EPA/600/2-90/055
November 1990
CHARACTERIZATION AND TREATMENT OF WASTES
FROM METAL-FINISHING OPERATIONS
by
PEI Associa-tes, Inc.
Cincinnati, Ohio 45246
EPA Contract No. 68-03-3389
Project Officer
Ronald J. Turner
Water and Hazardous Waste Treatment Research Division
Risk Reduction Engineering Laboratory
Cincinnati, Ohio 45268
RISK REDUCTION ENGINEERING LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
CINCINNATI, OHIO 45268
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DISCLAIMER
The information in this document has been funded wholly or in part by the
United States Environmental Protection Agency (EPA) under Contract No. 68-03-
3389 to PEI Associates, Inc. It has been subject to the Agency's review and it
has been approved for publication as an EPA document. Mention of trade names
or commercial products does not constitute endorsement or recommendation for use.
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FOREWORD
Today's rapidly developing and changing technologies and industrial
products and practices frequently carry with them the increased generation of
materials that, if improperly dealt with, can threaten both public health and
the environment. The EPA is charted bv Congress with protecting the Nation's
land, air, and water resources. Under a mandate of rational environments!
laws, the Agency strives to formulate and implement actions leading to a com-
patible balance between human activities and the ability of natural systems
to support and nurture life. These laws direct the EPA to perform research
to define our environmental problems, measure the impacts, and search for
solutions.
The Risk Reduction Engineering Laboratory is responsible for planning,
implementing, and managing research, development, and demonstration programs
to provide an authoritative, defensible engineering basis in support of the
policies, programs, and regulations of the EPA with respect to drinkinp
v.'eter, wastewater, pesticides, toxic substances, solid and hazardous wastes,
and Superfund-related activities. This publication is one of the products of
that research and provides a vital communication link between the researcher
and the user community.
This report is a summary of project activities related to the bench- and
pilot-scale treatment of various electroplating wastes scheduled for land
disposal ban. Treatment technologies discussed in this report include alka-
line chlorination, wet-air oxidation, ultraviolet light/ozonation, electro-
lytic oxidation, stabilization/solidification, and metals precipitation.
Some of the performance data generated from these technology evaluations were
used in the development of waste code-specific treatment standards for the
land disposal restrictions program.
E. Timothy Oppelt, Director
Risk Reduction Engineering Laboratory
i i i
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ABSTRACT
The Hazardous and Solid Waste Amendments (HSWA) to the Resource Conser-
vation and Recovery Act (RCRA) include specific provisions restricting the
land disposal of RCRA hazardous wastes. The purpose of these HSWA provisions
is to minimize the potential of future risk to human health and the environ-
ment by requiring treatment of hazardous wastes prior to their land disposal.
The EPA's Office of Research and Development (ORD) was responsible for treat-
ing several electroplating and metal-finishing waste codes and providing
performance data in support of the development of treatment standards for the
Land Disposal Restrictions Program.
This report summarizes the project activities associated with the charac-
terization and treatment of some metal-finishing wastes. Information and
data are presented on the waste generators' manufacturing and wastewater
treatment plant operations, the chemical composition of the untreated wastes,
and performance data generated from bench- and pilot-scale testing. Treat-
ment technologies discussed in this report include alkaline chlorination,
wet-air oxidation, ultraviolet 1ight/ozonation, electrolytic oxidation,
stabilization/solidification, and metals precipitation. Conclusions are
presented regarding the effectiveness of the various technologies in treating
selected electroplating and metal-finishing wastes.
In addition to the project-related material, this report also presents a
section on cyanide chemistry. Most of the wastes discussed in this report
contain cyanide salts or complexed cyanide; therefore, this section provides
a background of useful information on terminology, definitions, cyanide
chemistry, stability and toxicity of cyanide compounds, and analytical meth-
odologies.
An appendix to th-is report provides a summary of the land disposal
restriction treatment standards for the electroplating and metal-finishing
wastes discussed in the report.
This report summarizes work conducted under U.S. EPA Contract No.
68-03-3389 during the period December 1, 1986 to September 30, 1989.
i v
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CONTENTS
Page
Foreword i i i
Abstract iv
Figures vi
Tables vii
Acknowledgments x
1. Introduction 1
Background 1
Report overview 1
Report organization 1
2. Cyanide Chemistry, Analysis, and Toxicity 4
Terminology 4
Stability and toxicity of the various forms of
cyanide 11
Analytical methods 15
3. Cyanide Oxidation Treatment 22
Alkaline chlorination 22
Wet-air oxidation 33
Ultraviolet 1ight/ozonation 38
Electrolytic oxidation 39
4. Chemical Precipitation 42
Process description 42
Site description - John Deere and Company 46
5. Stabilization/Solidification of Metal-Finishing Wastes 49
Background 49
Description of the WES stabilization/solidification
process 49
6. Results and Conclusions 52
Waste characterization 52
Bench-scale testing 58
Pilot-scale testing results and discussion 72
Full-scale testing - electrolytic oxidation 74
Stabilization/solidification testing 74
References 110
Appendix - Regulatory Overview of Land Disposal Restrictions for
Selected Metal-Finishing Waste Codes 114
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1
9
L.
3
4
5
6
7
8
9
10
11
FIGURES
Pa^e
Relationship Between HCN and CN with pH 9
Schematic of Master Lock's Conventional Wastewater
Treatment System 25
Schematic of Master Lock's Complexed (Chelated Wastewaters)
Wastewater Treatment Process 26
Schematic of Master Lock's Batch Wastewater Treatment
System 27
Wastewater Treatment at Amerock Corporation 29
CyanoKEM Waste and Raw Material Flow Schematic 32
Schematic Diagram of Zimpro/Passavant Wet-Air-Oxidation
Process 35
Schematic Diagram of the Batch F011 Cyanide Treatment
Process at Woodward Governor, Rockford, Illinois 41
Flow Diagram of a Typical Continuous Precipitation System 44
Phosphoric Acid Metal Precipitation at John Deere 47
Flowchart for WES Stabilization/Solidification Processing 51
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Num
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Page
2
Q
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56
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61
62
63
TABLES
Summary of Metal-Finishing Waste Codes Evaluated Under the
Land Disposal Restrictions Program for U.S. EPA's Office
of Research and Development
Solubilities of Metal-Cyanide Compounds
Solubilities of Ferrocyanides and Ferricyanides
Cyanide Forms, Complex Stability, and Solubility
Stability Constants of Metal-Cyanide Complex Ions
Typical Operating Parameters of the WAO Process
Typical Wastewater Discharge Concentrations From Metal
Hydroxide Precipitation Processes
List of Amerock F006 Analytes
List of Master Lock F006 Analytes
Summary of Master Lock F006 Cyanide Analyses
Summary of Master Lock F006 Metal Analyses
Analysis of John Deere F006 Filter Cake
Analysis of John Deere F006 TCLP Extract for Metals
Summary of Master Lock F009 Analyses
Analysis of Ford F019 Filter Cake
Analysis of Ford F019 TCLP Extracts
Amerock F007 Wet-Air-Oxidation Results
vi i
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TABLES (continued)
Number Page
18 Pollutant Analyses of Treated Amerock F007 64
19 Metals Analyses of Treated Amerock F007 65
20 F019 Wet-Air-Oxidation Results 66
21 Wet-Air-Oxidation Results for PF.I Associates, Inc.,
Cyanide Coating Waste Sludge (F019) 67
22 Master Lock Wet-Air-Oxidation Results 69
23 Wet-Air-Oxidation Results for Master Lock Cyanide Coating
Waste Sludge 70
24 Summary of Experiments—Ozone/UV Treatment of Cyanide
Waste 73
25 Results of F007 Cyanide Run 75
26 Analytical Results for Metals and Inorganic Parameters -
Woodward Governor Electrolytic Oxidation 76
27 List of TCLP Analytes by Waste Code 78
28 Analytical Data Summary of Untreated F006 Waste 80
29 Total Waste Analysis of Untreated and Treated F006 Waste 81
30 TCLP Analysis Results of 28-Dav Amerock F006/Cement
Binder Test Samples 82
31 TCLP Analytical Results of 28-Day Amerock F006/Lime/Fly
Ash BinderTest Samples 83
32 TCLP Analytical Results of 28-Day Amerock F006/Kiln
Dust Binder Test Samples 84
33 Wet Analytical Results of 28-Day Amerock F006/Cement
Binder Test Samples 85
34 Wet Analytical Results of 28-Day Amerock F006/Lime/Fly
Ash Binder Test Samples 86
35 Wet Analytical Results of 28-Day Amerock F006/Kiln Dust
Binder Test Samples 87
36 Analytical Results of Master Lock F006 TCLP Leachates 88
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37
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52
Page
93
94
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108
TABLES (continued)
Analytical Data Summary of Untreated F011 Waste
Total Waste Analysis of Untreated and Treated F011 Waste
TCLP Analytical Results of 28-Day FOll/Cement Binder Test
Samples
TCLP Analytical Results of 28-Day FOll/Lime/Fly Ash Binder
Test Samples
TCLP Analytical Results of 28-Day FOll/Kiln Dust Binder
Test Samples
Wet Analytical Results of 28-Day FOll/Cement Binder Test.
Samples
Wet Analytical Results of 28-Dav FOll/Lime/Fly Ash Binder
Test Samples
Wet Analytical Results of 28-Day FOll/Kiln Dust Binder
Test Samples
Analytical Data Summary of Untreated F012 Waste
Total Waste Analysis of Untreated and Treated F012 Waste
TCLP Analytical Results of 28-Day F012/Cement Binder Test
Samples
TCLP Analytical Results of 28-Day F012/Lime/Flv Ash Binder
Test Samples
TCLP Analytical Results of 28-Day FO12/Ki1n Dust Binder
Test Samples
Wet Analytical Results of 28-Day F012/Cement Binder Test
Samples
Wet Analytical Results of 28-Day F012/Lime/Fly Ash Binder
Test Samples
Wet Analytical Results of 28-Day F012/KiIn Dust Einder
Test Samples
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ACKNOWLEDGMENTS
This report was prepared by PEI Associates, Inc. (PEI), Cincinnati,
Ohio, as part of the work conducted for the EPA Risk Reduction Engineering
Laboratory (RREL) under Contract No. 68-03-3389, Work Assignment No. 2-1A.
Mr. Ronald J. Turner of RREL's Hazardous Waste Treatment Branch was the EPA
Technical Project Monitor.
Mr. William F. Kemner served as PEI's Project Manager, and principal
authors of this report were Messrs. Michael M. Arozarena, Philip W. Utrecht,
and Jeffrey A. Willis. The authors wish to thank Dr. Terrence D. Chatwin,
President of Resource Recovery and Conservation Consultants for preparation
of the cyanide chemistry section of the report. The authors would also like
to acknowledge the input of the following individuals and companies involved
in this study: Mr. Rodger Jul in with Amerock Corporation, Mr. Mike Wismer
with Metro Recovery Systems (formerly with Amerock Corporation); Mr. John B.
Newman with Master Lock Company; Mr. Ralph D. Grotelueschen with John Deere
and Company; Messrs. William J. Ziegler and Norman E. Levitin with Cyanokem;
Mr. James M. Sproat with Ford Electronics and Refrigeration Corporation; Mr.
Douglas K. Parker with Circle-Prosco, Inc.; Ms. Linda Baehr with Woodward
Governor Company; Dr. William M. Copa, Dr. Tipton L. Randall, Mr. Richard K.
Lehmann, and Mr. Bruce L. Brandenburg with Zimpro Passavant, Inc.; and Dr.
Richard H. Snow with 11T Research Institute.
x
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SECTION 1
INTRODUCTION
1.1 BACKGROUND
The Hazardous and Solid Waste Amendments (HSWA) to the Resource Conser-
vation and Recovery Act (RCRA) include specific provisions restricting the
land disposal of RCRA hazardous wastes. The purpose of these HSWA provisions
is to minimize the potential of future risk to human health and the environ-
ment by requiring treatment of hazardous wastes prior to their land disposal.
A major section of these amendments is the requirement for EPA to set treat-
ment standards, which substantially reduce the likelihood of constituent
migration, for all RCRA hazardous waste. The treatment standards are to be
based upon the performance of the best demonstrated available technology
(BOAT) to treat the waste. Once set by the EPA, these standards must be met
before land disposal is allowed. The EPA's Office of Research and
Development (ORD) was responsible for conducting treatability studies on
several electroplating and metal-finishing wastes and providing performance
data in support of the development of treatment standards for the Land
Disposal Restrictions Program.
1.? REPORT OVERVIEW
This report summarizes the project activities associated with the
characterization and treatment of some metal-finishing wastes scheduled for
land disposal ban. Table 1 presents a listing of the waste codes under
study, a description of the waste, the basis for listing, the waste genera-
tors), the technology scale, and the technology evaluated for each waste
code. Information and data are presented on the waste generators' manufac-
turing and wastewater treatment plant operations, the chemical composition of
the untreated wastes, and performance data generated from bench- and pilot-
scale testing. Treatment technologies discussed in this report include
alkaline chlorination, wet-air oxidation, ultraviolet 1 ight/ozonation, elec-
trolytic oxidation, stabilization/solidification, and metals precipitation.
Conclusions are also made as to the effectiveness of the various technologies
in treating selected electroplating and metal-finishing wastes.
1.3 REPORT ORGANIZATION
Because most of the waste codes discussed in this report contain cyanide
salts or complexed cyanide, Section 2 of the report seemed an appropriate
place to present cyanide terminology, definitions, cyanide chemistry, stabil-
ity and toxicity of cyanide compounds, and analytical methodologies. Section
1
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TABLE 1. SUMMARY OF METAL-FINISHING WASTE CODES EVALUATED UNDER THE LAND DISPOSAL RESTRICTIONS PROGRAM FOR
U.S. EPA's OFFICE OF RESEARCH AND DEVELOPMENT
EPA
Hazardous
Waste No.
Waste description
Basis
for 1isting
Generators sampled
Technology/scal e
F006
Wastewater treatment sludges from electro-
plating operations except from 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 asso-
ciated with tin, zinc, and aluminum plating
on carbon steel; and 6) chemical etching and
mi 11i ng of aluminum
Cadmium,
chromium
cyanide
hexavalent
, nickel, and
(complexed)
Oeere S Company
Amerock Corp.
Master Lock Co.
o
o
Wet-air oxidation at
bench-scale
Stabi1i zati on/solid-
ification at bench-
scale
FOD7
Spent cyanide plating-bath solutions from
electroplating operations
Cyanide
(salts)
Amerock Corp.
Wet-air oxidation at
bench- and pilot-
scale
Form
Plating bath sludges from electroplating
operations where cyanides are used in the
process
Cyanide
(salts)
—
F009
Spent stripping and cleaning-bath solutions
from electroplating operations where cyanides
are used in the process
Cyanide
(salts)
Master Lock Co.
e
Ultraviolet light/
ozonation at bench-
scale
roll
Spent cyanide solutions from salt-bath pnt
cleaning from metal heat-treating operations
Cyanide (salts)
Woodward Governor
Co.
0
0
Flect.rolyt.ic oxida-
tion at full-scale
Stabi1i zation/solid-
ification at bench-
scale
F012
Quenching wastewater treatment sludges from
metal heat-treating operations where cyanides
are used in the process
Cyanide
(complexed)
Woodward Governor
Co.
0
Electrolytic oxida-
tion at full-scale
Stabilization/sol id-
ification at bench-
scale
F019
Wastewater treatment sludges from the chemical
conversion coating of aluminum
Wexavalent chromium
and cyanide (complexed)
Ford
o
Wet-air oxidation at
bench-scale
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3 discusses four cyanide oxidation treatment technologies that were evaluated
as potential BDAT for treating the wastes identified in Section 1. These
technologies include alkaline chlorination, wet-air oxidation, ultraviolet
1ight/ozonation, and electrolytic oxidation. Section 4 presents a brief
discussion on metals precipitation of oxidized waste streams, and Section 5
discusses stabilization/solidification o-f" Waste Codes F006, F011, and F012.
Section 6 presents the results and conclusions obtained from the engineering
site visits, bench- and pilot-scale tests, and stabilization/solidification
tests. Finally, the Appendix presents a summary of the first-third and
second-third land disposal restriction treatment standards 'or the electro-
plating and metal-finishing waste codes discussed in the report.
3
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SECTION 2
CYANIDE CHEMISTRY, ANALYSIS, AND TOXICITY
TERMINOLOGY
The characterization of cyanide species falls into four general categor-
ies: 1) analytical methods, 2) ionic structure, 3) strength of the cyanide-
metal complex bond, and 4) compound solubility.
The cyanide terms that relate to analytical procedures include free,
weak-acid-dissociable (WAD), amenable, and total. The free cyanide defini-
tion relates to the measurement of cyanide anions, CN~, and molecular hydro-
gen cyanide (HCN) in the solution. The definition of WAD cyanide is based on
an ASTM analytical procedure for measuring the free cyanide and cyanide-metal
complexes that are easily dissociated into free cyanide. The definition of
amenable cyanide is based on an analytical procedure (EPA 1987, ASTM 1981)
that was developed to determine cyanide species amenable to alkaline chlorin-
ation treatment. Although the total methods were designed to measure all
cyanide species in solution, as pointed out in Ingersoll et al. (1983), some
total cyanide methods are only partially successful in achieving this goal.
For example, the most widely accepted methodology for analyzing total cyanide
does not analyze for tightly bound cobalt, gold, or some platinum group com-
plexes. More recent methods have been able to measure the cyanide from all
species studied in the investigation (Ingersoll et al. 1983).
The cyanide relating to ion structure is described as simple and complex
cyanides. The simple cyanide dissociates into the cyanide anion, CN~, and
the complex cyanide dissociates into a cyanide-metal anion [i.e., Fe(CN)fi3"l.
The terms based on the strength of the complex bond are the dissociable,
nondissociable, and the WAD cyanides. Cyanide is also characterized by its
solubility. These cyanides are defined simply as insoluble and soluble
cyanides. Because these cyanide definitions are overlapping, they have
resulted in some confusion. For example, cuprous cyanide and cupric cyanide
[CuCN and Cu(CN)2] are both simple and insoluble cyanides; however, potassium
cuprocyanide [KCu(CN)2] is also soluble, complex, amenable, dissociable, and
a WAD cyanide. In addition, all of the species that are dissociable result
in a portion of the cyanide occurring as a cyanide ion, CN", in the solution.
Each of these definitions is discussed in the following subsections, and
examples are given of specific cyanide species that fall into each category
to help clear this confusion.
Free Cyanide
The term "free cyanide" is the sum of cyanide anions (CN~) and hydrogen
cyanide (HCN), which ere the two most toxic cyanide species. In aqueous
4
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solution, the HCN forms a weak acid with a dissociation constant of 4.365 x
10~10 at 20°C (Broderius 1974). The interrelationship between volatile
hydrogen cyanide and the cyanide ion can be shown by the hydrolysis reaction:
CN" + H20 —> HCN + OH"
As shown in Figure 1, The formation of free cyanide (either HCN or CN~)
depends on the solution pH. At a pH of 9.36, the concentration of HCN and
CN are equal. Below a pH of 7 the free cyanide is essentially all HCN, and
above a pH of 11 the free cyanide is all CN".
Weak-Acid-Dissociable Cyanide
Weak-acid-dissociable cyanide (WAD) refers to free cyanide and cyanide-
metal complexes that are readily dissociated into free cyanide ions. This
cyanide term is also described by an analytical procedure, which is defined
by the ASTM in D-2036-81 Method C (ASTM 1982). This method is not sensitive
to sulfide or thiocyanate interferences. Because it determines free and
readily dissociable cyanide-metal complexes, the method results in a cyanide
measurement that is more indicative of the solution toxicity due to cyanide
than that due to total cyanide.
- 2 _
Examples of WAD cyanide species include CN~, HCN, Cu(CN)?~, Zn(CN).
and Ni(CN)42".
Amenable Cyanide
Amenable cyanide CN(A) refers to those cyanide species amenable to
removal by alkaline chlorination. This method is based on analyzing for
total cyanide before and after treatment with chlorine. This procedure is
described in ASTM D-2036-81 Method B and SW-846 Methods 9010 and 9012 (EPA
1986). The alkaline chlorination oxidizes all cyanide-metal complexes except
the iron complexes. Hence, the value should be similar to that in the WAD
cyanide analysis.
Examples of amenable cyanide, CN(A), species are CN", NaCN, Cu(CN)?~,
Zn(CN)42', and Ni(CN)42~.
Total Cyanide
Total cyanide, CN(T) refers to all the cyanide groups in a sample re-
gardless of the cyanide-metal complex, if any. The total cyanide value,
however, is typically defined as the result of the analytical procedure,
which may not include all cyanide-metal complexes. The total cyanide method
generally used (the reflux mineral acid distillation) analyzes for all of the
CN" groups in the sample, including the cyanide-metal complexes (except
cobalt, gold, and some of the platinum group metals). This method is defined
in ASTM D-2036-81 and EPA's SW-846 Methods 9010 and 9012.
Examples of CN(T) are CN", NaCN, Zn(CNK2", and Fe(CN)64~. The
Co(CN)6u~ is an example of a total cyanide species that is not included in
5
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Figure 1. Relationship between HCN and CN with pH
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all total cyanide analyses. This element is discussed further under
Analytical Methods presented later in this section.
Simple Cyanide
"Simple cyanide" denotes a compound in which cyanide combines with a
single cation and does not form a cyanide complex. Simple cyanides are
represented by the formula A(CN) , where A is an alkali (sodium, potassium,
ammonium) or metal, and x, the valence of A, represents the number of cyanide
groups present in the molecule. The solubilities for the simple cyanides
vary widely. Soluble compounds, particularly the alkali cyanides, ionize to
release cyanide ions according to the following equation:
A(CN)x <--> A+x + xCN"
Examples of simple cyanides are NaCN, Ca(CN)2, and Nn(CN)^ (insoluble).
Complex Cyanide
"Complex cyanides" is a compound in which the cyanide is complexed with
a metal cation and results in a complex cyanide-metal anion on dissolution of
the substance. The complex alkali-metallic cyanides are represented by the
general formula A M(CN) , where A is the alkali, and y is the number of
alkali ions. M i^ the £eavy metal (i.e., iron, cadmium, copper, nickel,
silver, zinc, or others) and x is the number of CN groups. The value of x is
equal to the valence of A times y plus the valence of the heavy metal. The
soluble complex cyanides dissociate to release the complex cyanide-metal ion
M(CN) ^w~, where w is the oxidation state of A, rather than the CN" ion.
Thus,*when they are dissolved in water, they ionize as shown below.
AyM(CN)x <-> yA+X + MfCN)/""
Examples o^ complex cyanides include Na.Fe(CN)fi, K_Fe(CN)fi, K?Cu(CN)?,
NaCu(CN!)2, and K4Co(CN)6. J b L
Dissociable Cyanide
The cyanide-metal complex anion stability depends on the metal cation
with which it is associated. Zinc, cadmium, and copper are less stable and
partially dissociated into the metal cation and CN". Other complexes, particu-
larly the iron, gold, and cobalt, are very stable; however, even tightly
bound iron-complex anions can dissociate to release the cyanide (CN ) ion in
the presence of UV radiation or very strong acids (Broderius and Smith 1980,
Sharpe 1976, and Moggi et al. 1966). All complex cyanides dissociate to free
cyanide to some degree, as illustrated by the following reaction for chro-
mium:
Cr(CN)63~ < — > Cr3+ + 6 CN"
n
Examples of dissociable cyanide species include Cu(CN),", ZntCN)/", and
Ni(CN)42-. 2 4
7
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Nondissociable Cyanide
As was stated earlier, all cyanide complexes are dissociable to some
degree. Hence, "nondissociable cyanide" is only a relative term used to
describe cyanide complexes that are highly stable, such as Co(CN)61'-,
Au(CN)u~, and the platinum group metals, and do not readily dissociate into
free cyanide.
Soluble Cyanide
"Soluble cyanide" is defined as cyanide compounds or complexes that are
soluble in aqueous solutions. The major utility of cyanide in a commercial
sense is derived from its capacity to complex or chelate with metals (transi-
tion and precious) to form soluble cyanide-metal compounds. Consequently, it
is not unusual that many of the cyanide compounds are soluble. Table 2 lists
the solubilities of a number of cyanide compounds.
Insoluble Cyanide
"Insoluble cyanide" is defined as cyanide compounds insoluble in aqueous
solutions. These compounds fall into two general categories: the relatively
insoluble simple cyanides, such as 7.n(CN)2, CuCN, AgCN, and Ni(CN)2; and the
insoluble ferrocyanide and ferricyanide compounds, which are listed in Table
3. The insoluble simple cyanide complexes may be soluble in cyanide solu-
tions. For example, copper is present in an assemblage as:
CuCN (insoluble)
CuCN + CN" <-—> Cu(CN)r," (soluble)
Cu(CN)2~ + CN" <—> Cu(CN)3?" (soluble)
Cu(CN)32" + CN" < — -> Cu(CN)43" (soluble)
The complexes form in a stepwise fashion. As the cyanide ion concentra-
tion increases, the higher cyanide complexes become the stable species;
hence, the insoluble CuCN combines with CN" to form a soluble Cu(CN)^~ and
then the higher cyanide complexes.
Cyanate
Cyanide can be oxidized by ozone, hydrogen peroxide, sodium hypochlo-
rite, or sulfur dioxide and air to produce cyanate and, subsequently, ammo-
nium ion and carbon dioxide. Aerobic bacterial degradation of cyanide also
produces ryanate. A review of cyanide treatment systems by Huiatt et al.
(1983) discusses these treatment methods in greater detail (also, see Section
3). The oxidation of cyanide by peroxide is presented here:
CN" + H?02 <—> CNO" + H?0
8
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TABLE 2. SOLUBILITIES OF METAL-CYANIDE COMPOUNDS9
Compound Name Solubility, mole/liter Reference^
AoCN
Silver cyanide
1.64
X
10"5 (20'C)
1
Cd(CN)0
L.
Cadmium cyanide
1.51
X
10"5 (18"C)
1
Co(CN)0
L.
Cobaltous cyanide
3.77
X
10~4 (18°C)
1
CuCN
Cuprous cyanide
2.90
X
10'5 (18°C)
1
Hg(CN)0
L.
Mercuric cyanide
3.68
X
10'1 (20CC)
1
Hg2(CN)2
Mercurous cyanide
1.79
X
10"5 (25^)
1
Mi(CN) 2
Nickel cyanide
5.35
X
10"4 (18°C)
1
Zn(CN)2
Zinc cyanide
4.90
X
10"5 (18rC)
1
K[Ag(CN)2]
Potassium dicyanoargentate(I)
1
3 (20°C)
2
K2[Cd(CN)4]
Potassium tetracyanocadmate(11)
1
1
2
K3[Cr(CN)g]
Potassium hexacyanochromate(III)
1
(20r C)
2
K3[Fe(CN)6J
Potassium hexacyanoferrate(111)
(ferricyanide)
1
(4PC)
o
K4[Fe(CN)6]
Potassium hexacyanoferrate(11)
(ferrocyanide)
0.
