FINAL
BEST DEMONSTRATED AVAILABLE TECHNOLOGY (BDAT)
BACKGROUND DOCUMENT FOR
K031, K084, K101, K102, CHARACTERISTIC ARSENIC WASTES (D004),
CHARACTERISTIC SELENIUM WASTES (D010), AND P AND U WASTES
CONTAINING ARSENIC AND SELENIUM LISTING CONSTITUENTS
Larry Rosengrant, Chief
Treatment Technology Section
Laura Fargo
Project Manager
U.S. Environmental Protection Agency
Office of Solid Waste
401 M Street, S.V.
Washington, DC 20460
May 1990
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ACKNOWLEDGMENTS
This document was prepared for the U.S. Environmental Protection
Agency, Office of Solid Waste, by Versar Inc., under Contract No.
68-W9-0068. Mr. Larry Rosengrant, Chief, Treatment Technology Section,
Waste Treatment Branch, served as the EPA Program Manager during the
preparation of this document and the development of treatment standards
for the arsenic- and selenium-containing wastes. The technical project
officer for the wastes was Ms. Laura Fargo. Mr. Steven Silverman served
as legal advisor.
Versar personnel involved in the preparation of this document
included Mr. Jerome Strauss, Program Manager; Mr. Stephen Schwartz,
Assistant Program Manager; Mr. Edwin F. Rissmarm, Principal Investigator
and Author; Ms. Justine Alchowiak, Quality Assurance Officer; Ms. Martha
Martin, Technical Editor; and Ms. Sally Gravely, Program Secretary, and
the Versar secretarial staff.
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TABLE OF CONTENTS
Section Page No.
1. INTRODUCTION AND SUMMARY 1-1
2. INDUSTRIES AFFECTED AND WASTE CHARACTERIZATION 2-1
2.1 Industries Affected 2-2
2.1.1 Industries Producing and Using Arsenic
and Its Compounds 2-4
2.1.2 Industries Producing and Using Selenium
and Its Compounds 2-5
2.1.3 Processes That Generate Arsenic-Containing
Wastes 2-7
2.1.4 Processes That Generate Selenium-Containing
Wastes 2-8
2.2 Waste Characterization 2-9
2.2.1 Arsenic 2-9
2.2.2 Selenium 2-16
2.3 Determination of Waste Treatability Group 2-16
3. APPLICABLE AND DEMONSTRATED TREATMENT TECHNOLOGIES 3-1
3.1 Applicable Treatment Technologies 3-1
3.1.1 Applicable Technologies for Nonwastewaters .... 3-2
3.1.2 Applicable Technologies for Wastewaters 3-5
3.2 Demonstrated Treatment Technologies 3-8
2.2.1 Demonstrated Technologies for Nonwastewaters .. 3-8
2.2.2 Demonstrated Technologies for Wastewaters 3-12
4. PERFORMANCE DATA . . 4-1
4.1 Performance Data for Nonwastewaters 4-1
4.1.1 Incineration Performance Data 4-2
4.1.2 Stabilization Performance Data 4-3
4.1.3 Vitrification Performance Data 4-21
4.2 Performance Data for Wastewaters 4-25
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TABLE OF CONTENTS
(continued)
Section Page No.
5. DETERMINATION OF BEST DEMONSTRATED AVAILABLE TECHNOLOGY
(BOAT) 5-1
5.1 Nonwastewaters 5-1
5.2 Wastewaters 5-5
6. SELECTION OF REGULATED CONSTITUENTS 6-1
7. CALCULATION OF BOAT TREATMENT STANDARDS 7-1
7.1 Arsenic Nonwastewaters 7-1
7.1.1 D004, K031, K084, P010, P011, P012, P036,
P038, and U136 Nonwastewaters 7-2
7.1.2 K101 and K102 Nonwastewaters 7-4
7.2 Arsenic Wastewaters 7-4
7.2.1 D004 Wastewaters 7-4
7.2.2 K031, K084, P010, P011, P012, P036, P038,
and U136 Wastewaters 7-6
7.2.3 K101 and K102 Wastewaters 7-7
7.3 Selenium (D010, P103. P114, U204, and U205)
Nonwastewaters 7-8
7.4 Selenium (D010, P103, P114, U204, and U205)
Wastewaters 7-10
8. REFERENCES 8-1
APPENDIX A - HIGH-TEMPERATURE STABILIZATION TECHNOLOGIES A-l
A-l Applicability A-l
A-2 Underlying Principles of Operation A-2
A.2.1 Glass Vitrification A-2
A.2.2 Slag Vitrification A-3
A. 2. 3 High-Temperature Calcination A-3
iii
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TABLE OF CONTENTS
(continued)
Section Page No.
A-3 Description of the High-Temperature Stabilization
Processes A-4
A.3.1 Glass Vitrification A-4
A. 3. 2 Slag Vitrification A-5
A.3.3 High-Temperature Calcination A-5
A.4 Waste Characteristics Affecting Performance (WCAPs).... A-6
A.4.1 Waste Characteristics Affecting Performance
of Vitrification Processes A-6
A.4.2 Waste Characteristics Affecting Performance
of High-Temperature Calcination A-8
A. 5 Design and Operating Parameters A-9
A.5.1 Design and Operating Parameters for
Vitrification Processes A-9
A.5.2 Design and Operating Parameters for
High-Temperature Calcination Systems A-12
A. 6 References A-13
APPENDIX B - ANALYTICAL METHODS AND QUALITY ASSURANCE/QUALITY
CONTROL DATA B-l
iv
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LIST OF TABLES
Table No. Page No.
Table 1-1 Treatment Standards for Arsenic-Containing and
Selenium-Containing Wastes 1-2
Table 2-1 Current Manufacturers of Arsenic and Selenium Compounds. 2-4
Table 2-2 Characterization Data for D004 Characteristic
Arsenic Wastes 2-10
Table 2-3 Waste Characterization Data for K031 2-13
Table 2-4 Waste Characterization Data for K084 2-15
Table 2-5 Waste Characterization Data for K101 and K102 2-16
Table 2-6 Waste Characterization Data for P010, P011, and P012
Wastes 2-17
Table 2-7 Characterization Data for D010 Characteristic Selenium
Wastes 2-18
Table 4-1 Stabilization Treatment Performance Data
for Arsenic Wastes 4-4
Table 4-2 Stabilization Treatment Performance Data for K031 4-6
Table 4-3 Stabilization Treatment Performance Data for
Proprietary Process 4-7
Table 4-4 Effect of the pH on the Stability of Ferric
Arsenate Precipitates 4-9
Table 4-5 Chemical Treatment and Stabilization of Concentrated
Arsenic Streams 4-10
Table 4-6 Performance Data for the Stability of Calcium
Arsenate, Manganese Arsenate, and Ferric
Arsenate Precipitates 4-12
Table 4-7 Precipitation Treatment Performance Data for
D004 Wastewaters 4-13
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LIST OF TABLES
(Continued)
Table No.
Table 4-8
Table 4-9
Table 4-10
Table 4-11
Table 4-12
Table 4-13
Table 4-14
Table 4-15
Table 4-16
Table 4-17
Table 7-1
Table 7-2
Table 7-3
EP Toxicity Testing of Calcium Arsonate and Calcium
Arsenite-containing Precipitates
Stabilization of Arsenic Contaminated Soils and Arsenic
Sulfide Sludge
Stabilization of Selenium-Containing Mineral Processing
Waste
EP-Toxicity Testing of Calcium Selenate-Containing
Precipitates
Vitrification Treatment Performance Data for Slags
Containing Arsenic
Vitrification/Classification Treatment Performance Data.
Vitrification Glass Samples Using Arsenic-Containing
Sludge
Ferric Arsenate Precipitation Treatment Performance
Data for Different Iron-to-Arsenic Ratios
Incineration/Scrubber Water Treatment for Arsenic
Selenium Removal from Wastewaters by Chemical
Reduction with Ferrous Ion
Calculation of Treatment Standards for Arsenic
Calculation of Metal Treatment Performance Standards
for K101 and K102 Wastewaters
Calculation of Metal Treatment Standard for Selenium
Nonwastewaters
Table A-l Metal Hydroxide Decomposition Temperatures,
Page No,
4-18
4-19
4-21
4-23
4-24
4-25
4-27
4-29
4-30
4-31
7-3
7-9
7-9
A-12
vi
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LIST OF TABLES
(Continued)
Table No.
Table B-l
Table B-2
Table B-3
Table B-4
Table B-5
Analytical Methods for Regulation Constituents.
