentration are mg/1. For BDAT list metals in wastewaters, the
promulgated treatment standards reflect the total waste concentration,
and the units are mg/1.
The promulgated treatment standards for the wastewater and
nonwastewater forms of the metal finishing wastes are shown in Tables 1-2
through 1-5. The P-code cyanide-containing wastes for which standards
are promulgated contain soluble cyanide salts. These wastes are expected
to be similar in characteristics to the wastes generated in metal heat
treating (specifically F011 and F012); thus, the treatment standards
proposed for these wastes are also transferred to the P-code cyanide
wastes. The promulgated treatment standards for the P-code cyanide
wastes are presented in Table 1-6. Wastes that, as generated, contain
the regulated constituents at concentrations that do not exceed the
proposed treatment standards are not prohibited from land disposal units.
Treatment standards for the wastewater and nonwastewater forms of F019
have not been promulgated with the land disposal restrictions for Second
Third scheduled wastes. This waste was originally scheduled for regula-
tion in the First Third, with the statutory deadline of August 8, 1988.
The Agency believes that F019 wastes are dissimilar to the electroplating
and metal heat treating wastes because of the high concentration of iron
complex cyanides in F019 wastes. The Agency believes that the source of
the iron complex cyanides is the soluble ferrocyanide compounds (such as
2343g
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potassium ferrocyanide) that are used as constituents in aluminum conver-
sion coating compounds or baths. Therefore, the only cyanides present in
these conversion coating baths would be the iron complex cyanides that
are used as a component of the coating. The Agency believes that F019
nonwastewaters or the wastewater treated to generate this waste have sub-
stantial concentrations of iron complex cyanides and cannot be treated by
conventional oxidation-reduction processes upon which BOAT treatment
standards for the other metal finishing wastes are based. Since the
Agency did not promulgate standards for the wastewater and nonwastewater
forms of F019, land disposal of these wastewaters and nonwastewaters will
continue to be regulated by the "soft hammer" provisions in
40 CFR 268.8. EPA intends to promulgate numerical treatment standards
for cyanide and metal constituents for F019 by May 8, 1990.
2343g
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Table 1-1 Summary of Promulgated BDAT for Cyanide Wastes
Waste
codes
Type of
treatment
residual
Technologies upon
which BDAT treatment
standards are based
F007, F008,
F009, FOU, F012
Wastewater
Alkaline chlorination,
chemical precipitation,
polishing filtration
F006 (cyanide),
F007, F008, F009
Nonwastewater
Alkaline chlorination,
chemical precipitation,
sludge dewatering,
stabilization
F011, F012
Nonwastewater
Electrolytic oxidation,
alkaline chlorination,
chemical precipitation,
sludge dewatering,
stabi1ization
F010
Wastewater
Alkaline chlorination
F010
Nonwastewater
Incineration
2343g
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Table 1-2 BDAT Treatment Standards for F006
NONWASTEWATERS
Maximum for
any
sinale arab sample
Total composition
TCLP
Constituent
(mg/kg)
(mg/1)
Cyanide (total)
590
Not applicable
Cyanide (amenable)
30
Not applicable
Z343g
1-10
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Table 1-3 BOAT Treatment Standards for F007, F008, and F009
NONWASTEWATERS
Maximum for any
sinole grab sample
Total composition TCLP
Constituent [mg/kg) (mg/1)
Cyanide (total)
590
Not applicable
Cyanide (amenable)
30
Not applicable
Cadmium
Not applicable
0.066
Chromium (total)
Not applicable
5.2
Lead
Not applicable
0.51
Nickel
Not applicable
0.32
Si 1ver
Not applicable
0.072
WASTEWATERS
Maximum for
any
sinale arab samde
Total composition
TCLP
Consti tuent
(mg/1)
(mg/1)
Cyanide (total)
1.9
Not applicable
Cyanide (amenable)
0.10
Not applicable
Chromium (total)
0.32
Not applicable
Lead
0.04
Not applicable
Nickel
0.44
Not applicable
2343g
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Table 1-4 BDAT Treatment Standards for F010
NONWASTEWATERS
Constituent
Maximum for any
sinale arab sample
Total composition TCLP
(mg/kg) (mg/1)
Cyanide (total)
1.5 Not applicable
WASTEWATERS
Constituent
Maximum for any
sinale arab samDle
Total composition TCLP
(mg/1) (mg/1)
Cyanide (total)
Cyanide (amenable)
1.9 Not applicable
0.10 Not applicable
2343g
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Table 1-5 BDAT Treatment Standards for F011 and F012
NONWASTEWATERS
Maximum for any
sinale arab samole
Constituent
Total composition
(mg/kg)
TCLP
(mg/1)
Cyanide (total)
Cyanide (amenable)
110
9.1
Not applicable
Not applicable
Cadmium
Chromium (total)
Lead
Nickel
Silver
Not applicable
Not applicable
Not applicable
Not applicable
Not applicable
0.066
5.2
0.51
0.32
0.072
\
WASTEWATERS
Maximum for any
sinale arab sample
Constituent
Total composition
(mg/1)
TCLP
(mg/i)
Cyanide (total)
Cyanide (amenable)
1.9
0.10
Not applicable
Not applicable
>
Chromium (total)
Lead
Nickel
0.32
0.04
0.44
Not applicable
Not applicable
Not applicable
2343g
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Table 1-6 BDAT Treatment Standards for
P013, P021, P029, P030, P063, P074,
P098, P099, P104, P106, and P121
NONWASTEWATERS
Maximum for any
single arab sample
Constituent
Total
composition
(mg/kg)
TCLP
(mg/1)
Cyanide (total)
Cyanide (amenable)
110
9.1
Not applicable
Not applicable
Nickel (P074 only)
Silver (P099 and P104 only)
Not
Not
applicable
applicable
0.32
0.072
WASTEWATERS
Maximum for any
single grab sample
Constituent
Total
composition
(mg/1)
TCLP
(mg/1)
Cyanide (total)
Cyanide (amenable)
1.9
0.10
Not applicable
Not applicable
Nickel (P074 only)
0.44
Not applicable
?343g
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2. INDUSTRIES AFFECTED AND WASTE CHARACTERIZATION
According to the schedule shown in 40 CFR 268.10-11, the following
wastes from electroplating, metal heat treating, and chemical conversion
coating operations in the metal finishing industry, defined in 40 CFR
261.31, are subject to the land disposal restriction prohibitions of RCRA:
Electroplating Operations
F006: Wastewater treatment sludges from electroplating operations
except for the following processes: (1) sulfuric acid anodiz-
ing of aluminum; (2) tin plating on carbon steel; (3) zinc
plating (segregated basis) on carbon steel; (4) aluminum or
zinc-aluminum plating on carbon steel; (5) cleaning/stripping
associated with tin, zinc, and aluminum plating on carbon
steel; and (6) chemical etching and milling of aluminum.
F007: Spent cyanide plating bath solutions from electroplating
operations.
F008: Plating bath residues from the bottom of plating baths from
electroplating operations where cyanides are used in the
process.
F009: Spent stripping and cleaning bath solutions from electroplating
operations where cyanides are used in the process.
Heat Treating Operations
F010: Quenching bath residues from oil baths from metal heat treating
operations where cyanides are used in the process.
F011: Spent cyanide solutions from salt bath pot cleaning from metal"
heat treating operations.
F0I2: Quenching wastewater treatment sludges from metal heat treating
operations where cyanides are used in the process.
Section 2.1 describes the Industries affected by the land disposal
restrictions for F006-F012, and Section 2.2 presents descriptions of the
electroplating and heat treating processes generating these wastes.
2-1
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Section 2.3 summarizes the available waste characterization data for these
wastes.
2.] Industries Affected
The listed wastes F007, F008, and F009 are generated from electroplat-
ing operations where cyanides are used in the process. The listed waste
F006 is generated from electroplating operations and may contain cyanide.
The listed wastes F010. F011, and F012 are generated from metal heat
treating operations where cyanides are used in the process.
Electroplating operations consist of the following processes:
(]) common and precious metals electroplating, except tin, zinc
(segregated basis),* aluminum, and zinc-aluminum plating on carbon
steel; (2) anodizing, except sulfuric acid anodizing of aluminum;
(3) chemical etching and milling, except when performed on aluminum; and
(4) cleaning and stripping, except when associated with tin, zinc, and
aluminum plating on carbon steel.
Metal heat treating operations include tempering, carburizing, car-
bonitriding (cyaniding), nitriding, annealing, normalizing, austenizing,
austempering, quenching, siliconizing, martempering, and malleabilizing.
* Zinc plating (segregated basis) refers to noncyanidic zinc plating
processes. For example, wastewater treatment sludges from zinc plating
using baths formulated from zinc oxide and/or sodium hydroxide would be
excluded from the listing, while sludges from baths formulated from
zinc cyanide and/or sodium cyanide would not be excluded. Where both
cyanidic and noncyanidic baths are used, the exclusion applies to
sludges from the noncyanidic plating processes as long as they are
segregated from sludges that result from cyanidic plating processes.
2-2
2358g
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In the preamble to the Effluent Limitations Guidelines for the Metal
Finishing Industry (48 FR 32482, July 15, 1983), the Agency identified
13,500 facilities in the metal finishing industry that use 46
electroplating and metal finishing unit operations (including
electroplating, heat treating, and chemical conversion coating).
Users of electroplating and metal heat treating operations generally
fall under Standard Industrial Classification (SIC) code series 3000,
which comprises fabricated metal products except machinery and transporta-
tion equipment; machinery except electrical; electrical and electronic
machinery, equipment, and supplies; transportation equipment; measuring,
analyzing, and controlling instruments; and miscellaneous manufacturing
industries.
2.2 Process Description
Presented in this section are descriptions of each of the four opera-
tions that EPA has included as electroplating operations: electroplating,
anodizing, chemical etching and milling, and metal cleaning and stripping.
Also provided is a description of the metal heat treating operations.
2.2.1 Electroplating
Electroplating is the application of a thin surface coating of one
metal upon another by electrodeposition. This surface coating is applied
to provide corrosion protection, wear or erosion resistance, or antifric-
tional characteristics, or for decorative purposes. The electroplating
of common metals includes the processes in which ferrous or nonferrous
base material is electroplated with the following metals or metal alloys:
2-3
2356g
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copper, nickel, chromium, brass, bronze, zinc, tin, lead, cadmium, iron,
aluminum, or combinations thereof. The alloy brass consists of copper
and zinc; the alloy bronze consists of copper and tin. Precious metals
electroplating includes the processes in which a' ferrous or nonferrous
base material is plated with gold, silver, palladium, platinum, rhodium,
indium, ruthenium, iridium, osmium, or combinations thereof.
In electroplating, metal ions in acid, alkaline, or neutral solutions
are reduced to the metal on negatively charged (cathodic) surfaces. The
cathodic surfaces are the objects being plated. The metal ions in solu-
tion are usually replenished by the dissolution of metal from positively
charged surfaces (anodes) or small pieces contained in inert wire or metal
baskets. Replenishment by dissolving metal salts is also practiced,
especially for chromium plating. In this case, an inert material must be
selected for the anodes. Hundreds of different electroplating solutions
have been adopted commercially, but only two or three types are used wide-
ly for a particular metal or alloy. For example, cyanide solutions are
popular for copper, zinc, brass, cadmium, silver, and gold. However,
noncyanide alkaline solutions containing pyrophosphate have come into use
recently for zinc and copper. Acid sulfate solutions are also used for
plating zinc, copper, tin, and nickel, especially for relatively simple
shapes. Cadmium and zinc are sometimes electroplated from neutral or
slightly acidic chloride solutions.
Electroplating baths contain metals, metal salts, acids, alkalies,
and various bath control compounds. All of these materials contribute to
2-4
23S6g
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the wastewater streams through dragout of bath solutions on the plated
parts, through batch dumps, or through floor spills. The sludge from the
bottom of plating baths also contains metals and metal salts. Table 2-1
outlines some typical electroplating bath chemical compositions.
2.2.2 Anodizing
Anodizing is an electrolytic oxidation process that converts the
surface of the metal to an oxide. The oxide coatings formed in anodizing
provide corrosion protection, decorative surfaces, a base for painting
and other coating processes, and special electrical and mechanical proper-
ties. Aluminum is the most frequently anodized material, while some
magnesium and stainless steel (electropolish) and limited amounts of zinc
and titanium are also treated.
Most anodizing is carried out by the immersion of racked parts in
tanks; however, some continuous anodizing is done on large coils of
aluminum, in a manner similar to continuous electroplating. For aluminum
parts, the formation of the oxide occurs when the parts are made anodic
in dilute sulfuric acid or dilute chromic acid solutions. The oxide layer
begins formation at the outer surface of the base metal, and as the reac-
tion proceeds, the oxide grows into the metal. The oxide formed last,
known as the boundary layer, is located at the interface between the base
metal and the oxide. The boundary is extremely thin and nonporous.
Chromic acid anodic coatings are more protective than sulfuric acid coat-
ings and have a relatively thick boundary layer.
2-5
-------
2390g
Table 2*1 Ch»ic*l Comositions of Typical Electroplating Baths
Plating cta^ound
Const ituents
Concentration
(n bath (j/l)
Cattail* cyanide
Cattaiia ox Ida
Ca6nia (as muI)
Sodi lb cyanide
Sodiia hydroxide
22. S
19.5
77.9
14.2
Cacfclia fluotaorate
Ca
-------
2.2.3 Chemical Etching and Milling
These processes are used to produce specific design configurations and
tolerances or surface appearances on parts by controlled dissolution of
the base metal with chemical etchants. Included in this classification
are the processes of chemical milling, chemical etching, and bright dip-
ping. Chemical etching is the same process as chemical milling, but the
rates and depths of metal removal are usually much greater in chemical
milling. Typical solutions for chemical milling and etching include
solutions of ferric chloride, nitric acid, ammonium persulfate, chromic
acid, cupric chloride, hydrochloric acid, and combinations of these
etchants. Bright dipping is a specialized form of etching that is used
to remove oxide and tarnish from ferrous and nonferrous materials and is
frequently performed just prior to plating. Bright dipping solutions are
usually composed of mixtures of two or more of the following acids:
sulfuric, chromic, phosphoric, nitric, and hydrochloric.
2.2.4 Metal Cleaning and Stripping
Metal cleaning operations are designed to prepare metal surfaces for
electroplating by removing oil, grease, dirt, and metal oxides, using
water with or without a detergent or other dispersing agent. Cleaning can
be done with alkaline (either electrolytically or nonelectrolytically),
neutral, or acidic solutions. Nonelectrolytic cleaning, using both alka-
line and acid solutions, can be done by either soak or spray methods.
Acid cleaning can be referred to as pickling. Effective cleaning is also
accomplished by alkaline electrolytic cleaning, or electrocleaning.
Electrocleaning can be run cathodically (with the workpiece as the
2-7
2358g
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cathode), anodically (with the workpiece as the anode), or in periodic
reversal (PR) mode, in which the current is periodically reversed from
cathodic to anodic. Cleaning baths eventually become contaminated with
metals derived from the cleaned parts.
Metal stripping is the chemical removal of metal plating coatings from
base metal products by immersion of the plated part in an aqueous bath of
appropriate chemical composition. When a plated coating on a part does
not meet product quality specifications, it may be more economical to re-
move the metal plating and reuse the part than to scrap the entire plated
part. Stripping baths can contain strong alkaline solutions of cyanide
salts (to strip copper plating from steel parts, for instance) or strong
acids. The stripping solution dissolves the plated coating, leaving the
base metal essentially untouched.
2.2.5 Metal Heat Treating
Metal heat treating is the modification of the physical properties of
a metal piece through the application of controlled heating and cooling
cycles. Heat treating is most frequently accomplished by placing the
metal parts in an atmosphere (air or other gases) at the appropriate tern-
peratures for the appropriate period of time. Heat treating can also be
accomplished by placing parts (usually small items) in molten salt baths,
including baths using cyanide salts. After iiranersion in the salt bath,
parts are removed and cooled in either a water or an oil bath or in air.
Metal heat treating may be used to develop a surface coating on the
metal or to change the physical properties of the bulk metal. Cyanides
are most often used in the heat treating operations of carburizing,
2-8
2368g
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carbonitriding, and nitriding, which add carbon, nitrogen, or both to the
surface of the metal to form a hard surface coating.
2.3 Waste Characterization
This section summarizes the waste characterization data available to
the Agency for the F006 through F012 wastes and an estimate of the range
of these constituents that may be found in the cyanide-containing P-code
wastes. The exact composition of the P-code wastes depends upon the
waste matrix (e.g., off-specification chemical, contaminated soil, etc.).
The major constituents in the wastes and their approximate concentrations
are presented in Table 2-2, which is based on the available waste
characterization data summarized in Appendix B. Tables B-l through B-8
in Appendix B present, by waste code, the concentrations for BDAT list
constituents and other parameters identified for the specific wastes.
These data were obtained from a variety of sources, as referenced in the
tables, including literature sources, EPA sampling and analysis, and data
generated from industry.
Table 2-3 presents data on the composition of wastewaters treated in
electroplating operations. These data were collected by EPA's Office of
Water in the development of Effluent Limitations Guidelines for the metal
finishing industry. Treatment of these wastewaters results in the
generation of F006 waste.
F006 through F012 wastes contain BDAT metals and cyanides, as well as
other inorganic compounds and water. Iron often occurs as a contaminant
in these wastes. The concentrations of individual metals in F007, F008,
2-9
?3SBg
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23909
libit 2-Z Siaaury of Waste CxajJOlUion Data for F006-FOI? Mites
Cant Ituent/paraster
FOOO
Cwtwiritlw iwsrti
F007
F008
roo9
Cyeniita (as NaCN)
BOAT Ust Metals
Cattail*
Chraiia
Capper
lead
mctil
Zinc
T0TA4. BOAT KTALS
BOAT Organic!
Iron
Ottor Nan-gOAT Inorganics
(primarily todlia carbonate
and/or C4lciia hydroxide)
Meier
Oil and grease
<0.1-O.S
0-2
0-30
0-3
0-3
0-17
<0.1-30
<0 1
20-40
30-60
0-4
5-10
0-2
<0.1
0-1
<0.1
0-2
JbZ
-z
<0 1
20-40
55-70
<0.1
2-10
0-2
<0.1
0-2
<0.1
0-2
JL2
-2
<0 1
35-40
55
<0.1
S-20
0-2
«0.l
0-?
<0 1
0-2
<0.1
-2
<0 1
20
BO-73
ter
F010
Cawcewtrit ion [percent)
F011
F012
F-codes
Cyanide (as HaCM)
pgAT WitaH
1-4
Dtraalia
Copper
Leed '
Nickel
Zinc
TOTAL BOAT PCTALS
BOAT Organic!
Im
Other tai-BOAT Inorganics
(pr taarlly sodli* carbonate
and/or calc It* hydroside)
Water
Oil and grease
<1
<0.1
1-99
3-20
<0.1
<0.1
<0.1
<0.1
<0.1
0.2
•0.1
20-80
0-77
<0.1
<0.1-12
<0.1
<0.1
<0.1
<0.1
<0.1
±1
0.1
<0.1
21-40
60
<0.1
1-SO
0-50
0-50
0-50
0-50
<0.1
- ¦ Hot available
2-10
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£390g
Table 2-3 Co*»sition of Wasteoaters generated In
Electroplating Operations
Wastewaters fron
camon nets Is
Constituents plating
Inorganics Other Than Wetals
BOAT
Cyanide (total) 0.005 - 150
Cyanide (awnable) 0.003 - 130
Fluoride 0.022 - 141.7
BOAT List Hetals
Caffrnim 0.007 - 21.6
Chraniun (total) 0.088 - 525.9
Chronlim (hexavalent) 0.005 - 334.5
Copper 0.032 - 272.5
lead 0.663 - 25.39
Nickel 0.019 - 2954
Zinc 0.112 - 252
Other Parameters
Iron 0.41 - 1482
Phosphorus 0.0Z - 144
Tin 0.06 - 103.4
Total suspended solids 0.10 - 9970
Reference: USEPA 1983.
2-11
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and F009 wastes are dependent on the type of electroplating solutions used
at the particular facility generating the waste. Additionally, F007,
F008, F009, and F012 may contain low concentrations of volatile and semi-
volatile organic compounds as contaminants.
F007, F008, F009, and F011 wastes generally contain from 1 percent
cyanide (or approximately 2 percent, as NaCN) up to 15 percent cyanide.
These wastes also often contain dissolved metals (especially F007, F008,
and F009, which typically contain approximately 2 percent BOAT metals)
and must be treated for metals removal by chemical precipitation. F010
wastes may contain high concentrations of oil and grease, as well as
cyanide concentrations similar to those of the first group. F006 and F012
are wastewater treatment sludges typically containing less than 1 percent
metals in a hydroxide or sulfide sludge. These wastes may contain 5 per-
cent or more cyanide (i.e., 10 percent cyanide (as NaCN) in Table 2-2) but
typically contain less than 1,000 ppm cyanide.
F011 and F012 wastes, generated in metal heat treating operations,
differ from F007, F008, and F009 generated in electroplating operations,
in that they generally do not contain iron complex cyanides. The source
of cyanide in metal heat treating operations is the cyanide compounds
used in the heat treating bath. These compounds are always the alkali
cyanide compounds (sodium cyanide or potassium cyanide). Cyanide is used
because it reacts with the surface of the heated parts, forming a hard
surface coating. Iron is not likely to be present from the heat-treated
parts or the steel tanks. The source of cyanide in electroplating
2-12
2358g
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operations is the complexed metal cyanide compound or compounds used as a
constituent of the electroplating bath (see Table 2-1). Certain metals
are much more soluble in the bath in the complexed form. Iron-cyanide
complexes are never added as a constituent of the bath. Electroplaters
sometimes attempt to minimize the concentration of iron in these wastes
by segregating high-iron content wastewaters and by using rubber-lined
tanks (to minimize dissolution of iron from the tank). Some iron will be
present in waste electroplating solutions from dissolution of the steel
parts being plated. (Iron sometimes dissolves to replace the metal ions
plated out of solution.) However, because further reaction of the
dissolved iron with cyanide is necessary for formation of the complexes,
not all of this iron exists in the complexed iron cyanide form.
The presence of iron, and other metals that form metal-cyanide
complexes, may affect treatment of these wastes to the extent that the
complexed cyanides are resistant to chemical oxidation treatment. Data
are most often available only on the concentration of the metal, and it
is seldom the case that the metal is present completely in the complexed
form. The iron concentration in the electroplating wastes is higher, in
general, than that in the metal heat treating wastes.
The Agency wishes to emphasize that sludges generated from treatment
of spent cyanide plating baths may also be classified as F006. An example
is a wastewater treatment sludge generated from treatment of a spent
cyanide plating solution (an F007 wastewater). This bath solution may be
sent through cyanide destruction and chemical precipitation for metals
2-13
23509
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removal separately from other wastewaters. In this case, the
precipitated residual would be F007. If the F007 waste were combined
with other plant wastes (such as the listed wastes F008 or F009 or
electroplating rinsewaters) before cyanide destruction and chemical
precipitation treatment in a wastewater treatment system, then the
precipitated residual from this treatment would be F006.
In the January 11, 1989, proposed rule, the Agency defined three
subcategories of cyanide wastes from the metal finishing industry: Metal
Finishing Aqueous Liquids, Metal Finishing Organic Liquids, and Metal
Finishing Sludges. The Agency has reexamined the need for categorizing
these wastes into these subcategories and believes that it is not
necessary to use them. Rather, the Agency has decided that presentation
of the treatment standards on a waste code basis (according to the waste-
water and nonwastewater forms of the waste) provides a sufficient distinc-
tion of the treatability groups.
2358g
2-14
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3. APPLICABLE AND DEMONSTRATED TREATMENT TECHNOLOGIES
This section identifies the treatment technologies that are
applicable to F006 through FO12 for cyanide and metal constituents and
determines which, if any, of the applicable technologies can be
considered demonstrated for the purposes of establishing BDAT.
To be applicable, a technology must be theoretically usable to treat
the waste in question or to treat a waste that is similar 1n terms of the
parameters that affect treatment selection. To be demonstrated, the
technology must be employed in full-scale operation for the treatment of
the waste in question or a similar waste. Technologies that are
available only at research facilities or at pilot- and bench-scale
operations are not considered demonstrated technologies for the purpose
of identifying BDAT.
Also in this section, the Agency has provided a description of each
of the applicable technologies for cyanide-containing wastes and for
dissolved metals and metals within sludges. A description of other
treatment technologies can be found in EPA's Treatment Technology
Background Document (USEPA 1988c).
3.1 Applicable Treatment Technologies
3.1.1 Cyanides
EPA has identified six technologies as potentially applicable for
treatment of cyanides in both wastewaters and nonwastewaters:
(1) electrolytic oxidation; (2) chemical oxidation with several oxidizing
agents, such as hypochlorite or chlorine (alkaline chlorination),
2748g
3-1
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permanganate, ozone, or SO^/air (Inco process); (3) wet air oxidation;
(4) high temperature cyanide hydrolysis; (5) incineration; and
(6) stabilization. The first four of these may be followed by chemical
precipitation, filtration, and sludge dew'atering for metals removal. The
first four technologies are most effective in treatment of cyanide in
wastes that contain primarily dissolved or soluble cyanide salts, but are
also applicable to treatment of wastewater treatment sludges and other
solids that contain treatable concentrations of cyanide. Incineration
and stabilization are applicable to nonwastewater forms of the wastes.
Electrolytic oxidation followed by alkaline chlorination, chemical
oxidation (alkaline chlorination or other methods) alone, electrolytic
oxidation alone, wet air oxidation, and high temperature hydrolysis
reduce the concentration of cyanide in the wastewaters or nonwastewaters
treated. These technologies fully destroy the amenable cyanide present
in the waste but treat the complexed cyanides to varying degrees,
depending on, among other things, the stability of the metal-cyanide
complex and the severity of the oxidizing agent and reaction conditions.
Iron cyanide complexes are typically the most resistant to oxidation
treatment.
EPA has identified incineration as an applicable technology for
treatment of cyanide in F010 wastes containing high concentrations of oil
and grease. Incineration is a thermal treatment process that destroys
the organic and oxidizable inorganic waste constituents. Incineration of
this waste generates an ash and a scrubber water that may require further
274 Sg
3-2
-------
treatment. Phone contacts with generators of F010 wastes indicate that
these wastes may also be treated by an oil/water separation step,
followed by recycling or treatment of the oil phase and treatment of the
inorganic phase by one of the other cyanide destruction technologies
discussed above.
3.1.2 Dissolved Metals
Chemical precipitation treatment of the wastewater residual from
cyanide oxidation, followed by filtration of the treated wastewater and
dewatering of the precipitated solids, reduces the concentration of
metals in the wastewater and concentrates the metals in the treatment
sludge in a relatively insoluble form. Filtration and dewatering may
also concentrate cyanide in the treatment sludge residual. The treatment
sludge metal constituents may then require further treatment by the
applicable treatment technologies specified below for metals in
nonwastewaters.
3.1.3 Metals in Nonwastewaters
EPA has identified three technologies as potentially applicable for
treatment of the metals in wastewater treatment sludges (such as F012 and
residuals from treatment of F007-F009 and F011): stabilization,
vitrification, and high temperature metals recovery. The first two
technologies are designed to reduce the leachability of the metals; the
third reduces both the total concentration and the leachability of the
metals. Treatment standards for the metal constituents in F006
nonwastewaters have been developed with the First Third of RCRA listed
2748g
3-3
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hazardous wastes based on stabilization as BDAT (see 53 FR 31137,
August 17, 1988) and thus are not discussed here.
Stabilization may chemically reduce the mobility of metal
constituents in a waste. Stabilizing agents, binders, and chemicals are
added to a waste to minimize the quantities of metals that leach when the
waste is in contact with water. Commonly used stabilization agents
include portland cement, 1ime/pozzolan-based material, and cement kiln
dust.
The Agency believes that stabilization is also an applicable
technology for the treatment of cyanide in wastewater treatment sludges.
However, the Agency believes that stabilization only reduces the
leachability of constituents but does not destroy the constituents.
Furthermore, the Agency believes that stabilization is suited primarily
for stabilizing cationic species (such as some of the BDAT list metals);
therefore, it may not treat anionic species (such as cyanide) as
effectively as it does metals.
Vitrification has also been identified by the Agency as an applicable
technology. A vitrification process can be.used to immobilize hazardous
constituents in nonwastewaters by producing a vitreous or glass-like mass.
EPA has also identified high temperature metals recovery technologies
as applicable. High temperature metals recovery technologies reduce the
concentration of some metals in the waste through volatilization and
recovery of the volatilized metals and/or the metals remaining in the
?748g
3-4
-------
residual. High temperature metals recovery treatment results in a
residual (or slag) that is land disposed.
3.2 Demonstrated Treatment Technologies
3.2.1 Cyanide
Available information shows that electrolytic oxidation followed by
alkaline chlorination, alkaline chlorination alone, wet air oxidation,
high temperature hydrolysis, SO^/air oxidation, incineration, and
stabilization are demonstrated for treatment of cyanide in electroplating
and metal heat treating wastes. The Agency has identified at least one
full-scale facility that uses electrolytic oxidation followed by alkaline
chlorination to treat cyanide in F011 waste, at least five facilities
that use alkaline chlorination to treat cyanide in F006 through F012
wastes, at least one facility that treats cyanide-containing wastes by
high temperature cyanide hydrolysis, and one pilot-scale facility that
has treated F007 waste by wet air oxidation. In addition, wet air
oxidation and SO^/air oxidation are used to treat similar wastes in
full-scale processes.
The Agency also believes that incineration is demonstrated for
treatment of F010 wastes, which may contain high concentrations (up to
5 percent) of oil and grease. The Agency is aware of at least one
full-scale facility that has treated F010 and similar wastes by
incineration.
2748g
3-5
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3.2.2 Metals
EPA believes that chemical precipitation followed by filtration and
sludge dewatering is demonstrated at many facilities for treatment of
BOAT list metals in F007-F012 wastewaters and similar wastes (such as
K062, which was regulated with the First Third of the RCRA-listed
hazardous wastes).
Available information also shows that all of the applicable
technologies for treatment of BOAT metals in nonwastewaters are
demonstrated. The characteristics of F012 wastes and other wastewater
treatment sludges (high solids content, substantial concentrations of
BDAT list metals, very low concentrations of oil and grease and BDAT list
organic constituents) would allow these wastes to be treated by the same
methods used for F006. Stabilization is used by at least ten facilities
to treat F006 wastes. EPA knows of two full-scale facilities that use
metals recovery for F006 wastes and one full-scale facility that treats
FD06 wastes by vitrification.
3.3 Descriptions of Cyanide Treatment Technologies
3.3.1 Electrolytic Oxidation of Cyanide
(1) AddIicabilitv. Electrolytic oxidation is a treatment technology
applicable to wastes containing high concentrations of cyanide in
solution. Because of excessive retention time requirements, the process
is often applied as preliminary treatment for highly concentrated cyanide
wastes, prior to more conventional chemical cyanide oxidation
(Cushnie 1985).
?74Sg
3-6
I
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This treatment technology is used in industry for the destruction of
cyanide in (a) concentrated spent plating solutions and stripping
solutions, (b) spent heat treating baths, (c) alkaline descalers, and
(d) metal passivating (rust-inhibiting) solutions. Electrolytic
oxidation has been demonstrated successfully for treatment of wastes
containing concentrations of cyanide up to 100,000 mg/1 (Easton 1967).
However, for concentrations of cyanide lower than 500 mg/1, chemical
oxidation treatment may be more efficient. As a result of the
inefficiency of this technology for treatment of low-concentration
cyanide wastes, it is used only as a pretreatment step if treatment time
is a concern.
(2) Underlying principles of operation. The basic principle of
electrolytic oxidation of cyanide is that concentrated cyanide waste
subject to an electrolytic reaction with dissolved oxygen in an aqueous
solution is broken down to the gaseous products carbon dioxide (CO^),
nitrogen (N^), and ammonia (NH^). The process is conducted at
elevated temperatures for periods ranging from several hours to over a
week, depending on the initial cyanide concentration and the desired
final cyanide concentration. The theoretical destruction process that
takes place at the anodes is described by the following reaction:
2CN" + 20^
2C02 + ^ + 2e-
cyanide oxygen
ion
carbon nitrogen electrons
dioxide
2748g
3-7
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The effectiveness of electrolytic oxidation is dependent on the
conductivity of the waste, which is a function of several waste
characteristics including the concentration of cyanide and other ions in
solution. As the process continues, the waste becomes less capable of
conducting electricity as cyanide concentration is reduced, causing the
electrolytic reaction to be much less efficient at longer retention times.
(3) Description of electrolytic oxidation process. Typically,
electrolytic destruction of cyanide takes place in a closed cell. This
cell consists of two electrodes suspended in an aqueous solution, with
direct current (DC) electricity supplied to drive the reaction to
completion. The temperature of the bath containing the cyanide waste is
maintained at or above 52°C (125¦F). Sodium chloride may be
added to the solution as an electrolyte (conductor) to increase the
conductivity of the waste being treated. Since the reaction may take
days or weeks, water is usually added to the tank periodically to make up
for losses resulting from evaporation from the heated tank. This is
necessary to ensure that the electrodes remain fully submerged so that a
full flow of current is maintained in the solution during treatment.
Following treatment, the treated waste is generally further treated in a
conventional chemical oxidation system to destroy residual cyanides.
(4) Waste characteristics affecting performance (WCAPs). In
determining whether electrolytic oxidation will achieve the same level of
performance on an untested waste as on a previously tested waste and
whether performance levels can be transferred, EPA examines the following
?743g
3-8
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waste characteristics: (a) the concentration of other oxidizable
materials and (b) the concentration of reducible metals.
(a) Concentration of other oxidizable materials. The presence
of oxidizable organics (such as oil and grease and surfactants) and the
presence of inorganic ionic species in a reduced state (such as trivalent
chromium or sulfide) may increase the treatment time required to achieve
destruction of cyanide because these materials may be oxidized
preferentially to the cyanide in solution. If concentrations of other
oxidizable materials are significantly higher in the untested waste than
in the tested waste, the system may not achieve the same performance.
Longer reaction time may be required to oxidize cyanide and achieve the
same treatment performance, or other, more applicable treatment
technologies may need to be considered for treatment of the untested
waste.
(b) Concentration of reducible metals. The electrolytic
process may cause some of the more easily reduced metals in the waste,
such as copper, to plate out onto the anode as the pure metal. The
plating of metals onto the anode may result in changes in current density (
and, hence, may change the rate of cyanide oxidation. If the
concentration of reducible metals in the untested waste is significantly
higher than that in the tested waste, the system may not achieve the same
performance and other, more applicable treatment technologies may need to
be considered for treatment of the untested waste.
27489
3-9
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(5) Design and operating parameters. In assessing the effectiveness
of the design and operation of an electrolytic oxidation system, EPA
examines the following parameters: (a) the oxidation temperature,
(b) the residence time, (c) the pH, (d) the electrical conductivity,
(e) the electrode spacing and surface area, and (f) the degree of mixing.
(a) Oxidation temperature. For the electrolytic process,
elevated temperatures are used. Normal temperatures range from 52 to
93°C (125 to 200°F). The temperature can be raised by increasing
the flow of steam to the coils or jacket supplying heat to the reactor
contents. EPA monitors the oxidation temperature to ensure that the
system is operating at the appropriate design condition and to diagnose
operational problems.
(b) Residence time. Electrolytic oxidation is usually a batch
process. The time allowed to complete the reaction is an important
factor in electrolysis and is dependent on the initial concentration of
the waste and the desired final cyanide concentration. The rate of
cyanide destruction decreases as the cyanide concentration decreases
(i.e., the rate of cyanide destruction asymptotically approaches zero).
Typical residence times range from periods of several hours to more than
a week. EPA observes the residence time to ensure that sufficient time
is provided to effectively destroy the cyanides in the wastes.
(c) pH. Typical solutions for electrolytic oxidation have a pH
ranging from 11.5 to 12.0. The pH must be maintained in the alkaline
range to prevent liberation of toxic hydrogen cyanide. Typically, pH is
S
3-10
2748g
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controlled by the addition of caustic or lime. EPA monitors the pH to
ensure that the treatment system is operating at the appropriate design
condition and to diagnose operational problems.
(d) Electrical conductivity. The solution must have a high
enough electrical conductivity to allow the reaction to proceed at an
acceptable rate. If the conductivity is not high enough, it can be
improved by adding an electrolyte such as sodium chloride. The
conductivity of the waste during the reaction is normally determined by
monitoring both the current and voltage of the cell. EPA monitors the
electrical conductivity to ensure that the treatment system is operating
at the appropriate design condition.
(e) Electrode spacing and surface area. The spacing and
surface area of the electrodes directly impact the current flowing
through the waste. The reaction rate is increased by both closer
electrode spacing and more electrode surface area because each increases
the current density in the cell. EPA observes the electrode spacing and
surface area to ensure that sufficient current density is provided to
effectively destroy the cyanides in the waste.
(f) Degree of mixing. Electrolytic destruction of cyanide
requires good mixing in the reaction vessel. Mixing helps ensure an
adequate supply of oxygen (from the air) for the electrochemical reaction
(see Section 3.3.1 (2) Underlying Principles of Operation), enhances mass
transfer to promote the oxidation reaction, and keeps suspended solids in
suspension. Mixing may be provided by the bubbling of air from the
?748g
3-11
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bottom of the reactor, or an external source of mixing may be provided.
The quantifiable degree of mixing is a complex assessment that includes,
among other factors, the amount of energy supplied, the length of time
the material is mixed, and the related turbulence effects of the size and
shape of the reaction vessel used. This is beyond the scope of simple
measurement. EPA, however, evaluates the degree of mixing qualitatively
by considering whether mixing is provided and whether the type of mixing
device is one that could be expected to achieve uniform mixing of the
waste.
3.3.2 Chemical Oxidation
(1) AddIicabi1itv. Chemical oxidation is a treatment technology
used to treat wastes containing organics. In addition, it is used to
treat sulfide wastes by converting the sulfide to sulfate. Also, the
destruction of cyanides in wastes can be accomplished by chemical
oxidation.
Chemical oxidation of cyanide is applicable for dissolved cyanides in
aqueous solutions, such as wastewaters from metal plating and finishing
operations, or for inorganic sludges from these operations that contain
soluble cyanide compounds. Chemical oxidation is most applicable to
cyanides that are in a form that can be easily dissociated in water to
yield free cyanide ions. If the cyanide is present in water as a tightly
bound iron cyanide complex ion (ferrocyanide or ferricyanide), only
limited treatment may occur.
2748g
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Chemical oxidation may also be used in treatment of complexed metal
wastes. Organic compounds such as EDTA, NTA, citric acid, glutaric acid,
lactic acid, and tartarates are often used as chelating agents to prevent
metal ions from precipitating out in electroless plating solutions. When
these spent plating solutions require treatment for metals removal by
chemical precipitation, the organic chelating agents must first be
destroyed. Chemical oxidants, potassium permanganate in particular, are
effective in releasing metals from complexes with these organic compounds
(Schroeter and Painter 1987).
(2) Underlying principles of operation. The basic principle of
chemical oxidation is that inorganic cyanides, some dissolved organic
compounds, and sulfides can be chemically oxidized to yield carbon
dioxide, water, salts, simple organic acids, and, in the case of
sulfides, sulfates. The principal chemical oxidants used are
hypochlorite, chlorine gas, chlorine dioxide, hydrogen peroxide, ozone,
and potassium permanganate. The reaction chemistry for each is discussed
below.
(a) Oxidation with hypochlorite or chlorine (alkaline
chlorination). This type of oxidation is carried out using sodium
hypochlorite (NaOCl), calcium hypochlorite (Ca(0Cl)^)* chlorine gas
(CI^)» or sometimes chlorine dioxide gas (ClO^). The reactions are
normally conducted under slightly or moderately alkaline conditions.
Alkaline chlorination of cyanide is a two-step process usually operated
at a pH of 10 to 11.5 for the first step and 8.5 for the second step.
2748g
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The toxic gas cyanogen chloride (CNC1) is formed as a reaction
intermediate in the first step of this process and may be liberated if
the pH is less than 10 and incomplete reaction occurs. Example reactions
for the oxidation of cyanide, phenol, and sulfide using sodium
hypochlorite are shown below:
Cyanide: CN" + NaOCl - OCfT + NaCl (Step 1)
20CN" + 3NaOCl - C032" + C02 + N2 + 3NaCl (Step 2)
Phenol: C6H50H + 14NaOCl - 6C02 + 3H20 + 14NaCl
Sulfide: S* + 4Na0Cl - S04= + 4NaCl
Chlorine dioxide also oxidizes the same pollutants under identical
conditions. Chlorine dioxide first hydrolyzes to form a mixture of
chlorous (HCIO^) and chloric (HCIO^) acids. These acids act as the
oxidants, as shown in the equations below for phenol:
2C102 + H20 - HC102 + HC103
CgHjOH + 7HC102 -» 6C02 + 3H20 + 7HC1
3C6H5OH + 14HC103 - 18C02 + 9H20 + 14HC1
(b) Peroxide oxidation. Peroxide oxidizes the same
constituents that alkaline chlorination oxidizes under similar
conditions. The relevant reactions are:
Cyanide: 2CN" + 5H202 - 2C02 + N2 + 4H20 + 20H"
2746$
3-14
-------
Phenol: C6H50H + 14H202 - 6C02 + 17H20
Sulfide: S" + 4H202 - S04= + 4H20
(c) Oxidation with ozone (ozonation). Ozone is an effective
oxidizing agent for treatment of organic compounds and for the oxidation
of cyanide to cyanate. Cyanogen gas (C^) is a reaction
intermediate in this reaction. Further oxidation of cyanate to carbon
dioxide and nitrogen compounds (N or NH ) occurs slowly with ozone.