(12 0 C)
2
aSource: Ingersoll et al . 1983.
k References:
1. Kunz et. al 1978
2. Sill en and MarteH 1971
9
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TABLE 3. SOLUBILITIES OF FERROCYANIDES AND FERRICYANIDES9
Name Formula Solubility, g/liter T°C
Ammonium ferricyanide
(NH4)3Fe(CN)6
Very soluble
Ammonium ferrocyanide
(NH4)4Fe(CN)6'3HzC
Soluble
Barium ferrocyanide
Ba2Fe(CN)6'6H20
1.7 g (15°C)
Cadmium ferrocyanide
Cd2Fe(CN)6'xH20
Insoluble
Calcium ferrocyanide
Ca2Fe(CN)6'12H20
868 g (25°C)
Cobalt ferrocyanide
Co2Fe(CN)6-xH2C
Insoluble
Copper (I) ferricyanide
Cu2Fe(CN)6
insoluble
Copper (II) ferricyanide
Cu3[Fe(CN)6]2'4H20
Insoluble
Copper (II) ferrocyanide
Cu2Fe(CN)6'xH20
Insoluble
Iron (II) ferricyanide
Fe3[Fe(CN)6]2
Insoluble
Iron (III) ferricyanide
FeFe(CN)6
—
Iron (II) ferrocyanide
Fe2Fe(CN)6
Insoluble
Iron (III) ferrocyanide
Fe4[Fe(CN)6]3
Insoluble
Lead ferricyanide
Pb3[Fe(CN)6]2*5H20
SIightly soluble
Manganese (II) ferrocyanide
Mn2Fe(CN)6'7H20
Insoluble
Nickel ferrocyanide
Ni2Fe(CN)6'xH20
Insoluble
Potassium ferricyanide
K3Fe(CN)6
330 g (4°C)
Potassium ferrocyanide
K4Fe(CN)6'3H20
278 g (12°C)
Silver ferricyanide
Ag3Fe(CN)6
0.00066 (20cC)
Silver ferrocyanide
Ag4Fe(CN)6*H20
Insoluble
Sodium ferricyanide
Na3Fe(CN)6'H20
189 g (0°C)
Sodium ferrocyanide
Na4Fe(CN)6*10H20
318.5 g (20°C)
Strontium ferrocyanide
Sr9Fe(CN)6*15H20
500 g
Thallium ferrocyanide
Tl4Fe(CN)6'2H20
3.7 g (18CC)
Tin (II) ferricyanide
Sn3[Fe(CN)6]2
Insoluble
Tin (II) ferrocyanide
Sn2Fe(CN)6
Insoluble
Tin (IV) ferrocyanide
SnFe(CN)6
Insoluble
Zinc ferrocyanide
Zn2Fe(CN)6
Insoluble
aSource: Weast 1988.
10
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This reaction is followed by the hydrolysis of the cyanate to ammonium and
carbonate ions.
CNO" + 2 H?0 <—> NH4+ + C032"
STABILITY AND TOXICITY OF THE VARIOUS FORMS OF CYANIDE
Common Forms of Cyanide
The common forms of cyanide are 1) free cyanide as cyanide anion (CN~) and
hydrogen cyanide (HCN); 2) simple cyanides [i.e., CuCN, KCN, Hg(CN)z, etc.];
and 3) complex cyanides [i.e., Fe(CN)e'4". Cu(CN)32", etc.], which also
include ferro- and ferricyanide precipitates [i.e., Fe2Fe(CN)6]. Table 4
presents further delineation as to cyanide-metal complex stabilities and
solubilities of these forms of cyanide and gives typical examples. The
simple cyanides, by definition, form no complexes. The soluble cyanides
dissolve to form metal cations and the cyanide anion. The soluble complex
cyanides dissolve into metal cations and cyanide-metal complex anions. The
cyanide-metal anion can then further dissociate into cyanide anions and the
metal cation in a stepwise fashion, as shown here:
Cu(CN)32" < — > Cu(CN)2" + CN~
Cu(CN)2" < —> Cu(CN) + CN"
CuCN < > Cu+ + CN
Hence, the cyanide-metal complexes also result in free cyanide in the
solution. The concentration of the free cyanide depends on the solution pH
and the strength of the cyanide-metal bond, as measured by the dissociation
constant present for some complexes (Table 5).
TABLE 4. CYANIDE FORMS, COMPLEX STABILITY, AND SOLUBILITY
Common
cyanide forms
Complex cyanide
stability
Solubility
Examples
Free
No complexes
Soluble
CN", HCN
Simple
No complexes
Soluble
NaCN, Ca(CN)p
No complexes
Insoluble
CuCN, Zn(CN)2
Complex
Dissociable
Soluble
Zn(CN)4?~, Cu(CN)p"
Nondissociable
Soluble
Fe(CN)64", Co(CN)64"
Nondissoclable
Insoluble
Fe3[Fe(CN)6]2
11
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TABLE 5. STABILITY CONSTANTS OF METAL-CYANIDE COMPLEX IONS
Complex ion
Stability constant
Reference®
Cr(CN)63"
1033
1
Cr(CN')64"
1021
1
Fe(CN)g4~
1035-4
1
1047
2
Fe(CN)63"
1052
3
Co(CN)54*
1050
1
Co(CN)63"
1064
3
Ni(CN)42_
IO30
1
1o31"1
3
Pd(CN)42"
1042
1
Pt(CN)42"
104C
1
Cu(CN)2"
1023.9
1
Cu(CN)32"
io29-2
1
Cu ccn)42"
1Q30'7
1
Cu(CN)43"
IO30"3
3
1020-9
4
Ag(CN)32"
1021' 9
l
Au(CN)2"
103/
1
Au(CN)4"
1085 (estimate)
1
Zn(CN)42"
1021
3
1016.7
1
Cd(CN}42"
1019
3
10!6.9
1
Hg(CN)42"
IO39
3
10-41-1
3
Mn(CN)64"
IO9'7
1
a References:
1. Sharpe 1976.
2. Broderius 1973.
3. Kunz, G. G., J. P. Casey, J. E. Huff 1978.
4. L. S. Sill en and A. E. Kartell 1971.
12
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Cyanide Toxicity—Free Cyanide
Free cyanide is highly toxic to man and animals. The toxicity and
metabolism of free cyanide are well documented, particularly as they relate
to fish (Sax 1984, Doudoroff 1980, Ingersoll 1983, and U.S. EPA 1985). For
example, a hydrogen cyanide concentration of 0.3 mg/liter (270 ppn) in air is
immediately fatal to humans. Cyanide toxicity to fish is even mere acute;
concentrations as low as 0.1 ppm in water are fatal to a broad range of fish
(Ingersoll 1983).
Free cyanide uptake by man and animals occurs through inhalation, inges-
tion, or skin absorption. Absorption via membranes and skin occurs readily,
and the blood system rapidly distributes the cyanide throughout the body.
The free cyanide binds strongly to iron, copper, and sulfur, key constituents
of many enzymes and proteins important in life processes. The principal
compound affected is cytochrome oxidase, an enzyme contained within the body
cells and essential to the cell utilization of oxygen. This inactivation of
the oxidase results in cellular asphyxiation and tissue death.
Cyanide Toxicity—Complexed
The toxicity of the various metal-cyanide complexes is attributable
almost solely to the concentration of free cyanide in equilibrium with the
complex salt. The toxicity of the simple cyanide compounds depends on their
solubility or their ability to form ionic or free cyanide. The toxicity of
complex cyanide is a function of the solubility and stability of the complex
cyanide-metal ion. For example, weakly bound complexes such as zinc and
cadmium cyanide are much more toxic than iron or cobalt complexes. Ferro-
cyanide complex is approximately 1/200 to 1/300 (Sax 1984) times less toxic
to rats than is free cyanide. In fact, most investigators (Deichmann and
Gerande 1969) consider iron cyanide nontoxic. Excellent presentations on
cyanide toxicity can be found in Towill et al. (1978), Huiatt et al. (1983),
and Doudoroff (1980).
Cyanide-Metal Complex Stability
The stability of the cyanide-metal complex anion depends on the metal
cation with which it is associated. Zinc, cadmium, and copper are relatively
unstable and partially dissociate into the metal cation and CN~. Other com-
plexes, especially the iron, gold, and cobalt complexes, are very stable;
however, even tightly bound iron-complex anions can dissociate to release the
cyanide (CN~) ion in the presence of UV radiation or very strong acids. All
complex cyanides dissociate in aqueous solution to free cyanide to some
degree, as illustrated by the following reaction for chromium:
Cr(CN)63' <--> Cr3+ + 6 CN"
13
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The stability constant (K ) for this cyanide complex is defined as
follows: s
[Cr(CN)63"l
Ks = [Cr3+][CN~]6 = 1033
The inverse of the stability constant is the dissociation constant ():
Kd = l/K = 10"33 [for Cr(CN)63~]
Table 5 lists equilibrium stability constants for a number of complex
cyanide ions.
The dissociation constant 4.365 x 10 ^ for the dissociation reaction of
hydrogen cyanide can be used to determine the concentration of CN~ as a
function of pH:
H.CN < —> H+ + CN"
A decrease in the pH drives the dissociation reaction forward by remov-
ing the cyanide ion. Therefore, by controlling the pH of the solution, some
of the cyanide complexes can be totally dissociated into free cyanide. An
increase in temperature results in an acceleration of the dissociation rate.
These mechanisms are used in the acid reflux distillation methods to disso-
ciate cyanide-metal complexes to form volatile HCN so it can be trapped and
measured.
The complex alkali-metal1ic cyanides are represented by the general
formula A M(CN) , where A is the alkali, and y is the number of alkali ions.
M is the Keavy metal (i.e., iron, cadmium, copper, nickel, silver, zinc, or
others) and x is the number of CN groups. The value of x is equal to the
valence of A times y plus the valence o* the heavy M(CN) rather than the
CN" ion. Thus when they are dissolved in water they ionize as follows.
A M(CN)X <-> yA+X + M(CN)x"yW
where w is the oxidation state of A.
The complex cyanide-metal ion may then undergo further dissociation and
release cyanide ions as shown here.
M(CN)x-yW <—>Cfl" + M(CN)x_1~yw+1
M(CN) "yw+1 < —>CN" + M(CN) -yw+?
X -1 X""l
Metal-cyanide complex ions may be considered as the soluble products of
the reaction between the corresponding insoluble simple cyanide and excess
cvanide ion.
14
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Another aspect of cyanide-metal complex chemistry is the formation of
insoluble double-metal cyanide precipitates. This reaction has been used
successfully to remove free cyanide from solutions by the formation of ferric
ferrocyanide, Fe1+(Fe(CN)5)3, or other transition metal ferrocyanide
precipitates (Hendricksen and Daignault 1973).
4 Fe3+ + 3 Fe(CN)64~ <--> Fe4 [Fe(CN)6?3 (ppt)
ANALYTICAL METHODS
Four general catagories of cyanide analytical methods are commonly used:
1) total cyanide, 2) cyanide amenable to chlorination, 3) WAD cyanide, and 4)
free cyanide.
These techniques are typically designed for an aqueous waste or leach-
ate; however, the acid reflux/distillation method used for total, amenable,
and WAD analyses has also been applied to soils and sludges. Because the
corrosive action of the acid on the solid phase may release compounds that
could interfere with the cyanide analysis, this approach should be used with
caution. In situations where the solid could cause cyanide interferences,
100 grams of the solid may be leached with 1000 ml of 2 normal NaOH for 24
hours and then filtered and the leachate analyzed for cyanide species.
Total Cyanide, CN(T)
Total cyanide includes all inorganic species containing the CN radical,
including free cyanide and simple and complex cyanide-metal compounds. The
following paragraphs briefly describe total cyanide procedures.
Acid Reflux/Distillation—
Acid reflux/distillation (SW-846 Methods 9010 and 9012, ASTM D—2036—81
Method A) at a pH of 2 is the most commonly used method for total cyanide
analysis. A catalytic agent, MgClz, is added to the sample before "distil-
lation to ensure breakdown of the tightly bound iron cyanide complexes.
Hydrogen cyanide volatilized during the distillation is collected in an
alkaline absorbing solution. The free cyanide can then be measured by any of
the accepted techniques, such as titration, colorimetry, or specific ion
electrode (presented later in this section). Unfortunately, this procedure
has the following problems: it is quite susceptible to interferences from
thiocyanate, sulfides, thiosulfate and other sulfur compounds; it is affected
by nitrite, nitrate, and oxidizing agents; and it does not measure all
cyanide species as discussed previously.
Current published versions of the various standard cyanide procedures
have presented modified procedures (i.e., use of phosphoric acid rather than
sulfuric acid, additions of ascorbic acid to eliminate oxidizing agents, and
the addition of cadmium carbonate to remove the sulfides) that reduce these
interferences. The particular interferences of thiocyanate and sulfide
compounds, however, have made it difficult to compare data produced by various
industries.
15
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One modification developed by Knechtel and Conn (1981) has been designed
to determine cyanide in the presence of thiocyanate. This is a modified
version of the conventional acid reflux/distillation technique in which
hydrochloric acid and hydroxylamine hydrochloride are the decomposition
reagents. Cadmium chloride is added to the adsorber to precipitate any
sulfide that is distilled over. Cyanide determinations after distillation
are resolved by titrimetric or colorimetric methods, depending on the cyanide
concentration. This method has been successfully applied to measure cyanide
in process waters. Tartaric acid or phosphoric acid solutions have also
been used successfully in place of sulfuric acid for samples that show thio-
cyanate interference.
Final analysis of the ionic CN" obtained from distillation is commonly
obtainod by any of three methods: 1) titration, usually with_AgN03; 2)
colorirnetry via the reaction of chloramine-T derivative of CN" with a pyridine-
barbituric acid; and 3) ion-selective electrode techniques using the method
of known additions.
Automated Ultraviolet Digestion-
Automated Ultraviolet Digestion (SW-846 Method 9012) is being used by
many laboratories to replace the catalysts in the decomposition of complex-
metal cyanides in the total cyanide determinations (U.S. EPA 1979, Sekerka
and Lechner 1576). Phosphoric acid is the recommended digesting solution,
and the determination is performed with the Technicon Auto-analyzer. The
method has a major advantage in terms of its automation, but it exhibits
interferences from thiocyanates and sulfides. Broderius and Smith (1980)
found that light with wavelengths less than 420 nm and 480 nm acts to
decompose Fe(CN)e^- and Fe(CN)63-, respectively. Maximum absorption
wavelengths are 330 nm for Fe^Cri)^- and 330 and 420 nm for Fe(CN)63-
Ligand-Exchage—
Ligand-exchange, which is listed in a review by Ingersoll et al. (1983),
is another method for measuring total cyanide. This process involves the use
of ligands to aid the dissociation of the tightly bound cyano-metal com-
plexes. Lead acetate is added to precipitate sulfides. The pH is maintained
at 4.5, and the distillation time is reduced to 1/2 hour. The ligand used
was a mixture of TEP and Tiron (l,2-dehydroxy-3,5-benzenedisulfonic acid).
It uses high-temperature reflux distillation from acidic solutions of organic
complexing agents. This process requires neither UV radiation r.or strongly
acidic solutions to decompose the complex iron cyanides.
Ion Chromatography--
Ion chromatography methods have been developed to determine total cyanide,
WAD cyanide, and free cyanide. Much of this developmental work has been
performed by Pohlandt-Watson (1984, 1986a) in South Africa. These methods
are free from interferences and are quite precise. They have a limit of
determination of 10 yg/liter. The total cyanide content was determined by
ion chromatography after the strong metal-cyanide complexes had been resolved
in hypophosphorous acid by ultraviolet irradiation of wavelengths shorter
than 300 nm. The dissociation procedure (10 minutes) is faster than
conventional distillation methods.
16
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Amenable Cyanides, CN(A)
The cyanide amenable-to-chlorinatior method is based on the difference
between two total cyanide determinations on a sample both before and after
chlorination. One sample portion is analyzed for total cyanide. Another
portion is treated with calcium or sodium hypochlorite at an alkaline pH for
1 hour, the chlorine residual is removed, and the solution is analyzed for
total cyanide. The alkaline chlorination oxidizes all cyanides (except the
iron complexes) as well as thiocyanate. The difference between the two total
values is reported as cyanide amenable to chlorination.
Although this method is an accepted standard by the EPA and ASTM, it has
an obvious problem—the result is only as good as the initial total cyanide
value determinatior. before chlorination. If the interferences, such as
thiocyanate, are not eliminated or corrected, a low value could be obtained
for cyanide amenable to chlorination because the alkaline chlorination
removes thiocyanate. Using the phosphoric acid methodology for total cyanide
where thiocyanate is a problem eliminates this interference, however.
The test work at the Wastewater Testing Center in Canada confirms that
the iron cyanide complexes are not oxidized but that other metal complexes
(such as copper, nickel, and cadmium) and free cyanide and thiocyanate are.
When both process samples and synthetic solutions containing cyanide, iron,
ferricyanide, and thiocyanate were used, the relative standard deviation for
this method was about + or - 5 percent at. levels of 2.5 mg/liter for the
process sample and 0.2 mg/liter ^or the synthetic solution (Conn 1981).
Weak-Acid-Dissociable Cyanides (WAD)
The WAD metnod (ASTM D-2036 Method C) of cyanide determination and the
cyanide amenable to chlorination, CN(A), analyses (ASTM D-2036 Method B) are
both designed to measure free cyanide plus metal-cyanide complexes other than
iron, cobalt, and gold. Because the CN(A) procedure requires two separate
analytical procedures (one before and one after chlorination) that are sub-
ject to errors and interferences, many investigators use the ASTM Method C
approach, CN(WAD).
The WAD cyanide procedure is a variation of one proposed by Roberts and
Jackson (1971). A distillation is carried out in the same equipment and in
the same manner as described for total cyanide but with different reagents in
the distilling flask. The reagents used are an acetic acid-sodium acetate
solution buffered at pH 4.5 and zinc acetate. The purpose of the zinc ace-
tate is to prevent decomposition of any ferrocyanide present. At the
Chemical Congress of the North American Continent held in Mexico City in
1975, it was indicated that this analytical procedure is capable of totally
recovering cyanide from cadmium, copper, nickel, silver, and zinc complexes.
No thiocyanate interference occurs with this method.
Free Cyanide
The free cyanide analysis is_designed to measure the highly toxic
species (i.e., the cyanide ion CN~ and the HCN molecule). Solvent extraction
17
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or air sparging is used to separate the free cyanide from the process solu-
tion containing substances that could interfere with the analysis. These
techniques are also used to measure the free cyanide trapped in the alkaline
scrubber solution in the acid reflux/distillation method for total, amenable,
and WAD cyanide.
Titration with colorimetry, silver nitrate, or ion-selective electrode
techniques are typically used to measure free cyanide. Two other methods,
gas and ion chromatography, have recently been developed. An ion chromato-
graphic method for free cyanide, as well as for cyanide-metal complexes, was
developed in South Africa by Pohlant-Watson (1984, 1986b). This method is
particularly promising for both laboratory and process samples because it
measures both thiocyanate and cyanate and is not subject to interference by
these compounds.
Absorption Spectrophotometry--
The absorption spectrophotometry method is based on the formation of a
colored molecular species of cyanide. The absorbed light in the solution is
compared with a previously determined calibration plot. The cyanide concen-
tration in the sample is then determined by comparison with the calibration
data. Although various absorption compounds are used by different investiga-
tors, the most frequently used compound is the blue dye formed by treating
cyanide with chloramine-T and then with an aqueous pyridine solution of
bispyrazolone and 3-methyl-l-phenyl-5-pyrazolone. The detection limit is 0.5
ug in a 15-ml aqueous solution. The effective range is about 1 to 5 ug in a
25-ml aqueous solution. The relative standard deviation (RSD) of this method
is approximately 2 percent. If the blue dye is concentrated by extraction
into a small volume of organic solvent, greater sensitivity is obtained
(American Public Health Association, American Water Works Association, and
Water Pollution Control Federation, 1971). A modification of the pyridine-
pyrazolone method has reduced the detection limit to 5 ug/liter cyanide.
Sulfides, heavy metal ions, fatty acids, substances that hydrolyze to
give cyanide ions, and oxidizing agents that are likely to destroy cyanide
during the distillation step interfere with the determination of cyanide by
this method, but they can be eliminated or minimized by the appropriate
treatments.
Absorption spectrophotometry is probably the most widely used technique
for determining cyanide in concentrations of 1 mg/liter or less. Its accu-
racy is adequate for analysis of cyanide in natural waters as well as treated
industrial effluents. It is also amenable to automation.
Volumetric Titrimetry—
Volumetric titrimetry can be used if the cyanide content of the alkaline
distillate is sufficiently large, a minimum of 1 mg/liter (EPA 1979a). For
example, silver nitrate combines with cyanide according to the equation:
2CN~ + AgN03 <—> Ag(CN)2" + N03~
18
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One milliliter of 0.01 N silver nitrate is thus equivalent to 0.52 mg of
cyanide ion. When the end point of the titration is reached, excess silver
ions react with the indicator to produce a characteristic color change. A
blank reagent value is then subtracted from the result.
The indicator, p-dimethyl-aminobenzalrhodanine, for the silver nitrate
titration, is sensitive to about 0.1 mg/liter silver or about 0.05 mg cya-
nide. If a 500-ml sample is used, the minimum detectable concentration of
cyanide by the titration technique is about 0.1 mg/liter. The RSD is about 2
percent for distilled samples that contain at least 1 mg/liter cyanide (Ameri-
can Public Health Association, American Water Works association, and Water
Pollution Control Federation, 1971).
In summary, volumetric titration methocs are simple and widely used in
analyzing water samples and industrial effluents when the cyanide concentra-
tion is greater than 1 mg/liter. The use of simple equipment and a convention-
al laboratory procedure make this approach very attractive.
Ion-Selective Electrodes—
Ion-selective electrodes can be used to determine cyanide in certain
industrial wastewaters. A specially designed electrode that contains a
membrane of silver sulfide and silver iodide is used. When the electrode is
immersed in a sample, iodide is released at the membrane surface in an amount
proportional to the cyanide in the sample. The iodide is measured by the
electrode and determines the electrode potential. Consequently, the elec-
trode response follows the relationship,
E = E + S log [CN~]
x 3
where E = the electrode voltage, mV
[CN]~ = the concentration of the cyanide ion
S - slope of the electrode response curve
Only free cyanide ions, CN~, are detected; molecular hydrogen cyanide
and cyanide-metal complexes do not activate the electrode. Thus, samples
must be adjusted to pH greater than 11 before measurement to ensure that all
free cyanide is present as cyanide ion. In addition, complexing cations such
as nickel or copper must be sequestered with ethylenediaminetetra-acetic acid
to free complexed cyanide prior to analysis. Sample color and turbidity do
not interfere with the use of the cyanide-specific electrode. Time-consuming
sample distillations are eliminated; consequently, this method is appropriate
for direct field measurements as well as automated laboratory use.
The cyanide ion-selective electrode is slowly attacked by cyanide solu-
tions, which leads to inaccuracies. The electrode is also continually subject
to drift with time and requires frequent recalibration. Because sulfide
deactivates the electrode, the electrode must not be immersed in sulfide-
containing solutions.
19
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In conclusion, although the ion-selective electrode determination of
cyanide is attractive for selected applicatTon because sample preparation is
usually eliminated and analyses are obtained speedily, it is also subject to
drift and electrode attack that may cause analytical inaccuracies. The sil-
ver iodide membrane electrode is useful in the 10~3- to 10~5-K concentration
range; above 10"3-M cyanide, the electrode life is shortened by the cyanide
attack of the electrode. The technique is amenable to automation, but
strongly complexed metal ions must be limited by sample pretreatment.
Gas Chromatography—
Gas chromatography techniques readily distinguish various species of
cyanide compounds. In general, hydrogen cyanide and other cyanide-containing
compounds have different characteristic retention times in the chromatograph-
ic column and can be identified by this criterion. Hydrogen cyanide in an
aqueous cyanide solution can be removed from the sample by air sparging,
concentrated in a cold trap, and analyzed in chromatographic columns by using
a nitrogen carrier gas and a flame ionization detector. Samples containing
1 pg/liter hydrogen cyanide are readily analyzed. The calibration curve is
linear up to 2000 yg/liter (Claeys and Freund 1968).
In summary, the gas chromatographic method of determining cyanide is
sensitive and precise. In addition, it can distinguish speciated forms of
cyanide-containing molecules. These characteristics suggest its application
for the analysis of cyanide from biological materials, gaseous and liquid
effluents, and wastewaters. This technique is little used at present.
Ion Chromatography—
Ion chromatography methods have been developed to determine free cyanide.
A simplified flow-injection technique has been developed by Pohlandt-Watson
(1984, 1986b) that is suitable for the on-line determination of ionic cyanide
in process solutions. This method uses a ion-selective electrode, and it
improves the accuracy of the free cyanide determinations by ion-selective
electrode. With this technique, 60 samples can be analyzed in 1 hour, with
an RSD of 0.012 at the 100-mg/liter level.
The recently developed ion chromatographic method of determining free
cyanide is rapid, sensitive, and precise. In addition, it can distinguish
speciated forms of cyanide-containing ions. These characteristics recommend
its application for the analysis of cyanide from gaseous and liquid
effluents and wastewaters.
Analytical Interferences
Thiocyanate—
Thiocyanate ion interference, particularly when Cu2Cl2 catalyst is used,
has been well documented (Barton 1978). The Cu2Cl2 catalyst causes the
formation of cyanogen, (CN)2, in the distillation flask. This volatile
compound is hydrolyzed to CN~ and CN0" in the alkaline scrubber, which re-
sults in low analysis for cyanide. Because of this problem and others, the
ASTM procedure has been changed to use the MgC1^ catalyst (ASTM 1981).
20
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Thiocyanate is a well-recognized source of interference in several
analytical procedures for total cyanide measurement. For example, the UV
digestion methods for total cyanide require a determination of thiocyanate to
calculate the amount of iron cyanide present. Thiocyanate also interferes
with the calculation of cyanides amenable to chlorination. At the Chemical
Congress of the North American Continent held in Mexico City in 1975, it was
reported that artificially high values obtained after chlorination resulted
in a negative value for amenable cyanides in samples with a high ratio of
thiocyanate to free cyanides.
Sulfides--
Sulfides volatilized in the_distillation flask as H2S are trapped in the
alkaline scrubber solution as HS". The HS~ can react with cyanide to form
thiocyanates, which results in low cyanide analyses. Sulfides can also
interfere with the titrimetric and electrolytic determinations (Clysters
1976). During storage, sulfides also slowly react with cyanides (especially
at high pH) form thiocyanates, and reduce the cyanide values (ASTM 1981).
Nitrates, Urea, Glycine, and Others—
Nitrates, urea, glycine, and others can generate cyanide under test
conditions and cause false positive readings even when no cyanide is present
(Rapean et al. 1980). Other possible interferences include oxidizing agents,
aldehydes, glucose, carbonates, fatty acids, and amino acids.
The ASTM (1981) method statement sums up the magnitude of the interference
problem in the statement "It is beyond the scope of these methods to describe
procedures for overcoming all of the possible interferences that may be
encountered."
Storage-
Storage of the sample can also result in inaccuracies in the determina-
tion of cyanide. A clear filtered sample preserved by the addition of sodium
hydroxide to a pH of 12 and stored in the dark at 4°C will be stable for at
least 2 weeks. A pH of above 11 is essential to eliminate HCN volatiliza-
tion. Storage in the dark will eliminate dissociation of iron cyanides by
light. Samples containing solids are difficult to store, and adequate preser-
vation cannot be guaranteed (Conn 1981). The preparation-analysis alterna-
tives are either immediate analysis for cyanide or filtering the sample and
elevating the pH to 12. Any sulfides in a sample should be removed by
precipitation with lead carbonate before raising the pH for preservation.
Also, if alkaline chlorination is used for cyanide destruction, any residual
chlorine should be removed after chlorination.
21
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SECTION' 3
CYANIDE OXIDATION TREATMENT
This section presents an overview of the four cyanide oxidation treat-
ment technologies included in this study: alkaline chlorination, wet-air
oxidation, ultraviolet 1ight/ozonation, and electrolytic oxidation.