Page No.
B-2
Specific Procedures or Equipment Used in Preparation
for Analysis of Metals When Alternatives or
Equivalents Are Allowed in the SW-846 Methods.... B-3
Matrix Spike Recoveries for Treated D004 Waste B-4
Matrix Spike Recoveries Used to Calculate Correction
Factors for the Slag Vitrification EP-Tox Leachate
Value B-5
Matrix Spike Recoveries Used to Calculate Correction
Factors for the Selenium Stabilization TCLP
Leachate Value B-5
vii
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1. INTRODUCTION AND SUMMARY
Pursuant to section 3004(m) of the Hazardous and Solid Waste Amend-
ments (HSWA), enacted on November 8, 1984, the Environmental Protection
Agency (EPA) is establishing treatment standards based on best demon-
strated available technology (BOAT) for certain wastes containing arsenic
and selenium. The arsenic-containing wastes are D004, K031, K084, P010,
P011, P012, P036, P038, and U136. For these arsenic nonwastewaters, the
performance standards are based on vitrification. The selenium-containing
wastes are D010, P103, P114, U204, and U205. For selenium, nonwastewater
performance standards are based on stabilization. Additionally, the
Agency is changing the nonwastewater treatment standards for K101 and
K102, which were promulgated on August 17, 1988, by eliminating the low-
and high-level arsenic subcategories. The low-level standards were
originally based on incineration as BDAT. For arsenic and selenium
nonwastewaters, performance standards are based on chemical precipitation
technologies. This background document presents the development of new
treatment performance standards as BDAT for these wastes. The Agency is
also changing the treatment standards for K101 and K102 wastewaters
because of the discovery of an improperly operated component of the
wastewater system used to develop the standards.
It is important to mention that although the nonwastewater performance
standards for arsenic are based on vitrification as BDAT, the regulated
community is not required to use vitrification, but may use any
technologies that can achieve the performance standards. Moreover, the
Agency encourages recycle/recovery whenever applicable for a waste stream.
The BDAT treatment standards for wastewater and nonwastewater forms
of the wastes listed above are summarized in Table 1-1. A wastewater is
defined by the Agency as containing less than 1 percent (weight basis)
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Table 1-1 Treatment Standards for Arsenic-Containing and Selenitic-Containing Hastes
Haste
code
D004
D010
K031
K084
K101
K102
F010
P011
P012
P036
P038
F103
P114*
U136
U204
D20S
Regulated constituent
Arsenic
Seleniuo
Arsenic
Arsenic
2-Hitroaniline
Arsenic
Cadmium
Lead
Hercury
Ortbo-nitropbenol
Arsenic
Cadmium
Lead
Mercury
Arsenic
Arsenic
Arsenic
Arsenic
Arsenic
Selenium
Selenium
Arsenic
Selenium
Selenium
Total conn
losition
(Maximum for any single
grab sample)
Honwastewater Hastewater
Osg/kg) (Bg/1)
HA
HA
•A
HA
14
HA
HA
HA
HA
13
HA
HA
HA
HA
HA
HA
HA
HA •
HA
HA
HA
HA
HA
HA
S.O
1.0
0.79
0.70
0.27
0.70
0.24
0.17
0.082
0.028
0.70
0.24
0.17
0.082
0.70
0.70
0.70
0.70
0.70
1.0
1.0
0.70
1.0
1.0
Honwastewater
EP Toxicity*
(mg/1)
5.0
HA
S.6
S.6
HA
5.6
HA
HA
HA
HA
5.6
HA
HA
HA
5.6
5.6
5.6
5.6
5.6
HA
HA
5.6
HA
HA
leachate
TCLP
(•g/1)
HA
5.7
HA
HA
HA
HA
HA
HA
HA
HA
HA
HA
HA
HA
HA
HA
HA
HA
HA
5.7
5.7
HA
5.7
5.7
HA • Hot applicable.
This waste is also regulated for thallium. See OSEFA 1900.
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total suspended solids (TSS) and less than 1 percent (weight basis) total
organic carbon (TOC). Wastes not meeting this definition must comply
with the treatment standards for nonwastewaters. Compliance with these
treatment standards is a prerequisite for placement of these wastes in
facilities designated as land disposal units according to 40 CFR
Part 268. The effective date of these treatment standards is August 8,
1990.
This background document presents the Agency's technical support and
rationale for developing regulatory standards for these wastes. Section 1
presents available data regarding the industries affected by the land
disposal restriction, brief descriptions of the waste-generating
processes, and waste characterization data. Section 2 discusses the
technologies used to treat the wastes, and Section 3 presents available
treatment performance data, including the data upon which the treatment
standards are based. Section 4 explains EPA's determination of BDAT,
while Section 5 discusses the selection of constituents to be regulated.
Treatment standards are determined in Section 6.
EPA wishes to point out that, because of facility claims of
confidentiality, this document does not contain all of the data that EPA
used in its regulatory decision-making process. Under 40 CFR Part 2,
Subpart B, facilities may claim any or all of the data that are submitted
to EPA as confidential. EPA will make determinations regarding the
validity of the facility's claim of confidential business information
(CBI) according to 40 CFR Part 2, Subpart B. In the meantime, the Agency
will treat the data as CBI. Additionally, the Agency would like to
emphasize that it evaluated all available data (including CBI data) in
developing the BDAT treatment standards for the arsenic- and
selenium-containing wastes described in this background document.
The BDAT program and promulgated methodology are more thoroughly
described in two additional documents: Methodology for Developing BDAT
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Treatment Standards (USEPA 1988c) and Generic Quality Assurance Project
Plan for the Land Disposal Restrictions Program ("BOAT") (USEPA 1988b).
The petition process to be followed in requesting a variance from BDAT
treatment standards is discussed in the methodology document.
1-4
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2. INDUSTRIES AFFECTED AND WASTE CHARACTERIZATION
This section presents available information about the industries that
will be affected and the available characterization data for the wastes
discussed in this document. The arsenic- and selenium-bearing wastes
discussed in this document are listed by the Agency according to 40 CFR
Part 261 as follows:
D004 - Characteristic arsenic
P010 - Arsenic acid
P011 - Arsenic trioxide
P012 - Arsenic pentoxide
P036 - Dichlorophenyl arsine
P038 - Diethyl arsine
U136 - Cacodylic acid
K031 - By-product salts generated in the production of
monosodium methanearsonate (HSMA) and cacodylic acid
K084 - Wastewater treatment sludge generated during production
of veterinary Pharmaceuticals from arsenic or
organoarsenic compounds
K101 - Distillation tar residues from the distillation of
aniline-based compounds in the production of veterinary
Pharmaceuticals from arsenic or organoarsenic compounds
K102 - Residue from the use of activated carbon for decolorizing
in the production of veterinary pharmaceuticals from
arsenic or organoarsenic compounds
D010 - Characteristic selenium
P103 - Selenourea
P114 - Thallium selenite
U204 - Selenium dioxide
U205 - Selenium disulfide
The K-codes are for wastes from specific sources. The D-codes are
for wastes that exhibit the characteristic of TCLP (Toxicity
Characteristic Leaching Procedure) toxicity.* That is, a D004 waste has
a leachate concentration (based on the TCLP toxicity test)
*This rule will take effect in September 1990. Presently, the
characteristic test used is the EP toxicity test.
2-1
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greater than or equal to 5.0 mg/1 arsenic, and a D010 waste has a
concentration greater than or equal to 1.0 mg/1 selenium in the leachate,
using the TCLP toxicity test. The hazardous wastes with P-codes are
identified as acute hazardous wastes, while the hazardous waste codes
beginning with U identify toxic wastes. In essence, constituents in P
and U code wastes are hazardous only if they are discarded commercial
products or spilled commercial products. P and U constituents that are
normally contained in process waste streams are not hazardous wastes
unless they are determined to be D, F, or K wastes.
Arsenic and selenium have been discussed together in this background
document because of their similar chemical characteristics (e.g.,
existing as oxo-anions) and treatment properties (e.g., precipitation at
low pH, sublimation at low temperatures). As described later in this
section, EPA examined the sources of the wastes, the specific
similarities in waste composition, applicable and demonstrated
technologies, and attainable treatment performance in order to support
the regulatory approach for these wastes.