The oxidation of cyanide to cyanate proceeds by the following reaction:
CN* + 03 - CNO* + 02
The rates of ozonation reactions can be accelerated by supplying
ultraviolet (UV) radiation during treatment. Some literature sources
indicate that even the most difficult cyanide complexes to treat, the
iron-cyanide complexes, can be oxidized completely.
(d) Oxidation with potassium permanganate. Potassium
permanganate can also be used to oxidize the same constituents as the
other chemical oxidants. The reactions of potassium permanganate with
phenol and sulfide at acidic pHs and with cyanide at a pH of 12 to 14 are
as follows:
Phenol: SCg^OH + 28KMn04 + 28H+ - 18C02 + 28Mn02 + 23H20 + 28K+
Sulfide: 5S= + 8KMn04 + 24H+ - 5S04" + 8Mn+2 + 12H20 + 8K+
Cyanide: CN" + 2KMn04 + Ca(OH)2 - CNO" + K2Mn04 + CaMn04 + H20
2748s
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In cyanide oxidation using potassium permanganate, cyanide is oxidized
only to cyanate. Further oxidation of cyanate can be accomplished by
acid hydrolysis or by the use of another oxidizing agent.
(e) SO^/air oxidation. Cyanide can be oxidized to cyanate in
an aqueous solution by bubbling air containing from 1 to 10 percent S0^
through the waste. The SO^ is also oxidized to sulfate in this
reaction. Soluble sulfite salts (such as Na^SO^) can be used as a
source of oxidizable sulfur rather than S0^ gas. This treatment
process occurs by the following reaction:
CN" + S02 + 02 + H20 - CNO" + H2S04
This oxidation reaction requires the use of a soluble copper salt
catalyst. Copper sulfate (CuSOJ is most often used. SO /air
4 2
oxidation is used frequently in the treatment of wastewaters from gold
production, which contain both cyanide and thiocyanate, because SO^/air
oxidizes cyanide more strongly than thiocyanate while alkaline
chlorination and other common oxidizing agents oxidize thiocyanate more
strongly than cyanide. As with potassium permanganate, further oxidation
of cyanate can be accomplished by acid hydrolysis or by the use of
another oxidizing agent.
(3) Description of chemical oxidation processes
(a) Alkaline chlorination. Alkaline chlorination can be
accomplished by either batch or continuous processes. For batch
treatment, the wastewater is transferred to a reaction tank, where the pH
2748g
3-16
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is adjusted and the oxidizing agent is added. In some cases, the tank
may be heated to increase the reaction rate. For oxidation of most
compounds, a slightly to moderately alkaline pH is used. It is important
that the tank be well mixed for effective treatment to occur. After
treatment, the wastewater is either directly discharged or transferred to
another process for further treatment.
In the continuous process, automatic instrumentation is used to
control pH, reagent addition, and temperature. An oxidation-reduction
potential (ORP) sensor is usually used to measure the extent of reaction.
In both types of processes, agitation is typically provided to
maintain thorough mixing. Typical residence times for these and other
oxidation processes depend on the concentration of the constituents to be
treated and usually range from 1 to 2 hours.
(b) Peroxide oxidation. The peroxide oxidation process is run
under similar conditions, and with similar equipment, to those used in
the alkaline chlorination process. Hydrogen peroxide is added as a
liquid solution.
(c) Ozonation. Ozonation can be conducted in a batch or
continuous process. The ozone for treatment is produced onsite because
of the hazards of transporting and storing ozone as well as its short
shelf life. The ozone gas is supplied to the reaction vessels by
injection into the wastewater. The batch process uses a single reaction
tank. As with alkaline chlorination, the amount of ozone added and the
2748g
3-17
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reaction time used are determined by the type and concentration of the
oxidizable contaminants, and vigorous mixing should be provided for
complete oxidation.
In continuous operation, two separate tanks may be used for
reaction. The first tank receives an excess dosage of ozone. Any excess
ozone remaining at the outlet of the second tank is recycled to the first
tank, thus ensuring that an excess of ozone is maintained and also that
no ozone is released to the atmosphere. As with alkaline chlorination,
an ORP control system is usually necessary to ensure that sufficient
ozone is being added.
(d) Permanganate oxidation. Permanganate oxidation is
conducted in tanks in a manner similar to that used for alkaline
chlorination, as discussed previously. Potassium permanganate is
normally dissolved in an auxiliary tank and added as a solution. As with
the other oxidizing agents. ORP (for continuous processes) and excess
oxidizing agent (for batch processes) are monitored to measure the extent
of reaction.
(e) SO^/air oxidation. SO^/air oxidation of cyanide
depends on efficient mixing of air with the waste to ensure an adequate
supply of oxygen. Because of this factor, the equipment requirements for
this process are similar to those of ozonation. SO^ is sometimes
supplied with the air by using flue gas containing SO^ as the air
source. Otherwise, sulfur in the +4 oxidation state can be fed as
gaseous sulfur dioxide (SO^), liquid sulfurous acid (H^SO^), sodium
274dg
3-10
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sulfite (Na„SCL) solution, or sodium bisulfite (NaHSO ) solution.
2 3 3
Sodium bisulfite solution, made by dissolving sodium metabisulfite
(Na„S„0,.) in water, is the most frequently used source of SO,..
2 2 5 2
This process is usually run continuously, with the addition of oxidizing
agent and acid/alkali being controlled through continuous monitoring of
ORP and pH, respectively.
(4) Waste characteristics affecting performance fWCAPs). In
determining whether chemical oxidation will achieve the same level of
performance on an untested waste as on a previously tested waste and
whether performance levels can be transferred, EPA examines the following
waste characteristics: (a) the concentration of other oxidizable
contaminants (b) the concentration of metal salts, and (c) the
concentration of complexed metals.
(a) Concentration of other oxidizable compounds. The presence
of other oxidizable compounds in addition to the BDAT constituents of
concern will increase the demand for oxidizing agents and, hence,
potentially reduce the effectiveness of the treatment process. As a
surrogate for the amount of oxidizable organics present, EPA analyzes for
total organic carbon (TOC) in the waste. Oil and grease also provides an
indication of the amount of oxidizable organics present. Inorganic
reducing compounds such as sulfide may also create a demand for
additional oxidizing agent; EPA also attempts to identify and analyze for
these constituents. If TOC and/or inorganic reducing compound
concentrations in the untested waste are significantly higher than those
274Bg
3-19
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in the tested waste, the system may not achieve the same performance.
Additional oxidizing agent (ray be required to effectively oxidize the
waste and achieve the same treatment performance. Other, more applicable
treatment technologies also may need to be considered for treatment of
the untested waste.
(b) Concentration of metal salts. Metal salts, especially lead
and silver salts, will react with the oxidizing agent(s) to form metal
peroxides, chlorides, hypochlorites, and/or chlorates. These reactions
can cause an excessive consumption of oxidizing agents and potentially
interfere with the effectiveness of treatment.
(c) Concentration of complexed metals. An additional problem
with metals in cyanide solutions is that metal-cyanide complexes are
sometimes formed. These complexes are negatively charged metal-cyanide
ions that are extremely soluble. Cyanide in the conplexed form may not
be oxidizable, depending on the strength of the metal-cyanide bond in the
complex and the type of oxidizing agent used. Iron complexes (for
-4
example, the ferrocyanide ion, Fe(CN) ) are the most stable of the
0
complexed cyanides.
If the concentrations of metal salts and/or metal-cyanide complexes
in the untested waste are significantly higher than those in the tested
waste, the system may not achieve the same performance. Additional
oxidizing agent and/or a different oxidizing agent may be required to
effectively oxidize the waste and achieve the same treatment performance.
When the waste contains high concentrations of metal-cyanide complexes
3-20
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that are resistant to chemical oxidation treatment, other treatment
technologies may need to be considered for treatment of the untested
waste.
(5) Desian and operating parameters. In assessing the effectiveness
of the design and operation of a chemical oxidation system, EPA examines
the following parameters: (a) the residence time, (b) the amount and
type of oxidizing agent, (c) the degree of mixing, (d) the pH. (e) the
oxidation temperature, and (f) the amount and type of catalyst.
(a) Residence time. The residence time impacts the extent of
volatilization of waste contaminants. For a batch system, the residence
time is controlled by adjusting the treatment time in the reaction tank.
For a continuous system, the waste feed rate is controlled to make sure
that the system is operated at the appropriate design residence time.
EPA monitors the residence time to ensure that sufficient time is
provided to effectively oxidize the waste.
(b) Amount and type of oxidizing agent. Several factors
influence the choice of oxidizing agents and the amount to be added. The
amount of oxidizing agent required to treat a given amount of oxidizable
constituent(s) will vary with the agent chosen. Enough oxidant must be
added to ensure complete oxidation; the specific amount will depend on
the type of oxidizable compounds in the waste and the chemistry of the
oxidation reactions. Theoretically, the amount of oxidizing agent to be
added can be computed from oxidation reaction stoichiometry; in practice,
an excess of oxidant should be used. Testing for excess oxidizing agent
will determine whether the reaction has reached completion. In
2746q
3-21
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continuous processes, the addition of oxidizing agent is accomplished by
automated feed methods. The amount of oxidizing agent needed is usually
measured and controlled automatically by an oxidation-reduction potential
(ORP) sensor. EPA examines the amount of oxidant added to the chemical
oxidation system to ensure that it is sufficient to effectively oxidize
the waste and, for continuous processes, examines how the facility
ensures that the particular addition rate is maintained. EPA also tests
for excess oxidizing agent for batch processes and continuously monitors
the ORP for continuous processes to ensure that excess oxidizing agent,
if possible, is supplied.
(c) Degree of mixing. Process tanks must be equipped with
mixers to ensure maximum contact between the oxidizing agent and the
waste solution. Proper mixing also limits the production of any solid
precipitates from side reactions that may resist oxidation. Mixing also
provides an even distribution of tank contents and a homogeneous pH
throughout the waste, improving oxidation of wastewater constituents.
The quantifiable degree of mixing is a complex assessment that includes,
among other things, the amount of energy supplied, the length of time the
material is mixed, and the related turbulence effects of the specific
size and shape of the tank. This is beyond the scope of simple
measurement. EPA, however, evaluates the degree of mixing qualitatively
by considering whether mixing is provided and whether the type of mixing
device is one that could be expected to achieve uniform mixing of the
waste solution.
3-22
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(d) pH. Operation at the optimal pH maximizes the chemical
oxidation reactions and may, depending on the oxidizing agent being used,
limit the formation of undesirable reaction byproducts or the escape of
cyanide from solution as HCN, CNC1, or gas. The pH is
controlled by the addition of caustic, lime, or acid to the solution. In
most cases, a slightly or moderately alkaline pH is used, depending on
the type of oxidizing agent being used and the compound being treated
(see Section 3.3.2 (2), Underlying Principles of Operation). In alkaline
chlorination treatment of organics, a slightly acidic pH may be selected
as an optimum. In permanganate oxidation, a pH of 2 to 4 is often
selected. EPA monitors the pH continuously, if possible, to ensure that
the system is operating at the appropriate design condition and to
diagnose operational problems.
(e) Oxidation temperature. Temperature affects the rate of
reaction and the solubility of the oxidizing agent in the waste. As the
temperature is increased, the solubility of the oxidizing agent, in most
instances, is increased and the required residence time, in most cases,
is reduced. EPA monitors the oxidation temperature continuously, if
possible, to ensure that the system is operating at the appropriate
design condition and to diagnose operational problems.
(f) Amount and type of catalyst. Adding a catalyst that
promotes oxygen transfer and thus enhances oxidation has the effect of
lowering the necessary reactor temperature and/or improving the level of
destruction of oxidizable compounds. For waste constituents that are
2748g
3-23
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more difficult to oxidize, catalyst addition may be necessary to
effectively destroy the constituent(s) of concern. Catalysts typically
used for this purpose include copper bromide and copper nitrate. If a
catalyst is required, EPA examines the amount and type added, as well as
the method of addition of the catalyst to the waste, to ensure that
effective oxidation is achieved.
3.3.3 Wet Air Oxidation
(1) Add!icabi1itv. Wet air oxidation is a treatment technology
applicable to wastewaters containing organics and oxidizable inorganics
such as cyanide. The process is typically used to oxidize sewage sludge,
regenerate spent activated carbon, and treat process wastewaters.
Wastewaters treated using this technology include pesticide wastes,
petrochemical process wastes, cyanide-containing metal finishing wastes,
spent caustic wastewaters containing phenolic compcjnds, and some organic
chei.ical production wastewaters.
This technology differs from other treatment technologies generally
used to treat wastewaters containing organics in several ways. First,
wet air oxidation can be used to treat wastewaters that have higher
organic concentrations than are normally handled by biological treatment,
carbon adsorption, and chemical oxidation, but may be too dilute to be
effectively treated by thermal processes such as incineration. Wet air
oxidation is most applicable for waste streams containing dissolved or
suspended organics in the 500 to 15,000 mg/1 range. Below 500 mg/1, the
rates of wet air oxidation of most organic constituents are too slow for
3-24
-------
efficient application of this technology. For these more dilute waste
streams, biological treatment, carbon adsorption, or chemical oxidation
may be more applicable. For more concentrated waste streams (above
15,000 mg/1), thermal processes such as incineration may be more
applicable. Second, wet air oxidation can be applied to wastes that have
significant concentrations of metals (roughly 2 percent), whereas
biological treatment, carbon adsorption, and chemical oxidation may have
difficulty in treating such wastes.
It is important to point out that wet air oxidation proceeds by a
series of reaction steps and the intermediate products formed are not
always as readily oxidized as are the original constituents. Therefore,
the process does not always achieve complete oxidation of the organic
constituents. Accordingly, in applying this technology it is important
to assess potential products of incomplete oxidation to determine whether
further treatment is necessary or whether this technology is appropriate
at all.
Studies of the wet air oxidation of different compounds have led to
the following empirical observations concerning the susceptibility of a
compound to wet air oxidation based on its chemical structure:
]. Aliphatic compounds, even with multiple halogen atoms, can be
destroyed within conventional wet air oxidation conditions.
Oxygenated compounds (such as low molecular weight alcohols,
aldehydes, ketones, and carboxylic acids) are formed, but these
compounds are readily biotreatable.
2. Aromatic hydrocarbons, such as toluene, acenaphthene, or pyrene,
are easily oxidized.
Z7*6d
3-25
-------
3. Halogenated aromatic compounds can be oxidized provided there is
at least one nonhalogen functional group present on the ring
(e.g., pentachlorophenol (-0H) or 2,4,6-trichloroani1ine
(-NH2)).
4. Halogenated aromatic compounds, such as 1,2-dichlorobenzene, and
PCBs, such as Aroclor 1254, are resistant to wet air oxidation
under conventional conditions.
5. Halogenated ring compounds, such as the pesticides aldrin,
dieldrin, and endrin, are expected to be resistant to
conventional wet air oxidation.
6. DDT can be oxidized, but results in the formation of intractable
oils in conventional wet air oxidation.
7. Heterocyclic compounds containing oxygen, nitrogen, or sulfur are
expected to be destroyed by wet air oxidation because the 0, N,
or S atoms provide a point of attack for oxidation reactions to
occur.
(2) Underlying principles of operation. The wet air oxidation of
aqueous wastes occurs at high temperatures and pressures. The typical
operating temperature for the treatment process ranges from 175 to
325°C (347 to 617cF). The pressure is maintained at a level high
enough to prevent excessive evaporation of the liquid phase at the
operating temperature, generally between 300 and 3000 psi. At these
elevated temperatures and pressures, the solubility of oxygen in water is
dramatically increased, thus providing a strong driving force for the
oxidation. The reaction must take place in the aqueous phase because the'
chemical reactions involve both oxygen (oxidation) and water
(hydrolysis). The wet air oxidation process for a specific organic
compound generally involves a number of oxidation and hydrolysis
reactions in series, which degrade the initial compound by steps into a
274Bg
3-26
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series of compounds of simpler structure. Complete wet air oxidation
results in the conversion of hazardous compounds into carbon dioxide,
water vapor, ammonia (for nitrogen-containing wastes), sulfate (for
sulfur-containing wastes), and halogen acids (for halogenated wastes).
However, treatable quantities of partial degradation products may
remain in the treated wastewaters from wet air oxidation. Therefore,
effluents from wet air oxidation processes may be given subsequent
treatment including biological treatment, carbon adsorption, or chemical
oxidation before being discharged.
(3) Description of wet air oxidation process. A conventional wet
air oxidation system consists of a high-pressure liquid feed pump, an
oxygen source (air compressor or liquid oxygen vaporizer), a reactor,
heat exchangers, a vapor-liquid separator, and process regulators. A
basic flow diagram is shown in Figure 3-1.
A typical batch wet air oxidation process proceeds as follows.
First, a copper catalyst solution may be mixed with the aqueous waste
stream if preliminary testing indicates that a catalyst is necessary.
The waste is then pumped into the reaction chamber. The aqueous waste is
pressurized and heated to the design pressure and temperature. After
reaction conditions have been established, air is fed to the reactor for
the duration of the design reaction time. At the completion of the wet
air oxidation process, suspended solids or gases are removed and the
remaining treated aqueous waste is either discharged directly or fed to a
biological treatment, carbon adsorption, or chemical oxidation treatment
system if further treatment is necessary prior to discharge.
?748g
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PRESSURIZED
WASTE FEED
T
!\>
00
PRESSURIZED
AIR OR
OXYGEN
FEED HEAT
EXCHANGERS
REACTOR
STEAM
STEAM
GAS-LIQUID
SEPARATOR
Y
TREATED
WASTE
(TO
FURTHER
TREATMENT
OR
DISPOSAL)
Figure 3-1. WET AIR OXIDATION PROCESS FLOW DIAGRAM
-------
Wet air oxidation can also be operated in a continuous process. In
continuous operation, the waste is pressurized, mixed with pressurized
air or oxygen, preheated in a series of heat exchangers by the hot
reactor effluent and steam, and fed to the reactor. The waste feed flow
rate controls the reactor residence time. Steam is fed into the reactor
column to adjust the column temperature. The treated waste is separated
in a gas-liquid separator, with the gases treated in an air pollution
control system and/or discharged to the atmosphere and the liquids either
further treated, as mentioned above, and/or discharged to disposal.
(4) Waste characteristics affecting performance (WCAPsh In
determining whether wet air oxidation will achieve the same level of
performance on an untested waste as on a previously tested waste and
whether performance levels can be transferred, EPA examines the following
waste characteristics: (a) the chemical oxygen deirand and (b) the
concentration of interfering substances.
(a) Chemical oxygen demand. The chemical oxygen demand (COD)
of the waste is a measure of the oxygen required for complete oxidation
of the oxidizable waste constituents. The limit to the amount of oxygen
that can be supplied to the waste is dependent on the solubility of
oxygen in the aqueous waste and the rate of transfer of oxygen from the
gas phase to the liquid phase. This sets an upper limit on the amount of
oxidizable compounds that can be treated by wet air oxidation. Thus,
high-COD wastes may require dilution for effective treatment to occur.
If the COD of the untested waste is significantly higher than that of the
274Sg
3-29
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tested waste, the system may not achieve the same performance.
Pretreatment of the waste or dilution as part of treatment may be needed
to reduce the COO to within levels treatable by the dissolved oxygen
concentration and to achieve the same treatment performance, or other,
more applicable treatment technologies may need to be considered for
treatment of the untested waste.
(b) Concentration of interfering substances. In some cases,
addition of a water-soluble copper salt catalyst to the waste before
processing is necessary for efficient oxidation treatment (for example,
for oxidation of some halogenated organics). Other metals have been
tested and have been found to be less effective. Interfering substances
for the wet air oxidation process are essentially those that cause the
formation of insoluble copper salts when copper catalysts are used. To
be effective in catalyzing the oxidation reaction, :he copper ions must
be dissolved in solution. Sulfide, carbonate, and other negative ions
that form insoluble copper salts may interfere with treatment
effectiveness if they are present in significant concentrations in wastes
for which copper catalysts are necessary for effective treatment. If an
untested waste for which a copper catalyst is necessary for effective
treatment has a concentration of interfering substances (including
sulfide, carbonate, or other anions that form insoluble copper salts)
significantly higher than that in a tested waste, the system may not
achieve the same performance and other, more applicable treatment
technologies may need to be considered for treatment of the untested
waste.
2746c
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(5) Design and operatino parameters. In assessing the effectiveness
of the design and operation of a wet air oxidation system, EPA examines
the following parameters: (a) the oxidation temperature, (b) the
residence time, (c) the excess oxygen concentration, (d) the oxidation
pressure, and (e) the amount and type of catalyst. Optimization of these
parameters is often first performed on bench scale using an autoclave,
and then refined in a pilot-scale system.
(a) Oxidation temperature. Temperature is the most important
parameter affecting the system. The design temperature must be high
enough to allow the oxidation reactions to proceed at acceptable rates.
Raising the temperature increases the wet air oxidation rate by enhancing
oxygen solubility and oxygen diffusivity. The process is normally
operated in the temperature range of 175 to 325°C (347 to 617°F),
depending on the hazardous constituent(s) to be treated. EPA monitors
the oxidation temperature continuously, if possible, to ensure that the
system is operating at the appropriate design condition and to diagnose
operational problems.
(b) Residence time. The residence time impacts the extent of
oxidation of waste contaminants. For a batch system, the residence time
is controlled directly by adjusting the treatment time in the reaction
tank. For a continuous system, the waste feed rate is controlled to make
sure that the system is operated at the appropriate design residence
time. Generally, the reaction rates are relatively fast for the first
30 minutes and become slow after 60 minutes. Typical residence times,
2 7 43g
3-31
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therefore, are approximately 1 hour. EPA monitors the residence time to
ensure that sufficient time is provided to effectively oxidize the waste.
(c) Excess oxygen concentration. The system must be designed
to supply adequate amounts of oxygen for the compounds to be oxidized.
An estimate of the amount of oxygen needed can be made based on the COO
content of the untreated waste; excess oxygen should be supplied to
ensure complete oxidation. The source of oxygen is compressed air or a
high-pressure pure oxygen stream. EPA monitors the excess oxygen
concentration (the concentration of oxygen in the gas leaving the
reactor) continuously, if possible, by sampling the vent gas from the
gas-liquid separator to ensure that an effective amount of oxygen or air
is being supplied to the waste.
(d) Oxidation pressure. The design pressure must be high
enough to prevent excessive evaporation of water aid volatile organics at
the design temperature. This allows the oxidation reaction to occur in
the aqueous phase, thereby improving treatment effectiveness. EPA
monitors the oxidation pressure continuously, if possible, to ensure that
the system is operating at the appropriate design condition and to
diagnose operational problems.
(e) Amount and type of catalyst. Adding a catalyst that
promotes oxygen transfer and thus enhances oxidation has the effect of
lowering the necessary reactor temperature and/or improving the level of
destruction of oxidizable compounds. For waste constituents that are
2?<8g
3-32
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more difficult to oxidize, the addition of a catalyst may be necessary to
effectively destroy the constituent(s) of concern. Catalysts typically
used for this purpose include copper bromide and copper nitrate. If a
catalyst is required, EPA examines the amount and type added, as well as
the method of addition of the catalyst to the waste, to ensure that
effective oxidation is achieved.
3.3.4 Incineration
This section addresses the commonly used incineration technologies:
liquid injection, rotary kiln, fluidized bed, and fixed hearth. As
appropriate, the subsections are divided by type of incineration unit.
(1) Applicabilitv
(a) Liquid injection. Liquid injection is applicable to wastes
that have viscosity values low enough that the waste can be atomized in
the combustion chamber. A range of literature maximum viscosity values
are reported, with the low being 100 Saybolt Seconds Universal (SSU) and
the high being 10,000 SSU. It is important to note that viscosity is
temperature dependent so that while liquid injection may not be
applicable to a waste at ambient conditions, it may be applicable when
the waste is heated. Other factors that affect the use of liquid
injection are particle size and the presence of suspended solids. Both
of these can cause plugging of the burner nozzle.
(b) Rotary kiln/fluidized bed/fixed hearth. These incineration
technologies are applicable to a wide range of hazardous wastes. They
can be used on wastes that contain high or low total organic content,
3-33
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high or low filterable solids, various viscosity ranges, and a range of
other waste parameters. EPA has not found these technologies to be
demonstrated on most wastes that are composed essentially of metals with
low organic concentrations. In addition, the Agency expects that the
incineration of some of the high metal content wastes may not be
compatible with existing and future air emission limits without emission
controls far more extensive than those currently in use.
(2) Underlying principles of operation
(a) Liquid injection. The basic operating principle of this
incineration technology is that incoming liquid wastes are volatilized
and then additional heat is supplied to the waste to destabilize the
cheincal bonds. Once the chemical bonds are broken, these constituents
react with oxygen to form carbon dioxide and water vapor. The energy
needed to destabilize the bonds is referred to as the energy of
activation.
(b) Rotary kiln and fixed hearth. There are two distinct
principles of operation for these incineration technologies, one for each
of the two chambers involved. In the primary chamber, energy, in the
form of heat, is transferred to the waste to achieve volatilization of v
the various organic waste constituents. During this volatilization
process some of the organic constituent bonds destabilize and oxidize to
carbon dioxide and water vapor. In the secondary chamber, additional
heat is supplied to overcome the energy requirements needed to
destabilize the remaining chemical bonds and allow the constituents to
2748g
3-34
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react with excess oxygen to form carbon dioxide and water vapor. The
principle of operation for the secondary chamber is similar to that of
liquid injection.
(c) Fluidized bed. The principle of operation for this
incinerator technology is somewhat different from that for rotary kiln
and fixed hearth incineration, in that there is only one chamber, which
contains the fluidizing sand and a freeboard section above the sand. The
purpose of the fluidized bed is to both volatilize the waste and combust
the waste. Destruction of the waste organics can be accomplished to a
better degree in this chamber than in the primary chamber of the rotary
kiln and fixed hearth because of (i) improved heat transfer from
fluidization of the waste using forced air and (ii) the fact that the
fluidization process provides sufficient oxygen and turbulence to convert
the organics to carbon dioxide and water vapor. The freeboard volume
generally does not have an afterburner; however, additional time is
provided for conversion of the organic constituents to carbon dioxide and
water vapor (and hydrochloric acid if chlorine is present in the waste).
(3) Description of incineration technologies
(a) Liquid injection. The liquid injection system is capable ,
of incinerating a wide range of gases and liquids. The combustion system
has a simple design with virtually no moving parts. A burner or nozzle
atomizes the liquid waste and injects it into the combustion chamber,
where'it burns in the presence of air or oxygen. A forced draft system
supplies the combustion chamber with air to provide oxygen for combustion
2740g
3-35
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and turbulence for rnixing. The combustion chamber is usually a cylinder
lined with refractory (i.e., heat-resistant) brick, and it can be fired
horizontally, vertically upward, or vertically downward. Figure 3-2
illustrates a liquid injection incineration system.
(b) Rotary kiln. A rotary kiln is a slowly rotating,
refractory-lined cylinder that is mounted at a slight incline from the
horizontal (see Figure 3-3). Solid wastes enter at the high end of the
kiln, and liquid or gaseous wastes enter through atomizing nozzles in the
kiln or afterburner section. Rotation of the kiln exposes the solids to
the heat, vaporizes them, and allows them to combust by mixing with air.
The rotation also causes the ash to move to the lower end of the kiln,
where it can be removed. Rotary kiln systems usually have a secondary
combustion chamber or afterburner following the kiln for further
combustion of the volatilized components of solid wastes.
(c) Fluidized bed. A fluidized bed incinerator consists of a
column containing inert particles such as sand, which is referred to as
the bed. Air, driven by a blower, enters the bottom of the bed to
fluidize the sand. Air passage through the bed promotes rapid and
uniform mixing of the injected waste material within the fluidized bed.
The fluidized bed has an extremely high heat capacity (approximately
three times that of flue gas at the same temperature), thereby providing
a large heat reservoir. The injected waste reaches ignition temperature
quickly in the hot fluidized bed. Continued bed agitation by the
fluidizing air allows larger particles to remain suspended in the
combustion zone (see Figure 3-4).
2748g
3-36
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WATER
AUXILIARY FUEL
LIQUID OR GASEOUS.
WASTE INJECTION
-W BURNER
AIR
-Hburner
PRIMARY
COMBUSTION
CHAMBER
AFTERBURNER
(SECONDARY
COMBUSTION
CHAMBER)
I
rm
SPRAY
CHAMBER
GAS TO AIR
POLLUTION
CONTROL
HORIZONTALLY FIRED
LIQUID INJECTION
INCINERATOR
ASH
WATER
Figure 3-2. LIQUID INJECTION INCINERATOR
-------
GAS TO
AIR POLLUTION
CONTROL
i
SOLiO
WASTE
INFLUENT
AUXILIARY
FUEL.
AIR
COMBUSTION
GASES
ROTARY
KILN
LIQUID OR
GASEOUS
WASTE
AFTERBURNER
FEED
MEQHANISM
LIQUID OR
GASEOUS
WASTE
INJECTION
t
ASH
Figure 3-3. ROTARY KILN INCINERATOR
3-38
-------
WASTE
INJECTION
BURNER
FREEBOARD
SAND BED
GAS TO
AIR POLLUTION
CONTROL
MAKE-UP
SAND
AIR
ASH
Figure 3-4. FLUIDIZED BED INCINERATOR
3-39
-------
(d) Fixed hearth. Fixed hearth incinerators, versions of which
are also called controlled air or starved air incinerators, are another
major technology used for hazardous waste incineration. Fixed hearth
incineration is a two-stage combustion process (see Figure 3-5). Waste
is fed into the first stage, or primary chamber, and usually burned at
less than stoichiometric conditions (less than the theoretically required
amount of air). The resultant smoke and pyrolysis products, consisting
primarily of volatile hydrocarbons and carbon monoxide, along with the
normal products of combustion, pass to the secondary chamber. Here,
additional air is usually injected to complete the combustion. This
two-stage process generally yields low stack particulate and carbon
monoxide (CO) emissions. The primary chamber combustion reactions and
combustion gas volumes are maintained at low levels by the starved air
conditions so that particulate entrainment and carryover are minimized.
(e) Air pollution controls. Following incineration of
hazardous wastes, combustion gases are generally further treated in an
air pollution control system. The presence of chlorine or other halogens
in some waste requires a scrubbing or absorption step to remove hydrogen
chloride (HC1) and other halo-acids from the combustion gases. Ash in
the waste is not destroyed in the combustion process. Depending on its
composition, ash will exit either as bottom ash, at the discharge end of
a kiln or hearth for example, or as particulate matter (fly ash)
suspended in the combustion gas stream. Particulate emissions from most
hazardous waste combustion systems generally have particle diameters of
27«8g
3-40
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AIR
GAS TO AIR
POLLUTION
CONTROL
AIR
WASTE
injection'
BURNER
1
PRIMARY
SECONDARY
COMBUSTION
COMBUSTION
CHAMBER
CHAMBER
GRATE
I
AUXILIARY
FUEL
2rSTAGE FIXED HEARTH
INCINERATOR
ASH
Figure 3-5. FIXED HEARTH INCINERATOR
-------
less than 1 micron and require high-efficiency collection devices to
minimize air emissions. In addition, scrubber systems provide an
additional buffer against accidental releases of incompletely destroyed
waste products resulting from poor combustion efficiency or combustion
upsets.
(4) Waste characteristics affecting performance fWCAPs)
(a) Liquid injection. In determining whether liquid injection
will achieve the same level of performance on an untested waste as on a
previously tested waste, and whether performance levels can be
transferred, EPA examines the bond dissociation energies of the
constituents in the untested and tested wastes. This parameter is being
used as a surrogate indicator of activation energy which, as discussed
previously, destabilizes molecular bonds. In theory, the bond
dissociation energy would be equal to the activation energy; however, in
practice this is not always the case. Other energy effects (e.g.,
vibrational effects, the formation of intermediates, and interactions
between different molecular bonds) may have a significant influence on
activation energy.
Because of the shortcomings of bond energy calculations in estimating
activation energy, EPA analyzed other waste characteristic parameters to
determine whether these parameters would provide a better basis for
transferring treatment standards from an untested waste to a tested
waste. These parameters include heat of combustion, heat of formation,
?7 46g
3-42
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use of available kinetic data to predict activation energies, and general
structural class. All of these parameters were rejected for the reasons
provided below.
The heat of combustion measures only the difference in energy of the
products and reactants; it does not provide information on the transition
state (i.e., the energy input needed to initiate the reaction). Heat of
formation is used as a tool to predict whether reactions are likely to
proceed; however, there are a significant number of hazardous
constituents for which these data are not available. The use of kinetic
data was rejected because these data are limited and could not be used to
calculate dissociation requirements for the wide range of hazardous
constituents. Finally, EPA decided not to use structural classes because
the Agency believes that evaluation of bond dissociation energies allows
for a more direct determination of whether a constituent will be
destabi1ized.
(b) Rotary ki1n/f1uidized bed/fixed hearth. Unlike liquid
injection, these incineration technologies always generate a residual
ash. Accordingly, in determining whether these technologies will achieve
the same level of performance on an untested waste as on a previously
tested waste and whether performance levels can be transferred, EPA
examines the following waste characteristics that affect volatilization
of organics from the waste, as well as destruction of the organics once
volatilized. Relative to volatilization, EPA examines the thermal
conductivity of the entire waste and the boiling points of the various
274ag
3-43
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constituents. As with liquid injection. EPA examines bond energies in
determining whether treatment standards for scrubber water residuals can
be transferred from a tested waste to an untested waste. Below is a
discussion of how EPA arrived at thermal conductivity and boiling point
as the best means to assess volatilization of organics from the waste;
the discussion relative to bond energies is the same for these
technologies as for liquid injection and is therefore not repeated.
(i) Thermal conductivitv. Consistent with the underlying
principles of incineration, a major factor with regard to whether a
particular constituent will volatilize is the transfer of heat through
the waste. In the case of rotary kiln, fluidized bed, and fixed hearth
incineration, heat is transferred through the waste by three mechanisms:
radiation, convection, and conduction. For a given incinerator, heat
transferred through various wastes by radiation is nore a function of the
design and type of incinerator than of the waste being treated.
Accordingly, the type of waste treated has a minimal impact on the amount
of heat transferred by radiation. With regard to convection, EPA also
believes that the type of heat transfer is generally more a function of
the type and design of incinerator than of the waste itself. However,
EPA is examining particle size as a waste characteristic that may
significantly impact the amount of heat transferred to a waste by
convection and thus may impact volatilization of the various organic
compounds. The final type of heat transfer, conduction, is the one that
EPA believes has the greatest impact on volatilization of organic
2146c
3-44
-------
constituents. To measure this characteristic, EPA uses thermal
conductivity; an explanation of this parameter, as well as how it can be
measured, is provided below.
Heat flow by conduction is proportional to the temperature gradient
across the material. The proportionality constant is a property of the
material and is referred to as the thermal conductivity. (Note: The
analytical method that EPA has identified for measurement of thermal
conductivity is described in Appendix C.) In theory, thermal
conductivity would always provide a good indication of whether a
constituent in an untested waste would be treated to the same extent in
the primary incinerator chamber as the same constituent in a previously
tested waste.
In practice, thermal conductivity has some limitations in assessing
the transferability of treatment standards; however. EPA has not
identified a parameter that can provide a better indication of heat
transfer characteristics of a waste. Below is a discussion of the
limitations associated with thermal conductivity, as well as other
parameters considered.
Thermal conductivity measurements, as part of a treatability
comparison of two different wastes to be treated by a single incinerator,
are most meaningful when applied to wastes that are homogeneous (i.e.,
uniform throughout). As wastes exhibit greater degrees of nonhomogeneity
(e.g., significant concentration of metals in soil), thermal conductivity
becomes less accurate in predicting treatability because the measurement
2 748g
3-45
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essentially reflects heat flow through regions having the greatest
conductivity (i.e., the path of least resistance) and not heat flow
through all parts of the waste.
Btu value, specific heat, and ash content were also considered for
predicting heat transfer characteristics. These parameters can no better
account for nonhomogeneity than can thermal conductivity; additionally,
they are not directly related to heat transfer characteristics.
Therefore, these parameters do not provide a better indication of the
heat transfer that will occur in any specific waste.
(ii) Boil ina point. Once heat is transferred to a
constituent within a waste, removal of this constituent from the waste
depends on its volatility. As a surrogate for volatility, EPA is using
the boiling point of the constituent. Compounds with lower boiling
points have higher vapor pressures and, therefore, would be more likely
to volatilize. The Agency recognizes that this parameter does not take
into consideration the impact of other compounds in the waste on the
boiling point of a constituent in a mixture; however, the Agency is not
aware of a better measure of volatility that can easily be determined.
(5) Design and operating parameters
(a) Liquid injection. For a liquid injection unit, EPA's
analysis of whether the unit is well designed focuses on both the
likelihood that sufficient energy is provided to the waste to overcome
the activation level for breaking molecular bonds and whether sufficient
oxygen is present to convert the waste constituents to carbon dioxide and
3-46
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water vapor. In assessing the effectiveness of the design and operation
of a liquid injection unit, EPA examines the following parameters:
(i) the temperature, (ii) the excess oxygen concentration, (i i i) the
carbon monoxide concentration, and (iv) the waste feed rate. Below is a
discussion of why EPA believes that these parameters are important, as
well as a discussion of how these parameters are monitored during
operation.
It is important to point out, relative to the development of land
disposal restriction standards, that since liquid injection generally
does not produce bottom ash, EPA is concerned with these design
parameters only when a quench water or scrubber water residual is
generated from treatment of a particular waste. If treatment of a
particular waste in a liquid injection unit would not generate a
wastewater stream, then the Agency, for purposes of land disposal
treatment standards, would be concerned only with the waste
characteristics that affect selection of the unit, not with the
above-mentioned design parameters.
(i) Temperature. Temperature provides an indirect measure
of the energy available (i.e., Btu/hr) to overcome the activation energy
of waste constituents. As the design temperature increases, it becomes
more likely that the molecular bonds will be destabilized and the
reaction completed.
The temperature is normally controlled automatically through the use
of instrumentation that senses the temperature and automatically adjusts
27 -S3g
3-47
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the amount of fuel and/or waste being fed. The temperature signal
transmitted to the controller can be simultaneously transmitted to a
recording device and thereby continuously recorded. To fully assess the
operation of the unit, it is important to know not only the exact
location in the incinerator at which the temperature is being monitored
but also the location of the design temperature.
(ii) Excess oxygen concentration. It is important that the
incinerator contain oxygen in excess of the stoichiometric amount
necessary to convert the organic compounds to carbon dioxide and water
vapor. If insufficient oxygen is present, then destabilized waste
constituents could recombine to form the same or other BDAT list organic
compounds and potentially cause the scrubber water to contain higher
concentrations of BOAT list constituents than would be the case for a
wel1-operated unit.
In practice, the anount of oxygen fed to the incinerator is
controlled by continuous sampling and analysis of the stack gas. If the
amount of oxygen drops below the design value, then the analyzer
transmits a signal to the valve or damper controlling the air supply and
thereby increases the flow of oxygen. The analyzer simultaneously
transmits a signal to a recording device so that the amount of excess
oxygen can be continuously recorded. Again, as with temperature, it is
important to know the location from which the combustion gas is being
sampled.
2 7 dtg
3-48
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(Hi) Carbon monoxide concent rat ion. The carbon monoxide
concentration is an important operating parameter because it provides an
indication of the extent to which the waste organic constituents are
being converted to carbon dioxide and water vapor. An increase in the
carbon monoxide level indicates that greater amounts of organic waste
constituents are unreacted or partially reacted. Increased carbon
monoxide levels can result from insufficient oxygen, too much oxygen
(causing cooling), insufficient turbulence in the combustion zone, or
insufficient residence time of combustion gases.
(iv) Waste feed rate. It is important to monitor the waste
feed rate because it is correlated to the residence time. The residence
time is associated with a specific Btu energy value of the feed and a
specific volume of combustion gas generated. Prior to incineration, the
Btu value of the waste is determined through the use of a laboratory
device known as a bomb calorimeter. The volume of combustion gas
generated from the waste to be incinerated is determined from a waste
analysis referred to as an ultimate analysis. This analysis determines
the amount of elemental constituents present, which include carbon,
hydrogen, sulfur, oxygen, nitrogen, and halogens. Using this analysis
plus the total amount of air added, the volume of combustion gas can be
calculated. After both the Btu content and the expected combustion gas
volume have been determined, the feed rate can be fixed at the desired
combustion gas residence time. Continuous monitoring of the feed rate
determines whether the unit was operated at a rate corresponding to the
designed residence time.
27<8g
3-49
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(b) Rotary kiln. For this incineration technology, EPA
examines both the primary and secondary chamber in evaluating the design
of a particular incinerator. Relative to the primary chamber, EPA's
assessment of design focuses on whether it is likely that enough energy
is provided to the waste to volatilize the waste constituents. For the
secondary chamber, analogous to the sole liquid injection incineration
chamber, EPA examines the same parameters discussed previously under
liquid injection incineration. (These parameters will not be discussed
again here.)
In assessing the effectiveness of the design and operation of the
primary chamber, EPA examines the following parameters: (i) the kiln
temperature, (ii) the residence time of the waste solids, and (i i i) the
revolutions per minute. Below is a discussion of why EPA believes that
these parameters are important, as well as a discussion of how these
parameters are monitored during operation.
(i) Temperature. The primary chamber temperature is
important because it provides an indirect measure of the energy input
(i.e., Btu/hr) available for heating the waste. The higher the design
temperature in a given kiln, the more likely it is that the constituents
will volatilize. As discussed earlier in Section 3.3.4(5)(a), Liquid
Injection, temperature should be continuously monitored and recorded.
Additionally, it is important to know the location of the temperature
sensing device in the kiln.