ALKALINE CHLORINATION
General Description
Alkaline chlorination is the method the electroplating industry uses
most often for detoxifying cyanide. This process can be used both to destroy
free dissolved hydrogen cyanide and to oxidize all simple and many complex
inorganic cyanides in wastewater.
The destruction reaction is a redox process in which one or more elec-
trons are transferred from the cyanide complex to the oxidizing agent. The
most commonly used oxidizing agents are chlorine or hypochlorite salt.
The reaction scheme for the destruction of cyanide by alkaline chlorina-
tion, which is carried out at ambient temperatures, is shown by the following
(Alliance Technologies Corp. 1987):
CN" + Cl« + CNC1 + CI" (1)
CNC1 + 20H~ ¦* CNO" + CI' + H20 (2)
2CN0" + 40H" + 3C12 j 6C1~ + 2C02 + N2 + PHgO (3)
In the above reaction scheme, chlorine gas and hydroxide ion are used to
oxidize cyanide to cyanate (CNO") and, ultimately, to carbon dioxide and
nitrogen. Despite its higher cost, sodium hypochlorite (NaOCl) is often used
to replace chlorine because of the dangers and high equipment costs associ-
ated with the use of chlorine.
Alkaline chlorination treatment of cyanide solutions is conducted in
either one or two stages. Single-stage alkaline chlorination involves Reac-
tions 1 and 2, in which cyanide is oxidized to cyanate. In two-stage
22
-------
alkaline chlorination, the chemical reaction is taken one more step in which
cyanate is oxidized to carbon dioxide and nitrogen (Reaction 3). The two-
stage process is more commonly used by industry (Alliance Technologies Corp.
1987). In the two-stage process, the solution pH is first raised to 10 or
higher. Hydrolysis of the cyanogen chloride (CNC1) complex is rapid and
typically yields 80 to 90 percent completion to CNO" within 2 minutes (reac-
tion time depends on the composition of feed stream). The pH is then reduced
to a range of 8.0 to 8.5, which allows for rapid oxidation of cyanate (Reac-
tion 3). Generally, Reaction 3 requires between 30 minutes and 1 hour to
ensure the complete destruction of cyanide. An alternative method for carry-
ing out the two-stage process is to maintain a pH between 8.5 and 10 in a
single tank to allow for the simultaneous completion of both stages (Alliance
Technologies Corp. 1987; Cushnie 1985).
Single-stage alkaline chlorination carries out the reaction scheme only
through the formation of cyanate, which is about 1000 times less toxic than
cyanide (Sittig 1973). In areas where discharge of cyanate is allowed,
industry will select single-stage alkaline chlorination because of its lower
capital and operation and maintenance costs.
Overall reagent requirements for the complete destruction of cyanide
(two-stage alkaline chlorination) are 6.8 lb of chlorine and 7.3 lb of caus-
tic per pound of cyanide. Demonstration has shown, however, that a 10 per-
cent excess of chlorine (8 lb Cl2 per lb CN) is needed to destroy cyanide and
to meet current effluent guidelines (Alliance Technlogies Corp. 1987 and
Patterson 1985). Single-stage alkaline chlorination requires 3 lb of chlo-
rine per pound of cyanide treated.
A continuous-flow alkaline chlorination system is designed to handle
cyanide wastestream concentrations of 100 mg/liter or less at flow rates of
10 to 350 gal/min (flow rates are dependent on influent CN concentrations)
(Alliance Technologies Corp. 1987). Optimum influent cyanide concentrations
for continuous systems are less than 100 mg/liter. Wastestream cyanide
concentrations of up to 2 to 4 percent, however, can be treated in the b^tch
mode (Sittig 1973). Total cyanide levels of 0.5 mg/liter or less in the
effluent can typically be reached if feed is below 1000 mg/liter CN and no
stable inorganic complexes (i.e., iron, nickel, and zinc) are present in the
wastestream (Sittig 1973).
Site Description—Master Lock
Master Lock Company in Milwaukee, Wisconsin, manufactures a variety of
padlocks. Operations include forming, heat treatment, painting, assembly,
and electroplating. Electroplating operations involve a total of six plating
lines; five are barrel plating lines, and one is a rack plating line. The
rack plating line is dedicated to Ni-Cr plating of hardened steel. The
barrel plating lines include one line each for Cu-Ni plating of hardened and
nonhardened steel, Cu-Ni plating of zinc die cast, chromating/stripping, Cd
plating of lock bodies, and Cd plating of steel and zinc die cast internal
parts. In the performance of these electroplating operations, Master Lock
generates EPA Hazardous Waste Nos. F006, F007, F008, and F009. Annual gener-
23
-------
ation rates of the individual wastes codes were not available. Treatment of
these waste streams (except for F006) is provided by three onsite wastewater
treatment systems, which are described in detail in the following paragraphs.
The F006 is shipped offsite for stabilization/solidification and land dis-
posal .
Wastewaters and sludges generated by Master Lock's six electroplating
lines are treated in three onsite wastewater treatment systems: 1) a conven-
tional wastewater treatment system, 2) a complexed wastewater treatment
system, and 3) a batch wastewater treatment system. The conventional treat-
ment system receives copper cyanide rinsewaters, alkaline cleaner wastewaters
(F009) (cadmium plating lines only), cadmium cyanide rinse waters, acid rinse
waters, chromating rinse water, and chrome plating rinse water. The conven-
tional wastewater treatment system treats approximately 75,000 gal of waste-
water and sludge per day. It consists of chromium reduction, single-stage
alkaline chlorination, neutralization, flocculation, sedimentation, sand
filtration, sludge thickening, and pressure filtration. Figure 2 is a flow
schematic of the conventional wastewater treatment system.
The complexed wastewater treatment system receives washer rinse water
and alkaline cleaner rinse water (except that from the cadmium plating lines),
which may contain chelants. The complexed wastewater treatment system, which
processes about 65,000 gal/day, consists of a series of two neutralization
tanks to break the chelated metal bonds, followed by flocculation, sedimenta-
tion, sludge thickening, and pressure filtration. Master Lock indicated that
the wastewaters treated in this system contain no cyanide. Figure 3 is a
flow schematic of the complexed wastewater treatment system.
The batch treatment system receives spent alkaline cleaner bath solution
(F009), spent nickel cyanide bath solution (F007), spent cadmium cyanide bath
solution (F007), plating bath sludges (F008), cadmium stripping solutions
(F009), and chromium stripping solutions (F009). The spent nickel cyanide
bath solution is actually in the form of carbonate sludge. The spent solu-
tion is pumped to an outside tank that serves as a chiller to remove excess
carbonate. The treated bath solution is returned to the plating lines. The
nickel carbonate sludge (or residue) is pumped to the acid/chrome batch
transfer station and then to the acid/chrome hold tank (Tank 29) for batch
treatment. The spent cadmium cyanide bath solution, which is also in the
form of carbonate sludge, is treated similarly. The cadmium carbonate sludge
(or residue) is pumped to the alkaline/cyanide hold tank (Tank 25) for batch
treatment. The batch treatment system treats about 1000 gal/day and consists
of chromium reduction, two-stage alkaline chlorination, a sludge thickener,
and a filter press. Figure 4 is a flow schematic of the batch wastewater
treatment system.
Site Description--Amerock Corporation
Amerock Corporation in Rockford, Illinois, manufactures a wide variety
of decorative hardware for homes. Amerock's product line consists primarily
of brass-plated decorative hardware; however, they also perform copper, zinc,
nickel, and chrome plating. Some of the raw materials that Amerock uses in
24
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2 $.000 gpd
FEED FROM PLATING
SINGLE-STAGE ALKALINE
CHLORINATION
bleach
sulfuric acid
SODIUM
HYDROXIDE
calcium
SLUOGE RECYCLE To
¦5tfe6>SEtiCTXti6N
CONTAMlNATED EFfLUENT
SUPERNATANT
50.000 ppd
FEED FROM PLATING
_CHROME
REDUCTION
SULFURIC ACID
METABISULflTE
TO NEUTRALIZATION
OVERFLOW
TO
STORAGE
TANK 15
FILTER
PRESS
TANK 11
SLUOGE
THICKENER
TANK M
TANK 23
FLOW
EQUAL-
IZATION
SAND
FILTER
TANK 10
OVER-
FLOW
STORAGE
tank 22
CHROME
REDUCTION
OVER-
FLOW
STORAGE
TANK 21
OVER-
FLOW
STORAGE
TANK 19
OVER-
FLOW
STORAGE
NEUTRAL-
IZATION
*2
TANK 6
TANK 7
LIFT
STATION
TANKS
FLOW
EQUAL-
IZATION
TANK 4
COLL/
TRANSFER
STATION
TANK 16
COLLECT/
transfer
STATION
TANK 1
OVER-
FLOW
STORAGE
TANK 2
OVER-
FLOW
STORAGE
TANK 3
TANK S
TANK 6
OFF-S/TE
STABILIZATION
SOLIDIFICATION AND
DISPOSAL
FLOW
MEASUREMENT
OUTFALL
BOX
J
Figure 2. Schematic of Master Lock's conventional wastewater
treatment system.
25
-------
SODIUM SODIUM
SULFURIC ACID HYDROXIDE HYDROXIDE
SUPERNATANT
ANIONIC
POLYMER
SLUDGE
TO
CLARIFIER
FILTRATE
SEE FIG. NO.
FEED FROM
PLATING
65.000 gpd
POTW
TANK 15
FILTER
PRESS
TANK 35
FLOW
EQUAL-
IZATION
LIFT
STATION
TANK 30
FLOCC-
ULATION
TANK 39
NEUTRAL-
IZATION
TANK 37
LIFT
STATION
TANK 9
TANK 36
COMPLEX
CLARIFIER
TANK 40
OUTFALL
BOX '
TANK 13
SLUDGE
CONTAINER
TANK 17
COMPLEX
SLUDGE
THICKENER
TANK 42
OVER/
FLOW
STORAGE
TANK 34
OVER/
FLOW
STORAGE
TANK 33
OIL/
WATER
SEPARATOR
TANK 41
COLLECTION
TRANSFER
STATION
TANK 32
OFF-SITE
STABILIZATION/
SOLIDIFICATION
AND DISPOSAL
Figure 3. Schematic
wastewaters)
26
of Master Lock's complexed (chelated
wastewater tretment process.
-------
TWO-STAGE
ALKALINE
CMLORINAHON
SULFURIC ACID CALCIUM CHLORIDE
SODIUM HYDROXIDE
BLEACH
500 gpd
FEED FROM
PLATING
CATIONIC POLYMER
ANIONIC POLYMER
FILTRATE
SODIUM
SULFURIC ACID METABISULFITE
SCO gpd
FEED FHOM
PLATING
SEE
FIGURE
TO
CLARIFIER
ANIONIC POLYMER
FEED FROM
PLATING
ACID/CHROME BATCH TREATMENT
TANK 15
FILTER
PRESS
LIFT
STATION
TANK 9
NICKEL/
CYANIDE
STORAGE
TANK 2B
BATCH
THICKENER
TANK 27
SLUDGE
CONTAINER
TANK 17
ALK/CYN
BATCH
TREATMENT
TANK 26
ALK/CYN
BATCH
HOLDING
T/ NK
TANK 2S
ACID/CHROME
HOLD
TANK 29
ACID/CHROME
TREATMENT
TANK 30
OFF-SITE
STABILIZATION/
SOLIDIFICATION
AND DISPOSAL
Figure 4. Schematic of Master Lock's batch wastewater
treatment system.
27
-------
support of their manufacturing operations include steel, zinc, and plastics.
Production operations involve some 20 blanking processes, 20 molding and
melting, processes, 8 plastic molding machines, and 50 secondary processes
(such as tapping). Finishing operations consist of electroplating, cleaning,
antiquing, lacquering, and painting. Amerock's electroplating lines use both
rack and barrel plating, but barrel plating accounts for about 70 percent of
the products. In the performance of these electroplating operations, Amerock
generates EPA Hazardous Wastes Nos. F006, F007, F008, and F009. Treatment of
these waste streams (except for F006) is provided by onsite batch and con-
tinuous alkaline chlorination.
Wastewater and sludge generated by Amerock's electroplating operations
are treated in an enclosed onsite wastewater treatment plant. The plant
consists of three wastewater treatment lines, referred to by plant personnel
as the batch cyanide treatment line, the continuous cyanide destruction line,
and the continuous noncyanide precipitation line (Figure 5). Only the two
cyanide treatment lines are discussed in this report.
Wastewater and sludge influent to the batch cyanide treatment line
consists of F007, F008, and F009. Spent cyanide plating bath solutions
(F007) at Amerock are discharged in batch quantities to an onsite chiller*
(i.e, refrigeration unit), which reduces the carbonate concentration in the
spent plating bath solution from 28 to 30 oz/gal to 12 to 15 oz/gal. This
process generates a carbonate sludge that may contain 2 to 4 percent total
cyanide. After refrigeration, the plating bath solution is returned to the
plating line. Amerock does not dispose of its plating solutions in any way
except for the small amount retained in the carbonate crystals. Amerock
generates F008 only about three to four times a year.
In the batch cyanide treatment of wastes identified as F007, F008, and
F009, wastewater and sludge are pumped to a 28,000-gal equalization tank. In
the past, batch treatment took about 24 to 36 hours per batch; now the treat-
ment cycle takes only about 7 hours because Amerock is diluting about 660 gal
of raw waste with city water to a volume of about 2000 gal.
The wastewater is pumped from the equalization tank to a chlorination
tank in which cyanide is oxidized to cyanate (first-stage chlorination) by
the addition of sodium hydroxide and chlorine gas. After the batch retains a
chlorine residual for at least an hour, sodium thiosulfate is added to remove
this residual before the wastewater is pumped to the ammonia-stripping tank.
The chlorine is removed prior to ammonia stripping so chlorine gas and
amnonia are not released inside the treatment building. Chlorine also
affects the settling characteristics of the sludge. Steam and air are in-
jected into the ammonia-stripping tanks, and the vapors emitted from the tank
are directed to a sulfuric stripping column for the removal of ammonia. Exit
gas from the column is released to the atmosphere, and the column effluent
~
Chillers or refrigeration units are commonly used in the electroplating
business to remove excess carbonate that affects plating performance.
28
-------
ro
vo
MTCMCY#*DE
TWfATMBrfTUIE
EXrT OAS
(H20. AIR)
SOO'LM
NsOti i TMIOSULFATF .TEAU
STKPPM
COLUMN
MMONIA
STRIP
TAM<
CHLOBNATlW
TMW
EFFLUENT
K STAGE
CtflOnNATPON
420 au
t CCMC. MIXED ACfO
SLEEP
1 general ruse water
pjONCYAMW. NOfCL/RMBMWG
M»DNOfPJMGLNG)(1«00^^:
8! FID
LWE/UUfcSTf**
>0( YWeh
M*OH C*i
N*OM Cb
CCNTNUOU5 CY/W10E
PWBCIPTTATIffiUi£
EFFLUENT
177 000 TO
gpd
CHtOf NATION
UODIA.F
N«. 2
CHIOKNATION
MODULE
FlOCCULATiCN
I.CYANDERM5E
WATER
PPFC^rTATPON
FOUALCATKM
OVEf^LCW
i! STAGE
chlornatjon
SLUDGE
TIUCKLNlfl
"llHXiF
FILTRATE
POLYMER
FILTER
PUT&S
LANDFILL
C0NTNU04J8 NONCYANOc
PRECtPfTATlOML**
CArvE
CONTAKER
DM
fcDJUSrWfST
EFFLUENT
K«.OCOqp0
FLOCCULATION
CLAP -€R
PRECIPITATION
OVfPFlCW
SLUOOE
HIGKENER
SI JDCf
1 TIMN.NO AND BIWNISIWG ^
RUSE WATERS \
?. Oil lU FflOMBATCH CAUSTIC
ClEANERS
Figure 5. Wastewater treatment at Amerock Corporation.
-------
(about 1 gal/min or 420 gal/day) is discharged to the POTW (Sanitation Dis-
trict of Rockford). Upon completion of the ammonia-stripping and cooling-
cycle, the contents of the tank (about 3000 gal/day) are pumped to a sludge
thickener.
The continuous cyanide precipitation line receives cyanide rinse waters
and a bleed stream from the batch cyanide treatment line. After the chlori-
nation modules, general rinse waters consisting of noncyanide, nonburnishing,
and nontumbling wastewaters and concentrated mixed acid bleed are introduced.
The equalization tank receives about 15,000 to 30,000 gal/day of cyanide-
bearing wastewater for treatment. After equalization, the wastewater is
pumped to a series of two alkaline chlorination modules, where cyanide is
oxidized to cyanate (first-stage chlorination) by the addition of sodium
hydroxide and chlorine. Just prior to the precipitation tank, 162,000
gal/day of general rinse waters enter the precipitation line. Lime and
limestone are used for precipitation of heavy metals, followed by the addi-
tion of anionic polymer in the flocculation tank. After flocculation, the
wastewater gravity feeds to a rectangular clarifer. Underflow from the
clarifier and the discharge from the ammonia-stripping tank (batch cyanide
treatment) are directed to a sludge thickener. Overflow from the thickener
is returned to the flocculation tank, and the thickened sludge is pumped to a
filter press. The filtrate is returned to the precipitation tank in the
continuous noncyanide precipitation line, and the filter cake is collected in
20-yd3 containers for landfill disposal. The continuous cyanide precipita-
tion line treats and discharges to the publicly owned treatment works (POTW)
about 177,000 to 192,000 gal of wastewater per day.
Site Description—C.yanoKEM
CyanoKEM is a commercial hazardous waste treatment facility that re-
ceives industrial inorganic wastes, including acids, alkalis, and cyanide-
bearing wastes. Typical wastes treated at CyanoKEM are cleaning solutions,
stripping solutions, pickling liquors, and spent plating baths. The majority
of the wastes treated at CyanoKEM are drummed wastes made up of combinations
of salts, sludges, slurries, and liquids. Bulk liquids, including waste
rinses and baths, are handled in 5000-gal or larger volumes. Cyanide-bearing
wastes are oxidized with sodium hypochlorite under alkaline conditions to
cyanate (first-stage chlorination). Treated wastes are clarified, and the
effluent is discharged to the city of Detroit sewer system at a rate of about
50,000 gal/day. Stabilized, dewatered sludge is shipped to a hazardous waste
landfill. CyanoKEM's wastewater treatment facility has a design capacity of
35 million gallons per year.
All bulk cyanide waste tankers are sampled and checked in the laboratory
by fingerprint tests. If the tests show the waste to be acceptable and
treatable, the load (normally up to 5000 gal) is discharged into one of the
four 25,000-gal primary cyanide treatment tanks. If it is a predominantly
simple cyanide, it may be isolated in a cyanide treatment tank (C-l through
C-4) and treated individually. The simple cyanide load, however, may be
placed with another batch of simple cyanide waste in tanks C-l through C-4
30
-------
and treated as a combined batch to achieve proper dilution and optimum condi-
tions for cyanide treatment. A batch of simple cyanide may be present as a
bulk load or as a dissolved drum cyanide waste from a side tank (C-5 or C-6).
Cyanide bulk loads are generated from a variety of metal plating and finish-
ing operations. Typical examples are spent solutions of sodium, potassium,
zinc, or cadmium cyanide baths.
Cyanide bulk loads that are shown to contain certain heavy metals are
considered complex cyanides. These are unloaded into tanks C-l through C-4
in a manner that keeps them separate from simple cyanide batches. Typical
complex bulk cyanides contain dissolved and precipitated copper cyanides
alonq with some nickel and/or iron cyanides.
Primary treatment of simple cyanide wastes generally takes at'Out 12
hours (depending on the cyanide concentration), and complex cyanides require
about 36 hours, or three times longer. CyanoKEM has a proprietary seven-step
process for treating complex cyanide wastes.
Treated neutralized slurry from the acid and cyanide primary treatment
tanks (A-l through A-4 and C-l through C-4) is combined in a 350,000-gal
secondary treatment basin that serves as an equalization step for subsequent
continuous treatment (Figure 6). The wastewater is pumped from the treatment
basin to a 110,000-gal circular clarifier for solids removal, and overflow
from the clarifier is pumped to a continuous precipitator/settler unit. The
precipitator is the first unit in a series of effluent-polishing steps, where
iron sulfide and polymer are added to precipitate and settle any remaining
dissolved metals. After the metal precipitation step, the overflow is pumped
to two pressure sand filters and then through two carbon columns before being
discharged to a POTW. The carbon columns were installed to remove low con-
centrations of phenols from the effluent.
Backwash water from the two sand filters and the precipitator unit is
returned to the secondary treatment basin for equalization and treatment.
Sludae from the primary cyanide treatment tanks is pumped to a sludge-
conditioning tank, where lime is added to prepare the sludge for dewatering.
The sludge (F0P6) is pumped from the conditioning tank to a filter press,
which produces filter cake (47 to 48 percent solids) at a rate of 20 ft3 per
day. According to CyanoKEM, the sludge contains about 200 ppm total cyanide,
which consists primarily of ferri- and ferrocyanides. Effluent from the
filter press is returned first to a filtrate tank and then to a primary
cyanide treatment tank.
Clarifier underflow is directed to another filter press that generates
about 20 yd3 of filter cake per day, and filtrate is returned to the precipi-
tator tank for additional treatment. Stabilized filter cake from this opera-
tion is also shipped to a hazardous waste landfill.
31
-------
A-2
C-3
C-4
AS
Ftfter
Prms
C-1
C-2
Truck
Urr*
Slurry
T«**
Add
Doi<"n
BWg
Prdd»
liquor
Sodium
BituVft*
7ark*
Wasie vater ?
S'or.infl
'.\ as'e 'w'rife-
"Sceptio^
Figure 6. CyanoKEM waste and raw material flow schematic.
-------
WET-AIR OXIDATION
General Description
Wet-air oxidation (WAO) is the liquid-phase oxidation of organics or ox-
idizable inorganic components at elevated temperatures and pressures. Oxida-
tion is brought about by combining the wastewater with a gaseous source of
oxygen (usually air) at temperatures and pressures in the range of about 175°
to 327°C (360° to 620°F) and 2069 to 20,690 kPa (300 to 3000 psic), respec-
tively. A feed chemical oxygen demand (COD) concentration of ? percent is
sufficient to cause a temperature rise and to liberate volatile components.
The solubility of oxygen in aqueous solutions is enhanced at elevated pres-
sures, and the elevated temperatures provide a strong driving force for
oxidation.
Wet-air oxidation has been demonstrated at bench scale, pilot scale, and
full scale as a technology capable of breaking down hazardous compounds to
carbon dioxide and other less toxic end products (Dietrich 1985). Cyanide in
electroplating wastes is converted to carbonate and ammonium ions when oxi-
dized, as shown by the following reaction:
2NaCN + 02 + 4H20 - Na2C03 + (NH4)2C03 (4)
The major unit operations in the WAO process are wastewater pressuriza-
tion/air compression, preheat, reaction, cooling, depressurization, and
liquid/gas separation. Energy recovery is possible, depending on the tem-
perature of the effluent after the heat exchange with the feed.
There are two forms of continuous reactors: a tower reactor and a
cascade of completely stirred tank reactors (CSTR). The tower reactor is a
vertical vessel into which air is charged from the atmosphere to interface
with the feed. The reactor is sized to allowed 30 minutes to 2 hours reten-
tion of the feed (Freeman 1985). The CSTR system consists of a series of
horizontal reaction chambers continued within a horizontal cylinder. Air is
injected into each reaction chamber as the feed passes from chamber to cham-
ber. Again, the CSTR cascade should be sized to allow 30 minutes to 2 hours
reaction.
Off-gasses from WAO systems may have to be treated to reduce the concen-
tration of hydrocarbons. Wet scrubbing, which is commonly used to cool the
gas stream, reduces hydrocarbons somewhat. Adsorption columns or thermal
oxidation may be required to reduce organic emissions further.
Wastes containing up to 15 percent COD and 6 percent solids can be
treated by WAO. For wastes containing less than 2 percent COD, auxiliary
fuel must be provided to keep the reaction going (Alliance 1987). High-cyanide-
level wastestreams (greater than 1% CN~) have been successfully treated to
below 1 ppm effluent concentration (Sittig 1973). Cyanide destruction of
more than 99 percent is typical, and higher cyanide reductions have been
reported in some cases. Pretreatment to remove high-density solids (filtra-
tion or gravity settling), however, is required for some slurries.
33
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Site Description--Zimpro/Passavant
Zirnpro/Passavant is a vendor of waste treatment equipment, including WAO
systems; however, no full-scale system is currently in commerical operation
for cyanides.
Zimpro now conducts both bench- and pilot-scale WAO feasibility testing
on waste streams. The bench-scale testing consists of charging a 0.5-liter-
capacity titanium-shaking autoclave with a dilute waste sample and enough air
to provide 120 percent of the waste's autoclave oxygen demand (ADD). After
charging, the autoclave is placed in a heater shaker mechanism, heated to the
desired temperature, and maintained at that temperature for the desired
residence time. In the case of the wastes tested in this study, the auto-
clave oxidations were performed at temperatures of 200°, 240°, and 280°C and
a liquid residence time of 60 minutes. The autoclave is then cooled with tap
water, and the off-gases are analyzed by gas chromatography for nitrogen,
oxygen, carbon dioxide, carbon monoxide, total hydrocarbons (THC), and
methane. Each oxidation sample is then filtered and the suspended solids are
collected on filter paper. The filtrate and moist solids are then analyzed.
Figure 7 is a flow diagram of the Zimpro pilot-scale system that was
used to treat F007 from Amerock. The wastewater or slurry is brought to
system pressure by a high-pressure pump. Air from a compressor may be added
directly to the waste or to dilution water and preheated to raise the temper-
ature of the mixture at the reactor base so that the exothermic heat of
reaction will increase the mixture temperature to the desired maximum. Pre-
heating can be accomplished by an external heat source as shown in Figure 7
or by the reactor effluent. Startup energy is provided by the external heat
source to the preheater or an auxiliary heater. The reactor provides adequate
residence, time for the oxidation reaction the temperature of the wastewater-
air mixture rises as the reaction, occurs. The reactor effluent is cooled
with water (as shown in Figure 7) or with the wastewater-air mixture, usually
to about 95° to 135°F. A control valve reduces the pressure of the oxidized
liquor/spent air mixture. The gas phase is disengaged from the liquid phase
in the separator vessel.
The F007 pilot-scale treatment system at Zimpro/Passavant includes three
operations: 1) a blending step to control feed parameters, 2) wet-air-
oxidation processing, and 3) treatment of oxidized liquor. Table 6 presents
the design parameters and the following subsections discuss the importance of
those parameters.
Feed Blending Operation
Upon receipt of four 55-gal drums of F007 waste from Amerock, Inc.,
Zimpro/Passavant mixed the contents of the waste drums in a water-heated
stainless steel tank to ensure a homogenous feed composition. The waste
required heating to about 110° to 130°F to maintain its liquid state. Below
that temperature range, the waste crystallized because of the high concen-
tration of sodium carbonate, which made handling very difficult. After the
waste was thoroughly mixed, the drums were refilled and placed in a hot-water
34
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F —007 CYANIDE RUN
0ILUTI0N
water
ACID
TANK
CAS
chromatocraph
I
VENT CAS
TO AlMOSPHERt
HiGH
PRESSURE
PUMP
WASTE
TANK
CAS
SCRUBBER
57.
NaOH
REACTOR
KXJ '
RECIRCULATION
PUMP
—oa-
COOLER
CW.