2.1 Industries Affected
Because of the diverse nature and magnitude of industries generating
D004 and D010, EPA has not attempted to describe every industry that
could generate these wastes. Additionally, the Agency does not intend to
describe every industry that generates the P and U wastes containing
arsenic and selenium listing constituents, since any industrial facility
that produces, uses, stores, and/or transports chemicals containing these
constituents has the potential of generating the wastes. For the
process-specific wastes (i.e., K031, K084, K101, and K102), the
industries generating these wastes can be described accurately. The
following information is a summary of data in the National Survey of
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Treatment, Storage, Disposal, and Recycling (TSDR) Facilities (the TSDR
Survey), the National Survey of Hazardous Waste Generators (Generator
Survey), and related literature (i.e., Bureau of Mines Mineral Yearbook
and Mineral Commodity Summaries). The known producers of arsenic and
selenium compounds are presented in Table 2-1.
2.1.1 Industries Producing and Using Arsenic and Its Compounds
The primary commercial source of arsenic is arsenic oxide, As^O^,
which is generally recovered fr«m flue dusts generated by copper and lead
smelters processing arsenopyritic ores. Currently, no smelters in the
United States both produce and market arsenic oxide. One facility,
ASARCO, in Tacoma, Washington, did produce and market arsenic oxide until
it ceased production in 1985. ASARCO continues to market the arsenic
trioxide from earlier production. The remainder of the arsenic oxide
consumed in the United States is imported. Approximately 30,000 metric
tons of arsenic oxide, 600 metric tons of arsenic metal, and 1,100 metric
tons of arsenic compounds (e.g., arsenic sulfide, arsenic acid, sodium
arsenate, and lead arsenate) were consumed in the United States in 1988.
The estimated end-use distribution of arsenic in 1988 was 69 percent in
wood preservatives, 23 percent in agricultural chemicals (principally
herbicides and desiccants), 4 percent in glass, 2 percent in nonferrous
alloys, and 2 percent in other uses.
Most of the arsenic trioxide consumed is converted to arsenic acid
for use in the production of arsenical wood preservatives mainly by five
companies. Chromated copper arsenate, by far the most important of the
arsenical wood preservatives, is a waterborne, leach-resistant wood
preservative prepared by mixing arsenic acid with copper oxide or sulfate
and chromic acid. It is used to pressure-treat a variety of wood products
that are subject to outdoor or in-ground exposure, and may serve to
extend the service life of wood by a factor of at least 15.
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2991g
Table 2-1 Current Hanufacturers of Arsenic and Selenium Compounds
Industry
Manufacturer
Location
Product(s)
Wood preservation
Hickson Corp.
Osmose Wood Preserving
Mineral Research and
Development
WR Metals
Pennwalt
Conley. GA
Millington, TN
Harrisburg. NC
Laramie. UY
Bryan, TX
Copper chrone arsenate
Copper chrome arsenate.
arsenic acid
Copper chrome arsenate,
arsenic acid
Arsenic acid
Copper chrome arsenate
Pesticides
Vineland Chemical
Cedar Chemical
Fermenta
DREXEL Chemical
Vineland. NJ
Vicksburg, MS
Houston. TX
Tunica. MS
Cacodylic acid
Cacodylic acid
Cacodylic acid and salts
Cacodylic acid and salts
Veterinary
Pharmaceuticals
Fleming Laboratories
Salsbury Laboratories
Charlotte. NC
Charles City, IA
p-aminopnenyl arsonic acid
4-nitrophenyl arsonic acid
4-hydroxyl 3-nitrophenyl
arsonic acid
Chemical
manufacturing
Harshaw Filtrol
S. Kohnstamm, Inc.
SCM Corp.
A jay Chemical
Phillip Brothers
Chemical Company
Louisville, KY
Newark. NJ
Baltimore, MO
Powder Springs, GA
Bowroanstown. PA
Quincy, IL
Cadmium red pigment
Selenic acid and/or its salts
Source: SRI 1989.
2-4
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The principal agricultural market for arsenicals is in cotton growing,
where arsenic acid was used as a desiccant to aid in mechanical stripper
harvesting of cotton; other arsenical chemicals, such as monosodium
methanearsenate and disodium methanearsonate, were used as herbicides for
control of grassy and broadleaf weeds. To a lesser extent, arsenical
herbicides were used in noncrop areas such as railroad rights-of-way.
Arsenic trioxide and arsenic acid are used in the glass industry
primarily as fining agents to remove tiny, dispersed air bubbles, and
also as decolorizing agents. Use in recent years has been limited to the
pressed and blown glass sectors for products such as tableware, lead
glass, optical glass, and glass ceramics.
The bulk of metallic arsenic is used in lead- and copper-based alloys
as a minor additive (about 0.01 to 0.5 percent) to increase strength in
the posts and grids of lead-acid storage batteries and to improve
corrosion resistance and tensile strength in copper alloys.
High-purity arsenic metal is used in the electronics industry.
Gallium arsenide and its alloys have been used in such products as
light-emitting diodes and displays, room-temperature lasers, microwave
devices, solar cells, and photoemissive surfaces. Gallium arsenide
integrated circuits, currently undergoing commercial development, have,
compared with silicon circuits, higher operating frequencies, lower power
consumption, lower noise, and superior resistance to radiation damage.
Because of these superior properties, they are expected to have extensive
military and commercial applications.
2.1.2 Industries Producing and Using Selenium and Its Compounds
Elemental selenium is recovered from anode slimes as a byproduct of
electrolytic copper refining at five copper refineries. In 1988,
approximately 280 metric tons of selenium were produced and 660 metric
2-5
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tons were consumed in the United States. There was no reported domestic
production of secondary selenium; however, scrap xerographic materials
containing selenium were exported to Canada and the United Kingdom for
processing to recover selenium. The estimated consumption of selenium by
end use in 1988 is as follows: electronic and photocopier components,
43 percent; glass manufacturing, 20 percent; chemical and pigments,
20 percent; and other, including metallurgy and agriculture, 17 percent.
Almost half of the selenium produced is used by the electronics
industry. The major electronic use of elemental selenium is as a
photoreceptor in plain paper electrophotographic copiers.
The U.S. automobile and construction industries contributed to a
strong demand for selenium-containing pigments. These pigments, which
range in color from light orange to maroon, depending on the selenium
content, have good heat stability and are important colorants for
plastics, glass, and ceramics. The chief pigment produced is cadmium
red, a double salt of cadmium sulfide and cadmium selenide.
The primary use of selenium in the glass industry in 1986 was in
container glass, where it was used to decolor the yellow-green tint
imparted by ferrous ions. Also, selenium is used in architectural plate
glass, where it is used in combination with cobalt oxide and iron oxide
to reduce solar heat transmission.
The major chemical manufactured is selenic acid, which is produced
via a selenium dioxide intermediate. Selenic acid is used chiefly as an
additive to bright copper and bright chromium electroplating baths.
Lesser amounts of selenic acid are consumed to manufacture inorganic
selenate salts, which are used at trace levels as soil nutrients.
Production volumes of selenic acid and its salts are low, averaging only
a few hundred pounds per year for the past few years (King 1989).
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Research amounts of organoselenium compounds are produced using selenic
acid as a feedstock material. Selenium dioxide, the intermediate in
selenic acid production, is sold only in research quantities.
2.1.3 Processes That Generate Arsenic-Containing Wastes
Arsenic wastes generated in 1985 (USEPA 1987c) were as follows:
38,538 tons of D004, 12,571 tons of K031, 891 tons of K084, 117 tons of
K101, 278 tons of K102, 72 tons of P010, 1.4 tons of P011, 345 tons of
P012, 24 tons of P038, and 1 ton of U136. No P036 was generated in
1985. This section describes the potential generating processes for
these wastes.
As stated earlier, the largest consumption of arsenic oxide is for
the production of inorganic arsenates for use as wood preservatives. The
generalized production process involves oxidation of arsenic trioxide to
arsenic acid and then reaction of the arsenic acid with an oxide or
carbonate metal salt. The product precipitates from solution, is
collected by filtration, and then is washed, dried, and packaged.
Subsequent treatment of wastewaters from these processes generates
nonwastewaters containing metal arsenates. Furthermore, use of arsenate
salts for wood impregnation results in process sludges and wastewater
treatment residues that contain metal arsenates.
The second largest consumption of arsenic oxide is for the production
of MSMA, cacodylic acid, and similar compounds for use as pesticides.
Several production processes are involved and are held proprietary. All
of them, however, generate wastewater treatment sludges containing
inorganic and organic arsenic compounds. These processes also generate
the listed waste K031, which is by-product salts that are contaminated
with arsenic compounds. Pesticide formulators using these organoarsenic
compounds also generate wastewater treatment sludges, spilled materials,
and off-specification formulations containing organoarsenic compounds.
