SECOND DRAFT
BEST DEMONSTRATED AVAILABLE TECHNOLOGY (BOAT)
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
December 19, 1988
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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-
2.3 Waste Characterization 2-10
2.4 Determination of Waste Subcategories 2-12
3. APPLICABLE/DEMONSTRATED TREATMENT TECHNOLOGIES 3-1
3.1 Applicable Treatment Technologies 3-1
3.2 Demonstrated Treatment Technologies 3-3
3.3 Descriptions of Cyanide Treatment Technologies 3-5
3.4 Descriptions of BOAT List Metals Treatment Technologies . 3-5
4. 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 4-3
4.5 High Temperature Cyanide Hydrolysis Data 4-3
4.6 Chemical Precipitation Data 4-3
4.7 Stabilization Data : 4-4
4.8 Incineration Data 4-4
5. IDENTIFICATION OF BEST DEMONSTRATED AVAILABLE TECHNOLOGY (BOAT) 5-1
5.1 BOAT for the Metal Finishing Aqueous Liquids Subcategory. 5-2
5.2 BOAT for the Metal Finishing Sludges Subcategory 5-7
5.3 BOAT for the Metal Finishing Organic Liquids Subcategory. 5-9
6. SELECTION OF REGULATED CONSTITUENTS 6-1
6.1 Identification of BOAT List Constituents 6-1
6.2 Determination of Regulated Constituents 6-2
7. CALCULATION OF PROPOSED BOAT TREATMENT STANDARDS 7-1
7.1 Cyanide 7-2
7.2 BOAT List Metals 7-3
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TABLE OF CONTENTS
(Continued)
Section Page
8. P AND U 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 Proposed Treatment Standards 8-2
9. REFERENCE 9-1
Appendix A A-l
n i
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LIST OF TABLES
Paqe
Table 1-1 BOAT Treatment Standards - Metal Finishing Aqueous
Liquids Subcategory for F007, F008, F009, and F011... 1-5
Table 1-2 BOAT Treatment Standards - Metal Finishing Organic
Liquids Subcategory for F010 1-6
Table 1-3 BOAT Treatment Standards Metal Finishing Sludges
Subcategory for F006 1-7
Table 1-4 BOAT Treatment Standards Metal Finishing Sludges
Subcategory for F012 and F019 1-8
Table 1-5 BOAT Treatment Standards for P013, P021, P029, P030
P063, P074, P098, P099, P104, P106, and P121 1-9
Table 2-1 Chemical Compositions of Typical Electroplating Baths. 2-6
Table 2-2 Summary of Waste Composition for F006-F012 and
F019 Wastes 2-14
Table 2-3 F006 Waste Composition Data 2-15
Table 2-4 F007 Waste Composition Data 2-17
Table 2-5 F008 Waste Composition Data 2-19
Table 2-6 F009 Waste Composition Data 2-20
Table 2-7 F010 Waste Composition Data 2-22
Table 2-8 F011 Waste Composition Data 2-23
Table 2-9 F012 Waste Composition Data 2-24
Table 2-10 F019 Waste Composition Data 2-26
Table 2-11 Summary of Waste Characterization for K062 Waste 2-27
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 4-5
IV
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LIST OF TABLES
(Continued)
Table 4-2 Wet Air Oxidation Data Collected by EPA at Plant B for
F007 Waste 4-6
Table 4-3 Alkaline Chlorination Data Submitted by Plant C for
Various Wastes 4-12
Table 4-4 Electrolytic Oxidation treatment Data from Literature
Source A for Treatment of F007 and F009 Wastes 4-20
Table 4-5 High-Temperature Cyanide Hydrolysis Data from
Literature Source B for Treatment of F007, F008, and
F009 Wastes 4-21
Table 4-6 Incineration Data Submitted by Plant D for
Treatment of F010 - 4-22
Table 5-1 Summary of Accuracy Adjustment of Treatment Data
for Amenable Cyanide in Wastewaters 5-11
Table 5-2 Summary of Accuracy Adjustment of Treatment Data for
Total Cyanide in Wastewaters 5-12
Table 5-3 Summary of Accuracy Adjustment of Cyanide Data in
F012 Waste as Generated 5-13
Table 5-4 Summary of Accuracy Adjustment of Treatment Data for
Total Cyanide in F010 Waste 5-14
Table 6-1 Status of BOAT List Constituent Presence in Untreated
Tested Wastes 6-5
Table 7-1 Calculation of Proposed Treatment Standards for Total
and Amenable Cyanide Based on Wet Air Oxidation 7-4
Table 7-2 Calculation of Proposed Treatment Standards for Total
and Amenable Cyanide Based on Generation of F012
Waste by a Well-Operated Treatment Process Consisting
of Electrolytic Oxidation, Alkaline Chlorination,
Chemical Precipitation, Filtration, and Sludge
Dewatering 7-5
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LIST OF TABLES
(Continued)
Page
Table 7-3 Calculation of Proposed Treatment Standards for
Incineration of F010 7-6
Table 7-4 Proposed BOAT Treatment Standards for F007, F008, F009
and F011 7-7
Table 7-5 Proposed BOAT Treatment Standards for F006 (Cyanide).. 7-8
Table 7-6 Proposed BOAT Treatment Standards for F012 and F019... 7-9
Table 7-7 Proposed BOAT Treatment Standards for F010 '.': 7-10
Table 8-1 P and U Waste Codes Proposed for Regulation 8-3
Table 8-2 Proposed Treatment Standards for P-Code Cyanide
Wastes 8-4
Table A-l Analytical Methods - Plant A '. A-2
Table A-2 Specific Procedures or Equipment Used for Analysis of
Cyanide When Alternatives or Equipments Are Allowed in
SW-846 Methods - Plant A.... A-3
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
VI
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LIST OF FIGURES
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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
proposing treatment standards based on Best Demonstrated Available
Technology (BOAT) for the cyanide-containing electroplating and metal
heat treating wastes and similar off-specification product, leak, and
spill wastes. These wastes are identified in 40 CFR 261.32 as F006,
F007, F008, F009, F010, F011, F012, and F019 and in 40 CFR 261.33 as
P013, P021, P029, P030, P063, P074, P098, P099, P104, P106, and P121.
Compliance with these BOAT treatment standards is a prerequisite for the
placement of the waste in units designated as land disposal units
according to 40 CFR Part 268. The effective date of the final treatment
standards will be June 8, 1989.
This background document provides the Agency's technical support for
selecting and developing 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 characterization 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 BOAT for each waste. In
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Section 6 the rationale for selection of regulated constituents is
presented, and in Section 7 the proposed BOAT treatment standards are
calculated for the regulated constituents selected. 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 BOAT treatment standards
is described in two separate documents: Generic Quality Assurance
Project Plan for Land Disposal Restriction Program ("BOAT") (USEPA 1987)
and Methodology for Developing BOAT Treatment Standards (USEPA 1988c).
The second document also discusses the petition process to be followed in
requesting a variance from the BOAT treatment standards.
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.
*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).
1-2
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Cyanide-containing wastes generated in metal finishing operations
contain cyanide and BOAT list metals. These wastes are divided into
three subcategories: metal finishing aqueous liquids (F007, F008, F009,
and F011), metal finishing organic liquids (F010), and metal finishing
sludges (F006, F012, and F019). Wet air oxidation followed by chemical
precipitation and filtration is determined to be BOAT for cyanide and
BOAT list metals for the metal finishing aqueous liquid wastewaters and
for the metal finishing sludges wastewaters. For cyanide in
nonwastewaters for these two subcategories, BOAT treatment standards are
based on generation of these wastes from a treatment system consisting of
alkaline chlorination followed by chemical precipitation and sludge
dewatering. For metals in nonwastewaters, stabilization is determined to
be BOAT for the metal finishing aqueous liquids, and the metal finishing
sludges. For cyanide in the metal finishing organic liquids wastes,
incineration is determined to be BOAT for nonwastewaters and wet air
oxidation is determined to be BOAT for wastewaters, such as scrubber
water produced in incineration treatment of these wastes.
Testing procedures for all sample analyses performed for the
regulated constituents are specifically identified in Appendix A of this
background document. For cyanide, the proposed 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 BOAT list metals in nonwastewaters, the
proposed treatment standards reflect the leachate concentration from the
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TCLP. The units for the leachate concentration are mg/1. For BOAT list
metals in wastewaters, the proposed treatment standards reflect the total
waste concentration, and the units are mg/1. The proposed treatment
standards for the wastewater and nonwastewater forms of the metal
finishing wastes are shown in Tables 1-1 through 1-4. The proposed
treatment standards for the related P-code wastes are presented in Table
1-5. Wastes that, as generated, contain the regulated constituents at
concentrations that do not exceed the proposed treatment standards are
not restricted from land disposal units.
1-4
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Table 1-1. BOAT Treatment Standards - Metal
Finishing Aqueous Liquids Subcategory
for F007, F008, F009, and F011
NONWASTEWATERS
Maximum for any
single grab sample
Constituent
Cyanide (total)
Cyanide (amenable)
Cadmium
Chromium
Lead
Nickel
Si 1 ver
Total composition
(ing/ kg)
110 Not
0.064 Not
Not applicable
Not applicable
Not applicable
Not appl icable
Not appl icable
TCLP
(mg/1)
appl icable
appl icable
0.066
5.2
0.51
0.32
0.072
WASTEWATERS
Maximum for any
single grab sample.
Constituent
Cyanide (total)
Cyanide (amenable)
Chromium
Lead
Nickel
Total composi
(rag/ kg)
12
1.3
0.32
0.04
0.44
tion TCLP
(mg/1 )
Not applicable
Not applicable
Not applicable
Not applicable
Not applicable
1-5
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Table 1-2. BOAT Treatment Standards - Metal
Finishing Organic Liquids Subcategory
for F010
NONWASTEWATERS
Maximum for any
single grab sample
Total composition TCLP
Constituent .(mg/kg) (mg/1)
Cyanide (total) 1.5 Not applicable
WASTEWATERS
Maximum for any
single grab sample
Total Composition TCLP
Constituent (rogAg) (mg/1)
Cyanide (total) ~~12Not applicable
Cyanide (amenable) 1.3 Not applicable
1-6
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Table 1-3. BOAT Treatment Standards - Metals
Finishing Sludges Subcategory for F006
NONWASTEWATERS
Maximum for any
single grab sample
Total composition TCLP
Constituent (mg/kg) (mg/1)
Cyanide (total)flONot applicable
Cyanide (amenable) 0.064 Not applicable
WASTEWATERS
Maximum for any
single grab sample
Total composition TCLP
Constituent (rog/kg) (mg/1)
Cyanide (total) 12 Not applicable
Cyanide (amenable) 1.3 Not applicable
1-7
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Treatment Standards - Metal
i my Sludges Subcategory
for F012 and
Table 1-4. BOAT Treatment Standards
Finishing Sludges Subcategory
for F012 and F019
NONWASTEWATERS
Maximum for any
single grab sample
Constituent
Cyanide
Cyanide
Cadmium
Chromium
Lead
Nickel
Silver
(total)
(amenable)
Total composition
(mg/kg)
Not
Not
Not
Not
Not
110
0.064
applicabl
applicabl
appl icabl
applicabl
applicabl
Not
Not
e
e
e
e
e
TCLP
(mg/1 )
appl icabl
applicabl
0.066
5.2
0.51
0.32
0.072
e
e
WASTEWATERS
Maximum for any
single grab sample
Constituent
Cyanide (total)
Cyanide (amenable)
Chromium
Lead
Nickel
Total composition TCLP
(mg/kg) (mg/1)
12 Not applicable
1.3 ' Not appl icable
0.32 Not applicable
0.04 Not applicable
0.44 Not applicable
1-8
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Table 1-5. BOAT Treatment Standards
for P013, P021, P029, P030, P063, P074,
P098, P099, P104, P106, and P121
NONWASTEWATERS
Maximum for any
single grab sample
Constituent
Cyanide (total)
Cyanide (amenable)
Copper (P029 only)
Nickel (P074 only)
Silver (P099 and P104 only)
Zinc (P121 only)
Total composition
(mg/kg)
110 Not
0.064 Not
Not appl icable
Not applicable
Not applicable
Not applicable
TCLP
(mg/1)
appl icable
appl icable
0.71
0.30
0.07
0.086
WASTEWATERS
Maximum for any
single grab sample
Constituent
Cyanide (total)
Cyanide (amenable)
Total composition TCLP
(mg/kg) (mg/1)
12 Not applicable
1.3 Not applicable
Copper (P029 only)
Nickel (P074 only)
Silver (P099 and P104 only)
Zinc (P121 only)
0.42
0.44
Reserved
Reserved
Not applicable
Not applicable
Not applicable
Not applicable
1-9
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2. INDUSTRIES AFFECTED AND WASTE CHARACTERIZATION
According to 40 CFR 261.32,- the following wastes from electroplating,
metal heat treating, and chemical conversion coating operations in the
metal finishing industry are subject to the land disposal restriction
prohibitions of HSWA:
Electroplating Operations
F006: Wastewater treatment sludges from electroplating operations
except for the following processes: (1) sulfuric acid
anodizing 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 or 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.
F012: Quenching wastewater treatment sludges from metal heat
treating operations where cyanides are used in the process.
I Chemical Conversion Coating Operations
F019: Wastewater treatment sludge from the chemical conversion
coating of aluminum.
2-1
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The hazardous waste F006 was regulated with the First Third scheduled
wastes (53 FR 31138) except for cyanide, which is regulated with these
wastes. Section 2.1 describes the industries affected by the land
disposal restrictions for F006-F012 and F019, and Section 2.2 presents
descriptions of the electroplating, heat treating, and chemical
conversion coating processes generating these wastes. Section 2.3
presents the available waste characterization data for these wastes.
Section 2.4 discusses the Agency's rationale for dividing these wastes
into three separate subcategories.
2.1 Industries Affected
The listed wastes F006, F007, F008, and F009 are generated from
electroplating operations where cyanides are used in the process. The
listed wastes F010, F011, and F012 are generated from metal heat treating
operations where cyanides are used in the process. The listed waste F019
is generated in chemical conversion coating of aluminum.
Electroplating operations consist of the following processes:
(1) common and precious metals electroplating, except tin, zinc
*
(segregated basis), aluminum, and zinc-aluminum plating on carbon
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.
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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.
Heat treating operations include tempering, carburizing,
carbonitriding (cyaniding), nitriding, annealing, normalizing,
austenizing, austempering, quenching, siliconizing, martempering, and
malleabilizing.
In the preamble for the Effluent Limitations Guidelines for the Metal
Finishing Industry (40 CFR Part 413), the Agency identified 13,500
facilities in the metal finishing industry that use 46 electroplating and
metal finishing unit operations listed in 48 FR 32482 (including
electroplating, heat treating, and chemical conversion coating).
Users of electroplating and heat treating operations generally fall
under Standard Industrial Classification (SIC) code series 3000, which
comprises fabricated metal products except machinery and transportation
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
operations that EPA has included as electroplating operations:
electroplating, anodizing, chemical etching and milling, and metal
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cleaning and stripping. Also provided are descriptions of the chemical
conversion coating and 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
antifrictional 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: 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
solution 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
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electroplating solutions have been adopted commercially, but only two or
three types are used widely 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
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
properties. Aluminum is the most frequently anodized material, while
some magnesium and stainless steel (electropolish) and limited amounts of
zinc and titanium are also treated.