GAS
MEIER
RECIRCULATION
PUMP
—CX3-
PCV
AIR
KNOCKOUT
ORUW
AIR
COMPRESSOR
OXIDIZED
UOUOR
Figure 7. Schematic diagram of Zirnpro/Passavant wet-air-oxidation process.
-------
TABLE 6. TYPICAL OPERATING PARAMETERS OF THE WAO PROCESS
Operating parameter
Steady-state condition
Reactor inlet temperature
430°
- 470°F
Reactor outlet temperature
440°
- 480°F
Reactor pressure
1700
psig
Waste feed rate
2.5 -
3.0 gal/h
Dilution water feed rate
2.5 -
3.0 gal/h
High-pressure air injection rate
60 -
80 scfh
Residual oxygen content of the off-gas
16 -
ro
0
bath, which was maintained at 110°F. As waste was needed in the performance
of the test run, a drum of waste was removed from the water bath, thoroughly
agitated with a portable mechanical mixer, and then pumped into the treatment-
system feed tank. The feed tank is equipped with a heating coil, a mechani-
cal mixer, and 5 recycle line to ensure that the feed is maintained at the
proper temperature and is homogeneous.
Wet-Air-Oxidation Processinq--Amerock test
The steady-state operating conditions of the Zimpro/Passavant WAO
process are shown in Table 6. All the parameters listed in Table 6 are key
operating parameters; however, the single most important parameter used tn
determine steady state was the reactor outlet temperature of about 4500F.
Operating phases of the WAO process include warmup (with tap water
followed by waste feed), stabilization, steady state, and cool-down (with tap
water). The warmup period with tap water typically requires about 4 hours,
followed by an additional 2-hour warmup with the waste feed. Waste feed
warmup continues until the operating conditions are within approximately
5 percent of the desired conditions, which signals the beginning of the sta-
bilization period. During the stabilization period the operating conditions
are continually fine-tuned. Typically, one to three residence times (i.e.,
about 1 to 3 hours) are required before steady-state is achieved. The steady-
state period continues as long as needed to collect all the required samples
or until the system falls outside steady state conditions (Table 6). After
the test, the system is switched to tap water and cooled down over a period
of about 6 to 8 hours.
In the WAO treatment test, dilution water (i.e, tap water) was pumped at
a rate of 2.72 gal/h (1745 psig) and combined with 1.1 ft3/min of compressed
air prior to passing through an oil preheater (Figure 7). The preheater
heated the tap water/air stream to about 520°F as it entered the base of the
36
-------
pilot-scale titanium reactor at. 1710 psig. The waste feed was pumped approxi-
mately 2 feet from the bottom of the 3—in.-i.d., 15-ft-long. reactor at a
rate of 2.75 gal/h. Total influent flow rate to the reactor was 4.47 gal/h.
Heat tapes spaced evenly along the length of the reactor at 15-in. intervals
and the heat of reaction maintained the temperature at about 450°F. The
oxidized liquor left the reactor through one of two exit ports. One port was
used as the reactor outlet of the oxidized liquor; 18 percent nitric acid was
pumped at a rate of 0.55 gal/h (1735 psig) through the other port to remove
any carbonate plugging. Every 4 hours throughout the test run, the valves
controlling the exit ports were reversed to ensure that the reactor did not
plug. From the reactor, the oxidized liquor passed through a tube-in-tube
water cooler, which reduced the temperature to about 106°F. The liquor then
passed through a pressure control valve that returned the wastewater to
atmospheric pressure. The wastewater then entered a gas/liquid separator.
The oxidized liquor was collected from the bottom of the separator and the
off-gas passed through a caustic scrubber containing a 5 percent NaOH solu-
tion. The oxygen content of the off-gas was monitored continuously with an
02 meter, and a dry-gas meter measured the off-gas flow rate before it was
released to the atmosphere. Off-gas samples before and after the scrubber
were analyzed for the permanent gases, methane, and total hydrocarbons by a
gas chromatograph.
Treatment of Oxidized Liquor
Before discharge of the oxidized liquor to the PCTW, the wastewater re-
quired neutralization and metals precipitation, which was accomplished by the
following process:
1. The oxidized liquor was pumped into a IOC-gal holding tank.
2. Nitric acid was added for pH adjustment. Two types of acid were
used: 1) spent acid from the reactor acid wash, or 2) concentrated,
38-degree Baume acid.
3. Sufficient acid was added to lower the pF to 8.0 to 8.5. (Care
must be taken when the acid is added because a large quantity of
carbon dioxide is liberated and the reaction is somewhat violent.)
4. Sulfide in the form of sodium hydrosulfide (NaHS) or sodium sulfide
(^S) was added to the tank and mixed.
5. Because the sulfide precipitates are very difficult to filter,
diatomaceous earth was added as a filter aid to the slurry to
improve filterability.
6. A sample of slurry from the tank was filtered, and a chip of
sulfide was added to the filtrate. If the filtrate remained clear,
the metal ion precipitation was complete. If a brown precipitate
appeared, more sulfide was required. Additional sulfide was added
to the holding tank until the filtrate remained clear when a sul-
fide chip was added.
37
-------
7. A small plate and frame pressure filter was used for the filtering.
The press cloths were precoated with diatomaceous earth before the
sulfide solids were filtered to improve filterability and to prevent
the sulfide solids from blinding the filter cloth.
Filter cake generated from the treatment of the oxidized liquor was
disposed of at a hazardous waste landfill.
ULTRAVIOLET LIGHT/OZONATION
General Description
Ozone is one of the strongest oxidizing agents available. As an
oxidant, ozone is strong to break many carbon-carbon bonds and even
cleave aromatic ring systems. If ozonation of cyanide is taken to comple-
tion, bicarbonate, nitrogen, and oxygen are formed. Complete ozone oxidation
of cyanide (via a cyanate intermediate) to end products is as follows (Rice
and Browning 1981):
CN" + 03 + CNO" + 02 (5)
2CN0
303 +
H20
+ 2HC0.
n2 +
30,
(6)
Reaction 5 proceeds rapidly and yields the cyanate intermediate (CN0~).
Reaction 6, however, proceeds very slowly, which makes the complete destruc-
tion of cyanide to bicarbonate and nitrogen impractical. In general, 2 lb of
ozone is required to treat 1 lb of cyanide. Because oxidation by ozone
occurs nonselectively, it is generally used only for aqueous wastes that
contain a high proportion of oxidizable constituents. Ozonation is believed
to be particularly useful as a final treatment step for waste streams that
are dilute in oxidizable contaminants but do not meet effluent standards
(Alliance Technologies Corp. 1987).
Generally, in the ultraviolet 1ight/ozonation process (UV/03), the cya-
nide stream is mixed with ozone and then enters a reaction chamber in which
the stream passes numerous UV lamps. The UV radiation enhances oxidation by
direct disassociation of the cyanide radical or through excitation of the
various species in the waste stream (Alliance 198/). Complexed cyanides may
be more effectively oxidized by ozone in the presence of ultraviolet light
(Cushnie 1985). The destruction rate, especially at low cyanide concentra-
tions of a few parts per million, can be enhanced by conducting the treatment
at elevated temperatures (approximately 150°F) and/or higher ozone concentra-
tion. In industry, the UV/03 process is usually equipped with a recycle so
that more complete destruction can be achieved. Better cyanide destruction
efficiencies can be obtained by using certain metal ions as catalysts (i.e.
copper) (Patterson 1985).
38
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Site Description—IITRI
The Illinois Institute of Technology Research Institute (IITRI) in
Chicago, Illinois, conducted bench-scale studies of the UV/0- system for the
treatment of F009 waste. The Master Lock Company in Milwaukee, Wisconsin,
was the generator of this waste and provided the necessary quantity of the
waste needed to conduct the UV/O^ testing at IITRI.
ELECTROLYTIC OXIDATION
General Description
Electrolytic oxidation has been used to treat wastes containing high
concentrations of cyanide (> 1% CN~) (Sittig 1973). This technology is not
suitable for treating rinse waters because of their lower cyanide concentra-
tions .
In this process, the concentrated cyanide waste stream is subjected to
electrolysis at temperatures of about 200°F for several days. During this
treatment period, the cyanide gradually decomposes to carbon dioxide ar,d
ammonia, with cyanate as an intermediate. As the process continues, however,
the waste (electrolyte) becomes less capable of conducting electricity and
the reaction slows down. Alkaline chlorination may be required to decompose
any residual cyanate that may have formed. Electrolytic oxidation has been
shown to be less effective on cyanide wastes that contain sulfates (Sittig
1973). Heavy scaling will result at the anode, which will reduce current
flow. Wastes containing several tens of thousands of parts per million of
cyanide have been treated over 7- to 8-day periods and yielded cyanide levels
of less than 0.5 mg per liter (qreater than 99.99% destruction) (Sittig
1973).
Site Description—Woodward Governor
The Woodward Governor Company (WGC) of Rockford, Illinois, operates a
metal-heat treating facility to case harden carbon and alloy steels. The
case hardening process employeed by WGC uses a nolten salt bath, typically
composed of cyanide and cyanate salts. Residuals from cleanout of the salt-
bath pot (F011 waste) are treated by electrolytic oxidation. An F012 waste-
water sludge from metal heat treating operations is also generated by WGC.
This F012 waste is treated by alkaline chlorination.
In the electrolytic oxidation step, the quantity of solidified cyanide
salts (F011) to be treated is placed into the reactor. This reactor, which
is heated by internal steam coils, is first partially filled with a lime
slurry. The cyanide salt waste is then added by filling a basket with the
waste and lowering the basket into the reactor to dissolve the waste. The
reactor is then completely filled with tap water and/or lime slurry to its
250-gal capacity and an electrical current is passed through the solution
across two sets of electrodes to oxidize cyanide, first to cyanate and then
completely to nitrogen or ammonia and carbon dioxide. A typical initial
39
-------
cyanide concentration in the reactor ranges from 10,000 to 20,000 mg per
liter. The cyanide concentration is checked periodically during the course
of electrolytic oxidation by a spot test. The single spot test used by plant
personnel consists of precipitate formation and color change upon addition of
a drop of chloramine-T and a barbituric acid solution to a specified amount
of waste. Operators typically allow at least 1 hour of treatment time for
each 5 lb of cyanide waste added to the electrolytic oxidation reactor at the
start of treatment.
After electrolytic oxidation, the waste is fed into a steam-heated batch
reactor, where chemical oxidation occurs over a 1- to 2-hour period by reac-
tion of the cyanide with sodium hypochlorite. This chlorination treatment
step further reduces the cyanide concentration. A second-stage alkaline
chlorination is conducted to convert cyanate to carbon dioxide and nitrogen.
(See Figure 8 for a schematic diagram of the F011 Treatment Operation.)
40
-------
PARTIALLY-
TREATED
TREATtO fOf 1
WASTEWATER
(TO POTW)
LIME
SLURRY
TREATEO
MIXED
WASTEWATER
rro potw)
STEAM
B001UM
HYPOCH LORTTE
SOLIDS
(TO LAMOfILL)
CLARIFICATION
FLOCCULATtOM
CRAvnt
SETTLING
AND POCISHIMO
FflTflATlOK
FILTER PRESS
ELECTROLYTIC
OXIOATION
ALKALINE
CMLORINATION
A*D
PRECIPITATION
Figure 8. Schematic diagram of the batch F011 cyanide treatment process at
Woodward Governor, Rockford, Illinois.
-------
SECTION 4
CHFKICAL PRECIPITATION
Chemical precipitation is the most common treatment method used by the
electroplating industry for removal of metals from wastewaters. Sludges
generated by this technique are typically solidified/stabilized for disposal.
This section presents a general process description of the chemical precipi-
tation used by the individual sites in this study. It also describes the
site of the John Deere and company facility.
PPOCESS DESCRIPTION
Precipitation of metal-laden wastewaters involves the addition of chemi-
cals to alter the physical state of the dissolved or suspended metals and to
facilitate their removal through sedimentation. Chemicals used to precipi-
tate metals for aqueous streams include caustic soda, lime, sodium sulfide,
ferrous sulfide, soda ash, and sodium borohydride. Complexed metal waste-
waters cannot be effectively treated by such chemical additions; therefore,
the use of reducing agents is needed before their removal from the water
matrix by precipitation. The reduction process involves the transfer of
electrons to the chemical being reduced (reductant) from the chemical initi-
ating the transfer (the reducing agent). Four commonly used reducirg agents
are sulfur dioxide, ferrous sulfate, sodium borohydride, and sodium bisul-
fite. For collodial suspensions, characterized by their balance of attrac-
tive and repulsive forces, the use of coagulants/flocculants is required for
adequate precipitation. Coagulants/flocculants destabilize the suspension by
reducing the repulsive forces so the particles can agglomerate. Examples of
coagulants/flocculants include lime, alum, and synthetic polyelectrolytes.
Precipitation, reduction, and coagulation/flocculation are followed by
sedimentation (settling). Typical settling times for heavy metal particles
are between 90 and 150 minutes, depending on the waste being treated (Metcalf
& Eddy 1979). Precipitation can occur in both batch or continuous sedimenta-
tion systems. With continuous systems, sedimentation tankage (clarifiers)
should be sized to accommodate a wastewater flow of 0.5 gal/min per square
foot of clarifier surface area (Metcalf & Eddy 1979). After settling has
occurred, a sludge layer (which typically contains about 1 to 2 percent
solids) forms at the bottom of the tank. This sludge is then sent to addi-
tional tanks (sludge thickeners), which provide subsequent settling to
approximately 5 to 10 percent solids. The resultant sludge is then sent
through pressure or vacuum filtration to increase the sludge solids content
to about 15 to 50 percent, depending on the type and amount of chemical
42
-------
additives used. The sludge cake is then shipped for treatment and disposal
at a hazardous waste landfill. Figure 9 is a flow diagram of a typical
continuous precipitation treatment system. The reduction step is only re-
quired for certain applications.
Specific precipitation processes, including the use of reducing agents
and coagulation aids, are discussed in the following subsections.
Hydroxide Precipitation
For many heavy metals, precipitation is accomplished by adjusting the pH
of the wastewater to alkaline, which causes the soluble metal ions to form
insoluble metal hydroxides. This pH adjustment is usually achieved by the
addition of caustic (sodium hydroxide) or lime (calcium hydroxide). For
metal hydroxide species, the solubilities are known to increase with both
rising and falling pH values outside the pH 7 to 10 range. Table 7 presents
the pH ranges typically used to precipitate a metal hydroxide and the approxi-
mate effluent discharge after sedimentation (in a well-run treatment system).
Because the discharge must be in the proper pH range (pH of 6 to 9) and
because of the differences in industrial waste compositions, actual indust-
rial effluent concentrations from precipitation systems tend to be greater
than their minimal solubilities. Sand filtration of the effluent arter
sedimentation can further reduce the metal concentrations in the discharge
(Patterson 1985). Coprecipitation with other metals can enhance the removal
of a given metal species.
TABLE 7. TYPICAL WASTEWATER DISCHARGE
CONCENTRATIONS FROM METAL HYDROXIDE PRECIPITATION PROCESSES9
Metal hydroxide
pH range for
treatment
Typical effluent discharge
after sedimentation, ma/liter
Aluminum
6-7
0.10
Cadmium
>10
0.5
Chromium (III)
7-8
0.10
Copper
9-10
0.50
Nickel
10-11
>1.0
Zinc
8-11.5
>1.0
Lead
9.5-10.5
>1.0
Si 1ver
10.5-11.5
0.50
aSource: Alliance Technologies Corporation (1987).
Sulfide Precipitation
Chelated wastewaters (e.g., those containing EDTA) can severely hinder
the metals removal of precipitation systems. Sulfide precipitation, however,
which drops out metal ions as very insoluble sulfides, has been shown to
yield high metal removals even in highly chelated wastewater (Cushnie 1985).
This process is used as an alternative to hydroxide precipitation or as a
polishing step after hydroxide precipitation. Two different processes are
43
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REDUCING PRECIPITATION COAGULANT/
AGENT REAGENT FLOCCULANT
WASTEWATER
FEED
SETTLING
TANK
(CLARIFIED)
REDUCTION
WASTEWATER TO
DISCHARGE OR
ADDITIONAL
TREATMENT UNITS
1 -?%
SOLIDS
SLUDGE
THICKENER
SLUDGE
15-50%
SOLIDS
TO METALS
RECOVERY OR SOLID
WASTE DISPOSAL
5-10%
SOLIDS
EQUALIZATION
FLASH
MIX
TANK
FILTER
PRESS
SAND
FILTRATION
Figure 9. Flow diagram of a typical continuous precipitation system.
-------
used for sulfide precipitation--the soluble sulfide process and the insoluble
sulfide process. The soluble sulfide process uses sodium sulfide as the
treatment reagent, whereas the insoluble sulfide process uses ferrous sulfide.
Both processes generate metal sulfide sludges that tend to be more difficult
to dispose of properly because of potential sulfide reactivity (Cushnie
1985). The insoluble sulfide process generates a larger volume of sludge
than does hydroxide precipitation because of the liberation of ferrous ions
during treatment and the subsequent conversions of these ions to ferrous
hydroxide (Cushnie 1985). Removal levels for arsenic, cadmium, lead, mercury,
nickel, silver, and zinc are significantly better with sulfide precipitation
than with hydroxide precipitation because their sulfide solubilities are
lower than their corresponding hydroxide solubilities.
For effective metals removal, the pH of the waste water must be main-
tained within the neutral to slightly alkaline range. Contact with acidic
wastewaters will result in poorer removal and can cause the emission of
hydrogen sulfide (H^S) gas (Cushnie 1985).
Phosphate Precipitation
Pilot studies have been conducted to evaluate phosphate precipitation as
a treatment alternative for recovering chromium from mixed metal solutions
(Twidwell 1987). Phosphate, in the form of phosphoric acid ^POi*, can effec-
tively strip trivalent cations from solution in preference to divalent cations
under low pH conditions. Phosphate products filter easily and can be compacted
to a high solids content. Results of work conducted on metal sludge leachates
have shown greater than 99 percent removals of chromium at pH 3.5 using
phosphate (Twidwell 1987).
Chromium Reduction
Ferrous sulfate (FeS0i+) is industry's reagent of choice for chromium
reduction because of its abundance and low cost. With the use of FeS0i+, the
pH of the chromate waste stream must be between 2 and 3 for rapid reduction,
as shown in the following:
3Fe+2 + HCr04" + 7H+ -* 3Fe+3 + 4H20 + Cr+3 (7)
Subsequent neutralization results in large volumes of iron hydroxide
sludges, which makes disposal costly. An alkaline ferrous sulfate reduction
process is currently being studied. This process requires that the pH be
maintained between 7 and 10; therefore, it can take place in the neutral-
ization/precipitation tankage (Cushnie 1985). One deficiency of this alka-
line process is the difficulty encountered in accurately controlling ferrous
sulfate additions to the wastewater. Sulfur dioxide, sodium bisulfate, and
metabisulfate are other reagents used for reduction of chromium.
Coagulation/Coprecipitation (Alum, Lime, and Polyelectrolytes)
Coagulation/flocculation systems improve sedimentation of precipitated
metal particles. The rate at which coagulated particles coalesce is related
45
-------
primarily to the frequency of the collisions between the particles. Colli-
sions occur as a result of the heavier faster particles overtaking the lighter
slower particles. As a result, the frequency of collisions is proportional
to the particle concentration and the difference in settling velocity. ,
Because the number of collisions typically increase with time, the degree of
flocculation usually increases with the residence time (EPA 1987). Other
factors that affect the agglomeration of particles include the nature of the
surface, the presence of electrical charges, the shape, and the density.
Inorganic coagulants are used primarily for waste streams having dilute
concentrations of insoluble constituents. These coagulants, however, add to
the overall sludge generation. Lime, alum, and ferric chloride are the
inorganic coagulants of choice by industry. Synthetic polyelectroytes are
used mainly with heavy metal precipitates. These chemicals use chemical
bridging and physical entrapment to coalesce the precipitated metals.
Anionic polymers are generally used because heavy metal precipitates tend to
carry slightly positive charges. A natural anionic polymer, ISX, has also
been developed as a coagulant. Because of handling difficulties and disposal
problems, however, the natural anionic polymer has not been as widely ac-
cepted as have the synthetic polyelectroytes and inorganic coagulants.
Coprecipitation is the process of precipitating a given metal species in
association with other metal species. For some metal ionic forms, such as
arsenate (AsOu"3), coprecipitation is the treatment method of choice.
Coprecipitation involves both absorption of the soluble ior. onto a bulk solid
and coagulation of fine solids by the bulk precipitate.
SITE DESCRIPTION—JOHN1 DEERE AND COMPANY
John Deere's Waterloo, Iowa, operations include four major facilities:
John Deere Engine Works, John Deere Tractor Works, John Deere Components
Works, and John Deere Product Engineering Center. These facilities generate
a variety of wastes that are treated on site in the wastewater treatment
plant. The wastes include electroplating sludges, spent electroplating
baths, painting wastes, caustic paint-stripping wastes, kolene sludge from
castings cleaning, spent pickling acids, aluminum conditioner, caustic
cleaners, waste oils, and miscellaneous acids and alkaline wastes. The
wastewater treatment plant receives about 300 gal of copper cyanide sludge
(F008, ] to 2% CN) twice a year, 500 gal o47 spent copper cyanide plating bath
solution {F007, 1 to 2% CN) once a year, and a total of 75,000 gal of cyanide
rinse waters per year {100 ppm CN). The treatment plant does not receive any
F009. This report focuses on the wastewater treatment units involved in the
phosphoric acid metal precipitation process and alkaline chlorination.
John Deere operates both a batch and continuous phosphoric acid metal
precipitation process (Figure 10). Cyanide treatment occurs only in the
batch mode. In the batch process, which takes about 4 hours per batch,
wastewater is pumped to a 16,000-gal equalization tank (T-41) followed by a
9000-gal reactor tank (T-45). Depending on the type of wastewater and the
level of treatment desired, the reactor tank is equipped with chemical feed
46
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-p*
BATCH
PROCESS
CONTINUOUS
PROCESS
(50 gpm)
EFFLUENT
fl.OOO ^ilGATCH '
POTW
h,po4
h?so4
3
CtfOH)
> POLYMFR
T-i
EQUALIZATION
T-IbA
AEACTOfl
EFFLUENT HOLDING
SUPERNATANT
TANK
SLUDGE
Ca(CH)
Vj T-ao
SLUDGE
ccnotcmng
FILTER CAKE
TO LANDFILL
SLUDGE
FILTER PRESS
THICKENER
jSUPERNATANT
FILTRATE
H.PO
r c^oh)
POLrK®1 R
2 4
1 V
&) CHROME
reouctton
T U
NEUTTUUZATION
T tA
EQUALIZATION
T-10A
EFFLUENT HOLDING
OVERFLOW
EFFLUENT
46.0QC opO
CLARIF1ER
1-UtOHl
vj T^ao
SLUDGE
CONDI TIONNG
V i MS
SLUDGE
FILTER PRESS
TH(CKfcNER
supernatant
POTW
FILTER CAKE
10 LAND FILL
FILTRATE
© VENTS
Figure 10. Phosphoric acid metal precipitation at John Deere.
-------
lines for the addition of phosphoric acid, sulfuric acid, ferric chloride,
lime, sodium disulfite, sodium hypochlorite, and polymer. The reactor tank
serves as a flash mix tank, a flocculation tank, and a sedimentation tank.
The reactor tank is also equipped with pF meters and oxidation-reduction
potentiometers (ORPs) for use on one- and two-stage alkaline chlorination
during the treatment of cyanide-bearing waste streams. Supernatant from the
reactor tank is pumped to a 40,000-gal holding tank prior to discharge to the
POTW. Sludge from the reactor tank is pumped to a 7500-gal sludge thickener
(T-15). The thickened sludge is pumped to a 5500-gal conditioning tank
(T-60), where 12 to 13 percent lime is added to prepare the sludge for dewater-
ing in the filter press. The Netzsch filter press generates about 65 ft3 of
¦filter cake per batch, which takes about 1.5 hours. John Deere runs about
two batches a day. The filtercake (50 to 60 percent solids) is disposed of
at a hazardous waste lancfill. Supernatant from T-15 and filtrate from the
filter press are pumped to the equalization tank (T-9A) in the continuous
treatment process.
48
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SECTION 5
STABILIZATION/SOLIDIFICATION OF METAL-FINISHING WASTES
Stabilization/solidification involves the mixing of a hazardous waste
with a binder material for enhancement of the physical and chemical proper-
ties of the waste and the chemical binding of any free liquid (EPA 1986).
The binder is typically a cement, pozzolan, or thermoplastic. Stabilization
involves a chemical reaction that converts inorganic waste material to its
least soluble and most environmentally inert form. Solidification systems
improve the handling and physical characteristics of the waste and decrease
the surface area from which volatilization, leaching, or spillage losses can
occur. A solidified waste is encapsulated in a monolithic solid of hiah
structural integrity. The encapsulation may be of fine waste particles
(microencapsulation) or a large block or container cf wastes (macroencapsula-
tion). The two terns stabilization and solidification are commonly used
together because they are both instrumental in immobilizing hazardous con-
stituents in the waste.
BACKGROUND
The U.S. Army Corps of Engineers Waterways Experiment Station (WES) in
Vicksburg, Mississippi, conducted stabilization/solidification testing on
selected metal-finishing hazardous wastes under an interagency agreement with
the EPA. Following stabilization/solidification of the metal-finishing
wastes, WES performed the toxicity characteristic leaching procedure (TCLP)
on the untreated and treated material and forwarded the extracts to an inde-
pendent laboratory for chemical analysis. The TCLP extracts processed by WES
represented EPA Hazardous Waste Nos. F006, F011, F012. Hazardous Waste F006
is described as wastewater treatment sludges from electroplating operations,
F011 is described as spent cyanide solutions from salt-bath-pot cleaning ir
metal heat-treating operations, and F012 is described as quenching wastewater
treatment sludges from metal heat-treating operations where cyanides are used
in the process. The WES stabilized/solidified three F006 waste streams from
John Deere in Waterloo, Iowa; Amerock in Rockford, Illinois; and Master Lock
in Milwaukee, Wisconsin. The F011 and F012 wastes were both collected at
Woodward Governor in Rockford, Illinois.
DESCRIPTION OF THE WES STAB ILIZATION/SOL IDIFICATION PROCESS
Three different pozzolan binders (lime/fly ash, portland cement, and
kiln dust) were tested by WES to determine their potential application to
metal-finishing waste codes. Lime/fly ash and kiln dust pozzolanic processes
49
-------
use a finely divided, noncrystalline silica in the fly ash and calcium in the
lime to produce low-strength cementation, "waste containment is obtained by
entrapping the waste in the pozzolan concrete mix (microencapsulation).
Pozzolan-portland cement systems produce a type of waste/concrete composite.
Microencapsulation of the contaminants in the concrete matrix provides con-
tainment. The addition of soluble silicates to the mix helps to accelerate
hardening.
The stabilization/solidification process involves the addition of water
and binder material to the waste, followed by mixing and a curing period.
The waste-binder mix samples are cured at room temperature for over 48 hours.
The samples are placed in a curing box under specific temperature and
humidity conditions. The samples are then removed from the curing box to a
cool place. The cooled concrete test cubes are subjected to a compressive
strength test to evaluate the technical and economical feasibility of the
binders, or are subjected to a leaching performance evaluation [toxicity
characteristic leaching procedure (TCLP) and waste extraction test (WET)].
Figure 11 is a flow diagram of the stabilization/solidification process used
at WES (U.S. Army 1988).