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The two veterinary pharmaceutical facilities producing organoarsenic
compounds manufacture different products. Each uses proprietary
technology. However, both plants can generate the listed wastes K084,
K101, and K102, which consist of wastewater treatment sludges,
distillation bottoms, and spent carbon, respectively. All these wastes
can contain inorganic and organic arsenic compounds.
Production of chemicals from elemental phosphorus is a significant
source of arsenic-bearing wastes. In producing elemental phosphorus from
phosphate rock, arsenic impurities become incorporated as elemental
arsenic in the product. One metric ton of phosphorus typically contains
about 0.3 kilogram of arsenic. Conversion of the phosphorus to other
products such as foodgrade phosphoric acid, phosphorus trichloride, or
phosphorus pentasulfide generates solid and liquid wastes containing
either arsenic chlorides or arsenic sulfides. The phosphorous segment of
the inorganic chemicals industry generates product purification sludges
and distillation bottoms containing arsenic sulfides and arsenic
trichloride, respectively.
2.1.4 Processes That Generate Selenium-Containing Wastes
The chief use of selenium is in the electronics industry, where it is
incorporated into individual electronic components. The selenium is
melted and cast into desired shapes, machined, and further processed.
Wastes from these operations consist of fines, scrap, and
off-specification materials that have a high selenium content. Most of
these wastes are reprocessed either onsite or offsite.
The production of cadmium red pigment generates wastewater treatment
sludges that contain cadmium, zinc, and selenium. These are generally
sold to reclaimers to recover metal values.
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Selenic acid is used chiefly as an additive to bright copper and
bright chromium electroplating formulations. Thus, selenium may appear
as a constituent in wastewater treatment sludges generated by the metal
finishing industries.
Other selenium chemicals (selenic acid, etc.) are produced only in
small quantities at three facilities. While the Agency does not have
process-specific information on these operations, total production is
only a few hundred pounds per year (King 1989). Thus, the amounts of
selenium-bearing wastes produced are likely to be small. According to
the Biennial Report in 1985, only 765 tons of D010 and 0.001 ton of U204
were generated (USEPA 1987c). No generation is reported for P103, P114,
or U205 wastes. Likewise, no selenium-bearing wastes were reported from
any of the three production facilities manufacturing selenic acid and its
derivatives (USEPA 1988g).
2.2 Waste Characterization
The Agency examined data in the 1986 TSDR Survey, the Generator
Survey, EPA reports, and literature sources regarding those facilities
that generate and manage wastes containing arsenic and selenium.
Characterization data available to the Agency for the arsenic and
selenium wastes are summarized below.
2.2.1 Arsenic
The characterization data in Table 2-2 are from the 1986 Generator
Survey and are for D004 single streams. Any D004 streams listed in
combination with other wastes were not used to characterize D004 wastes
because it cannot be determined whether the proportion of D004 is so
small that the mixed stream is no longer representative of D004 wastes.
2-9
2990g
-------
Table 2-2 Characterization Data for D004 Characteristic Arsenic Wastes
PHYSICAL WASTE
DESCRIPTION
WASTE DESCRIPTION
INDUSTRIAL DESCRIPTION
SOURCE OF WASTE GENERATION
SOLIDS WATER
QUANTITY (%) |%)
ARSENIC
CONTENT
Aqueous Inorganic tqulds Scrubber water
Leachate
Wastewater or aqueous mixture
Aqueous waste wlm low other toxic organic*
ContamlnaMo *oB
Inorganic fquld*
I
I—'
o
Inorganic stodge*
Inorganic »^jflu»
Sol contaminated with Inofgarnc* only
Sol contamlnaMd with Inorganic* only
Sol oorflarnfrialed with organic*
Contaminated sou or dMnup residue
Contan*iated sot! or cleanup residue
Other Inorganic sludge
Other Inorganic sludge
Other horganfc liquid
Oner knrganlc liquid
Ottwc InofQAnlc Ikfuld
Other horgante sludge
COm Inorganic liquid
aher horganfc sludge
Other Inorganic liquid
SpM MM with maun
Other Inorganic liquid
Other InorQflnlc liquid
Omar Inorganic toUi
CttMr reactrve sais/cherrfcab
Other Inorganic soUl
Oner Inorganic loMt
OttwrhorganlctoMa
Other Inorganic tcMt
Other torganfc solds
Oner Inorganic solds
aher mewl talta'chemlcals
Oher Inorganic aoldi
Spent eolld filters or adiort>enta
Spent solid Allen or adsorbents
Other Inorganic aoldB
Spent ulld (Mere or adsorbents
Metal scale, flings or scrap
Other Inorganic solds
Other Inorganic soUs
aher Inorganic soUs
Spent solid niters or adsorbents
aher Inorganic totds
Other Inorganic solds
Other Inorganic solds
Qher Inorganic solds
Other Inorganic solds
aher Inorganic sludge
Metal scaMlngs or scrap
Spent solid filters or adsoibents
Spent solid Niters or adsorbents
aher waste iwrganfc chemicals
Other Inorganic solids
aher waste Inorganic chemicals
aher Inorganic solids
Other Inorganic solds
aher waste Inorganic chemicals
Spent solid litters or adsorbents
Industrial Inorganic chemicals, nee
Noncommercial research organizations
Semiconductors and related devices
Semiconductors and related devices
Agrtculural chemicals, nee
DK
Radio and TV oonvnunlCeUlon xyjlpfntnt. Aircraft
Swnloonductofei and ralatad dtvlcM
Wood praMrvfng -
Aflrtcuturfll the9fflicilit IMC
Agrtculural chwncate. n«e
Electronic computing equtoment
IndustfW InotQeVtlc chwnlcslv* iwc
(ndustfial fnofgAnlc ch0.1%
MOppm
10-IOOppm
10-IOOppm
MOppm
0.1-tppm
100-SOOppm
MOppm
10-IOOppm
MOppm
10-IOOppm
P
0.1-1%
0.1-1%
. 0.1-lppm
MOppm
DK
• 10-IOOppm
P
DK
30,
DK
1
0
0
17
87 .
NP
15
20
NA
P
0
NA
DK
1 >
0'
0
0
0-
1
OK
10
0
NA
0
0
0
NA
0
0
0
0
0
:""'~" 1
OK
OK
10-IOOppm
100-SOOppm
0.1-tppm
0.1-1%
0.1-1%
DK
1-10%
0.1-1%
P
1-10%
MOppm
0.1-1%
P
0.1-1%
P
MOppm
MOppm
100-SOOppm
P
DK
1-10%
P
1-10%
P
10-25%
1-10%
1-10%
100-SOOppm
10-IOOppm
. 0.1-1%
SOOppm-0.1%
Ippb-O.tppm
r 'r""-i
-------
Table 2-2 (continued)
t\3
i
PHYSICAL WASTE
DESCRIPTION
Inorganic soOds(conl.)