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Table 2-1 Chemical Compositions of Typical Electroplating Baths
Plating compound
Constituents
Concentration (g/1)
Cadmium cyanide
Cadmium oxide
Cadmium (as metal)
Sodium cyanide
Sodium hydroxide
22.5
19.5
77.9
14.2
Cadmium fluoborate
Cadmium fluoborate
Caotanum (as metal)
Ammonium fluoborate
Boric acid
251.2
94.4
59.9
27.0
Chromium electroplate
Chromic acid
Sulfate
Fluoride
172.3
1.3
0.7
Copper cyanide
Copper cyanide
Free sodium cyanide
Sodium carbonate
Rocnelle salt
26.2
5.6
37.4
44.9
Gold cyanide
Acid nickel
Si Iver cyanide
Zinc sulfate
Gold (as potassium
gold cyanide)
Potassium cyanide
Potassium carbonate
Di potassium phosphate
Nickel sulfate
Nickel chloride
Boric acid
Si Iver cyanide
Potassium cyanide
Potassium carbonate (min.)
Silver (as metal)
Free cyanide
Zinc sulfate
Sodium sulfate
Magnesium sulfate
8
30
30
30
330
45
37
35.9
59.9
15.0
23.8
41.2
374.5
71.5
59.9
Reference: USEPA 1980.
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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
reaction 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 coatings and have a relatively thick boundary layer."
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 dipping. 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.
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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 nonelectrolyti-
cally), neutral, or acidic solutions. Nonelectrolytic cleaning, using
both alkaline and acid solutions, can be done by either soak or spray
methods. Aci'd 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 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 remove 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
2-8
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instance) or strong acids. The stripping solution dissolves the plated
coating, leaving the base metal essentially untouched.
2.2.5 Chemical Conversion Coating
The conversion coating operation includes processes such as
chromating, phosphating, metal coloring, and passivating. In chromating,
a portion of the base metal is converted to a protective film formed by
the coating solution. Aqueous solutions containing hexavalent chromium
and other active organic or inorganic compounds are used. Chromate
coatings are most frequently applied to aluminum, magnesium, cadmium,
copper, brass, bronze, silver, and zinc.
Phosphating and coloring involve formation of surface metallic
phosphates, oxides, or other compounds that impart a color to the metal
while also forming a protective coating. Passivating is the formation of
a protective film on metals, particularly stainless steel and copper, by
immersion in an acid solution. Coloring is the only one of these three
operations that may sometimes be used on aluminum.
2.2.6 Heat Treating
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
temperatures 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 immersion in the salt
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bath, parts are removed and cooled in either a water or an oil bath or in
air.
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,
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 presents the waste characterization data available to
the Agency for the F006-F012 and F019 wastes. 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 Tables 2-3 through 2-10. Tables 2-3 through 2-10 present,
by waste code, the concentration for BOAT 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 and EPA sampling and analysis. Tables 2-11 and 2-12
present a major constituent summary and all waste characterization data,
respectively, for K062 waste. (Tables 2-2 through 2-12 are at the end of
Section 2.)
The metal finishing industry wastes are divided into three distinct
groups based on the process generating the waste and the waste
composition. F007, F008, F009, and F011 wastes generally contain from
1 percent cyanide (or approximately 2 percent, as NaCN) up to 15 percent
2-10
-------
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, F012, and F019 are wastewater treatment sludges typically
containing less than 1 percent metals in a hydroxide or sulfide sludge.
These wastes may contain 5 percent or more cyanide (i.e., 10 percent
cyanide (as NaCN) in Table 2-2) but typically contain much less cyanide
(<0.1 percent).
F007-F012 and F019 wastes contain BOAT metals and cyanides, as well
as other inorganic compounds and water. Metals typically used in cyanide
bath plating or metals that are stripped by cyanide stripping solutions
include cadmium, copper, nickel, silver, and zinc. The concentrations of
individual metals in F007, F008,-an.d F009 wastes are dependent on the
type of electroplating solutions used at the particular facility
generating the waste. Additionally, F007-F009, F012, and F019 may
contain low concentrations of volatile and semivolatile organic compounds.
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 removal separately from other wastewaters. In this case, the
2-11
-------
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, then the precipitated residual from this
treatment would be F006.
2.4 Determination of Waste Subcateqories
In cases where EPA believes that constituents present in different
waste codes can be treated to similar concentrations using the same
treatment technologies, the Agency may combine the codes into a single
subcategory.
Based on review of the processes generating the electroplating and
metal heat treating wastes and all available data characterizing these
wastes, the Agency has determined that these wastes represent three
separate waste subcategories. The first subcategory, the metal finishing
aqueous liquids subcategory, contains the inorganic electroplating and
metal heat treating wastes that are likely to contain high concentrations
of cyanide salts (F007, F008, F009, and F011). These wastes also may
require treatment by chemical precipitation for dissolved metals
removal. Treatment of these wastes results in generation of wastewater
treatment sludges that are similar to the listed wastes F006 and F012.
(Treatment sludges from treatment of F007-F009 wastes, if these wastes
are mixed before or during treatment, are the listed waste F006.) The
second subcategory, the metal finishing sludges subcategory, contains the
wastes that are characterized as wastewater treatment sludges (F006,
2-12
-------
F012, F019) and consequently do not require treatment by chemical
precipitation to treat dissolved metals. These wastes also may not
require treatment of cyanides by a cyanide destruction technology (e.g.,
alkaline chlorination or wet air oxidation) if the wastewaters treated to
generate the F006, F012, or F019 wastes have been properly treated for
cyanide prior to chemical precipitation treatment. These wastes usually
contain cyanides in lower concentrations than those in the wastes in the
first group. The third subcategory is the metal finishing organic
liquids subcategory, which contains the waste code F010. F010 is
typically generated with a high oil and grease content and little or no
water and thus requires treatment for organics as well as for cyanides.
Although the concentrations of specific constituents 'will vary from
waste code to waste code within each subcategory identified, all of the
wastes within each subcategory contain similar constituents that are
expected to be treatable to similar concentrations using the same
technologies. EPA will therefore propose BOAT treatment standards that
are applicable to all wastes in each subcategory.
2-13
-------
Table 2-2 Sunmary of Waste Characteristics for F006-F012 and F019 Wastes
Const ituent/parameter
F006
Concentration (percent)
F007
F008
F009
Cyanide (as NaCN)
BDAI Metals
Cadmium
Chromium
Copper
Lead
Nickel
Zinc
TOTAL BOAT METALS
BOAT organics
Non-BDAT Inorganics
(primarily sodium
carbonate, iron, calcium
hydroxide)
<0.1-0.5
0-2
0-30
0-3
0-3
0-17
0-9
<0.1-30
20-40
5-10
0-2
0-1
0-2
0-2
20-40
2-10
0-2
0-2
0-2
0-2
35-40
5-20
0-2
0-2
0-2
20
Water
Oi 1 and grease
Constituent/parameter
30-90 55-70 55
0-4 <0.1 <0.1
Concentration (percent)
F010 F011 F012
60-70
F019
Cyanide (as NaCN)
BOAT Metals
Cadm i urn
Chromium
Copper
Lead
Nickel
Zinc
TOTAL BOAT METALS
1-4
3-20
0.2
0.
<0.1-0.8
<0.1
<0.1
1-10
BDAI Organics
Non-BDAT Inorganics
(primarily sodium carbonate,
iron, calcium hydroxide)
Water
20-80
0-80
28-36
60
30-40
60
Oi 1 and grease
- - Not available
2-14
-------
2344g
Table 2-3 F006 Waste Composition Data
01
Constituent/
parameter (units)
BOAT
169.
169.
170.
BOAT
154.
155.
156.
157.
158.
159.
160.
161.
162.
163.
164.
165.
166.
167.
168.
221.
Concentration (source)
(1) (2)
(3)
(4)
(5)
(6) (7) (8)a
(8)a
Inorganics Other Than Metals (mq/kq)
Cyanide (total)
Cyanide (amenable)
Fluoride
Metals (mg/kg)
Ant imony
Arsenic
Barium
Beryllium
Cadmium
Total chromium
Copper
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Hexavalent chromium
<0. 1-506 84.1-226
<0. 10-0. 22 <1-153
-
-
-
0.74-85.5
-
1.3-720 1.280-4.070
2-49.000 147-8.610
1.4-27,400 345-28.100
1.69-24.500 -
-
234-23.700 1,330-26,000
-
0.51-38.9
-
-
8.86-90.200 611-41.200
-
<2
<2
-
<10
2-5
20-45
<2
10-20
3.200-75.000
90-775
85-134
<1
7,300-49,000
<10
<2
<10
-
68-3,700
0.14-1.0
.
-
268
22.4
<0.4
28.8
<0.1
0.37-1.75
1,650-2.625
1.87-135
184-305
<0.2
11.8-17
<0.03
<0.6-<1.0
<20
1.26
2.510-3.687
-
0.1-5.8
0.1
-
-
<6.24
9-57
<97.6
-------
2344g
Table 2-3 (continued)
Constituent/
parameter (units)
(1)
(2)
Concentration (source)
(3)
(4)
(5)
(6)
(7)
(8)a
(8)a
Other Parameters
Oil and grease (tng/g)
Moisture (%)
SP gravity (g/ml)
Acidity as CaCO, (mg/1)
Sulfide (mg/kg)
Total organic
carbon (mg/kg)
0.03-37.7
29.1-91.2
47.4-48.94
1.38-1.493
1,412
<5.800
69.1-76.3
21
The ranges presented represent six samples analyzed from the same process.
- = Not analyzed
ND = Not detected
References:
(1) Chemical Waste Management 1987.
(2) MRI 1987.
(3) USEPA 1986.
(4) John Deere Company 1988.
(5) Environ 1985.
(6) USEPA 1980.
(7) Versar 1986.
(8) PEI 1988.
-------
Table 2-4 F007 Waste Composition Data
Constituent/parameter (units)
(1)
Concentration (source)
(2)
(3)
(4)
BDAT Inorganics Other Than Metals (mg/1)
Cyanide (amenable) CBI
Cyanide (iron) CBI
Cyanide (total) CBI
Fluoride CBI
BDAT Hetals (mg/1)
Cadmium CBI
Chromium (total) CBI
Chromium (hexavalent) CBI
Copper CBI
Nickel CBI
Zinc CBI
Non-BDAT Hetals (mg/1)
Calcium CBI
Iron CBI
Magnesium CBI
Manganese CBI
Sodium CBI
4,000-67.000
170
41,000
2,000-15.000
BDAT Volatiles (mq/1)
Methanol
CBI
Other Parameters
Carbonate (mg/1)
Total solids (%)
Ash (%)
Total suspended solids (mg/1)
Suspended ash (mg/1)
Chemical oxygen demand (mg/1)
PH
Specific gravity
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
a Cyanide (iron) is interpreted as a measurement of cyanide not amenable to chlorination.
- = Not analyzed.
2-17
-------
2324g
Table 2-4 (continued)
Concentration (source)
Constituent/parameter (units) (5) (5) (5)
BOAT Inorganics Other Than Metals (mg/1)
Cyanide (amenable) 28,200 64,200 5.700
Cyanide (iron) -
Cyanide (total) 30,200 66,900 8.010
Fluoride -
(5) (6)
25,600
27.600 20.000-25,000
BOAT Metals (mg/1)
Cadmium - 16,300 - 10,600 1.500
Chromium (total) -
Chromium (hexavalent) - - 400
Copper - - 2,880 383
Nickel - 7,000-8,000
Zinc 15.700 ...
Non-BDAT Metals (mg/1)
Calcium
Iron -
Magnesium -
Manganese -
Sodium - -
BOAT Volatiles (mq/D
1.1-Dichloroethane <0.002 <0:002 <0.010 0.0348
Methanol -
Methylene chloride <0.002 <0.002 0.0262 0.0324
Toluene 0.0137 <0.002 0.0562 0.0023
1,1.1-Trichloroethane <0.002 <0.002 <0.010 0.011
Other Parameters
Carbonate (mg/1) -
Total solids (%) -----
Ash (%) -----
lota I suspended solids (mg/1) -
Suspended ash (mg/1) -
Chemical oxygen demand (mg/1) - - - - • -
pll ---•,-
Specific gravity -
a Cyanide (iron) is interpreted as a measurement of cyanide not amenable to chlorination.
i- = Not analyzed.
References:
(1) USCPA 1988f. (4) USEPA 1980.
(2) Patterson and Minear 1973. (5) MR1 1987.
(3) Versar 1986. (6) CyanoKEM 1987.
2-18
-------
Table 2-5 P008 Waste Composition Data
Constituent/parameter (units)
(1)
Concentration (source)
(2)
(2)
(2)
(3)
BOAT Inorganics Other Than Metals (mg/kg)
Cyanide (amenable)
Cyanide (total)
BOAT Metals (mg/kg)
Cadmium
Chromium (hexavalent)
Copper
Lead
Nickel
Zinc
BOAT Volatiles (mg/kg)
Methylene chloride
64
11,700
11,900
13,100
<1.20
21.700
26,600
13.000
<0.008
34,200
34,900
21.600
50,000-55,000
<100
300
150-200
300
14.4
- = Not analyzed.
References:
(1) USCPA 1980.
(2) MRI 1987.
(3) CyanoKEM 1987.
2-19
-------
2324g
Table 2-6 F009 Waste Composition Data
Concentration (source)
Constituent/parameter (units) (1) (2) (2) (3) (4)
BOAT Inorganics Other Than Metals (mg/1)
Cyanide (amenable) • - 52,000-90,000 - - 62.900
Cyanide (iron)3 - 100 - -
Cyanide (total) 350,000 - 40,000 4.000-8,000 64.600
BOA I Metals (mg/1)
Cadmium - - - - -
Chromium (hexavalent) - - - -
Copper - 19.000
Lead - - - -
Nickel - 5,100-5,500 - - 7,310
Non-BDAT Metals (mg/1)
Iron - 720-15.000
a Cyanide (iron) is interpreted as a measurement of cyanide not amenable to chlorination.
-. = Not analyzed.
References:
(1) USFPA 1980.
(2) Versar 1986.
(3) Patterson and Minear 1973.
(4) MRI 1987.
(5) CyanotCEM 1987.
2-20
-------
Table 2-6 (continued)
Concentration (source)
Constituent/parameter (units) (4) (4) (4) (5)
BOAT Inorganics Other Than Metals (mg/1)
Cyanide (amenable) 109.000 14.400 47.400
Cyanide (iron)a - - -
Cyanide (total) 115,000 14,500 52,500 40,000-45.000
BOAT Metals (mg/1)
Cadmium 388 - • - 200
Chromium (hexavalent) - - - <100
Copper - 6,990
Lead - - - 200
Nickel - - 7.510 12,000-15.000
Non-BDAT Metals (mg/1)
Iron - -
a Cyanide (iron) is interpreted as a measurement of cyanide not amenable to chlorination.
- = Not analysed.
References:
(1) USEPA 19HO.
(2) Versar 1986.
(3) Patterson and Minear 1973.
(4) MRI 1987.
(5) CyanoKEM 1987.
2-21
-------
Table 2-7 F010 Waste Composition Data
Concentration (source)
Constituent/parameter (units) (1) (2)
BDAT Inorganics Other Than Metals (mg/kg)
Cyanide (total) 8.530 22.000
Other Parameters
Heat content (Btu/lb) - 5.000
Water (%) - ND
- = Not analyzed
ND = Not detected
References:
(1) USEPA 1980.