An initial screening test is used by WES to determine the appropriate
water-to-binder/waste ratio for each of the binders used and to narrow the
range of binder-to-waste ratios used in the more detailed evaluation. The
optimal water-to-binder/waste ratio is determined by a Cone Index (CI) Test
on test samples after 48-hour curing at room temperature. The CI value is
reported as the force per unit surface area of a cone base required to push
the cone through the test sample at a rate of 72 in./min. Once these ratios
are determined by the CI, new specimens are created for detailed unconfined
compressive strength (UCS) testing to be conducted on cubes cured 7, 24, 21,
and 28 days. The UCS test subjects each test cube to crushing with a com-
pression apparatus to define and characterize trie effects of the stabiliza-
tion/solidification process on the physical characteristics of the waste.
The UCS is reported as the force required to fracture the test cube. A
conservative pass/fail criterion of 50 pounds per square inch (psi) was used
to select samples for chemical analysis.
Leaching performance is the primary criterion in all treatability work,
and is therefore the most relevant of parameters. WES performed the TCLP and
WET tests on samples cured for 24 hours and 28 days. The TCLP was developed
to determine which trial mix leached the least on a unit basis.
The test cubes were subjected to TCLP extractions in accordance with
Test Methods for Evaluating Solid Waste: Physical/Chemical Methods, SW-846,
3rd ed., 1986. The WET testing was performed in accordance with State of
California regulations (California Administrative Code, Title 22).
Section 6 includes a detailed discussion of the results of the stabiliza-
tion/solidification tests conducted on EPA Hazardous Wastes F006, F011, and
F012.
50
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WATER BINDER
WATER BINDER
WASTE TO
BE
STABILIZED/
SOLIDIFIED
CURING
ANALYSIS
OF
LEACHATE
WATER-TO-
WASTE AND
BINDER-TO-
WASTE RATIO
SELECTION
BATCH
PREPARATION
DETERMINATION
OF CONFINED
COMPRESSIVE
STRENGTH AT 7,
14,21 AND 20 DAYS
TOXICITY
CHARACTERISTIC
LEACHING
PROCEDURE
(AFTER 28 DAY
CURE)
INITIAL SCREEN TESTING
UCS TESTING
TCLP TESTING
Figure 11. Flowchart for WES stabilization/solidification processing.
-------
SECTION 6
RESULTS AND CONCLUSIONS
WASTE CHARACTERIZATION
The following subsections summarize the results of the sampling of
metal-finishing sites for RCRA-listed F006 filter cakes, F007 and F009 waste-
waters, and FO19 filter cakes to obtain information on specific waste
characteristics.
F006 Fi1ter Cake
A total of six raw F006 filter cake samples were collected by PEI at
Amerock Corporation, Rockford, Illinois, on September 1, 1988. Three 8-oz
glass jars of the filter cake were obtained for analysis by PEI1s laboratory
in Cincinnati, Chin. Three additional 6-gallon buckets of the filter cake
were collected to send to the U.S. Army Corps of Engineers' WES in Vicksburg,
Mississippi, for stabilization/solidification testing if the waste proved to
contain appreciable levels of complexed cyanide. Testing details were pre-
sented in Section 4 of this report.
The 8-oz filter cake samples were analyzed for BOAT metals, total compo-
sitional cyanide (total and amenable), and TCLP cyanide {total and amenable).
A list of specified analytes is provided in Table 8. Matrix spikes and
matrix spike duplicates (for all constituents) were performed on one sample
of the filter cake. Data obtained in the analysis of the filter cake are
confidential; however, some key analytical points should be discussed.
Analysis of the TCLP residue revealed that more than half (56%) of the total
cyanide in raw waste remained in the residue and did not leach. Cyanide
spike recoveries were found to satisfy OSWER QA objectives of greater than 20
percent. Metal spike recoveries satisfied OSWER QA objectives of greater
than 20 percent except for silver, for which spike recoveries were about 10
percent. Because silver is a noncritical parameter, no repeat analysis was
taken.
Master Lock—
On October 18, 1988, PEI collected raw F006 filter cake samples at the
Master Lock Company, Milwaukee, Wisconsin, for chemical analysis and stabili-
zation/solidification ' - ¦ --> --dicated that the conventional
batch wastewaters) had the highest cyanide and metal concentrations. There-
fore, PEI collected a total of six samples of conventional treatment filter
Amerock--
wastewater treatment
treatment of complexed and
52
-------
cake. Two 8-oz clear glass jars were required for each of the six samples.
PEI also collected three 6-gallon plastic buckets of the waste filter cake
for WES stabilization/solidification testing. It was noted that some of the
waste placed in the buckets may have come from the complexed or batch waste
streams. PEI's laboratory in Cincinnati, Ohio, performed all the chemical
analysis.
TABLE 8. LIST OF AMEROCK F006 ANALVTES
BDAT metals
154 Antimony
155 Arsenic
156 Barium
157 Beryllium
158 Cadmium
159 Chromium (total)
221 Chromium (hexavalent)
160 Copper
Inorganic nonmetallics
169 Cyanide (total)
169 Cyanide (amenable)
161 Lead
162 Mercury
163 Nickel
164 Selenium
165 Silver
166 Thallium
167 Vanadium
168 Zinc
TCLP
169 Cyanide (total)
169 Cyanide (amenable)
The filter cake samples were analyzed for BDAT metals and total composi-
tional cyanide. The TCLP leachate and residue were analyzed for cyanide
(total, amenable, and WAD). Table 9 lists the specific analytes. Matrix
spikes and matrix spike duplicates for all constituents were performed on one
of the samples.
TABLE 9. LIST OF MASTER LOCK F006 ANALVTES
BDAT metals
154 Antimony 161 Lead
155 Arsenic 162 Mercury
156 Barium 163 Nickel
157 Beryllium 164 Selenium
158 Cadmium 165 Silver
159 Chromium (total) 166 Thallium
221 Chromium (hexavalent) 167 Vanadium
160 Copper 168 Zinc
Inorganic nonmetallics
169 Cyanide (total)
169 Cyanide (amenable)
169 Cyanide (WAD)
TCLP
169 Cyanide (total)
169 Cyanide (amenable)
169 Cyanide (WAD)
53
-------
Tables 10 and 11 present the analytical data obtained from the Master
Lock F006 filter cake.
Total cyanide concentrations in the raw waste averaged 2392 ya/g, and
total cyanide detected in the TCLP leachate of the raw waste averaged less
than 0.04 mg/liter (or 0.8 yg/g), which is slightly above the method
detection limit of 0.02 mg/liter or 0.5 yg/g. Analysis of the TCLP residue
showed that about half (49%) of the total cyanide in the raw waste remained
in the residue and did not leach. Amenable cyanide in the raw and TCLP
residue samples could not be determined; however, EPA Method 9010 did appear
to work on the TCLP leachate. The concentration in the leachate ranged from
undetected to 0.16 mg/liter.
The WAD cyanide was determined on the Master Lock samples in an effort
to quantify the amenable cyanide fraction of the total cyanide in the raw
waste. In the raw waste, WAD cyanide accounted for about 5 percent of the
total cyanide, whereas it represented about 15 percent of the total cyanide
in the TCLP residue. Negligible concentrations of WAD cyanide were found in
the TCLP leachate. Analytical discrepancies, however, make the significance
of these data questionable.
Metal analyses of the Faster Lock F006 samples indicate elevated concen-
trations of cadmium, nickel, copper, chromium, and zinc. Cadmium concentra-
tions averaged 39,867 yg/g, nickel averaged 11,650 yg/g, copper averaged 7928
yg/g, chromium averaged 4820 yg/g, and zinc averaged 4682 yg/g. Silver was
the only constituent that did not satisfy the 0SWER QA objective of greater
than 20 percent for spike recoveries. Again, because silver is not a criti-
cal parameter, no repeat analysis was taken.
John Deere and Company—
On May 21, 1987, PEI collected raw F006 filter cake samples at John
Deere and Company, Waterloo, Iowa, for characterization analysis and stabili-
zation/solidification testing. A sample of electroplating wastewater
from T-9A (influent to the continuous phosphoric acid metal precipitation
process! was collected, along with a sample of F006 filter cake from the
dewatering of the precipitated sludge. About 15 gallons of the filter cake
was also collected for stabilization/solidification testing at WES.
The influent wastewater was analyzed for Appendix IX volatile and semi-
volatile organics, Appendix IX metals, sulfide, fluoride, ammonia, purqeable
organic carbons (POCs), and nonpurgeable organic carbons (NPOCs). The filter
cake was analyzed for Appendix IX volatile organics, Appendix IX metals, sul-
fide, fluoride, ammonia, P0C, NP0C, TCLP volatile organics, and TCLP metals.
PEI*s laboratory in Cincinnati, Ohio, performed all the chemical analyses.
Tables 12 and 13 present the results of the analyses of John Deere's
F006 waste. Metal analyses of the samples indicate elevated concentrations
of chromium (1650 mg/liter). Ammonia levels were also high (6850 yg/g).
Analysis of the TCLP extract for meta"!s showed only arsenic to be above
detection limits. The value for arsenic, however, was three orders of magni-
tude below the regulatory limit.
54
-------
TABLE 10. SUMMARY OF MASTER LOCK F006 CYANIDE ANALYSES3'b
Raw
samples, u
Vl
rcLP
leachate, m/L uiq/g)
TCtP
res idufi,
ug/g
Prrcent
recovered
Sample No.
CN(T)
' WfST
CNpiSB)
CNfTJ
CN(A)
CM(WAD)
CN (T)
CM (A
CN(WAC)
CNfTl
CNfWAOT
ML0CK-CK-1
2080
NA
89
0.16(3.2)
0.16(3.2)
<0.02(<0.4)
94
NA
451
4
510
ML0CK-CK-Z
??ao
NA
130
0.03(0.6)
0.03(0.8)
-------
TAB IF II. SUMMARY OF MASTFR LOCK F006 METAL ANALYSES
Samplp Number
Constltuent
MIOCK-CK-1,
uq/o
MLOCK-CK-2,
Hi/q
IHl.OCK-CK-3,
«n/n
M10CK-CK-4,
9/ n
MLOCK-CK-'j.
vq/q
ML0CK-CK-6.
-i/q
3ari)P
Average
MS,
m.OCK-CK-3.
t recovered
MSO,
HI OCK-CK
X rrrove
Antimony
<6.14
<5.90
<6.02
-------
TABLE 12. ANALYSIS OF JOHN DEt-RE F006 FILTER CAKE
Consti tuent
Concentration, yg/g
F1 uoride
268
Sulfide
21
Ammonia
6,850
NPOC
16
POC
305
Aluminum
270
Antimony
22.4
Arsenic
<0.4
Barium
28.8
Beryllium
<0.1
Cadmi um
0.37
Calcium
88,200
Chromium
1,650
Cobalt
<2
Copper
135
Iron
5,930
Lead
184
Magnesium
998
Manganese
79.1
Mercury
<0.2
Ni ckel
11.8
Osmium
29.7
Potassium
52.2
Seleni um
<0.03
Silver
<0.6
Sodium
384
Thai 1ium
<20
Tin
35.6
Vanadium
1.26
Zi nc
2,510
TABLE 13. ANALYSIS OF JOHN DEEP.E F006 TCLP EXTRACT FOR METALS
(mg/1iter)
Metal
Regulatory limit
Results
Arsenic
5.0
0.004
Barium
100.0
<0.002
Cadmium
1.0
<0.003
Chromium
5.0
<0.02
Lead
5.0
<0.083
Mercury
0.2
<0.0003
Selenium
1.0
<0.003
Si 1ver
5.0
<0.006
57
-------
F0Q9 Wastewater—Master Lock Company
On March 16, 1989, PEI collected an alkaline chlorinated effluent (F009)
sample at the Master Lock Company, Milwaukee, Wisconsin. Three 30-qal poly-
ethylene drums were filled with this wastewater for testing purposes. IT
Analytical Services in Pittsburgh, Pennsylvania, performed all of the chemi-
cal analyses. Table 14 presents the analytical data for the F009 wastewater.
The total cyanide level in the wastewater was 20 mg/L. The wastewater con-
tained elevated concentrations of cadmium and copper. Matrix spike analyses
yielded good recoveries (>20%) for all metals except copper, iron, and sil-
ver. For copper and iron, the sample concentrations were greater than four
times the spike concentration, resulting in 0% recovery. With the matrix
spike analysis of silver, the spike was either diluted out or diluted to a
concentration near the detection limit.
Ford Electronics and Refrigeration Corporation—
On May 11, 1989, PEI collected a raw F019 filter cake sample at Ford
Electronics and Refrigeration Corporation, Connersville, Indiana. PEI's
laboratory in Cincinnati, Ohio, performed all of the chemical analyses.
Table 15 presents the analytical data for the F019 filter cake. The total
cyanide level of the waste filter cake was 2470 ug/g. The waste also con-
tained an elevated concentration of nonpurgeable organics (19,400 ug/g) and
fluoride (1980 ug/g). Metal analyses of the sample revealed elevated concen-
trations of chromium (10,700 ug/g) and silicon (2970 ug/g)- Matrix spike and
spike duplicate (MS/MSD) analyses yielded good recoveries (>20%) for all the
metals except chromium (VI) and copper. Cyanide recoveries were also less
than 20 percent. Table 16 presents the results of TCLP leachate analyses for
the F019 waste. Elevated TCLP leachate levels were detected for total chro-
mium (116 mg/L). The TCLP levels were above the 20 percent OSV'FP OA objec-
tives for all the constituents analyzed except cyanide, for which two sepa-
rate analyses yielded zero recoveries.
BENCH-SCALE TESTING
This section presents results obtained from the autoclave oxidation
testing of F006, F007, and F019 wastes. (See Subsection 3.2 for details on
Zimpro's autoclave unit.)
Amerock
The Amerock F007 waste received by Zimpro/Passavant for wet-air-oxida-
tion testing had a chemical oxygen demand (COD) of approximately 33 g/L and
contained 15.85 g/L suspended solids, which were black. The raw waste con-
tained a total cyanide concentration of 23,667 ppm and an amenable cyanide
concentration of 21,750 ppm. An initial autoclave oxygen demand (A0D) of 96
g/L was determined for the waste, and a dilution of 1:1 was needed for test-
ing. Table 17 presents analyses of the autoclave off-gases. Tables 18 and
19 show the analytical results of the dilute raw waste and the filtrate and
solids from each autoclave oxidation condition.
58
-------
TABLE 14. SUMMARY OF MASTER LOCK F009 ANALYSES
Concentration, Analytical spike Matrix spike
Parameter mg/L recovery, % recovery, %
Antimony
Arsenic
NDO. 5/NDO . 5
0.007/0.007
109
75
139/150
69/71C
Barium
Beryl 1ium
NDO.05/ND0.05
NDO.05/NDO.05
100
99
97 I
178/176
Cadmium
Chromium
85/82
0.2/0.2
103
103
0/0d
100
Copper
1 ron
71/62
12/8
103
102
0/°J
o/c°
Lead
Mercury
0.006/0.006
0.0003/0.0003
62
69/67
92
Nickel
Selenium
0.8/0.7
ND0.025/ND0.025
104
88
92
80
Silver
Thai 1ium
NDO.1/NDO.1
ND0.004/ND0.004
97 c
28/24
0/0b
29/30
Vanadium
Zinc
NDO.1/ND0.1
2.0/2.0
99
114
110
100
pH
12.38/12.39 SU
Cyanide,
amenable
2.5/7.9
448/69
Cyanide,
total
20/21
90
Hexavalent
chromium
0.16/0.16
63/64
Settleable
matter
33
(conti nued)
59
-------
TABLE 14 (continued)
Parameter
Concentra£i on.
mg/L
Analytical spike
recovery, %
Matrix spike
recovery, %
Total residue 10,000/10,000
9000/9000
Residue:
filterable
at 180rC
Residue:
nonfilter-
able at 180°C
790/800
Except as otherwise noted.
The matrix spike has either been diluted out or was diluted to a
concentration near the detection limit.
The spike was prepared and analyzed in duplicate to confirm matrix
i nterferences.
The sample concentration is greater than four times the spike concentra-
tion.
60
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TABLE 15. ANALYSIS OF FORD F019 FILTER CAKE
Spike recoveries, %
Ford F0I9 r
Parameter filter cake MS MSDC
Soil pH, SU 8.62
Ammonia-N'
191
79.7
60.5
Cyanide total
2,470
3.2
0.0
Cyanide amenable
d
F1uoride
1,980
92.8
95.2
N'POC
19,400
e
e
POC
7.76
e
e
Moisture, %
79.8
Chi oride
14.9
67.7
90.3
Ni trate-N
81.0
92.8
104.0
Antimony
<3.48
93.6
93.8
Arsenic
9.05
88.0
152.0
Barium
21.3
91.2
96.6
Beryl 1ium
0.09
78.3
80.0
Boron
25.7
84.3
85.5
Cadmium
7.24
76.4
77.9
Chromium, VI
3.76
8.6
9.1
Chromium, total
10,700
139.4
139.1
Copper
1.19
8.2
10.8
Iron
1,481
131.7
132.1
Lead
<2.61
90.6
91.8
Mercury
0.19
86.3
79.1
Nickel
1.65
22.3
20.5
Selenium
<0.08
45.3
49.7
Si 1i con
2,970
129.3
134.2
Silver
<0.30
78.1
79.7
Thai 1ium
<4.08
80.3
83.7
Vanadium
6.69
55.9
52.7
Zinc
31,400
103.3
100.1
a yg/g unless otherwise indicated,
k MS = Matrix spike.
r
MSD = Matrix spike duplicate.
Because of an interference in the sample, cyanide amenable to chlo-
rination could not be determined.
0
Not requested.
61
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TABLE 16. ANALYSIS OF FORD F019 TCLP EXTRACTS
Ford F019 Spike recoveries, %
filter cake, r r—
Parameter mg/L MS MSD
Cyanide, total
0.89
0.0C
0.0C
Antimony
0.070
95.5
93.7
Arsenic
0.11
106.7
118.7
Barium
0.34
93.7
93.9
Beryl 1ium
0.001
77.4
77.4
Cadmi um
0.31
79.4
79.6
Chromium, VI
0.97
99.5
98.3
Chromium, total
116
104.9
105.3
Copper
0,020
93.2
94.7
Iron
1.25
76.9
77.4
Lead
0.052
81.6
82.6
Mercury
0.0012
106.3
107.5
Ni ckel
0.072
78.8
78.1
Selenium
0.002
30.1
26.4
Si 1ver
0.006
80.2
81.2
Thai 1ium
0.082
81.5
86.0
Vanadium
0.050
77.4
77.0
Zinc
1180
107.6
107.4
a MS = Matrix spike,
k MSD = Matrix spike duplicate.
c The cyanide analyses were performed twice with the same lack of
recovery for the spikes.
62
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TABLE 17. AMEROCK F007 WET-AIR-OXIDATION RESULTS
Test runs
Parameter
Dilute waste
1
2
3
Oxidation temperature, °C
-
200
240
280
Time at temperature, min.
-
60
60
60
Oxygen uptake, g/liter
16.685a
7.48
16.
.12
24.
,49
Percent of feed COD
-
44.8
96.
,6
146.
,8
Offgas THC, ppm
-
9
12
9
Offgas CH^, ppm
-
0.5
0.
,7
0.
,3
Suspended solids, a/liter
-
9.5
9.
,0
8.
,8
a COD of dilute wastewater.
A COD reduction of 79 to 86 percent was observed compared with the
dilute waste. Total cyanide was reduced by 99.0 percent at 200°C and 99.5
percent at 280°C. The amenable cyanide concentration in the raw waste was
reported as 9? percent of the total cyanide value. Amenable and total
cyanide were equal in all filtrate samples. Total solids and total ash
decreased with increasing oxidation temperature. Significant ammcnia-nitro-
gen (NH3-N) was produced from cyanide oxidation at 200CC, whereas much lower
NH3-N concentrations were found at higher temperatures. Oxidation of ammo-
nia to nitrogen gas and water apparently occurs at higher temperatures. Mo
significant amount of sulfide was present in the raw waste.
About 65 percent of the solids in each oxidized sample consisted of ash.
Total cyanide analysis of the solids showed 183 yg/g (ppm) total cyanide
associated with the solids from the 200°C oxidation. Of this amount, 78
percent was amenable cyanide (143 yg/g). At 9.5 g/liter solids concentra-
tion, the solids would contribute only 1.7 mg/L total cyanide to the 117
mg/liter value for the filtrate. Total cyanide destruction would remain at
99.0 percent when both filtrate and solids are considered together. The
total cyanide and amenable cyanide contents of the solids from the 240° and
280CC oxidations were below the detection limit of 1.0 yg/g. The solids
essentially contribute nothing to total cyanide values for the oxidized
wastes. Total cyanide destruction remained at 99.3 and 99.5 percent when
both filtrate and solids are considered together.
In general, the concentration of metals in the filtrates (soluble)
decreased with increasing oxidation temperature. The major metal species
identified were copper and zinc. Generally, the total mass of a metal
species accounted for in the filtrate and solids from an oxidation condition
ranged ^rom 30 to 90 percent of the input from the dilute raw waste.
63
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TARLE 18. POLLUTANT ANALYSES OF TREATED AMEROCK F007
Parameter
Raw
waste
Di1ute
waste
200°C
240"C
280°C
Ml trate
Sol ids
Fi1trate
Soli rts
Filtrate
Sol ids
COD, mg/L
33,370
16,685
3,060
-
2,315
-
3,578
-
COD reduction, t
-
-
81.7
-
86.1
-
78.6
-
Cyanide (T), mg/L
23,667
11,834
117
183 ug/g
86
<1.0 ug/g
58
<1.0 ug/g
Cyanide (T), red., %
-
-
99.0
-
99.3
-
99.5
-
Cyanide (A), mg/L
21,750
10,875
114
143 ug/g
86
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TABLE 19. METALS ANALYSES OF TREATED AMFROCK F007
200
°C
200°C
200
°C
Raw waste,
Dilute waste,
Fi1trate,
Sol ids,
Filtrate,
Sol ids,
Filtrate,
Sol ids,
Parameter
mg/L
mg/La
mg/L
ug/g
mg/L
w/9
mg/L
ng/g
Arsenic
<1.2
<1.2
<1.2
<35
<1.2
<35
<1.2
<32
Rarium
3.23
1.62
0.017
104
0.012
83.4
0.003
68.0
Cadmium
<0.04
<0.04
<0.004
<1.15
<0.004
<1.15
<0.004
<1.07
Chromium (T)
7.5
3.75
3.24
30.5
3.33
13.5
3.04
13.3
Chromium (+6)
<0.1
<0.1
0.90
IS
0.66
<3.4
0.18
<3.9
Copper
7663
3832
863
261,440
553
234,600
316 219
,450
Lead
0.81
0.40
2.3
464
1.4
229
0.80
172
Mercury
0.0048
0.0024
0.0095
0.23
0.0106
0.14
0.0106
0.153
Nickel
8.46
4.23
0.38
1,305
0.099
408
0.067
337
Selenium
31.2
15.6
13.0
90
9.2
89
5.5
116
Silver
<0.05
<0.05
<0.05
<1.4
<0.05
<1.4
<0.05
<1.3
Zinc
4180
305
305
75,890
159
79,270
29.8 82
,565
a Concentrations calculated on 1:1 dilution of raw wastewater.
^ IS = Insufficient sample.
-------
Ford
The F019 waste received by Zimpro/Passavant for WAO testing was analyzed
at a COD of 43 g/liter and 5000 mg/kg total cyanide. A dilution of 1:4 waste
to water was determined to be needed for proper testing of the F019 waste
stream. Table 20 presents results of the off-gas analyses for the WAO auto-
clave runs.
TABLE 20. F019 WET-AIR-OXIDATION RESULTS
Sample description
Dilute waste
Products
from oxidation
Oxidation temperature, °C
-
200
240
280
Time at temperature, min.
-
60
60
60
Oxygen uptake, g/L
10.5a
3.28
7.08
9.07
Percent of feed COD
-
31.2
67.4
86.4
Off-gas THC, ppm
-
<5
<5
<5
Off-gas CH^, ppm
-
<1
<1
<1
Suspended solids, g/L
-
39.9
21.6
31.5
Suspended ash, g/L
-
33.1
17.2
28.3
a COD of dilute wastewater.
Analytical results for the dilute raw waste and the filtrate and solids
for each autoclave oxidation condition are presented in Table 21. A 68 to 83
percent COD reduction was observed compared with the dilute waste. Analysis
of the dilute feed yielded only 293 mg/L total cyanide, rather than the
approximately 1250 mg/L total cyanide expected. The reason for this discrep-
ancy is unknown. Basing the data on the 293 mg/L cyanide value, total cya-
nide was reduced by 98 percent at 200°C and 99.9 percent at 280°C. Amenable
cyanide concentration in the raw waste was 82.2 percent of the total cyanide.
Only the solids from the 240°C oxidation contained significant cyanide (3.07
mg/L). Ammonia-nitrogen (NH3-N) produced from cyanide oxidation reached a
maximum of about 760 mg/liter at the 280° oxidation. No significant amount
of sulfide or fluoride was present in the raw waste.
The solids in each sample dried easily and contained approximately 80 to
90 percent ash. Total and amenable cyanide analyses of the solids showed
142 yg/g cyanide associated with the solids from the 240°C oxidation. At
21.6 g/L solids concentration, the solids would contribute only 3.07 mg/L
total cyanide to the 0.058 mg/L value for the filtrate. Total cyanide destruc-
tion remains near 99 percent when both the filtrate and solids are considered
together. The total cyanide and amenable cyanide content of the solids from
the 200° and 280°C oxidations contribute less than 1 mg/L cyanide. Even when
filtrate and solids are considered together, cyanide destruction was 98 to 99
percent for all temperatures investigated. In general, the concentration of
metals in the filtrates (soluble) changed little with increasing
oxidation temperature.
66
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TABLE 21. WET-AIR-OXIDATION RESULTS FOR PEI ASSOCIATES, INC.,
CYANIDE COATING WASTE SLUDGE (F019)
Parameter
Autoclave
feed
Oxidized product
Fi1trate
Cake
Fi1trate
Cake
Filtrate
Cake
Analytical No. 19639
Oxidation tempera-
ture, °C
Time at tempera-
ture, min
COD, g/L 10.5
COD reduction, %
pH, SU 8.54
NH3-N, mg/L 27.7
Total solids, g/L 41.7
except as noted
Total ash, g/L 28.1
except as noted
Cyanide, total, 293.1
mg/L except as noted
Total CN from solids,
mg/L
Total cyanide reduc-
tion, %
Cyanide amenable, 240.9
mg/L except as noted
Amenable CN from
snlids, mg/L
Amenable CN reduc-
tion, %
19770
200
60
1.75
83.3
7.95
527.50
2.78
1.45
5.07
98
98
19773
200
60
73.7
98.8%
83.9%
0.91
0.91
19771
240
60
3.04
68
7.9
668
2.55
1.26
99.9
22.9 uq/g 0.02
>99.9
19774
240
60
160
100%
79.6%
22.9 ug/g 0.058 142 ug/g
3.07
3.07
19772
280
60
2.12
7.8
2.08
1.35
99.9
142 ug/g 0.02
>99.9
19775
280
60
25.3
79
766
100%
89.7%
0.133 18 ug/g
0.57
18 ug/g
0.57
(continued)
-------
TABLE 21 (continued)
Oxidized product
Autoclave
Parameter feed, Filtrate, Cake, Filtrate, Cake, Filtrate, Cake,
mq/L mg/L gg/g mg/L ug/g mg/L yg/g
Sulfides
<1
<1
-
<1
-
<1
-
Fl uoride
38.9
24.7
0.17
30.9
0.15
3R.9
0.23
Arsenic
0.080
0.132
114
0.221
135
<0.005
109
Antimony
<0.005
<0.005
465
<0.005
460
<0.005
469
Barium
2.7
0.21
138
0.35
145
0.77
166
Beryl 1ium
0.007
0.001
0.32
0.001
0.29
<0.01
0.32
Cadmium
2.11
0.013
102
0.007
99
<0.04
104
Chromium(T)
1231
1.92
72,767
1.86
68,590
24
74,072
Copper
0.355
0.053
48.7
0.046
34
0.12
66
Iron
189
0.13
12,000
0.08
11,034
0.08
15,238
Lead
14.7
0.003
816
0.008
586
0.916
584
Mercury
0.0004
0.0011
<0.02
0.0010
<0.02
0.008
0.02
Nickel
0.875
0.007
46
0.011
43
0.21
48
Selenium
0.051
0.250
20
<0.005
<20
<0.005
20
Silver
<0.01
<0.005
<0.5
<0.005
<0.5
<0.05
0.5
Thai 1ium
<0.14
0.010
<5
0.005
<5
0.005
5
Vanadium
0.31
0.006
<0.5
<0.005
<0.5
<0.05
0.5
Zinc
4902
4.6
61,000
4.6
257,000
15.2
279,000
-------
Master Lock
The Master Lock F006 waste for WAO testing contained a COD of 37,000
mg/L and 400 mg/L total cyanide. The COD of the waste required a 1:10 dilu-
tion, so the sludge was spiked with potassium hexacyanoferrate III to raise
the cyanide content back to about 350 mg/liter. Table 22 shows the results
of off-gas testing.