?748g
3-50
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(ii) Residence time of the waste solids. This parameter is
important in that it affects whether sufficient heat is transferred to a
particular constituent for volatilization to occur. As the time that the
waste in the kiln is increased, a greater quantity of heat is transferred
to the hazardous waste constituents. The residence time is a function of
the specific configuration of the rotary kiln, including the length and
diameter of the kiln, the waste feed rate, and the rate of rotation.
(Hi) Revolut ions per minute (RPM). This parameter
provides an indication of the turbulence that occurs in the primary
chamber of a rotary kiln. As the turbulence increases, the quantity of
heat transferred to the waste would also be expected to increase.
However, as the RPM value increases, the residence time of waste solids
decreases, resulting in a reduction of the quantity of heat transferred
to the waste. This parameter needs to be carefully evaluated because it
provides a balance between turbulence and residence time.
(c) Fluidized bed. As discussed previously in Section
3.3.4(2), Underlying Principles of Operation, the primary chamber
accounts for almost all of the conversion of organic wastes to carbon
dioxide and water vapor (and acid gas if halogens are present). The
freeboard volume will generally provide additional residence time for
combustion gases for thermal oxidation of the waste constituents.
Relative to the primary chamber, the parameters that EPA examines in
assessing the effectiveness of the design are temperature, residence
2746a
3-51
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time, and bed pressure differential. The first two were included in the
rotary kiln discussion and will not be discussed here. The last, bed
pressure differential, is important in that it provides an indication of
the amount of turbulence and, therefore, indirectly the amount of heat
supplied to the waste. In general, as the pressure drop increases, both
the turbulence and heat supplied increase. The pressure drop through the
bed should be continuously monitored and recorded to ensure that the
designed valued is achieved.
(d) Fixed hearth. The design considerations for this
incineration unit are similar to those for a rotary kiln with the
exception that rate of rotation (i.e., RPM) is not an applicable design
parameter. For the primary chamber of this unit, the parameters that EPA
examines in assessing how well the unit is designed are the same as those
discussed under Rotary kiln (Section 3.3.4(5)(b)); for the secondary
chamber (i.e., afterburner), the design and operating parameters of
concern are the same as those discussed under Liquid Injection
(Section 3.3.4(5)(a)).
3.4 Descriptions of 8DAT List Metals Treatment Technologies
3.4.1 Hexavalent Chromium Reduction
(1) Add!icabilitv. Hexavalent chromium reduction is a treatment
technology applicable to wastes containing hexavalent chromium wastes,
including plating solutions, stainless steel acid baths and rinses,
"chrome conversion" coating process rinses, and chromium pigment
manufacturing wastes. Because this technology requires that the pH be in
?746g
3-52
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the acidic range, it would not be applicable to a waste that contains
significant amounts of cyanide or sulfide. In such cases, lowering of
the pH can result in the release of toxic gases such as hydrogen cyanide
or hydrogen sulfide. It is important to note that additional
precipitation treatment is required to remove trivalent chromium from the
solution following reduction of the hexavalent chromium.
(2) Underlying principles of operation. The basic principle of
hexavalent chromium reduction is to reduce the valence of chromium in
solution (in the form of chromate or dichromate ions) from the hexavalent
state to the trivalent state. "Reducing agents" used to effect the
reduction include sodium sulfite (Na S CL), sodium bisulfite
2 2 3
(NaHSO^), sodium metabisulfite (Na^S^O^), sulfur dioxide (SO^),
+2
sodium hydrosulfide (NaHS), and the ferrous form of iron (Fe ).
A typical reduction reaction, using sodium sulfite as the reducing
agent, is as follows:
H„(Cr+Vo, + 3Na.SC) + 3H SO, - (Cr+3) JSO) + 3Na SO, + 4H 0
2 2 7 2 3 2 4 '2V 4 3 2 4 2
The reaction is usually accomplished at pH values from 2 to 3.
At the completion of the chromium reduction step, the trivalent
chromium compounds are precipitated from solution by raising the pH
above 8. The insoluble trivalent chromium [in the form of chromium
hydroxide) is then allowed to settle from solution. The precipitation
reaction is as follows:
Cr2(S°4)3 + 3Ca(0H)£ - 2Cr(0H)3 + 3CaS04
2 7 4 Hg
3-53
-------
(3) Description of chromium reduction process. The chromium
reduction treatment process can be operated in a batch or continuous
mode. A batch system consists of a reaction tank, a mixer to homogenize
the contents of the tank, a supply of reducing agent, and a source of
acid and base for pH control.
A continuous chromium reduction treatment system, as shown in
Figure 3-6, usually includes a holding tank upstream of the reaction tank
for flow and concentration equalization. It also includes instrumentation
to automatically control the amount of reducing agent added and the pH of
the reaction tank. The amount of reducing agent is controlled by the use
of a sensor called an oxidation reduction potential (ORP) cell. The ORP
sensor electronically measures, in millivolts, the level to which the
redox reaction has proceeded at any given time. It must be noted,
however, that the ORP reading is very pH dependent. Consequently, if the
pH is not maintained at a steady value, the ORP will vary somewhat,
regardless of the level of chromate reduction. Following chromium
reduction, the trivalent chromium is precipitated and settled out of the
solution, which is further treated and/or disposed of. Precipitated
trivalent chromium is either reused or further treated by stabilization
and land disposed.
(4) Waste characteristics affectina performance (WCAPsl. In
determining whether hexavalent chromium reduction will achieve the same
level of performance on an untested waste as on a previously tested waste
and whether performance levels can be transferred, EPA examines the
2 7 leg
3-54
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CO
I
t_n
u
HEXAVALENT
CHROMIUM
CONTAINING
WASTEWATER
>¦ TO SETTLING
~ ~
ORP pH
SENSORS
pl<
SENSOR
REDUCING
AGENT
FEED
SYSTEM
ACID
FEED
SYSTEM
ALKALI
FEED
SYSTEM
REDUCTION
PRECIPITATION
ELECTRICAL CONTROLS
MIXER
Figure 3-6. CONTINUOUS HEXAVALENT CHROMIUM REDUCTION SYSTEM
-------
following waste characteristics: (a) the concentration of oil and grease
and (b) the concentration of other reducible metals.
(a) Concentration of oil and grease. EPA believes that oil and
grease compounds could cause monitoring problems because of fouling of
instrumentation (e.g.. electrodes for pH and ORP sensors). If the
concentration of oil and grease in the untested waste is significantly
higher than that in the tested waste, the system may not achieve the same
performance and other, more applicable treatment technologies may need to
be considered for treatment of the untested waste.
(b) Concentration of other reducible metals. Ionized metals
(such as silver, copper, and mercury) can compete with chromium for
reducing agents, thereby requiring greater amounts of reducing agents to
completely reduce the chromium. If the concentration of reducible metals
in the untested waste is significantly higher than :hat in the tested
waste, the system may not achieve the same performance. Additional
reducing agents may be required to reduce the chromium and achieve the
same treatment performance, or other, more applicable treatment
technologies may need to be considered for treatment of the untested
waste.
(5) Design and operating parameters. In assessing the effectiveness
of the design and operation of a hexavalent chromium reduction system,
EPA examines the following parameters: (a) the amount and type of
reducing agent, (b) the pH, (c) the residence time, and (d) the degree of
mi xi ng.
Z74ag
3-56
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(a) Amount and type of reducing agent. The choice of a
reducing agent establishes the chemical reaction upon which the chromium
reduction system is based. The amount of the reducing agent must be
monitored and controlled in both batch and continuous systems to ensure
complete reduction. In batch systems, the reducing agent is usually
controlled by analysis of the hexavalent chromium remaining in solution,
but it may also be controlled by using an ORP monitoring system. For
continuous systems, the ORP reading is used to monitor and control the
addition of the reducing agent.
The ORP will slowly change until the reduction reaction is completed,
at which point the ORP will change rapidly. The set point for the ORP
monitor is approximately the reading just after the rapid change has
begun. The reduction system must then be monitored periodically to
determine whether the selected set point needs furtner adjustment. EPA
monitors the hexavalent chromium remaining in solution for batch systems
and monitors the ORP continuously, if possible, for continuous systems to
ensure that an effective amount of the reducing agent has been added to
the system.
(b) pH. For batch and continuous systems, pH affects the
reduction reaction. The reaction speed is significantly reduced at pH
values above approximately 4.0. For a batch system, the pH can be
monitored intermittently during treatment. For a continuous system, the
pH must be monitored continuously because of its effect on the ORP
reading. EPA monitors the pH to ensure that the system is operating at
the appropriate design condition and to diagnose operational problems.
27
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(c) Residence time. The residence time impacts the extent to
which the hexavalent chromium reduction reaction goes to completion. For
batch systems, the residence time is controlled directly by adjusting the
treatment time in the reaction tank. For continuous systems, the feed
rate is controlled to make sure that the system is operated at the
appropriate design residence time. EPA monitors the residence time to
ensure that sufficient time is provided to effectively reduce the waste.
(d) Degree of mixing. The reduction system should be designed
to provide adequate mixing in order to ensure uniform distribution of the
reducing agent and chromium throughout the reactor. The quantifiable
degree of mixing is a complex assessment that includes, among other
things, the amount of energy supplied, the length of time the material is
mixed, and the related turbulence effects of the specific size and shape
of the reaction vessel. This is beyond the scope cf simple measurement.
EPA, however, evaluates the degree of mixing qualitatively by considering
whether mixing is provided and whether the type of mixing device is one
that could be expected to achieve uniform mixing of the waste.
3.4.2 Chemical Precipitation
(1) Aoplicabilitv. Chemical precipitation is a treatment technology
applicable to wastewaters containing a wide range of dissolved and other
metals, as well as other inorganic substances such as fluorides. This
technology removes these metals and inorganics from solution in the form
of insoluble solid precipitates. The solids formed are then separated
from the wastewater by settling, clarification, and/or polishing
fi1trat i on.
3-58
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For some wastewaters, such as chromium plating baths or plating baths
containing cyanides, the metals exist in solution in a very soluble
form. This solubility can be caused by the metal's oxidation state (for
hexavalent chromium wastewaters) or by complexing of the metals (for high
cyanide-containing wastewaters). In both cases, pretreatment, such as
hexavalent chromium reduction or oxidation of the metal-cyanide
complexes, may be required before the chemical precipitation process can
be applied effectively.
(2) Underlying principles of operation. The basic principle of
operation of chemical precipitation is that metals and inorganics in
wastewater are removed by the addition of a precipitating agent that
converts the soluble metals and inorganics to insoluble precipitates.
These precipitates are settled, clarified, and/or filtered out of
solution, leaving a lower concentration of metals end inorganics in the
wastewater. The principal precipitation agents us?d to convert soluble
metal and inorganic compounds to less soluble forms include: lime
(Ca(OH)^), caustic (NaOH), sodium sulfide (Na^S), and, to a lesser
extent, soda ash (Na^CO^), phosphate (PO^ ), and ferrous sulfide
(FeS).
The solubility of a particular compound depends on the extent to
which the electrostatic forces holding the ions of the compound together
can be overcome. The solubility changes significantly with temperature,
with most metal compounds becoming more soluble as the temperature
increases. Additionally, the solubility is affected by other
2 ? 4 09
3-59
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constituents present in the wastewater, including other ions and
complexing agents. Regarding specific ionic forms, nitrates, chlorides,
and sulfates are, in general, more soluble than hydroxides, sulfides,
carbonates, and phosphates.
Once the soluble metal and inorganic compounds have been converted to
precipitates, the effectiveness of chemical precipitation is determined
by how successfully they are physically removed. Removal usually relies
on a settling process; that is, a particle of a specific size, shape, and
composition will settle at a specific velocity, as described by Stokes'
Law. For a batch system, Stokes' Law is a good predictor of settling
time because the pertinent particle parameters essentially remain
constant. In practice, however, settling time for a batch system is
normally determined by empirical testing. For a continuous system, the
theory of settling is complicated by such factors as turbulence,
short-circuiting of the wastewater, and velocity gradients, thereby
increasing the importance of empirical tests to accurately determine
appropriate settling times.
(3) Description of chemical precipitation process. The equipment
and instrumentation required for chemical precipitation vary depending on^
whether the system is batch or continuous. Both systems are discussed
below.
For a batch system, chemical precipitation requires a feed system for
the treatment chemicals and a reaction tank where the waste can be
treated and allowed to settle. When lime is used, it is usually added to
2718g
3-60
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the reaction tank in a slurry form. The supernatant liquid is generally
analyzed before discharge to ensure that settling of precipitates is
adequate.
For a continuous system, additional tanks are necessary, as well as
the instrumentation to ensure that the system is operating properly. A
schematic of a continuous chemical precipitation system is shown in
Figure 3-7. In this system, wastewater is fed into an equalization tank
where it is mixed to provide more uniformity, thus minimizing the
variability in the type and concentration of constituents sent to the
reaction tank.
Following equalization, the wastewater is pumped to a reaction tank
where precipitating agents are added. This is done automatically by
using instrumentation that senses the pH of the system for hydroxide
precipitating agents, or the oxidation-reduction pc'.ential (ORP) for
non-hydroxide precipitating agents, and then pneumatically adjusts the
position of the treatment chemical feed valve until the design pH or ORP
value is achieved. (The pH and ORP values are affected by the
concentration of hydroxide and nonhydroxide precipitating agents,
respectively, and are thus used as indicators of their concentrations in
the reaction tank.)
In the reaction tank, the wastewater and precipitating agents are
mixed to ensure commingling of the metal and inorganic constituents to be
removed and the precipitating agents. In addition, effective dispersion
of the precipitating agents throughout the tank is necessary to properly
monitor and thereby control the amount added.
;
3-61
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o*
ro
COAGUI UNI on
FlOCCUtAHr fffO SVS1IM
WASH WAIf R
rcco
f QU All? A 1 ION
TANK
fliCIPIICAL COHIROll
WASHWAKH flO W
SLUDGE 10
01 WA ftR
-------
Following reaction of the wastewater with the stabilizing agents,
coagulating or flocculating compounds are added to chemically assist the
settling process. Coagulants and flocculants increase the particle size
and density of the precipitated solids, both of which increase the rate
of settling. The coagulant or flocculating agent that best improves
settling characteristics varies depending on the particular precipitates
to be settled.
Settling can be conducted in a large tank by relying solely on
gravity or it can be mechanically assisted through the use of a circular
clanfier or an inclined plate settler. Schematics of the two settling
systems are shown in Figures 3-8 and 3-9. Following the addition of
coagulating or flocculating agents, the wastewater is fed to a large
settling tank, circular clarifier, or inclined plate settler where the
precipitated solids are removed. These solids are generally further
treated in a sludge filtration system to dewater them prior to disposal.
This technology is discussed in Section 3.4.3 of this document.
The supernatant liquid effluent can be further treated in a polishing
filtration system to remove 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 Section 3.4.4
of this document.
(4) Waste characteristics affecting performance (WCAPs). In
determining whether chemical precipitation will achieve the same level of
performance on an untested waste as on a previously tested waste and
whether performance levels can be transferred, EPA examines the
3-63
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SLUDGE
Figure 3-8. INCLINED PLATE SETTLER
3-64
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EFfwUENT
SLUDGE
INFLUENT
CENTER FEED CLARIFIES WITH SCRAPER SLUDGE REMOVAL SYSTEM
INFLUENT
EFFLUE1*
SLUDGE
RIM FEED - CENTER TAKEOFF CLARIFIEF. WITH
HYDRAULIC SUCTION SLUDGE REMOVAL SYSTEM
INFLUENT
EFFLUENT
SLUOCE
RIM FEED - RIM TAKEOFF CLARIFIER
Figure 3-9. CIRCULAR CLARIFIERS
3-65
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following waste characteristics: (a) the concentration and type of
metals, (b) the concentration of total dissolved solids (TDS), (c) the
concentration of complexing agents, and (d) the concentration of oil and
grease.
(a) Concentration and type of metals. For most metals, there
is a specific pH at which the metal precipitate 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 or ORP value 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 respective concentrations. One alternative is to operate multiple
precipitations, with intermediate settling, when the optimum pH occurs at
markedly different levels for the metals present. If the concentration
and type of metals in an untested waste differ fror and are significantly
higher than those in the tested waste, the system ¦"ay not achieve the
same performance. Additional precipitating agents, alternate pH/ORP
values, and/or multiple precipitations may be required to achieve the
same treatment performance, or other, more applicable treatment
technologies may need to be considered for treatment of the untested
waste.
(b) Concentration of total dissolved solids (TDS). High
concentrations of total dissolved solids can interfere with precipitation
reactions, as well as inhibit settling. Poor precipitate formation and
flocculation are results of high TDS concentrations, and higher
2743;
3-66
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concentrations of solids are found in the treated wastewater residuals.
If the TDS concentration in an untested waste is significantly higher
than that in the tested waste, the system may not achieve the same
performance. Higher concentrations of precipitating agents may be
required to achieve the same treatment performance, or other, more
applicable treatment technologies may need to be considered for treatment
of the untested waste.
(c) Concentration of complexing agents. A metal complex
consists of a metal ion surrounded by a group of other inorganic or
organic ions or molecules (often called ligands). In the complexed form,
metals have a greater solubility. Also, complexed metals inhibit the
reaction of the metal with the precipitating agents and therefore may not
be removed as effectively from solution by chemical precipitation.
However, EPA does not have analytical methods to determine the
concentration of complexed metals in wastewaters. The Agency believes
that the best indicator for complexed metals is to analyze for complexing
agents, such as cyanide, chlorides, EDTA, ammonia, amines, and methanol,
for which analytical methods are available. Therefore, EPA uses the
concentration of complexing agents as a surrogate wdste characteristic
for the concentration of metal complexes. If the concentration of
complexing agents in an untested waste is significantly higher than that
in the tested waste, the system may not achieve the same performance.
Higher concentrations of precipitating agents may be required to achieve
the same treatment performance, or other, more applicable treatment
Z 7 4Sg
3-67
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technologies may need to be considered for treatment of the untested
waste.
(d) Concentration of oil and grease. The concentration of oil
and grease in a waste inhibits the settling of the precipitate by
creating emulsions that require a long settling time. Suspended oil
droplets in water tend to suspend particles such as chemical
precipitates, which would otherwise settle out of solution. Even with
the use of coagulants or flocculants, the settling of the precipitate is
less effective. If the concentration of oil and grease in an untested
waste is significantly higher than that in the tested waste, the system
may not achieve the same performance. Pretreatment of the waste may be
required to reduce the oil and grease concentration and achieve the same
treatment performance, or other, more applicable treatment technologies
may need to be considered for treatment of the untested waste.
(5) Design and operating parameters. In assessing the effectiveness
of the design and operation of a chemical precipitation system, EPA
examines the following parameters: (a) the pH/ORP value; (b) the
precipitation temperature; (c) the residence time; (d) the amount and
type of precipitating agents, coagulants, and flocculants; (e) the degree
of mixing; and (f) the settling time.
(a) pH/ORP value. The pH/ORP value in continuous chemical
precipitation systems is used as an indicator of the concentration of
precipitating agents in the reaction tank and, thus, to regulate their
addition to the tank. The pH/ORP value also affects the solubility of
?7<8g
3-68
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metal precipitates formed and therefore directly impacts the
effectiveness of their removal. EPA monitors the pH/ORP value
continuously, if possible, to ensure that the system is operating at the
appropriate design condition and to diagnose operational problems.
(b) Precipitation temperature. The precipitation temperature
affects the solubility of the metal precipitates. Generally, the lower
the temperature, the lower the solubility of the metal precipitates and
vice versa. EPA monitors the precipitation temperature continuously, if
possible, to ensure that the system is operating at the appropriate
design condition and to diagnose operational problems.
(c) Residence time. The residence time impacts the extent of
the chemical reactions to form metal precipitates and, as a result, the
amount of precipitates that can be settled out of solution. For batch
systems, the residence time is controlled directly Dy adjusting the
treatment time in the reaction tank. For continuous systems, the
wastewater feed rate is controlled to make sure that the system is
operating at the appropriate design residence time. EPA monitors the
residence time to ensure that sufficient time is provided to effectively
precipitate from the wastewater.
(d) Amount and type of precipitating ager.ts, coagulants, and
flocculants. The amount and type of precipitating agent used to
effectively treat the wastewater depends on the amount and type of metal
and inorganic constituents in the wastewater to be treated. Other design
and operating parameters, such as the pH/ORP value, the precipitation
274Bg
3-69
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temperature, the residence time, the amount and type of coagulants and
flocculants, and the settling time, are determined by the selection of
precipitating agents.
The addition of coagulants and flocculants improves the settling rate
of the precipitated metals and inorganics and allows for smaller settling
systems (i.e., lower settling time) to achieve the same degree of
settling as a much larger system. Typically, anionic polyelectrolyte
flocculating agents are most effective with metal precipitates, although
cationic or nonionic polyelectrolytes also are effective. Typical doses
range from 0.1 to 10 mg/1 of the total influent wastewater stream.
Conventional coagulants, such as alum (aluminum sulfate) and iron
chlorides or sulfates, are also effective, but must be dosed at much
higher concentrations to achieve the same result. Therefore, these
coagulants add more to the settled sludge volume requiring disposal than
do the polyelectrolyte flocculants. EPA examines the amount and type of
precipitating agents, coagulants, and flocculants added, and their method
of addition to the wastewater, to ensure effective precipitation.
(e) Degree of mixing. Mixing provides greater uniformity of
the wastewater feed and disperses precipitating agents, coagulants, and
flocculants throughout the wastewater to ensure the most rapid
precipitation reactions and settling of precipitate solids possible. The
quantifiable degree of mixing is a complex assessment that includes,
among other things, the amount of energy supplied, the length of time the
material is mixed, and the related turbulence effects of the specific
27409
3-70
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size and shape of the tank. This Is beyond the scope of simple
measurement. EPA, however, evaluates the degree of mixing qualitatively
by considering whether mixing 1s provided and whether the type of mixing
device is one that could be expected to achieve uniform mixing of the
wastewater.
(f) Settling time. Adequate settling time must be provided to
make sure that removal of the precipitated sol Ids from the wastewater has
been completed. EPA monitors the settling time to ensure effective
sol ids removal.
3.4.3 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 (10,000 mg/1). Sludge filtration is commonly applied to
waste sludges, such as clarifier solids, for dewatering. These sludges
can be dewatered to 20 to 50 percent solids concentration using this
technology.
(2) Underlying principles of operation. The basic principle of
operation for sludge filtration is the separation of particles from a
mixture of fluid and particles by a medium that permits the flow of the
fluid but retains the particles. The larger the particles, the easier
they are to separate from the fluid.
Extremely small particles, in the colloidal range, may not be
filtered effectively in a sludge filtration system and may appear in the
3-71
27*8g ,
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filtrate. To mitigate this problem, the waste can be treated prior to
filtration to modify the particle size distribution in favor of the
larger particles by using appropriate precipitants, coagulants,
flocculants, and filter aids. The selection of the appropriate
precipitant and coagulant is important because they affect the type of
waste particles formed. For example, lime precipitation usually produces
larger, less gelatinous particles (which are easier to separate from
waste sludges using this technology) than caustic soda precipitation.
For particles that become too small to filter effectively because of poor
resistance to shearing, the use of coagulants and flocculants improves
shear resistance in addition to increasing the size of the particles.
Also, if pumps are used, shear can be minimized by lowering the pump
speed or using a low-shear type of pump. Filter aids such as
diatomaceous earth are used to precoat cloth-type f:lter media and
provide an initial filter cake onto which additional solids can be
deposited during the filtration process. The presence of the precoat
aids in the removal of small particles from the waste being filtered.
These particles adhere to the precoat solids during the filtration
process.
(3) Description of sludge filtration process. For sludge
filtration, waste is pumped through a cloth-type filter medium (also
known as pressure filtration, such as that performed with a plate and
frame filter), drawn by vacuum through the cloth medium (also known as
vacuum filtration, such as that performed with a vacuum drum filter), or
27«8g
3-72
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gravity-drained and mechanically pressured through two continuous fabric
belts (also known as belt filtration, such as that performed with a belt
filter press). In all cases, the solids "cake" builds up on the filter
medium and acts 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 using an adjustable knife
mechanism to scrape the solids off (a batch process). For the vacuum
filter, cake is removed continuously by using an adjustable knife
mechanism to scrape the sludge from the vacuum drum as the drum rotates.
For the belt filter, the cake is continuously removed by a discharge
roller and blade, which dislodge the cake from the belt. For a specific
sludge, the plate and frame type filter will usually produce the driest
cake (highest percentage of solids). The belt filter produces a drier
cake than a vacuum filter, but not as dry as that p oduced by a plate and
frame filter.
(4) Waste characteristics affecting performance (WCAPs). In
determining whether sludge filtration will achieve the same level of
performance on an untested waste as on a previously tested waste and
whether performance levels can be transferred, EPA examines the following
waste characteristics: (a) the solid waste particle size and (b) the
type of solid waste particles.
(a) Solid waste particle size. 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 (such as a
?743g
3-73
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plate and frame), smaller particles may require higher pressures for
equivalent fluid throughput because the smaller pore spaces between
particles collected on the filter medium create resistance to flow. If
the solid waste particle size distribution of an untested waste is
significantly lower than that of the tested waste, the system may not
achieve the same performance. Pretreatment of the waste with coagulants
and flocculants may be required to increase the particle sizes and
achieve the same treatment performance, or other, more applicable
treatment technologies may need to be considered for treatment of the
untested waste.
(b) Type of solid waste particles. Some solids formed during
metal precipitation are gelatinous in nature and cannot be dewatered well
by sludge 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 settling/clarifi-
cation or after settling/ clarification but prior to filtration. In
addition, the use of lime instead of caustic in chemical precipitation of
metals reduces the formation of gelatinous solids. Also, adding filter
aids, such as lime or diatomaceous earth, to a gelatinous sludge
increases its fllterability significantly. Finally, precoating the
filter with diatomaceous earth prior to sludge filtration assists In
dewatering gelatinous sludges. If an untested waste is significantly
more gelatinous than the tested waste, the system may not achieve the
same performance. Pretreatment of the waste with coagulants and filter
2 7 48g
3-74
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aids or precoating of the filter may be required to decrease the
gelatinous nature of the waste and achieve the same treatment
performance, or other, more applicable treatment technologies may need to
be considered for treatment of the untested waste.
(5) Design and operating parameters. In assessing the effectiveness
of the design and operation of a sludge filtration system, EPA examines
the following parameters: (a) the type and size of filter; (b) the
filtration pressure; (c) the amount and type of coagulants, flocculants,
and filter aids used; and (d) the hydraulic loading rate.
(a) Type and size of filter. The type and size of the
filtration system used is dependent on the nature of the particles to be
separated, the desired solids concentration in the cake, the amount and
concentration of solids in the feed, and the required downtime for solids
removal and maintenance. Typically, a pressure-type filter (such as a
plate and frame) will yield a drier cake than a belt or vacuum type
filter and will also be more tolerant of variations in influent sludge
characteristics. Pressure-type filters, however, are batch processes.
When cake is built up to the maximum depth physically possible
(constrained by filter geometry) or to the maximum design pressure, the
filtration system is taken off-line while the cake is removed. (An
alternate unit can be put on-line while the other is being cleaned.)
Belt and vacuum type filters are continuous systems (i.e., cake
discharges continuously), but each of these filters is usually much
larger than a pressure filter with the same capacity.
Z746g
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For all filter types, the larger the filter, the greater its
hydraulic capacity (overall throughput) and, for pressure-type filters,
the longer the filter runs between cake discharges. EPA examines the
type and size of the filter chosen to ensure that it is capable of
achieving effective dewatering and filtration of the waste sludge.
(b) Filtration pressure. Pressure impacts both the design pore
size of the filter media and the design feed flow rate. For plate and
frame filters, the higher the feed pressure, the drier the cake will be
and the longer the runs will be prior to cake discharge. However, for
gelatinous solids, such as some metal hydroxides, excessive pressures may
cause the solids to clog the filter pores and prevent additional sludge
filtration. Also, high pressures may force particles through the filter
medium, resulting in ineffective filtration. For vacuum filters, the
maximum amount of vacuum typically applied ranges from 20 to 25 inches of
mercury. (The absolute maximum amount of vacuum that can be applied is
29.9 inches of mercury, or atmospheric pressure.) For belt filters,
neither pressure nor vacuum is applied to the waste feed (although
mechanical pressure is applied). For plate and frame and vacuum-type
filtration systems, EPA monitors the filtration pressure (or vacuum)
applied to the waste feed continuously, if possible, to ensure that the
system is operating at the appropriate design conditions and to diagnose
operational problems.
ZMBj
3-76
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(c) Amount and type of coagulants, flocculants, and filter
aids. Coagulants, flocculants, and filter aids may be mixed with the
waste feed prior to filtration. Coagulants and flocculants affect the
type and size of waste particles in the waste and, hence, their ease of
removal. Their effect is particularly significant for vacuum filtration
since they may make the difference between no cake and the formation of a
relatively dry cake. In a pressure filter, coagulants, flocculants, and
filter aids significantly improve overall throughput and cake dryness.
Filter aids, such as diatomaceous earth, can be precoated on all filters
for particularly difficult-to-filter sludges (those containing a high
concentration of gelatinous solids). The precoat layer acts somewhat
like a filter in that sludge sol Ids are trapped in the precoat pore
spaces. Coagulants, flocculants, and filter aids are particularly useful
when the sludge has a high percentage of very small particles and/or when
the concentration of solids in the waste feed is low. Inorganic
coagulants include alum, ferric sulfate, and lime. Organic flocculants
are polyelectrolytes. Diatomaceous earth is the most commonly used
filter aid. The use of coagulants, flocculants, and filter aids
significantly increases the amount of solids in the sludge requiring
disposal, although polyelectrolyte flocculant usage usually does not
increase sludge volume significantly because the required dosage is
relatively low. If the addition of coagulants, flocculants, and filter
aids is required, EPA examines the amount and type added to the waste
sludge, along with their method of addition, to ensure effective
dewatering and filtration.
?7«8g
3-77
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(d) Hydraulic loading rate. Lower hydraulic loading rates
generally improve filtration performance. Higher hydraulic loading rates
yield greater overall throughput, but result in the formation of wetter
cakes (lower percent solids) and, for plate and frame filters, shorter
cycle times. EPA monitors the hydraulic loading rate to ensure effective
dewatering and filtration of the waste sludge.
3.4.4 Polishing Filtration
(1) AodIicabi1itv. Polishing filtration is a treatment technology
applicable to wastewaters containing relatively low concentrations of
solids (less than 1,000 mg/1).' This type of filtration is typically used
as a polishing step for the supernatant liquid following chemical
precipitation and settling/clarification of wastewaters containing metal
and other inorganic precipitates. Polishing filtration removes particles
that are difficult to settle because of their shape and/or densi ty, as
well as precipitated particles from an underdesigned settling system.
(2) Underlying principles of operation. The basic principle of
operation for polishing filtration is the removal of particles from a
mixture of fluid and particles by a medium that permits the flow of the
fluid but retains the particles. The larger the particles, the easier
they are to remove from the fluid.
Extremely small particles, in the colloidal range, may not be removed
effectively in a polishing filtration system and thus may appear in the
treated wastewater. To mitigate this problem, the wastewater can be
274Bg
3-7B
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treated prior to filtration to modify the particle size distribution in
favor of the larger particles by using appropriate precipitants,
coagulants, flocculants, and filter aids. The selection of the
appropriate precipitant and coagulant is important because they affect
the type of waste particles formed. For example, lime precipitation
usually produces larger, less gelatinous particles (which are easier to
remove from aqueous wastes using this technology) than does caustic soda
precipitation. For particles that become too small to remove effectively
because of poor resistance to shearing, the use of coagulants and
flocculants both improves shear resistance and increases the size of the
particles. Also, if pumps are used, shear can be minimized by lowering
the pump speed or using a low-shear type of pump. Filter aids such as
diatomaceous earth are used to precoat cloth-type filter media and to
provide an initial filter cake onto which additional solids can be
deposited during the filtration process. The presence of the precoat
aids in the removal of small particles from the solution being filtered.
These particles adhere to the precoat solids during the filtration
process.
(3) Description of polishing filtration processes. During polishing
filtration, wastewater may flow by gravity or under pressure to the
filter. The two most coirenon polishing filtration processes are cartridge
and granular bed filtration. Both processes remove particles that are
much smaller than the pore size of the filter media by straining,
2748g
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adsorption, and coagulation/flocculation mechanisms; they are also
capable of producing an effluent with a low level of solids (less than
10 mg/1).
(a) Cartridge filtration. Cartridge filters can be used for
relatively low waste feed flows. In this process, a cylindrically shaped
cartridge with a matted cloth-type filter medium is placed within a
sealed vessel. Wastewater is pumped through the cartridge until the flow
drops excessively or until the pumping pressure becomes too high because
of plugging of the filter media. The sealed vessel is then opened, and
the plugged cartridge is removed and replaced with a new cartridge. The
plugged cartridge is then disposed of. Cartridge filters may be
assembled in a parallel arrangement to increase the overall system flow.
(b) Granular bed filtration. For relatively large volume
flows, granulated media such as sand or anthracite coal are used singly
or in combination to trap suspended solids within the pore spaces of the
media. Dual and multimedia filter arrangements allow higher flow rates
and efficiencies. Typical hydraulic loading rates range from 2 to
2 2
5 gal/ft -min for single-medium filters and from 4 to 8 gal/ft -min
for multimedia filters.
In this process, wastewater is either gravity fed or pumped through
the granular bed media and filtered until either the flow drops
excessively or the pumping pressure becomes too high because of plugging
of the filter media. Granular media filters are cleaned by backwashing
with filtered water in an upflow manner to expand the bed, loosen the
media granules, and resuspend the entrapped filtered solids. The
2 748g
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backwash water, which may be as much as 10 percent of the volume of the
filtered wastewater, is then returned to the wastewater treatment system
so that the filtered solids in the backwash water can be settled out of
solution prior to discharge.
(4) Waste characteristics affectina performance (WCAPsh In
determining whether polishing filtration will achieve the same level of
performance on an untested waste as on a previously tested waste and
whether performance levels can be transferred, EPA examines the following
waste characteristics: (a) the solid waste particle size and (b) the
type of solid waste particles.
(a) Solid waste particle size. Extremely small particles, in the
colloidal range, may not be filtered effectively 1n a polishing filter
and thus may appear in the filtrate. If the solid waste particle size
distribution of an untested waste is significantly lower than that of the
tested waste, the system may not achieve the same performance.
Pretreatment of the waste with coagulants and flocculants may be required
to increase the particle sizes and achieve the same treatment
performance, or other, more applicable treatment technologies may need to
be considered for treatment of the untested waste.
(b) Type of solid waste particles. Some solids formed during
metal precipitation are gelatinous in nature and are difficult to
filter. In most cases, solids can be made less gelatinous by use of the
appropriate coagulants and coagulant dosage prior to settling/clarifica-
tion, or after settling/clarification but prior to filtration. In
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addition, the use of lime instead of caustic in chemical precipitation of
metals reduces the formation of gelatinous solids. If solids in an
untested waste are significantly more gelatinous than those in the tested
waste, the system may not achieve the same performance. Pretreatment of
the waste with coagulants may be required to decrease the gelatinous
nature of the waste and achieve the same treatment performance, or other,
more applicable treatment technologies may need to be considered for
treatment of the untested waste.
(5) Oesion and operating parameters. In assessing the effectiveness
of the design and operation of a polishing filtration system, EPA
examines the following parameters: (a) the type and size of the filter;
(b) the filtration pressure; (c) the amount and type of coagulants,
flocculants, and filter aids used; (d) the hydraulic loading rate; and
(e) the pore size of the filter media.
(a) Type and size of filter. The type and size of the
polishing filtration system used is dependent on the nature of the
particles to be removed, the desired solids concentration in the
filtrate, and the amount and concentration of solids in the feed. As
noted earlier, cartridge filtration is limited to lower volume
wastewaters and/or those with lower solids concentrations than is
granular bed filtration. For granular bed filtration, when more than one
medium is used (dual and multimedia filter arrangements such as sand and
anthracite coal), a higher capacity can be expected for the same size
filter bed. For both filtration processes, the larger the filter size,
the greater its hydraulic capacity (overall throughput) and the longer
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the filter runs between solids removal. EPA examines the type and size
of the filter chosen to ensure that it is capable of achieving effective
filtration of the wastewater.
(b) Filtration pressure. Pressure impacts both the design pore
size of the filter media and the design feed flow rate (hydraulic loading
rate). The higher the feed pressure, the longer the run will be prior to
solids removal. For gelatinous solids, such as metal hydroxides,
however, excessive pressure may cause the solids to clog the filter pores
and prevent additional polishing filtration. Also, high pressures may
force particles through the filter medium, resulting in ineffective
filtration. EPA monitors the filtration pressure applied to the waste
feed continuously, if possible, to ensure that the system is operating at
the appropriate design condition and to diagnose operational problems.
(c) Amount and type of coagulants, flocculants, and filter
aids. Coagulants, flocculants, and filter aids may be mixed with the
wastewater prior to filtration. Coagulants and flocculants affect the
type and size of waste particles in the wastewater and, hence, their ease
of removal. Filter aids both improve the effectiveness of filtering
gelatinous particles and increase the time that the filter can stay
on-line by increasing the surface area available for filtration.
Coagulants, flocculants, and filter aids are particularly useful when the
wastewater contains a high percentage of very small particles and/or when
the concentration of solids in the wastewater is low. Inorganic
coagulants include alum, ferric sulfate, and lime; organic flocculants
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are polyelectrolytes. Diatomaceous earth is the most commonly used
filter aid. The use of coagulants, flocculants, and filter aids
significantly increases the amount of solids requiring removal and
disposal. Polyelectrolyte flocculant usage, however, usually does not
increase the solids volume significantly because the required dosage is
relatively low. If the addition of coagulants, flocculants, and filter
aids is required, EPA examines the amount and type added, as well as
their method of addition to the wastewater, to ensure effective
filtration.
(d) Hydraulic loading rate. Lower hydraulic loading rates
generally improve filtration performance. Higher hydraulic loading rates
yield greater throughput, but result in shorter cycle times. EPA
monitors the hydraulic loading rate to ensure effective filtration of the
wastewater.
(e) Pore size of the filter media. The pore size of the filter
media determines the particle size that will be effectively removed from
the wastewater. EPA examines the pore size of the filter media to ensure
effective filtration of the wastewater.
3.4.5 Stabilization of Metals
(1) Add!icabilitv. Stabilization is a treatment technology
applicable to wastes containing leachable metals and having a high
filterable solids content, low total organic carbon (TOC) content, and
low oil and grease content. This technology is commonly used to treat
residuals generated from treatment of electroplating wastewaters and
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incineration ash residues. For wastes with recoverable levels of metals,
high temperature metals recovery and retorting technologies may be
applicable.
Stabilization refers to a broad class of treatment processes that
immobilize hazardous constituents in a waste. Solidification and
fixation are other terms that are sometimes used synonymously for
stabilization or to describe specific variations within the broader class
of stabilization. Related technologies are encapsulation and
thermoplastic binding. However, EPA considers these technologies to be
distinct from stabilization in that their operational principles are
significantly different.
(2) Underlying principles of operation. The basic principle of
operation for stabilization is that leachable metals in a waste are
immobilized following the addition of stabilizing agents and other
chemicals. 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.
The two principal stabilization processes used are cement-based and
lime/pozzolan-based processes. A brief discussion of each is provided
below. In both cement-based or 1ime/pozzolan-based techniques, the
stabilizing process can be modified through the use of additives, such as
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silicates, that control curing rates, reduce permeability, and enhance
the properties of the solid material.
(a) Portland cement-based process. Portland cement is a
mixture of powdered oxides of calcium, silica, aluminum, and iron,
produced by kiln burning of materials rich in calcium and silica at high
temperatures (i.e., 1,400 to 1,500°C (2,552 to 2,732'F)). When
the anhydrous cement powder is mixed with water, hydration occurs and the
cement begins to set. The chemistry involved is complex because many
different reactions occur, depending on the composition of the cement
mixture.
As the cement begins to set, a colloidal gel of indefinite
composition and structure is formed. Over 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 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 insoluble silicates or hydroxides and are incorporated into the
interstices of the binder matrix, thereby inhibiting leaching.
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(3) Description of stabilization process. The stabilization process
consists of a weighing device, a mixing unit, and a curing vessel or
pad. Commercial concrete mixing and handling equipment is typically used
in stabilization processes. Weighing conveyors, metering cement hoppers,
and mixers similar to concrete batching plants have been adapted in some
operations. When extremely dangerous materials are treated,
remote-control and in-drum mixing equipment, such as that used with
nuclear waste, is employed.
In most stabilization processes, the waste, stabilizing agent, and
other additives, if used, are mixed in a mixing vessel and then
transferred to a curing vessel or pad and allowed to cure. The actual
operation (equipment requirements and process sequencing) depends on
several factors, including 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 used, and the curing rate.
Following curing, the stabilized solid formed is recovered from the
processing equipment and disposed of.
(4) Waste characteristics affecting performance (WCAPsl. In
determining whether stabilization will achieve the same level of
performance on an untested waste as on a previously tested waste and
whether performance levels can be transferred, EPA examines the following
waste characteristics: (a) the concentration of fine particulates,
(b) the concentration of oil and grease, (c) the concentration of organic
compounds, and (d) the concentration of sulfate and chloride compounds.
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(a) Concentration of fine particulates. For both cement-based
and 1ime/pozzolan-based processes, very fine solid materials (i.e., those
that pass through a No. 200 mesh sieve (less than 74-um particle size))
weaken the bonding between waste particles and the cement or
1ime/pozzolan binder by coating the particles. This coating inhibits
chemical bond formation, thereby decreasing the resistance of the
material to leaching. If the concentration of fine particulates in an
untested waste is significantly higher than that in the tested waste, the
system may not achieve the same performance. Pretreatment of the waste
may be required to reduce the fine particulate concentration and achieve
the same treatment performance, or other, more applicable treatment
technologies may need to be considered for treatment of the untested
waste.