Lab packs
Organic Hqukfe
Organic soldi
WASTE DESCRPTION
Other horpanlc solds
O)m mat salts/ chemfcaJs
Other horgardc sold*
Other horganfc coUs
Other horganfc solds
GUier horganfc toUs
Other horganfc solos
dhor Inorganic soM§
Other horganfc soUs
Metal teals, flings or scrap
DK
Spent soDd flam or adsorbents
Otfw horganfc squid
Lab partis of old chemicals only
Let) packs of old ctiernicals only
Lab packs at ok) chemical* only
Mbed lab packs
Lab packs of old chemkflli only
Other horganlc liquid
Other horganfc liquid
Omsr Inorganic solds
Lab packs of debris only
ahsr Inorganic solas
Lab pack* or oW chemicals only
Other aqueous waste wMi low dissolved colds
Other horganfc liquid
Empty or crushed metal drums or containers
Other horganfc solds
Mbed lab packs
Mbod lab packs
Lab packs of debris only
Utud lab packs
Lab packs of old chemicals only
Other organic flquld
Other organic IkjuU
alter organic liquid
Waste 08
Other organic liquid
Waste oO
Waste oU
Waste or)
Nonhalogenated sotvert
Other nonhatogenated organic sold
Other nonhatogenatad organic sold
Other habgenated organic sold
Spent carbon
Other nonhatogenated organic sold
Other nonhabgenated organic sold
MDUSTRML DESCRFTION
Serrtoonductors and related devices
Serrsoonductors and related device*
Semiconductors and related devices
Osnemnlmluii and related devlcee
Seiistiunductors and related devices
Serrtonductort and related devices
Semiconductors and related devices
3psce vehicle squtament. nee
Special warehousing and storage
Plating and pcttNng. Semiconductors and related devices
Wood pmMVRiQ
Wood praMfvtnQ
Agrtcutural chemicals, nee
Colleges and urdverarUe*
CoDegee and universities, nee
CoDegee and universities, nee
Colleges and universities, nee
Colleges and urdversMes, nee
Colleges and universities, nee
OK
Eloctrontc oonyonxiH, noc
Eupbslves
General government, nee
Industrial Inorganic chemicals, nee
Industrial Inorganic chemicals, nee
Material security. Ammunition, except tor smd arms, nee
Ordnance and accessories, nee
Pressed and Mown glass, nee
Semiconductors and related devices
Semiconductors and related devices
Surgical and medical Instruments
Agnculrursl chemicals, nee
Agrtcutural chemicals, nee
DK
Electronic computing equipment. Semiconductors
Nitrogenous fertilizers
Semiconductors and related devices
Semiconductors and related devices
Semiconductors and related devices
Chemical products, nee
Chemical products, nee
Industrial organic chemfcab. nee
Industrial organic chemteais, nee
Industrial organic chemfcate. nee
Surface active agents
SOURCE Of WASTE GENERATION
Other one-time procen
Other waste production process
Closure d procesi equipment
Clean out of procesjc efjutpfneni
nescttorViynthesis media pfocsssInQ
Other nmte pfoducdon process
Surface coating
FUtrattontoentrluglng
Tanli botjoms removal
Lsborstory wastee
Laburatury wastes
Discarding of out-ol-date products or chemicals
Discarding d off-spec material
Laboratory waste*
Laboratory waste*
Laboratory wastes
Discarding of out-of-date products or chemicals
Laboratory wastes
Laboratory wastes
Discarding of out-of-date products or chemicals
Laboratory wastes
Laboratory waste*
Discarding of contaminated cleanup equbment
Laboratory wastes
Other one-time process
Clean out ol process equipment
Laboratory wastes
Discarding ol out-of-date products or cherrtadi
Wastewater treatment
Discarding of off-spec material
Clean out ol process equbment
By-product processing
Other waste production process
Clean out ol process equbment
Clean out ol process equipment
Rush rinsing
Other dean out or closure process
Other dean out Of closure process
Other waste production process
Clean out of process equipment
Discarding of contamlnaled cleanup aqutormnt
Other processes
QUANTITY
IT
IT
IT
ST
IT
48 Q
20
ST
16 T
1 497.8660
3T
OK
210 Q
SO
SO
IT
IT
DK
220 Q
IT
180 Q
IT
275 Q
72 Q
1Q
10 Q
20 T
IT
1MQ
10
ST
IT
IT
6.612.000 Q
37.600 Q
0
0
134.000 Q
ST
215 Q
550
110Q
11T
IT
1SST
3T
IT
102 Q
SOLOS
w
00
NA
00
NA
00
100
00
00
OS
so
00
DK
88
DK
OK
DK
NA
NA
S
P
00
00
00
DK
0
P
OS
NA
20
DK
DK
00
NA
0.02
1
1
NA
1
0
DK
OK
0.1
100
43
85
60
NA
DK
WATER
0)
0
NA
NA
NA
OK
NA
0
0
S
DK
0
OK
10
OK
DK
DK
NA
NA
OS
00
1
NA
OK
DK
OK
SO
S
NA
NA
DK
DK
0
0
00
09
0
NA
S
0
0
DK
SO
0
67
S
40
NA
DK
ARSENC
CONTENT
1-10%
1ppt>O.1ppm
0.1-1W
0.1-1%
DK
SOOppnX>.1%
10-100ppm
0.1-1ppm
DK
P
10-25%
>00%
1-10%
25-50%
10-25%
25-60%
P
50-75%
DK
S00ppn>0.1%
75-90%
1-10%
25-50%
OK
DK
1-10%
0.1-1%
>00%
DK
DK
SOOppnvO.1%
DK
50-75%
1pptX>.1ppm
10-IOOppm
1-10%
1-IOppm
10-IOOppm
1-tOppm
1-IOppm
DK
500ppm-0.1%
25-50%
0.1-1%
10-IOOppm
DK
10-IOOppm
P
DK-DONTKNOW
Q. GALLONS
NA. NOT AVAILABLE
NP. NOT PRESENT
P-PRESENT
T.TONS
Source: USEPA 1989b.
-------
The data show D004 wastes divided into eight categories: aqueous
inorganic liquids, contaminated soil, inorganic liquids, inorganic
sludges, inorganic solids, lab packs, organic liquids, and organic
solids. The inorganic liquids category accounts for 85 percent of the
D004 wastes, the organic liquids category accounts for 12 percent of the
D004 wastes, the inorganic solids category accounts for 2 percent of the
D004 wastes, and all the remaining categories are 1 percent of the D004
wastes generated in 1986.
For the purposes of BDAT, wastewaters are defined as wastes
containing less than 1 percent TOC and less than 1 percent TSS. All
other wastes are defined as nonwastewaters. According to the data, the
arsenic concentration in D004 wastewaters ranges from 1 ppb to 1,000 ppm.
For D004 arsenic nonwastewaters, the highest concentrations of
arsenic are 75 to 90 percent generated from the "discarding of out of
date products or chemicals" and greater than 90 percent for "laboratory
wastes." Both of these types of wastes are generated in small volumes
(i.e., approximately 30 tons per year). The wood preserving industry
generates an inorganic solid from a filtration/centrifuging process that
also contains greater than 90 percent arsenic. The volume of this waste
stream is unknown. The semiconductor industry generates inorganic
nonwastewaters with a total concentration of 10 to 25 percent arsenic,
and the chemical products industry generates an organic solid
nonwastewater containing 25 to 50 percent arsenic. The D004 wastes from
the semiconductor industry also have high arsenic concentrations;
however, most D004 nonwastewaters appear to contain 1 to 10 percent
arsenic.
Table 2-3 presents characterization data for K031. This waste,
generally a nonwastewater, contains up to 18 percent arsenic and various
organic constituents.
2-12
2990g
-------
Table 2-3 Waste Characterization Data for K031
Constituents (ppn)
(1)
(2)
Data sources
(3)
(4)
(5)
(6)
(7)
BOAT List Organics:
Methylene chloride
14
11
BDAT List Metals:
Arsenic
Barium
Cadmium
Chromium
10.000
6.300
0.5
4.6
26
15.000.
180.000
1.000.-10.000
Others:
Ash content
Baron
Bicarbonate
Cacodylate contaminants
Calcium
Carbonate
COD
MSHA (as arsenic)
Nitrate
Sodium chloride
Sodium sulfate
Solids
Solid content (X)
Water content (X)
0.02
1.800
116
3.920
0.06
400.000.-600.000
400.000.-600.000
920.000.-980.000
10.500
5.000.-14.000
10.000.-15.000
18.500
400.000.-500.000
400.000.-500.000
300.000.
950.000.-990.000
95
5
Sources:
(1) MSHA and cacodylic acid waste (Environ 1985).
(2) MSMA salt cake (Environ 1985).
(3) MSHA acid waste (Environ 1985).
(4) Solid waste that is a mixture of sodium chloride and sodiura sulfate generated during cacodylic acid production (Environ 1985).
(5) K031 acidifier (USEPA 1988f).
(6) K031 tank bottoms (USEPA 1988f).
(7) Reported arsenic content for 1.759.841 tons of K031 (USEPA 1989a).
-------
Table 2-4 summarizes the available characterization data for K084.
The data show that K084 wastes are nonwastewaters containing up to
16 percent total organic carbon and up to 25 percent arsenic.
The characterization data for K101 and K102 are located in Table 2-5.
Waste K101 can contain up to 19 percent 2-nitroaniline and up to
2,000 ppm of arsenic. Waste K102 can contain up to 900 ppm 2-nitrophenol
and up to 8,500 ppm arsenic. Both K101 and K102 are generated as
nonwaste- waters.
The only available data for P and U wastes containing arsenic listing
constituents are shown in Table 2-6. Characterization data are presented
for P010, P011, and P012. Most of these waste sources are described as
"laboratory wastes" or "discarding of out-of-date products/chemicals."
They are nonwastewaters and can contain up to 50 percent arsenic. The
wastes are generated in relatively small volumes (i.e., less than 50 tons
in 1985).