TABLE 22. MASTER LOCK WE~-AIR-0XIDATI0N RESULTS
Sample description
Dilute waste Products
from
oxidation
Oxidation temperature, °C
200
240
280
Time at temperature, min.
60
60
60
Oxygen uptake, g/L
3.7a 0.67
1.55
3.27
Percent of feed COD
18.1
41.9
88.4
Off-gas THC, ppm
<5
<5
<5
Off-gas CH^, ppm
<1
<1
<1
Suspended solids, g/L
14.8
17.9
15.4
Suspended ash, g/L
12.6
15.5
13.5
a COD of dilute wastewater.
Table 23 presents the results of the raw waste and the filtrate and
solids from each autoclave oxidation condition. A COD reduction of 91 to 95
percent w?s observed compared with the dilute waste. Cyanide recovery from
the spiked waste slurry was only 122 mg/L, or about 35 percent. This recovery
was based on the 315 mg/L cyanide added by the spiking compound plus 40 mg/L
cyanide from the diluted sludge itself. Amenable cyanide concentration in
the spiked diluted sludge was 74 mg/L, or 60 percent of the recovered total
cyanide value. Amenable and total cyanide concentrations were equal in all
filtrate and solids samples. Based on the 122 mg/L total cyanide value for
the raw spiked slurry, total cyanide was reduced by 78 percent at ?00°C and
by 99+ percent at 240° and 280CC. Ammonia-nitrogen produced from the cyanide
oxidation reached a maximum of about 300 mg/L for the 240° and 280°C oxida-
tions. No significant amount of sulfide or fluoride was present in the raw
waste.
The solids contained approximately 85 percent ash. Total and amenable
cyanide analysis of the solids showed 102 yg/g total cyanide associated with
the solids from the 200°C oxidation. At 14.8 g/L solids concentration, the
solids would contribute only 1.5 mg/L total cyanide to the 26.3 mg/L value
for the filtrate. Total cyanide destruction, therefore, remains near 78
percent when both the filtrate and solids are considered together. The total
and amenable cyanide content of the solids from the 240° and 280°C oxidations
contribute about 1 mg/liter cyanide, which is approximately equal to the
cyanide concentration in the filtrates obtained. Even when the filtrate and
69
-------
TABLE 23. WET-AIR-OXIDATION RESULTS FOR MASTER LOCK
CYANIDE COATING WASTE SLUDGE (F006)
Parameter
Autoclave
feed
Oxidized product
Filtrate
Cake
Filtrate
Cake
Filtrate
Cake
Analytical No. 1G320 17341
Oxidation tempera- - 200
ture, °C
Time at tempera- - 60
ture, min.
COD, g/L 3.7 0.166
COD reduction, % - 95.5
pH 11 9.9
NH0-N, mg/L - 203.60
Total solids, g/L 17.3 1.92
Total ash, g/L 15.9 1.77
except as noted
Cyanide, total, 122.4 26.3
mg/L except as noted
Total cyanide reduc- - 78
tion, %
Cyanide amenable, 73.9 26.3
mg/L except as noted
Amenable CN reduc- - 64
tion, %
17344
200
60
197
100%
85.37-
102 ug/g
102 ug/g
17342
240
60
0.269
93
9.7
305.1
1.25
1.17
0.82
17345
60
24
100%
86.5%
20 pg/ci
99
0.82 20 pg/g
99
17343
280
GO
0.311
92
10.1
306
1.79
1.79
1.1
99
1.1
98
17346
280
60
29
100%
87.8%
81 ug/g
81 ug/g
(continued)
-------
TABLE 23 (continued)
Autoclave
feed,
mg/L
Oxidized product
Parameter
Filtrate,
mg/L
Cake,
wg/g
Fi1trate,
mg/L
Cake,
U9/9
Filtrate,
mg/L
Cake,
ug/g
Sulfides
<1
<1
-
<1
-
<1
-
FT uoride
3.59
2.12
690
1.8
700
3.5
630
Arseni c
<0.0012
<0.005
<2400
<,.005
<2400
<0.005
2400
Antimony
<0.005
<0.005
72.8
<0.005
84.8
<0.005
81.4
Bari um
0.54
0.17
40
0.17
43
0.19
39
Beryl 1i um
<0.01
0.018
0.28
0.014
<0.2
0.015
<0.2
Cadmium
220.5
0.53
241,000
0.25
254,000
0.27
241,000
Chromium (T)
348.4
44.4
29,000
16.7
31,000
<0.09
32,000
Chromium (+6)
Interfer-
ence
33.8
1980
15.3
830
<0.2
73
T
79,000
Copper
729.1
25.9
78,000
5.4
85,000
5.9
Iron
1177
0.73
9500
0.07
10,100
0.08
9700
Lead
1.12
<0.5
48
<0.5
103
<0.5
127
Mercury
0.0004
0.0021
1.1
0.0051
0.12
0.00411
0.12
Nickel
643.9
2.4
62,000
0.12
63.000
0.33
62,000
Seleni um
<0.0002
0.0038
<4000
0.019
<4000
0.036
<4000
SiIver
<0.05
<0.05
<1
<0.05
<1
<0.05
<1
Thalli um
<0.005
0.040
<14
0.050
<14
0.040
<14
Vanadium
<0.05
<0.05
<1
<0.05
<1
<0.05
<1
Zinc
355.1
0.44
33,000
0.26
35,000
0.29
33,000
-------
solids are considered together, cyanide destruction was 99 and 98 percent,
respectively, at 280°C.
IITRI UV/03 Testing
On March 16, 1989, PEI collected three 30-gallon drums of F009 waste
from the Master Lock Company in Milwaukee, Wisconsin. IITRI received one
drum of the waste and began UV/03 testing on June 6, 1989. The IITRI analysis
of the raw waste showed total cyanide levels of 62.5 ppm. Operational problems
caused delays throughout testing. The 1-L reactor, which housed a 1.9-watt
medium-pressure lamp, was broken after the first experimental run, which
forced the premature use of the 5.0-watt medium-pressure lamp. IITRI did not
have any other 1-L reactors, and procurement of a new reactor would have
taken several weeks. The Work Plan called for four runs with the 1.9-watt
lamp that were not performed. As a result, four additional runs were made
with the 5.0-watt lamp. Table 24 summarizes the UV/0, experiments conducted
by IITRI. A maximum of 65 percent cyanide reduction (62.5 to 22 ppm) was
obtained during testing. Larger spiked quantities of iron cyanides proved to
be even more difficult to treat, with only 10 percent cyanide reduction (1355
to 1170 ppm) after 4 hours of treatment, which could be considered an exces-
sive time period for treatment. After completion of these experiments, IITRI
believed the UV/0^ reactor system may rot have been properly set up (see
Figure 8). The rate of the ozone decomposition is extremely fast at an
elevated temperature of 65°C; therefore, no residual ozone may have been
present when the waste stream reached the separate UV reactor. This could
account for the apparent comparability of the treatment effectiveness between
ozone and UV/ozone test runs. A separate run (Run 15) conducted by IITRI et
a later date introduced the ozone directly into the UV reactor, however, and
gave comparable results.
PILOT-SCALE TESTING RESULTS AND DISCUSSION
Introduction
Two pilot-scale testing sessions (March 1988 and June 1988) were con-
ducted on Amercck F007 electroplating waste. The initial pilot runs in March
showed system fouling problems; therefore, full runs could not be accom-
plished. Lessons learned from this session, however, helped to achieve good
operation during the June runs.
The second testing was conducted on June 6 and 7, 1988, at the pilot
plant facilities of Zimpro/Passavant. The WAG study was performed on the
F007 wastes, which contained total cyanides in excess of 30 g/L (3 percent).
The 24-hour study was conducted in a 5.4-gal pilot unit constructed of
titanium. The ma.ior oxidation operating parameters for this test were:
Reactor temperature
Reactor pressure
Reactor residence time
454°F
1700 psig
54 minutes
72
-------
TABLE 24. SUMMARY OF EXPERIMFNTS - OZOME/UV TREATMENT OF CYANIDE WASTE
Run
Waste
volume,
L
pH
Temper- UV
ature, output, 03,
°C watts wt.%
Gas flow, Time, Sparger
L/min h type
Complex
cyanide as CN~,
oig/L
— Analysis^
Feed Product delay, h
1
6
10.5-11.8
65-40
1.9
3.5
0.5
1
SS
60, 62.5
53
190
2
6
10.6-12
66-38
3.5
3.0
0.5
1
SS
49
190
3
6
10.6
66-63
3.5
3.0
0.5
1
SS
53
170
4
6
10.4
62-66
5.0
3.0
0.5
1
SS
36
145
4a
5
O
t
SS
25
145
5
6
10.8-11.3
22-27
5.0
3-3.1
0.5
1.
,1
SS
49
48
6
6
9-8.5
66-64
5.0
3.0
0.5
0.
,5
SS
44
48
7
6
8
66
5.0
3
0.5-0.2
1,
,1
SS
37
145
8
6
8
66
5.0
0
0
1
SS
63
24
9
6
8
62-68
0
3
0.5
1
SS
22, 27
260
10
6
8
66
5.0
2.5-4
0.5-0.25
1
SS
1355
1170
260
11
7
P.
67-64
0
3.9-3.1
0.5
1
gi
39
0
12
6
10.9
65
0
3.2°
0.5
2
gi
67
24b
13a
5
4
gl
67
24b
13
6
10.5
66
5.0
3.1
0.5
4
gi
1890
1690
24b
15
2
10.5
65-79
5.0
3.0
0.5
2
gi
60
22
0
a SS = stainless steel spargers; gl - glass spargers.
b Preserved by bubbling air, adding ascorbic acid, and adjusting pH to 12.
c Ozone measured 1.6% at outlet.
-------
For details concerning the Zimpro/Passavant wet-air-oxidation treatment
system refer to Section 3.2. Table 25 contains the analyses of the oxidized
1 iquor.
P.esul ts
The cyanide destruction as shown by the contractor's analyses is very
high, 99.991 percent., with a residual cyanide concentration in the oxidized
liquor of 1.57 ppm. A loose, brown, sand-like deposit was found at the
bottom of the reactor, which indicates that these solids were held in suspen-
sion in the reactor during operation. The primary metal components of this
material are zinc, sodium, phosphorus, and copper. A scale deposit was also
found on the reactor walls, the primary metal components of which are copper,
sodium, and phosphorus. Both deposits contain 5 to 10 percent carbonate.
Analysis of the caustic scrubber solution used during the run revealed
it to contain less than 1.0 mg/liter of cyanide. This indicates that the
off-gas cyanide concentration was less than 0.08 ppm. The off-gases were
analyzed for ammonia and total hydrocarbons (THC) and found to contain 0.71
percent ammonia and 15 ppm THC. No specific hydrocarbon compounds could be
detected in the off-gas.
FULL-SCALE TESTING - ELECTROLYTIC OXIDATION
Table 26 presents data obtained during Versar's sampling visit to the
Woodward Governor Company on October 7, 1987. Amenable cyanide levels were
reduced by 48 percent after 1 day treatment and by 91 percent after full
electrolytic treatment. In combination with alkaline chlorination, a reduc-
tion of 99.5 percent in amenable cyanide was achieved. Total cyanide was
reduced by 43 percent after 24 hours of treatment and by 91 percent after
full treatment. Alkaline chlorination further reduced cyanide levels by 97
percent of the original feed. The COD levels were reduced by 73.5 percent
after electrolytic oxidation.
STABILIZATION/SOLIDIFICATION TESTING
This subsection summarizes the results and conclusions obtained from the
bench-scale stabilization/solidification testing of F006, FO11, and F012
wastes. Stabilization/solidification was performed on three F006 wastes
generated by John Deere and Company in Waterloo, Iowa; Amerock Corporation in
Rockford, Illinois; and Master Lock Company in Milwaukee, Wisconsin. The
F011 and F012 wastes were both generated at Woodward Governor Company in
Rockford, Illinois.
F006 Waste
As discussed in Section 5, three binders were used in the stabiliza-
tion/solidification of the F006 wastes: portland cement, lime/fly ash, ard
kiln dust. After allowing the mixture to cure for 28 days, the optimum
binder-to-waste ratio for each binder was selected based on unconfined
compressive strength tests. Selected samples were subjected to the TCLP, and
extracts were analyzed for the parameters listed in Table 27.
74
-------
TABLE 25. RESULTS OF F007 CYANIDE RUN
Parameter
Oxidized sample
pH
9.7
Total solids
185.0 g/L
Total ash, 600°C
-
Suspended solids
0.18 g/L
Suspended ash
-
COD
2.54 g/L
MH3-N
4527 mg/L
CI
147 mo/L
Total P
1.7 g/L
S04-S
0.45 g/L
co?
42.4 g/L
CN, total
1.57 mg/L
no2-n
142 mg/L
N0--N
3484 mg/L
Cu
1.05 g/L
Zn
0.005 g/L
Na
67.8 g/L
Fe
6.0 mg/L
Specific gravity
1.164
75
-------
TABLE 26.
ANALYTICAL RESULTS FOR METALS AND INORGANIC PARAMETERS -
WOODWARD GOVERNOR ELECTROLYTIC OXIDATION
(mg/L)
Parameter
Electrolytic oxidation reactor
Before After 24 h After full
treatment of treatment treatment
Alkaline chlo-
rination reactor
after treatment
Antimony
Arsenic
Barium
Beryl 1ium
Cadmium
Chromium
(hexavalent)
Chromium
(total)
Copper
Lead
Mercury
Nickel
Selenium
Silver
Thai 1ium
Vanadium
Zinc
Cyanide
(amenable)
Cyanide (total)
Total solids
Total suspended
sol ids
Chemical oxygen
demand
Total organic
carbon
Oil and grease
(continued)
0.029
1.23
1.0
0.0012
0.01
0.01
5.42
1.03
1.1
0.00025
2.88
0.123
0.0072
0.123
0.156
0.338
5,350b
5,350
197,000
38,400
7,140
19,500
11.0
2800
3030
0.283
1.4
2.37
0.0014
0.057
0.01
57.8
0.469
3.61
0.028
2.62
0.28
0.0028
0.56
0.784
1.27
473
484
304,000
1,890
24,600
15.1
0.021
0.188
0.495
0.0072
0.004
23.4
16.7
0.225
0.672
0.00027
8.06
0.05
0.002
0.10
0.805
0.187
26
153
83,500
25,500
76
-------
TABLE 26 (continued)
Electrolytic oxidation reactor
After 24 h Alkaline chlo-
Before of treatment After rination reactor
Parameter treatement treatment after treatment after treatment
Carbonate
87,000
-
-
Chloride
21,300
-
-
F1uoride
5.55
-
-
Iron
27.8
168
122
Potassium
18,500
25,900
4,320
Sodium
32,200
37,800
10,300
Sulfate
90.5
-
-
Sulfide
1.0
-
-
a - = Not analyzed.
k Result may be high because of analytical interference.
77
-------
TABLE 27. LIST OF TCLP ANALYTES BY WASTE CODE
F006 Woodward Governor
Analyte
Deere
Amerock
Master
Lock
F011
F012
Cyanide (T)
X
X
Cyanide (A)
X
X
A1uminum
X
X
X
X
X
X
Antimony
X
X
X
X
X
X
Arsenic
X
X
X
X
X
X
Barium
X
X
X
X
X
X
Beryl 1ium
X
X
X
X
X
X
Cadmium
X
X
X
X
X
X
Calcium
X
X
X
X
X
X
Chromium (T)
X
X
X
X
X
X
Chromium (+6)
X
X
X
X
X
X
Cobalt
X
X
X
X
X
X
Copper
X
X
X
X
X
X
I ror,
X
X
X
X
X
X
Lead
X
X
X
X
X
X
Magnesium
X
X
X
X
X
X
Manganese
X
X
X
X
X
X
Mercury
X
X
X
X
X
X
Molybdenum
X
X
X
X.
X
X
Nickel
X
X
X
X
X
X
Selenium
X
X
X
X
X
X
Silver
X
X
X
X
X
X
Sodium
X
X
X
X
X
X
Thallium
X
X
X
X
X
X
Tim
X
X
X
X
X
X
Vanadium
X
X
X
X
y
X
Zinc
X
X
X
X
X
X
78
-------
Analytical results for the Deere and Company TCLP extracts showed low
residual concentrations of cadmium, hexavalent chromium, and nickel, which
are the metals used as the basis for listing F006. Complexed cyanide is
another hazardous constituent for which F006 is listed; however, John Deere
and Company does not use cyanide in their processes; therefore, cyanide is
not expected in their F006 waste. Many of the other metals listed in Table
?7 also were present in very low concentrations. Calcium and sodium were the
only metals found in high concentrations; however, this was attributed to the
binders. The only notable difference in the effectiveness of the binders was
that the zinc concentrations were much higher in the kiln dust extracts than
in the cement or lime/fly ash extracts. Zinc concentrations in the cement
and lime/fly ash extracts were nondetectable (less than 0.02 mg/L) to 0.83
mg/L, whereas the concentrations in the kiln dust extracts ranged from 2.6 to
3.2 mg/L.
The analytical results obtained from the Amerock TCLP extracts are
listed in Tables 28 through 35. Amerock stabilization/solidification TCLP
data showed low concentrations of metals in the extracts for all three
binders. Cadmium, which is not used at the plant, was nondetectable at 0.003
mg/L in all TCLP extracts, hexavalent chromium ranged from 0.04 to 0.23 mg/L,
and nickel was nondetectable (0.025 and 0.042 mg/L) in all TCLP extracts.
The cement binder was noted to be more effective in containing copper and
zinc. Average TCLP extract concentrations of copper and zinc with the cement
binder were 0.83 and 0.20 mg/L, respectively; the lime/fly ash binder ex-
tracts showed an average of 7.36 mg/L copper and 2.63 mg/L zinc, and the kiln
dust binder extracts showed an average of 5.89 mg/L copper and 3.13 mg/L
zinc.
Total cyanide was nondetectable at 0.02 mg/L in the lime/fly ash and
kiln dust extracts; however, it was detected at an average concentration of
0.39 mg/liter in the cement binder extracts.
The TCLP extracts of the Master Lock stabilized/solidified F006 waste
did not demonstrate the same level of effectiveness (in terms of extract
quality) as did the John Deere and Amerock wastes. Table 36 shows the
analytical results obtained from the Master Lock TCLP leachates. With the
kiln dust binder, extracts contained 42.2 to 77.5 mg/L cadmium, 0.054 to
0.078 mg/L hexavalent chromium, 4.63 to 11.3 mg/L nickel, and 106 to 112 mg/L
magnesium. The cement and lime/fly ash binders were much more effective than
the kiln dust binder. The cement binder extracts showed 0.26 to 0.28 mg/L
cadmium, 0.023 to 0.074 mg/L hexavalent chromium, nickel at below detectable
limits (0.031 mg/L), and 0.096 to 0.13 mg/L magnesium. The lime/fly ash
binder extracts showed 0.031 to 0.17 mg/L cadmium, 0.30 to 0.37 mg/L
hexavalent chromium, nondetectable (0.031 mg/L^ nickel, and 1.04 to 3.47 ma/L
magnesium.
It can be concluded from these tests that the stabilization/solidifica-
tion process is an effective technology for containing metals in F006 waste;
however, binder selection may have a significant impact on the quality of the
TCLP extract. This was clearly demonstrated earlier in this section with the
John Deere, Amerock, and Master Lock F006 wastes and the portland cement,
79
-------
TABLE 28. ANALYTICAL DATA SUMMARY OF UNTREATED AMEROCK F006 WASTE
PARAMETER
TOTAL UASTE
ANALYSIS
(ug/g) *
A
TCLP LEACHATES (reg/l)
B
C
MEAN *»
STD DEV *"
PEL STD DEV ****
CYANIDE (T) 3
CBl
< 0.02
< 0.02
< 0.02
CYANIDE (A) 33
C81
NA
NA
NA
pH s.u.
CBl
CHLORIDE
CBl
MOISTURE (X)
CBl
OIL & GREASE
CBl
SULFATE
CBl
SULFIDE
CBl
TOC
CBl
ALUMINUM
0.065
0.067
0.08
0.071
0.006649
9.366167
ANTIMONY
CBl
2.09
2.11
2.11
2.1
0.009428
0.448956
ARSENIC
CBl
0.005
0.006
0.006
0.006
0.000471
7.856742
BARIUM
CBl
< 0.002
< 0.002
< 0.002
BERYLLIUM
CBl
< 0.002
< 0.002
< 0.002
CADMIUM
CBl
0.029
0.029
0.029
0.029
CALCIUM
798
812
769
793
17.90716
2.258154
CHROMIUM (t)
C81
0.012
0.012
0.14
0.055
0.060339
109.7086
CHROMIUM (+6)
CBl
< 0.006
0.011
0.013
COBALT
CBl
< 0.023
0.026
< 0.023
COPPER
CBl
138
130
136
135
3.J99346
2.518034
IRON
CBl
< 0.023
< 0.023
< 0.023
LEAD
CBl
< 0.001
< 0.001
< 0.001
MAGNESIUM
302
291
279
291
9.392668
3.227721
MANGANESE
1.88
1.91
1.9
1.9
0.012472
0.656431
MERCURY
CBl
< 0.0003
< 0.0003
< 0.0003
MOLYBDENUM
CBl
0.19
0.19
0.17
0.18
0.009428
5.237828
NICKEL
CBl
26.7
26.8
26.8
26.8
0.047140
0.175897
SELENIUM
CBl
0.91
0.99
0.99
0.96
0.037712
3.928371
SILVER
CBl
< 0.006
< 0.006
< 0.006
SOOIUM
52.3
49.3
49.6
50.4
1.349073
2.676733
THALLIUM
CBl
< 0.004
< 0.004
< 0.004
TIM
< 0.103
< 0.10.5
< 0.10J
VANADIUM
CBl
< 0.008
< 0.008
< 0.008
2 INC
CBl
248
244
239
244
3.681787
1.508929
NA - Mot snalyzBble by Method 9010 - matrix interference
•* • Arithmetic mean of TCLP leachate data
•** - Standard deviation
****
aa -
Relative standard deviation CBl
Total cyanide
Cyanide amenable to alkaline elorination
Confidential business information
-------
TABLE 29. TOTAL WASTE ANALYSIS OF UNTREATED AND TREATED AMEROCK F006 WASTE
PARAMETER
UNTREATED
F006
(ug/gi
TREATED F006 (ug/g)
UET-14-CEM-19
WET-14-KD-0.7
UET-14-LF-44
pH, S.U.
CBI
12.25
12.28
12.31
CHIOSIOE
CBI
<>02
1520
241
MOISTURE (X)
CBI
29.6
36.9
40.1
OIL & GREASE
CBI
1200
1370
750
SULFATE
CBI
725
3510
43
SULFIDE
CBI
44
56
56
TOC
CBI
5690
11600
17400
ANTIMONY
CBI
<
5.61
65.8
72.1
ARSENIC
CBI
23
9.25
16.8
BARIUM
CBI
86.3
51
115
BERYLLIUM
CBI
<
0.10
0.49
1.34
CADMIUM
CBI
0.66
1.41
0.9
CHROMIUM (T)
CBI
213
336
349
CHROMIUM (+6)
CBI
0.62
<
0.60
<
0.60
COBALT
CBI
3.94
2.56
4.9
COPPER
CBI
3130
6470
6620
LEAD
CBI
6.2
14.6
9.35
MERCURY
CBI
0.3
<
0.14
<
0.14
MOLYBDENUM
CBI
<
4.42
<
4.42
5.48
NICKEL
CBI
325
567
591
SELENIUM
CBI
24.1
59.5
32.8
SILVER
CBI
<
0.27
<
0.27
<
0.27
THALLIUM
CBI
<
0.21
<
0.21
<
0.21
VANADIUM
CBI
29.2
12
29.1
ZINC
CBI
3600
6120
6240
CBI - Confidential business information
81
-------
TABLE 30. TCLP ANALYSIS RESULTS OF 28-DAY AMEROCK F006/CEMENT BINDER TEST SAMPLES
I I
| TCLP LEACHATES |
I !
PARAMETER I a 9 C I MEAN STD DEV DEL STD OEV
CYAN IDE (T)
0.4B
0.37
0.3?
0.39
0.066833
17.13669
CYANIDE (A)
0.34
0.??