(b) Concentration of oil and grease. Oil and grease in both
cement-based and 1ime/pozzolan-based systems results in the coating of
waste particles and the weakening of the bonding between the particle and
the stabilizing agent, thereby decreasing the resistance of the material
to leaching. If the concentration of oil and grease in the untested
waste is significantly higher than that in the tested waste, the system
may not achieve the same performance. Pretreatment may be required to
reduce the oil and grease concentration and achieve the same treatment
performance, or other, more applicable treatment technologies may need to
be considered for treatment of the untested waste.
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(c) Concentration of organic compounds. Organic compounds in
the waste interfere with the stabilization chemical reactions and bond
formation, thus inhibiting curing of the stabilized material. This
results in a stabilized waste having decreased resistance to leaching.
If the total organic carbon (TOC) content of the untested waste is
significantly higher than that of the tested waste, the system may not
achieve the same performance. Pretreatment may be required to reduce the
TOC and achieve the same treatment performance, or other, more applicable
treatment technologies may need to be considered for treatment of the
untested waste.
(d) Concentration of sulfate and chloride compounds. Sulfate
and chloride compounds interfere with the stabilization 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 leachability
potential. If the concentration of sulfate and chloride compounds in the
untested waste is significantly higher than that in the tested waste, the
system may not achieve the same performance. Pretreatment may be
required to reduce the sulfate and chloride concentrations and achieve
the same treatment performance, or other, more applicable treatment
technologies may need to be considered for treatment of the untested
waste.
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(5) Design and operating parameters. In assessing the effectiveness
of the design and operation of a stabilization system, EPA examines the
following parameters: (a) the amount and type of stabilizing agent and
additives, (b) the degree of mixing, (c) the residence time, and (d) the
stabilization temperature and humidity.
(a) Amount and type of stabilizing agent and additives. The
stabilizing agent and additives used will determine the chemistry and
structure of the stabilized material and therefore its leachability.
Stabilizing agents and additives must be carefully selected based on the
chemical and physical characteristics of the waste to be stabilized. To
select the most effective type of stabilizing agent and additives, the
waste should be tested in the laboratory with a variety of these
materials to determine the best combination.
The amount of stabilizing agent and additives is a critical parameter
in that sufficient stabilizing materials are necessary to properly bind
the waste constituents of concern, making them less susceptible to
leaching. The appropriate weight ratios of stabilizing agent and
additives to waste are established empirically by setting up a series of
laboratory tests that allow separate leachate testing of different mix
ratios. The ratiD 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
Z74Bg
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completed. EPA evaluates the amount of stabilizing agent, water, and
other additives used in the stabilization process to ensure that
sufficient stabilizing materials are added to the waste to effectively
immobilize the waste constituents of concern.
(b) Degree of mixing. Mixing is necessary to ensure
homogeneous distribution of the waste, stabilizing agent, and additives.
Both undermixing and overmixing are undesirable. The first condition
results in a nonhomogeneous mixture; therefore, areas will exist within
the waste where waste particles are neither chemically bonded to the
stabilizing agent nor physically held within the lattice structure.
Overmixing, on the other hand, may inhibit gel formation and ion
adsorption in some stabilization systems. Optimal mixing conditions
generally are determined through laboratory tests. The quantifiable
degree of mixing is a complex assessment that includes, among other
factors, the amount of energy supplied, the length of time the material
is mixed, and the related turbulence effects of the specific size and
shape of the mix tank or vessel. This is beyond the scope of simple
measurement. EPA, however, evaluates the degree of mixing qualitatively
by considering whether mixing is provided and whether the type of mixing
device is one that could be expected to achieve homogeneous distribution
of the waste, stabilizing agent, and additives.
(c) Residence time. The residence time or duration of curing
ensures that the waste particles have had sufficient time in which to
incorporate into lattice structures and/or form stable chemical bonds.
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The time necessary for complete stabilization depends upon the waste and
the stabilization process used. The performance of the stabilized waste
(i.e., the levels of waste constituents in the leachate) will be highly
dependent upon whether complete stabilization has occurred. Typical
residence times range from 7 to 28 days. EPA monitors the residence time
to ensure that sufficient time is provided to effectively stabilize the
waste.
(d) Stabilization temperature and humidity. Higher
temperatures and lower humidity increase the rate of curing by increasing
the rate of evaporation of water from the stabilization mixtures. If
temperatures are too high, however, the evaporation rate can be
excessive, resulting in too little water being available for completion
of the stabilization reaction. EPA monitors the stabilization
temperature and humidity continuously, if possible, to ensure that the
system is operating at the appropriate design conditions and to diagnose
operational problems.
3.4.6 High Temperature Metals Recovery
(1) Add!icabi1itv. High temperature metals recovery (HTMR) is a
technology applicable to wastes containing metal oxides and metal salts
(including cadmium, chromium, lead, nickel, and zinc compounds) at
concentrations ranging from 10 percent to over 70 percent with low levels
(i.e., below 5 percent) of organics and water in the wastes. There are a
number of different types of high temperature metals recovery systems,
which generally differ from one another in the source of energy used and
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the method of recovery. These HTMR systems include the rotary kiln
process, the plasma arc reactor, the rotary hearth electric furnace
system, the molten slag reactor, and the flame reactor.
HTMR is generally not used for mercury-containing wastes even though
mercury will volatilize readily at the process temperatures present in
the high temperature units. The retorting process is normally used for
mercury recovery because mercury is very volatile and lower operating
temperatures can be used. Thus, the retorting process is more economical
than HTMR for mercury-bearing wastes.
The HTMR process has been demonstrated on wastes such as baghouse
dusts and dewatered scrubber sludge from the production of steels and
ferroalloys. Zinc, cadmium, and lead are the metals most frequently
recovered. The process has not been extensively evaluated for use with
metal sulfides. The sulfides are chemically identical to natural
minerals ordinarily present in ores used as feedstocks by primary
smelters. Some sulfide-bearing wastes from the chrome pigments industry
have been sent to such primary smelters. However, with sulfides, a
possibility exists for formation of either carbon disulfide from reaction
with carbon or sulfur dioxide from reaction with oxygen in the HTMR
processes.
Metal halide salts are also not directly used in HTMR processes.
They, however, may be converted to oxides or hydroxides, which are
acceptable feedstocks for HTMR processes.
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(2) Underlying principles of operation. The basic principle of
operation for this technology is that metal oxides and salts are
separated from a waste through a high temperature thermal reduction
process that uses carbon, limestone, and silica (sand) as raw materials
The carbon acts as a reducing agent and reacts with metal oxides to
generate carbon dioxide and free metal. The silica and limestone serve
as fluxing agents. This process yields a metal product for reuse and
reduces the concentration of metals in the residuals and, hence, the
amount of waste that needs to be land disposed. An example HTMR reacti
is the recovery of zinc, which proceeds as follows:
2 ZnO + C - 2 Zn + C02
(3) Description of hioh temperature metals recovery process. The
HTMR process consists of a mixing unit, a high temperature processing
unit (kiln, furnace, etc.), a product collection system, and a residual
treatment system. A schematic diagram for a high temperature metals
recovery system is shown in Figure 3-10.
The mixing unit homogenizes metal-bearing wastes, thus minimizing
feed variations to the high temperature processing unit. Before the
wastes are fed into the high temperature processing unit, fluxing agent
and carbon can be added to the mixing unit and mixed with the wastes.
The fluxes used (sand and limestone) are often added to react with
certain metal components, preventing their volatilization and resulting
in an enhanced purity of the desired volatile metals removed.
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AIR OR O2
EXHAUST GAS
TO ATMOSPHERE
UNTREATED,
PRODUCT
COLLECTION
UNIT
(CONDENSER OR
CONDENSER AND
BAGHOUSE)
WASTE
CARBON
(REDUCING
AGENT)
FLUXES
REUSE OF
VOLATILE
METAL
PRODUCTS
OR FURTHER
REFINEMENT
PRIOR TO
REUSE
(LIMESTONE,
SANO)
RESIDUAL
COLLECTION
(QUENCH TANK)
HIGH
TEMPERATURE
PROCESSING
UNIT
MIXING '
UNIT
REUSE OF NONVOLATILE METAL PRODUCTS,
FURTHER RECOVERY IN A FURNACE,
STABILIZATION FOLLOWED BY LAND DISPOSAL.
OR DIRECTLY TO LAND DISPOSAL
FIGURE 3-10 HIGH TEMPERATURE METALS RECOVERY SYSTEM
-------
The blended waste materials are fed to a furnace, where they are
heated to temperatures ranging from 1100 to 1400'C (2012 to
25520F), resulting in the reduction and volatilization of the desired
metals. The combination of temperature, residence time, and turbulence
provided by rotation of the unit or addition of an air or oxygen stream
helps ensure the maximum reduction and volatilization of metal
constituents.
The product collection system can consist of either a condenser or a
combination condenser and baghouse. The choice of a particular system
depends on whether the metal is to be collected in the metallic form or
as an oxide. Recovery and collection are accomplished for the metallic
form by condensation alone, and for the oxide by reoxidation,
condensation, and subsequent collection of the metal oxide particulates
in a baghouse. There is no difference in these two types of metal
recovery and collection systems relative to the kinds of waste that can
be treated; the use of one system or the other simply reflects the
facility's preference relative to product purity. In the former case,
the direct condensation of metals allows for the separation and
collection of individual metals in a relatively uncontaminated form; in
the latter case, the metals are collected as a combination of several
metal oxides.
The treated waste residual slag, containing higher concentrations of
the less-volatile metals than the untreated waste, is sometimes cooled in
a quench tank and (a) reused directly as a product (e.g., a waste
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residual containing mostly iron can be reused in steelmaking); (b) reused
after further processing (e.g., a waste residual containing oxides of
iron, chromium, and nickel can be reduced to metallic form and then
recovered for use in the manufacture of stainless steel); or, if the
material has no recoverable value, (c) stabilized, to immobilize any
remaining metal constituents, and land disposed; or (d) directly land
disposed as a slag.
(4) Waste characteristics affecting performance (WCAPs). In
determining whether high temperature metals recovery will achieve the
same level of performance on an untested waste as on a previously tested
waste and whether performance levels can be transferred, EPA examines the
following waste characteristics: (a) the concentrations of undesirable
volatile metals, (b) the metal constituent boiling points, and (c) the
thermal conductivity of the waste.
(a) Concentration of undesirable volatile metals. Because HTMR
is a recovery process, the product must meet certain purity requirements
prior to reuse. If the waste contains other volatile metals, such as
arsenic or antimony, which are difficult to separate from the desired
metal products and whose presence may affect the ability to reuse the
product or refine it for subsequent reuse, HTMR may not be an appropriate
technology. If the concentration of undesirable volatile metals in the
untested waste is significantly higher than that in the tested waste, the
system may not achieve the same performance and other, more applicable
treatment technologies may need to be considered for treatment of the
untested waste.
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(b) Metal constituent boiling points. The greater the ratio of
volatility of the waste constituents, the more easily the separation of
these constituents can proceed. This ratio is called relative
volatility. EPA recognizes, however, that the relative volatilities
cannot be measured or calculated directly for the types of wastes
generally treated by high temperature metals recovery, because the wastes
usually consist of a myriad of components, all with different vapor
pressure-versus-temperature relationships. However, because the
volatility of components is usually inversely proportional to their
boiling points (i.e., the higher the boiling point, the lower the
volatility), EPA uses the boiling point of waste components as a surrogate
waste characteristic for relative volatility. If the differences in
boiling points between the more volatile and less volatile constituents
are significantly lower in the untested waste than in the tested waste,
the system may not achieve the same performance and other, more
applicable treatment technologies may need to be considered for treatment
of the untested waste.
(c) Thermal conductivity of the waste. The ability to heat
constituents within an HTMR process feed matrix is a function of the heat
transfer characteristics of the individual feed components (coke,
limestone, untreated waste, etc.). The constituents being recovered from
the waste must be heated to near or above their boiling points in order
for them to be volatilized and recovered. The rate at which heat will be
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transferred to the feed mixture is dependent on the mixture's thermal
conductivity, which is the ratio of the conductive heat flow to the
temperature gradient across the material. Thermal conductivity
measurements, as part of a treatability comparison of two different
wastes to be treated by a single HTMR system, are most meaningful when
applied to wastes that are homogeneous (i.e., uniform throughout). As
wastes exhibit greater degrees of nonhomogeneity, thermal conductivity
becomes less accurate in predicting treatability because the measurement
reflects heat flow through regions having the greatest conductivity
(i.e., the path of least resistance) and not heat flow through all parts
of the waste. Nevertheless, EPA believes that thermal conductivity may
provide the best measure of performance of heat transfer. If the thermal
conductivity of the untested waste is significantly lower than that of
the tested waste, the system may not achieve the same performance and
other, more applicable treatment technologies may need to be considered
for treatment of the untested waste.
(5) Design and operating parameters. In assessing the effectiveness
of the design and operation of an HTMR system, EPA examines the following
parameters: (a) the HTMR temperature, (b) the residence time, (c) the
degree of mixing, (d) the carbon content of the feed, and (e) the
calcium-to-silica ratio of the feed.
(a) HTMR temperature. Temperature provides an indirect measure
of the energy available (i.e., Btu/hr) to volatilize the metal waste
constituents. The higher the temperature in the high temperature
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processor, the more likely it is that the constituents will react with
carbon to form free metals and volatilize. The temperature must be at
least equal to or greater than the boiling point of the metals being
volatilized for recovery. However, excessive temperatures could
volatilize less-volatile, undesirable metals into the product, possibly
inhibiting the potential for reuse of the product. EPA monitors the HTMR
processor temperature continuously, if possible, to ensure that the
system is operating at the appropriate design condition (at or above the
boiling point(s) of the metal or metals being recovered, but not
excessively high so as to volatilize other unwanted constituents) and to
diagnose operational problems.
(b) Residence time. The residence time impacts the amount of
volatile metals volatilized and recovered. It is dependent on the HTMR
processor temperature and the thermal conductivity of the feed blend.
EPA monitors the residence time to ensure that sufficient time is
provided to effectively volatilize the volatile constituents for recovery.
(c) Degree of mixing. Effective mixing of the waste with coke,
silica, and limestone is necessary to produce a uniform feed blend to the
system. The quantifiable degree of mixing is a complex assessment that
includes, among other things, the amount of energy supplied, the length
of time the material is mixed, and the related turbulence effects of the
specific size and shape of the tank or vessel. This is beyond the scope
of simple measurement.
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EPA, however, evaluates the degree of mixing qualitatively by considering
whether mixing is provided and whether the type of mixing device is one
that could be expected to achieve uniform mixing of the waste.
(d) Carbon content of the feed. The amount of carbon added to
the waste must be sufficient to ensure complete reduction of the volatile
metals being recovered. EPA examines the basis for calculation of the
amount of carbon added to the waste to ensure that sufficient carbon is
being used in the feed blend to effectively reduce metal compounds.
(e) Calcium-to-silica ratio of the feed. The calcium-to-silica
ratio in the feed blend must be controlled to limit precipitation of
metallic iron in the high temperature processor. The iron forms as solid
calcium iron silicate, which is very difficult to subsequently process
into any useful material. Aluminum oxide will also undergo reactions
with lime and silica to form calcium aluminosilicates, which will lower
the density and increase the volume of slag generated.
Precipitates and modified slags affect the reduction, volatilization,
and recovery of volatile metals by changing heat flow characteristics in
the system and by undergoing secondary, high temperature chemical
reactions with metal oxides in the feed, converting them to the
previously noted inert metal silicates or silicoaluminates. The ratio of
calcium to silica to be used is dependent on the waste composition.
Generally, a one-to-one silica-to-calcium oxide ratio is highly desired,
so amounts of limestone and sand need to be adjusted based on the calcium
and silica content of the waste to achieve this ratio.
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Excess lime may also be added to fix sulfur in the feed as calcium
sulfate. This will prevent the volatile metals from reacting with sulfur
to form metal sulfides, thereby lowering the recovery of metals or
oxides. EPA monitors the amounts of limestone and sand added to the
waste to ensure that the calcium-to-silica ratio selected to maximize
metal or oxide recovery is maintained during treatment.
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4. TREATMENT PERFORMANCE DATA BASE
This section presents all data available to EPA on the performance of
the demonstrated technologies discussed in Section 3 for treating F006
through F012 wastes. These data are used elsewhere in this document for
determining which technologies represent BDAT (Section 5), for selecting
constituents to be regulated (Section 6), and for developing the proposed
treatment standards (Section 7). In addition to full-scale demonstration
data, available data may include data developed at research facilities,
or through other applications at less than full-scale operation, as long
as the technology is demonstrated in full-scale operation for a similar
waste or wastes as defined in Section 3.
Performance data include the untreated and treated waste
concentrations for a given constituent, the values of operating
parameters that were measured at the time the waste was being treated,
the values of relevant design parameters for the treatment technology,
and data on waste characteristics that affect performance of the
treatment technology. EPA has provided all such data, to the extent that
they are available, in Tables 4-1 through 4-14 found at the end of this
section.
Where data are not available on the treatment of the specific wastes
of concern, the Agency may elect to transfer data on the treatment of a
similar waste or wastes using a demonstrated technology. To transfer
data from another waste category, EPA must find that the wastes covered
by this background document are no more difficult to treat (based on the
waste characteristics that affect performance of the demonstrated
4-1
23609
-------
treatment technology) than the treated wastes from which performance data
are being transferred.
4.1 Electrolytic Oxidation/Alkaline Chlorination Data
At Plant A, the Agency collected one set of untreated and treated
F011 waste samples from a batch treatment system that consisted of
electrolytic oxidation, alkaline chlorination, chemical precipitation,
filtration, and sludge dewatering (shown as Sample Set No. 1 in
Table 4-1). The Agency also collected one set of samples from treatment
of heat treating quenching wastewaters by the same treatment system as
above except for the electrolytic oxidation step (shown as Sample Set
No. 2 in Table 4-1). These data show, along with design and operating
information, the total concentrations of metals and cyanide in the
untreated waste, the treated wastewater (after precipitation of metals
and filtration for removal of suspended solids), the treated
nonwastewater (the precipitated solids from chemical precipitation,
treated further by sludge dewatering), and concentrations of metals in
the treated nonwastewater.
4.2 Met Air Oxidation Data
In an EPA test at Plant B, the Agency collected six sets of data for
untreated and treated F007 waste using a pilot-scale wet air oxidation
treatment system. These data, presented in Table 4-2, show, along with
design and operating information, the total concentration of metals and
cyanide in the untreated waste, the treated wastewater, and the treated
nonwastewater, as well as the TCLP leachate concentrations of metals in
the nonwastewater treatment residual (reactor wall scale and reactor
4-2
2360g
-------
bottom solids). Concentration ranges are presented for the untreated
waste composition data. For exact concentrations, refer to the CBI
docket for Second Third land disposal restrictions, which is available
through the OSVJ Document Control Officer.
4.3 Alkaline Chlorination Data
The Agency reviewed data submitted by Plant C on treatment of a
variety of cyanide wastes by batch alkaline chlorination (CyanoKEM 1989).
The data show concentration of total cyanide and metals in the untreated
waste and concentration of total cyanide in both the treated wastewaters
and the treated nonwastewaters. These data, for 14 sample sets, are
presented in Table 4-3. (Treatment data for mixed cyanide wastes were
also submitted by Plant C prior to calculation of the proposed treatment
standards for these wastes (CyanoKEM 1987). These data are presented in
Table 4-7. The data show concentrations of total cyanide and metals in
the untreated waste and amenable cyanide in the treated wastewater, as
well as design and operating information for each test.)
The treatment process used at Plant C is a several step batch
alkaline chlorination process. The cyanide wastes that are received by
the plant are first separated into bulk simple cyanides and bulk complex
cyanides. The bulk simple cyanides are treated by alkaline chlorination
followed by chemical precipitation and decantation. This liquid phase is
tested for total cyanide concentration. If the total cyanide
concentration is less than 1.9 ppm, the liquid is sent to secondary
treatment. The secondary treatment consists of equalization and
clarification. The solids are held in a holding tank.
4-3
Z360g
-------
The bulk complex cyanides are treated in several steps. The first
step is to destroy the simple cyanides by alkaline chlorination. The
effluent from the alkaline chlorination process is sent through
precipitation and decantation. The liquid phase will contain most of the
simple cyanides. These simple cyanides are then treated in a manner
similar to the bulk simple cyanides. The total cyanide concentration of
the solids is tested and if the concentration of total cyanide is greater
than 1,000 ppm, the solids are resolubilized and treated by alkaline
chlorination followed by chemical precipitation and decantation. The
liquid phase is treated by bulk simple cyanide process and the solids are
further tested for total cyanide concentration. This repetitive
treatment process continues until the solids concentration is less than
1,000 ppm.
The Agency believes that this process incorporates repetitive
treatment for the concentrated cyanide wastes, i.e., greater than 30,000
ppm of total cyanides. The fact that repetitive treatment occurs does
not call into question the achievability of the cyanide standard by
one-step alkaline chlorination processes. In the first place, the wastes
at Plant C require multistage treatment (in some cases) because they are
heavily concentrated with cyanide and complexing metals. Normal
electroplating wastes contain much lower concentrations of these key
parameters. Thus, based on characterization data for electroplating
wastes provided in Table 2-3 and the F006 waste composition data
submitted in the Generator Survey (see Table B-12), the wastes treated at
Plant C are much more concentrated than wastes from the electroplating
process that are treated for cyanide destruction. Also, the Agency notes
4-4
2360g
-------
that if F006 wastewater treatment sludges at electroplating facilities do
not meet the cyanide treatment standards, these wastes can be held in a'
holding tank and resolubi1ized and treated again by the plant's alkaline
chlorination system. Most important, all existing data (public comments
to this rulemaking and the Agency's review of the Generator Survey data,
which corroborates the information in the public comments) show that the
final cyanide treatment standard is being achieved by over 90 percent of
the industry by performance of existing treatment systems.
Facility C supplied data to EPA on the proportion of cyanide and
noncyanide wastes fed to the clarifier during treatment tests. The
treated waste concentrations reported in Table 4-3 were adjusted to take
into account these dilution factors. The clarification step is followed
by chemical precipitation, polishing filtration, and sludge dewatering
for metals removal. The clarification tank holds a large volume of
wastes (approximately 4 days' residence time), thus also serving as an
equalization tank between batches. Precipitation and filtration
treatments are performed on the equalized waste, so that each treated
waste sample corresponds to the treatment of four days' waste, rather
than a specific treatment batch. The retention step in CyanoKEM's
chemical precipitation of the metals process is not even related to
cyanide treatment. (Cyanide destruction by alkaline chlorination
actually occurs in 2 to 3 hours in the CyanoKEM batch process and occurs
even more quickly in continuous alkaline chlorination processes.) This
type of retention is not needed for successful treatment at a normal
electroplating operation using alkaline chlorination. CyanoKEM treats
4-5
2360g
-------
much larger volumes of waste than the usual electroplater, and requires
the extra retention to equalize the large volumes of waste before
chemical precipitation.
The Agency also collected two sets of treatment data at Plant E,
presented in Table 4-8. These data show total cyanide concentrations for
both the influent and the effluent from alkaline chlorination treatment
(USEPA 1985).
4.4 Electrolytic Oxidation Data
Table 4-4 presents II data sets obtained from the literature on the
performance of electrolytic oxidation treatment of cyanide wastes (Easton
1967). The data show cyanide concentrations in the untreated and treated
wastewater, as well as design and operating information obtained during
the tests.
4.5 High-Temperature Cyanide Hydrolysis Data
Table 4-5 presents six data sets obtained from the literature from
full-scale testing of high-temperature cyanide hydrolysis (Robey 1983).
Wastes tested were actual F007-F009 electroplating wastes, in the form of
both bulk liquids (wastewaters) and drummed solids (nonwastewaters).
4.6 SO^/Air Oxidation Data
Table 4-9 presents seven sets of data on SO^/air oxidation
treatment of electroplating wastewaters, from various literature sources,
submitted during the public conment period (Inco 1989). These data
present total cyanide, BDAT list metals, and iron concentrations in both
the untreated waste and the treated wastewater, as well as the available
operating data for each test.
4-6
Z3SDg
-------
4.7 UV/Ozonolvsis Data
Plant C also submitted two sets of data on ultraviolet light-enhanced
ozonolysis treatment of a synthetic waste with a high iron cyanide
content. The waste was prepared as a mixture of high-iron content wastes
and then treated by bench-scale alkaline chlorination prior to "untreated
waste" analysis. These data, presented in Table 4-10, include analysis
of total cyanide, BDAT list metals, and iron in the untreated waste and
total cyanide in the treated waste, as well as operating parameters for
each test.
4.8 Chemical Precipitation Data
The data for BDAT metals from Plant A, shown in Table 4-1, show
treatment of metals in wastewater by chemical precipitation followed by
filtration and sludge dewatering. Additionally, the Agency has data for
chromium reduction followed by chemical precipitation, filtration, and
sludge dewatering for treatment of K062 and other wastes. (See EPA's
BDAT Background Document for K062 (USEPA 1988b),)
Stabilization Data
The Agency has data on treatment of BDAT list metals in F006 waste by
stabilization. (See EPA's BDAT Background Document for F006 (USEPA
1988a).) EPA has not Identified any metals treatment data for F012 or
similar wastes other than the data considered 1n developing treatment
standards for F006, for which stabilization was determined to be BDAT.
Table 4-11 presents data on stabilization of an aluminum coil plating
sludge containing cyanide, collected by EPA (USEPA 1988g). These data
show total composition data for BDAT list metals and cyanide for the
4-7
2360g
-------
untreated waste and TCLP data for the same parameters for the treated
waste. The table also presents data on other parameters affecting
stabilization treatment.
4.10 Incineration Data
Plant D submitted two data sets on treatment of F010 waste and a
similar waste by incineration, presented in Table 4-6 (CyanoKEM 1988).
These data show total cyanide concentration in both the untreated waste
and the treated solid residual (ash). No data were presented for the
scrubber water.
4.11 Other Agency Data on Cyanide Treatment
The Agency has examined the data used for development of the effluent
limitations guidelines (ELG) for the metal finishing point source
category. Most of the treatment data used to develop the ELG standards
consisted of treated waste data from monitoring of plant effluent streams
and did not present associated untreated waste data. Tables 4-12 and
4-13 present those data that were presented as paired influent-effluent
data (USEPA 1983). These data are for chemical precipitation and
ozonation treatment, respectively. The data presented in these tables
show untreated waste cyanide concentrations much lower than for the
treatment data that are presented in Tables 4-1 through 4-11. Table 4-14
summarizes the data used to develop the effluent guidelines limitations
and standards for the metal finishing point source category (effluent
data only).
4-8
-------
239Cg
Table 4-1 Electrolytic Oxidation, Alkaline Chlorinat ion, Chanical Precipitation,
and Sludge Dewatering Data Collected by EPA at Plant A for
Treatment of F011 and Heat Treating Quenching Wastewaters
Saa^>le Set Mo. 1*
Concent rat ion
Untreated Treated
waste wastewater Treated nonwastewater
Total Total Total TCLP
Constituent (¦>/!) (¦»/!) («»/kg) (¦»/!)
Ant imny
0.029
<0 021
<2.1
<0.021
Bar iian
1.0
0.084
19
0.301
Ca11.0 10.6-11.6
Alkaline chlorination reactor pH >11.0; 7.0-9.0 11.2; 6.0
(2-step)
Excess chlorine in alkaline NS 30 ag/1
chlorination reactor
I * Saa^>le result is indeterminate because of analytical interference, but is less than
5.130 ag/1 based on laboratory analysis of total and amenable cyanides for the
partially treated waste.
- - Hot analyzed.
NS = Not specified.
'Electrolytic oxidation was used only with S«ple Set No. 1.
^Accuracy-adjusted concentration.
Reference: USEPA 1988e.
' h-<3
-------
?390g
Table 4-1 (continued)
Alkaline Chlorination, Chen teal Precipitation, and Sludge Devatering
Data Collected by CPA at Plant A for Heat Treating Quenching Wastewaters
Sa*>1e Set No. 2
Concentration
Untreated Treated
MJigfltl Treated noo»aste»ater
Total Total Total TCLP
Constituent t«9/1) (ag/kg) ("g/D
Ant ilBny
<0.021
<0.021
<2.1
<0.021
Bariiau
oise
0.102
98
0.312
Cadiim
0.0S7
0.0092
5.31
0.052
Chrcnnun (hexavalent)
<0.01
0.625
-
0.436
Chran tun (total)
0.175
1.63
11
0.31
Copper
1.08
0.035
307
0.354
Iron
11.14
2.96
2.880
0-029
Lead
0.063
<0.005
28
0.01
Mercury
11.0;
7.0-9.0
11.6: 7.6
reactor pH
Excess chlorine in alkaline
NS
120 ag/l
chlorination rc*ctor
- =¦ Not analyzed.
NS = Not specif led.
Reference: USER* 1988e
4-10
-------
?390g
Table 4-2 Ucl Air Oxidation Data Collected by EPA at Plant B for F007 Waste
Sm*>1b Set No. 1
Concentrat ion
Const ituent
Treated nonwastwwter
Untreated
¦aste
Total
(>9/1)
In
¦as
fated
tewat«r
Total
(¦g/1)
Reactor solids A
Reactor solids B
Total
(¦B/kg)
TCLP
(¦B/l)
Total
(¦gAg)
TCLP
<¦9/1)
BOAT Oroanics
Methanol
BOAT Inorganics
Ant irony
Arsenic
Bariun
Beryl Iiub
Cactonun
Chrvrnn [hexavalent)
Chroaiiixa (total)
Copper
Lead
Mercury
Nickel
Seleniun
Silver
Thai! iin
Vanadium
Z inc
Cyanide (wenable)
Cyanide (total)
Fluoride
CB1
CBI
CB1
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
266
<4.0
<0.05
0.047
<0.075
<0.06
I
0.628
759
<1.75
<0.015
<0.25
<0.045
<0.55
<2.0
<0.125
7.91
0.3
11.9
4.20
<15
<350
<1.0
1.25
<0.15
<1.25
I
2.55
151.000
<35
<1.0
33.7
<1.0
<10
<40
<2.5
29.600
<25
<25
<0.01
0.20
<0.10
1
<0.10
<2.0
<0.05
<0.01
<1.0
<15
<35
<1.0
6.4
<1.5
<1.0
I
6.09
44.400
<35
<1.0
26.5
<1.0
<8.0
<40
5.3
139.000
<25
<25
<0.01
0.17
<0.10
1
<0.10
<2.0
<0.05
<0.01
<1.0
Note: Design and operating parameters are as follows:
Parameter Design value
Operating value
Reactor to^ierature
Residence tiae
Oxygen concentration (off-gas)
Reactor pressure
440-4M*F
55-66 Bin (5.D-6.0 gal/hr)
16-20X
1700 psig
449-487'F
57.1 ain
17.BX
1690-1707 psig
I - Matrix interference.
- ' Not analyzed.
aReactor wall scale; one sa^le collected for all six sa^ile sets.
^Reactor bottaa solids; one saaple collected for all six sa^ile sets.
Reference: USEPA 19BSf.
<•-11
-------
?390g
Table 4-2 (continued)
Sa^)le Set No. 2
Constituent
Untreated
¦aste
Total
(¦g/D
In
was
talk
Total
(«g/l)
Concentrat i
_Tregted nonwdstewater
Reactor solids A
Reactor solids B
Total
(¦g/kg)
TCLP
(¦9/U
Total
(¦g/kg)
TCLP
(¦g/1)
BDAT Organ ICS
Methanol
C BI
<150
<15
*15
BOAT Inorganics
Ant imony
Arsen ic
Bar inn
Beryl linn
Cackniin
Chrtniun (hexava lent)
Chrcniim (total)
Copper
Lead
Hercury
Nickel
Selen inn
Silver
Tha 11 iin
Vanadiin
Zinc
CB1
CB1
CB1
CB1
CB1
CBI
CB1
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
<4.0
<0.05
<0.03
<0.0/5
0.17
I
D.47B
566
<1.75
<0.015
<0.25
<0.045
<0.55
<2.0
<0.125
7 .48
<350
<1.0
1.25
<0.15
<1 25
I
2.55
151.000
<35
<1.0
33.7
<1.0
<10
<40
<2.5
29,600
<0.01
0.20
<0.10
I
<0.10
<2.0
<0.05
<0.01
<1.0
<35
<1.0
6.4
<1.5
<1.0
I
6.09
44,400
<35
<1.0
26.5
<1.0
<8.0
<40
5.3
139.000
<0.01
0.17
<0.10
I
<0.10
<2.0
<0.05
<0.01
<1.0
Cyanide (aaenable)
Cyanide (total)
Fluoride
CBI
CBI
CBI
<0.25
<0.25
4.02
<25
<25
<25
<25
Note: Design and operating parMeters are as follows:
Parameter Design value
Operating value
Reactor to^erature
Residence t ioe
Oxygen concentration (off-gas)
Reactor pressure
44O-4B0*F
55-66 Bin (5.0-6.0 gal/hr)
16-20*
1700 psig
440-489 *F
60.5 «tn
17.OX
1709-1725 psig
1 = Matrix interference.
- = Not analyzed.
aReactor ma 11 scale; one sa^>le collected for all six sa^>le sets.
^Reactor bottaa solids: one sa^>le collected for all six sa^>1e sets.
Reference: USEPA 1988f.
4-12
-------
2 39 Og
Tabic 4-2 (continued)
Saqjle Set No. 3
at
waste
Const ituent
Total
(¦9/1)
Treated
wastewater
Total
(-J/1)
Concentrat ion
Treated nonwastewater
Reactor solids A
Total
(¦g/kg)
Reactor solids B
TCLP
(¦B/l)
Total
l«g/kg]
TCLP
(¦9/1)
BDAT Organ ICS
Methanol
CBI
110
<15
<15
(hexavalent)
(total)
BOAT Inorganics
Ant irony
Arsenic
Bar im
Beryl 1 iusi
Cadi) inn
Chraniifi
Chraniiai
Copper
Lead
Mercury
Nickel
Selenim
Si lver
Thalliun
Vanadiud
Z inc
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
<4.0
<0.05
0.038
<0.075
0.48
I
0.568
B34
<1.75
<0.015
<0.25
<0.045
<0.55
<2.0
<0.125
4.63
<350
<1.0
1.25
<0.15
<1.25
I
2.55
151,000
<35
<1.0
33.7
<1.0
<10
<40
<2.5
29.600
<0.01
0.20
<0.10
1
<0.10
<2.0
<0.05
<0.01
<1.0
<35
<1.0
6.4
<1.5
<1.0
I
6.09
44.400
<35
<1.0
26.5
<1.0
<8.0
<40
5.3
139.000
<0.01
0.17
<0.10
I
<0.10
<2.0
<0.05
<0.01
<1.0
Cyanide (amenable)
Cyanide (total)
Fluoride
CBI
CBI
CBI
<0.25
3.22
4.02
<25
<25
<25
<25
Mute: Design and operating parameters are as follows:
Paravter Design value
Operating value
Reactor tMperature
Residence tine
Oxygen concentration (off-gas)
Reactor pressure
440-480-F
5S-66 Bin (5.0-6.0 gal/hr)
16-20%
1700 psig
431-488*F
59.2 ain
17.51
1701-1718 psig
1 » Matrix interference.
- » Wot analyzed.
'Reactor wall scale; one sa^>1e collected for all six
Reactor boltoa solids; one staple collected for all six
Reference: USEPA 1988f.
le sets,
le sets.
*-13
-------
?390g
Table 4-2 (continued)
Sa^>1e Set No. 4
Constituent
Untreated
¦iw
Total
(¦g/1)
Treated
wvWTr
Total
l-g/1)
Concentration
Treated noowastewater
Reactor solids A
Beactor solids B
Total
(¦g/tg)
TCLP
(¦9/1)
Tota 1
(¦9/fcg)
TCLP
{¦g/U
BOAT Organics
Methanol
BOAT Inorganics
Ant irony
Arsenic
Bariun
Beryl 1 inn
Cadniun
Chroniua [hexavalent)
Chramiun (total)
Copper
Lead
Mercury
Nicfcel
Selemiai
5i lver
Tha 11 iias
Vanadiin
Zinc
Cyanide (anenable)
Cyanide (total)
Fluoride
CB1
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
64
<4.0
<0.05
<0.30
<0.75
<0.60
1
<0.90
766
<17.5
<0.015
<2.5
<0.045
<5.5
<20
<1.25
6.26
<0.25
<0.25
4.07
<15
<350
<1.0
1.25
<0.15
<1.25
1
2.55
151.000
<35
<1.0
33.7
<1.0
<10
<40
<2.5
29,600
<25
<25
<0.01
0.20
<0.10
1
<0.10
<2.0
<0.05
<0.01
<1.0
<15
<35
<1.0
6.4
<1.5
<1.0
I
6.09
44.400
<35
<1.0
26.5
<1.0
<8.0
<40
5.3
139,000
<25
<25
<0.01
0.17
<0.10
1
<0.10
<2.0
<0.05
<0.01
<1.0
Nrte: Design and operating par^eters are as follows:
Parameter Design value
Operating value
Reactor t«*wrature 440-480'F 424-493'F
Residence tiae 55-66 Bin (5.0-6.0 gal/hr) 53.3 Bin
Oxygen concentration (off-gas) 16-201 16.5%
Reactor pressure 1700 psig 1675-1740 psig
I » Matrix interference.
- • Not analyzed.
aReactor Mil scale; one sa^le collected for all si* sa^>le sets.
^Raactor bottai solids; one u^ili collected for all six sa^ile sets.
Reference: USEPA 198Bf.
4-14
-------
2390g
Table 4-2 (continued)
Staple Set No. 5
Constituent
Untreated
waste
Total
(¦g/1)
Treated
Stealer
Total
(¦9/1)
Concentration
Treated nonwastewater
Reactor solids A
Total
(«g/kg)
Reactor solids B
TCIP
(¦9/1)
Total
(¦g/kg)
TCIP
(¦g/l)
BOAT Organics
Methanol
BDAT Inorganics
Ant irony
Arsenic
Bariun
Beryl 1 iijn
Cartiiun
Chrcaim (hexavalent)
Chrcaiia (total)
Copper
Lead
Mercury
Nickel
Seleniro
Si lver
Thalliun
Vanad iin
Zinc
Cyanide (aaenable)
Cyanide (total)
Fluoride
CB1
CB1
CB1
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
SO
<4.0
<0.05
<0.03
<0.075
<0.72
1
0.499
946
<1.75
<0.015
<0.25
<0.045
<0.55
<2.0
<0.125
4.07
<0.25
<0.25
4.06
<15
<350
<1.0
1.25
<0.15
<1.25
I
2.55
151.000
<35
<1.0
33.7
<1.0
<10
<40
<2.5
29,600
<25
<25
<0.01
0.20
<0.10
1
<0.10
<2.0
<0.05
<0.01
<1.0
<15
<35
<1.0
6.4
<1.5
<1.0
I
6.09
44,400
<35
<1.0
26.5
<1.0
<8.0
<40
5.3
139,000
<25
<25
<0.01
0 17
<0.10
1
<0.10
<2.0
<0.05
<0.01
<1.0
Njte: Design and operating parameters are as follows:
Parameter Design value
Operating value
Reactor taqierature 440-480"F 417-484'F
Residence tiae 55-66 Bin (5.0-6.0 pal/hr) 51.6 Bin
Oxygen concentration (off-gas) 16-201 16.6X
Reactor pressure 1700 psig IBM-1694 psig
I = Matrix interference.
- = Not analyzed.
aReactor wall scale; on* sa^ile collected for all six sa^slt sets.
Reactor bottca solids; one sa^>le collected for all iti M^tle sets.
Reference: USEPA 19B6f.
4-15
-------
?390g
Table 4-2 (continued}
Saafile Set No. 6
Concent rat ion
Treated nowaitoater
Untreated
¦aste
Treated
wastewater
Reactor solids
A*
b
Reactor solids B
Total
Total
Total
TCIP
Total
TCLP
Constituent
i-g/U
(¦g/i)
(¦g/kg)
(¦g/1)
(¦g/kg)
("j/D
BOAT Draamcs
Methanol
CBl
36
<15
-
<15
-
BOAT Inoruamcs
Ant iaony
CBI
<4 0
<350
-
<35
-
Arsenic
CBI
<0.05
<1.0
<0.01
<1.0
<0.01
Bariwi
CBI
<0.6
1.25
0.20
6.4
0.17
Beryl) 1UD
CBl
<1.5
<0.15
-
<1.5
-
Catfniun
CBI
<1.2
<1.25
<0.10
<1.0
<0.10
Chraniin (hexavalent)
CBl
I
I
I
I
1
ChrtniuB (total)
CBI
<1.6
2.55
<0.10
6.09
<0.10
Copper
CBI
994
151.000
-
44.400
-
Lead
CBl
<35
<35
<2.0
<35
<2.0
Mercury
CBI
<0.015
<1.0
<0.05
<1.0
<0.05
Nickel
CBl
<5.0
33.7
-
26.5
-
Seleniun
CBI
<0.045
<1.0
<0.01
<1.0
<0.01
Silver
CBI
<11
<10
<1.0
<8 0
<1.0
Thallma
CBl
<40
<40
-
<40
-
Vanadiia
CBI
<2.5
<2.5
-
5.3
-
Zinc
CBl
6.46
29,600
-
139.000
-
Cyanide (aaenable)
CBI
<0.25
<25
-
<25
-
Cyanide (total)
CBI
<0.25
<25
-
<25
Fluoride
CBI
3.95
Note: Design and operating pan
Meters are as
follows:
Paraoeter
Design value
Operating value
Reactor to^erature
440-4WF
412-494-F
Residence ti«e
55-66 Bin (5.0-6.0 gal/hr)
50.8 «in
Oxygen concentrat ion (off-gas)
16-20X
17.OX
Reactor pressure
1700
psig
1674-1690
psig
^Reactor sail scale; one sa^>l«
^Reactor bottcai solids; one saaq
collected for
}!¦ collected
all six sa^
for all six a
>le sets,
lae^le sets.