2.2.2 Selenium
The data in Table 2-7 show D010 as wastewater and nonwastewater
forms. The wastewaters contain up to 500 ppm of selenium, and the
nonwastewaters contain up to 25 percent selenium. The table shows that
approximately 99 percent of D010 waste generated in 1986 contains
98 percent water and up to 10 ppm selenium and is generated by one
generator from the petroleum refining industry. No data are available to
characterize any of the P and U wastes containing selenium listing
constituents.
2.3 Determination of Waste Treatabilitv Group
EPA believes that wastes with different waste codes produced in
similar processes in an industry or in similar industries can be treated,
2-14
2990g
-------
Table 2-4 Waste Characterization Data for K084
Constituents (ppm)
BOAT List Organ ics:
1 . 1-Oichloroethene
1.1. 2-Tr ichloroethene
Phenol
4-Nitrophenol
BOAT List Metals:
Arsenic
Others:
Arsenic acid (as arsenic)
COD
pH
Sulfate
Sodiun arsenates (as arsenic)
Sod inn
Solids (X)
TOC
Water (X)
(1)
1.400
70
240
342
45,200
-
9.700
-
641
-
-
-
12.900
74.1
(2)
400
900
360
258
47.400
-
65.500
-
5.220
-
-
-
75.300
73.8
(3)
680
760
570
20.020
9.760
-
109.000
-
6.080
-
-
-
156.000
76.5
Data sources
(«) (4) (5) (5) (5) (5) (5)
_
_
_ - _
- - - -
10. 000. -70. 000 1-10X 1-10X 10-25X 10-25X 10-100
<3.500 - - -
_
6-8 ___-._
160. 000. -200. 000 - - - -
80. 000. -100. 000 - - - -
300.000 - 30 28 28 33 15
50 50 70 72 72 67 85
Sources:
(1) USEPA 1987a (K084 calcium precipitate).
(2) USEPA 1987a (K084 manganese precipitate).
(3) USEPA 1987a (K084 iron precipitate).
(4) Environ 1985.
(5) USEPA 1989a.
- No data available.
-------
2991g
Table 2-5 Waste Characterization Data for K101 and K102
Constituents (ppm)
Untreated K101 waste
concentration
ranges
Untreated K102 waste
concentration
ranges
BOAT List Volatile Organics
Acetone
Toluene
Total Xylenes
<50 - 81
<25 - 42
ND
NO
5.4 - 26
<1.5 - 5.3
BDAT List Semivolatile Organics
Bis(2-ethylhexyl)phthalate
Phenol
<36,000 - <38.000
ND
<19.4 - <194
<19.4 - <194
BDAT List Metals
Antimony
Arsenic
Barium
Beryllium
Cadnium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
<3.3 - 7.4
590 - 1.950
3.5 - 108
<0.1
<5.0
2.0 - 22
128-289
<0.5 - 6.7
1.5 - 4.2
1.8 - 5.4
<0.5
<0.7 - 1.6
<5.0
<0.4 - 1.7
35 - 111
8.960 - 18.800
3.060 - 8.320
16 - 52
<0.10 - 0.20
8.9 - 26
16 - 22
4.7 - 6.6
1.6 - 25.9
<0.1 - 3.5
<1.1 - 13
9.1 - 17
<0.7
<1.0 - 2.1
<0.40 - 0.58
3.1 - 8.7
BDAT List Inorganics
Cyanide
Fluoride
Sulfide
<0.67
7.74
65.6 - 778
3.21 - 5.06
4.35
4.250 - 8,150
Other Analyses
2-Nitroaniline
2-Nitrophenol
Chlorides
Sulfate
Total solids
Total organic carbon
<172,000 - 191.000
ND
9,960 - 38.700
5,690 - 11,800
604,000 - 804.000
254.900 - 407.400
ND
220-870
336 - 7.080
37 - 338
333.000 - 395.000
163.100 - 216.500
ND - Not detected.
Source: USEPA 1988a.
2-16
-------
Table 2-6 Waste Characterization for P010. P011, and P012 Wastes
RCRA
waste codes
P010
D004.D007.P011
0002. 0004, P011
D002.9.P011.P098
D001.2.4.7.P011
P012
Waste description
Contaminated soil or cleanup residue
Other untreated waste
Other inorganic liquid
Contaminated soil or cleanup
Other inorganic sludge
Metal-cyanide salts/chemicals
Mixed lab packs
Other F/K wastes, as described
Waste source
Cleanout of process equipment
Physical scraping
Laboratory wastes
Tank bottoms removal
F i Itrat ion/centr if ug ing
Discarding of off-spec chemicals
Laboratory wastes
Discarding of out-of-date products/chemicals
Solids
X
DK
99
0
70
80
99
100
99
Water
X
DK
0
0
30
20
1
0
0
Arsenic
content
500 ppm
0.1-1 ppm
50-75X
1-10X
1-10X
10-25X
25-50X
25-50X
1986
quant i ty
generated
1.010 G
250 G
1 G
1 T
26 T
1 T
1 T
1 T
Source: USEPA 1989a.
DK = Don't know
G = Gallons
T = Tons
-------
Table 2-7 Characterization Data for D010 Characteristic Selenium Wastes
WASTE CATEGORY
Aquaoua Inorganic IquUa
hoc guito A|uUi
kwgantoaludgaa
(norgmtowU*
Labpaeka
WASTE DESCRIPTION
Wutwitar of aquaoua mhtum
AquaouamttawMikNriolrarta
Omar tergal*) Iquld
Spar* add Bttimalali
Untnatad paring akidgt wthoul cyankkw
MaUd aeak».Mnga.or acrap
Otntf wutv nofQwito cnffflbuB
Omar Inorganic aofcfc
Otter malalaati/charnlcafc
Olliar horaankj adds
Ottwr nwm iUi/dMnikali
Cancantntad olMpw or dko*nM pradUd
Ijb p«k« o« oU dwmlodi ortjr
Ub pack* ol oU chwntalt only
OUorknrartefcnJri
MDU8TRUL DESCRPTION
Ctoclionlr oompuiiij «|u^KMnl
BUst knncoH and «*•! mlk.P*lrelium and ootf product!
PMrehun mlnfeig
Hflfdww, MO
Ptauno, VHJ poHNnQ,MootfOivo oofnpoMnis, noo
Pu-fcjiluMn j^fljiLm
rvwoMuni rennn0
SpooUwarahoiKhainditorag*. n*o
Scmloontfuoton «nd ralu>d dcvtoM
Nubral toouity. low* cwunh and toolinobgy
Hirdmre. noe^Whg «nd pobMng
Coating, «ognivtng.tnd ilM Mraton
Chwnlcal pnpwitlofiai MO
PUstloi nm»tak and nMta
cwolionlo OOIT^UWIQ •o^u^rnafli
Cotegta and unlMnMaa, MO
Colinn and unhcnMa*. nao
SOURCE OF WASTE GENERATION
ElaolioplrtnB
Quaneh oooUng
Oxidation (ottiaf than ooncjuatlon)
cMotfOplnng
ElaGlfDplBvng
Waitawalar traatmam
Otrnt pohMon control or m«to taatmant prooMa
DbeaRfcig ol ofl-tpao matarW
Othar otoanou or otoaura praoaai
Tank bottom* removal
Pnyateal (craptnoXrwrioval
MaMitak handing
Matwtobhandtog
Dbcanlng of out-ol-dala praduoii or ohamfcab
Lflboratofy wastaa
Lataoialonr uratiaa
QUANTITY
2Q
381J01T
229.3SOT
26.000 O
4250 a
27 .489 Q
443.6000
IT
IT
55O
4T
ST
13T
IT
0
IT
SOLIDS
<*)
OK
1
0
DK
90
11
00
(»
DK
M
100
M
100
89
OK
p
WATER
<*)
•5
M
M
OK
10
77
DK
0
OK
20
0
1
0.5
0
OK
aa
SELENIUM
CONTENT
0.1-1%
1-10ppm
MOppm
10-100ppm
MOppm
MOppm
P
P
P
0.1-1%
P
MOppm
MOppm
P
10-25%
im.
-------
in some cases, to similar concentrations using the same technologies. In
these instances, the Agency may combine the codes into a single
treatability group.
The arsenic and selenium wastes discussed in this document all
contain either arsenic or selenium as the primary hazardous constituent.