(2) CyanoKEM 1988.
2-22
-------
Table 2-8 F011 Waste Composition Data
Concentration (source)
Constituent/parameter (units) (1) (2) (2) (3)
BOAT Inorganics Other Than Metals (mq/1)
Cyanide (amenable) I - 34.000-35,000
Cyanide (total) 5,350 10,000-12,000 - 85,000-90,000
Fluoride 5.55 - -
BOAT Metals (mq/1)
Antimony 0.029
Barium 1.0 -
Cadmium 0.01 - - <100
Chromium (hexavalent) <0.01 - - 1,000-1,500
Chromium (total) 5.42
Copper 1.03
Lead 1.1 - - 500-1,000
Nickel 2.88 - - 300
Silver 0.0072 - -
Vanad i urn 0.156
Zinc 0.338 -
Non-BDAT Metals (mq/11
Iron 27.8
Potassium 18,500 - -
Sodium 32,200 -
Non-BDAT Inorganics Other Than Metals (mg/1)
Carbonate 87,000
Chloride 21,300
Sulfate 90.5 -
Other Parameters
Total solids (%) 19.7
Total suspended solids (%) 3.84
Chemical oxygen demand (mg/1) 7,140 -
Total organic carbon (mg/1) 19,500 - -
Oil and grease (mg/1) 11.0
1 = Analytical interference. Analysis of partially treated sample indicates that this
value is <5120 mg/1.
- = Not analyzed.
References:
(1) USFPA 1988e.
(?) Environ 1985.
(3) CyanoKCM 1987.
2-23
-------
Table 2-9 F012 Waste Composition Data
Concentration (source)
Constituent/parameter (units)
BOAT Inorganics Other Than Metals (mq/kq)
Cyanide (total)
Fluoride
BOAT Metals (mg/kg)
Barium
Cadmium
Chromium (hexavalent)
Chromium (total)
Copper
Lead
Nickel
Silver
Vanadium
Zinc
BOAT Volatile Orqanics Uq/kq)
Acetone
Chloroform
Methylene chloride
To luene
(1)
21
6.5
98
5.31
-
11
307
28
758
0.73
6.7
54
250
110
11
28
(2) (2) (3) (4)
26,800 8,400 1.500 60,000-65.000
- - - -
_
<100
350
-
-
500-600
400-500
-
-
- - -. -
-
-
_
BOAT Semivolatlle Orqanics
Bis(2-ethylhexyl) phthalate
PCBs (Mg/kg)
Aroclor 1254
Non-BDAT Metals (mg/kg)
Iron
Sod i urn
1.600
35
2.880
1,276
Non-BDAT Inorganics Other Than Metals (mg/kg)
Chloride
Sulfate
992
6,900
2-24
-------
2324g
Table 2-9 (continued)
Constituent/parameter (units)
Concentration (source)
(1)
(2)
(2)
(3)
(4)
Other Parameters
Total solids (%)
Total organic carbon (mg/kg)
Oil and grease (mg/kg)
pH
60.5
540
432
10.5-11.0
- = Not analyzed
References:
(1) USFPA 1988e.
(2) USEPA 1980.
(3) Environ 1985.
(4) CyanoKEM 1987.
2-25
-------
Table 2-10 F019 Waste Composition Data
Constituent/parameter (units)
(1)
Concentration (source)
(1)
(2)
(3)
BOAT Inorganics Other Than Metals (mg/kg)
Cyanide (total) 7.76
Cyanide (amenable) 7.76
BOAT Metals (mg/kg)
Cadmium 0.212
Chromium (hexavalent)
Chromium (total) 6,540
Copper
Nickel 3.25
Other Parameters
3.93
NO
0.288
150
<0.001-3,824
3.08
289
68
1,275
<0.01-28
<0.04-25
14-90,000
<4-47
Total solids
2-35
- = Not analyzed
ND = Concentration reported as "zero"
References:
(1) MRI 1987.
(2) -AES 1981.
(3) Versar 1986.
2-26
-------
2324g
Table 2-11 Sunmary of Waste Characterization for K062 Waste
Constituent Concentration (percent)
BOAT List Mutals
Chromium
Copper
Nickel
TOTAL BOAT LIST METALS
Water
Other inorganics
TOTAL
<0.1 - 1
<0.1
<0.1 - 10
1 - 10
84 - 93
6
100%
Table 2-12 K062 Waste Composition Data
Constituent/parameter Concentration (source)
(units) (1) (2)
BOAT List Hetals (mg/1)
Arsenic
Barium
Cadmium
Chromium (hexavalent)
Chromium (total)
Copper
Lead
Nickel
Zinc
<0.1 to 3
<10
<5
0.079 to 1
6 to 7.000
5 to 865
<10
4 to 100.310
<0.4 to 9
-
-
-
0.005
2 to
-
0.12
-
-
to 19
12,400
to 1.550
References:
(1) USEPA 1986. Tables 6-1 through 6-12.
(2) Environ 1985.
2-27
-------
3. APPLICABLE AND DEMONSTRATED TREATMENT TECHNOLOGIES
Section 2 established three subcategories for F006-F012 and F019
wastes. This section identifies the treatment technologies that are
applicable to these subcategories and determines which, if any, of the
applicable technologies can be considered demonstrated for the purposes
of establishing BOAT.
To be applicable, a technology must be theoretically usable to treat
the waste in question or to treat a waste that is similar in 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 BOAT.
3.1 Applicable Treatment Technologies
EPA has identified five technologies as potentially applicable for
treatment of cyanides in the metal finishing aqueous liquids subcategory
(F007, F008, F009, and F011 wastes): (1) electrolytic oxidation;
(2) chemical oxidation with several oxidizing agents, such as
hypochlorite or chlorine (alkaline chlorination), permanganate, or ozone;
(3) wet air oxidation; (4) high-temperature cyanide hydrolysis; and
(5) SO /air oxidation (INCO process). Each of these may be followed by
chemical precipitation, filtration, and sludge dewatering for metals
removal.
3-1
-------
Electrolytic oxidation followed by alkaline chlorination, chemical
oxidation (alkaline chlorination or other methods) alone, electrolytic
oxidation alone, wet air oxidation, high-temperature hydrolysis, and
SO /air oxidation reduce the concentration of cyanide in the
wastewaters or nonwastewaters treated. Chemical precipitati.on 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 nonwastewater treatment
technologies specified below for the wastes F006, F012, and F019.
EPA has identified three technologies as potentially applicable for
treatment of the wastewater treatment sludges in the metal finishing
sludges subcategory (F006, F012, and F019): stabilization,
vitrification, and high temperature metals recovery. The first two
technologies are designed to reduce the Teachability of the metals; the
third reduces both the total concentration and the Teachability of the
metals.
Stabilization chemically reduces the mobility of hazardous 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
3-2
-------
waste is in contact with water. Commonly used stabilization agents
include portland cement, 1ime/pozzolan-based material, and cement kiln
dust.
Vitrification has also been identified by the Agency as an applicable
technology. A vitrification process can be used to immobilize hazardous
constituents in F012 or F019 waste by producing a vitreous or glass-Tike
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
residual. High temperature metals recovery may result in a residual (or
slag) that is land disposed.
EPA has identified incineration as the only applicable technology for
wastes in the metal finishing organic liquids subcategory (F010).
Incineration is a thermal treatment process that destroys the organic and
oxidizable inorganic waste constituents.
3.2 Demonstrated Treatment Technologies
Available information shows that electrolytic oxidation followed by
alkaline chlorination, alkaline chlorination alone, wet air oxidation,
high temperature hydrolysis, and SO /air oxidation are demonstrated for
treatment of cyanide in F007, F008, F009, and F011 wastes. EPA knows of
at least one full-scale facility that uses electrolytic oxidation
followed by alkaline chlorination to treat cyanide in F011 waste, at
3-3
-------
least five facilities (there are probably many more) that use alkaline
chlorination to treat cyanide in F007-F009 or F011 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. EPA
believes that chemical precipitation followed by filtration and sludge
dewatering is demonstrated at many facilities for treatment of BOAT
metals on these wastes 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 F012 and F019 wastes are
demonstrated. The characteristics of F012 and F019 wastes (high solids
content, substantial concentrations of BOAT metals, very low
concentrations of oil and grease and BOAT 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 F006 waste by
vitrification.
The Agency also believes that incineration is demonstrated for
treatment of metal finishing organics liquids (F010). Phone contacts
with generators of F010 wastes indicate that these wastes may also be
3-4
-------
treated by an oil/water separation step, followed by recycling of the oil
phase and treatment of the inorganic phase by one of the other cyanide
destruction technologies discussed above.
3.3 Descriptions of Cyanide Treatment Technologies
3.3.1 Electrolytic Oxidation
3.3.2 Chemical Oxidation
3.3.3 Wet Air Oxidation
3.3.4 Incineration
3.4 Descriptions of BOAT List Hetals Treatment Technologies
3.4.1 Chemical Precipitation
(1) Applicability and use of chemical precipitation. Chemical
precipitation is used when dissolved metals are to be removed from
solution. This technology can be applied to a wide range of wastewaters
containing dissolved BOAT list metals and other metals as well. This
treatment process has been practiced widely by industrial facilities
since the 1940s.
(2) Underlying principles of operation. The underlying principle of
chemical precipitation is that metals in wastewater are removed by the
addition of a treatment chemical that converts the dissolved metal to a
metal precipitate. This precipitate is less soluble than the original
metal compound and therefore settles out of solution, leaving a lower
concentration of the metal present in the solution. The principal
chemicals used to convert soluble metal compounds to the less soluble
3-5
-------
forms include lime (Ca(OH) ), caustic (NaOH), sodium sulfide (Na S),
and, to a lesser extent, soda ash (Na CO ), phosphate, and ferrous
sulfide (FeS).
The solubility of a particular compound will depend on the extent to
which the electrostatic forces holding the ions of the compound together
can be overcome. The solubility will change significantly with
temperature; most metal compounds are more soluble as the temperature
increases. Additionally, the solubility will be affected by the other
constituents present in a waste. As a general rule, nitrates, chlorides,
and sulfates are more soluble than hydroxides, sulfides, carbonates, and
phosphates.
An important concept related to treatment of the soluble metal
compounds is pH. The pH of an aqueous solution provides a measure of the
extent to which a solution contains an excess of either hydrogen or
hydroxide ions. The pH scale ranges from 0 to 14, with 0 being the most
acidic, 14 representing the highest alkalinity or hydroxide ion (OH )
content, and 7 being neutral.
When hydroxide is used to precipitate the soluble metal compounds,
the pH is frequently monitored to ensure that sufficient treatment
chemicals are added. It is important to point out that pH is not a good
measure of treatment chemical addition for compounds other than
hydroxides; when sulfide is used, for example, facilities might use an
oxidation-reduction potential meter (ORP) correlation to ensure that
sufficient treatment chemical is used.
3-6
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Following conversion of the relatively soluble metal compounds to
metal precipitates, the effectiveness of chemical precipitation is a
function of the physical removal, which usually relies on a settling
process. A particle of a specific size, shape, and composition will
settle at a specific velocity, as described by Stokes' Law. For a batch
system, Stokes' Law is a good predictor of settling time because the
pertinent particle parameters remain essentially constant. Nevertheless,
in practice, settling time for a batch system is normally determined by
empirical testing. For a continuous system, the theory of settling is
complicated by factors such as turbulence, short-circuiting, and velocity
gradients, increasing the importance of the empirical tests,
(3) Description of the technology. The equipment and
instrumentation required for chemical precipitation vary depending on
whether the system is batch or continuous. Both operations are discussed
below; a schematic of the continuous system is shown in Figure 3-3.
For a batch system, chemical precipitation requires only a feed
system for the treatment chemicals and a second tank where the waste can
be treated and allowed to settle. When lime is used, it is usually added
to the reaction tank in a slurry form. In a batch system, the supernate
is usually analyzed before discharge, thus minimizing the need for
instrumentation.
In a continuous system, additional tanks are necessary, as well as
instrumentation to ensure that the system is operating properly. In this
system, the first tank that the wastewater enters is referred to as an
3-7
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Figure 3-3
3-8
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equalization tank. This is where the waste can be mixed in order to
provide more uniformity, minimizing wide swings in the type and
concentration of constituents being sent to the reaction tank. It is
important to reduce the variability of the waste sent to the reaction
tank because control systems inherently are limited with regard to the
maximum fluctuations that can be managed.
Following equalization, the waste is pumped to a reaction tank where
treatment chemicals are added; the chemicals are added automatically by
using instrumentation that senses the pH of the system and then
pneumatically adjusts the position of the treatment chemical feed valve
such that the design pH value is achieved. Both the complexity and the
effectiveness of the automatic control system will vary depending on the
variation in the waste and the pH range that is needed to properly treat
the waste.
An important aspect of the reaction tank design is that it be well
mixed so that the waste and the treatment chemicals are both dispersed
throughout the tank, in order to ensure commingling of the reactant and
the treatment chemicals. In addition, effective dispersion of the
treatment chemicals throughout the tank is necessary to properly monitor
and thereby control the amount of treatment chemicals added.
After the waste is reacted with the treatment chemical, it flows to a
quiescent tank where the precipitate is allowed to settle and
subsequently be removed. Settling can be chemically assisted through the
use of flocculating compounds. Flocculants increase the particle size
3-9
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and density of the precipitated solids, both of which increase the rate
of settling. The particular flocculating agent that will best improve
settling characteristics will vary depending on the particular waste; the
flocculating agent is generally selected by performing laboratory bench
tests. 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
clarifier or an inclined separator. Schematics of the latter two
separators are shown in Figures 3-4 and 3-5.
Filtration can be used for further removal of precipitated residuals
both in cases where the settling system is underdesigned and in cases
where'the particles are difficult to settle. Polishing filtration is
discussed in a separate technology section.
(4) Waste characteristics affecting performance. In determining
whether chemical precipitation is likely to achieve the same level of
performance on an untested waste as on a previously tested waste, EPA
will examine the following waste characteristics: (a) the concentration
and type of the metal(s) in the waste, (b) the concentration of total
suspended solids (TSS), (c) the concentration of total dissolved solids
(IDS), (d) whether the metal exists in the wastewater as a complex, and
(e) the oil and grease content. These parameters affect the chemical
reaction of the metal compound, the solubility of the metal precipitate,
or the ability of the precipitated compound to settle.
(a) Concentration and type of metals. For most metals, there
is a specific pH at which the metal hydroxide is least soluble. As a
result, when a waste contains a mixture of many metals, it is not
3-10
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Figure 3-4
3-11
-------
Figure 3-5
3-12
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possible to operate a treatment system at a single pH that is optimal for
the removal of all metals. The extent to which this affects treatment
depends on the particular metals to be removed and their concentrations.
An alternative can be to operate multiple precipitations, with
intermediate settling, when the optimum pH occurs at markedly different
levels for the metals present. The individual metals and their
concentrations can be measured using EPA Method 6010.
(b) Concentration and type of total suspended solids (TSS).
Certain suspended solid compounds are difficult to settle because of
either particle size or shape. Accordingly, EPA will evaluate this
characteristic in assessing transfer of treatment performance. Total
suspended solids can be measured by EPA Wastewater Test Method 160.2.