1 ¦= Matrix interference.
- = Not analyzed.
Reference: USEPA 1988f.
1-16
-------
2 744g
Table i-3 Alkaline Chlormation Data Submitted by
Plant C During the Public Conrwnt Period
Sample Set Ho la - for Treatment of F007. FQ08. D003. and P106
Constiiuent/parameter
Concent'at ion
Untreated Treated Treated
waste wastewater nonwastewater
(mg/1) (mg/1) (mg/1)
BDAT Iraraamcs Othe'- Than Metals
Cyanide (total) 71,759 0 95 357
BOAT lis: wetaIs
Copper 4,193
Nickel 136
Caonium 2,995
Chromium 3? 3
^ead 184
: inc 2,319
£on^BQAT_^s£_!l£liiL
[ron 2.936
0t_2£r_p£-£rnet£r£
p« 11.2-
TOC <27.
- * Sot analyzed
dB#tcn corsisted of a muture of liquids and drunmed solids including
waste codes FC07. '308. DQ03, ana P106
Reference: CyanoF.EW 19fl9.
4-17
-------
2 7 44g
Table 4-3 (continued)
Sample Set No 2a ¦ 'or Treatment of F009. P012
Concentration
Untreated Treated Treated
waste wastewater nonwastewater
Constituent/parameter (mg/1) J mg/1) (mg/1)
£2£l_J,S£!3i2i£—p
Cyanide (total) 12.000 0.95 153
BOAT l>s; Ngtals
Copper 1,339
Nickel 4,088
Catfnium 300
Chromium 59Z
Lead 3Z7
Zinc 750
Non-BOA- US'. Heta's
Iron 6,200
Other Parameters
pH 11.0
T0C <2*
- « Not analyzed.
'Batch corststeo of a mixture of liquids and drunned solids including
waste codes F009 and F01?
Refe-ence; CyanokEM 1989.
4-18
-------
Z?44g
Tide 4-3 (continued)
Sample Set No 3d - for Treatment of F009. 0002. 0003, ana P030
Coneentrafon
Untreated Treated Treated
waste wastewater nonwastewater
Const'tuent/pararoeter (mg/1) lmg/1) {mg/1}
B3AT Inorganics PtEe"- Tnan Hetals
Cyanide (total) 17.206 <0.014 351
BDA~ Hit Meta's
Copper 8.400
hicnil 1.290
Caanium 7.610
Chromum 239
Lead 129
Zinc b.ISO
Son-BCAT . ist Heta's
Iron 5,520
Otnei" Parameters
pM 11.2-
TQC <2* -
- « Not analyzed.
aBatch consisted of a mixture of liquids and drunmed solids including
waste codes FC09. 0002. 0003. and P030.
Refe-ence: Cyano>>tH 1989
<~-19
-------
2744g
Taole 4-3 (cont inued)
Sample Set No. Ja - for Treatment of F007, F009. and 0002
Concentration
Untreated Treated Treated
tfaste wastewater nonwastewater
Constituent/parameter (™g/l) (mg/1) (mg/1)
B3*T Ino-oanics Other Than Hetals
Cyanide (tota'l 2S.936 <0.014 374
BDA* nit Meta's
Copper 3,266
Nickel 7.172
Cam urn 1,482
Cnromium 707
Lead 173
. ; in; 2,389
J£n^6DAT_^£|_>2££a2!i
Iron 11.917
Otner Parameter
pH 11. S
T0C <2S
- • Not analyied
aBatch consisted a' a mixture of liquids and drunmed solids including
¦aste codes FQ0?. ?009, and 0002.
Re'erence Cyanon-EN 1989.
4-^0
-------
2744g
Table 1-3 (continued)
Sample Set No S1* - for Treatment of F007, FOOB. 0003, and P029
Const' luent,'parameter
^t_ion__
Untreated Treated Treated
waste wastewater nonwastewater
(mg/1) (ng/1) (mg/1)
BEAT Inorganics Other Tlan Metals
Cyanide {tota '>) 16.911 <0.014 235
B^AMj^J^gtaJ^
Copper 5.343
Nickel 151
Cacrnun 3.412
Chromium 408
lead 99
Zinc 3.483
Non2B2*T_y_2j_jje2a_U
Iron 3.670
Other Parameter
pM 11.0
TOC «2X
¦ ¦ hot analyzed
a6atcn consisted of a mature of liquids and drunrned solids including
¦aste codes F007, f008. 0003, and P029.
Reference: Cyano*>£M 1989
4-21
-------
?744g
Table <-3 (continueo)
Sample Set No bd - for Treatment of FOll. POl2. 000?. and Pi06
Concentratinn
Untreated Treated Treated
waste wastewater nonwaste«ater
Constituent/parameter (mg/1) (mg/1) (mg/1]
BDAT_J^or£anj£j_2llJ£^I£2£_J!£i£ii
Cyanide (total] 59.4?l 0.0?8 245
SPAT List Metals
Copper 9?2
N ickel ? 59
Cadmium 3,2?3
Chrofliium 180
Lead 14?
Zinc S.M3
Non-B0ftT List Heta's
Iron 3,BIO
Other Parameters
pH 11.3
T0C <2X
- = Not analyzed
a9atch consisted of a mixture of liquids and drufftned solids including
waste codes FOll, F012, 0002, and P106.
Reference: Cyano^EH 1989.
4-22
-------
2Tiig
Table 4-3 (continued)
Sample Set No 7a - for Treatment of P007 and P009
Concentration
Untreated Treated Treated
waste wastewater nonwastewater
Constituent/parameter (mg/1) (rag/1) (mg/1)
BDAT Inorganics Other Than Hetals
Cyanide [total) 31.994 0.028 169
BOAT list Hetals
Copper 15,739
Nickel 1.897
Cainium 944
Chromium 1DD - r
Lead 124
Zinc 3.187
Non-BDftT List Metals
Iron 403
Dther Parameters
pH 11.2
TOC <2*
- ¦ Not analyzed.
iBatch consisted of a mixture of liquid* and druimd solids including
waste codes F007 and F009.
Reference: CyanoKIM 1989.
4-23
-------
2744g
Table 4-3 (continued)
Sample Set No. 8 - for Treatment of F007
Csncentration
Untreated Treated Treated
waste wastewater nonwastewater
Const'tuent/parameter !mg/l) (mg/1) (mg/l)
BOAT Inorganics Other Than Hetals
Cyanide (total) 41,900 <0.014 1B9
BQAT List Weials
Copper 19,510
N i c k. e 1 2,683
Cattrium 1.350
Chromum 100
LeaC 138
Zinc 4,708
Nor-BDAT .isi Heta's
Iror 498
Other Parameters
pH 11.5
T0C
-------
2 744g
Table 4-3 (continued)
Sample Set No 9d - for Treatment of F006. F009. FO11.
DD02. and D003
Constitjent/parameter
Concentration
Untreated Treated Treated
¦aste aastevater nonwastewater
fog/1) (mg/l) (mg/l)
B££J_L22L3i2,i£i_&!££!_
Cyanide (total) 18.88? <0.014 106.3
SPAT Llst «etaIs
Copper 11.654
Nickel 1.925
Cadmium 792
Chromium 3,658
Lead 289
Zinc 5.357
Non-BDA* list He Ij's
I-on 6.713
Otner Parameters
pH 10.3
TCC
-------
2744g
Table 4*3 (continued)
Sample Set No. !0a - for Treatment of F006 and F012
Concent rat ion
Untreated Treated Treated
¦aste aastewater non»aste*«ter
Const ituent/parameter (nig/ 1) (mg/ 1) (mg/ 1)
BDAT Inaroancs Otier Than Hetals
Cyanide (total) 1.270 0 17 143
BOAT List Metals
Copper 2.319
Nickel 6.739
Cairnum 1.903
Chromium 14.079
Lead 66Z
Zinc 19.163
Non-BOAT L'it ",tais
Iron 7.7B6
Otner Pai-aipgters
prl 1C.0
TCC <21
- « Not ana'yzed.
aBatc*i consisted of a mixture of liomds and drurmed solids including
¦aste codes F006 and F012.
Reference: CyanoKEH 1989.
4-2C
-------
27Aig
Taole 4-3 (continued)
Sample Set No ll4 - for Treatment of F007, F009. DOOZ,
P029. and P030
Concent rat ion
Untreated Treated Treated
¦aste wastewater nonwastewater
Const'tuent/parameter {mg/11 (mg/1) (mg/1)
SPAT Inoroaries Otier Than Metals
Cyanide (total) 22.820 1.16 1)4.1
8CAt i'st Metals
Copper 7,910
Nicie' 450
Caon'um 3.109
Cnromium <100
Lead 124
'inc 4.695
Nor-BCAT L-St HetilS
1ror 832
Other ^aramete-s
oh 11?
T0C <2%
- « Not analyted
d6atcr consisted of a mixture of liquids and drumwd solids including
«aste codes F007. F009. 0002, P029. and P030
Reference CyanokEH 1989
4-27
-------
2 744g
Table 4-3 (continued)
Samplg Sat No I?4 - for Treatment of F007. F009, F012. ind 0003
Concert rati on
Untreated Treated Treated
¦aste wastewater nonwastewater
Constituent/parameter (mg/1) (mg/1) {mg/1)
B£A2_J-nor2a^£S_£t-her_^han_Ne£aiTsi
Cyanide (cola') 12.OSS <0.014 252 4
BOAT List beta's
Copper 8.165
Nickel 138
Cadmus 128
Crtromiuffi <116
Lead 10S
line 325
Non-30
-------
27449
Table 4-3 (continued)
Sample Set No. 13 • for Treatment of 0002
Concentration
Untreated Treated Treated
waste wastewater nonwastewater
Constituent/oarameter (mg/1) (mg/1) (mg/1)
9D*T Inorganics Other Than Httals
Cyanide (total) 10.902 0 07 203 1
BOAT ust Hgtals
Copper 355
Nickel 160
Catfnium 7,050
Chromiun 120
Leaa 125
Zinc 9.940
Nsn-9DAT List »eta is
Iron 1.530
£the^_P£ram£ter^
OH II!
T0C <2X
- ¦ Not analyzed
Reference. Cyano^EH i9(J9
4-29
-------
27iig
Table 4-3 (continued)
Samp'e Set No N4 - for Treatment of F009, F011. 0002. and D003
Concent rat'on
Untreated Treated Treatea
¦aste «aste«ater nonwastenater
Cons: ituent/parameter (fng/1) (mg/ 1) {mg/ 1)
9PAT Inoroariss Otner Tr>an Metals
Cyamoe [total) 16.010 0.07 94-4
BOAT List Metals
Cooper 6.272
Niciie' 223
Cadn'um J.063
Cnrcm'um 133 - t
Lead 124
• Zinc 6.012
Non-30AT List Metals
iron 3.511
Ct"er Parameters
ph 11.5
"C <2X
- • Not analyzed
'Batch consisted of a mixture of liquids and drutmed solids including
waste codes F009, F011. 0002. and 0003
Reference: C/anoK.EM 1989.
4-30
-------
«' jCIq
Tabic 4-4 electrolytic On Ait ion Treatment Dot a frwi Literature Source A
for Ircalnent of F00/ and fOOy Wastes
Constituent
Concentration (units!
Untreated
¦aste
(¦g/1)
Treated
wastewater
(¦g/i)
React ion
11 me
(days)
Sjmole Set 11:
Cyanide (total)
95.000
0.1
16
Cyjnide (total)
75,000
0?
i;
Sample Set >3:
Cy.inidc (totjl)
SO.000
0.4
10
Samp le Set tA :
Cyanide (loLal)
/b.000
0.?
18
Sjwolo Set f 5
Cyanide (total)
65.000
0 2
12
S>imii to Sot /6:
Cyanide (tat a I)
100.000
0 3
17
iani^U£_SuL_#-/.
Cyjnicle (loloi)
55.000
0.4
!4
Sample Set #8:
Cyanide (tola!)
4b.000
0.1
Sannle Set 10:
Cyan id* (tola))
50.000
0.4
14
S.urolr Set #10:
Cyanide (total)
55,000
0.7
SrtjjjJe_Set_^j_L:
Cyanide (total)
48,000
0 4
1?
Mole : Do lyn valuer for operating condi Lions are presented be Ion.
Parameter
Temperature
lutaI current
Anorlr current density
Valuc/Descriotion
?00T uniui
1,200 a^> 9 6 vo lis
35 an/ft7
Hl-Terence. toil, on 146/. treatment of 100/ and f009 copper plating msIcs.
4-31
-------
Table 4-5 High-Ioverature Cyanide Hydrolysis Data frtn Literature Source B
for Treatment of F007, F008. and F009 Wastes
Concenlrat ion
lufl its )
OoeratmQ Data (units)
Constltuent
Untreated
Mite
(¦g/ 0
treated
¦astewter
(¦9/1)
Has tu
tonwrature
en
HaiiMA Reaction tin
pressure at ini iiui
(psi) laijierature (hr)
Sanole Set Mo. 1:
Cyanide (total)
10.000
19.8
477
700 1 hr
Sarole Set No 2:
Cyanide {total)
30.000
0.8
492
B7S 1 hr
Sairole Set *o. 3:
Cyanide (total)
10.000
2.S
4S0
-* 1 hr
Samole Set Ho. 4
Cyanide (lota 1)
10.000
IS
460
620 1 hr
Samole Set Mo. 5:
Cyanide (total)
33.000
1.2
500
875 1 hr
Same le Set No 6:
Cyanide (lota 1)
38.000
2.1
458
87S 1 hr
aPressure gauge malfunction: 875 psi is assmed.
Reference: Robey 1983. Treatment of f007-f009 wastes containing cadiiiji. copper, and/or nickel cyanides.
-------
?301g
Table 4-6 Incineration Data SufcBitted by Plant D for Treatment of F010 and D003
Concentration (units)
Untreated —ate Treated nonwastewa ter
(total) (total)
(ag/kg) (ag/kg)
Saaple Set No. 1:
Cyanide (total) 21.000s 0.4S
Saaple Set No.
Cyanide (total) 21.000* 0.40
Saaole Set No. 3:
Cyanide (total) 21.000* 0.BB
- = Not analyzed.
aThis concentration represents the Mean of two untreated waste sables, an oil
contaminated with cyanide (F010/D003, 22,000 ppa) and a lacquer contaminated with
cyanide (0003, 20.000 Pfn)
Reference: CyanoUH 1988.
4-33
-------
2 3 01 g
Table 4-7 Alkaline Chlorination Data Sutnitted by Plant C
for Various Uastes
Saa^>le Set No. 1* - for Treatment of 0003 and F007
Const ituent/parameter
Concentration (units)
Untreated
•aste
(¦b/D
1 rated
wastewater
(-3/1)
BOAT Inorganics Other Than Retals
Cyanide (anenable)
Cyanide (total)
BOAT List Wet a Is
Cattaim
Chrmlta (total)
Copper
Lead
Nickel
Zinc
Non-BPAT List Itetals
Iron
60,000
117
<100
4,000
<100
1.500
1, BOO
1,700
<1.0
Nate: Design and operating parameters are as follars:
Parameter Design value Operating value
Alkaline chlorination reactor pN 1Z.5-13.0 12.9
Retention tw for alkaline Z-6 hr ¦iniwib 96 hr
chlorination
0RP for alkaline chlorination >200 aV 380 *V
- • Not analyzed.
aBatch consisted of a Mixture of aest* codes D003 and FD07.
bActual retention tiae is based on a "not detected" result for the
analysis of the waste for aaenablt cyanide.
Reference: CyancttH 1967.
4-34
-------
Table 4-7 (continued)
Sam>le Set No 24 - for Mixed F006-F0i2. P03C
Constituent/pjramrtcr
Concentra I'on (units)
Untreated
¦aste
(mg/1)
1reated
«aste«ter
(n^/1!
BDAT lnprajnics Other Thjn Metals
Cyanide (amenable!
Cyanide (total)
BOAT List Metj Is
Cacftn'in
Chromic (tota 1)
Copper
Lead
N icke)
Z inc
Non-BQAT List Metals
1 ron
11.400
25
1,300
3.400
250
7.300
1B.S00
3,000
<0 1
Note: Design and operating parameters are a's follows:
Parameter Design value
Operating value
Alkaline chlormation reactor pH 12.5-13 0
Retention tine for alkaline
ch lor mat ion
0RP for alkaline cn lor mat ion
2-6 hr mininun
>200 mV
12 4b
24 hr
345 mV
- = Hot analyzed.
aBatch consisted of a mixture of liquids and drifimed solids including
¦aste codes F006, F007. F0D8. FOOT, P011, F012, and P030.
''Actual retention time is based on a "not detected" result for the
analysis of the «aste for amenable cyanide.
4-3b
-------
Table 4-7 (continued)
idnip le iel No. 3a - for Ireatment of fOO/
Constltuent/parameter
Concentration (units)
Untreated
waste
(mg/1)
Treated
¦astevater
(mg/1)
BOAT inorganics Other Than Metals
Cyanide (amenable] - <01
Cyanide [total) 100
BOAT Iist HetaIs
Catfniun
Chrcmiun (total) 780
Copper 440
Lead c100
Nickel 1.740
Zinc <100
Non-BDAT L ist Heta Is
Iron 470
Note: Design and operating parameters are as follows:
Parameter Design value Operating value
Alkaline chlorinatior reactor pH IZ.5-13.0 IZ 65
Retention time for alkaline 2-6 hr minieuti'' 5.S hr
chlor inat ion
ORP for alkaline chlorination >ZO0 mV 350 mV
- = Not analyzed.
aBatch aas oaste code F007.
''Actual retention time is based on a "not detected" result for the
analysis of the waste for amenable cyanide.
4-3b
-------
Table 4-7 (cont inued)
S«Vle SeL No 4d - for Treatment of 0003
ConsLiluenl/parameter
Concentration (units]
Untreated
waste
(mg/1)
Treated
wastewater
(mg/1)
BOAT Inorganics Other Than Hetals
Cyanide (anenable)
Cyanide (totall 13.000
BDA1 List HetaIs
Catfrniun
Chranitm (total)
Copper <100
Lead
Nickel <100
Zinc
Non-BDAT List Metals
Iron 320
<0.1
Note; Design and operating paraneters are as follows:
Parameter Design value
Operat ing value
Alkaline chlorination reactor pH 12.5-13.0 11.B
Retention time for alkaline 2-6 hr minimm^ 2 hr
chlorination
0RP for alkaline chlonnation >200 raV b20 qiV
- = Not analyzed.
aBatch tested consisted of solid sodiim and potassiun cyanide salts of
130.000 ppn cyanide concentration (D003).
^Actual retention time is based on a "not detected" result for the
analysis of the waste far amenable cyanide.
4-37
-------
lable 4-7 (continued)
Sample Set No. Sa - for Treatment of F009
Const iluent/parameler
Concentration limits)
Oitreated
•aste
(¦9/1)
TrMtid
MfteMter
BOAT Inorganics Other Than Hetals
Cyanide (anenable)
Cyanide (total)
BOAT List Wet a Is
27,200
«].0
CaiAniun
Chroniioi (total)
Copper
Lead
Nickel
I inc
Non-BDAT List Retals
Iron
270
1.050
3,070
3.320
Note: Design and operating paraaeters are as follows:
Parameter Design value
Operating value
Alkaline ch lor mat ion reactor pH 12.5-13.0
Retention time for alkaline 2-6 hr ainia
chlorination
ORP for alkaline chlorination >200 mV
12.6
20 hr
460
- = Not analyzed.
®Vaste tested was F009.
bActual retention tin* is based on a "not detected- result for tht
analysis of the waste for alienable cyanide.
4-38
-------
Table 4-7 (continued]
San?>1e Set No 6a - for Treatment of F011 and D002
Constituent/parame:er
Concentrattor (un-tsi
Untreated
aaste
Treated
wastewater
(o^/ 1 )
BOAT inorganics Olht/r 'han Helals
Cyanioe (amenable)
Cyanide (total) 6.000
BOAT List Hetals
CacfrTitun
Chromium (total)
Copper
Lead
Nickel
Zinc 11,000
Non-BDAT List KelaH
'1.0
4.000
Note: Design and operating parameters are as follows:
Parameter Design value
Operating value
Alkaline chlorination reactor pH 12.5-13.0 12 8
Retention time for alkaline 2-6 hr minin**n') 48 hr
chlorination
0RP for alkaline chlorination >200 biY 424 mV
- = Not analyzed.
aBatch consisted of a mixture of F011 and D002.
bActual retention iime is based on a "not detected" result For the
analysis of the waste for amenable cyanide
4-39
-------
Table 4-7 (continued)
Sample Set ho. 7* - for Treatment of f009
Concentration (unitsl
Unt reated
waste
T reated
wastewater
Constituent/parameter
(mg/1)
l«g/1)
BOAT Inorganics Other Thjn Metals
Cyanide (amenable)
Cyanide (total)
30,000
<1.0
BOAT List Hetals
Cainiun
Chromiun (total)
Copper
Lead
Nickel
Zinc 19,250
Non-BOAT List Hetals
Iron
Note: Design and operating parameters are as follows:
Parameter Design value Operating value
Alkaline chlorination reactor pH 1?.5-13.0 1?.B
Retention time for alkaline Z-6 hr minimm'3 1Z hr
chiorination
0RP for alkaline chlorination >200 mV 400 mV
- = Not analyzed.
aBatch consisted of a mixture of F009 (zinc plating waste) and a waste
hypochlorite solution
''Actual retention time is based on a "not detected" result for the
analysis of the waste for amenable cyanide.
4-40
-------
Table 4-7 (continued)
Sample Set No. Bd - for Treatment of F007
Const ltuent/parameter
Concentrat)pn (units!
Untreated
¦aste
Treated
wastewater
(wg/ !)
BOAT Inorganics Other Thdn Metals
Cyanide (amenable)
Cyanide (total)
BOAT L ist Wet a h
Ca<±imm
Chraniin (total)
Copper
Lead
Nickel
Zinc
Hon-BDAT list Hela Is
Iron
6,000
<100
1.SO0
seo
490
<1.0
Note: Design and operating parameters are as fotlovs:
Parameter Oesign value
Operating value
Alkaline chlorination reactor pH 12.5-13.0
Retention tine for alkaline 2-6 hr mm in
ch lor mat ion
0RP for alkaline chlorination >200 mV
12.9
8 hr
3B0 mV
Not analyzed.
Batch was F007 waste
Actual retention time is based on a "not detected" result for the
analysis of the aaste for amenable cyanide.
4-41
-------
; 3 0: c
\ib > i'ltanne Cnic^at'or 3a: a Cc «-«c:eo
Dy [pA at p 'ar: t
¦ 3^>cer
-------
1jb?c 4 4 SO /A if Oinjjlion Trcdtncn; Ddia Sukimllcd by PUnt F
Sample jp; Nu 1 • for Ireatment of Cyanide (Batch-Type)
Concent rat*3" (units)
Untrealeo
1^edted
Const itucni/DO-dff*.-tcr
waste
(mg/l)
wastewater
lmg/1)
bDAT Inorganics OWur' Itidn Hetais
Cyanide (total)
150
0 2
BDAT (. is'. Wotj
Cadtrun
Chromium (tola l!
Copper 90 1 ?
lead
Nickel
I inc -
Hon-flDAT List HcUils
Iron 2 8 <0.!
Other Parameters
pH 9.5 8.5
Note Design and operating parameters are as follows
Parameter Design value Operating value
50j added 3-7 g S0-,/g CNj h 0 g S0^/g CNT
- = Not analyjed
Reference: lnco lsib9. Appendix B.
4-43
-------
Ijble 4-9 (continued)
San^le bt'i No ' tor treatment of Cyanide (Lont inuous-Hode)
Concentration I urn:si
Untreated
¦ aste
Const ltuer.t/pardnvier (nq/1)
T rcated
wastewater
(mg/1)
BOAT Inorqancs Otncr Than Metals
Cyanide (total! 151
0.Z
BDAT t ist Metalb
Caomifti
Chraniim (tola 1!
Copper 90
Lead
Nickel 9.7
Zinc <0.2
1 .2
0.2
<0 2
Non-BDAT list Metals
Iron ? fl
<0.2
Other Parameters
pH 9.5
8.5
Note: Design and uporaling parameters are as follows:
Paraneter Design value
Operating value
SOp aoded 2-S g/g CNy
t 0 g/g CN,
Cu2* added <50 mg/L Cu
C g/g CNT
FIon rate
0 1 m3/hr
Total retention
60 min
- - Not analyzed
Reference. Inca lyoi. Apoendu C.
4-44
-------
2/Ajq
Table 4-9 (continued)
Sampii' but No 3 - for Treatment of Cyanide f ran
Plat inq Rinse Waters and Bleeds (Teed H Stream)
Const itucnt/parHTO'liT
Concentration (jr. us j
Untreatea
¦aste
(rng / !)
1-eated
¦astevater
(mg/ I)
BDAT Inorganics Oilier lhan Metals
Cya nide (total)
BDftT L ist Neta is
CaAmun
Chromium (total]
Copper
Lead
N icke1
I tnc
Non-BDAT L ist Hl".j Is
I ron
Other Parameters
ph
6?.400
3600
S400
26.4
13 1
1? 7
2 6
0.9
3.0
9.0
Note: Design and opera(ing parameters are'as follows:
Parameter Design value Operating value
S0? added
Base
(NaOH)
9/9 CN,
Cu?* added
Relent ion lime
i?l SO,/alr
(»o liane percent)
g/g CHj
50 mg/1 Cu
C g/g CNy
1.200 mm
» Not analyzed
Reference Iniu I'tMH. Append n E.
4-45
-------
-------
?/43g
Idb 'e 4-9 (corn\nued)
Sjhic If M". No S - for Treatment of Cyanide from
PUiinn Kmse Waters and Bleeds (Teed J Streair.)
Const 11 jont/paramli-r
Concpnlrat'on j un ' Is)
Untrealed
¦dsle
(mg/ 1)
frented
¦jslewdter
(mg/ 1)
BOAT InorQdniL^ Ultw i Utah Held Is
Cyanide (total)
BOAT L 'si M^Ui Is
Cadrmn
Chromiun (tola I)
Copper
Lead
Nicke 1
I inc
Hon-BOAT list Ml'I.i Is
I ron
Other Parameters
V40
90
0.2
1 2
2 2
8 4
<0.2
pH
11.3
9.0
Note: Design and operating parameters are as follows:
Parareler Design value Operating value
SOj added
Base (NaOH)
Cu'+ added
Retent ion t line
<7% S02/air
I vol Line percent)
SO mg/L Cu
4.7 g/g CNj
3. ^ q/g CHt
0.09 g/g CN1
80 mm
= Not analyzed
Reference. !nco lbe^. Appendix E
4-47
-------
? 743q
I dD )u 4-9 (corn inuedl
Samt; c- iet No 6 - for 1reatment of Cyanide from
Pint ny Hinse Waters and Bleeds (Teed *¦ Streaml
Const"tuent/parameter
Concentration l^nnsl
Untreated
¦aste
(mg/1)
1 rea'.ed
¦astevate*
(mg/J)
BDftT Inorganics O'vhrr Ih.ir Hetals
Cyanide (tola!) 142
BOAT [ist MetJ
CaitniuTi 10.0
Chror. iun {lei d I)
Copper *7 3
Lead
Niciel
Zinc 14.3
Non-BSAT l. ist Het J Is
Iron 18.0
Other Parameters
pH
<0 4
<0.1
? 6
<0.1
o.z
9.0
Note: Design and operating parameters are as follows:
Parameter Design value Operating value
S0? added
Base (Lime)
Cu^+ added
S0^/air
(volune percent)
50 mg/L Cu
4.7 g/g CM,
1.4 q/g CNt
6 4 q;g CHy
3.2 y/g CNj
0 g/g CNy
0 g/g CNy
Retention t ime
14.4 mm
- * Not ana'.y/uu
Reference Inco 1989. Appendix C
4-48
-------
2?43g
table 4-9 (continued)
bdmy'i' iet Ho 7 - for Treatment of Cyanide from
^Idling Rinse Water (Continuous)
Const . Vuenl/'pdrdn*;l lt
Concentration (unit-.)
Untreated
¦aste
(mg/ U
I red led
¦astevate'
(mg/ 1)
BOAT Inorganics tithe1" lhar Hetals
Cyan ide ( tota I) U?
BDAT L iSt. Met a lb
CdiJnujn 10 0
Chrcm-.um (totdi)
Copper 47 3
Lead
Nickel 0
Zinc 14.3
Non-BOAT List Meld la
Iron 18 0
Other Parameters
pH
0 Bti
<0.1
0 8
<0 05
0.4
10 0
Note; Design and operating paranclers are as follows:
Parameter Design value Operating value
Retention tin*;
Redox (S.C.L.)
SOj added
Lime added
0.5-10 vol. X
(1-3 vol X S02 in
air is optimum)
36 Tin
4.69 g/g CN; (Rl)
2.3^ g/g CNj (R2)
0 g/g CNf (effluent)
6 4 g/g CN, (Rl)
3.21 g/g CNj IR?)
0.1 g/g CNy (effluent)
- » Not analyzed
Reference: Incu ,Htiy. Appendix t.
4-49
-------
2 7 50g
!d D I c J IC JV/Ozonolysis Ireatment Oata from
Pilot Tests Submitted by Plant C
SaJi^ile Set do ld - for Treatment of f009, D003. F006,
F008, D002, and PI06
Concentration (units')
Untreated Treated
¦aste naste
Constituent/parameter lmg/1) (mg/1)
BOAT Inorganics Other lhan Hetals
Cyanide (total) Z050 1SI0
BOAT List Held Is
Caamun
Chronun (total)
Copper 35
Lead
Nickel 60
Zinc 150
Non-BDAT List Hetais
Iron 1400
Other Parameters
pH 12.68
Note. Design and updating parameters are as follows:
Parameter Design value Operating value
Relent ion Iime - 3.5 hr
Batch s ue - 1.7b qa 1
Recirculation rate - 1.7 gal/min
Operating tonperaturc 73"r
Ozone feed rate - 14 g'hr
- * Not analyzed
a Batch was a mature uf K0D9, D003, F006, ^006, 0002, and °106,
pretreatcd by alkjhne chlor inat ion.
Reference: CyanoM H I9u9.
4-50
-------
27SOg
lable 4-10 (continued)
Saro^e 2a ¦ for Treatment of F009, 0003. T006.
F 008. 0002, «nd P106
Concentration ijnits)
Const l tuent/parameter
Untreated
¦aste
(n^/1)
I realed
¦aste
(n^/1)
BOAT Inorganics Other Than Helals
Cyanide (total) USO
BOAT t'St Held Is
Cadniun
Chromium (tota'l
Copper 48
Lead
Xickei 24
Zinc 180
Hpn-BOM list WclJ is
Iron 1240
Other Parameters
pH 12.42
BOO
Note: Design and operating parameters are as follows:
Parameter Design value
>erat ing va lue
Retention tlme
Batch size
Recirculation rate
Operating toiperature
Ozone feed rate
4 rir
1.7S gal
1.7 gal/min
73-F
14 g/hr
- = Not analyzed.
aBatch ms a mixture of F009. 0003. F006. P008. 0002, and PJ06.
pretreated by alkaline chlorinat)on.
Reference: CyanoKfH 1989
4-51
-------
*48'e 4-; 1 Staa1ion freatrrert Data fc'
iiuii:ijn Cc ' f'a".'"9 sludge Cc:'eciea oy E?4
Sanple Set '(o 1
;:-st :jer;
-rsl rei'.ec
»as:e
;t3ta')
>9/kg)
reateo «as:e
ii-sen -:
5j<" il-~
CdOn„»
C-i-c-'.r
Csooe'
,ed3
"e1-: jry
Nic«.e'
^11
Cyarine
. 3 S
3 5
i 5
. 9C3
.'CO
*2 4
5 9
5
.955
<0 CC5 <0.005
3068
30
- • No: mi'yiec
le'e'e^ce !JSE?A ;968g.
4-52
-------
*«SD^e -- . (CITt
Simc'e Set No 2
tcrst • tuer;
jnt reatec
»as:e
I :;u';
"ga;e: -jste
A-ser is
8a !• 'ur
Caor i tr.
,_r
C33ce"
.eda
He-:.-,
N -cue 1
T na' nurr
C.ar.ioe :::: j ')
.8 9
5 5
'. 6
,?00
42 J
5 3
<0.
i 92
<: oos o dc.
19! i;
•o.c:; o ooi «c oc2
'0.oci 'C ooi
¦;:a ' sol ;os :% p. «*]
aep5i:. tj.-sn^)
Scec i' 'c erav t /
2i 45
1 1
:c 64
.355
64 ?9
: .35
2 -19
- - So: n yiec
3efe-e-ce .$£?- 19S8g.
4-53
-------
" a 3 '¦ e -
icon :ijec)
iai-aie ie: to 3
jnc rearec
-asce *-ej:?c -^s:e -is
Ccn5• t je-". ; '.ota ¦!
1 ir.g ' k g ) I• 2 » 3
Arse--; Ie • ;.9C3 o c:s :.c;j o o.3
Cjsce1" J. ; 30
,ea5 •!' J <0 C31 * ~ 0C1 i j»r
;.?cc
0
c: i
3
CU
<3 06
«o :e
Ccope1-
- 7 c c
-
•
.eaa
* i
4
'0
cc.
<3
301
<3.5
cQ 6
ye':-r v
c
;
-
-
-
-
s ciei
c
9
-
-
-
-
" -*d ' 1 Iw.T
25
6
'0
001
-------
Title i -1: i cont mi.ec!
iamsie set sc a
Const 11 ue-u
untreated
waste
i -eta I!
; -ng.- «-g)
"ej',53 ...-
Arsen i:
Zaam 1
C* rO^ l u""
Cosce"-
.tS3
lerzurj
N >ck.e'
'u' :!LH
Cvari'oe tela'
la 9
3 2
1 6
.90C
.730
ii J
j .
i 5
6
.3S5
>0 og; !
icec.f'c g'avt,
23 iS
1 3J
i.Zt
4-55
-------
"ac ie J - i 1 (;or t '.lues ]
Saircie 3et He i
Un;rea:ea
«asie "'°3te2 »
Const' t^en: Itsta1.!
.-g.'«-g! *1
4-se' 'c
.e
3
n
1
"*C
=
O
a
<0.32
-------
Tae >e --11 I :cn: ',ruea;
Sample Set Nj 6
jrt-eateo
waste *reate:: waste
Co"st
. tota'1
;-ng, >9)
»i »l
» j
a 1
*rsen >c
3i"IL"
Catmi^
C^'omur ;.
¦acoer i.
.ead
N irk.e "
T"a';u~
16 9
3 3
i 6
2CC
?0C
12 i
r. >
5 9
.'S 5
0 004 C 33a
0.022 3.016
O.CGZ <0.002
'0.1 <0.1
<0 30C2
2 n
- = Sot dralyjea
3efe-er.ce w 5 E ? A 1983g.
4-57
-------
TaDle ic3". 'r.jec'/
Sanc'.e Set ns ?
jrx-ea:ec
«as'.e
Ccnsl tuert ;'.3ld ;;
1-g.k.g) ». »•
Arse"! 1 C
'.5
9
j
CD7 2
3
306
3
03 C«
*.
3ar '.wP
j
2
-
•
Caw '¦ jr
5
-
-
-
Z^rz" i -
-
-
-
-
i-o-el
5
.9
•
-
-
-
rha ' ' 'ur1
•) &
5
<0
.32
e
I *
3
31
I
3C
2
r
. V
w ne*~ »3raire *. e-s
Untreated TreatM
"i-ameier «as:e «asie
;n 7 3 3 49
Ave'aqe L C i
*;t a ' sc ' 1 =s ¦! . « «* i 28. »S
Su'k. aers •••.» Jj. :t.j; 1.2 1.38
Spec'ic grav-ty - 45
- = No: ana i yfec
?e-e^ence jSEPa .953g
4-58
-------
"at le --1 i (can*, inues!
Samp'.e Set Nc 8
^orst 1
jrtreated
«as:e
{Total;
:-ig/ng)
¦ -saiga -as'.e
Arsenic
Sar•un
CdOni i u~
C P.^QT I or
Cospe-
kead
"e-Cu-.
n i:ke I
T.-a' i.it
Cvan-.ae
15 9
3 3
1 5
?CC
*cc
J2 J
5 9
.'5 6
s;S
< 0 CCS
0.319
<0 jc:
'0 cc:
.c :o:
2 77
2 56
2. iS
i.cnst I'.er*.
jnfeatea
-aste
Icli 1 )
("i? •' * a!
»5
rea.gC »aste TC'..g (nq/V
»6
<7
'S
4rse^'c
c 6 r • jrr
CdC^"Jff-
Cr.r^ir • un
Cssze"
ISiO
Sc». e
* naI' • jm
! i 9
* i
<03
j? j
5 9
25.e
Zyi~•ae ;: ct a i; 555
•0.305
0.326
02;
0 033
0.263 5 3
<0 001 <0 001
C 302
'0 001 <0 001
-------
lac ie i-il . con*. T.uec I
iample Set Nc 3
untreated
adSte
Cons", •tje'*: ;:cidi;
3a r i i»m
Cd3n' ur
;i-oit '.l.-
Cssoe-
.eac
"e'CJr>
•r c*e ¦
"la ' ' iv,".
C>an ae ,:;:a
18 3
3 3
: .33C
J. ' CO
42 J
35 £
CCS
0 0C9
dcs <: oos
307 3 COS
<-c oc: q ' 1'
C 304
~e- Pa-^ete1";
Pararrete-
Jnt-tattd
¦aste
Tr»a:ta
Haste
ph
Average U C i ii?a1
Tcta 1 so' -as .... «• «»)
8oi«. aeis .;. z*3:
Specific g-avi>
7 3
28 45
2
8 49
54 48
1 45
2 25
¦ • Set ara'yjer
fiefe'e-ce- !jSE = & :9o8g
4-60
-------
"aeie i-1i Icon::rjed!
Sairpie Set Nc .0
Csnsi't-en:
nt rea'.ed
*as:e
i tOia')
(rg/ig)
rfjtec -as.e
»2
Ai-SB" :c
Sarlun
wdOTlJff1
C h - 3fT> • UTT.
CoDce-
.eac
Mercury
S 'CUB I
T ha ¦ I' uir
C/ar, iae ;:ota:
;a 3
3 I
1 b
i . 93C
J. -CD
42 J
0 1
5.9
25 5
«0 005 . -eis » 19. ;t" '
ioec • f 1: 5-3,
7.3
28 J5
1.2
9 57
63 94
1 27
2 41
- = Not Jr.j ,;e.1
Kefe"-er.ce :?66a
4-61
-------
Tao'ie J-il icoicnuea;
Sarrjie 5et Nc 11
.ens:-:-er;
Jnt-eated
waste
1:ota 1;
(mg/ng;
i-pates «as".e
Arse^i c
Bar 'uir.
Cdflp'uffl
C"iraff • un
Z0Z09m
Lead
Me-;jry
s i c * e i
Va • '< jit.
Cyin»ae
18 9
; i
1 6
: ?ou
J. 700
4? 4
C 1
5 9
?5 6
1.355
O 331
0 155
<0.0C1
<0 0?
5 41
<0 001
0 GCC7
C 39? <3.38
<0 CC1 ;ec
Se'e'ence jSEPA 19689
4-62
-------
Tio'e ¦*~.i vcsnt'nued)
Saup le Set No 12
• onst ' '.LeH
Jn [ "ea t e<3
waste
1:ota 1!
(mq/fcgj
rrea:ec »as:e 'C.3 .^q
• 1
Arse" ic
Ear • jit-.
Cj3T"un
Chram¦un
Cccier
leao
"e-c.~y
s ¦ c t e 1
T ?a; i •un
i)tr\ ce ,j ¦
:6 9
3 3
i s
?30
. ::o
• 2 i
V i
25 6
D 0025 <0 001 C 3004 «C J3C3
C 11!
0 096 '0 OS ty
7 3
28 45
1.2
S. 58
1 23
2 56
- « Nol anai/zea
peiereice L'St'4 IS88g
4-63
-------
>e J-iI [cent
sar.o-e Set He
nuec
13
jr:-eat eo
waste T^eatg3 -asf.e WZ**
wo^st'twe". v:sta ;
[Tig; K})
4rser erase o w j ,irji
7 3 1C . 3
"eta. sc''cs 23 45 -3 29
3u'«. aens-'.y !g/cm^) 1.2 1.21
Spec;''c grav11 y - 2 59
• ' nj: analyzes
Sefs'ence viis4 i?56g
4-64
-------
r~ ;a" ^
't «j>*j*e'
*.rtfeAter
'•'c »»d s * e
.:r$:
f re<**. S3
•» J 5" P
¦ Tiq 1;
j f* • »Oi'g*
»ast e
-e 2;~s:s :* rre; : .
iej "i—.n -e^cva '• c* - r.
-as w> -s" c* s- *3;e. 'c 3-.ec c *
-•3T3 '5"? " ¦ iP.' •
nc' z:'£~^e
4-65
-------
-: -e •
2 5 • p
Cwns: :we-t
¦ oSI€
r?3:ec
»nie
-ea:en
¦.es:e
. to ';
Je vj^e'iw 'e
v";^ -;.ie ;:;• i "¦
c:-; »;s c ccr.'.jc; • .. e: :.»cre se' -c'.e o' -yarije it j pJ s"* ?• j-f i
Cat a a-e *"-3ir ?'ar: ¦ :!0zr a : .• • • «'e:t-as'stes cc is. $• '*er. copper, a-ic ni>e': 'c f.»
e ie:*.*:r.tcs
"?*sr5"'f «. S; 5 ^ 195;
4-66
-------
T*t-%e - of Cloe-Ccr.ta*^c *ast®»3te~: 5>
-A a' ?re CH'or ''at -o-
-e^rej
*»* s t e
C;r;e«:i
.* jwiit ec
:rt rat *cr.