They are combined for determination of treatability groups because the
arsenic and selenium in wastes generally exhibit positive valence states
and have similar chemical behavior. They both show little tendency to
exist as solitary cationic species in aqueous solutions and typically
exist in aqueous conditions as oxo-anions (e.g., arsenic appears
primarily as anionic arsenite (AsO,~ ) or arsenate (AsO,~ )).
This behavior is important in that selection and performance of treatment
technologies for other metals are based primarily on the cationic
behavior of the metals in aqueous conditions. Thus, treatment
technologies for wastes containing arsenic and selenium are different
when compared with wastes containing only other metal constituents.
To support the selection of just one treatability group, EPA
performed a careful review of the generators of the various arsenic- and
selenium-bearing wastes and available waste characterization data. Based
on this review, the Agency has determined that the nonwastewater forms of
wastes D004, D010, K031, K084, K101, K102, P010, P011, P012, P036, P038,
P103, P114, U136, U204, and U205, all of which contain arsenic or
selenium compounds, have a very limited number of stable nonleachable
nonwastewater residuals, and hence similar types of treatment trains are
required to manage these wastes.
The same analysis applies to wastewater forms of all the arsenic- and
selenium-containing wastes, where, again, similar technologies must be
employed to remove the arsenic or selenium, resulting in stable insoluble
arsenic- or selenium-bearing residuals precipitated from the wastewater
stream.
2-19
2990g
-------
3. APPLICABLE AND DEMONSTRATED TREATMENT TECHNOLOGIES
This section identifies the treatment technologies that are
applicable to the treatment of arsenic and selenium-containing wastes and
determines which of the applicable technologies may be considered
demonstrated for the purpose of establishing BDAT.
To be applicable, a technology must be theoretically usable to treat
the waste in question or to treat a waste that is similar in terms of the
parameters that affect treatment selection. (For detailed descriptions
of the technologies applicable to these wastes, or for wastes judged to
be similar, see EPA's Treatment Technology Background Document (USEPA
1988e) and Appendix A of this document.) To be demonstrated, the
technology must be employed in full-scale operation for the treatment of
the waste in question or a similar waste.
3.1 Applicable Treatment Technologies
The previous section presents characterization data for the arsenic
and selenium wastes of concern. The data show that the wastes can be in
wastewater or nonwastewater forms and may or may not contain high levels
of organic compounds. The data also show that arsenic may be present in
concentrations greater than 90 percent and that selenium may be present
at levels as high as 25 percent. The physical and chemical properties
for each waste determine which treatment technologies are likely to be
applicable. Technologies that are considered applicable for the
treatment of organics are those that destroy or remove the organic
constituents. For treatment of the arsenic or selenium, and other
metals, those technologies considered applicable are those that reduce
leaching or remove the metals.
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Information on treatment of the arsenic and selenium wastes has been
obtained from the TSDR Survey, the Generator Survey, literature sources,
telephone interviews with generators and treaters of hazardous wastes,
and a limited number of site visits.
3.1.1 Applicable Technologies for Nonwastevaters
For the purposes of determining BOAT, nonwastewaters are defined as
wastes containing greater than 1 percent total organic carbon (TOC)
and/or greater than 1 percent total suspended solids (TSS). There are
basically five applicable treatment technologies for arsenic and selenium
nonwastewaters; these technologies are described in the following
paragraphs. It should be noted that each of these technologies may not
be applicable to all types of arsenic wastes.
(1) Incineration. Incineration is an applicable technology for
treatment of arsenic and selenium wastes containing organic compounds.
The technology converts the organics present in the wastes to carbon
dioxide and water. One complication encountered when treating arsenic or
selenium wastes is the formation of arsenic trioxide or selenium dioxide,
which have low sublimation temperatures (i.e., 193°C and 315°C,
respectively) (Weast 1978) and consequently volatilize as created. For
this reason, incinerators treating these wastes should be equipped with
air pollution control devices (e.g., wet scrubbers) to remove the arsenic
or selenium compounds from the off-gases before these gases may be vented
to the atmosphere. Individual types of incinerators are discussed in the
Treatment Technology Background Document (USEPA 1988e).
Only one facility is known currently to incinerate arsenic-containing
wastes. Such wastes accepted are normally blended with other wastes to
reduce arsenic levels in the feed material. Scrubbing of vent gases is
used to control air emission (American NuKEM 1990). Incineration is
applicable only to organoarsenic wastes.
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(2) Stabilization. Stabilization processes involve mixing of the
waste with stabilizing agents such as asphalts or pozzolanic materials
(lime, kiln dust, cement, etc.) and water. The mixture undergoes
reaction and sets into a hard solid material. The particles of waste
present are thus incorporated into the solid matrix. Stabilization is
discussed in detail in the Treatment Technology Background Document
(USEPA 1988e). Stabilization is effective only with insoluble inorganic
compounds such as ferric arsenate.
(3) Vitrification. Glass vitrification and slag vitrification are
high-temperature stabilization technologies that are applicable for
treatment of arsenic- and selenium-containing wastes. These technologies
are described in more detail in Appendix A.
Glass vitrification is a process wherein the waste is blended at
fairly low concentrations (a few percent) into a mixture of lime, soda
ash, silica, and other ingredients normally used for glassmaking. The
blended waste and glass constituent mixture is then fed to a glassmaking
furnace. Material is normally introduced near the top of the furnace and
descends to the surface of a pool of molten glass maintained at 1100 to
1200°C. At these temperatures, organic constituents of the waste are
combusted, and inorganic constituents dissolve into the glass melt.
Molten glass is withdrawn from the base of the furnace and cooled into
chunks or blocks. The waste inorganic constituents become physically and
chemically incorporated into the glass matrix. Depending on combustion
efficiencies in the glass furnace, and the type and concentration of any
organic constituents present, afterburners may be needed to combust
organics present in the vent gases from the vitrification furnaces.
Glassmaking furnaces are normally designed so that vapors of more
volatile constituents (such as arsenic oxide) condense in the cooler roof
sections of the furnace and fall back as solids into the glass melts
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where they undergo chemical reactions leading to glass formation.
Additionally, glassmaking furnaces are normally equipped with air
emissions control systems to minimize emissions of volatilized
materials. Process vent gases are normally passed through baghouses and
wet scrubbers in series to remove entrained particulates and vapors prior
to release to the atmosphere. The collected baghouse dusts and scrubber
blowdowns can be collected and recycled to the vitrification process.
Slag vitrification is very similar to glass vitrification and
involves the addition of the arsenic or selenium waste into molten slag
using basically the same type of furnace used in glass vitrification.
The arsenic or selenium undergoes chemical reactions with the molten slag
constituents to form complex silico compounds. Cooling of the slag
generates a solid mass containing the complex materials in a form that
resists leaching of the arsenic and selenium.
(4) Recycle and recovery. Recycling technologies are potentially
applicable to most concentrated selenium and arsenic wastes. Recycling
technologies for selenium recovery depend on the form of the selenium and
can range from simple wet mechanical removal of selenium followed by
filtration to chemical processes that convert the selenium compounds to
elemental selenium. During these chemical processes, the waste is
treated with an alkaline solution containing an oxidizing agent, such as
hydrogen peroxide. The selenium is oxidized, forming a sodium selenite
solution. The sodium selenite solution is then filtered. The filtrate
(liquid) is treated with a reducing agent (sulfur dioxide). Elemental
selenium precipitates, is recovered by filtration, and then is washed,
dried, and reused (Elkin 1978).
In theory, arsenic oxide could be recovered as a result of the use of
incineration processes. Since the arsenic oxide has a low sublimation
temperature (193°C), it could be recovered as it volatilizes.
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However, arsenic is not as valuable a commodity as selenium, and thus
there is little economic incentive to attempt to recycle arsenic-bearing
waste.
(5) Chemical precipitation. Chemical precipitation, although
applicable to some nonwastewaters, is generally conducted in aqueous
solutions and is primarily used to treat wastewaters. Hence, the
technology is discussed in the wastewater section.
3.1.2 Applicable Technologies for Wastewaters
For the purposes of determining BDAT, the Agency defines wastewaters
as wastes containing less than 1 percent total organic carbon (TOC) and
less than 1 percent total suspended solids (TSS). Chemical precipitation,
ion exchange, and carbon adsorption technologies are applicable for
treating selenium and arsenic wastewaters. These technologies are
discussed separately in the following sections.