(c) Concentration of total dissolved solids (TDS). Available
information shows that total dissolved solids can inhibit settling. The
literature states that poor flocculation is a consequence of high TDS and
shows that higher concentrations of total suspended solids are found in
treated residuals. Poor flocculation can adversely affect the degree to
which precipitated particles are removed. Total dissolved solids can be
measured by EPA Wastewater Test Method 160.1.
(d) Complexed metals. Metal complexes consist of a metal ion
surrounded by a group of other inorganic or organic ions or molecules
(often called ligands). In the complexed form, the metals have a greater
solubility and, therefore, may not be as effectively removed from
solution by chemical precipitation. EPA does not have an analytical
3-13
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method to determine the amount of complexed metals in the waste. The
Agency believes that the best measure of complexed metals is to analyze
for some common complexing compounds (or complexing agents) generally
found in wastewater for which analytical methods are available. These
complexing agents include ammonia, cyanide, and EDTA. The analytical
method for cyanide is EPA Method 9010. The method for EDTA is ASTM
Method D3113. Ammonia can be analyzed using EPA Wastewater Test
Method 350.
(e) Oil and grease content. The oil and grease content of a
particular waste directly inhibits the settling of the precipitate.
Suspended oil droplets float in water and tend to suspend particles such
as chemical precipitates that would otherwise settle out of the
solution. Even with the use of coagulants or flocculants, the separation
of the precipitate is less effective. Oil and grease content can be
measured by EPA Method 9071.
(5) Design and operating parameters. The parameters that EPA will
evaluate when determining whether a chemical precipitation system is well
designed are: (a) design value for treated metal concentrations, as well
as other characteristics of the waste used for design purposes (e.g.,
total suspended solids), (b) pH, (c) residence time, (d) choice of
treatment chemical, and (e) choice of coagulant/flocculant. Below is an
explanation of why EPA believes these parameters are important to a
design analysis; in addition, EPA explains why other design criteria are
not included in the Agency's analysis.
3-14
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(a) Treated and untreated design concentrations. EPA pays
close attention to the treated concentration that the system is designed
to achieve when determining whether to sample a particular facility.
Since the system will seldom outperform its design, EPA must evaluate
whether the design is consistent with best demonstrated practice.
The untreated concentrations that the system is designed to treat are
important in evaluating any treatment system. Operation of a chemical
precipitation treatment system with untreated waste concentrations in
excess of design values can easily result in poor performance.
(b) pH. The pH is important because it can indicate that
sufficient treatment chemical (e.g., lime) has been added to convert the
metal constituents in the untreated waste to form's that will
precipitate. The pH also affects the solubility of metal hydroxides and
sulfides and therefore directly impacts the effectiveness of removal. In
practice, the design pH is determined by empirical bench testing, often
referred to as "jar" testing. The temperature at which the "jar" testing
is conducted is important in that it also affects the solubility of the
metal precipitates. Operation of a treatment system at temperatures
above the design temperature can result in poor performance. In
assessing the operation of a chemical precipitation system, EPA prefers
continuous data on the pH and periodic temperature conditions throughout
the treatment period.
(c) Residence time. The residence time is important because it
impacts the completeness of the chemical reaction to form the metal
precipitate and, to a greater extent, the amount of precipitate that
3-15
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settles out of solution. In practice, it is determined by "jar"
testing. For continuous systems, EPA will monitor the feed rate to
ensure that the system is operated at design conditions. For batch
systems, EPA will want information on the design parameter used to
determine sufficient settling time (e.g., total suspended solids).
(d) Choice of treatment chemical. A choice must be made as to
what type of precipitating agent (i.e., treatment chemical) will be
used. The factor that most affects this choice is the type of metal
constituents to be treated. Other design parameters, such as pH,
residence time, and choice of coagulant/flocculant agents, are based on
the selection of the treatment chemical.
(e) Choice of coagulant/flocculant. This is important because
these compounds improve the settling rate of the precipitated metals and
allow for smaller systems (i.e., lower retention time) to achieve the
same degree of settling as much larger systems. In practice, the choice
of the best agent and the required amount is determined by "jar" testing.
(f) Mixing. The degree of mixing is a complex assessment that
includes, amorrg other things, the energy supplied, the time the material
is mixed, and the related turbulence effects of the specific size and
shape of the tank. EPA will, however, consider whether mixing is
provided and whether the type of mixing device is one that could be
expected to achieve uniform mixing. For example, EPA may not use data
from a chemical precipitation treatment system where an air hose was
placed in a large tank to achieve mixing.
3-16
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3.4.2 Sludge Filtration
(1) Applicability. Sludge filtration, also known as sludge
dewatering or cake-formation filtration, is a technology used on wastes
that contain high concentrations of suspended solids, generally higher
than 1 percent. The remainder of the waste is essentially water. Sludge
filtration is applied to sludges, typically those that have settled to
the bottom of clarifiers, for dewatering. After filtration, these
sludges can be dewatered to 20 to 50 percent solids.
(2) Underlying principles of operation. The basic principle of
filtration is the separation of particles from a mixture of fluids and
particles by a medium that permits the flow of the fluid but retains the
particles. As would be expected, larger particles are easier, to separate
from the fluid than smaller particles. Extremely small particles, in the
colloidal range, may not be filtered effectively and may appear in the
treated waste. To mitigate this problem, the wastewater should be
treated prior to filtration to modify the particle size distribution in
favor of the larger particles, by the use of appropriate precipitants,
coagulants, flocculants, and filter aids. The selection of the
appropriate precipitant or coagulant is important because it affects the
particles formed. For example, lime neutralization usually produces
larger, less gelatinous particles than does caustic soda precipitation.
For larger particles that become too small to filter effectively because
of poor resistance to shearing, shear resistance can be improved by the
3-17
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use of coagulants and flocculants. Also, if pumps are used to feed the
filter, shear can be minimized by designing for a lower pump speed or by
using a low-shear type of pump.
(3) Physical description of the process. For sludge filtration,
settled sludge is either pumped through a cloth-type filter medium (such
as in a plate and frame filter) that allows solid "cake" to build up on
the medium or drawn by vacuum through a cloth medium (such as on a drum
or vacuum filter), which also allows the solids to build. In both cases,
the solids themselves act as a filter for subsequent solids removal. For
a plate and frame-type filter, removal of the solids is accomplished by
taking the unit off line, opening the filter, and scraping the solids
off. For the vacuum-type filter, cake is removed continuously. For a
specific sludge, the plate and frame-type filter will usually produce a
drier cake than a vacuum filter. Other types of sludge filters, such as
belt filters, are also used for effective sludge dewatering.
(4) Waste characteristics affecting performance. The following
characteristics of the waste will affect performance of a sludge
filtration unit: (a) size of particles and (b) type of particles.
(a) Size of particles. The smaller the particle size, the more
the particles tend to go through the filter medium. This is especially
true for a vacuum filter. For a pressure filter (such as a plate and
frame), smaller particles may require higher pressures for equivalent
throughput since the smaller pore spaces between particles create
resistance to flow.
3-18
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(b) Type of particles. Some solids formed during metal
precipitation are gelatinous in nature and cannot be dewatered well by
cake-formation filtration. In fact, for vacuum filtration a cake may not
form at all. In most cases, solids can be made less gelatinous by use of
the appropriate coagulants and coagulant dosage prior to clarification,
or after clarification but prior to filtration. In addition, the use of
lime instead of caustic soda in metal precipitation will reduce the
formation of gelatinous solids. Also, the addition of filter aids, such
as lime or diatomaceous earth, to a gelatinous sludge will help
significantly. Finally, precoating the filter with diatomaceous earth
prior to sludge filtration will assist in dewatering gelatinous sludges.
(5) Design and operating parameters. For sludge filtration, the
following design and operating variables affect performance: (a) type of
filter selected, (b) size of filter selected, (c) feed pressure, and
(d) use of coagulants or filter aids.
(a) Type of filter. Typically, a pressure-type filter (such as
a plate and frame) will yield a drier cake than a vacuum-type filter and
will also be more tolerant of variations in influent sludge
characteristics. Pressure-type filters, however, are batch operations,
so that when cake is built up to the maximum depth physically possible
(constrained by filter geometry), or to the maximum design pressure, the
filter is turned off while the cake is removed. A vacuum filter is a
continuous device (i.e., cake discharges continuously), and will usually
3-19
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be much larger than a pressure filter with the same capacity. A hybrid
device is a belt filter, which mechanically squeezes sludge between two
continuous fabric belts.
(b) Size of filter. As with in-depth filters, the larger the
filter, the greater its hydraulic capacity and the longer the filter runs
between cake discharges.
(c) Feed pressure. This parameter impacts both the design pore
size of the filter and the design flow rate. It is important that the
design feed pressure not be exceeded; otherwise, particles may be forced
through the filter medium, resulting in ineffective treatment.
(d) Use of coagulants. Coagulants and filter aids may be mixed
with filter feed prior to filtration. Their effect is particularly
significant for vacuum filtration in that it may make the difference in a
vacuum filter between no cake and a relatively dry cake. In a pressure
filter, coagulants and filter aids will also significantly improve
hydraulic capacity and cake dryness. Filter aids, such as diatomaceous
earth, can be precoated on filters (vacuum or pressure) for sludges that
are particularly difficult to filter. The precoat layer acts somewhat
like an in-depth filter in that sludge solids are trapped in the precoat
pore spaces. Use of precoats and most coagulants or filter aids
significantly increases the amount of sludge solids to be disposed of;
however, polyelectrolyte coagulant usage usually does not increase sludge
volume significantly because the dosage is low.
3-20
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4. 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-F012 and F019 wastes. These data are used elsewhere in this
document for determining which technologies represent BOAT (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 was.te 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 the tables 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
4-1
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waste characteristics that affect performance of the demonstrated
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 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 and
treated wastewater (after precipitation of metals and filtration for
removal of suspended solids) and the total and TCLP leachate
concentrations of metals and cyanide in the treated nonwastewater (the
precipitated solids from chemical precipitation, treated further by
sludge dewatering).
4.2 Wet 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 and the treated wastewater, as well as the
4-2
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total and TCLP leachate concentrations of metals and cyanide in the
nonwastewater treatment residual (reactor wall scale and reactor bottom
sol ids).
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
1987). These data, for eight sample sets, are presented in Table 4-3.
The data show concentration of cyanide in the untreated waste and the
treated wastewater, as well as design and operating information for each
test.
4.4 Electrolytic Oxidation Data
Table 4-4 presents 11 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).
These data present cyanide concentrations in the untreated and treated
wastes as well as operating data for each test. Wastes tested were
actual F007-F009 electroplating wastes, in the form of both bulk liquids
(wastewaters) and drummed solids (nonwastewaters).
4-3
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4.6 Chemical Precipitation Data
The data for BOAT 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
BOAT Background Document for K062 (USEPA 1988b).)
4.7 Stabilization Data
The Agency has data on treatment of BOAT list metals in F006 waste by
stabilization. (See EPA's BOAT Background Document for F006 (USEPA
1988a).) EPA has not identified any treatment data for F006, F012, or
F019 wastes for BOAT list metals other than the data considered in
developing treatment standards for F006, for which stabilization was
determined to be the "best" technology.
4.8 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.
4-4
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Table 4-1 Electrolytic.Oxidation, Alkaline Chlorination. Chemical
Precipitation, and Sludge Oewatering Data Collected by EPA at Plant A
for Treatment of F011 and Heat Treating Quenching Wastewaters
Sample Set No. la
Concentration
Constituent
Antimony
Barium
Cadmium
Chromium (hexavalent)
Chromium (total)
Copper
Lead
Mercury
Nickel
Silver
Vanadium
Zinc
Cyanide (amenable)
Cyanide (total)
Untreated
waste
Total
(mg/1)
0.029
1.0
0.01
<0.01
5.42
1.03
1.1
<0. 00025
2.88
0.0072
0.156
0.338
I
5.350
Treated
wastewater
Total
(mg/1)
<0.021
0.084
<0.004
8.95
6.55
0.043
<0.05
0.00022
0.58
0.012
0.032
0.03
3.0 b
117 b
Treated
Total
(mg/kg)
<2.1
19
1.4
-
39
72
22
<0.10
519
<0.20
7.0
31
19.9
99.4
nonwastewater
TCLP
(mg/1)
<0.021
0.301
0.016
0.259
0.236
0.076
0.011
<0.0002
3.06
<0.002
0.014
0.352
0.147
0.818
Note: Design and operating parameters are as follows:
Parameter Design value
Operating value
Electrolytic oxidation reactor 170-180*F
temperature
Electrolytic oxidation reactor pH >11.0
Alkaline chlorination reactor pH >11.0; 7.0-9.0
(2-step)
Excess chlorine in alkaline NS
chlorination reactor
175-180'F
10.6-11.6
11.2; 8.0 ,
30 mg/1
I = Sample result is indeterminate because of analytical interference, but is less than
5,130 mg/1 based on laboratory analysis of total and amenable cyanides for the
partially treated waste.
- = Not analyzed.
NS = Not specified.
aElectrolytic oxidation was used only with Sample Set No. 1.
Accuracy-adjusted concentration.
Reference: USEPA 1988e.
4-5
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2324g
Table 4-1 (continued)
Sample Set No. 2
Concentration
Constituent
Antimony
Barium
Cadmium
Chromium (hexavalent)
Chromium (total)
Copper
Lead
Mercury
Nickel
Silver
Vanadium
Zinc
Cyanide (amenable)
Cyanide (total)
Note: Design and operating
Parameter
Untreated
waste
Total
(mg/1)
<0.021
0.158
0.057
<0.01
0.175
. 1.08
0.063
<0.0002
10.9
0.064
0.043
0.60
29.2
62.6
parameters are as
Design
Treated
wastewater
Total
(mg/1)
<0.021
0.102
0.0092
0.625
1.63
0.035
<0.005
0.00032
0.64
0.094
0.011
0.147
<0.01
<0.01
follows:
value
Treated nonwastewater
Total
(mg/kg)
<2.1
98
5.31
-
11
307
28
<0.1
758
0.73
6.7
54
5.6
34.7
Operating
TCLP
(mg/1)
<0.021
0.312
0.052
0.436
0.31
0.354
0.01
<0.0002
5.9
0.034
0.0061
0.377
<0.01
<0.01
value
Alkaline chlorination
reactor pH
Excess chlorine in alkaline
chlorination reactor
>11.0; 7.0-9.0
NS
11.6; 7.6
120 mg/1
- = Not analyzed.
NS = Not specified.
4-6
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Table 4-2 Wet Air Oxidation Data Collected by EPA at Plant B for F007 Waste
Sample Set No. 1 '
Concentration
Constituent
BOA! Organ ics
Methanol
BOAT Inorganics
Antimony
Arsenic
Barium
Beryll ium
Cadmium
Chromium (hexavalent)
Chromium (tota 1)
Copper
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Cyanide (amenable)
Cyanide (total)
Fluoride
Untreated
waste
Total
(ing/D
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
Note: Design and operating parameters are as
Parameter
Reactor temperature
Residence time
Oxygen concentration (off -gas)
Reactor pressure
Treated
wastewater
Total
(mg/1)
266
Treated nonwastewater
a b
Reactor solids A Reactor solids B
Total
(nig/kg)
<15
<4.0 <350
<0.05
0.047.
<0.075'
<0.06
I
0.628
759 151.
<1.75
<0.015
<0.25
<0.045;
<0.55
<2.0
<0.125
7.91 29.