" e d r ^
wast e
5*>cer.t -at *
(mg- ¦;
j*s, ^
H '• w ' 5
C.I.- 3
2 C 0 7 C
15:70
;:C?0
.'.370
33C73
33073
33073
09326
C?0£6
:?:-e
305
035
¦ r c.
.'.5
005
00=1
rAc
OOf
:oi
C2
005
005
327
. 06
CZ,
03'.
225
mc.
024
C24
06£
- ; i
035
034
C2?
CZe
06i
ou
.012
. ;j7
041
156
324
021
0:5
005
01:
033
.02
01
COS
COS
CO*"
305
.*.7
.00?
005
COS
04
005
.005
31
C05
005
C5
2?
.02
.254
. 129
. 013
C6
03
C2
4 5
7 9
5 i
5 0
4 6
5
4 &
4 S
6 5
7 0
5 9
2 S
2.5
5 5
5 1
5.5
2 6
2 4
3 8
157
C9b
04 j
031
039
. 031
1C5"
224
:5c
02 4
024
266
03 7
C35
359
02?
o za
:c:
91 £
.05
1.39
6£
.071
. 2Cs
.0':
C-76
4-67
-------
rei'^2
co"ce":-a:
itc *!
-ea:e^
«as:e
CP"* ~d* 'C~
;-r.g M
¦ej'.'V'. o. i '.r.c--j:e^ cj_.
.- ;-.e * • - si -s:er. s ;>* ...: ..
sees-:: stec. c»a*3te is :: ;
"G • " 0» Jil 3' ct
? r,. * "n? jcc '. • 0"
3-; ~>'zrzge~ a:
Cydr 1 ce '
:' c n 1 c r i •
a 3M o* :
5rton ana r.troae-
: a pr- cf f " -1C ' - : -e
• ei:?: «ss;e c«^er!"i: cf - '."fe v-
:i-:. c^^-se -jstes i~e -^er « t~
c* ine nrji er• i^e
ir;er i'ea:neri
«^s:e«^:e*s
•-t'Ci *a:i3r - ire i^o«rr. 5* a• -*. „ t-.e ;.»ariae -a* ««:« stream d> z:~*r 'a* *as:e streams 1: is
Jt'.erir-nea fc* C.'OTJ tr-v \zh • t .: CJ'- t 'o» Qy :*»e Cyafi'CV sl-ed~> • .>
-r'-itec ::r:e*t*«: >cr. - crc-cu.ci o** ' • •*¦•: *asie conce'"*. 'at icn a~a a'.ut-cr
"ai «e "c'-^et, aa: j \ z -.v*:-.. . :»e.i s* :re *9erc> ic oe »e ;' des . ed and »e' operated
"Zaia S--C-W ^3 not be *sed *re iC* ^ :: -1 no* De used because *t . d i*gh owi^er he
% *r r»g' ' ccm snou'a not be usee ; »s a rv.gr oui 1 'er ana Because ' -ere >5 rc cor-esco^ng
c^erao''e cyanide point
Wje-t {ram waste) co"*:ert- at • c • - r. *ven *.n :nt tso'e io*e%er. no :»:a 00m: s bsteo m the
tac'ie un-ess \r.f 1«,ev. ca^ce-i-st .• v .efoe-2 tne 1 je^t concert^ai
Sp^^rpice -SEC- ls5."
4-6B
-------
5. IDENTIFICATION OF BEST DEMONSTRATED AVAILABLE TECHNOLOGY iBD-'
This section presents the Agency's rationale for determining Dest
demonstrated available technology (BOAT) for F006 (cyanide)
nonwastewaters and F007 tnrough F012 nonwastewaters and wastewaters. Tc
determine BOAT, the Agency examines all available performance data fo^
the technologies that are identified as demonstrated to determine whether
one of these technologies performs significantly better than the others.
All performance data used for determination of best technology must first
be adjusted for accuracy, as discussed in EPA's publication Methodology
for Developing BDAT Treatment Standards.* BDAT must be specifically
defined for all strearrs associated with the management of the listed
waste or wastes; this includes the original waste as well as any residual
waste streams created by the treatment process.
The technology that performs best on a partic. :r waste or waste
subcategory is then evaluated to determine whether t is "available." To
be available, the technology must (1) be commercially available to any
generator and (2) provide "substantial" treatment of the waste, as
determined through evaluation of accuracy-adjusted data. In determining
whether treatment is substantial, EPA may consider 3ata on the
Accuracy adjustment accounts for the ability of an analytical
technique to recover a particular constituent frorr the waste in a
particular test. The recovery of a constituent is determined by spiking
a sample with a known amount of the target constituent and then
comparing the result of analysis of the spiked sample with the result
from the unspiked sample.
5-1
-------
performance of a waste similar to the waste in question, proceed '.'"¦a'
the similar waste is at least as difficult to treat.
5.1 Wastes from Electroplating Operations: F006. FCC?. FQQS. ar-:
F 009
5.1.1 Cyanide Treatment
EPA reviewed the available treatment performance data for all wastes
generated from electroplating operations for cyanide treatment
technologies, presented in Section 4, to determine whether they represent
the operation of wel1 -designed and wel1-operated systems, whether
sufficient quality assurance/quality control (QA/QC) data were collected
to assess the accuracy of the treated waste analyses, and whether the
data presented provide the appropriate measure of performance for the
technology tested.
The treatment performance data for wet air ox" ;tion of F007 waste,
presented in Table 4-2. provide amenable and tota": :yanide concentrations
in the untreated waste and in both wastewater and onwastewater
residuals. The F0C7 waste tested had concentrations of total BDAT metals
and total and amenable cyanide similar to the concentrations of these
constituents found in ether F007 wastes and in F008. F009, and F011
wastes (see Section 2.3 and Appendix B). Design arj operating data
collected during the test indicate that the system was well designed and
well operated during the collection of five of the six sets of
performance data. The appropriate QA/QC data were supplied with these
performance data. The data collected for Sample Set No. 1 show higher
5-2
-------
concentrations of both amenable and total cyanide in the feed
(approximately 20 percent higher) than for any of the other five iamp'r
sets, without a corresponding increase in residence time. This -nay
account for poorer systen performance, as shown by the data. This
problem might have been alleviated in operation either by better mixing
the feed or by increasing the residence time (i.e., by decreasing the
feed flow rate for higner concentration feed streams). The data for
Sample Set No. 1 were not considered further in the development of BOAT
standaras on the basis of poor system operation (insufficient reactor
residence time) at the time of treatment data collection. The data on
tne composition of the nonwastewater residuals were not considered in
further development of nonwastewater treatment standards for these waste
codes. These data represent the composition of solids precipitated on
the wet air oxidation reactor and thus are not dir tly comparable to
data representing the co-position of wastewater tr- :tment sludges that
may be generated following wet air oxidation or other cyanide treatment.
Treatment performance data for alkaline chlorination submitted by
Plant C during the public comment period are presented in Table 4-3.
These data provide total cyanide concentration in tne untreated waste and
the treated wastewater and nonwastewater. These da:a represent treatment*
of F006-F009, F011, F012. and other metal finishing wastes, both
nonwastewater and wastewater. This facility also supplied information on
the volumes of cyanide and noncyanide wastes treated so that the data
submitted could be adjusted to take into account the dilution caused by
:i'0g
5-3
-------
addition of the noncyanide wastes (e.g., chromium and acid wastes) trat
are first treated separately and then combined with the cyanide waste:
prior to chemical precipitation treatment. For one data point from
Sample Set No. 14, insufficient information was available to correct tre
treated nonwastewater cyanide concentration for this dilution.
Therefore, this data point was not considered further for wastewaters.
For another data point f>orr Sample Set No. 11, data supplied by the
commenter indicate that poor treatment system operation allowed an
unusually high cyanide concentration in the wastewater residual. This
data point was not considered further for regulation of cyanide in
wastewaters. With the exception of these two data points, the design and
operating data submitted indicate that the system was well designed and
well operated during the tests. QA/QC data are provided.
Additional treatment performance data for the :;ne system were
presented in Table 4-3 of the background document -or the proposed rule.
These data, presented in Table 4-7 of this document, provide total
cyanide concentration in the untreated waste and amenable cyanide
concentration in the treated wastewater. No grab sample data on the
treated nonwastewater and insufficient QA/QC data were provided;
therefore, these data were not used in the development of BDAT standards
for the electroplating wastewaters.
Treatment performance data for electrolytic oxidation were obtained
from literature source A and are presented in Table 4-4. These data
provide total cyanide concentrations for both the untreated waste and the
Z i J Jq
5-4
-------
treated wastewater. The design values given indicate that the syiterr Je-
well designed, and the treated waste cyanide concentration, as well a-;
the reaction time, indicate that the system was well operated at in* i'.~e
of treatment data collection. No QA/QC data were available for these
tests. Also, data for nonwastewaters were not presented.
Treatment performance data for high temperature cyanide hydrolysis
were obtained from literature source B and are presented in Table 4-5.
These data provide total cyanide concentrations for both the untreated
waste and the treated wastewater after subsequent chemical precipitation
treatment followed by filtration to remove suspended precipitated
solids. No system design data were specified. The operating data
provided indicate that the system was well operated during the collection
of treatment data sets Nos. 2, 3, 5, and 6. for data sets No. 1 and
No. 4, the operating data indicate that low reactc pressure (700 psi and
620 psi versus 875 psi for the other four runs) cc ".ributed to the higher
effluent cyanide concentration; therefore, these data sets were not
further considered in assessing the performance of this technology (based
on poor operation). No QA/QC data were given for these tests.
Treatment performance data for SO^/air oxidation from various
literature sources, submitted to the Agency during the comment period,
are presented in Table 4-9. These data show total cyanide concentration
in the untreated waste and the treated wastewater for seven sets of data
for treatment of electroplating wastewaters. QA/QC data were requested
by the Agency, but have yet to be submitted by the company. The
? S-S Cg
5-5
-------
coirmenter also did not present data on the composition of the
nonwastewater treatment residual for any of these tests.
The treatment performance data for the demonstrated cyanide treatment
technologies presented in Section d were adjusted for analytical recover
to take into account analytical interferences associated with the
chemical makeup of the treated waste samples. In the QA/QC test for
analytical recovery. [PA first analyzes a waste for a constituent and
then adds a known amount (i.e.. a spike) of the same constituent to the
waste material and reanalyzes the sample for that constituent. The
difference between the total amount detected after spiking and the
concentration detected in the unspiked sample divided by the amount of
spike added is the recovery value. (If recovery tests are run in
duplicate. EPA uses the lower recovery value.) Thn reciprocal of the
recovery multiplied by the analytical value obtair : during performance
testing is the accuracy-corrected value used in cc paring treatment
effectiveness and subseqjently in calculating treatment standards.
Percent recovery values for constituents detected in the wastes tested in
the wet air oxidation and alkaline chlorination tests are presented in
Appendix A. In the cases for which no analytical recovery data were
>
available (Tables 4-4. 4-5. and 4-9), EPA believes that QA/QC adjustment
of the data was not performed. Therefore, the Agency cannot directly
compare these data to the data for which accuracy correction factors are
available. The data presented in Tables 4-4, 4-5. and 4-9 for
electrolytic oxidation, nigh temperature cyanide hydrolysis, and
:mc-s
5-6
-------
SO /air oxidation, respectively, were not considered ir. the
determination of "best' treatment of cyanide in F007-"009 wastewater- .- a' :
nonwastewaters.
(1) Wastewaters. Accuracy-adjusted cyanide concentrations for a:",
data considered in developing BDAT cyanide standards for the F007. -008.
and F009 waste codes for wastewaters are presented in Tables 5-1 and 5-2
for total and amenable cyanide, respectively. (All tables are at the end
of the section.) The Agency considered the data on treated wastewaters
presented in Tables 4-2 and 4-3 in development of BDAT treatment
standards for these wastes. Statistical comparison of the 13 data sets
from alkaline chlorination with the 5 data sets from wet air oxidation
from treatment of similar wastes shows that the performance of alkaline
chlorination is better fo-- treatment of total cyan-1e. No data are
available for amenable cyanide concentration in t1" treated waste from
the alkaline chlorination treatment system (see Ta ie 4-3).
EPA's determination that substantial treatment occurs for alkaline
chlorination is based on the reduction in total cyanide concentration in
the waste tested. In addition to providing substantial treatment,
alkaline chlorination is commercially available; therefore, this
*
technology is "available" to treat cyanide in F007. FOOB, and F009 wastes.
(2) Nonwastewaters. Accuracy-adjusted cyanide concentrations for
all data considered in developing BDAT cyanide standards for the F006,
F007, F008, and F009 waste codes for nonwastewaters are presented in
Table 5-3. EPA received data during the public comment period from
2 j-
5-7
-------
corrrercial cyanide treatment that involved treating F006. F007. FQQe.
F009, F011. and F012 wastes. Although the relative proportion o* F0C6
wastes in these data was small (approximately 2 percent by volume). EP-
has evaluated these data carefully and believes that they are
representative of treatment performance for F006 nonwastewaters. as well
as for F007, F008, and F009 wastes. As explained in more detail •
elsewhere in this document, this is because the wastes treated are as
difficult or more difficult to treat than F006-F009 wastes or F006
precursor wastewaters would be if treated separately. The basis for this
conclusion is comparison of untreated waste concentrations of cyanide and
of the completing metals iron, nickel, zinc, and copper. Concentrations
of these key parameters are as high (or higher) in the waste from the
commercial treatment faci'ity (see Table 4-3) as i" F007-F009 wastes and
F0C6 precursor wastestreans (see Table 2-3 for da; on the composition of
F006 precursor wastewaters).
FC06 waste, as defined by its listing, is generated from chemical
precipitation treatment, which usually follows a cyanide oxidation step
if the waste treated originally contained cyanide. Thus, treatment of
the waste for cyanide Defore generation of these whites is the Agency's
*
"best" technology for determination of cyanide treatment standards for
F006 nonwastewaters and tne nonwastewater treatment residuals from
treatment of F007-F009 wastes and similar wastes. The cyanide oxidation
technologies (e.g., alkaline chlorination) are also applicable to be used
for further treatment of the wastewater treatment sludges prior to the
5-8
-------
dewatering steps; therefore, these wastes could be slurried with water
and tnen treated by the BOA' technologies (as is demonstrated by tne
treatment data presented in Table 4-3). While the Agency does not
believe that slurrying these wastes is necessarily the most
cost-effective way to perform alkaline chlorination (or other cyanide
treatment), this treatment option is available. In addition, generators
of these sludges need not dewater them but rather may send the high-water
content sludges to alkaline chlorination. In either of these situations,
cyanide treatment would be performed on the listed waste itself.
As discussed in Section 4 and previously in this section, alkaline
chlorination, chemical precipitation, filtration, and sludge dewatering
are coT.T.erci al ly available technologies for the treatment of F006-F009
and similar wastes and thus are "available" to be used in treatment of
cyanide-containing wastes prior to generation of : )6 and similar wastes.
Also, as shown in Table 4-3, the treatment trc n discussed above
substantially reduces the concentration of cyanide in F006 waste compared
to the concentration in the waste from which it was generated.
Stabilization treatment of the treatment sludges generated by chemical
precipitation has been shown previously, in the Ccie of F006, to result
%
in substantial reductions in leachate concentration of BDAT list
metals. Therefore, the treatment train discussed ^Dove, followed by
stabilization of the F006 or similar waste thus generated, is "available"
and thus is BDAT for F006 and is the basis for cyanide standards for
wastewater treatment sludge residuals from the treatment of F007, F008,
and F009 wastes.
5-9
-------
5.1.2 BOAT List MetaH Treatment
Characterization data *"or F007. FOOS, and F009 wastes snow tia; :r;-.r
wastes may contain high concentrations o* dissolved netals and tr.er&f3^e
nay require treatment by chemical precipitation followed by f'ltrat-.or
and sludge dewatenng. Chromium reduction nay also be necessary prior tc
chemical precipitation if the waste has a treatable concentration of
hexavalent chromium following cyanide oxidation. This treatment train
can be added after application of one of the demonstrated technologies
for cyanide removal, and it results in a wastewater and nonwastewater
treatment residual.
(1) Wastewaters. Data on the performance of chromium reduction
followed by chemical precipitation and filtration for wastewaters were
developed for regulation of K062 waste. Two data "=ts were also
presented, in Table 4-1, for chemical precipitatic followed by
fiHration and sludge oewatering treatment of FOli «aste mixed with heat
treating rinsewaters. These two sets of performance data are not
directly comparaole oecause the K062 waste treated had significantly
higher concentrations of 8DAT list metals (approximately 100,000 ppm)
than the metal heat treating wastes tested. The t-eatment data used in
regulation of K062 car, be transferred to the wastewater residual from
treatment of F007, FOOS. and F009 because the dissolved metals
concentrations of these wastes are similar to or 1Dwer than those of
K.062; thus, these wastes will treat similarly to KC62, whereas the F011
5-10
-------
treatment data represent treatment of a waste with significantly 'owr-'
metals concentrations t^ar expected for most F007. F008. and F009
and thus cannot be transferred. Because the <062 treatment data are f-
only data available to [PA on the performance level of chemical
prec i d i tat ion and fi1 tranon treatment of a waste with high BOAT metals
concentration, the Agency has determined that the performance of chemical
precipitation and filtration is "best" for treatment of BOAT list metals
in these wastes following cyanide treatment. As was presented for K062
(see EPA's BOAT Background Document for K062). this technology is
"available" and thus meets the Agency's criteria for BDAT.
(2) Nonwastewaters. EPA has previously promulgated treatment
standards for BDAT list metal constituents for F006 based on the
performance of stabilization (see EPA s BDAT Background Document for
F 006). EPA believes thai the nonwastewater treatr t residuals from
treatment of F007-FC09 wastes by chemical precipit :ion followed by
filtration are similar to F006 both in waste composition and in the
process generating the waste. Also, substances such as oil and grease or
sulfates that interfere with stabilization are not expected to be present
in significant concentrations in these wastes. It -ollows. therefore,
that since no data on treatment of F006 or similar wastes are available
other than the data used to develop stabilization treatment standards for
F006, stabilization represents the best treatment for BDAT list metals
for F006 and the nonwastewater residuals (i.e., wastewater treatment
sludges) from chemical precipitation and sludge dewatering treatment of
5-11
-------
F007. F008. and F009 based on the similarities discussed above betweer.
F006 and these wastes.
5.2 Metal Heat Treating Wastes: F011 and F012
5.2.1 Cyanide Treatment
EPA reviewed the available treatment performance data for wastes
generated in metal heat treating operations for cyanide treatment
technologies, presented in Section 4, to determine whether they represent
the operation of wel1-designed and wel1-operated systems, whether
sufficient quality assurance/quality control (QA/QC) data were collected
to assess the accuracy of the treated waste analyses, and whether the
data presented provide the appropriate measure of performance for the
technology tested. The treatment performance data for electrolytic
oxidation followed by alkaline chlorination of F011 waste and heat
treating quenching wastewaters collected at Plant presented in
Table 4-1, provide the appropriate measure of perf. -nance for this
technology (amenable and total cyanide concentrations in the untreated
waste and in both the wastewater and nonwastewater residuals). Design
and operating data collected during the test indicate that the system was
well designed and well operated during the test. Additionally, the
appropriate QA/QC data were supplied with these performance data.
EPA also considered all data that were considered for regulation of
the electroplating waste codes (F006-F009), as identified in
Section 5.1.1, as also representing treatment of the wastes generated in
metal heat treating operations. This is because the information that the
5-12
jq
-------
Agency has about the processes generating these wastes (see Sect-on 2:
and the available waste characterization data (summarized Sect on 2 :•
and presented in Appendix B) indicate that the wastes generated ui
electroplating operations are at least as difficult to treat, in terns of
concentration of complexed cyanide and iron and other complexing metais.
as the wastes generated in metal heat treating operations. Wastes from
metal heat treating operations are expected to contain mostly the soluble
cyanide salts (such as sodium cyanide and potassium cyanide).
(1) Wastewaters. Accuracy-adjusted cyanide concentrations for all
data considered in developing BDAT cyanide standards for F011 and F012
wastes for wastewaters a,-e presented in Tables 5-4 and 5-5 for total and
amenable cyanide, respectively. The Agency considered the data on
treated wastewaters presented in Tables 4-1 and 4-2 in development of
BDAT treatment standards for these wastes. (The c a on alkaline
chlorination, as presented in Table 4-3, have prev jusly been shown to
represent better treatment than the data on wet air oxidation, as
presented in Table 4-2. for similar wastes.) Statistical comparison of
the 13 data sets from alkaline chlorination with the 2 data sets from
electrolytic oxidation followed by alkaline chlorination shows that the
performance of alkaline chlorination alone is bett-- for treatment of
total cyanide. No data are available for amenable cyanide concentration
in the treated waste from the alkaline chlorination treatment system (see
Table 4-3).
5-13
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EPA's determination that, substantial treatment occurs for aluanne
chlorination is based on the reduction in tota1 cyanide conce-tra: -.c —
the waste tested. In addition to providing substantial treatment,
alkaline chlorination is commercially available; therefore, this
technology is "available'1 to treat cyanide in the metal neat treating
wastewaters (waste codes F011 and F012).
(2) Nonwastewaters. Accuracy-adjusted cyanide concentrations for
all data considered in developing BOAT cyanide standards for F011 and
F012 wastes for nonwastewaters are presented in Table 5-6. The Agency
considered two data sets on the generation of F012 waste from a
wel1-designed and wel1 - operated treatment system consisting of
electrolytic oxidation followed by alkaline chlorination, chemical
precipitation, filtration, and sludge dewatering (-—esented in
Table 4-1). The Agenc> also considered 13 data se from treatment of
mixed electroplating and metal heat treating waste in development of
these standards. Statistical comparison of the two data sets from
electrolytic oxidation followed by alkaline chlorination with the 13 data
sets from alkaline chlorination alone shows that the performance of
electrolytic oxidation followed by alkaline chloriration is better for
>
treatment of total cyanide. No data are available -'or amenable cyanide
concentration in the treated waste from the aTkalire chlorination
treatment system (see Table 4-3).
Treatment of the waste for cyanide before generation of these wastes
is the Agency's "best" technology for determination of cyanide treatment
5-14
-------
standards for F012 and s-.n-lar wastes. The cyanide oxidation
technologies are also applicable to be used for further treatment of r.r.~
wastewater treatment s'udges prior to the dewatering steps: therefor?,
these wastes could be slurried with water and then treated by the BDAT
technologies. While the Agency does not believe that slurrying these
wastes is necessarily the most cost-effective way to perforrr alkaline
chlorination (or other cyanide treatment), this treatment option is
available. In addition, generators of these sludges need not dewater
them but rather may send the high-water content sludges to alkaline
chlorination. In either of these situations, cyanide treatment would be
performed on the listea waste itself.
As discussed in Section 4 and previously in this section, alkaline
chlorination, electrolytic oxidation, chemical pre'•pitation, filtration,
and sludge dewatering are commercially available : ;hnologies for the
treatment of F007-F009. F011, and similar wastes a : thus are "available"
to be used in treatment of cyanide-containing wastes prior to generation
of F012 and similar wastes.
Also, as shown in Table 4-1, the treatment tra;n discussed above
substantially reduces the concentration of cyanide in FO12 waste compared
v
to the waste from which it was generated. Stabi1i;ition treatment of the
treatment sludges generated by chemical precipitat on has been shown
previously, in the case of F006, to result in substantial reductions in
leachate concentrations of BOAT list metals. Therefore, the treatment
train discussed above, followed by stabilization of the F012 or similar
5-15
-------
waste thus generated, is "available" and thus is BDAT for FC12 and :r;~
basis for cyanide standards for wastewater treatnent sludge res'dua';i
froTi :he treatnent of foil wastes.
Alternatively, the Agency believes that the cyanide treatment
standards for this subcategory can be achieved by treatment of these
wastes by wel1 -des1gned and wel1-operated alkaline chlorination treatment
alone. The only data for alkaline chlorination considered by the Agency
in development of these standards (i.e., the only data that included
design and operating ana QA QC information) were derived from treatment
of mixed metal finishing wastewaters. The waste codes F011 and F012
composed only 10 percent of the wastes treated in this test.
Approximately 50 percent of these wastes were waste codes F0Q6-F009. EPA
believes that the electrolytic oxidation treatment step in the BDAT
treatment t^ain speci(r,ed above is essentially a ' ^treatment" step that
lowers the cyan-,de concentration of the waste fed o alkaline
chlorination. The primary purpose of this step is to reduce the demand
for alkaline chlorination treatment chemicals, thereby reducing the cost
of treatment. In the absence of data on alkaline chlorination of metal
heat treating wastes alone, the Agency thus believes that the data
%
presented for electrolytic oxidation followed by a saline chlorination
are indicative of the performance achievable for a'
-------
(see EPA's BDAT Background Document for F006). EPA believes that the
waste F012 is similar to F006 from the standpoint of BDAT metal
treatability, both in terms of waste composition and in terms of the
processes generating the wastes. These wastes are also similar to the
nonwastewater treatment residuals from treatment of F011 wastes by
chemical precipitation followed by filtration. Specifically, the types
and concentrations of metals and inorganics in F006 and F012 wastes and
the wastewater residuals from treatment of FO11 wastes are similar.
Also, substances such as oil and grease or sulfates that interfere with
stabilization are not expected to be present in significant
concentrations in these wastes. It follows, therefore, that performance
data from stabilization treatment of F006 can reasonably be transferred
to FO12 nonwastewaters.
5.3 F010 Wastes
The data available to the Agency on incineration of FO10 waste
(presented in Table 4-6) indicate that incineration achieves a
substantial reduction in cyanide concentration in the incinerator ash
compared to the concentration in the untreated waste. Accuracy
adjustment of these data is detailed in Table 5-7. No data were
submitted on BDAT metals in the untreated waste or the ash residual. The
Agency has no information as to which, if any, metals are present in FO10
waste or the ash residual from incineration of this waste.
23«0g
5-17
-------
No data are available on the composition of the scrubber water from
incineration of F010. but the Agency expects this scrubber water to be
less difficult to treat than the other wastewaters regulated (F007 and
F009 wastewaters) because the concentrations of cyanide and BDAT list
metals would be lower. Therefore, the best demonstrated technology for
these scrubber waters is alkaline chlorination followed by precipitation
and filtration. No commenters submitted waste characterization data for
FO10 wastewaters or indicated that this waste would be more difficult to
treat than other metal finishing wastes. EPA expects, however, that
scrubber waters from incineration of cyanide wastes would meet the
treatment standards promulgated for F007-F009, F011, and F012 wastewaters
if generated from a wel1-designed and wel1-operated incineration
treatment system because cyanide has been shown to be incinerable to
nondetectable concentrations.
Incineration and alkaline chlorination are both commercially
available technologies and thus are "available" for the purposes of
establishing BDAT. Therefore, BDAT for F010 wastes is incineration
followed by alkaline chlorination of the scrubber waters.
5.4 Wastes from Aluminum Conversion Coatino: F019
Treatment standards for the wastewater and nonwastewater forms of
F039 have not been promulgated with the Land Disposal Restrictions for
the Second Third Scheduled Wastes. This waste was originally scheduled
for regulation in the First Third, with the statutory deadline of August
8, 1988. Since the Agency did not promulgate standards for the
23409
5-18
-------
wastewater and nonwastewater forms of F019, land disposal of these
wastewaters and nonwastewaters will continue to be regulated by the "soft
hammer" provisions in 40 CFR 268.8. EPA intends to promulgate numerical
treatment standards for cyanides and metals constituents for F019 by
May 8, 1990.
The Agency believes that F019 wastes are in a different treatability
group because of the high concentration of iron complex cyanides in both
the wastewaters and nonwastewaters. The Agency is investigating
ultraviolet-1ight enhanced (UV) ozonation, wet air oxidation, and
incineration as potential candidates for BDAT. Recovery or reuse of the
iron cyanides is also being considered. The Agency believes that the
source of the iron complex cyanides is the soluble ferrocyanide compounds
(such as potassium ferrocyanide) that are used as constituents in
aluminum conversion coating compounds or baths. Therefore, the only
cyanides present in these conversion coating baths would be the iron
complex cyanides that are used as a component of the coating. The Agency
believes that F019 nonwastewaters or the wastewater treated to generate
this waste have substantial concentrations of iron complex cyanides and
cannot be treated by conventional oxidation-reduction processes. The
Agency believes that the source of iron for the F019 waste is a
legitimate source of iron and also believes that the F019 is a different
subgroup within the metal finishing industry treatability group.
Therefore, the Agency will continue to "soft hammer" the wastewater and
nonwastewater forms of this waste.
2340g
5-19
-------
? 390g
Table 5 1 Sianary of Accuracy Adjustvnt of Treatment Data
for Total Cyanide in Electroplating Wastewaters
Untreated Measured Percent Accuracy-
¦aste treated aaste recovery for Accuracy- adjusted
concentration concentration aatrii correction concentration
(¦9/1) I"9/1) spike test factor (ag/1)
Wet Air Oxidation
Sa«*>le Set Ho.
2
CBI
<0.25
52
1.923
<0.48
Sa^>le
Set
No.
3
CB1
3.22
S2
1.923
6.19
Saople Set No.
4
CBI
<0.25
52
1.923
<0.46
Staple Set No.
5
CBI
<0.25
52
1.923
<0.46
Staple Set No.
6
CBI
<0.25
52
1.923
<0.48
lkaTine Chlorination
Sa^)le
Set
No.
1
71,759
0.95
94
1.06
1.01
Sa^)le
Set
No.
2
1Z.000
0.95
94
1.06
1.01
Sa^)le
Set
No.
3
17.206
<0.014
94
1.06
<0.015
Suple
Set
No.
4
25.936
<0.014
94
1.06
<0.015
Saaple
Set
No.
5
16.914
<0.014
94
1.06
<0.015
Sanple
Set
No.
6
59,4?1
0.028
94
1.06
0.030
Sasple
Set
No.
7
31.994
0.028
94
1.06
0.030
Saeple
Set
No.
B
41.900
<0.014
94
1.06
<0.015
San*)le
Set
No.
9
IB.88?
<0.014
94
1.06
<0.015
Saaple
Set
No.
10
1,270
0.17
94
1 06
0.16
Sa^jle
Set
No.
12
12.085
<0.014
94
1.06
<0.015
S«vle
Set
No.
13
10.902
0.070
94
1.06
0.074
Sea^> le
Set
No.
14
16.010
0.070
94
1.06
0.074
5-20
-------
2390g
Table 5-2 Siaaury of Accuracy Adjustment of Treatment Data
for Amenable Cyan ide in C lectroplat ing UtstCMters
Untreated Measured Percent Accuracy-
waste treated waste recovery for Accuracy- adjusted
concentration concentration Matrix correction concentration
(¦g/1) (mg/1) spike test factor Img/l)
Wet Air Oxidation
Saaple Set Ho. 2
CB1
«0.25
52
1.923
<0.48
Socle Set No. 3
CB1
<0.25
52
1.923
*0.48
Sample Set No. 4
CBI
<0.25
52
1.923
<0.46
Saddle Set No. S
CBI
<0.25
52
1.923
<0.48
S«*>le Set No. 6
CBI
<0.25
52
1.923
<0.48
5-21
-------
?390g
Table 5-3 StMMry of Accuracy Adjustment of Cyanide Data
In F006 Waste as Generated
Untreated Percent Accuracy-
waste recovery for Accuracy- adjusted
concentration Matrix correction concentration
lag/1) spike test factor (og/1)
Alkaline Chlorination
Sao*) le
Set
NO. 1
3S7
91.6
1.092
390
Sanple
Set
NO. ?
1S3
91.6
1.092
167
San^le
Set
No 3
351
91.6
1.092
384
Saa*)le
Set
No. 4
374
91.6
1.092
408
Saaple
Set
No. S
235
91.6
1.092
256
Sa^>le
Set
No. 6
245
91.6
1.092
267
Sa^>le
Set
No. 7
169
91.6
1.092
IBS
SMpla
Set
No. B
189
91.6
1.092
207
Saop I*
Sat
No. 9
106.3
91.6
1.092
116
S*file
Set
No. 10
143
91.6
1.092
156
Sam: le
Set
No. 11
114.1
91.6
1.09?
125
Sai^ile
Set
No. 1?
252 4
91.6
1.092
276
Sanjile
Set
No. 13
203.1
91.6
1.092
222
5-22
-------
2390g
Table i < SiBoary of Accuracy Adjustment of Trutmt Data
for Total Cyanide In Electroplating and
Netal Heat Treating Wastewaters
Untreated Measured Percent Accuracy-
•aste treated waste recovery for Accuracy- adjusted
concentration concentration Mtrii correction concentration
(¦g/1) (ag/1) spike test factor (ag/l)
Alkaline Chlorination
Saq>le
Set
No. 1
71.759
0.95
94
1.06
1.01
Sanfile
Set
No. 2
12.000
0.95
94
1.06
1.01
Saaple
Set
No. 3
17,206
<0.014
94
1.06
<0.015
Sample
Set
No. 4
2b,936
<0.014
94
1.06
<0.015
Saafile
Set
No. 5
16,914
<0.014
94
1.06
<0.015
Sa«*)le
Set
No. 6
59,421
0.028
94
1.06
0.030
Saaple
Set
No. 7
31,994
0.02B
94
1.06
0.030
5a*?le
Set
No. 6
41,900
<0.0)4
94
1.06
<0.015
SdB^ile
Set
No. 9
18.882
<0.014
94
1.06
<0.015
Sanple
Set
No. 10
1.270
0.17
94
1 06
0.18
Sao^le
Set
No. 12
12.085
<0.0)4
94
1.06
<0 015
S affile
Set
No. 13
10.902
0.070
94
1.06
0.074
Saav le
Set
No. 14
16.010
0.070
94
1 06
0.074
lectrolvt ic
Oxidation/Alkali
ne Chlorination
San^i le
Set
NO. 1
5,350
103
88
1.136
117
Senile Set No. 2
62 6
<0.01
BB
1.136
<0.011
5-?3
-------
23909
lab Is S-S Siaeury of Accuracy Adjustment of Trvatwit Data
for Aaenable Cyanide in Electroplating and
Metal Heat Treating Wastewaters
Untreated Measured Percent Accuracy-
Mste treated Mste recovery for Accuracy- adjusted
concentration concentration Matrix correction concentration
|«g/l) (ag/l) spike test factor ta/1)
Electrolytic 0» idat ion/A Ika 1 ine Chlorination
5ancle Set No. 1
Cyanide IdHenable)
Cyanide (chlorinated)
Cyanide (total)
Sa—le Se* 2
Cyanide (wenable)
Cyanide (chlorinated)
Cyanide (total)
I
S3 SO
Z9.2
33.4
67 6
114
103
<0.01
<0.01
100
88
60
sa
1.0
1.136
1.67
1 136
3.0
114
117
<0.017
<0.017
<0.011
- • Not available. Quantities actually Kasured acre total cyanide and "chlorinated cyanide."
¦rtiich acre both adjusted for accuracy. The accuracy-adjusted value for chlorinated cyanide
ms then subtracted froa the accuracy-adjusted value for total cyanide to obtain the
accuracy-adjusted concentration of aaanable cyanide. |Sm Appendix A for analytical recoveries
and Appendix 0 For detailed calculations.)
1 - Analytical interference. Value for total cyanide concentration ms S350.
5-24
-------
2 3 9 Og
Idble 5-6 Siawry of Accuracy Adjustment of Cyanide Data
in F0I2 Wast* as 6enerated
Untreated
¦aste
concentration
(¦9/1)
Percent
recovery for
¦atrix
spike test
Accuracy-
correction
factor
Accuracy-
adjusted
concent rat ion
(-9/1)
Electrolytic Oxidation/Alkaline Chlorination
Sancle Set Wo. 1
Cyanide (amenable)
Cyanide (chlorinated)
Cyanide (total) 99.4
102
0.98
<2.3
97.4
Sawale Set Ho 2
Cyanide (aaenable)
Cyanide (chlorinated)
Cyanide (total)
Alkaline Chlonnatiwi
34.7
93
1.06
7.9
37.3
Saijile
Set
No. 1
357
91. S
1.092
390
Saople
Set
No. 2
153
91.S
1.092
167
S«*>le
Set
No. 3
351
91.6
1.092
384
Sa^le
Set
No. 4
374
91.6
1.092
408
Saafile
Set
No. 5
235
91.6
1.092
256
Sa^>le
Set
Mo. 6
245
91.6
1.092
267
Saa^ le
Set
No. 7
169
91.6
1.092
185
Sa^le
Set
No. 8
189
91.6
1.092
207
Sa^>1e
Set
No. 9
106.3
91.6
1.092
116
Sa^>le
Set
No. 10
143
91.6
1.092
156
Staple
Set
No. 11
114.1
91.6
1.092
125
Saa^le
Set
No 1?
252 4
91.6
1.09?
276
Saaple
Set
Ho. 13
203.1
91.6
1.092
222
Not available. Quantities actually Measured were total cyanide and "chlorinated
cyanide," which acre both adjusted for accuracy. The accuracy-adjusted value for
chlorinated cyanide was than subtracted fnm the accuracy-adjusted value for total
cyanide to obtain the accuracy-adjusted concentration of —injti 1« cyanide.
(See Appendix A for QA/QC and Appendix D for detailed calculations.)
5-25
-------
23?0g
Table S-) Stannary of Accuracy AdjustJKnt of Treatiwit Data
for Total Cyanide in F010 Waste
Sanple Set Mo 1
Cyanide (total)
Sanple Set Ho 2
Cyanide (total)
Saimle Set No. 3
Cyanide (total)
Untreated Measured Percent Accuracy-
¦asle treated Mste recovery for Accuracy- adjusted
concentration concentration Mtris correction concentration
(ng/kq) («g/kg) spike test factor to/kg)
21.000 0.45
96
1.04 0.46S
21.000" 0.40
96
1.04 0.416
21.000a 0.88
96
1.04 0.91S
aAverage of tso untreated aaste saaples.
5-26
-------
6. SELECTION OF REGULATED CONSTITUENTS
This section presents the rationale for selection of the promulgated
regulated constituents for the treatment of F006-F012 wastes.
Constituents selected for regulation must satisfy the following
criteria:
1. They must be on the BDAT list of regulated constituents or must
be indicators for other BDAT list constituents. (Presence on
the BDAT list implies the existence of approved techniques for
analyzing the constituent in treated wastes.)
2. They must be present in, or suspected of being present in, the
untreated waste. For example, in some cases, analytical
difficulties (such as masking) may prevent a constituent from
being identified in the untreated waste, but its identification
in a treatment residual may lead the Agency to conclude that it
is present in the untreated waste.
3. Where performance data are transferred, the selected
constituents must be easier to treat than the waste
constituent(s) from which performance data are transferred.
Factors for assessing ease of treatment will vary according to
the technology of concern. For instance, for incineration the
factors include bond dissociation energy, thermal conductivity,
and boiling point.
From the group of constituents that are eligible to be regulated, EPA
may select a subset of constituents as representative of the broader
group. For instance, out of a group of constituents that react similarly
to treatment, the Agency might name only those found in the highest
concentrations or those that are the most difficult to treat as regulated
constituents for the purpose of setting a standard.
6.1 Identification of BDAT List Constituents
Table 6-1 shows which BDAT list constituents were analyzed for in all
wastes tested by EPA and submitted by industry (F007, F011, F012), which
constituents were detected, and which constituents the Agency believes
2361 g
6-1
-------
may be present even though they were not detected in the untreated waste
on which treatment tests were performed. BDAT list metals and cyanide
were detected in all of the wastes sampled.
For the F007 waste tested, one volatile organic compound, methanol,
was detected. One PCB compound, Aroclor 1254, Mas detected at a
concentration slightly above the detection limit, and several volatile
and semivolatile organic compounds were detected in the F012 waste
tested. No other BDAT list organic compounds were detected, or are
believed to be commonly present, in any of the wastes tested or any of
the wastes regulated by this document based on the Agency's knowledge of
the electroplating and heat treating processes. The detection of a PCB
compound in the F012 waste tested is probably attributable to a cleanup
of PCB transformers that had recently occurred at the plant where this
waste was collected.
The methanol detected in the F007 waste tested was probably a
constituent of the electroplating bath; since methanol is not commonly
used in such an application, 1t 1s not proposed for regulation. The
organic compounds detected in F012 (bis(2-ethylhexyl) phthalate, acetone, »
chloroform, methylene chloride, and toluene) were probably contaminants
of the rinsewaters treated along with the quenching wastewaters. These
organic compounds were all found at very low concentrations and are not
believed to be treatable at these concentrations.
6.2 Determination of Regulated Constituents
For the F007, F008, and F009 wastes, EPA is promulgating treatment
standards for total and amenable cyanide in both wastewater and
2361g
6-2
-------
nonwastewater treatment residuals based on the performance of alkaline
chlorination. The Agency is also promulgating treatment standards for
chromium, lead, and nickel in wastewaters based on the performance of
chemical precipitation followed by filtration, and cadmium, chromium,
lead, nickel, and silver in F007, F008, and F009 nonwastewaters based on
the performance of stabilization. For F006, EPA is promulgating
nonwastewater treatment standards for amenable and total cyanide based on
alkaline chlorination.
Standards for amenable and total cyanides are promulgated based on
the total waste composition analysis. EPA feels that because these
standards are based on a destruction technology, the appropriate measure
of performance is total waste composition. Also, because there may be a
difference in the performance of cyanide destruction technologies between
complexed and noncomplexed cyanide, both amenable and total cyanide
standards are promulgated.
All of the metals listed above are commonly found in electroplating
and heat treating wastes, based on the waste characterization data
presented in Appendix 6. The Agency has no data on the treatment of
wastewaters for cadmium and silver by chemical precipitation, but
believes that these constituents will be controlled by treatment of the
other metals for which treatment standards are promulgated. The Agency
may propose numerical standards for these constituents at a later date if
more treatment data become available.