0.18
0.25
0.067986
27.1947/
ALUMINUM
0.04
0.014
<
0.023
ANTIMONY
0.094
< 0.076
<
0.076
ARSENIC
0.002
0.002
0.003
0.002
0.000471
23.57022
BARIUM
0.85
0.92
0.97
0.91
0.049216
5.408360
BERYLLIUM
< 0.001
< 0.001
<
0.001
CADMIUM
< 0.003
< 0.003
<
0.003
CALCIUM
2510
2560
2600
2557
36.81787
1.439885
CHROMIUM (T)
0.21
0.2
0.18
0.2
0.012472
6.236095
CHROMIUM (+6)
0.16
0.17
0.23
0.19
0.030912
16.26950
COBALT
< 0.010
< 0.010
<
0.010
COPPER
0.89
0.81
0.8
0.83
0.040276
4.852628
1 ROM
0.65
0.053
0.047
0.25
0.282853
113.1413
LEAD
0.004
0.006
0.007
0.006
0.001247
20.78698
MAGNESIUM
0.069
0.049
0.053
0.057
0.008640
15.15962
MANGANESE
< 0.001
< 0.001
<
0.001
MERCURY
< 0.0012
< 0.0006
<
0.0003
MOLYBDENUM
0.062
0.104
0.081
0.082
0.017172
20.94186
NICKEL
< 0.025
< 0.025
<
0.025
SELENIUM
0.012
0.0H
0.012
0.013
0.000942
7.252377
SILVER
< 0.004
< 0.004
<
0.004
SOOIUM
31.6
28.7
28.9
29.7
1.322455
4.452712
THALLIUM
< 0.004
< 0.004
<
0.004
TIN
< 0.105
<0.105
<
0.105
VANADIUM
< 0.007
< 0.007
<
0.007
ZINC
0.17
0.19
0.?5
0.2
0.033993
16.99673
-------
TABLE 31. TCLP ANALYTICAL RESULTS OF 28-DAY AMEROCK F006/L1ME/FLY ASH BINDER TEST SAMPLES
TCLP LEACHATES
PARAMETER
B
c
"CAN
STD OFV
REL STD CEV
CYANIDE
-------
TABLE 32. TCLP ANALYTICAL RESULTS OF 28-DAY AMF.ROCK F006/KILN DUST BINDER TEST SAMPLES
I TCLP LEACHATES
PARAMETER
I * «
B
C
j MEAN
ST0 DEV
REL STD 1
CYANIDE (T)
I
| < 0.04
< 0.04
< 0.04
1
1
CYANI0E (A)
| < 0.04
< 0.04
< 0.04
I
ALUMINUM
j < 0.022
< 0.022
< 0.022
1
ANTIMONY
j < 0.062
< 0.062
•c 0.062
I
ARSENIC
j < 0.002
0.002
0.002
1
BARIUM
| 0.39
0.4
0.48
I 0.42
0.04 0276
9.589719
BERYLLIUM
| < 0.002
< 0.002
< 0.002
1
-
CADMIUM
| < 0.003
< 0.003
< 0.003
1
CALCIUM
| 2771
2960
3040
| 2993
112.7839
3.76825B
CHROMIUM (t)
| 0.11
0.11
0.12
j 0.12
0.004714
3.928371
CHROMIUM (+6)
| 0.114
0.084
0.077
j 0.09
0.016048
17.83170
COBALT
j < 0.014
< 0.014
< 0.014
I
COPPER
| 5.67
5.99
5.57
| 5.89
0.179133
3.041319
IRON
| < 0.015
< 0.015
< 0.015
I
LEAD
j 0.03
0.03
0.033
| 0.03
0.001414
4.714045
MAGNESIUM
j 0.005
< 0.002
< 0.002
I
MANGANESE
j < 0.002
< 0.002
•c 0.002
I
MERCURY
j < 0.0003
0.0003
< 0.0003
I
MOLYBDENUM
j 0.12
0.13
0.13
| 0.13
NICKEL
j < 0.025
< 0.025
< 0.025
I
SELENIUM
| 0.058
0.067
0.054
| 0.06
0.005436
9.060836
SILVER
1 < 0.009
< 0.009
< 0.009
I
SODIUM
1 «
43.7
42.5
| 44.8
1.020892
2.276778
THALLIUM
| < 0.004
< 0.004
< 0.004
I
TIN
j < 0.37
< 0.37
< 0.37
I
VANADIUM
j < 0.014
< 0.014
< 0.014
I
2 INC
1 3.06
2.99
3.1
I 3.13
0.045460
1 .452415
* During the TCLP, the kiln dust 'A' sample was extracted at a ratio of 1:18.6 (190g of waste to 3530 ml
of extraction fluid # 2) rather than 1 : 20 (190g of waste to 3800 ml of fluid); therefore, analytical data for sample A" uas mathematically
corrected by multiplying the laboratory reported value by 0.93 to obtain the value representative of 1:20 dilution.
Detected values shown in this table for sairple A' have all been corrected.
-------
TABLE 33. WET ANALYTICAL RESULTS OF 28-DAY AMEROCK F006/CEMENT BTNDER TEST SAMPLES
I UET LEACHATES
PARAMETER
*
B
c
MEAN
STO DFV
REl STD DEV
ANTIMONY
1.?
2
1.9
1.7
0.355902
20.93544
ARSENIC
0.08
0.071
0.073
0.075
0.003858
5.144816
BARIUM
2.2
5.2
3.6
3.7
1.225651
33.12572
BERYLLIUM
< 0.05
< 0.05
< 0.05
CADMIUM
0.15
0.24
0.23
0.21
0.040276
19.17943
CHROMIUM (T)
3.2
4.3
4.2
3.9
0.496655
12.73475
CHROMIUM (+6)
0.07
0.07
0.07
0.07
COBALT
O.J
0.5
0.5
0.4
0.094280
23.57022
COPPER
170
250
260
227
40.27681
17.74309
LEAD
0.029
0.055
0.03
0.038
0.012027
31.65196
MERCURY
< 0.0002
< 0.0002
< 0.0002
MOLYBDENUM
0.5
0.8
0.8
0.7
0.141421
20.20305
NICKEL
4
5.9
5.7
5.2
0.852447
16.39322
SELENIUM
< 0.025
< 0.025
< 0.025
SILVER
0.2
0.3
0.3
0.3
0.047140
15.71348
THALLIUM
< 0.004
< 0.004
< 0.004
VANADIUM
1.4
1.8
1.9
1.7
0.216024
12.70733
ZINC
42
54
54
50
5.656854
11.31370
-------
TABLE 34. WET ANALYTICAL RESULTS OF 28-DAY AMEROCK F006/LIME/FLY ASH BINDER TEST SAMPLES
UE( IEACHATES
PARAMETER
*
B
C
MEAN
S7D CEV
REL STO DEV
ANTIMONY
2.5
3.1
3.1
2.9
0.282842
9.753196
ARSENIC
0.1
0.19
0.18
0.16
0.040276
25.17301
BARIUM
0.65
0.91
1.4
0.98
0.318224
32.47186
8ERYIL1UH
< 0.05
< 0.05
< 0.05
CADMIUM
0.07
0.08
0.07
0.07
0.004714
6.734350
CHROMIUM (T)
3.9
4.6
4.5
4.3
0.309120
7.188851
CHROMIUM (+6)
0.04
0.04
0.04
0.04
COBALT
0.1
0.1
< 0.1
COPPER
uo
550
600
530
66.83312
12.61002
LEAD
0.027
0.036
O.OJ2
0.032
0.003681
11.50558
MERCURY
< 0.0008
o.oooa
0.0008
MOLYBDENUM
1
1.2
1.3
1.2
0.124721
10.39349
NICKEL
13
12
12
12
0.471404
3.928371
SELENIUM
2.6
3.1
3.3
3
0.294392
9.613067
SILVER
0.2
0.2
0.2
0.2
THALLIUM
< 0.004
< 0.004
< 0.004
VANADIUM
0.4
0.4
0.4
0.4
ZINC
42
62
70
58
11.77568
20.30289
-------
TABLE 35. WET ANALYTICAL RESULTS OF 28-DAY AMEROCK F006/KILN DUST BINDER TEST SAMPLES
PARAMETER
A
B
C
WAN
STO DEV
REL STD DEV
ANTIMONY
3.4
1.4
1.6
?.1
0.899382
42.82773
ARSENIC
0.038
0.045
0.046
0.043
0.003559
8.276804
BARIUM
2.3
0.33
0.4
1.01
0.912615
90.35794
BERYLLIUM
< 0.05
< 0.05
< 0.05
CADMIUM
0.15
0.06
0.07
0.09
0.0402 76
44.75202
CHROMIUM (T)
7.5
3.2
4
4.9
1.867261
38.10738
CHROMIUM (*6)
0.15
0.14
0.14
0.14
0.004714
3.367175
COBALT
0.2
< 0.1
0.1
COPPER
720
290
380
463
185.1725
39.99408
LEAD
0.22
0.26
0.16
0.21
0.041096
19.56956
MERCURY
< 0.0008
< 0.0008
< 0.0008
MOLYBDENUM
1.2
0.5
0.6
0.77
0.309120
40.14553
NICKEL
17
7.2
8.4
10.9
4.364 503
40.04131
SELENIUM
2.3
3.1
3.4
2.9
0.464 2 79
16.00964
SILVER
0.3
0.1
0.2
0.2
0.081649
40.82482
THALLIUM
< 0.02
< 0.004
< 0.004
VANADIUM
0.5
0.2
0.3
0.3
0.124721
41 .5739 7
ZINC
75
100
94
90
10.65624
11.84027
-------
TABLE 36. ANALYTICAL RESULTS OF MASTER LOCK F006 TCLP LEACHATES
Raw FQ06 (riq/1)
TCLP- TCLP- TCLP-
F006(2)- F006(2)- F006(2)
Parameter RAW-A RAW-B RAW-C
Aluminum
0.057
0.096
0.088
Antimony
0.079
<0.070
<0.070
Arseni c
0.003
0.002
0.002
Barium
0.42
0.41
0.34
Beryl 1ium
<0.002
<0.002
<0.002
Cadmium
1304
1340
1250
Calci um
654
708
733
Chromium, VI
<0.006
0.007
0.011
Chromium, total
0.74
0.65
0.59
Cobalt
<0.017
0.020
<0.017
Copper
16.0
15.8
14.2
Iron
<0.013
<0.013
0.021
Lead
<0.001
<0.001
<0.001
Magnesi um
172
176
172
Manganese
4.58
4.62
4.53
Mercury
0.0006
0.0006
<0.0006
Molybdenum
<0.044
<0.044
<0.044
Nickel
257
261
248
Selenium
<0.00?
<0.002
<0.002
Si 1ver
<0.006
<0.006
<0.006
Sodium
85.6
124
89.1
Thai 1 i urr
<0.003
<0.003
<0.003
Tin
0.17
0.21
0.17
Vanadium
<0.012
<0.012
<0.012
Zinc
93.0
90.5
81.7
a "(2)" refers to the second F006 waste stabilized at WES under Work
Assignment Nos. 1-9 and 2-9. Under Contract No. 68-03-3389 this was
the third F006 waste stabilized at WES.
88
-------
TABLE 36 (continued)
F006 treated with kiln dust (mq/1)
TCLP- TCLP- TCLP-
F006 ( ?.)- F006 (2)- F006(2)-
Parameter KD-l-A KD-l-B KD-I-C
Aluminum
0.055
0.061
0.053
Antimony
<0.070
<0.070
0.091
Arsenic
0.002
0.002
<0.002
Barium
0.29
0.31
0.27
Beryl!iurn
<0.002
<0.002
<0.002
Cadmi um
42.2
72.9
77.5
Calcium
1640
1580
1605
Chromium, VI
0.078
0.054
0.059
Chromium, total
0.079
0.065
0.069
Cobalt
0.02?
<0.017
<0.017
Copper
0.40
0.5?
0.54
Iron
<0.013
0.034
<0.013
Lead
<0.001
<0.001
<0.001
Magnesium
106
131
112
Manganese
0.64
1.06
1.15
Mercury
0.0008
0.0007
<0.0006
Molybdenum
<0.044
<0.044
<0.044
Nickel
4.63
10.4
11.3
Selenium
0.002
0.002
<0.002
Si 1ver
<0.006
<0.006
<0.006
Sodium
154
131
137
Thai 1ium
<0.003
<0.003
<0.003
Tin
<0.062
<0.062
<0.062
Vanadium
<0.012
<0.012
<0.012
Zinc
0.80
1.46
1.65
89
-------
TABLE 36 (continued)
F006 treated with cement (mq/1)
TCLP- TCLP- TCLP-
F006(2)- F006(2)- F006(2 )-
Parameter CEM-3-A CEM-3-B CEM-3-C
A1umi num
0.39
0.36
0.49
Antimony
<0.070
<0.070
0.071
Arseni c
0.002
<0.00?
0.00?
Barium
0.37
0.40
0.34
Beryl 1ium
<0.002
<0.002
:0.002
Cadmi um
0.28
0.29
0.26
Calci um
1740
1740
1810
Chromium, VI
0.037
0.074
0.023
Chromium, total
0.43
0.43
0.47
Cobalt
<0.017
<0.017
<0.017
Copper
0.25
0.26
P.27
Iron
0.98
0.80
1.32
Lead
<0.001
<0.001
<0.001
Magnesium
0.13
0.096
0.10
Manganese
<0.002
<0.002
<0.002
Mercury
<0.0006
0.0006
0.0011
Molybdenum
<0.044
<0.044
<0.044
Nickel
<0.031
<0.031
<0.031
Selenium
0.002
0.002
<0.002
Si 1ver
<0.006
0.019
<0.006
Sodi um
100
99.8
104
Thai!i um
<0.003
<0.003
<0.003
Ti n
0.13
0.17
0.064
Vanadium
<0.012
<0.012
<0.012
Zinc
0.067
0.13
0.081
90
-------
TABLE 36 (continued)
F0Q6 treated with 1ime/flvash (mq/1)
TCLP- TCLP- TCLP-
F006(2)- F006(2)- F006(2)-
Paraneter LF-ll-A LF-ll-B LF-ll-C
Aluminum
<0.024
<0.024
<0.024
Antimony
<0.070
<0.070
<0.070
Arseni c
<0.002
<0.002
<0.002
Barium
0.36
0.33
0.28
Beryl 1ium
<0.002
<0.002
<0.002
Cadmium
0.17
0.031
0.051
Calcium
1590
1590
1550
Chromium, VI
0.35
0.37
0.30
Chromium, total
0.29
0.28
0.28
Cobalt
<0.017
<0.017
<0.017
Copper
0.23
0.22
0.19
Iron
0.17
0.12
0.13
Lead
<0.001
<0.001
<0.001
Magnesium
1.43
1.04
3.47
Manganese
<0.002
<0.002
<0.002
Mercury
<0.0012
<0.0012
<0.0012
Molybdenum
<0.044
<0.044
<0.044
Nickel
<0.031
<0.031
<0.031
Seleni um
<0.002
<0.002
<0.002
Si 1ver
<0.006
<0.006
<0.006
Sodium
146
159
139
Thai 1i um
<0.003
<0.003
<0.003
Ti n
<0.062
<0.062
<0.062
Vanadium
<0.012
<0.012
<0.012
Zinc
0.11
0.082
0.073
91
-------
lime/fly ash, and kiln dust binders. Portend cement was found to be effec-
tive in containing all metals in the wastes and producing a relatively clean
extract. Lime/fly ash was very effective on the John Deere Waste F006 waste;
however, concentrations of zinc and copper 1n the Amerock extracts and magne-
sium in the Master Lock extracts were somewhat elevated. The kiln dust
binder was not as effective as the cement and lime/fly ash binders. With the
John Deere F006, the kiln dust failed to bind the zinc effectively; with the
Amerock F006, both zinc and copper appeared in the TCLP extracts at elevated
concentrations; and with the Master Lock F006, cadmium was detected in high
concentrations.
Stabilization/solidification was shown to be an effective technology for
containing cyanide in the Amerock F006 waste when bound in lime/fly ash.
F011 Waste
The basis for listing F011 is cyanide (salts). No metals were identi-
fied as a basis for listing. The analytical results obtained from the F011
TCLP extracts are presented in Tables 37 through 44. On a total waste
analysis basis, the F011 waste collected at Woodward Governor contained 17.?,
4.23, 81.6, 4.76, 535, 5.79, and 31.6 yg/g total chromium, cobalt, copper,
lead, nickel, vanadium, and zinc, respectively. Untreated F011 average TCLP
concentrations were reported to be 0.37, 37.6, and 2.45 mg/L barium,
magnesium, and nickel, respectively. Others were at low or nondetectable
concentrations.
Cement-treated F011 TCLP extracts showed average concentrations of 0.3,
45.8, and ?..66 mg/L barium, magnesium, and nickel, respectively. Lime/fly
ash extracts had average TCLP concentrations of 0.29, 34.5, and 2.06 mg/L
barium, magnesium, and nickel, respectively. Kiln dust extracts had average
TCLP concentrations of 0.2, 37.1, and 3.21 mg/L barium, magnesium, and
nickel, respectively. As these data indicate, little if any reduction in
pollutant concentrations was evident in the treated versus the untreated
F011. Because of the contributions of the binder constituents, some of the
treated samples actually showed higher concentrations than did the untreated
samples.
Total cyanide concentrations in the treated F011 TCLP leachates averaged
1.8 mg/L with the cement binder, 0.49 mg/L with the lime/fly ash binder, and
from nondetectable (0.05 mg/L) to 0.17 mg/L with the kiln dust binder.
A comparison of the TCLP data for the untreated F011 extracts with the
data for treated F011 extracts indicates that stabilization/solidification is
not an effective technology for F011 waste.
F012 Waste
The basis for listing F012 is cyanide (complexed). No metals were
identified as a basis for listing. The analytical results obtained from the
F012 TCLP extracts are presented in Tables 45 through 52. The F01? waste
9?
-------
TABLE 37. ANALYTICAL DATA SUMMARY OF UNTREATED FOll WASTE
PARAMETER
TOTAL WASTE
ANALYSIS
Cug/g) *
A
TCLP LEACHATES (mg/l)
B
c
MEAN **
STD DEV ***
REL STD DEV ****
pH, s.u.
12.42
CHLORIDE
639
MOISTURE , (%)
30.1
OIL & GREASE
5
SULFATE
16800
SULFIDE
32
TOC
239
ALUMINUM
0.094
0.085
0.072
0.084
0.009030
10.75096
ANTIMONY
< 22.6
< 0.076
0.079
<
0.076
ARSENIC
1.95
0.002
< 0.002
<
0.002
BARIUM
19.8
0.36
0.39
0.35
0.37
0.016996
4.593711
BERYLLIUM
< 0.27
< 0.001
< 0.001
<
0.001
CADMIUM
< 0.81
0.009
0.008
0.008
0.008
0.000471
5.892556
CALCIUM
2320
2360
2310
2330
21.60246
0.927144
CHROMIUM (T)
17.2
0.23
0.14
0.081
0.15
0.061266
40.84417
CHROMIUM (+6)
0.12
0.16
0.17
0.12
0.15
0.021602
14.40164
COBALT
4.23
< 0.010
< 0.010
<
0.010
COPPER
81.6
0.05
0.053
0.045
0.049
0.003299
6.734350
1 RON
0.68
0.2
0.054
0.31
0.267413
86.26256
LEAD
4.76
< 0.001
< 0.001
<
0.001
MAGNESIUM
37.7
40.5
34.7
37.63
2.368309
6.293673
MANGANESE
0.55
0.58
0.57
0.57
0.012472
2.188103
MERCURY
< 0.14
< 0.0006
< 0.0003
<
0.0003
MOLYBDENUM
< 11.1
< 0.037
< 0.037
<
0.037
NICKEL
535
2.41
2.56
2.37
2.45
0.081785
3.338188
SELENIUM
< O.Ofi
0.002
0.003
<
0.002
SILVER
< 1.20
< 0.004
< 0.004
<
0.004
SODIUM
82.4
80.9
74.2
79.2
3.564952
4.501203
THALLIUM
< 0.21
< 0.004
< 0.004
<
0.004
TIN
< 0.11
< 0.11
<
0.11
VANADIUM
5.79
< 0.007
< 0.007
<
0.007
ZINC
31.6
0.26
0.25
0.27
0.26
0.008164
3.140371
NA - Not analy/able by Method 9010 • matrix interference »*»• . Relative standard deviation,
* - Except as otherwise noted *** - Standard deviation
** - Arithmetic mean of TCLP leachate data
-------
TABLE 38. TOTAL WASTE ANALYSIS OF UNTREATED AND TREATED FOll WASTE
PARAMETER
UNTREATED
F011
(ug/g> *
TREATED
F011 (ug/g) *
WET -12-CEM-1
WET-12-CEM-4
WE T -12 - KD -1
WET-12-KD-4
WET-12-LF-11
WET-12-LF-33
pH, S.u.
12.42
12.5
12.62
12.71
12.58
12.58
12.63
CHLORIDE
639
449
160
760
780
472
381
MOISTURE X
30.1
29.9
20.4
30.5
22.1
28.5
21.8
Oil & GREASE
5
5
<
5.0
254
5
243
10
SULFATE
16800
14900
14200
13900
13400
14000
13000
SULFIDE
32
22
20
32
32
22
20
TOC
239
Q51
1720
401
4390
3060
5780
ANTIMONY
< 22.6
< 22.6
<
22.6
<
22.6
<
22.6
<
22.6
<
22.6
ARSENIC
1.95
2.6
6.75
3.05
5.55
8.1
15.8
BARIUM
19.8
30.6
56
26
55.1
44
99.4
BERYLLIUM
< 0.27
< 0.27
<
0.27
<
0.27
0.68
0.51
1.35
CADMIUM
< 0.81
0.81
<
0.81
<
0.81
<
0.81
1.38
<
0.81
CHROMIUM <+6)
0.12
0.23
2.32
<
0.06
<
0.06
0.23
<
0.06
CHROMIUM (T)
17.2
20.7
29.9
18.6
17
18.8
19.6
COBALT
4.23
< 3.06
5.76
<
3.06
7.14
<
3.06
6.57
COPPER
81.6
75.1
64.7
72.2
72.4
69.6
67
LEAD
4.76
3.71
4.41
4.88
6.98
4.91
4.82
MERCURY
< 0.14
< 0.14
<
0.14
<
0.14
<
0.14
<
0.14
<
0.14
MOLYBDENUM
< 11.1
< 11.1
<
11.1
<
11.1
<
11.1
<
11.1
<
11.1
NICKEL
535
443
359
447
405
383
366
SELENIUM
< 0.08
< 0.08
<
0.08
<
0.08
<
0.08
<
0.08
<
o.oa
SILVER
< 1.20
< 1.20
<
1.20
<
1.20
<
1.20
<
1.20
<
1.20
THALLIUM
< 0.21
< 0.21
<
0.21
0.21
<
0.21
<
0.21
<
0.21
VANADIUM
5.79
10.8
19.2
8.91
16.1
13.9
28.7
ZINC
31.6
38.8
38.5
37.9
33.1
46.4
32.7
* Except as otherwise noted
-------
TABLE 39. TCLP ANALYTICAL RESULTS OF 28-DAY FO11/CEMENT BINDER TEST SAMPLES
PARAHEIER
A
TCLP LEACMATES (mg/l)
B
C
MEAN
STD DEV
REL STD DEV
CYANIDE (T) *
1.08
2.25
2.06
1.8
0.512661
28.48121
CYANIDE (A) **
NA
NA
NA
ALUMINUM
<
0.023
< 0.023
0.023
AN'T 1MONY
<
0.076
< 0.076
< 0.076
ARSENIC
<
0.002
0.002
0.002
BARIUM
0.26
0.31
0.33
0.3
0.029439
9.813067
BERYLLIUM
<
0.001
< 0.001
< 0.001
CADMIUM
<
0.003
< 0.003
< 0.003
CALCIUM
2320
2490
2440
2416.66
71.33644
2.951861
CHROMIUM (*6)
0.45
0.36
0.33
0.38
0.050990
13.41847
CHROMIUM (T)
0.26
0.21
0.21
0.227
0.023570
10.38335
COBALT
<
0.010
< 0.010
< 0.010
COPPER
0.029
0.027
0.022
0.026
0.002943
11.32277
IRON
0.76
0.68
0.72
0.72
0.032659
4.536092
LEAD
<
0.001
< 0.001
< 0.001
MAGNESIUM
46.4
47
44.1
45.8
1.2498S8
2.729015
MANGANESE
0.048
0.049
0.047
0.048
0.000816
1.701034
MERCURY
0.002
0.0024
0.0021
0.0022
0.000169
7.725787
M0LYB0ENIW
<
0.037
< 0.037
< 0.037
NICKEL
2.82
2.66
2.5
2.66
0.130639
4.911257
SELENIUM
<
0.002
< 0.002
< 0.002
SILVER
0.01
0.007
0.006
0.008
0.001699
21.24591
SODIUM
63.2
56.3
57.7
59.1
2.978067
5.039032
THALLIUM
<
0.004
< 0.004
0.007
TIN
0.16
0.18
0.17
0.17
0.008164
4.802921
VANAO IUM
0.022
0.024
0.024
0.023
0.000942
4.099169
ZINC
0.11
0.17
0.14
0.14
0.024494
17.49635
* - Total cyanide
** - Cyanide amenable to alkaline chlorinntion
NA - not analyzable by Method 9010 - matrix interference
-------
TABLE 40. TCLP ANALYTICAL RESULTS OF 28-DAY F011/LIME/FLY ASH BINDER TEST SAMPLES
PARAMETER
TCLP LEACHATES (mg/l)
A
B
c
MEAN
ST0 DEV
REL STD DEV
CYANIDE (T)
0.45
0.19
0.81
0.49
0.254209
51.87939
CYANIDE (A)
*
< 0.05
<
0.05
ALUMINUM
<
0.023
< 0.023
<
0.023
ANT1MONY
<
0.076
< 0.076
<
0.076
ARSENIC
0.004
0.005
0.002
0.004
0.001247
31.18047
BARIUM
0.23
0.24
0.4
0.29
0.077888
26.85821
BERYLLIUM
<
0.001
< 0.001
<
0.001
CADMIUM
<
0.003
< 0.003
<
0.003
CALCIUM
2330
2930
2870
2710
269.8147
9.956263
CHROMIUM (+6)
0.21
0.11
0.09
0.14
0.052493
37.49527
CHROMIUM (T)
0.12
0.098
0.098
0.105
0.010370
9.877047
COBALT
0.013
< 0.010
<
0.010
COPPER
<
0.018
0.029
0.032
IRON
0.38
0.32
0.32
0.34
0.028284
8.318903
LEAD
<
0.001
< 0.001
0.005
MAGNESIUM
32.5
33.5
37.5
34.5
2.160246
6.261585
MANGANESE
0.24
0.26
0.26
0.26
0.009428
3.626188
MERCURY
0.0013
0.0003
0.003
0.0024
0.001114
46.43959
MOLYBDENUM
0.045
0.061
0.061
0.056
0.007542
13.46870
NICKEL
1.68
2.24
2.24
2.06
0.263986
12.81488
SELENIUM
<
0.002
0.002
<
0.002
SILVER
0.004
< 0.004
<
0.004
SOOIUM
52.9
68.2
37.9
53
12.37012
23.33985
THALLIUM
0.004
< 0.002
<
0.002
TIN
0.14
< 0.10
<
0.10
VANADIUM
0.018
0.013
0.013
0.015
0.002357
15.71348
ZINC
0.093
0.17
0.24
0.17
0.060035
35.31480
* interferent in sample
-------
TABLE 41. TCLP ANALYTICAL RESULTS OF 28-DAY FOli/KILN DUST BINDER TEST SAMPLES
TCLP LEACHATES (irg/1)
PARAMETER
A
B
C
MEAN
STD DEV
REL STD DEV
CYANIDE (1)
0.11
< 0.05
0.17
CYANIDE (A)
*
< 0.05
< 0.05
ALUMINUM
< 0.023
0.043
0.12
ANTIMONY
< 0.076
< 0.076
< 0.076
ARSENIC
< 0.002
< 0.002
0.002
BARIUM
0.18
0.25
0.17
0.2
0.035590
17.79513
BERYLLIUM
< 0.001
< 0.001
< 0.001
CADMIUM
< 0.003
0.004
0.006
CALCIUM
2400
2980
2870
2750
251.5286
9.146496
CHROMIUM (+6)
0.16
0.07
0.08
0.11
0.040276
36.61529
CHROMIUM (T)
0.077
0.069
0.076
0.074
0.003559
4.809494
CO0ALT
< 0.010
< 0.010
0.011
COPPER
0.027
0.044
0.057
0.042
0.012283
29.24686
IRON
0.21
0.089
0.091
0.13
0.056574
43.51879
LEAD
< 0.001
< 0.001
0.001
MAGNESIUM
38.8
42.6
29.8
37.1
5.367391
14.46736
MANGANESE
0.35
0.32
0.32
0.33
0.014142
4.285495
MERCURY
< 0.0006
< 0.0003
0.0004
MOLYBDENUM
< 0.037
< 0.037
< 0.037
NICKEL
1.85
2.45
2.34
2.21
0.260810
11.80138
SELENIUM
0.004
0.005
0.006
0.005
0.000816
16.32993
SILVER
0.007
< 0.004
< 0.004
SODIUM
67.7
77.5
65.1
70.1
5.339163
7.616495
THALLIUM
< 0.004
< 0.002
< 0.002
TIN
< 0.105
< 0.10
< 0.10
VANADIUM
0.018
0.009
0.008
0. 012
0.004496
37.47427
ZINC
0.19
0.25
0.37
0.27
0.074833
27.71598
* interferent in sample
-------
TABLE 42. WET ANALYTICAL RESULTS OF 28-DAY F011/CEMENT BINDER TEST SAMPLES
PARAMETER
WET LEACHATES
(mg/1)
A
B
c
MEAN
STD DEV
REL STD DEV
ANTIMONY
<
0.5
<
0.5
<
0.5
ARSENIC
0.09
0.04
0.03
0.05
0.026246
52.49338
BARIUM
0.12
0.11
0.09
0.11
0.012472
11.33835
BERYLLIUM
<
0.05
<
0.05
<
0.05
CADMIUM
<
0.05
<
0.05
<
0.05
CHROMIUM (t)
1.9
1.8
1.8
1.9
0.047140
2.481076
CHROMIUM (+6)
0.29
0.26
0.25
0.26
0.016996
6.537204
COBALT
0.1
0.1
<
0.1
COPPER
5.6
5.8
5.8
5.7
0.094280
1.654050
LEAD
<
0.002
<
0.002
<
0.002
MERCURY
0.0005
0.001
0.0005
0.0006
0.000235
39.28371
MOLYBDENUM
<
0.5
<
0.5
<
0.5
NICKEL
17
18
16
17
0.816496
4.802921
SELENIUM
<
0.05
<
0.025
<
0.05
SILVER
0.1
<
0.1
<
0.1
THALLIUM
<
0.004
<
0.004
<
0.004
VANADIUM
0.8
0.9
0.7
0.8
0.081649
10.20620
ZINC
0.2
0.2
0.2
0.2
-------
TABLE 43. WET ANALYTICAL RESULTS OF 28-DAY FO11/LIME/FLY ASH BINDER TEST SAMPLES
PARAMETERS
WET LEACHATES (mg/l)
A
B
C
HEAN
STD DEV
REL STD DEV
ANT 1 HONY
0.5
1
0.9
0.8
0.216024
27.00308
ARSENIC
0.1
0.035
0.037
0.057
0.030180
52.94901
BARIUM
0.15
0.16
0.12
0.14
0.016996
12.14052
BERYLULM
0.05
0.06
0.05
0.05
0.004714
9.428090
CADMIUM
< 0.05
0.11
0.13
CHROMIUM (T)
2.2
2.1
1.9
2.1
0.124721
5.939130
CHROMIUM (+6)
0.16
0.14
0.16
0.15
0.009428
6.285393
COBALT
0.1
0.2
0.2
0.16
0.047140
29.46278
COPPER
0.6
7.9
10
8.8
0.873053
9.921061
LEAD
0.002
< 0.01
< 0.01
1
MERCURY
0.001
0.0006
0.0026
0.0014
0.000864
61.72133
MOLYBDENUM
0.6
< 0.5
< 0.5
NICKEL
26
27
29
27
1.247219
4.619330
SELENIUM
0.2
< 0.005
< 0.005
SILVER
< 0.1
0.2
< 0.5
THALLIUM
< 0.004
< 0.004
< 0.004
VAMADIUM
1.1
1.1
0.7
0.96
0.188561
19.64105
ZINC
0.4
1.4
1.1
0.96
0.418993
43.64515
-------
TABLE 44. WET ANALYTICAL RESULTS OF 28-DAY F011/KILN DUST BINDER TEST SAMPLES
WET LEACHATES (mg/l)
PARAMETER
A
B
C
MEAN
STD DEV
REL STD DEV
ANT 1 HON If
<
0.5
0.6
0.6
ARSENIC
0.06
0.078
0.075
0.071
0.007874
11.09015
BARIUM
0.11
0.1
0.12
0.11
0.008164
7.422696
BERYLLIUM
<
0.05
< 0.05
< 0.05
CADMIUM
<
0.05
0.12
0.11
CHROMIUM (T)
1.6
1.7
2
1.8
0.169967
9.442628
CHROMIUM <*6)
0.09
0.11
0.09
0.1
0.009428
9.428090
COBALT
<
0.1
0.1
0.1
COPPER
7.7
7.8
8
7.8
0.124721
1.598998
LEAD
0.01
0.01
0.02
0.01
0.004714
47.14045
MERCURY
<
0.0004
< 0.0002
< 0.0004
MOLYBDENUM
0.6
< 0.5
< 0.5
NICKEL
28
28
31
29
1.414213
4.876598
SELENIUM
<
0.025
< 0.025
< 0.025
SILVER
<
0.1
0.1
0.1
THALLIUM
<
0.004
< 0.004
< 0.004
VANADIUM
0.7
0.7
0.8
0.7
0.047140
6.734350
ZINC
1.7
1.1
1.3
1.4
0.249443
17.81741
-------
TABLE 45. ANALYTICAL DATA SUMMARY OF UNTREATED F012 WASTE
PARAMETER
TOTAL UASTE
ANALYSIS
(ug/g) *
A
TCLP LEACHATES (mg/l)
B
c
HEAN **
STD OEV **•
REL STD CEV ••••
pH, S.U.