0.3
11.9
4.20
follows:
Design value
440-480'F
55-66 min (5
16-20%
1700 psig
<1.0
1.25
<0.15
<1.25
I
2.55
000
<35
<1.0
33.7
<1.0
<10
<40
<2.5
600
<25
<25
-
.0-6.0 gal/hr)
TCLP Total
(mg/1) (mg/kg)
<15
<35
<0.01 <1.0
0.20 6.4
<1.5
<0.10 <1.0
I I
<0.10 6.09
44.400
<2.0 <35
<0.05 <1.0
26.5
<0.01 <1.0
<1.0 <8.0
<40
5.3
139,000
<25
<25
-
Operating
449-487-F
57.1 min
17.8%
1690-1707
TCLP
(mg/1)
-
-
<0.01
0.17
-
<0.10
1
<0.10
-
<2.0
<0.05
-
<0.01
<1.0
-
-
-
-
-
-
value
psig
Reactor wall scale; one sample collected for all six sample sets.
Reactor bottom solids; one sample collected for all six sample sets.
I = Matrix interference.
- = Not analyzed.
Reference: USEPA 1988f.
4-7
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2324y
Table 4-2 (continued)
Sample Set No. 2
Concentration
Treated nonwastewater
Const ituent
BOAT Organ ics
Methanol
BOAT Inorganics
Ant imony
Arsenic
Ba r i urn
Beryll ium
Cadmium
Chromium (hexavalent)
Chromium (total)
Copper
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Cyanide (amenable)
Cyanide (total)
Fluoride
Untreated
waste
Total
(mg/1)
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
Note: Design and operating parameters are as
Parameter
Reactor temperature
Residence time
Oxygen concentration (off-gas)
Reactor pressure
Treated , , a
wastewater Reactor solids A
Total Total TCLP
(mg/1) (mg/kg) (mg/1)
<150 <15
<4.0 <350
<0.05 <1.0 <0.01
<0.03 1.25 0.20
<0.075 <0.15
0.17 <1.25 <0.10
I 1 I
0.478 2.55 <0.10
568 151.000
<1.75 <35 <2.0
<0.015 <1.0 <0.05
<0.25 33.7
<0.045 <1.0 <0.01
<0.55 <10 <1.0
<2.0 <40
<0.125 <2.5
7.48 29,600
<0.25 <25
<0.25 <25
4.02
f o 1 lows :
Design value
440-480T
55-66 min (5.0-6.0 gal/hr)
16-20%
1700 psig
b
Reactor solids B
Total
(mg/kg)
<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
Operating
440-489'F
60.5 min
17.0%
1709-1725
TCLP
(mg/1)
-
-
<0.01
0.17
-
<0.10
I
<0.10
-
<2.0
<0.05
-
<0.01
<1.0
-
-
-
-
-
value
psig
Reactor wall scale; one sample collected for all six sample sets.
Reactor bottom solids; one sample collected for all six sample sets.
1 - Matrix interference.
- = Not analyzed.
4-8
-------
2324g
Table 4-2 (continued)
Sample Set No. 3
Concentration
Treated nonwastewater
Constituent
BOAT Organ ics
Methanol
BOAT Inorganics
Antimony
Arsenic
Barium
Beryllium
Cadmium
Chromium (hexavalent)
Chromium (total)
Copper
Lead
Mercury
Nickel
Selenium
Silver
Thall ium
Vanadium
Zinc
Cyanide (amenable)
Cyanide (total)
Fluoride
Untreated
waste
Total
(mg/1)
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
Note: Design and operating parameters are as
Parameter
Reactor temperature
Res idence t ime
Oxygen concentration (off -gas)
Reactor pressure
Treated a
wastewaler Reactor solids A
Total Total TCLP
(mg/1) (mg/kg) (mg/1)
110 <15
<4.0 <350
<0.05 <1.0 <0.01
0.038 1.25 0.20
<0.075 <0.15
0.48 <1.25 <0.10
I I I
0.568 2.55 <0.10
834 151,000
<1.75 <35 <2.0
<0.015 <1.0 <0.05
<0.25 33.7
<0.045 <1.0 <0.01
<0.55 <10 <1.0
<2.0 <40
<0.125 <2.5
4.63 29,600
<0.25 <25
3.22 <25
4.02
follows:
Design value
440-480'F
55-66 min (5.0-6.0 gal/hr)
16-20%
1700 psig
Reactor sol ids B
Total
(mg/kg)
<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
Operating
431-488'F
59.2 min
17.5%
1701-1718
TCLP
(mg/1)
-
-
<0.01
0.17
-
<0.10
I
<0.10
-
<2.0
<0.05
-
<0.01
<1.0
-
-
-
-
-
value
psig
aReactor wall scale; one sample collected for all six sample sets.
Reactor bottom solids; one sample collected for all six sample sets.
I = Matrix interference.
- = Not analyzed.
4-9
-------
Table 4-2 (continued)
Sample Set No. 4
Concentration
Const ituent
BDAT Organ ics
Methano 1
BDAT Inorganics
Ant imony
Arsenic
Barium
Beryl 1 ium
Cadmium
Chromium (hexavalent)
Chromium (total)
Copper
Lead
Mercury
Nickel
Selenium
Si Iver
Thallium
Vanadium
Zinc
Cyanide (amenable)
Cyanide (total)
Fluoride
Untreated
waste
Total
(mg/1)
CBI
CBI
CBI
CBI
CBI
CBI
- CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
Note: Design and operating parameters are
Parameter
Reactor temperature
Residence time
Oxygen concentration (off -gas)
Reactor pressure
Treated nonwastewater
Treated a b
wastewater Reactor solids A Reactor solids B
Total Total
(mg/1) (mg/kg)
64 <15
<4.0 <350
<0.05 <1.0
<0.30 1.25
<0.75 <0.15
<0.60 <1.25
I I
<0.90 2.55
766 151.000
<17.5 <35
<0.015 <1.0
<2.5 33.7
<0.045 <1.0
<5.5 <10
<20 <40
<1.25 <2.5
6.26 29.600
<0.25 <25
<0.25 <25
4.07
as follows:
Design value
440-480'F
55-66 min (5.0-6.0 gal/hr)
16-20%
1700 psig
TCLP Total
(mg/1) (mg/kg)
<15
<35
<0.01 <1 .0
0.20 6.4
<1.5
<0.10 <1.0
I I
<0.10 6.09
44,400
<2.0 <35
<0.05 <1.0
26.5
<0.01 <1.0
<1.0 <8.0
<40
5.3
139,000
<25
<25
Operating
424-493'F
53.3 min
16.5%
1675-1740
TCLP
(mg/1)
-
-
<0.01
0.17
-
<0.10
1
<0.10
-
<2.0
<0.05
•
<0.01
<1.0
-
-
-
-
-
value
psig
aReactor wall scale; one sample collected for all six sample sets.
Reactor bottom solids; one sample collected for all six sample sets.
I = Matrix interference.
- - Not analyzed.
4-10
-------
2324g
Table 4-2 (continued)
Sample Set No. 5
Concentration
Treated nonwastewater
Const ituent
BOAT Organ ics
Methanol
BOAT Inorganics
Ant imony
Arsenic
Barium
Beryl 1 ium
Cadmium
Chromium (hexavalent)
Chromium (total)
Copper
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Cyanide (amenable)
Cyanide (total)
Fluoride
Untreated
waste
Total
(mg/1)
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
Note: Design and operating parameters are as
Parameter
Reactor temperature
Residence time
Oxygen concentration (off-gas)
Reactor pressure
Treated „ , , a
wastewater Reactor solids A
Total Total T.CLP
(mg/1) (mg/kg) (mg/1)
50 <15
<4.0 <350
<0.05 . <1.0 <0.01
<0.03 1.25 0.20
<0.075 *0.15
<0.72 <1.25 <0.10
I I I'
0.499 2.55 <0.10
946 151.000
<1.75 <35 <2.0
<0.015 <1.0 <0.05
<0.25 33.7
<0.045 <1.0 <0.01
<0.55 <10 <1.0
<2.0 <40
<0.125 <2.5
4.07 29.600
<0.25 <25
<0.25 <25
4.06
follows:
Design value
440-480'F
55-66 min (5.0-6.0 gal/hr)
16-20%
1700 psig
b
Reactor solids B
Total
(mg/kg)
<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
Operating
417-484'F
51.6 min
16.6%
1680-1694
TCLP
(mg/1)
-
-
<0.01
0.17
-
<0.10
I
<0.10
-
<2.0
<0.05
-
<0.01
<1.0
-
-
-
-
-
value
psig
aReactor wall scale; one sample collected for all six sample sets.
Reactor bottom solids; one sample collected for all six sample sets.
I = Matrix interference.
- = Not analyzed.
4-11
-------
2324g
Table 4-2 (continued)
Sample Set No. 6
Concentration
Treated nonwastewater
Constituent
BOAT Organ ics
Methanol
BOAT Inorganics
Ant imony
Arsenic
Barium
Bery 11 ium
Cadmium
Chromium (hexavalent)
Chromium (total)
Copper
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Cyanide (amenable)
Cyanide (total)
Fluoride
Untreated
waste
Total
(mg/1)
CBI
• CBI
CBI
CB1
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
CBI
-CBI
CBI
Note: Design and operating parameters are as
Parameter
Reactor temperature
Residence time
Oxygen concentration (off -gas)
Reactor pressure
Treated
wastewater
Total
(mg/D
36
a
Reactor solids A
Total TCLP
(mg/kg) (mg/1)
<15
<4.0 <350
<0.05
<0.6
<1.5
<1.2
I
<1.8
994 151,
<35
<0.015
<5.0
<0.045
<11
<40
<2.5
8.46 29.
<0.25
<0.25
3.95
follows:
Design value
440-480'F
55-66 min (5
16-20%
1700 psig
<1.0 <0.01
1.25 0.20
<0.15
<1.25 <0.10
I I
2.55 <0.10
000
<35 <2.0
<1.0 <0.05
33.7
<1.0 <0.01
<10 <1.0
<40
<2.5
600
<25
<25
.0-6.0 gal/hr)
b
Reactor solids B
Total
(mg/kg)
<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
Operating
412-494'F
50.8 min
17.0%
1674-1690
TCLP
(mg/1)
-
-
<0.01
0.17
-
<0.10
I
<0.10
-
<2.0
<0.05
-
<0.01
<1.0
-
-
-
-
-
value
psig
aReactor wall scale; one sample collected for all six sample sets.
Reactor bottom solids; one sample collected for all six sample sets.
I = Matrix interference.
- = Not analyzed.
4-12
-------
2301g
Table 4-3 Alkaline Chlorination Data Submitted by Plant C
for Various Wastes
Sample Set No. la - for Treatment of D003 and F007
Const ituent/parameter
Concentration (units)
Untreated
waste
(mg/1)
Treated
wastewater
(mg/1)
BOAT Inorganics Other Than Metals
Cyanide (amenable)
Cyanide (total)
BOAT List Hetals
60,000
Cadm i urn
Chromium (total)
Copper
Lead
Nickel
Zinc
Non-DDAT List Metals
Iron
117
<100
4,000
<100
1 . 500
1,800
.1.700
Note: Design and operating parameters are as follows:
Parameter Design value
Operating value
Alkaline chlorination reactor pH
Retention time for alkaline
chlorination
ORP for alkaline chlorination
12.5-13.0 12.9
2-6 hr minimum 96 hr
>200 mv 380 mv
- = Not analyzed.
aBatch consisted of a mixture of waste codes D003 and F007.
Actual retention time is based on a "not detected" result for the
analysis of the waste for amenable cyanide.
Reference: CyanoKCM 1987.
4-13
-------
Table 4-3 (continued)
Sample Set No. 2 - for Mixed F006-F012, P030
Constituent/parameter
Concentration (units)
Untreated
waste
(mg/U
Treated
wastewater
(ng/D
BOAT Inorganics Other Than Hetals
Cyanide (amenable)
Cyanide (total) 11,400
BDAT List Hetals
Cadmium 25
Chromium (total) 1,300
Copper 3,400
Lead 250
Nickel 7,300
Zinc 18.500
Non-BDAT List Hetals
Iron 3,000
Note: Design and operating parameters are as follows:
Parameter Design value Operating value
Alkaline chlorination reactor pH
Retention time for alkaline
chlorination
OKP for alkaline chlorination
12.5-13.0 12.45
2-6 nr minimum 24 hr
>200 mv 345 mv
- = Not analyzed.
aBatch consisted of a mixture of liquids and drummed solids including
waste codes F006, F007, F008, F009, F011, F012. and P030.
Actual retention time is based on a "not detected" result for the
analysis of the waste for amenable cyanide.
4-14
-------
2301g
Table 4-3 (continued)
Sample Set No. 3 - for Treatment of F007
Constituent/parameter
Concentration (units)
Untreated
waste
(mg/1)
Treated
wastewater
(mg/1)
BOAT Inorganics Other Than Metals
Cyanide (amenable)
Cyanide (total)
BOAT List Hetals
100
Cadmium
Chromium (total)
Copper
Lead
Nickel
Zinc
Non-BOAT List Metals
Iron
-
780
440
<100
1,740
<100
470
Note: Design and operating parameters are as follows:
Parameter Design value
Operating value
Alkaline chlorination reactor pH
Retention time for alkaline
chloririat ion
ORP for alkaline chlorination
12.5-13.0
2-6 hr minimum
>200 mv
12.65
5.5 hr
350 mv
- = Not analyzed.
aBatch was waste code F007.
Actual retention time is based on a "not detected" result for the
analysis of the waste for amenable cyanide.
4-15
-------
2301g
Table 4-3 (continued)
Sample Set No. 4 - for Treatment of 0003
Const i tuent/parameter
Concentration (units)
Untreated
waste
(mg/1)
Treated
wastewater
(mg/D
BOAT Inorganics Other Than Metals
Cyanide (amenable)
Cyanide (total) 13,000
BOAT List Metals
Cadmium
Chromium (total)
Copper <100
Lead
Nickel <100
Zinc
Non-BDAT List Metals
Iron 320
Note: Design and operating parameters are as follows:
Parameter Design value Operating value
Alkaline chlorination reactor pH
Retention time for alkaline
chlorination
ORP for alkaline chlorination
12.5-13.0 11.8
2-6 hr minimum 2 hr
>200 mv 520 mv
- = Not analyzed.
Batch tested consisted of solid sodium and potassium cyanide salts of
130,000 ppm cyanide concentration (D003).
Actual retention time is based on a "not detected" result for the
analysis of the waste for amenable cyanide.
4-16
-------
2i01g
Table 4-3 (continued)
Sample Set No. 5 - for Treatment of F009
Constituent/parameter
Concentration (units)
Untreated
waste
(mg/1)
Treated
wastewater
(mg/D
BDAT Inorganics Other Than Metals
Cyanide (amenable)
Cyanide (total) 27,200
BDAT List Metals
Cadmium
Chromium (total)
Copper 270
Lead
Nickel 1.050
Zinc 3,070
Non-BDAT List Metals
Iron 3,320
Note: Design and operating parameters are as follows:
Parameter Design value Operating value
Alkaline chlorination reactor pH
Retention time for alkaline
chlorination
ORP for alkaline chlorination
12.5-13.0 12.6
2-6 hr minimum 20 hr
>200 mv 460 mv
- = Not analyzed.
"Waste tested was F009.