2361g
6-3
-------
The only other metals that are commonly detected in these wastes at
high concentrations, according to the waste characterization data
presented in Section 2, are copper and zinc. EPA is not regulating
copper and zinc for the wastes in this subcategory because these
constituents are not listed in Appendix VIII of 40 CFR Part 261 as
elemental constituents but rather as specific compounds (i.e., copper
cyanide, zinc phosphide, and zinc cyanide). In any case, treatment of
the other BDAT list metals by chemical precipitation and/or stabilization
will also reduce leachate concentrations of both of these metals in
wastewater and nonwastewater treatment residuals.
The Agency is promulgating standards for both amenable and total
cyanide for F011 and F012 wastewaters and nonwastewaters. Regulated
constituent selection for wastewaters is based on alkaline chlorination.
Regulated constituent selection for nonwastewaters is based on
electrolytic oxidation followed by alkaline chlorination. Treatment
standards for amenable and total cyanides are based on the total waste
composition analysis. EPA feels that because these standards are based
on a destruction technology, the appropriate measure of performance is
total waste composition. Also, because there may be a difference in the
performance of cyanide destruction technologies between complexed and
noncomplexed cyanide, both amenable and total cyanide standards are
promulgated.
For metals in F011 and F012 wastewaters, the Agency is promulgating
treatment standards for chromium, lead, and nickel. For F011 and F012
236 lg
6-4
-------
nonwastewaters, the Agency Is promulgating treatment standards for
cadmium, chromium, lead, nickel, and silver. Regulated constituent
selection for wastewaters is based on treatment of the effluent from
alkaline chlorination by chemical precipitation followed by filtration
for the wastewaters. Regulated constituent selection for nonwastewaters
is based on stabilization of the nonwastewater residual. All of the
metals listed above are commonly found in electroplating and heat
treating wastes based on the waste characterization data presented in
Appendix B. The Agency has no data on the treatment of wastewaters for
cadmium and silver by chemical precipitation, but believes that these
constituents will be controlled by treatment of the'other metals
regulated. The Agency may propose numerical standards for these
constituents at a later date if more treatment data become available.
For F010, EPA is promulgating treatment standards for total cyanide
in the total composition analysis for both wastewater and nonwastewater
residuals and amenable cyanide for wastewaters. For incineration, the
Agency believes that total cyanide is the appropriate measure of
performance, as it has no evidence that complexed cyanides are any more
difficult to treat by thermal treatment methods such as incineration than
are free cyanides. As discussed in Section 5.3, EPA has no data on
metals in this waste and therefore is not promulgating treatment
standards for metals. The Agency is not precluded from regulating these
metals in the future if more treatment data become available.
2361g
6-5
-------
2?86q
table G-I Status of BOAT List Constituent Presence
in Untreated Tested Wastes
BOAT
reference
U£^
Const ituent
F007
F0I1
F01Z
Volatile Organic*
222
1.
2.
3.
4.
5.
6.
223.
I.
B.
9
10.
II.
12.
13.
14.
15.
IE.
17
IB.
19.
20.
21.
22.
23.
24.
25
2G.
21.
2B.
23.
224.
Z2S.
226.
30.
227.
31.
214.
32
33.
228.
34.
Acetone
Acetonitrile
Acrolein
Acrylonitri le
Benzene
Brand ich loroaelhane
Brtanaethane
n-Butyl alcohol
Carbon tetrachloride
Carbon disulf ide
Chlorobenzene
2-Chloro-1,3-butad»ene
Chlorodibr«BDBeth*ne
Chloroethane
2-Chloroethyl vinyl ether
Chloroform
Ch loroKthene
3-Ch loropr-opene
1,2-Dibra*i-3-Chloropropjne
1.2-Dibroeoethane
Oibroacaethane
trans-I,4-Dichloro-2-butene
Oich lorod if luoraaethane
1,1 Dichloroethane
I,2-Dichloroethane
1.1-Dich loroethylene
trans-1,2-0ichloroethene
1.2-Dichloropropane
trans-1,3-0ichloropropene
cis-1,3-01ch I oropropene
I,4-Diozane
2-Cthnyethanol
Ethyl acetate
Ethyl benzene
Ethyl cyanide
Ethyl ether
Ethyl aethacrylate
Ethylene oxide
lodaaetfcane
Isotoutyl alcohol
Methanol
Methyl ethyl ketone
NO
NO
NO
NO
NO
NO
NO
NO
NO
M>
NO
ND
NO
NO
NO
NO
N)
m
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
N)
NO
NO
0
NO
NO
NO
NO
NO
NO
ND
ND
NA
ND
ND
NO
NO
ND
ND
NO
NO
NO
NO
NO
ND
ND
NO
ND
ND
HO
NO
NO
ND
NO
NO
NO
NA
NA
NO
NO
NA
NO
NO
NO
NO
NA
ND
D
NO
NO
ND
ND
ND
ND
NA
ND
ND
ND
ND
ND
ND
ND
D
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NA
NA
ND
NO
NA
NO
NO
ND
ND
NA
NO
6-6
-------
22B6g
Table 6-1 (continued)
BOAT
reference Canttituent F007 F0I1 F012
SSL
Volatile Organics (continued)
229. Methyl isotoutyl ketone NO ND ND
35. Methyl aethecrylate ND NO NO
37. Methacrylonitrile NO NO NO
3D. Methylene chloride ND ND 0
230. 2-Nitropropane ND NA NA
39. Pyridine NO ND NO
40. 1,1,1,?-Tetrachloroelhane NO NO NO
41 1,1.2,2-Tetrachloroethane ND ND NO
42. Tetrachloraethene ND ND NO
43. Toluene ND ND D
44 T r ibroaoaethane ND NO NO
46 1.1,1-Trichloroethane NO NO NO
46 1.1.2-Trichloroethane NO NO ND
47. Trichloroethene NO ND NO
48. Trichlor«aonoriuoraKth«ne ND ND ND
49. 1.2,3-Trichloropropane NO NO ND
231. 1.1.2-Trich1oro-l.2.2-
tr if 1 uo roe thane NA NA NA
50. Vinyl chloride NO NO ND
215. 1.2-Xy lene NO ND ND
216. 1.3-Xylene NO NO ND
217. 1.4-Xylene ND NO NO
51. Acenaphthy lene NO NO ND
5?. Acenaphthene NO NO NO
53. Acetoptonone NO ND NO
54. 2-AcetylMinof luorene NO ND NO
66. 4-Aainob (phenyl NO NO NO
56. Aniline NO NO NO
57. Anthracene NO NO ND
56. Araaite NA NO NO
59. Beni(a)anthracene NO NO NO
7IB. Ben/a 1 chloride NO NA NA
(0. Bervzene t h i o 1 NA NO ND
CI. Deleted
62. Beiuo(a)pyr«ne ND NO NO
63. Benzolb)fluoranthenc NO NO NO
64. Beiuolgtii Ipery lene NO ND NO
65. Benzo(k)fluoranhene ND NO ND
y 66. p-Benjoquinane NA ND NO
6-7
-------
22Mg
Table 6-1 (continued)
BOA!
reference
no
Constituent
F007
FOU
FOl
SfluxaiAljle Orwnies tconltmjad)
67.
Bis(2-chlon>athDxy}HtK*ne
ND
NO
NO
M.
Bii(2-chlorc»thy t) ether
ND
NO
NO
19.
Bit(?-chloroi»opajpjr)) ether
ND
NO
NO
70.
Bis(?-cthylheiy]) phthilate
NO
NO
0
71
4-Broaophenyt phenyl ether
NO
NO
NO
n.
Butyltamzyl phthalete
NO
ND
NO
73.
2-sec-Buty M,6-dinureetwno1
NO
NO
NO
71
p-Chlonwoi tine
NO
NO
ND
75
Chloroben/i Ute
ND
NO
NO
76
p-Chlore-«-er«sol
ND
NO
ND
77
2-Ch1oron*phthi leoe
NO
NO
ND
78.
2-Chlorophenol
NO
NO
ND
73.
3-Chloroprppiointri le
NO
NO
ND
80.
Chryscne
NO
NO
NO
81.
ortho-Creso)
NO .
ND
NO
82.
parj-Creaol
NO
NO
HO
232.
Cyc lohexinone
NO
NA
NA
83.
Oibetu(i.h)anihricme
ND
NO
ND
H4.
D i betuoi *, e J py rmm
NA
NO
NO
si.
Dibm2o(i, i )pyrvne
NA
NO
NO
86
¦-Dtchtonsbenrene
NO
NO
NO
87.
o-0tchla robenzene
NO
NO
NO
88.
p-0ichlorotenzene
NO
NO
NO
69.
3.3*-0ic»ilorotoWWidine
NO
NO
ND
90
2.4 - 0 ich 1 sropheno 1
ND
NO
NO
91.
2.6-Oichlorophenel
NO
NO
NO
92.
Diethyl phthaUlc
NO
NO
NO
93
3.3"-0laettosyten/idint
ND
NO
NO
94.
p-D i«t t hy 1m 1 neat obetuM*
NO
ND
NO
95.
3.3" -Otaethy Ibwu id in«
ND
NO
ND
96.
2.4-Omttiylptanal
NO
NO
ND
97.
OiBcthyl phth* Ute
NO
NO
NO
96,
Ol-ii-butyl phthtlite
NO
NO
NO
99.
1,4-Oinitratefizmt
NO
NO
100,
4,6-8 initro-w-cresoI
NO
NO
NO
101.
2.4-Olnitrophenol
NO
NO
NO
102.
2.4-0lnitrotolye«i®
ND
NO
NO
103.
2,6-OtnitrotoluHW
NO
NO
NO
104.
Oi-n-octj 1 phthelete
HO
NO
NO
IDS.
Oi-n-pnjpy Intt rosMine
NO
M
NO
106.
Oi phenyl mi me
NO
NO
NO
219.
0 ipheny In it rOMM i ne
NO
ND
NO
6-8
-------
22B&9
lablc G-l (continued)
BOAT
reference
no
Const ituenl
F007
F 011
F01?
km lvolatiIt Orainics (continued)
107.
108.
109.
11C.
111.
112.
113.
114.
lis
116
117.
I IB.
115.
120
36.
121
122
123.
124.
125.
126.
127
I2B.
129.
130.
131.
132.
133.
134
135.
136.
137.
136.
139.
HD.
Ml.
M2.
220.
143.
144.
145.
146.
I,2-Diptonylhydra*ina
Fluoranthene
Muorana
Huuc h lo rabafuena
Hexachlorobutad iene
Hexachlorocyclopentadiene
Hexachloroethane
Heiachlarophene
rtcuch loropropene
1ndeno(I,2,3-cd)pyrene
Isosafrala
NathapyriIene
3-NethyIcholanthrene
4.4'-Aethylenebis-
(2-chlaroam I ine)
Methyl aethanesulfonate
Naphtha Iene
1,4-Hiphthoquinone
1-Naphthy laainc
2-Naphthy laaine
p-Nitroaniline
nitrobenzene
4-Nitrophenol
K-Nitrosod i-n-buty laaine
N-Nitrvsodiethylaaine
N-Nitroiodiaethy laaine
N-N i troioaethy 1 et hy Ida i ne
N-Nitrosaaorpholine
N-Nttrosopipcrid ine
N-Nltrosopyrrolidine
5-Nltro-o-toluidine
Pantach larctoeoiena
PenUch I a roe thine
PenUch loranitrotoenzene
PantachlorophenoI
Phenacetin
Phenanthrene
Phenol
Phthalic anhydride
2-Pico1ine
Pronaaida
Pyrana
Resorc iriol
NO
NO
NO
NO
NO
NO
NO
MA
NO
NO
NO
NO
NA
NO
NO
NO
NO
NA
NO
NO
NO
NO
NO
NO
NO
ND
NO
NO
NO
ND
NO
NA
NO
NO
NO
NO
NO
NO
NO
NO
ND
NO
NO
NO
ND
NO
ND
NO
ND
NO
ND
ND
NO
NO
ND
NO
NO
ND
ND
NO
NO
ND
NO
NO
NO
ND
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NA
NO
NO
ND
NO
ND
ND
ND
ND
ND
ND
ND
ND
ND
NO
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NO
ND
ND
ND
ND
ND
ND
ND
ND
NO
ND
ND
NO
NO
NA
NO
NO
ND
ND
6-9
-------
22B6g
Table 6-1 (continued)
BOAT
reference Constituent F007 F011 F012
02-
5«n»olatil* Oroanics (continued)
147. Safrole NO NO ND
MM. 1.2,4,5-1 etrachlorobetuene NO ND ND
149. 2.3.4,6-Tetrachlorophenol NO NO NO
150. 1.2,4-Trichlonjbeniene NO NO NO
151. 2.4, 5-Trichlonjphenol NO NO NO
152. 2.4.6-rrichloraphenol NO NO NO
153. Tri:>(?,3-dibraaopropy 1)
phosphate NO NO NO
154. Antiaony NO 0 NO
155. Arsenic NO NO NO
156. Ban* NO 0 0
157. Beryl Iiim NO NO NO
15a. C*
-------
2286g
Table 6-t (continued)
HOAl
reference Constituent POO 7 FOU fQl 2
no.
Oraanochlor.ne Pesticides (continued)
176. qmm-BHC NO NA NA
177. Chlordan* NO NA NA
178 DOC NO NA NA
170 DOE NO NA NA
180 DOT NO NA NA
181. Dialdr in NO NA NA
162 Endosulfan 1 NO NA NA
1E3 CndosuIfjn II NO NA NA
164. Cndrin NO NA NA
180. Cndrin aldehyde NO NA NA
186 Heptachlor NO NA NA
187. HepUchlor epoxide NO NA NA
IBS. Isodrin NO NA NA
169. Kepone NO NA NA
190. NeLhoxyc lor NO NA NA
191. Toxjphene NO NA NA
Phenwcetic Acid Herbicides
197. 2.4-0 tchloropheno»yacettc acid NO NA NA
193. Silvtx NO NA NA
194. Z.4.S-T NO NA NA
Organophosphorous Insecticides
195. Oisulfoton NO NA NA
196. Fa«phur ND NA NA
197. Methyl parathlon ND NA NA
196. Parathion ND NA NA
199. Ptorate NO NA NA
P£fii
200. Aroc lor 1016 NO ND ND
201. Artie lor 122] NO ND ND
20?. Aroclor 1232 NO ND NO
203. Aroclor 1242 NO NO ND
204. Aroclor 1248 NO NO NO
20b. Aroclor 12*4 NO NO O
206. Aroclor 1260 NO NO NO
6-11
-------
22B6g
Table 6-1 (continued)
BOAT
reference Constituent f007 F011 F01Z
no.
Dioiins and Purans
207.
Hexachlorodibenzo-p-dloiins
>0
NO
NO
?oe.
Heitach hi rod ibenxof urans
NO
NO
NO
?09.
Pentach lorod ibewo-p-dio» ins
M
NO
NO
210.
Pentach lorod t benzofurans
W>
NO
NO
211.
Tetrachlorodibenzo-p-dioiins
NO
NO
NO
212.
1etrachlorod i benjof urans
NO
NO
NO
213.
2.3.7.8-Tetrachlorodibeiwo-
p-dioz in
NA
NO
NO
0 - Detected
NO < Mot detected.
MA ' Mot analysed.
1 » Analytics I interference (aalrix effects) prevented analysis.
X ¦ Believed to be present based on engineering analysis of -aaste-^enerating
process. *"
T • Believed to be present based on detection in treated residuals.
References. USEPA 19B8e, !9ftSf.
6-12
-------
7. CALCULATION OF PROMULGATED BDAT TREATMENT STANDARDS
This section presents the calculation of the promulgated treatment
standards for F006 through F012 wastes using analytical treatment data
for the regulated constituents selected in Section 6. The Agency bases
treatment standards for regulated constituents on the performance of
well-designed and wel1-operated BDAT treatment systems. These standards
must account for analytical limitations in available performance data and
must be adjusted for variabilities related to treatment, sampling, and
analytical techniques and procedures.
BDAT standards are determined for each constituent by multiplying the
arithmetic mean of accuracy-adjusted constituent concentrations detected
in treated waste by a "variability factor" specific to each constituent
for each treatment technology defined as BDAT. Accuracy adjustment of
performance data has been discussed in Section 5 in relation to defining
"substantial treatment." Variability factors correct for normal
variations in the performance of a particular technology over time. They
are designed to reflect the 99th percentile level of performance that the
technology achieves in commercial operation. (For more information on
the principles of calculating variability factors, see EPA's publication
Methodology for Developing BDAT Treatment Standards (USEPA 1988d).)
Details on the calculation of variability factors for F006 through F012
wastes are presented in this section.
Where EPA has identified BDAT for a particular waste, but because of
data limitations or for some other compelling reason cannot define
2362g
7-1
-------
specific treatment standards for that waste, the Agency can require the
use of that treatment process as a technology standard. Similarly, where
there are no known generators of a waste, or where EPA believes that the
waste can be totally recycled or reused as a raw material, the-Agency may
specify a "no land disposal as generated" standard, which effectively
amounts to setting the performance standard at zero for all waste
constituents.
7.1 Cvanide
EPA is promulgating both nonwastewater and wastewater treatment
standards for amenable and total cyanide for FQ07, F008, F009, F010,
F011, and F012. Promulgated cyanide standards for wastewaters for all of
the wastes listed above are based on performance data from alkaline
chlorination. The performance data on alkaline chlorination were
received by the Agency during the comment period and are part of the
Administrative Record for this rule. These data were collected from
treatment of a mixture of wastes including F006, F007, F008, F009, F011,
F012, P030, PI061 and other cyanide-containing wastes generated by the
metal finishing industry. Promulgated nonwastewater cyanide treatment
standards for F006, F007, F008, and F009 are based on analysis of F006
waste generated as a residual from treatment of F0Q6, F007, F008, F009,
and other metal finishing wastes by alkaline chlorination followed by
chemical precipitation and sludge dewatering. The Agency has taken into
account the precision of the analytical methods for cyanide analysis in
the calculation of the treatment standards for amenable cyanide from the
alkaline chlorination data presented in Table 4-3.
7-2
2362g
-------
The promulgated nonwastewater treatment standards for F011 and F012 are
based on analysis of F012 waste generated as a residual from treatment of
F011 waste and heat treating quenching wastewaters by electrolytic
oxidation followed by alkaline chlorination, chemical precipitation,
filtration, and sludge dewatering. Promulgated nonwastewater standards
for F010 are based on data from treatment of this waste and a similar
waste by incineration.
7.2 BOAT List Metals
EPA is promulgated nonwastewater treatment standards for BOAT list
metals For F007-F009, F011, and F012 based on the treatment standards
established for treatment of F006 by stabilization. (See EPA's Best
Demonstrated Available Technology (BOAT) Background Document for F006
(USEPA 1988a).) Wastewater treatment standards for these wastes are also
being promulgated by the Agency based on transfer of the treatment
standards established for treatment of K062 waste by chemical
precipitation followed by filtration. (See EPA's Best Demonstrated
Availability Technology (BDAT) Background Document for K062 (USEPA
1988b).)
2362g
7-3
-------
2390^
Table 7-1 Calculation of Wasteoater Tmlirit Standards for Total Cyanide for Waste Codas
F007, F008, F009. F010. FOU, and F012 Based on AlUliiw Chlonnat ion
Accuracy-ad jus ted
Mean treated
Treatment
Regulated
treated easte
NSte
Variability
standard (total
constituent (units)
concentration*
concentrat ion
factor (VF)
cohosh ion)
Wastewater (en/l):
Cyanide (total)
1.01
0.192
9.8
1.9
1.01
0.015
0.015
0.015
0.030
0.030
0.015
0.01S
0.1S
0.01S
0.074
0.074
Tables 5-1 and 5-4.
82390g
-------
2390g
Title 7-2 Calculation of Won— ton tar Trcataent Standards for Total and Aaenable
Cyanide for F006, F007, F008, and F009 Hastes Based on Generation of F006
Haste by a Hell-Operated Traatwnt Process Consisting of Alkaline
Chlorination, Chaaical Precipitation, Filtration, and Sludge Oeaatering
Accuracy-adjusted Mean treated Trvatvnt
Regulated treated Baste aaata Variability standard (total
constituent (units) concentration* concentration factor (VF) Reposition)
Norwaste»ater (¦o/kql:
Cyanide (total) 390.U 242.9 2.4 590
166.56
383.68
408.0
256.5
267.43
185.01
206.78
116.02
156.11
124.54
275.58
221.83
*S«e Table 5-3.
82390g
7-5
-------
2390g
Table 7-3 Calculation of Ita wastewater TreetKnt Standards for Total and AaBnable
Cyanide for F011 and F012 Hastes Based on Generation of F012 Haste by a
Uell-Operated Treatment Prtxus Consisting of Electrolytic Oxidation, Alkaline
Chlorirvtt ion, C ha leal Precipitation, Filtration, and Sludge Deaatering
Accuracy-adjusted Mean treated Treatment
Regulated treated easte eeste Variability standard (total
constituent (units) concentration* arantratton factor (VF) co^nsition)
Nonwastenater (we/kni:
Cyanide (total)
97.4
37.3
67.35
1.58
110
Cyanide (aeaeble)
«2.3
7.9
5.1
1.79
9.1
'See Table 5-6.
82390^
7-6
-------
2390g
Table 7-4 Calculation of Mon«esteiiater Treatment Standards for Incineration of FD1D
Accuracy-adjusted Mean treated Treatment
Reflated treated eaate east* Variability standard (total
constituent (ixitts) concentration* concentration factor (VF) abolition)
Mowwastewater (i/ka):
Cyanide (total) 0.468 0.60 2.53 l.S
0.416
D.91S
*Sm Table 5-7.
7-7
-------
2390g
Table 7-5 BOAT Treatment Standards for F007. F008, and F009
Constituent Wastewater Ncnwastewater
Tota 1
Total
ctaposition
cta^osit Ion
TCIP
(¦9/1)
(¦g/kg)
(¦g/D
Cyanide (amenable)
0.10
30
NA
Cyanide (total)
1.9
590
NA
Cacti ii*i
-
NA
0.066
Chraaiian
0.32
NA
5.Z
Lead
0.04
NA
0.51
Nickel
0.44
NA
0.3Z
S ilver
-
NA
0.07?
NA = Not applicable.
- ¦ Do treatment standard.
7-8
-------
23S>Og
Table 7-6 BOAT Tr*ata*nt Standards for F006 (Cyanide)
Constituent Homwatewater
Tota 1
coders it Ion TCIP
(¦g/kg) (ag/1)
Cyanide (awnable) 3D NA
Cyanide (total) 590 NA
NA = Not applicable.
7-9
-------
Z390g
v
Table 7-7 BOAT Treatment Standards for F011 and F01Z
Constituent Wastewater Nonwasttmater
Total Total
co^wsition ca^osition TCLP
(¦9/1) ("g/k?) (*g/i)
Cyanide (aiwenable) 0.10 9.1 NA
Cyanide (total) 19 110 NA
Ca<*niian NA 0 066
Chraniu* 0.32 NA 5.2
Lead 0.04 NA 0.51
Nickel 0.44 NA 0.32
Silver NA 0,072
NA • Not applicable.
- = No treatment standard.
7-10
-------
i 3?0g
Table 7-8 BOAT Treatment Standards for F010
Constituent
Vast<^ater
Nonvastewate
r
Total
Total
envoi it ton
CW4>03 It Ion
TCLP
(¦g/1)
(¦q/kg)
1*9/1)
Cyanide (amenable)
0.10
-
NA
Cyanide (total)
1.9
1.5
NA
NA = Not applicable.
- = No treatment standard.
7-11
-------
-------
8. P WASTE CODES
This section addresses regulation of those P wastes that are similar
to the metal finishing cyanide wastes. These wastes, listed in
Table 8-1, are identified in 40 CFR 261.33 as "discarded commercial
chemical products, off-specification species, container residues, and
spill residues thereof."
8.1 Industries Affected
Industries that may generate these wastes are the manufacturers of
cyanide compounds listed in Table 8-1 as well as electroplaters, heat
treaters, and other industries that use inorganic cyanide salts. In
addition, hydrogen cyanide is a chemical intermediate used in the
production of acetone cyanohydrin, adiponitrile, cyanuric chloride,
methyl methacrylate, methionine, sodium cyanide, and other chemicals.
Thus, P063 wastes may be generated by producers of these chemicals.
8.2 Applicable and Demonstrated Treatment Technologies
The compounds listed in Table 8-1 are soluble in water to form waste
solutions that are similar in nature to the F011 waste tested by the
Agency and other wastes generated from metal finishing operations.
Therefore, the Agency believes electrolytic oxidation, alkaline
chlorination, wet air oxidation, high temperature cyanide hydrolysis,
SO^/air oxidation, incineration, and stabilization are applicable and
demonstrated to treat off-specification product, wastewater, and
contaminated soil and sludge forms of the P codes listed.
2363g
8-1
-------
Metals can be treated by chemical precipitation followed by
filtration, sludge dewatering, and stabilization for wastewaters, and by
stabilization for nonwastewaters.
8.3 Identification of Best Demonstrated Available Technology
EPA believes that these wastes are similar to F011 wastes generated
from metal heat treating operations. These P-code wastes are soluble
cyanide compounds or leak or spill residues containing these compounds.
Therefore, the Agency believes that the best way to treat these P-code
wastes is to dissolve them in water and then treat them by one of the
demonstrated treatment technologies identified above. Upon dissolution,
these P-code wastes liberate free cyanide and not metal-cyanide
complexes. These discarded cousnercial chemical products do not contain
significant concentrations of Iron, and therefore the Agency believes
that the treatment standards need not reflect the difficulties of
treating complexed cyanides.
Of the demonstrated technologies identified in Section 8.2, the
"best" technology for cyanide treatment for wastewaters for the P-code
cyanide wastes is alkaline chlorination. For treatment of BDAT metal
constituents for these wastes where regulated, the "best" technology is
chemical precipitation followed by filtration for wastewaters and
stabilization for nonwastewaters. Cyanide standards for nonwastewater
residuals are based on generation of treatment sludges by a treatment
system consisting of electrolytic oxidation followed by alkaline
chlorination, chemical precipitation, and sludge dewatering.
2363g
8-2
-------
Determination of "best" technology and "availability" for both cyanides
and metals follows the rationale that was presented in Section 5.2 for
the waste codes F011 and F012, generated from metal heat treating
operations, because these wastes are most similar to the P-code cyanide
wastes.
8.4 Selection of Regulated Constituents
EPA is promulgating treatment standards for total and amenable
cyanide in both wastewaters and nonwastewaters for all of the P-code
wastes listed in Table 8-1. The BOAT list metals proposed for
regulation, also listed in Table 8-1, are nickel for P074 and silver for
P099 and P104. Silver standards for P099 and P104 for wastewaters and
barium standards for P013 wastewaters and nonwastewaters have not been
promulgated because the Agency has no treatment performance data for
these metals.
The Agency had proposed copper and zinc as regulated constituents
only for the copper cyanide (P029) and zinc cyanide (PI21) wastes. The
Agency is not promulgating treatment standards for copper and zinc. For
the P029 and P121 waste codes, copper and zinc, as the primary metal
constituents, may be present in very high concentrations (up to
55 percent in the pure compound wastes). EPA has determined that these
wastes are aquatic toxins and considered adding them to Appendix VIII for
that reason. The Agency does not, however, consider these metals to be
as hazardous in a land disposal environment as they are in an aquatic
2363g
8-3
-------
environment and has not included them on Appendix VIII. Thus, standards
for copper and zinc have not been promulgated for P029 and P121,
respectively.
8.5 Promulgated Treatment Standards
Treatment standards for cyanide in the P-code wastes listed in
Table 8-1 are based on electrolytic oxidation followed by alkaline
chlorination for the nonwastewaters and on alkaline chlorination for the
wastewaters. Treatment standards for these wastes were transferred from
the performance of the BDAT for the F011 and F012 waste codes generated
from metal heat treating operations. These discarded commercial chemical
products do not contain high concentrations of iron, and therefore the
Agency believes that the treatment standards need not reflect
difficulties of treating complex cyanides. The Agency is thus
promulgating these concentration-based treatment standards because of the
similarity of these P-code wastes to the listed metal heat treating
wastes.
Treatment standards for nickel in P074 and silver in P099 and P104
nonwastewaters are based on the performance of stabilization of F006
nonwastewaters. Treatment standards for nickel in P074 wastewaters are
based on the performance of chemical precipitation and filtration of K062
wastewaters. The Agency believes that these wastes are more difficult to
treat than the corresponding P wastes based on the higher concentrations
of metals and dissolved solids anticipated to be present in F006 and K062
as compared to the P wastes (i.e., up to 100,000 ppm).
2363g
8-4
-------
All wastewater and nonwastewater residuals from treatment of these
wastes must meet the wastewater and nonwastewater standards presented in
Table 8-2 for the constituents listed in Table 8-1.
2363g
8-5
-------
239 Dg
I*ble B-l P Waste Codes Proposed for Regulation
Wait*
ChMical eo^ound
Regulated constituents
P013
P021
P029
PO30
P063
P074
POM
P099
PI04
P106
P121
tariia cyenide
Cdlcius cyanide
Copper cyanide
Cyanides (soluble cyanide
salts). H.O.S.
Hydrocyanic acid, hydrogen
cyanide
Nick.el Cyanide
Potassiw cyanide
Potassiw silver cyanide
Silver cyanide
Sodtia cyanide
Zinc cyanide
Cyanide
Cyanide
Cyan ide
Cyanide
Cyanide
Nickel, cyanide
Cyanide
Silver, cyanide
Silver, cyanide
Cyanide
Cyanide
823909
-------
?390g
Table 8-2 Proposed Treataent Standards for P-Code Cyanide Wastes
Constituent Wastewater Nonwastawter
Total Total
co^KHltion covosttion TCLP
(¦9/1) ("9/kg) ("9/1)
Cyanide la—jlable) 0.10 9.1 NA
Cyanide (total) 1.9 110 NA
Nickel (P074 only) 0.44 NA 0 32
Silver (P099 and P104 only) NS NA 0.07?
HA = Not applicable.
NS - No treatment standard.
8-7
-------
-------
9. REFERENCES
Ackerman, D.G., McGaughey, J.F., and Wagoner, O.E. 1983. At sea
incineration of PCB-containing wastes on board the M/T Vulcanus.
600/7-83-024. Washington, D.C.: U.S. Environmental Protection Agency.
AES. 1981. American Electroplaters' Society. Electroplating wastewater
sludge characterization. Prepared for U.S. Environmental Protection
Agency Industrial Environmental Research Laboratory, Cincinnati, Ohio.
Prepared by American Electroplaters' Society, Inc., Winter Park, Fla.
EPA-600/2-81-064. NTIS PB81-190928.
Ajax Floor Products Corp. n.d. Product literature: technical data
sheets. Hazardous Waste Disposal System. P.O. Box 161, Great Meadows,
N.J. 07838.
Aldrich, J.R. 1985. Effects of pH and proportioning of ferrous and
sulfide reduction chemicals on electroplating waste treatment sludge
production. In Proceeding of the 39th Purdue Industrial Waste
Conference. May 8-10, 1984. Stoneham, Mass.: Butterworth Publishers.
Anonymous. 1985. Feature report. Wastewater treatment. Chemical
Engineering 92(18):71 -72.
APHA, AWWA, and WPCF. 1985. American Public Health Association,
American Water Works Association, and Water Pollution Control
Federation. Standard methods for the examination of water and
wastewater. 16th ed. Washington, O.C.: American Public Health
Association.
Austin, G„T. 1984. Shreve's chemical process industries. 5th ed.
New York: McGraw-Hill Book Co.
*
Bishop, P.L., Ransom, S.B., and Grass, D.L. 1983. Fixation mechanisms
in solidification/stabilization of inorganic hazardous wastes. In
Proceedings of the 38th Industrial Waste Conference. May 10-12, 1983,
at Purdue University, West Lafayette, Ind.
Bonner, T.A., et al. 1981. Engineering handbook for hazardous waste
incineration. Prepared by Monsanto Research Corporation for U.S.
Environmental Protection Agency. PB81-248163.
Center for Metals Production. 1985. Electric arc furnace dust--
disposal. recycle and recovery. Pittsburgh, Pa.
Cherry, K.F. 1982. Plating waste treatment. Michigan: Ann Arbor
Science Publishers, Inc.
9-1
2364g
-------
Conner, J.R. 1986. Fixation and solidification of wastes. Chem.
Eng.. Nov. 10, 1986.
Crain, R.W. 1981. Solids removal and concentration. In Third
Conference on Advanced Pollution Control for the Metal Finishing
Industry, pp. 56-62. Cincinnati, Ohio: U.S. Environmental Protection
Agency.
Cullinane, M.J., Jr., Jones, L.W., and Malone, P.G. 1986. Handbook for
stabilization/solidification of hazardous waste. U.S. Army Engineers.
Cincinnati, Ohio: U.S. Environmental Protection Agency.
Cushnie, G.C. 1985. Electroplating wastewater pollution control
technology. Park Ridge, N.J.: Noyes Publications, p. 205.
CyanoKEM. 1987. Public comment submitted in response to EPA proposed
California disposal restriction levels, August 12, 1987. EPA RCRA
Docket No. F-87-LDR6-FFFFF. Washington, D.C.: U.S. Environmental
Protection Agency.
CyanoKEM. 1988. Submission of data on characterization and treatment of
oily cyanide wastes, August 29, 1988. Washington, D.C.: U.S.
Environmental Protection Agency.
CyanoKEM. 1989. Public comment submitted in response to EPA proposed
land disposal restrictions for Second Third Scheduled Wastes,
January 11, 1989. EPA RCRA Docket No. F-89-LD10-FFFFP.
Washington, D.C.: U.S. Environmental Protection Agency.
Dietrich, M.J., Randall, T.L., and Canney, P.J. 1985. Wet air oxidation
of hazardous organics in wastewater. Environmental Progress 4:171-197.
Duby, P. 1980. Extractive metallurgy. In Kirk-Othmer encyclopedia of
chemical technology. 34th ed. Vol. 9, p. 741. New York: John Wiley
and Sons.
Easton, J.K. 1967. Electrolytic decomposition of concentrated cyanide
plating wastes. J. Water Poll. Contr. Fed. 39(10):1621-1626.
Eckenfelder, W., Jr., Patoczka, J., and Watkins, A. 1985. Wastewater
treatment. Chem. Eng.. September 2, 1985.
Electric Power Research Institute. 1980. FDG sludoe disposal, manual.
2nd ed. Prepared by Michael Baker, Jr., Inc. EPRI CS-1515 Project
1685-1. Palo Alto, Calif.: Electric Power Research Institute.
9-2
?364g
-------
Environ. 1985. Characterization of waste streams listed in 40 CFR
Section 261, waste profiles, Vols. I and II. Prepared for Waste
Identification Branch, Characterization and Assessment Division, Office
of Solid Waste, U.S. Environmental Protection Agency.
Washington, D.C.: U.S. Environmental Protection Agency.
Gurnham, C.F. 1985. Principles of industrial waste treatment.
New York: John Wiley and Sons.
Gurol, M.D., and Holden, T.E. 1988. The effect of copper and iron
complexation on removal of cyanide by ozone. Ind. Ena Chem. Res.
27(7): 1 157-1162.
Inco. 1989. Public comment submitted in response to EPA proposed land
disposal restrictions for Second Third Scheduled Wastes, January 11,
1989. EPA RCRA Docket No. F-89-LD10-FFFFP. Washington, D.C.: U.S.
Environmental Protection Agency.
Kirk-Othmer. 1980. Encyclopedia of chemical technology. 3rd ed.,
Vol. 10. New York: John Wiley and Sons.
Lanouette, K.H. 1977. Heavy metals removal. Chem. Eng.. October 17,
1977, pp. 73-80.
Lloyd, T. 1980. Zinc compounds. In Kirk-Othmer encyclopedia of
chemical technology. 3rd ed. Vol. 24, p. 824. New York: John Wiley
and Sons.
Maczek, H., and Kola, R. 1980. Recovery of zinc and lead from
electric furnace steelmaking dust at Berzelius. Journal of Metals
32:53-58.
Malone, P.G., Jones, L.W., and Burkes, J.P. Application of
solidification/stabilization technology to electroplating wastes.
Office of Water and Waste Management. SW-873. Washington, D.C.: U.S.
Environmental Protection Agency.
McGraw-Hill. 1982. Encyclopedia of science and technology. Vol. 3,
p. 825. New York: McGraw-Hill Book Co.
Metcalf & Eddy, Inc. 1986. Briefing: Technologies applicable to
hazardous waste. Prepared for U.S. Environmental Protection Agency,
Hazardous Waste Engineering Laboratory. Cincinnati, Ohio: U.S.
Environmental Protection Agency.
Mishuck, E., Taylor, D.R., Telles, R., and Lubowitz, H. 1984.
Encapsulation/fixation (E/Fl mechanisms. Report no.
DRXTH-TE-CR-84298. Prepared by S-Cubed under Contract no.
DAAK11-81-C-0164.
9-3
2364g
-------
Mitre Corp. 1983. Guidance manual for hazardous waste incinerator
permits. NTIS PB84-]00577.
Moller, J.J., and Christiansen Q.B. 1984. Dry scrubbing of hazardous
waste incinerator flue gas by spray dryer absorption. In Proceedinas
of the 77th Annual APCA Meeting.
MRI. 1987. Midwest Research Institute. Analytical data report for six
facilities included in the electroplating sampling and analysis
program. Draft final report for Office of Solid Waste, Contract
no. 68-01-7287. Washington, O.C.: U.S. Environmental Protection
Agency.
NAMF. 1989. Public comment submitted in response to EPA proposed
land disposal restrictions for Second Third Scheduled Wastes,
January 11, 1989. EPA RCRA Docket No. F-89-LD10-FFFFP.
Washington, D.C.: U.S. Environmental Protection Agency.
Novak, R.G., Troxler, W.L., and Dehnke, T.H. 1984. Recovering energy
from hazardous waste incineration. Chem. Eno. Proa. 91:146.
Nutt, S.G., and Zaidi, S.A. 1983. Treatment of cyanide-containing
wastewaters by the copper-catalyzed SOj/air oxidation process. In
Proceedings of the 38th Industrial Waste Conference. May 10-12, 1983,
Purdue University, West Lafayette, Ind. Boston: Butterworth
Publishers.
Oppelt, E.T. 1987. Incineration of hazardous waste. JAPCA. Vol. 37,
No. 5 (May 1987).
Patterson, J.W. 1985. Industrial wastewater treatment technology.
2nd ed. Boston: Butterworth Publishers.
Pearson, G.J., and Karrs, S.R. 1984. Electrolytic cyanide destruction.
In Proceedings for Plating and Surface Finishing, pp. 2 and 3.
Perry, R.H., and Chilton, C.H. 1973. Chemical engineers' handbook.
5th ed., pp. 19-57 and Section 19. New York: McGraw-Hill Book Co.
Pojasek, R.B. 1979. Sol id-waste disposal: Solidification. Chem. Eno.
86(17):141-145.
Price, L. 1986. Tensions mount in EAF dust bowl. Metal Producing.
February 1986.
Randall, T.L. 1981. Wet oxidation of toxic and hazardous compounds.
Zimpro technical bulletin 1-610. Presented at the 13th Mid-Atlantic
Industrial Waste Conference, June 29-30, 1981, University of Delaware,
Newark, Del.
9-4
?364g
-------
Robey, H.L. 1983. AES Research Project 53A: Cyanide destruction r a
coroerc i al - seal e hydrolysis reactor. PI at. and Surf. f7 i n . 7C: "?9 - 82
Roy, C.H. 1981. Electrolytic wastewater treatment. In a series of
American Electroplaters' Society, Inc., illustrated lectures, pp 8-13
Rudolfs, W. 1953. Industrial wastes: their disposal and treatment.
Valley Stream, N.Y.: L.E.C. Publishers Inc.
Santoleri. J.J. 1983. Energy recovery--a by-product of hazardous waste
incineration systems. In Proceedings of the 15th Mid-Atlantic
Industrial Waste Conference on Toxic and Hazardous Waste.
Schroeter, J., and Painter, C. (n.d.) Potassium permanganate oxidation
of electroless plating wastewater. Carus Chemical Company, 1001 Boyce
Memorial Drive. P.O. Box 1500, Ottawa, 111. 61350.
Shucosky, A.C. 1988. Feature report. Filtration. Chem. Eng.
January 18, 1988.
USEPA. 1980. U.S. Environmental Protection Agency. U.S. Army Engineer
Waterways Experiment Station. Guide to the disposal of chemically
stabilized and solidified waste. Prepared for P~3L/0RD under
Interagency Agreement No. EPA-1AG-D4-0569. PB ; 181 505. Cincinnati,
Ohio.
USEPA. 1980. U.S. Environmental Protection Agenc . Office of Solid
Waste. RCRA listing Dackground document. Washngton, D.C.: U.S.
Environmental Protection Agency.
USEPA. 1981. U.S. Environmental Protection Agency. Engineering
handbook on hazardous waste incineration. SW-889, NTIS PB81 - 248163.
USEPA. 1983. U.S. Environmental Protection Agenc... Office of Water.
Development document for effluent limitations guidelines and standards
for the metal finishing point source category, -.ashington, D.C.: U.S\
Environmental Protection Agency.
USEPA. 1985. U.S. Environmental Protection Agenc.-. Office of Research
and Development. Facility test report for Front er Chemical Waste
Process, Inc., Niagara Falls, New York. Prelirrr-ary draft, November
1985. Cincinnati, Ohio: U.S. Environmental Protection Agency.
USEPA. 1986a. U.S. Environmental Protection Agency, Office of Solid
Waste. Onsite engineering report of treatment technology performance
and operation for Envirite Corporation, York, Pennsylvania.