11.64
CHLORIDE
1200
MOISTURE (X)
42.3
OIL I GREASE
66500
SULfATE
150DO
SULFIDE
24.4
TOC
1200
AIUNI HUH
0.031
0.023
0.01
0.028
0.003559
12.71080
ANTIMONY
< 3.78
<
0.076
< 0.076
<
0.076
ARSENIC
5.2
<
0.002
< 0.002
<
0.002
BARIUM
84.2
0.32
0.34
0.32
0.33
0.00942R
2.856997
BERYLLIUM
< 0.05
<
0.001
< 0.001
<
0.001
CADMIUM
5.9
0.04
0.036
0.032
0.036
0.003265
9.072184
CALCIUM
2750
2620
2S3Q
2633
90.30811
3.429856
CHROMIUM
-------
TABLE 46. TOTAL WASTE ANALYSIS OF UNTREATED AND TREATED P012 WASTE
PARAMETER
UNTREATED
F 012
TREATED F012 (ug/g)
(ug/g) *
TCA-F012
TCA-F012
TCA-F012
TCA-F012
TCA-F012
TCA-F012
-CEM-1
-CEH-25
-KD-1
-KD- 25
- L F -1
-L F-25
pH. s.u.
11.84
11.93
11 .91
11 .96
11.96
11.99
11.73
CHIOBIOE
1200
1030
750
1250
1500
900
750
MOISTURE X
42.3
37.8
32.6
38.8
??
37.9
29.8
OIL ft GREASE
66500
62600
64600
64900
730
174
682
SULFATE
15000
14000
13600
16000
15400
14800
16600
SULFIDE
24.4
36.4
10
18.4
<6.4
4.5
27
TOC
1200
2770
807
953
1120
3550
5640
ANTIMONY
< 3.78
< 3.78
<3.78
<3.78
< 3.78
< 3.78
< 3.78
ARSENIC
5.2
5.25
6.95
4.75
7.45
11.6
15.5
BARIUM
84.2
99.4
86
78.1
77. 3
81.5
104
BERHLIUM
< 0.05
< 0.05
< 0.05
< 0.05
0.35
0.65
1.2
CADMIUM
5.9
4.56
4.89
5.34
3.04
4.53
3.71
CHROMIUM (T)
27.T
26. T
31.2
23.6
24.4
23.9
24.8
CHROMIUM (+6)
3.66
2.22
2.33
1.24
1.27
3.24
< 0.055
COBALT
0.82
1.28
1.97
1.34
1.79
2.36
3.63
COPPER
423
313
286
311
278
277
236
LEAD
15.9
14.9
11.5
17.1
12.6
19.4
16
MERCURY
* 0.18
< 0.14
< 0.15
< 0.16
< 0.14
< 0.14
< 0.14
MOLYBDENUM
< 1.86
< 1.86
< 1.86
< 1.86
< 1.86
2.03
2.74
NICKEL
640
596
605
655
573
559
446
SELENIUM
< 0.08
< 0.08
< 0.08
< 0.08
< 0.08
< 0.08
< 0.08
SILVER
1.82
< 0.30
< 0.30
< 0.30
< 0.30
< 0.30
< 0.30
THALLIUM
< 0.12
< 0.12
< 0.12
< 0.12
< 0.12
< 0.12
< 0.12
VANADIUM
6.55
9.54
14.8
7.92
10.8
16.2
24.8
ZINC
60.7
49.7
55.2
59
68
55.3
60.5
* Except as otherwise r*>t«J
-------
TABLE 47. TCLP ANALYTICAL RESULTS OF 28-DAY F012/CEMENT BINDER TEST SAMPLES
PARAMETER
A
TCLP LEACHAIES (mg/l)
B
C
MEAN
STD DEV
REL STD DEV
ALUMINUM
0.044
0.053
<
0.024
ANTIMONY
<
0.070
< 0.070
<
0.070
ARSENIC
<
0.002
< 0.002
<
0.00?
BARIUM
0.31
0.36
0.29
0.32
0.029439
9.199750
BERYLLIUM
<
0.001
< 0.001
<
0.001
CADMIUM
0.004
0.005
0.005
0.005
CALCIUM
2420
2550
2590
2520
72.57160
2.879833
CHROMIUM (T)
0.16
0.14
0.15
0.15
0.008164
5.443310
CHROMIUM (*6)
0.21
0.37
0.19
0.26
0.080553
30.98216
COBALT
<
0.017
< 0.017
<
0.017
COPPER
0.094
0.092
0.1
0.095
0.003399
3.578259
IRON
0.032
0.037
0.032
0.034
0.002357
6.932419
LEAD
<
0.001
< 0.001
<
0.001
MAGNESIUM
47
48.9
46.7
47.5
0.974109
2.050756
MANGANESE
0.27
0.25
0.27
0.26
0.009428
3.626188
MERCURY
<
0.0003
0.0004
<
0.0003
MOIYBOENUM
<
0.044
< 0.044
<
0.044
NICKEL
2.73
2.74
2.31
2.6
SELENIUM
0.002
< 0.002
0.005
SILVER
<
0.006
<0.006
<
0.006
SOOIUM
61.8
65.3
63.8
63.6
1.433720
2.254278
THALLIUM
0.004
0.004
0.003
0.004
0.000471
TIN
<
0.062
< 0.062
<
0.062
VANADIUM
<
0.012
< 0.012
<
0.012
ZINC
0.16
0.18
0.16
0.17
0.009428
5.545935
-------
TABLE 1*8. TCLP ANALYTICAL RESULTS OF 28-DAY F012/LIME/FLY ASH BINDER TEST SAMPLES
PARAMETER
A
TCLP LEACHATES
B
-------
TABLE 49. TCLP ANALYTICAL RESULTS OF 28-DAY F012/KILN DUST BINDER TEST SAMPLES
PARAMETER
A
TCLP LEACHATES
B
(mg/l)
C
MEAN
STD DEV
REL STD OEV
ALUMINUM
0.035
0.033
0.027
0.032
0.003399
10.62295
ANTIMONY
<
0.070
< 0.070
<
0.070
ARSENIC
<
0.002
< 0.002
<
0.002
BARIUM
0.45
0.37
0.33
0.38
0.041096
10.81476
BERYLLIUM
<
0.001
< 0.001
<
0.001
CADMIUM
<
0.003
0.004
<
0.003
CALCIUM
2420
2410
2350
2393
30.91206
1.291770
CHROMIUM (T)
0.25
0.29
0.31
0.29
0.024944
8.601511
CHROMIUM («6)
0.29
0.34
0.36
0.33
0.029439
8.920970
COBAll
<
0.017
0.026
<
0.017
COPPER
0.069
< 0.021
<
0.021
IRON
0.078
0.072
0.04«
0.066
0.012961
19.63860
LEAD
0.004
< 0.001
<
o.ooi
MAGNESIUM
48.6
45.6
45.9
46.7
1.349073
2.888808
MANGANESE
o.ia
0.19
0.15
0.17
0.016996
9.990077
MERCURY
<
0.0003
0.0003
<
0.0003
MOLYBDENUM
0.044
< 0.044
<
0.044
NICKEL
1.6
1.39
1.43
1.47
0.091043
6.193424
SELENIUM
<
0.002
< 0.002
<
0.002
SILVER
0.006
< 0.006
<
0.006
SODIUM
63.4
61.2
66.7
63.8
2.260285
3.542766
THALLIUM
<
0.003
0.004
0.003
TIN
<
0.062
< 0.062
0.11
VANADIUM
<
0.012
< 0.012
<
0.012
2 INC
0.15
0.15
0.11
0.14
0.018856
13.46870
-------
TABLE 50. WET ANALYTICAL RESULTS OP 28-DAY FO
12/CEMENT BINDER TEST SAMPLES
WET LEACHATES (mg/l)
PARAMETER
A
B
C
MEAN
STD DtV
REl STD DEV
ANTIMONY
<
2.5
< 2.5
<
2.5
ARSENIC
*
0.03
< 0.03
0.08
BARIUM
0.27
< 0.25
<
0.25
BERYLLIUM
<
0.25
< 0.25
<
0.25
CADMIUM
<
0.25
< 0.25
<
0.?5
CHROMIUM (T)
2
1.6
2
1.9
0.188561
9.924305
CHROMIUM (+6)
0.4
0.39
0.41
0.4
COBALT
<
0.5
< 0.5
<
0.5
COPPER
16
16
14
15.3
0.942809
6.162150
LEAD
<
2.5
< 2.5
<
2.5
MERCURY
0.0005
< 0.0002
<
0.0002
MOLYBDENUM
<
0.5
< 0.5
<
0.5
NICKEL
9
11
6
8.6
2.054804
23.89307
SELENIUM
<
0.05
< 0.05
<
0.05
SILVER
<
0.5
< 0.5
<
0.5
THALLIUM
<
0.004
0.004
0.004
VANADIUM
<
0.5
< 0.5
<
0.5
ZINC
<
0.5
< 0.5
<
0.5
-------
TABLE 51. WET ANALYTICAL RESULTS OF 28-DAY FO12/LIME/FLY ASH RTNDER TEST SAMPLES
PARAMETER
A
WEI LEACHATES
B
(rug/1 >
C
MFAN
STD OFV
PEL STD DFV
ANTIMONY
<
2.5
< 2.5
<
2.5
ARSENIC
o.ooa
0.009
0.005
0.007
0.001699
24.20104
BAB 1UH
0.29
0.25
0.25
0.27
0.018856
6.983770
BERYLLIUM
<
0.25
< 0.25
<
0.25
CADMIUM
<
0.25
< 0.25
<
0.25
CHROMIUM (T)
3
3
2
2.6
0.471404
18.13094
CHROMIUM (+6)
0.49
0.62
0.68
0.6
0.079302
13.21708
COBALT
<
0.5
< 0.5
<
0.5
COPPER
24
25
23
24
0.816'.96
3.402069
LEAD
<
2.5
< 2.5
<
2.5
MERCURY
<
0.0004
< 0.0002
<
0.0002
MOLYBDENUM
<
0.5
< 0.5
c
0.5
NICKEL
24
24
19
22
2.357022
10.71373
SELENIUM
<
0.025
< 0.025
<
0.025
SILVER
<
0.5
< 0.5
<
0.5
TKALl1UM
<
0.004
< 0.004
c
0.004
VANADIUM
0.6
< 0.5
<
0.5
ZINC
<
0.5
< 0.5
<
0.5
-------
TABLE 52. WET ANALYTICAL RESULTS OF 28-DAY F012/KTLN DUST BINDER TEST SAMPLES
WET LEACHA1ES (mg/1)
PARAMETERS
A
B
C
MEAN
SID DEV
RFL SID DEV
ANTIMONY
<
2.5
< 2.5
<
2.5
ARSENIC
0.016
0.017
<
0.0O3
BARIUM
<
0.25
< 0.25
<
0.25
BERYUIUH
<
0.25
< 0.25
<
0.25
CADMIUM
<
0.25
< 0.25
<
0.25
CHROMIUM (T)
2
2
2
2
CHROMIUM <-»6)
0.54
0.31
0.31
0.32
0.014142
4.419417
COBALT
<
0.5
< 0.5
<
0.5
COPPER
27
27
26
26.6
(1.471404
1.772197
LEAD
<
2.5
< 2.5
<
2.5
MERCURY
<
0.0002
< 0.0002
<
0.0002
MOLYBDENUM
<
0.5
< 0.5
<
0.5
NICKEL
37
31
33
33.6
2.494438
7.423923
SELENIUM
<
0.025
< 0.025
<
0.025
SILVER
<
0.5
< 0.5
<
0.5
THAUTUM
<
0.004
< 0.004
<
0.004
VANADIUM
<
0.5
< 0.5
<
0.5
ZINC
<
0.5
< 0.5
<
0.5
-------
collected at Woodward Governor contained a total waste analysis basis of 5.?,
84.2, 5.9, 27.1, and 3.66 yg/g arsenic, barium, cadmium, chromium, and
hexavalent chromium, respectively, and 423, 15.9, 848, 6.55, and 60.7 yg/g
copper, lead, nickel, vanadium, and zinc, respectively. (Cyanide analysis
was not requested by the Agency.) Untreated F01? average TCLP concentrations
were reported to be 40.6 mg/L magnesium and 4.14 ma/L nickel. Other metals
were at low or nondetectable concentrations.
Cement-treated F012 TCLP extracts showed average concentrations of 47,5
mg/L magnesium and 2.6 mg/L nickel. Lime/fly ash extracts showed 1.01 mg/L
aluminum, 12.9 mq/L magnesium, and nondetectable (0.031 mg/L) to 0.034 mg/L
nickel. Kiln dust extracts showed TCLP extract concentrations of 46.7 mg/L
m?gnesium and 1.47 mg/L nickel.
A comparison of the untreated TCLP data with the treated TCLP data indi-
cates that stabilization/solidification with lime/fly ash is very effective
for treating nickel and has limited effectiveness in treating magnesium.
Cement and kiln dust, however, demonstrated limited effectiveness in contain-
ing nickel and had no effect on magnesium.
109
-------
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-------
APPENDIX
REGULATORY OVERVIEW OF LAND DISPOSAL
RESTRICTIONS FOR SELECTED METAL-FINISHING
WASTE CODES
Hazardous waste treatment, storage, and disposal practices, formerly
controlled under the Clean Water Act or restricted by State regulations, were
regulated by the Resource Conservation and Recovery Act (RCRA) when the Act
was passed by Congress in 1976. Recognizing that liquid hazardous wastes
placed into land disposal units contributed to the formation of uncontrolled
toxic and hazardous waste sites, the EPA developed regulations under RCRA
restricting their disposal. On November 8, 1984, however, Congress enacted
the Hazardous and Solid Waste Amendments (HSWA). A major section of the 1984
amendments to RCRA is the requirement for EPA to set treatment standards for
all RCRA hazardous wastes. The treatment standard set by EPA must be met
before land disposal is allowed. Treatment standards are based upon the
performance of the best demonstrated available technology (BDAT) to treat the
waste. The EPA defines "demonstrated" technologies as those currently used
treat the waste or hazardous constituent(s) in the waste, or those used to
treat wastes or their hazardous constituents that are similar to the waste
being evaluated for BDAT. "Available," according to the EPA definition,
means that the technology 1) is commercially available, and 2) substantially
diminishes the toxicity of the waste or reduces the probability of hazardous
constituents migrating from the waste. The amendments also set a
congressionally mandated schedule for phasing out the land disposal of all
listed and characteristic RCRA hazardous wastes. The HSWA definition of
"land disposal" includes disposal into the following types of units:
landfills, surface impoundments, waste piles, injection wells, land-treatment
units, salt dome formations, salt bed formations, and underground mines or
caves [42 USC 6924(k)j.
The statutory deadlines mandated by HSWA required EPA to restrict land
disposal of hazardous wastes within a limited time frame. The first category
of wastes to be banned from land disposal include the F001 through F005
solvents, and dioxin-containing hazardous wastes. Subsequent to the ban of
these wastes, EPA restricted the "California list" wastes, which include
certain hazardous wastes containing metals, free cyanides, PCBs, low-pH
wastes, and liquid and nonliquid wastes containing halogenated organic com-
pounds (HOCs) above specified levels. All other listed RCRA wastes were
separated into thirds, based on volume and toxicity. The so-called "First-
Third" listed hazardous wastes were restricted from land disposal on August
8, 1988; the "Second-Third" were restricted from land disposal on June 8,
1989; and the "Third-Third", along with all characteristic wastes, were
restricted from land disposal in May 1990 (see Table A-l).
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TABLE A-l. SCHEDULE FOR LAND DISPOSAL RESTRICTION REGULATIONS3
Chemicals
Effective date of ban
Status
Solvents and dioxins
11/8/86
Promulgated
California list
7/8/87
Promulgated
Scheduled wastes
First-third
8/8/88
Promulgated
Second-third
6/8/88
Promulgated
Third-third
5/8/90
Pending
3 Source: U.S. EPA, OSWER.
The HSWA requirements include setting a schedule for treatment standards
for all listed and characteristic hazardous wastes. If EPA fails to set
treatment standards for any of the listed hazardous wastes, RCRA §3004(g)(6)
states that those wastes may be land-disposed only if the following condi-
tions apply: 1) the land-disposal facility is in compliance with the require-
ments of RCRA §3004(o), which are minimum technology requirements (i.e.,
double-liner system, 1eachate-col1ection system, ground-water monitoring);
and 2) prior to disposal, the generator has certified to the Administrator
that availability of treatment capacity is insufficient to treat the waste
and that land disposal is the only practical alternative available. These
provisions are known as the "soft-hamner" provisions.
The land-disposal restriction rules promulgated by EPA define waste
treatability groups by waste codes and identify BDAT for each waste code.
Treatment standards for each identified treatability group are based on the
demonstrated level of treatment achievable by the corresponding BDAT identi-
fied for that treatability group. Use of the BDAT identified for each treat-
ability group is not required to meet the concentration-based treatment
standards; any technology not otherwise prohibited may be used to achieve the
level of treatment required as a prerequisite to land disposal. Dilution of
a waste with either aqueous or nonaqueous materials, however, is prohibited
as a substitute for meeting or partially meeting the treatment standards.
The wastes evaluated in this report include primarily electroplating
wastes containing cyanides; i.e., F006 (wastewater treatment sludges from
electroplating operations), F007 (spent cyanide plating bath solutions from
electroplating operations where cyanides are used in the process), F009
(spent stripping and cleaning bath solutions from electroplating operations
where cyanides are used in the process), 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), and F019 (wastewater treatment sludges
from the chemical conversion coating of aluminum). A wastewater is defined
as those wastes that contain less than 1 percent total organic carbon and
less than 1 percent total suspended solids. Those wastes that do not meet
these criteria are defined as nonwastewaters and thus would contain greater
than or equal to 1 percent TOC, or greater than or equal to 1 percent total
suspended solids. The technologies identified by EPA as BDAT for these
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listed wastes include alkaline chlorination, followed by precipitation,
filtration, and stabilization of metals for Waste Code F006 (nonwastewaters
only); and electrolytic oxidation followed by alkaline chlorination, followed
by precipitation, settling, filtration, and stabilization of metals for F012.
The technology identified as BDAT for Waste Codes F007, F009, and F011 is
alkaline chlorination, followed by precipitation, settling, and sludge dewater-
ing. Concentration-based treatment standards for F006 wastewaters and F019
will be promulgated with the "Third-Third" wastes on May 8, 1990. Until that
time, cyanide-bearing F006 wastewaters and F019 wastes are subject to the
"soft-hammer" provisions.
With the exception of noncyanide-bearing F006 and F019 wastes [which
were included in the "First-Third" category (53 FR 31152)], F006 wastewaters,
and cyanide-bearing F019 wastes, the electroplating wastes discussed in this
report (F006, F007, F009, F011, and F012) were all included in the "Second-
Third" listed waste category (54 FR 26594).
Tables A-2 through A-5 list the BDAT treatment standards for each of
these wastes.
TABLE A-2. BDAT TREATMENT STANDARDS, METAL-FINISHING LIQUIDS
SUBCATEGORY FOR F007 AND F009 (NONWASTEWATERS)
Maximum for any single grab sample
Consti tuent
Total
composition,
mg/kg
TCLP, mg/L
Cyanides (total)
590
a
Cyanides (amenable)
30
a
Cadmium
a
0.066
Chromi urn
a
5.2
Lead
a
0.51
Nickel
a
0.32
Silver
a
0.072
a Not applicable
TABLE A-3. BDAT TREATMENT STANDARDS, METAL-FINISHING LIQUIDS
SUBCATEGORY FOR F006, F007, AND F009 (WASTEWATERS)
Consti tuent
Maximum for any single
grab sample (total
composition, mg/kg)
Cyanides
Cyanides
Chromium
Lead
Ni ckel
(total)
(amenable)
1.9
0.1
0.32
0.04
0.44
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TABLE A-4. BDAT TREATMENT STANDARDS, METAL-FINISHING LIQUIDS
SUBCATEGORY FOR FOll AND F012 (NCNWASTEWATERS)
Maximum for any single
grab sample
Total
composition,
Constituent mg/kg TCLP, mg/L
Cyanides (total) 110 a
Cyanides (amenable) 9.1 a
Cadmium a 0.066
Chromium a 5.2
Lead a 0.51
Nickel a 0.32
Silver a 0.072
a Not applicable.
TABLE A-5. BDAT TREATMENT STANDARDS, METAL-FINISHING LIQUIDS
SUBCATEGORY FOR FOll AND F012 (NONWASTEWATERS)
Maximum for any single
grab sample (total
Constituent composition, mg/kg)
Cyanides (total) 1.9
Cyanides (amenable) 0.1
Chromium 0.32
Lead 0.04
Nickel 0.44
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TECHNICAL REPORT DATA
(Please read Instructioni on the reverse before compter'
1. REPORT NO. 2.
EPA/600/2-90/055
3.
4. TITLE AND SUBTITLE
CHARACTERIZATION AND TREATMENT OF WASTES FROM
METAL-FINISHING OPERATIONS
5. REPORT DATE
November 1990
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
PEI Associates, Inc.
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
11499 Chester Road
Cincinnati, Ohio 45246
10. PROGRAM ELEMENT NO.
D109
11. CONTRACT/GRANT NO.
68-03-3389
12. SPONSORING AGENCY NAME AND ADDRESS
Risk Reduction Engineering Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Cincinnati, Ohio 45268
13. TYPE OF REPORT AND PERIOD COVERED
10/86 - 9/89
14. SPONSORING AGENCY CODE
EPA/600/14
15. SUPPLEMENTARY NOTES
Project Monitor: Ronald J. Turner (513) 569-7775; FTS 684-7775
16. ABSTRACT
This Report is a Summary of Project Activities related to bench-and-pilot-scale
Treatment of Electroplating Wastes scheduled for RCRA Land Disposal Restrictions
(F006, F007, F009, F019).
17. KEY WORDS AND DOCUMENT ANALYSIS
a. DESCRIPTORS
b.IDENTIFIERS/OPEN ENDED TERMS
c. COS ATI Field/Group
Cyanide
Heavy Metals
Chemical Oxidation
Wet-Alr-Oxidation
Stabilization
IB. DISTRIBUTION STATEMENT
RELEASE TO PUBLIC
19. SECURITY CLASS (This Report)
UNCLASSIFIED
21. NO. OF PAGES
128
20. SECURITY CLASS (This page)
UNCLASSIFIED
22. PRICE
EPA F»mi 2220-1 (R»v. 4-77) psevioui edition is obiolete
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