Actual retention time is based on a "not-detected" result for the
analysis of the waste for amenable cyanide.
4-17
-------
230Ig
Table 4-3 (continued)
Sample Set No. 6 - for Treatment of F011 and D002
Constituent/parameter
Concentration (units)
Untreated
waste
(mg/1)
Treated
wastewater
(•9/1)
BOAT Inorganics Other Than Hetals
Cyanide (amenable)
Cyanide (total) 6.000
BOAT List Metals
Cadmium
Chromium (total)
Copper
Lead
Nickel
Zinc 11,000
Non-BDAT List Hetals
1ron 4.000
Note: Design and operating parameters are as follows:
Parameter Design value Operating value
Alkaline chlorination reactor pH
Retention time for alkaline
chlorination
ORP for alkaline chlorination
12.5-13.0 12.8
2-6 hr minimum 48 hr
>200 mv 424 mv
- = Not analyzed.
aBatch consisted of a mixture of F011 and D002.
Actual retention time is based on a "not detected" result for the
analysis of the waste for amenable cyanide.
4-18
-------
2301g
Table 4-3 (continued)
Sample Set No. 7 - for Treatment of F009
Constituent/parameter
Concentration (units)
Untreated
waste
(mg/1)
Treated
wastewater
(mg/1)
BOAT Inorganics Other Than Hutals
Cyanide (amenable)
Cyanide (total) 30,000
BOAT List Metals
Cadmium
Chromium (total)
Copper
Lead
Nickel
Zinc 19.250
Non-BDAT List Metals
Iron
Note: Design and operating parameters are as follows:
Parameter Design value Operating value
Alkaline chlorination reactor pH
Retention time for alkaline
chlorination
ORP for alkaline chlorination
12.5-13.0 12.8
2-6 hr minimum 12 hr
>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.
4-19
-------
2301g
Table 4-3 (continued)
Sample Set No. 8 - for Treatment of F007
Constituent/parameter
Concentration (units)
Untreated
waste
(mg/D
Treated
wastewater
(mg/1)
BOAT Inorganics Other Than Metals
Cyanide (amenable)
Cyanide (total) 6,000
BOAT List Hetals
Cadmium
Chromium (total) <100
Copper 1,500
Lead
Nickel
Zinc 580
Non-BDAT List Hetals
Iron 490
Note: Design and operating parameters are as follows:
Parameter Design value Operating value
Alkaline chlorination reactor pH
Retention time for alkaline
chlorination
ORP for alkaline chlorination
12.5-13.0 12.9
2-6 hr minimum 8 hr
>200 mv 380 mv
- = Not analyzed.
aBatch was F007 waste.
Actual retention time is based on a "not detected" result for the
analysis of the waste for amenable cyanide.
4-20
-------
2301g
Table 4-4 Electrolytic Oxidation Treatment Data from Literature Source A
for Treatment of F007 and F009 Wastes
Constituent
Sample Set 11:
Cyanide (total)
Sample Set *2:
Cyanide (total)
Sample Set #3:
Cyanide (total)
Sample Set #4:
Cyanide (total)
Sample Set #5:
Cyanide (total)
Sample Set #6:
Cyanide (total)
Sample Set #/:
Cyanide (total)
Sample Set #8:
Cyanide (total)
Sample Set #9:
Cyanide (total)
Samp In Set #10:
Cyanide (total)
Sample Set 111:
Cyanide (total)
Note: Design values for
Parameter
Temperature
Total current
Anode current density
Concentration (units)
Untreated Treated
waste wastewater
(mg/1) (mg/1)
95.000 0.1
75.000 0.2
50,000 0.4
75,000 0.2
65,000 0.2
100.000 0.3
55,000 0.4
45.000 0.1
50,000 0.4
55,000 0.2
48,000 0.4
operating conditions are presented below:
Value/Description
200*F minimum
1,200 amp P 6 volts
35 amp/ft2
Reaction
time
(days)
16
17
10
18
12
17
14
7
14
8
12
Reference: Easton 1967. Treatment of F007 and F009 copper plating wastes.
4-21
-------
2301g
Table 4-5 High-Temperature Cyanide Hydrolysis Data from Literature Source B
for Treatment of F007. F008. and F009 Wastes
Constituent
Samp le Set No. 1 :
Cyanide (total)
Sample Set No. 2:
Cyanide (total)
Sample Set No. 3:
Cyanide (total)
fcmplc Set No. 4:
Cyanide (total)
Sample Set No. 5:
Cyanide (total)
Sample Set No. 6:
Concentration (units)
Untreated Treated
waste wastewater
(mg/D (mg/D
10,000 19.8
30,000 0.8
10,000 2.6
10,000 15
33,000 1.2
Operating Data
Maximum Maximum
temperature pressure
CF) (psi)
477 700
492 875
450 -a
460 620
500 875
(units)
Reaction time
at maximum
temperature (hr)
1 hr
1 hr
1 hr
1 hr
1 hr
Cyanide (total)
38,000
2.1
458
875
1 hr
Pressure gauge malfunction; 875 psi is assumed.
Reference: Robey 1983. Treatment of F007-F009 wastes containing cadmium, copper, and/or nickel cyanides.
4-22
-------
Table 4-6 Incineration Data Submitted by Plant D for Treatment of F010
Concentration (units)
Untreated waste Treated nonwastewater
(mg/kg) (total) (leachate)
(rog/1) (mg/1)
Sample Set No. 1:
Cyanide (total) 22.000 0.45 <0.025
Sample Set No. 2:
Cyanide (total) . 20.000 0.40 <0.025
Sample Set No. 3:
Cyanide (total) -a 0.88 <0.025
aThe treatment data were obtained from treatment of two different wastes. The three
treated waste samples represent samples taken over the course of treatment of the two
wastes.
Reference: CyanoKEM 1988.
4-23
-------
5. IDENTIFICATION OF BEST DEMONSTRATED AVAILABLE TECHNOLOGY (BOAT)
This section presents the Agency's rationale for determining best
demonstrated available technology (BOAT) for F006 (cyanide), F007-F012,
and F019 nonwastewaters and wastewaters. To determine BOAT, the Agency
examines all available performance data for 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 BOAT
*
Treatment Standards. BOAT must be specifically defined for all
streams 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 particular waste or waste
subcategory is then evaluated to determine whether it 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 data on the
performance of a waste similar to the waste in question, provided that
the similar waste is at least as difficult to treat.
Accuracy adjustment accounts for the ability of an analytical
technique to recover a particular constituent from 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
-------
5.1 BDAT for the Metal Finishing Aqueous Liquids Subcateqorv
5.1.1 Cyanide Treatment
EPA reviewed the available treatment performance data for wastes in
this subcategory for cyanide treatment technologies, presented in
Section 4, to determine whether they represent the operation of
well-designed and well-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 collected at Plant A, presented in Table 4-1,
provide the appropriate measure of performance 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 was well operated during the test. Additionally, the appropriate
QA/QC data were supplied with these performance data.
The treatment performance data for wet air oxidation, presented in
Table 4-2, also provide amenable and total cyanide concentrations in the
untreated waste and in both wastewater and nonwastewater residuals.
Design and operating data collected during the test indicate that the
system was well designed and was 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
5-2
-------
Set No. 1 show higher concentrations of both amenable and total cyanide
in the feed (approximately 20 percent higher) than for any of the other
five sample sets, without a corresponding increase in residence time.
This may account for a poorer system performance, as shown by the data.
This problem might have been alleviated in operation either by better
mixing of the feed or by decreasing the feed flow rate for higher
concentration feed streams. The data for Sample Set No. 1 were not
considered further in the development of BOAT standards on the basis of
poor system operation (insufficient reactor residence time) at the time
of treatment data collection.
Treatment performance data for alkaline chlorination submitted by
Plant C, presented in Table 4-3, provide total cyanide concentration in
the untreated waste and amenable cyanide concentration in the treated
wastewater. The design and operating data submitted indicate that the
system was well designed and was well operated during the tests. No
QA/QC data were submitted.
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
treated wastewater. The design values given indicate that the system was
well designed, and the treated waste cyanide concentration, as well as
the reaction time, indicates that the system was well operated at the
time of treatment data collection. No QA/QC data were given for these
tests.
5-3
-------
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 reactor pressure (700 psi and
620 psi versus 875 psi for the other four runs) contributed 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.
The treatment performance data for the demonstrated cyanide treatment
technologies presented in Section 4 were adjusted for analytical recovery
to take into account analytical interferences associated with the
chemical makeup of the treated waste samples. In the QA/QC test for
analytical recovery, EPA 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.) The reciprocal of the
5-4
-------
recovery multiplied by the analytical value obtained during performance
testing is the accuracy-corrected value used in comparing treatment
effectiveness and subsequently in calculating treatment standards.
Percent recovery values for constituents detected in the F007 and F011
wastes tested are presented in Appendix A. In the cases for which no
analytical recovery data were available (Tables 4-3 through 4-5), EPA
cannot directly compare these data to the data for which accuracy
correction factors are available. Therefore, the data presented in
Tables 4-3 through 4-5 for alkaline chlorination, electrolytic oxidation,
and high-temperature cyanide hydrolysis were not considered in the
determination of "best" treatment of cyanide in F007-F011 wastewaters and
nonwastewaters.
Accuracy-adjusted cyanide concentrations for all data considered in
developing BOAT for metal finishing aqueous liquids for wastewaters are
presented in Tables 5-1 and 5-2 (all tables are at the end of the
section) for amenable and total cyanide, respectively. Statistical
comparison of the one data set from electrolytic oxidation followed by
alkaline chlorination with the five data sets from wet air oxidation from
treatment of similar wastes shows that the performance of wet air
oxidation is better for both amenable and total cyanides.
EPA's determination that substantial treatment occurs for wet air
oxidation is based on the reduction in both total and amenable cyanide
concentrations in the waste tested. In addition to providing substantial
5-5
-------
treatment, wet air oxidation is commercially available; therefore, this
technology is "available" to treat cyanide in the wastes in the metal
finishing aqueous liquids subcategory.
5.1.2 BOAT List Metals Treatment
Characterization data for F007, F008, F009, and F011 wastes show that
these wastes may contain high concentrations of dissolved metals and
therefore may require treatment by chemical precipitation followed by
filtration and sludge dewatering. Chromium reduction may also be
necessary prior to 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 sets were also
presented, in Table 4-1, for chemical precipitation followed by
filtration and sludge dewatering treatment of F011 waste mixed with heat
treating rinsewaters. These two sets of performance data are not
directly comparable because the K062 waste treated had significantly
higher concentrations of BOAT list metals than the F011 waste treated.
The treatment data used in regulation of K062 can be transferred to the
wastewater residual from treatment of F007, F008, F009, F010 (inorganic
subgroup), and F011 because these wastes have similar or lower dissolved
5-6
-------
metals concentrations and thus will treat similarly to K062, whereas the
F011 treatment data represent treatment of a waste with significantly
lower metals concentrations than expected for most F007, F008, F009, and
F011 wastes and thus cannot be transferred. Because the K062 treatment
data are the only data available to EPA on the performance level of
chromium reduction followed by chemical precipitation and filtration
treatment of a waste with high BOAT metals concentration, the Agency has
determined that the performance of chromium reduction followed by
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 BOAT.
(2) Nonwastewaters. The nonwastewater treatment residual from the
chemical precipitation step, either before or after dewatering, is a
waste that is similar to the wastes in the metal finishing sludges
subcategory. The selection of BOAT for these wastes is discussed in the
next section.
5.2 BDAT for the Metal Finishing Sludges Subcategory
5.2.1 BDAT List Metals Treatment
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 F006). EPA believes that the
wastes F012 and F019 are similar to F006 both in waste composition and in
the process generating the waste. These wastes are also similar to the
5-7
-------
nonwastewater treatment residuals from treatment of F007-F009 and F011
wastes by chemical precipitation followed by filtration. It follows,
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 BOAT
list metals for F012, F019, and the nonwastewater residuals (i.e.,
wastewater treatment sludges) from chemical precipitation and sludge
dewatering treatment of F007, F008, F009, and F011 based on the
similarities discussed above between F006 and these wastes.
5.2.2 Cyanide Treatment
For cyanide, no data are available to the Agency on treatment of
F006, F012, F019, or similar wastes by any of the technologies identified
as demonstrated for F007, F008, F009, and FOIL As stated in
Section 2.4, however, these wastes are generated from chemical
precipitation treatment, which usually follows a cyanide oxidation step
if the waste treated originally contained cyanide. Therefore, these
wastes are not expected to contain treatable concentrations of cyanide if
generated following treatment by a well-designed and well-operated
cyanide treatment step. The Agency has two data sets on the generation
of F012 waste from a well-designed and well-operated treatment system
consisting of electrolytic oxidation followed by alkaline chlorination,
chemical precipitation, filtration, and sludge dewatering (presented in
Table 4-1). The accuracy-adjusted data for cyanides in this waste as
generated are presented in Table 5-3. Treatment of the waste for cyanide
5-8
-------
before generation of these wastes is the Agency's "best" technology for
determination of cyanide treatment standards for F006, F012, F019, and
similar wastes.
As discussed in Section 4 and previously in this section, alkaline
chlorination, electrolytic oxidation, chemical precipitation, filtration,
and sludge dewatering are commercially available technologies for the
treatment of F007-F009, F011, and similar wastes and thus are "available"
to be used to generate F006, F012, F019, and similar wastes.
Also, as shown in Table 4-1, the.treatment train discussed above
substantially reduces the concentration of cyanide in F012 waste compared
to the waste from which it was generated. Stabilization treatment of the
treatment sludges generated by chemical precipitation 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 F006, F012, F019,
or similar waste thus generated, is "available" and thus is BOAT for
F006, F012, and F019 and is the basis for cyanide standards for
wastewater treatment sludge residuals from the treatment of F007, F008,
F009, and F011 wastes.
5.3 BOAT for the Metal Finishing Organic Liquids Subcateqory
The data available to the Agency on incineration of F010 waste
(presented in Table 4-6) indicate that incineration achieves a
substantial reduction in cyanide concentration in the incinerator ash
compared to the untreated waste. Accuracy adjustment of these data is
5-9
-------
detailed in Table 5-4. No data were submitted on BOAT metals in the
untreated waste or the ash residual. The Agency has no information as to
which, if any, metals are present in F010 waste or the ash residual from
incineration of this waste.
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) in terms of the concentration of cyanide and the type
and concentration of BOAT list metals. Therefore, "best" technology for
these scrubber waters is wet air oxidation.
Incineration and wet air oxidation are both commercially available
technologies and thus are "available" for the purposes of establishing
BOAT. Therefore, BOAT for the metal finishing organic liquids
subcategory is incineration followed by wet air oxidation treatment of
the scrubber waters.
5-10
-------
Table 5-1 Summary of Accuracy Adjustment of Treatment Data
for Amenable Cyanide in Wastewaters
Untreated
waste
concentration
(mg/1)
Measured
treated waste
concentration
(mg/1)
Percent
recovery for
matrix
spike test
Accuracy
correction
factor
Accuracy-
adjusted
concentration
(mg/1)
Wet Air Oxidation
Sample Set No. 2
Sample Set No. 3
Sample Set No. 4
Sample Set No. 5
Sample Set No. 6
CBI
CBI
CBI
CBI
CBI
<0.25
<0.25
<0.25
<0.25
<0.25
electrolytic Oxidation/Alkaline Chlorination
52
52
52
52
52
1.923
1.923
1.923
1.923
1.923
Sample Set No. 1
5,350
<0.48
<0.48
<0.48
<0.48
<0.48
3.0
aValue is total cyanide concentration.