Washington, D.C.: U.S. Environmental Protection Agency.
USEPA. 1986b. Best demonstrated available technology (BOAT) background
document for F001-F005 spent solvents, Vol. 1, EPA/530-SW-056.
9-5
-------
USEPA. 1987. U.S. Environmental Protection Agency, Office of Sc'-J
Waste. Generic quality assurance project plan for land cisposa'
restrictions program '/'BDAT"). Washington, D.C.: U.S. Environment'
Protection Agency.
USEPA. 1988a. U.S. Environmental Protection Agency. Office of Solid
Waste. Best demonstrated available technology (BDAT) background
document for F006. EPA '530 -SW- 031L. Washington, D.C.: U.S.
Environmental Protection Agency.
USEPA. 1988b. U.S. Environmental Protection Agency, Office of Solid
Waste. Best demonstrated available technology (BDAT) background
document for K062. EPA/530 -SW-88 - 031E- Washington, D.C.: U.S.
Environmental Protection Agency.
USEPA. 1988c. U.S. Environmental Protection Agency, Office of Solid
Waste. Treatment technology background document. Washington, D.C.:
U.S. Environmental Protection Agency.
USEPA. 1988d. U.S. Environmental Protection Agency, Office of Solid
Waste. Methodology for developing BDAT treatment standards.
Washington, D.C.: U.S. Environmental Protection Agency.
USEPA. 1988e. U.S. Environmental Protection Age j, Office of Solid
Waste. Onsite eng-ineering report of treatment chnology performance
and operation for Woodward Governor Corporation Rockford, Illinois.
Washington, D.C.: U.S. Environmental Protectio- Agency.
USEPA. 1988f. U.S. Environmental Protection Agency, Office of Solid
Waste. Onsite engineering report of treatment technology performance
and operation for wet air oxidation of F007 at Zimpro/Passavant, Inc.,
in Rothschild, Wisconsin. Washington, D.C.: U.S. Environmental
Protection Agency.
USEPA. 1988g. U.S. Environmental Protection Ager:y, Office of Research
and Development. Draft report: Short term lab: atory test methods for
evaluating solidified/stabilized waste materials: a cooperative
program. Cincinnati, Ohio: U.S. Environmental Protection Agency,
UTC Pratt & Whitney. 1989. Public comment submitted in response to EPA
proposed land disposal restrictions for Second ihird Scheduled Wastes,
January 11, 1989. EPA RCRA Docket No. F-89-LD1C-FFFFP. Washington,
D.C.: U.S. Environmental Protection Agency.
Vogel. G., et al. 1983. Composition of hazardous waste streams
currently incinerated. Mitre Corp. U.S. Environmental Protection
Agency.
9-6
Z364g
-------
Vogel, G., et al. 1986. Incineration and cement k-ln capacity for
hazardous waste treatment. In Proceedings of the 12th Arrua1 Reseat
Symposium on Inc;nerat'on and Treatment of Hazaroous Wastes. Apr;¦
1986, Cincinnati. Ohio.
Versar Inc. 1986. 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. Draft
report prepared under Contract no. 68-01-7053 for U.S. Environmental
Protection Agency, Office of Solid Waste. Washington, D.C.: U.S.
Environmental Protection Agency.
Weast, R.C., ed. 1978. Handbook of chemistry and physics. 58th ed.
Cleveland, Ohio: CRC Press.
-------
APPENDIX A
ANALYTICAL METHODS AND QA/QC
This appendix presents analytical methods and the matrix sp-ke
recovery data fcr the treated waste samples from testing of r 00 7. F01'.
and F012 wastes.
A-1
-------
A-2
-------
* Z "'ZZZZjr** Z' iZ*~Z~"i~'.
-at *es 7' izm•»d"«^is i
* 2-S 6
mefca *«iQwo:
- *e 3' scu *d e".
d ' 0»e2 Oy S«*s4S "^ef"DC5
:;e- :•- • * cs i-ea^e"
ce -e^w•rfcg
M-3
-------
Z338g/p.
Table A-3 Hatri* Spike Recoveries for Cyanide - Plant A
Constltuent
Original
mount
delected
t^/U
Amount
sp tked
1*5/1)
Spike
Amount
recovered Percent
l(jfl/l) r*CO*erya
Duphcate scike'
•mount
recovered Percent
M/l) recovery*
X« -dt
pe'cen;
3'f *ere->ce"
Sdiiyle W6S4-1Q1
Cyanide, cnlorinated 114.000 160.000 279.000 103 274.000 100
Cyanide, total 103.000 160.000 243.000 80 252,000 93
: a
3 5
Sanple WGSB-101
Cyanide, chlorinated '10
Cyanide, total <10
200
200
140
<10
70
0.0C
120
<10
60
0.0C
15
NC
Sample WGSS-101
Cyanide, chlorinated*1 79.5 71.1 110 43
Cyanide, total0 99 4 69.3 170 102
Cyanide. TCLP 854 1000 1820 97
173
1990
10B
114
1.0
8.9
Sarnie W6S9-101
Cyanide, chlorinated*^ 29.1 30.7 59.5 99
Cyanide. totald 34.7 7.99 42.1 93
Cyanide, TCLP 4Q 8 200 225 92
44,0
222
116
91
23
1.3
NC » Not calculable.
- = No analysis performed.
dPercent recovery = 100 (Cj - CQ) / Cj. where C| is the anount recovered. CQ is the original aisunt detected
Relative percent difference - | 100 I0j - D^) / [0| ~ Dj) / 2] |, where Dj and 0^ are the percent
recoveries of the spike and duplicate spike.
'"Zero percent recovery is attributed to matru interference.
dllnits for solids san*>le concentrations are aq/kg.
eAirciunt spiked for the matrix duplicate spike ms 68.1 nq/kg.
^Amount spiked for Mtrtii spike duplicate was 7.96 mg/kg.
A-4
-------
ue*. ~?r.
Ct'_ . '.-la ' sT.t'aL t;
..
-------
A l?r":*.
'~€ r *
~e:e .-.a-. • •
«'s.Ty:n -•".'ate .Ta* :e
. f -e: d-e c^ese^t
• - •: - s*: -«¦-
¦"?! *®i*.->er *:
¦e:«ssr - •*'
* j- c c T.d,
f tes - testes o^e 2'ese"
ci»- ) -.:c"ne- c ecw^d er:
A L.Dfew ' "ZM^-Z '»O'^e* t" :w • :»L "6 r'0f 'te'.-rtn8r»f, - ^d--C*, a'.J .C*n»- y:-fc
m c.~.x « .: r- 0! . D-C" ce-i d- i a rge •- :oec * c l\ *¦*¦' -'¦?•
A-fe
-------
?338g/p
Table A 6 Hitni Sp ike/Mat r\x Spike Duplicate Results 'or Cyanide p;ant 9
Sample
Sp ike
Sp ike
Samp- le
cone
added
resuIt
Spike dup icate
numbc*
!(»q/ 0
!*S'"')
(«g/ U
I Reco»ery
resj 11 '')
X Hit.. *' »
»^ _
01-03
16 11
24 75
?9 16
52,7
28 97
5? 0
-
01-03 1 Treated waste sample, Sample Set Sc 3
RPD . 100 [spike result - spike dupl.L-l* l)/i5Plke rESU U * SPllie duP1,Cdte reSuU)
2
A-7
-------
Z338g/p
table A-7 Analytical ttethods - Plant C
Treated aaste Analytical method Method nunber Reference
Treated norwastevater
Treated aasteaater
Cyanides (total and
amenable)
Metals (EP toxicity)
Cyanides (total and
amenable)
9012 1
1310 1
901? 1
1. U5EPA. 1986. U.S. Environmental Protection Agency, Office of Solid
Waste. Test method for evaluating solid waste. 3rd cd. Washington.
D.C.: U.S. Environmental Protection Agency.
A-8
-------
2338g/p 1
Table A-8 Nairn Spike/H»tru Spike Duplicate Results Tor Total
Cyanide Untreated F006 Nomasteaater
Spike
Sanple
Sp ike
Spike
dup 1 icate
result
added
result
Percent
result
Percent
Iptw)
(ug)
(ug)
recovery
(ug!
recover
120
30
144.0
80
139.0
63
4?
30
75 B
96
71.3
81
13
30
27 .4
48
37.6
82
3.7
30
33 7
100
32.5
96
0 40
30
26 2
86
29.2
96
S3
30
81.2
94
77.6
82
270
30
298.0
93
299.0
97
270
30
3M. 0
113
305 0
116
160
30
197.6
92
192.7
109
230
30
261 8
106
264 5
IIS
410
30
433.7
79
437.3
91
Percent recovery = [(spike result-original a*»unt )/spike adde^] x 100.
A-S
-------
2336g/p
Idbie A-y Malm Spike Results for lota) Cyanide
in Aqueous Effluent - Plant C
Spike
dJTOunt
(pprn)
Spike
recovery
IPP"!
Percent
recovery
?.0 1 88 94
2.0 1.94 97
2 0 1.93 96 S
2.0 1.9 9b
2 0 19 95
A-10
-------
APPENDIX B
SUMMARY OP WASTE COMPOSITION DATA
B-l
-------
i M4q
Idlile B I IOOIi W.istc (un)Hjsi| toil |)j1j
Constituent/ Concentration Isomer)
parameter (units) (I) (?) (3) (4) (5) (b) (/) (8)a (8)a
No ol data points
¦ith cyanide
11
2
6
17
100
6
6
BOAI
Inorganics Other lhan Metals (aq/kq)
169
Cyanide (total)
<0 1-506
84 1 226
<1
0 1 5 B
<0 075 1.9/0
554 859
1.800 ?,8b0
169
Cyaniile (amenable)
<0 10 0 72
<1 153
<7
0 1
0 003 167
I/O
1 luuride
768
BDAI Mvtals (mi/ka)
154.
Ant imuny
-
-
<10
77 4
771 339
<6 2
155
Arsen ic
-
2-5
<0 4
<6 74
0 353 0 19/
0 48 0/6
156.
Bar iin
0.74-85 5
-
20 45
7B 8
9 5/
35 8 54 0
6.39-7.92
15/
Beryl 1 iin
-
<7
<0 1
<97 6
<0 19
<0 05
158
Catfcniim
1.3 720
1.780 4.0/0
10 70
0 37 1 75
<11 1.370
NO 77.000 0 003 1.180
1 63 1 9/
35.500 47.900
159.
lota 1 chrtnim
2-49.000
147 8.610
3.700 75.000
1.650 7.675
35-/30
700 13/.000 <0 007 790.000
677 803
4.790 5.3B0
160.
Copper
1.4 27.400
345-28.100
90 775
1.87-135
<6 760
10.200 13.600
/.I00 8. /00
161.
lead
1 69-74.500
-
85-134
IB4 305
<6 408
<0 001 13.900
9 4 II 3
<6 9? 9 /
16?.
Mercury
-
-
«l
<0 Z
<0 37
-
<0 144 0 616
<0 13/
163.
Nickel
234 23.700
1.330-26.000
7.300 49.000
II B 17
0 06 1/0.000
1.1/0 1.4/0
10.300 17.500
IM
So leu inn
<10
<19 <73
114 16/
<0 16
165.
Si l»er
0.5I-3B 9
-
<2
<0 b <10
-
<1 7h 1 99
<0 8k
166.
lha 1 liin
-
-
<10
<70
<6 0
<1? /
167
Vanadiin
-
-
1 26
-
1 I'j ?.'»
3 t>6 4 44
168.
I inc
8 86-90.200
611-41.200
68 3.700
2.510 3.687
<29 220
9.130 1?.700
4. IbO 5.370
221.
llexavalenl chrmikjo
-
0.14 1 0
0 75 75 4
<0 001 910
-------
? t44g
Idlllu H I (cOflt IIIUL'll)
Constituent/ Concent rat ion (source)
paiaiacter (units) (9)
No. of data points
Kith cyanide 13
BDAI Inorganics Other llun Mill (mq/kq)
169 Cyanide (total) 3./ S60
Iby Cyanide (amenable) < 0?S 6?
I/O I luor ide
BOA I Held Is (mq/kq)
IM
Ant imony
IS5
Arsenic
156
Bar im
IS/.
Berylliui
1 Sfl
Cadniua
159.
lotal chraniin
160
Copper
161.
1 ead
16?
Mercury
163
N icke 1
lt«.
Sir Ilii ii*o
165
SiIver
166
lha11iua
16/
Vanadiim
I6fl
I int
??l
Hexavalent chroni
Other Paraiieters
Oil and grease |ag/g)
Moisture (X)
SP gravity (g/nl)
Acidity as CaCflj (og/1)
Sulfidc (mq/kg)
lota I organic
caiUin (mj/ky)
-------
Idh Ic I) I (conl inui'il)
Const ituent/
parameter (units)
(I)
(?)
Concentration (source)
(3)
(<)
(*»)
(«.)
(/)
(Al-
ter
Other Parameters
Iron (ray/kg)
Oil am) qrease (my/q)
Moisture (X)
SP gravity (q/*il)
Acidity .1', Cal.Oj (mq/l)
Su II i
-------
Idl' Ii* B-? F007 Waste Ccnvosition Oala
Constituent/parameter (units)
Hi
Concent rat ion (source)
(?)
ID
HI
BOA! Inorqan ics Other Than Hetah (nq/ )
Cyanide (aacnable! C8I
Cyanide (iron)* CB1
Cyanide (total) CB1
Fluoride CBI
BOAT Hetals (ng/1)
Cattimi CBI
Chrtjniun (total) CB I
Chraniun (hesatalent) CB[
Copper TBI
Nickel CBI
Zinc CBI
Npn-BDAf Metab |ng/ 1)
Calciu* CBI
ir0n CBI
Nagresiun CBI
Manganese CBI
SOdiun CBI
B3A1 Volat i les (mq/1)
Methanol CBI
4,000-67.000
170
41.000
2.000 - lb.300
ti 30C r joc
i soc
40C
7.000-8,000
Other Parameters
Carbonate (mg/1)
Total solids (1)
Ash (X)
Total suspended solids (nig/I)
Suspended ash tnq/1)
Chanical oxygen denund (mg/ 1)
ph
Specific gra* ity
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
4 Cyanide (iron) is interpreted as a nca^urement of cyanide not aaenable to c lorination.
- = Hot analyzed.
B-5
-------
lable B-?
(continued)
Concentration (source;
CofislHuent/paranKler (units) (6! (6) (6) t&)
90AT Inorganics Ot'wr Than Wetals (••»• .i
Cyanide (amenable) 64,700 5,'00 75.600 73,700
Cyanide (iron)a
Cyanide (total) 66.900 8.010 r 7.600 30.7D0 «1 ^OC
fluoriQe
BOAT Helals (mq/1)
i
Chranun (total)
Chraniun (hemvalenl)
Copper
H icie I
I inc
Kon-BOAT Hetals (nq/1)
Ci 1c inn
: ron
Nagnesinn
Hanganese
Sod i jti
9DAT Volatiles [ma/ I)
1,1 -D 'Ch lorocthane
Aetharuil
Hethylene chloride
To(bene
1.1,1-lricHloroelhane
Ot^er Parameters
Carbonate (irq/ I)
Total solids (1)
Ash («)
Total suspended solids (og/1)
Suspended ash (rag/ I)
Chonical oxygen donand (og/1)
pH
Spec ific gravity
1L.300
10,600
1. 3b0
:jo
.'30
2.BB0
303
-.5.700
19.S10
7,683
4, 736
440
1.740
' ioa
498
470
-------
Table B-3 f008 Waste Cai^osit'cn Oata
Constituent/parameter (units)
Concentration iiOu-cel
(I) 12) (2)
BOOT Inoraanics Other Than Hetals (nq/hq)
Cyanide (amenable) 11.TOO 21.700 3>.?00
Cyan ids (total) 64 11.900 26.600 3«.90C $0.3C0£.; :r
B0«T Xetals (mq/hq)
Cadniun
Chranm* (beiana'ent)
Copper
. ead
N icke 1
line
BOAT Volatile* (wn/fca)
Methylene chloride - <1.20 <0 008 14.4
13.000 <0C
300
21.600
150-ZOO
300
13.100
- • Not analyzed.
Defertnces:
(1) USEPA 1980
(Z) MRt 1987
(3) CyanoWH 1987.
B-7
-------
Table 8-« P009 Waste Coros'Iion Dan
Conctnlrat on 'source;
Const ituent/paramter (units) (1) (2) (2) !3l
BOAT Inorganics Other Than Beta Is (n^/ 1)
Cyanide (amenable! - S2.000-90.000 - 52 900
Cyanide (iron)4 - - 100
Cyanide (total) 350.000 - 40.000 4.000-8 300 64.60C 5
BOA' Met. Is (iwg/n
Cfl^' - —
Chromiun (total) - - - - <:CC
Chromium (beidvalent) - - - ...
Copper - 19.000 - ¦ - 1.500
Lead - - - - -
Nickel - 5.100-5.500 - - 7.310
Z inc - .... 58Q
Won-BOAT wenls
-------
IdDie 6-4 icont iriued)
Corcentrat'3n lioi-cf'
Constituent/parameter [units) (4) [4) (4) (S)
BDAI Inorqdnics Other Ihdn Held Is (n*)/li
Cyanide (amenable)
Cyanide (iron)4
Cyanide (total)
POT Mftals (n^/l)
CdOniun
Chrcniun (he»avalenl)
Copper
Lead
Nickel
I inc
Hon-BOAT Hetals (mg/1)
Iron - - 3,320
- = Not ana lyzed
d Cyan iOC (iron) is interpreted as d ni'.isurt9im.'nt of cyanide not aoenable to cr rination
b A mixture of F009 (zinc plating «aste) and a aaste hypothlor11« solution.
References:
(1) USEPA 1980
(2) Versar 1988.
(j) Patterson and Hinear 1973
(4) Wl 1987,
(5) CyanoKEM 1987,
135,000 14.400 47,400
lib.000 14.500 52.5D0 27.200 <0,000-45,00C j0 00:
3ttb - 200 -
* 100
6,990 - 270 -
200
7.510 1,050 12.000-15.000
3.070 - 19,250
B-9
-------
Tab le B-S F010 Waste Canxis 11 > on Data
Concentration [^ource|
Constltuent/pararaeter [units) (1) [2)
BOAT Inoroanics Other Than Wetals {mq/kg)
Cyanide (total) B.&30 22.000
Other Pararetcs
Heat content (Btu/lb) - b.000
water (I! - NO
Oi 1 and grease - »5 *
- - Not analysed.
NO ¦ Not detected
' Data submitted to the Agency did not report an oil and grease concentra
can^osition data represent a waste that us incinerated, and Cyanofc£N >
oil and grease concentration of at least S percent in order to be inciri
.n. However, these Mste
cated that a vast* nhst have
ited.
References:
(1) USEPA 1980.
(2) CyanoKEA 1988
3-10
-------
Tdble 3-6 c 011 Waste Conpos il ion Data
Constituent/parameter (units)
11)
Conce.itrjl inn (source)
(2)
(?)
HDS I
'¦ncroamcs Other Than Me'als ; mo /'')
Cyanide lancnaDie)
Cyanide (total)
FIjgride
1
S.3S0d
5 SS
34.OOC-35.OOC
10.000-12.000 - 35.000-90 200
BDftT Metals !mq/l)
AnL imony
0 029
-
Bar lufl
1.0
-
-
CactniL»n
0 0!
-
<100
Chroroiun (hexavalent)
<0.01
1.000-
:. soo
Chraniutn (lota 1)
5 42
-
-
Copper
I 03
-
Lead
1 i
CT>
o
o
1,000
N icne>
2 88
-
300
S i l»er
0 007?
-
-
Vanad i ufli
0 156
-
-
Z inc
0 338
-
-
Ncn-30A' Helals (n*)/l)
[ron
27.B
-
-
Potasslun
18.S00
-
-
Sod i jn
32,230
hon-30AT Inorganics Other rhan Metals |inq/l)
CarDonate
Chloride
Sulfate
Other Parameters
Total solids (X)
Total suspended solids (X!
Chemical oiygen denano (mq/
Total organic carbon (mg/1)
Oi 1 and grease (mg/ 1)
t)
87.000
21.300
90. 5
19.7
3.84
7.140
19.500
11 0
! - Analytical interference Analysis of partially treated sample indic.es that this
«alue ls <5120 mg/1.
- * Not analyzed.
0 The concent-jtion of total cyanide -eferred to here is based on testing of a aastc that had been
dissolved in aqueous solution for electrolytic treatment. The concentration of tola! cyanide in the
solid waste IrealeC «as appro* imale I y 90.0C0 irrjAq, and the concentration of amenable cyanide »as
-------
Tabie B-7 F0'.? waste Cofflpos >t ion Oata
Concen'.rat ior jba>.r:fl
Const itueni/oarametcr (units', ;i) {?) |?1
HHM I rcrp.ir ¦ ls O'.rrr Ihm Mrtnis Tq/kgl
Cyamae (total)
F luoride
9DAT Net ah (mq/kq)
Bar
-------
fab !e B¦7 (cont inued)
Concentration (vOurcci
Const it'jen'./parameter (units) (1! (2J (J) , i
Other Parameters
local solids (X)
lotal organic carbon (mg/kg)
Oil and grease (mq/kg)
pH
- - Hoi ana ly/cd
References
(11 JStPA 13BBe
(?) LStPA 1980
(3) environ 1985.
(4) C»ant*[M 1987
60 5
540 - -
432 - -
1C •} 1 1 3
B-13
-------
"ace r-i r:c5 »as:e Cr,ara:*.e--ia*. ion 3aia - lampcs ;e ia-s es
Tcta' -«.a -e
i-rcred:ea «as:e .i"-. ~ea »ds:e
Cms:':,e^:'carjme;er ^g/kg) . .
5 a-:'e S e'. * i
C>ai'fle i 31r.er.dEie)
C jarvae ::td';
54
2 1
1 ? 5 eb3 T ?1 ^
Cya-i3e a-erae'.e!
Cjdn ae ;:::3 i i
32C
0 :
z *:
Sdtic^- Set '3 3?'
¦->dr iae .d-e^i;
Cydnae ;*.ctd )
120
0 29
0 76
sdur ie Se: *-
Lydniae iireiiD e.
Cjarrje ;:c:a';
47
3.55
0 55
Sdr-le Sf. »5 :¦*'
./arise iacenat ie;
Cyarice itcla'.)
13
<0 CZ5
0.64
Same'g Set *5
-yd.-iae ,a-is-.aD ie;
Zydr.'CB [:cCd )
.12
5amo Se'. »? i * 'B*'
Cyanide lameiaa'e)
Cyar, iae (tola j
240
3 46
0.5
B-14
-------
laole 3-5 ico^-t''uec
worst tgent. ?a raster
"cii ' A \d - • "e eiZ'i
urtreatec adste -r:~edte£ «as*
• "s ' 3 < '*3-;
Same ie Set *v li 3^
Cyan.ce i'luc 'e :
Cyarise i tsta ¦ J
3 0 C
Set »U i2/S8j
Cyamae (amenable)
Cyanioe (total;
230
<0.025
3 42
B-15
-------
'aDle 5-5 ;cort'.nuec1
c2-5: ;t^en: sarair.etsr
-ante"*.* a* 21 -r ' -S '
Tsu- 4 «.a'"-e eac-ate
unfea'.ea .aste jnt'eate: -aste
; -ng.- K.g) :
Sa^p'e Set «'.
65'
Cyanioe :am«ra2 e!
C j a" 1 de ;c: a "
433
3 i
2 i
Sa^5 'e St'. * : - - 63 j
„ya.T.ce ; jner.acic;
Cvaniae .tstall
410
c :
0 :
San;'e Set 'I7 !i'58i
C/an'fle ;aTW.able 1
Cyan'ae itsiall
25
0.26
0.31
Sa-S'g Set 'IS -I ^ - g 8 '1
Cyanoe laTenacit!
Z/t-ze (:cta')
S60
1.3
: i
B-16
-------
Table B-9 f006 Waste Characterizat'or Data Sunt it ted by Plant f
Untreated F006 Waste ^
Date of Total A«nable .eacmte
Sailing CM CN Total Awenable
09/09/B2
30.108
0.3B6
0.110
-
12/01/8?
45 753
17.214
0.190
-
03/08/83
18 032
18.032
0.0O9
0.009
06/07/83
3.171
0.272
<0.002
<0 002
09/13/83
1 416
<0.002
<0.002
<0.002
12/19/83
14 985
2.430
<0.002
<0 002
03/22/84
10.469
9.747
<0.002
<0.002
06/26/84
0.249
«0.002
<0.002
<0.002
09/06/84
14 904
14 904
0.050
-
12/10/84
IE 192
16.192
<0 002
<0.002
03/17/85
44.800
30.400
<0.002
<0.002
06/24/85
9 455
<0.002
<0.002
<0.002
09/04/85
40 500
23 400
<0.002
<0.002
12/03/85
2.753
0.741
<0.002
<0.002
03/05/86
7.484
0.151
0.080
<0.002
06/11/86
1.988
1.988
<0.002
<0.002
09/08/86
0.114
0.114
<0.002
<0.002
12/08/86
0.125
0.125
<0.002
<0.002
03/04/8/
9.430
9.438
<0.00"
<0.002
06/10/87
6149
0.427
-------
2745g
Table B-10 F006 Waste Characteri*at ion Data Sutvitled by Plant 6
Untreated FQ06 Waste
Date of
Tota 1
Amenable
3
Leachate
Samp 1i nq
CN
CN
Tota 1
Anenae1e
09/09/62
25.272
3.240
0.005
12/01/82
14 306
2.920
0.040
-
03/10/83
19.136
6.578
0.088
0 065
06/07/83
23 332
16.271
<0.002
-
09/13/83
27 307
4 606
<0.002
-
12/09/83
22.848
0.674
<0.002
<0.002
03/15/84
11.718
7.182
<0.002
N
o
o
o
V
06/20/84
51.840
36.000
<0.002
<0.002
09/10/84
28.797
3.972
<0.002
<0 002
12/13/84
23.596
23.596
0.018
-
03/10/8S
34.797
0.037
<0.002
<0.002
06/04/65
2.841
2.841
<0.002
<0.002
09/03/85
8.876
8.876
<0.002
<0.002
12/03/85
5.989
0.108
<0.002
<0 002
03/11/86
2.106
0.130
<0.002
<0.002
06/10/86
6.495
0.433
<0.00?
<0.002
09/09/86
0.122
<0.002
<0.002
<0.002
12/16/66
3.302
0.034
0.036
0.036
03/17/87
0.249
<0.002
<0.C!2
<0.002
06/16/87
3.190
3.190
<0 ?
<0.002
09/15/87
9.600
2.400
<0 2
<0.002
12/01/87
12.800
72.000
<0 Z
<0.002
03/08/88
19.110
6.468
<0 ,.:-2
-
06/07/88
<0 119
-------
"jo'e :• . -:ce waste Comics ' t ic- -a", a ttes 3y
waste Management, Inc
Tela', cyai^ae Tata! cyamfle Tota- :ya.i'Oe
5in-;'e cci;er--31-3r Sample cor.cent-at ion Saro't concent-a-. 3r
-urroe- ippw; ijmoer (ppm) nunoer (ppml
£.
C
£5'
18
A6
V
£2
V
£38
149
A7
10
[3
c
£3S
0
AB
3
i i
s:
£ JO
n
A9
0
r c
"CC
£41
3
A1C
0
:
£J£
3
AH
3
£7
i
£4 j
937
A12
0
c«
IS
£44
28
a; 3
187
•:;o
6
£45
0
A14
0
Ell
0
E4E
71
A15
9
E12
L
£47
3
A16
9
£12
SS
£43
273
A17
10
£i4
1
E49
0
A16
56
E15
*£
E5G
3
5
18
£1£
£51
0
;
185
£ i 7
j
E52
30
75
£18
0
E53
524
• ">
331
£21
2
£54
0
:3
25
£2?
0
E55
0
3
< ?"
0
E55
3
A25
0
:2i
19
£57
9
A26
3
E25
0
E58
0
A27
0
£25
;a-i
E59
3
A28
0
£2?
£63
27
A23
335
£29
; 73
£51
18
i30
0
E3G
31S
41
0
-jl
739
£32
0
A2
9
-i2
71
£53
214
A3
C
«i3
J5
E34
68
A4
0
-i4
0
£35
18
A5
c
4:5
Q
£36
64
3ata are 'rom a survey co"Oi,ctsa 5y Chencal Waste Management. !nc . a subsidiary of
'Waste Managei^ent. !-ic. 'n lid.1 at t«o Waste Management, inc. sites Data on the
treatment acoi'ea (:f aryj j-iir ts sampling »as not submitted to £5A.
^efere-ce: Waste "anacerer:. !~c .385
32;s^3
B-19
-------
'i e'.e 6-it "Oc .aste Caieosifsr. 'rcr 1366 ^a: o-a : i.rve>
-aiai'CSJS waste Gene'itars
~3ta> ;yar:se
£ -A ;3 >c wj s i e ceae(j| :sn:e-trjt 'C icon)
NC2
065
o
o
<•->
579
F 306
0
nco
065
300
579
F336
3K
NCO
C-65
33C
573
rC05
0>i
NCC
C"» 4
466
257
•3C6. F3C7.'F008/F009
?;
NCO
04:
166
257
F 306
71
*3
:ce
090
•,8^
'006
< \
:c6
C9C
13?
FC05/fCC8
>
,Aj
OS?
824
450
PC06/C0C'2''CC38
0
"N3
03 J
318
732
F336
3
-so
960
559
' * L
fC0E,"307
0
-N3
980
559
702
- 3C?
o
7X3
04;
126
C92
F 006
0
pa:
002
05C
546
FC05
NA
PAC
0C3
053
845
F3C6/CCC2
o*
PAD
003
050
848
FC06
3
"O
067
441
3S4
" COS
NA
NCC
003
229
358
c 006
OH
L>
1.
o
OOi
453
3'5
f 006
0
OhC
COS
052
493
;C0£
;6
ORC
365
435
16 C
FCC6
0
0*0
030
725
:32
F006
0
PAO
.OO
6CC
680
:CC6/OCOo/3007
.0
PAD
121
331
f 006
2
u;d
CO:
095
152
F006
95
HID
006
409
367
f006
0
Mtc
006
407
55?
F0C6/F019
0
Htc
006
024
639
F 006
c<
HAD
C01
034
0'. 6
r006
50C
K.3D
CCS
325
313
f006
33
HTC
006
362
M?
"0C6
0*
MAD
M 1
Vwl
014
026
"006
0
-------
i 796g
'j]"e 6-.2 ;:an: -.r.-jeoi
• c:i :.jn:e
•PA "3 No xdste ccceis'. csncert-j; IP ;
a:*
C50
010
536
'"006
0
aid
098
04 6
857
•006
I*
AID
C73
S6C
234
r006
DS
:ao
009
153
932
"006
0
cad
C4?
7B4
87!
•006
0
PRO
090
519
7 52
'006
0
NTD
002
113
975
r 006
i
STD
002
204
543
roc6/:oj6/coo7;Dooe
'1.000
NT 0
DC?
204
543
*306.0003
oo.occ
j^O
053
CCD
765
; 006
*!C
* 7'
553
750
=¦006
K,
«;D
009
305
565
•205-3002/0007
;
MIC
009
•05
6:5
"006
V
^: d
009
305
665
-006
c
'SO
:C5
421
143
"006;F0CB/F0O9
10.000
PSO
09C
592
544
"006
350
=R0
090
5S2
544
"006
0*
NCC
067
203
752
~006/F007
233
NCO
067
2C3
7 52
"006
0
3RD
993
650
703
"006
0
5 AD
002
327
7 08
r 006
1
PAO
COJ
2J6
085
" 006,'" 006
p
3 AD
CC3
346
086
r006/^006
:
PAD
003
006
798
-006
1
:ND
C67
879
1C6
•306
£
;nd
067
875
106
' 006
5
1 ND
005
932
305
•006
1
:sC
DCs
932
335
"006
D*
a :o
009
300
050
"006
;
;at
200
on
187
?006
u
~.d
304
U7
077
•006/0008
P
nhD
001
079
04 5
"006
hi
nho
CGI
os;
073
f006/0006/C007/C008
?
NTD
CIO
783
967
•006
NrD
002
217
834
"006/FOC6
0
Nrc
002
217
834
r006
0*.
NTO
000
813
394
r006
17
"AD
osa
445
313
F0C6
0
PAD
058
445
313
¦006
24
PAD
990
'52
095
f0C6/"006.'f 009/0008
-¦. 555
PAC
993
7 52
099
"006/-006
•..000
PAC
990
152
039
"006/-00S/D002
0
'RD
090
363
850
r006
1
PRC
991
291
857
-006
0
no
oo;
477
773
"006
<0
3-21
-------
ac e 3-.i (:sn: iiuea]
E'A 13 Ns
Waste :;ae(s!
3*.d Cydr 3e
C3'Ce-'."3: 'or .;;ir
h;: :os
' * 7
? ?3
¦006
^ 0
x:d :c;
4*7
?T1
C006
<0
MAC 3/1
.'05
222
¦036
c
PA! 033
324
205
: 006
*
one 094
029
063
P0C6
ICO
kIC 300
>91
06.
•306
0
"SO 333
37a
665
"306.-319/'330
32
T fiD 303
5S1
12 5
¦ 306
0
VIZ 398
J4:
313
r005
0
vAC 930
7 ; 5
5'0
• 3CE
0
¦>ac :;s
.39
4 70
•306
a: 35i
397
;r.r
" CCS
d*
TNC 00:
55 i
0?J
" 3C6
us
*NC 30/
025
*•* i
-'306
c
TXD 053
63
200
998
' 006
i
'LO 333
233
9SS
-006
1
r'.y 067
242
164
"3C6
3
0£C 002
365
*0^
fooe
Ck.
C" 001
166
453
•006/P007
OK
MID COS
379
68B
P3C6
NA
P.C 395
553
466
•006
0
ThD i73
440
124
•006
0
1 AD 04 7
303
7 71
;oo6
DK
iAC 347
303
771
F006
3K
[A3 34?
303
771
P0C6
300
ILD 305
215
421
F 006
C
aic 3d
201
508
>'006
0
R i D 001
201
5C8
F0C6
0
MD 379
674
016
r006
0
SOD 367
0'. 2
070
" 006
NA
MD 305
383
385
F006/P008
0
MOD 303
073
349
P006
0
CA3 096
314
162
F0C6
NA
cad ose
Cli
162
P006
NA
CAC 396
CM
161
c 006
NA
C"3 COi
'.67
519
f 3C6
0
B-22
-------
'at 5-.? tccni >r1Lea)
*otd :/ivce
E?A ID No Waste :3de
FCCS
NA
39 C
980
333
65:
F0C6
n
V
«.VD
054
233
213
"CCS
0
SCO
:o:
32C
575
FCC5
13
CDC
356
:sa
77c
F OC 6
3
cud
055
986
203
CC06
\
>
-------
:an; -.^ec)
" 0 No
*dste cooeisi
C* i ' Z 7 i"
ccncertrat-o
HSC
1
c::
j I 6
306
*10
550
T9r
?s
C06
:26
iAD
103
306
7:0
006
:
GAC
003
3C5
?5C
COS
4ZC
C 7 a
440
4?C
006
0
^yC
046
659
6C3
00c
?
VT3
032
063
164
006
NA
TJC
931
9:3
666
006
OH
IxD
9a:
3:3
666
:o6
4
CTD
C01
;e:
¦26
0C6/F007
250
CAC
005
-32
= Q1
006
C
ACL
006
i: j
C?0
0C6
j
2? j
^ 1 z
6SS
006
C
HID
COS
o:i
104
006
Die
HOD
n « i
pi
465
006
0
MOD
COO
822
566
006
OK
HOC
oca
822
566 F006
OK
HND
sac
7CC
900 rCOS
DK
MID
930
7 00
576
'006
0
HI C
980
703
876 "036
DK
H.I j
00;
356
784
'006
12
HID
COS
356
666 F006
OK
HAD
oo;
13s
726
"006
126
KfD
cos
366
056 c 0C6
160
OrO
C57
59 i
133
'006
18
SCO
C03
95:
376
"0C6
120
ChD
052
;
701
"006
7
OmD
360
* •
325
"306
OK
CAD
990
643
939 f006
OK
CAO
99C
643
985
"006
OK
CAD
390
843
9es F006
DK
.AD
070
i?;
375
"006
C
HAD
coo
644
571 F006
OK
HOC
930
855
607 F006
DK
CiAD
003
460
530 "006/0002
35C
GAD
C-03
48C
530 F006/0007
0
3AD
003
180
530 f005/0007
<¦0
*LD
050
455
276 '006
NA
ARD
035
500
818 "006
1
ARD
035
soc
816 f0C6
9
AZT
000
523
702 FO-36
0
CAC
008
344
265 r006
NA
CAD
coa
468
025
"006
0
CAD
009
125
535
"006/F008
p
CAD
C46
569
305 F0C6
B-24
-------
*ac ;e 3-12 !coit'^ued)
"eta-
no- taste coce!s) :on;en;rai or • 33r.#
:ad ¦:•=>
jC6
556
F 006
Ok
:to :co
79 i
095
F 006
0
CD 00C
31<
192
"006
131
cto coo
544
252
F006
¦ e
:to oci
149
4 59
FC06
20
CD 001
149
4 59
"006
iC
CO CO]
149
4 59
"006
40
co :::
; «c
453
"006
4 c
n .*» •
V 1 l> ww>
166
157
F 006
625
¦CD co;
i 73
316
F006
Ok
CO "V-
• C ^
F006
0
cc :::
4-!5
511
•005
;
cd cc
-J3
734
¦"006
Ok
C TO CC1
-5"
216
• :o6
D».
c: 032
496
909
.6
15
CD C53
865
072
"006
r
CC 080
846
666
"006
P
FlD OOj
si?
015
•006
c
rL0 001
647
215
¦006/FD07/F008
62
jAO v 05
324
572
"006
Ok
GAC 306
924
872
"006
1
OAD 075
920
801
~006
40
GAO C37
3S2
971
F006
: 1
r.c 000
6C5
471
"006
1
ILD coo
'16
394
¦006
.00
1lo ::s
103
525
"006
Dk
;lo 006
211
535
"006/"C07
5
UD COS
2 7
536
•006
NA
:ld cos
271
596
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APPENDIX C
ANALYTICAL METHOD FOR MEASUREMENT
OF THERMAL CONDUCTIVITY
C-l
-------
METHOD OF MEASUREMENTS FOR THERMAL CONDUCTIVITY
The comparative method of measuring thermal conductivity has been
proposed as an ASTM test method under the name "Guarded, Comparative.
Longitudinal Heat Flow Technique." A thermal heat flow circuit is used
which is the analog of an electrical circuit with resistances in series.
A reference material is chosen to have a thermal conductivity close to
that estimated for the sample. Reference standards (also known as heat
meters) having the sarre cross-sectional dimensions as the sample are
placed above and below the sample. An upper heater, a lower heater, and
a heat sink are added to the "stack" to complete the heat flow circuit.
See Figure 1.
The temperature gradients (analogous to potent al differences) along
the stack are measured with type K (chromel/alume thermocouples placed
at known separations. The thermocouples are plact: into holes or grooves
in the references and also in the sample whenever the sample is thick
enough to accommodate them.
For molten samples, pastes, greases, and other materials that must be
contained, the material is placed into a cell consisting of a top and
bottom of Pyrex 7740 and a containment ring of mar mite. The sample is
2 inches in diameter and 0.5 inch thick. Thermocojples are not placed
into the sample, rather, the temperatures measured in the Pyrex are
extrapolated to give the temperature at the top and bottom surfaces of
the sample material. The Pyrex disks also serve as the thermal
conductivity reference material.
C-2
-------
GUARD
GRADIENT N,
STACK
GRADIENT
/O
UPPER
GUARD
H E A T E R
CLAMP
THERMOCOUPLE
UPPER STACK
HEATER
TOP
REFERENCE
SAMPLE
HEAT FLOW
DIRECTION
SAMPLE
BOTTOM
REFERENCE
SAMPLE
LOWER STACK
HEATER
LIQUID COOLED
HEAT SINK
LOWER
GUARD
HEATER
Figure l. schematic diagram of the comparative method
C-3
-------
The stack is clamped with a reproducible load to ensure inti-rate
contact between the components. To produce a linear flow of heat down
the stack and reduce the amount of heat that flows radially, a guard tube
is placed around the stack and the intervening space is filled with
insulating grains or powder. The temperature gradient in the guard is
matched to that in the stack to further reduce radial heat flow.
The comparative method is a steady-state method of measuring thermal
conductivity. When equilibrium is reached, the heat flux (analogous to
current flow) down the stack can be determined from the references. The
heat into the sample is given by
Qn. - x (dT/dx)
in top top
and the heat out of the sample is given by
q = a (dT/dx)L
out bottom bottc
where
x » thermal conductivity
dT/dx = temperature gradient
and top refers to the upper reference while bottom refers to the lower
reference. If the heat was confined to flow just down the stack, then
Q and Q would be equal. If Q and Q are in reasonable
in out in out
agreement, the average heat flow is calculated fro^
q - (q. + q y2,
in out
The sample thermal conductivity is then found from
, = Q/(dT/dx)
sample sample
C-4
-------
The result for the <102 Activated Charcoal Waste tested nere is
in Table 1. The sample was held at an average temperature of 42C
with a 53°C temperature drop across the sample for approximately
20 hours before the temperature profile became steady and the
conductivity measured. At the conclusion of the test, it appeared that
some "drying" of the sample had occurred.
Table i The Results of the Measurement of the Thermal
Conductivity Using the Comparative Method
Sample
Temperature
T rmal
con .ctivity
(•C)
,U/mK)*
K1C1 waste
39
.273
K102 activated
charcoal waste 42 .136
*1 W/mK - 6.933 8tu in/h ft2 *F = .57*3 Btu/h ft 'F.
------- |