- = Not available. Quantities actually measured were total cyanide and "chlorinated cyanide.
which were both adjusted for accuracy. (See Appendix B for detailed calculations.)
5-11
-------
2324g
Table 5-2 Seminary of Accuracy Adjustment of Treatment Data
for Total Cyanide in Wastewaters
Untreated
waste
concentration
(mg/1)
Measured
treated waste
concentration
(mg/D
Percent
recovery for
matrix
spike test
Accuracy
correction
factor
Accuracy-
adjusted
concentration
(mg/1)
Wet Air Oxidation
Sample Set No. 2
Sample Set No. 3
Sample Set No. 4
Sample Set No. 5
Sample Set No. 6
CBI
CBI
CBI
CBI
CBI
<0.25
3.22
<0.25
<0.25
<0.25
Electrolytic Oxidation/Alkaline Chlorination
Sample Set No. 1 5.350 ' 103
52
52
52
52
52
88
1.923
1.923
1.923
1.923
1.923
1.136
<0.48
6.19
<0.48
<0.48
<0.48
117
5-12
-------
Table 5-3 Summary of Accuracy Adjustment of Cyanide Data
in F012 Waste as Generated
Untreated Percent Accuracy-
waste recovery for Accuracy adjusted
concentration matrix correction concentration
(mg/1) spike test factor (mg/1)
Sample Set No. 1
Cyanide (amenable)
Cyanide (total)
99.4
102
0.98
'-0.023
97.4
Sample Set Mo. 2
Cyanide (amenable)
Cyanide (total)
34.7
93
1.08
<0.023
37.3
- - Not available. Quantities actually measured were total cyanide and "chlorinated
cyanide," which were both adjusted for accuracy. (See Appendix B for detailed
calculations.)
5-13
-------
Table 5-4 Summary of Accuracy Adjustment of Treatment Data
for Total Cyanide in F010 Waste
Untreated Measured Percent Accuracy-
waste treated waste recovery for Accuracy adjusted
concentration concentration tna.tr 1x correction concentration
(mg/kg) (mg/kg) spike test factor (mg/kg)
Sample Set No. 1
Cyanide (total)
Sample Set No. 2
Cyanide (total)
Sample Set No. 3
Cyanide (total)
22.000
20,000
0.45
0.40
0.88
96
96
96
1.04
0.468
1.04 ' 0.416
1.04
0.915
- = Not available. Only two untreated waste samples were collected.
5-14
-------
6. SELECTION OF REGULATED CONSTITUENTS
This section presents the rationale for selection of the proposed
regulated constituents for the treatment of F006-F012 and F019 wastes.
Constituents selected for regulation must satisfy the following
criteria:
1. They must be on the BOAT list of regulated constituents.
(Presence on the BOAT 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 boil ing 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, which constituents were detected, and which
constituents the Agency believes may be present even though not detected
6-1
-------
in the untreated waste on which treatment tests were performed. BOAT
list metals and cyanide were detected in all of the wastes sampled.
For the F007 waste tested, one volatile organic compound was
detected, methanol. One PCB compound, Aroclor 1254, was 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 BOAT 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 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 that are not believed to be treatable. The
methanol detected in the F007 waste tested was probably a constituent of
the electroplating bath, but is not commonly used in such an application;
thus, it is not proposed for regulation.
6.2 Determination of Regulated Constituents
For the metal finishing aqueous liquids subcategory, EPA is proposing
to regulate total and amenable cyanide in both wastewater and
nonwastewater treatment residuals based on the performance of wet air
6-2
-------
oxidation. The Agency is also proposing to regulate chromium, lead, and
nickel in wastewaters and cadmium, chromium, lead, nickel, and silver in
nonwastewaters. Regulated constituent selection for nonwastewaters and
wastewaters is based on treatment of the effluent from wet air oxidation
by chemical precipitation followed by filtration for the wastewaters and
subsequent dewatering followed by stabilization of the nonwastewater
residual. All of the metals listed above are commonly found in
electroplating and heat treating wastes. Amenable and total cyanides are
proposed for regulation 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 performance of
cyanide destruction technologies between complexed and noncomplexed
cyanide, both amenable and total cyanide standards are proposed. 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 proposed for regulation.
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 because the 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 BOAT list metals by chemical
6-3
-------
precipitation and/or stabilization will also reduce leachate
concentrations of both of these metals in wastewater and nonwastewater
treatment residuals.
For the metal finishing treatment sludges subcategory (F006, F012,
and F019), EPA is proposing to regulate amenable and total cyanide in
both wastewaters and nonwastewaters. For F012 and F019 wastewaters, the
Agency is proposing to regulate chromium, lead, and nickel. For F012 and
F019 nonwastewaters, the Agency is proposing to regulate cadmium,
chromium, lead, nickel, and silver. These metals have been previously
regulated for F006 nonwastewaters (see EPA's BOAT Background Document for
F006).
For the metal finishing organic liquids (F010), EPA is proposing to
regulate total cyanide in the total composition analysis for both
wastewater and nonwastewater residuals. 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 has no reason to expect BOAT metals to be detected in the
organic F010 waste.
6-4
-------
2286g
Table 6-1 Status of BOAT List Constituent Presence
in Untreated Tested Wastes
BOAT
reference
no.
222.
1.
2.
3.
4.
5.
6.
223.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
25.
26.
27.
28.
29.
224.
225.
226.
30.
227.
31.
214.
32.
33.
228.
34.
Constituent
Volati le Orqanics
Acetone
Acetonitrile
Acrolein
Acrylonitrile
Benzene
Bromod i ch loromethane
Bromomethane
n-Butyl alcohol
Carbon tetrachloride
Carbon disulfide
Chlorobenzene
2-Chloro-l,3-butadiene
Chlorodibromomethane
Chloroethane
2-Chloroethyl vinyl ether
Chloroform
Ch loromethane
3-Chloropropene
l,2-Dibromo-3-chloropropane
1 ,2-Dibromoethane
Dibromomethane
trans-1 ,4-Dichloro-2-butene
D i ch lorod i f luoromet hane
1.1-Dichloroethane
1,2-Dichloroethane
1 , 1-Dichloroethylene
trans- 1 , 2-D ich loroethene
1.2-Dichloropropane
trans-1 ,3-Dichloropropene
cis- 1,3-0 ich loropropene
1,4-Dioxane
2-Ethoxyethanol
Ethyl acetate
Ethyl benzene
Ethyl cyanide
Ethyl ether
Lthyl methacrylate
Ethylene oxide
lodomethane
Isobutyl alcohol
'hethanol
Methyl ethyl ketone
F007
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
D
ND
F011
NO
ND
ND
ND
ND
ND
ND
NA
ND
ND
NO
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NA
NA
ND
ND
NA
ND
ND
ND
ND
NA
NO
F012
D
ND
ND
ND
ND
ND
ND
NA
ND
ND
ND
ND
ND
ND
ND
D
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NO
ND
ND
ND
NA
NA
ND
ND
NA
ND
ND
ND
ND
NA
ND
6-5
-------
2286g
Table 6-1 (continued)
BOAT
reference
no.
229.
35.
37.
38.
230.
39.
40.
41.
42.
43.
44.
45.
46.
47.
48.
49.
231.
50.
215.
216.
217.
51.
52.
53.
54.
55.
56.
57.
58.
59.
?18.
60.
61.
62.
63.
64.
65.
66.
Constituent
Volatile Orqanics (continued)
Methyl isobutyl ketone
Methyl methacrylate
Methacrylonitrile
Methylene chloride
2-Nitropropane .
Pyridine
1,1,1 ,2-Tetrachloroethane
1,1,2, 2-Tetrachloroethane
Tetrachloroethene
Toluene
Tribromomethane
1 , 1 , 1-Tr ichloroethane
1,1, 2-Tr ichloroethane
Trichloroethene
Tr ich loromonof luoromethane
1,2,3-Trichloropropane
l,l,2-Trichloro-l,2,2-
trif luoroethane
Vinyl chloride
1,2-Xylene
1,3-Xylene
1 ,4-Xylene
Semivolati le Orqanics
Acenaphthylene
Acenaphthene
Acetophenone
2-Acetylaminof luorene
4-Aminobiphenyl
Ani line
Anthracene
Aramite
Benz ( a ) anthracene
Bcn7.il chloride
Benzenethiol
Deleted
Benzo(a)pyrene
Benzo(b)f luoranthene
Benzo(ghi Jperylene
~ Benzo(k)f luoranhene
p-Benzoquinone
F007
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NA
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NA
ND
ND
NA
ND
ND
ND
ND
NA
F011
ND
ND
ND
ND
NA
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NA
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NA
ND
ND
ND
ND
ND
ND
F012
ND
ND
ND
D
NA
ND
ND
ND
ND
D
ND
ND
ND
ND
ND
ND
NA
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NA
ND
ND
ND
ND
ND
ND
6-6
-------
2286g
Table 6-1 (continued)
BOAT
reference
no.
67.
68.
69.
70.
71.
72.
73.
74.
75.
76.
77.
78.
79.
80.
81.
82.
232.
83.
84.
85.
86.
87.
88.
89.
90.
91.
92.
93.
94.
95.
96.
97.
98.
99.
100.
101.
102.
103.
104.
105.
106.
219.
Const ituent
Semivolat ile Orqanlcs (continued)
Bis(2-chloroethoxy)methane
Bis(2-chloroethyl) ether
Bis(2-chloroisopropyl) ether
Bis(2-ethylhexyl) phthalate
4-Bromophenyl phenyl ether
Butylbenzyl phthalate
2-sec-Butyl-4,6-dinitrophenol
p-Chloroani line
Chlorobenzilate
p-Chloro-m-cresol
2-Chloronaphthalene
2-Chlorophenol
3-Chloropropionitri le
Chrysene
ortho-Cresol
para-Cresol
Cyclohexanone
Oibenz(a,h)anthracene
Dibenzo(are)pyrene
Dibenzo(a, ijpyrene
m-D ich lorobenzene
o-D ich lorobenzene
p-D ich lorobenzene
3,3'-Dichlorobenzidine
2,4-Oichlorophenol
2,6-Dichlorophenol
Diethyl phthalate
3 , 3 ' -D imethoxybenz id i ne
p-Dimethylaminoazobenzene
3.3'-Dimethylbenzidine
2.4-Dimethylphenol
Dimethyl phthalate
Di-n-butyl phthalate
1.4-Dinitrobenzene
4 , 6-Din itro-o-cresol
2,4-Dinitrophenol
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Di-n-octyl phthalate
Di-n-propylnitrosamine
Diphenylamine
D i pheny 1 n i t rosam i ne
F007
ND
NO
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NA
NA
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
F011
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NA
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
F012
ND
ND
ND
D
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NA
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
6-7
-------
2286g
Table 6-1 (continued)
BOAT
reference
no.
107.
108.
109.
110.
111.
112.
113.
114.
115.
116.
117.
118.
119.
120.
36.
121.
122.
123.
124.
125.
126.
127.
128.
129.
130.
131.
132.
133.
134.
135.
136.
137.
138.
139.
140.
141.
142.
220.
143.
144.
145.
146.
Constituent
Semivolati le Organics (continued)
1 , 2-D ipheny Ihydraz ine
Fluoranthene
Fluorene
Hexachlorobenzene
Hexach lorobutad i ene
Hexach lorocyc lopentad iene
Hexachloroethane
Hexachlorophene
Hexach loropropene
Indeno(l,2,3-cd)pyrene
Isosafrole
Methapyri Iene
3-Methylcholanthrene
4,4'-Methylenebis-
(2-chloroaniline)
Methyl methanesulfonate
Naphthalene
1,4-Naphthoquinone
1-Naphthylamine
2-Naphthylamine
p-Nitroani line
Nitrobenzene
4-Nitrophenol
N-N i trosod i -n-buty lam ine
N-Nitrosodiethylamine
N-N i trosod i methyl am ine
N-Nitrosomethylethylamine
N-N i t rosomorpho 1 i ne
N-Nitrosopiperidine
N-Nitrosopyrrol idine
5-Nitro-o-toluidine
Pentachlorobenzene
Pentachloroethane
Pentachloron i trobenzene
Pentach loropheno 1
Phenacetin
Phenanthrene
Phenol
Phthalic anhydride
2-Picoline
Pronamide
Pyrene
Resorcinol
F007
NO
ND
ND
ND
ND
ND
ND
NA
ND
ND
ND
ND
NA
ND
ND
ND
ND
NA
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NA
ND
ND
ND
ND
ND
ND
ND
ND
ND
NA
F011
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NA
ND
ND
ND
ND
F012
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NA
ND
ND
ND
ND
6-8
-------
2286g
Table 6-1 (continued)
BOAT
reference
no.
147.
148.
149.
150.
151.
152.
153.
154.
155.
156.
157.
158.
159.
221.
160.
161.
162.
163.
164.
165.
166.
167.
168.
169.
170.
171.
172.
1/3.
174.
175.
Constituent
Semivolati 1e Orqanlcs (continued)
Safrole
1,2,4, 5-Tetrachlorobenzene
2,3,4, 6-Tetrach loropheno 1
1,2,4-Trlchlorobenzene
2.4,5-Trichlorophenol
2, 4, 6-T rich loropheno 1
Tr i s ( 2 , 3-d i bromopropy 1 )
phosphate
Hetals
Ant Imony
Arsenic
Barium
Beryl 1 ium
Cadmium
Chromium (total)
Chromium (hexavalent)
Copper
Lead
Mercury
Nickel
Selenium
Si Iver
Thallium
Vanadium
Zinc
Inorqanics Other Than Metals
Cyanide
Fluoride
Sulfide
Orqanochlorinc Pesticides
Aldrin
alpha-BHC
beta-BHC
delta-BHC
F007
ND
NO
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND-X
D
1-Y
D
ND
D
ND-X
ND
ND-X
*
ND
ND
D
D
D
NA
ND
ND
ND
ND
F011
ND
ND
ND
ND
ND
ND
ND
D
ND
D
ND
D
D
ND
D
D
ND
D
ND
D
ND
D
D
D
D
ND
NA
NA
NA
NA
F012
ND
ND
ND
ND
ND
ND
ND
ND
ND
D
ND
D
D
I
D
D
ND
D
ND
D
ND
D
D
D
D
ND
NA
NA
NA
NA
6-9
-------
2286g
Table 6-1 (continued)
BOAT
reference
no.
176.
177.
178.
179.
180.
181.
182.
183.
184.
185.
186.
187.
188.
189.
190.
191.
192.
193.
194.
195.
196.
197.
198.
199.
200.
201.
202.
203.
204.
205.
206.
Constituent
Orqanochlorine Pesticides (continued)
gamma-BHC
Chlordane
ODD
ODE
DDT
Dieldrin
Endosulfan 1
Endosulfan 11
Endrin
Endrin aldehyde
Heptachlor
Heptachlor epoxide
Isodrin
Kepone
Methoxyclor
Toxaphene
Phenoxvacetic Acid Herbicides
2,4-Dichlorophenoxyacetic acid
Silvex
2,4,5-T
Orqanoohosphorous Insecticides
Disulfoton
Famphur
Methyl parathion
Parathion
Phorate
PCBs
Aroclor 1016
Aroclor 1221
Aroclor 1232
Aroclor 1242
Aroclor 1248
Aroclor 1254
Aroclor 1260
F007
ND
NO
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
F011
NA
NA
NA
.NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
ND
ND
ND
ND
ND
ND
ND
F012
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
ND
ND
ND
ND
ND
D
ND
6-10
-------
2286g
Table 6-1 (continued)
BOAT
reference Constituent F007 F011 F012
no.
Dioxins and Furans
207. Hexachlorodibenzo-p-dioxins ND ND ND
208. Hexachlorodibenzofurans ND ND ND
209. Pentachlorodibenzo-p-dioxins ND ND ND
210. Pentachlorodibenzofurans ND ND ND
211. Tetrachlorodibenzo-p-dioxins ND ND ND
212. Tetrachlorodibenzofurans ND ND ND
213. 2,3,7,8-Tetrachlorodibenzo-
p-dioxin NA ND ND
D = Detected
ND = Not detected.
NA = Not analyzed.
I = Analytical interference (matrix effects) prevented analysis.
X = Believed to be present based on engineering analysis of waste generating
process.
Y = Believed to be present based on detection in treated residuals.
References: USEPA 1988e. 1988f.
6-11
-------
7. CALCULATION OF PROPOSED BOAT TREATMENT STANDARDS
This section presents the calculation of the proposed treatment
standards 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
well-operated BOAT 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.
BOAT 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 BOAT. 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 BOAT Treatment Standards (USEPA 1988d).)
Details on the calculation of variability factors for F006-F012 and F019
wastes are presented in this section.
Where EPA has identified BOAT for a particular waste, but because of
data limitations or for some other compelling reason cannot define
specific treatment standards for that waste, the Agency can require the
7-1
-------
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 Cyanide
EPA is proposing both nonwastewater and wastewater treatment
standards for amenable and total cyanide for each of the three waste
subcategories established in Section 2.4. These subcategories are as
follows: (1) metal finishing aqueous liquids subcategory (F007, F008,
F009, and F011; (2) metal finishing sludges subcategory (F006, F012, and
F019); and (3) metal finishing organic liquids subcategory (F010).
Proposed cyanide standards for wastewaters for all three subcategories
are based on performance data from wet air oxidation of F007 waste.
Proposed nonwastewater treatment standards for the second subcategory, as
generated, 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. These proposed
nonwastewater standards are also transferred to nonwastewater residuals
generated by treatment of wastes in the first subcategory. Proposed
nonwastewater standards for the third subcategory are based on data from
treatment of F010 and a similar waste by incineration.
7-2
-------
7.2 BDAT List Metals
EPA is proposing nonwastewater treatment standards for BDAT list
metals for F007-F009, F011, F012, and F019 based on the treatment
standards established for treatment of F006 by stabilization. (See EPA's
Best Demonstrated Available Technology (BDAT) Background Document for
F006 (USEPA 1988a).) Wastewater treatment standards for these wastes are
also being established 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).)
7-3
-------
Table 7-1 Calculation of Proposed Treatment Standards for Total and
Amenable Cyanide Based on Wet Air Oxidation
Regulated
constituent (units)
Accuracy-adjusted
treated waste
concentration3
Mean treated
waste
concentration
Variability
factor (VF)
Treatment
standard (total
composition)
Wastewater (mq/1):
Cyanide (amenable)
•
Cyanide (total)
<0.48 0.48 2.8 1.3
<0.48
<0.48
<0.48
<0.48
<0.48 1.62 7.09 12
6.19
<0.48
<0.48
<0.48
aSee Tables 5-1 and 5-2.
7-4
-------
2324g
Table 7-2 Calculation of Proposed Treatment Standards for Total and Amenable Cyanide
Based on Generation of F012 Waste by a Well-Operated Treatment Process
Consisting of Electrolytic Oxidation, Alkaline Chlorination, Chemical
Precipitation, Filtration, and Sludge Dewatering
Regulated
constituent (units)
Accuracy-adjusted
treated waste
concentration3
Mean treated
waste
concentration
Variability
factor (VF)
Treatment
standard (total
composition)
Nonwastewater (mg/kg):
Cyanide (amenable) <0.023 0.023 2.8 0.064
<0.023
Cyanide (total) . 97.4 67.35 1.58 110
37.3
aSee Table 5-3.
7-5
-------
Table 7-3 Calculation of Proposed Treatment Standards for Incineration of F010
Accuracy-adjusted
Regulated treated waste
constituent (units) concentration3
Mean treated
waste Variability
concentration factor (VF)
Treatment
standard (total
composition)
Nonwastewater (rug/kg):
Cyanide (total)
0.468
0.416
0.915
0.60
2.53
1.5
"See Table 5-4.
7-b
-------
Table 7-4 Proposed BOAT Treatment Standards for f007, F008. F009. and F011
Constituent
Cyanide (amenable)
Cyanide (total)
Cadmium
Chromium
lead
Nickel
Silver
Uastewater
Total
composition
(rng/D
1.3
12
-
0.32
0.04
0.44
-
Nonwastewater
Total
composition
(mg/kg)
0.064
110
NA
NA
NA
NA
NA
TCLP
(mg/D
NA
NA
0.066
b.2
0.51
0.32
0.072
NA = Not applicable.
- = No treatment standard.
7-7
-------
Table 7-5 Proposed BOAT Treatment Standards for F006 (Cyanide)
Constituent
Nonwastewater
Total
composition
(mg/kg)
TCLP
(mg/1)
Cyanide (amenable)
Cyanide (total)
0.064
110
NA
NA
NA = Not applicable.
7-8
-------
Table 7-6 Proposed BOAT Treatment Standards for F012 and F019
Constituent
Cyanide (amenable)
Cyanide (total)
Cadmium
Chromium
Lead
Nickel
Silver
Wastewater
Total
composition
(mg/1)
1.3
12
-
0.32
0.04
0.44
-
Nonwastewater
Total
composition
(mg/kg)
0.064
110
NA
NA
NA
NA
NA
TCLP
(mg/D
NA
NA
0.066
5.2
0.51
0.32
0.072
NA - Not applicable.
- = No treatment standard.
7-9
-------
2324g
Table 7-7 Proposed BOAT Treatment Standards for F010
Constituent
Wastewater
Total
composition
(mg/1)
Nonwastewater
Total
composition TCLP
(mg/kg) (mg/1)
Cyanide (amenable)
Cyanide (total)
1.3
12
1.5
NA
NA
NA = Not applicable.
- = No treatment standard.
7-10
-------
8. P AND U WASTE CODES
This section addresses regulation of those P and U 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 (P063) 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 F007 and F011 wastes tested
by the Agency and other wastes composing the metal finishing aqueous
liquids subcategory as identified in Section 2.4. Therefore, the Agency
believes electrolytic oxidation, alkaline chlorination, wet air
oxidation, high-temperature cyanide hydrolysis, and SO /air oxidation
are applicable and demonstrated to treat off-specification product,
wastewater, and contaminated soil and sludge forms of the P codes listed.
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
Of the demonstrated technologies identified in Section 8.2, the
"best" technology for cyanide treatment for these wastes is wet air
oxidation. For treatment of BOAT metal constituents, the "best"
technology is chemical precipitation followed by filtration and sludge
dewatering. Cyanide standards for wastewater treatment sludge residuals
are based on generation of these sludges by electrolytic oxidation
followed by alkaline chlorination, chemical precipitation, and sludge
dewatering. Determination of "best" technology and "availability" for
both cyanides and metals follows the rationale that was presented in
Section 5.1 for the metal finishing aqueous liquids subcategory and in
Section 5.2 for the metal finishing sludges subcategory (for the
treatment sludges).
8.4 Proposed Treatment Standards
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. The Agency currently
has no data on treatment of silver and zinc in wastewaters by chemical
precipitation.
8-2
-------
Table 8-1 P and U Waste Codes Proposed for Regulation
Waste code Chemical compound Regulated constituents
P013 Barium cyanide Cyanide
P021 Calcium cyanide Cyanide
P029 Copper cyanide Copper, cyanide
P030 Cyanides (soluble cyanide Cyanide
salts). N.O.S.
P063 Hydrocyanic acid, hydrogen Cyanide
cyanide
P074 Nickel cyanide Nickel, cyanide
P098 Postassium cyanide Cyanide
P099 Postassium silver cyanide Silver, cyanide
P104 Silver cyanide Silver, cyanide
P106 Sodium cyanide Cyanide
P121 Zinc cyanide Zinc, cyanide
8-3
-------
23249
Table 8-2 Proposed Treatment Standards for P-code Cyanide Wastes
Constituent
Cyanide (amenable)
Cyanide (total)
Copper (P029 only)
Nickel (P074 only)
Silver (P099 and P104 only)
Zinc (P121 only)
Wastewater
Total
composition
(mg/1)
1.3
12
0.42
0.44
reserved
reserved
Nonwastewater (treatment sludqe)
Total
composition
(mg/kg)
0.064
110
NA
NA
NA
NA
TCLP
(mg/1)
NO
ND
0.71
0.30
0.07
0.086
NA = Not applicable.
8-4
-------
9. REFERENCES
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, FL.
EPA-600/2-81-064. NTIS PB81-190928.
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, D.C.: American Public Health
Association.
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.
Easton, John K. 1967. Electrolytic decomposition of concentrated
cyanide plating wastes. J. Water Poll. Contr. Fed. 39(10):1621-1626.
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. Washington, D.C.: U.S. Environmental Protection
Agency.
MRI. 1987. Midwest Research Institute. Analytical data report for six
facilities included in the electroplating sampling and analysis
program. Contract No. 68-01-7287, draft final report for Office of
Solid Waste. Washington, D.C.: U.S. Environmental Protection Agency.
Robey, H.L. 1983. AES Research Project 53A: Cyanide destruction in a
commercial-scale hydrolysis reactor. Plat, and Surf. Fin. 70:79-82.
USEPA. 1980. U.S. Environmental Protection Agency, Office of Solid
Waste. RCRA listing background document. Washington, D.C.: U.S.
Environmental Protection Agency.
9-1
-------
USEPA. 1986. 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. 1987. U.S. Environmental Protection Agency, Office of Solid
Waste. Generic quality assurance project plan for land disposal
restrictions program ("BOAT"). Washington, D.C.: U.S. Environmental
Protection Agency.
USEPA. 1988a. U.S. Environmental Protection Agency, Office of Solid
Waste. Best demonstrated available technology (BOAT) 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 (BOAT) 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 BOAT treatment standards.
Washington, D.C.: U.S. Environmental Protection Agency.
USEPA. 1988e. U.S. Environmental Protection Agency, Office of Solid
Waste. Onsite engineering report of treatment technology performance
and operation for Woodward Governor Corporation, Rockford, Illinois.
Washington, D.C.: U.S. Environmental Protection 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.
Versar. 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.
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.
9-2
-------
APPENDIX A
ANALYTICAL METHODS AND QA/QC
This appendix presents analytical methods and the matrix spike
recovery data for the treated waste samples from testing of F007, F011,
and F012 wastes.
A-l
-------
2338g/p.C
Table A-l Analytical Methods - Plant A
Analytical method • Method number Reference
Cyanides (total and amenable) • 9012
1. USEPA. 1986. U.S. Environmental Protection Agency, Office of Solid
Waste. Test methods for evaluating solid waste. 3rd ed.
Washington, D.C.: U.S. Environmental Protection Agency.
A-2
-------
2338g/p.l
Table A-2 Specific Procedures or Equipment Used for Analysis of Cyanide When
Alternatives or Equivalents Are Allowed in SW-846 Methods - Plant A
Analysis
Total and
amenable
cyanide
SW-846 Sample
method aliquot
9012 500 ml
Alternative or equivalent
allowed by SW-846 methods
Hydrogen sulfide treatment
may be required.
Specific
procedure used
Hydrogen sulfide
treatment was not
required.
A Fisher-Mulligan absorber
or equivalent should be used.
A Wheaton Distilling
Apparatus absorber was
used.
A-3
-------
2336g/p.6
Table A-3 Matrix Spike Recoveries for Cyanide - Plant A
Const ituent
Original
amount
detected
Ug/D
Amount
spiked
Ug/D
Spike
Amount
recovered Percent
Ug/1) recovery3
Duplicate spike
Amount
recovered Percent
Ug/1) recovery3
Relative
percent
difference
S
Cyanide, chlorinated
Cyanide, total
Sample WGS8-101
114,000
103,000
160,000
160,000
279,000
243,000
103
88
274,000
252,000
100
93
1.8
3.6
Cyanide, chlorinated
Cyanide, total
Sample WGS5-10
Cyanide, chlorinated
Cyanide, total
Cyanide, TCLP
,d
<10
<10
79.5
99.4
854
200
200
71.1
69.3
1000
140
110
170
1820
70
0.0C
43
102
97
120
173e
1990
60
0.0C
108
114
15
NC
1.0
8.9
Sample WGS9-101
Cyanide, chlorinated
Cyanide, total
Cyanide, TCLP
• 29.1 30.7 59.5 77
34.7 7.99 42.1 93 44. Of 116
40.8 200 225 92 222 91
23
1.3
NC = Not calculable.
- = Mo analysis performed.
aPercent recovery = 100 (C
is the amount recovered,
CQ is the original amount detected.
C ) / C+, where
'
Relative percent difference - | 100 (D^ - D2) / [D^ + D^) / 2] |, where Dj and D2 are the percent
recoveries of the spike and duplicate spike.
Zero percent recovery is attributed to matrix interference.
Units for solids sample concentrations are mg/kg.
eAmount spiked for the matrix duplicate spike was 68.1 mg/kg.
Amount spiked for'matrix spike duplicate was 7.96 mg/kg.
A-4
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Table A-4 Analytical Methods - Plant B
Analytical method Method number Reference
Cyanides (total and amenable) 9010
1. USEPA. 1966. U.S. Environmental Protection Agency, Office of Solid
Wdste. Test method for evaluating solid waste. 3rd ed. Washington,
D.C.: U.S. Environmental Protection Agency.
A-5
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233Sg/p.6
Table A-S Specific Procedures or Equipment Used for Analysis of Cyanide When
Alternatives or Equivalents Are Allowed in SW-846 Methods - Plant B
Analysis
Method
Alternative or equivalent allowed
Specific equipment or
procedure used
Cyanide
9010
Pretreatment with bismuth nitrate may be
necessary if su If ides are present.
Pretreatment was not necessary.
Pretreatment with sulfamic acid may be
necessary if nitrites/nitrates are present.
Pretreatment was not necessary.
A Fisher-Mulligan absorber or equivalent
should be used.
An ACE smog bubbler absorber
was used.
A tpectrophotometer suitable for measurements
at 578 nm with a 1.0-cm cell or larger is
required.
A Bausch and Lomb Model
Spectronic 21 was used.
A-6
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2338g/p.6
lable A-6 Matrix Spike/Matrix Spike Duplicate Results for Cyanide - Plant B
Samp le
Sample cone.
number (/ig/1)
OL-03 16.11
Spike
added
(M9/D
24.75
Spike
result
Ug/D
29.16
Spike duplicate
% Recovery result, (/ig/1)
52.7 28.97
% Recovery RPD
52.0 0.7
OL-03 = treated waste sample; Sample Set No. 3.
RPD = 100 (spike result - spike duplicate result)/(sP1ke resu1t + sPike d"P"cate result)
2
A-7
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