(1) Chemical precipitation. Chemical precipitation is a
technology that removes dissolved metals from solution. The choice of
precipitating agent used is generally dictated by the cost of chemicals
and process conditions. However, consideration should also be given to
the stability of the nonwastewater residual (i.e., precipitate) before
choosing the precipitating agent. Stability results for several
precipitates are discussed in Section 3. Lime, manganese, ferric, and
sulfide precipitation are all applicable precipitating agents for
treatment of arsenic wastewaters. Arsenic precipitation occurs only at
very high pH (i.e., 12) when lime is used to form calcium arsenate
(Bhattacharyya et al. 1981). Hydroxide precipitation of arsenic cannot
be achieved at any pH. When manganese sulfate is added, manganese
arsenate is precipitated from solution.
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Sulfide is applicable for treatment of arsenic in the form of
arsenates but relatively ineffective for arsenites at pH 7 (Patterson
1985). Normally, sulfide precipitation is conducted under neutral or
alkaline conditions to precipitate most metals. However, the sulfides of
arsenic (As2S- and As^S,-) are insoluble in an acid medium, but
they become rapidly soluble at pH levels above 8. Consequently, this
process requires the precipitation to be conducted under highly acidic
conditions. The wastewater must first be acidified to a pH of 3.9 or
less. Hydrogen sulfide is then added to the solution or slurry. Arsenic
sulfides precipitate and are collected by filtration; the wastewater or
slurry can then be treated for sulfide removal and neutralization.
Another chemical precipitation process for treatment of arsenic
wastewaters is ferric coprecipitation. Generally, ferric coprecipitation
of arsenic requires the use of at least a fivefold excess of ferric salt
above the stoichiometric amount that would be required for ferric
precipitation. During the coprecipitation process, the wastewater is
first mixed with a solution of a ferric salt (e.g., ferric chloride or
ferric sulfate). The pH is adjusted to about 5.0. A ferric hydroxide
floe precipitates; this floe also contains some solid ferric arsenate.
After the initial precipitation, the pH is raised to about 8.0 by the
addition of alkaline agents such as lime, soda ash, or caustic. The
residual ferric salts in the solution then precipitate as ferric
hydroxide. The solids (ferric arsenate and ferric hydroxide) are then
removed from the solution by clarification and filtration.
Ferric coprecipitation is effective for arsenic in the form of
arsenate salts or for arsenic forms that can be converted to inorganic
arsenate salts. Therefore, before the process is used, all arsenic forms
should be converted to the pentavalent (arsenate) state. Chemical
oxidation will convert trivalent arsenic (arsenite) and other lower
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valence state arsenic compounds into arsenates. Several types of
oxidants, such as hydrogen peroxide, alkaline permanganate solutions, and
solutions of sodium hypochlorite, are useful for these purposes.
Permanganates have the disadvantage of generating large amounts of
manganese oxide sludge, requiring additional treatment.
Selenium may be contained in several chemical forms in wastes.
Elemental selenium can be removed with filtration or settling since it is
insoluble in water. Oxidized forms of selenium (selenium dioxide,
seleneous and selenic acids, and their salts) are generally soluble in
water, but can be precipitated as elemental selenium by reducing the
oxidized forms with a reducing agent such as sulfur dioxide. A pH of
less than 3.0 is normally used to achieve rapid reaction. Iron
coprecipitation is capable of above 80 percent selenium removal, with the
efficiency increasing with decreasing pH (Patterson 1985). Selenates and
selenites become adsorbed onto the ferric hydroxide precipitate formed
and are removed from solution. The sulfur dioxide reduction process is
similar, with respect to operating conditions, to the sulfite or sulfur
dioxide process for reduction of chromates discussed in the Treatment
Technology Background Document (USEPA 1988e). Selenite and selenate
salts may also be reduced to elemental selenium with hydrogen sulfide at
a pH below 2.0 (ASARCO 1990).
(2) Ion exchange. In the ion exchange process, wastewater
containing low levels of ionic selenium (e.g., selenides, selenates, or
selenites) or ionic arsenic wastes (e.g., arsenites, arsenates, or
organoarsenic acids) is passed through an anionic exchange resin bed.
Negatively charged selenium ions or arsenic ions replace chloride or
other negative ions in the bed and are thus removed from the solution.
The resultant wastewater is then either discharged or subjected to
additional treatment. Periodically, the resin column is removed from
service and regenerated. The regeneration process generates a
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concentrated solution containing selenium or arsenic compounds, which
requires additional treatment. Ion exchange is described in greater
detail in the Treatment Technology Background Document (USEPA 1988e).
(3) Carbon adsorption. Carbon adsorption may also be used to
remove low levels of dissolved selenium or arsenic compounds from
wastewaters. Unlike ion exchange, this process is also applicable to
nonionic compounds containing selenium or arsenic. Here, the wastewater
is passed through a bed of activated carbon. Selenium or arsenic compound
molecules or ions adsorb onto the carbon particles and thus are removed
from the solution. The treated wastewater may then be either discharged
or further treated to remove other toxic species. Periodically, the
carbon adsorption columns are removed from service and the spent carbon
is replaced. The spent carbon is normally regenerated by thermal
processes. When selenium or arsenic wastes are regenerated, a release of
volatile arsenic or selenium compounds could result; thus, an air
emissions control system should be employed. Carbon adsorption is
discussed in greater detail in the Treatment Technology Background
Document (USEPA 1988e).
3.2 Demonstrated Treatment Technologies
The information in the following paragraphs has been gathered by
review of the 1986 TSDR Survey, the Generator Survey, data submitted to
the Agency, and data in literature sources. The sources are listed in
the reference section and can be found in the Administrative Record for
this background document.
3.2.1 Demonstrated Technologies for Nonwastewaters
At present, the most widely used method of disposal for arsenic
nonwastewaters is landfilling at hazardous waste landfills. Currently,
most nonwastewaters containing high concentrations of selenium are
reprocessed onsite or offsite to recover metal values.
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(1) Incineration. The Agency believes chat incineration is
demonstrated to treat organic wastes containing arsenic or selenium
because the Agency has identified at least one facility incinerating
arsenic wastes and one facility incinerating selenium wastes. Generally,
incineration is used to treat low-level arsenic and selenium wastes.
Incineration of high-level (i.e., greater than 1 percent) arsenic-bearing
or selenium-bearing wastes is not commonly practiced because of the need
for special air emission control systems on incinerators. However, most
commercial incineration facilities have the capability to blend high-
level arsenic wastes with other wastes to meet their fitu, chlorine, metal
emissions, particulate emissions, and other requirements.
EPA believes that the technology to remove high concentrations of
arsenic or selenium from incineration off-gases is demonstrated because
smelters are currently removing such concentrations from flue gases.
Copper smelters that process ores containing arsenic and sulfur, and that
produce sulfuric acid from the sulfur dioxide-rich smelter flue gases,
generally cool the flue gases to below 120°C. At this temperature,
arsenic oxide condenses as a solid dust. The arsenic oxide dust is
collected in baghouses, and the gases are further cleaned by wet
scrubbing prior to use in sulfuric acid production. The baghouse and the
scrubber blowdown contain arsenic oxide. Presently, commercial waste
treatment incinerators are not equipped with this type of two-stage vent
gas treatment system, but they could be so equipped in the future to
effectively remove volatile metals from off-gases.
(2) Stabilization. Stabilization is demonstrated to treat both
arsenic and selenium wastes because the Agency has identified several
facilities treating such wastes. The Agency knows of at least one
facility using a proprietary cement/silicate mixture to stabilize D004
wastes. A second facility has been identified using a proprietary
stabilization process for treatment of arsenic wastes (Solidiwaste
Technology 1990). A third facility has been identified which uses a
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combination of chemical treatments and stabilization to treat a variety
of arsenic-containing wastes (American NuKEM 1990). The Agency, however,
also has data developed during an effort to stabilize K031 wastes with
pozzolanic materials, which show that wastes containing organoarsenates
cannot readily be stabilized (USEPA 1988f). The Agency has also
identified an additional facility which has stabilized selenium-
containing wastes (Hazardous Waste Treatment Council 1989).
(3) Vitrification. EPA has identified one facility performing
pilot-scale vitrification tests on slags containing up to 24 percent
arsenic. The Agency believes this to be a similar matrix to arsenic
wastes of concern based on the high arsenic concentration. In addition,
the Agency has identified a second facility, which has been evaluating
the vitrification process for management of arsenic sulfide-containing
wastes and has submitted data to the Agency (Rhone-Poulenc 1990).
Consequently, EPA believes that vitrification is demonstrated to treat
arsenic wastes. Because of the similarities in chemical behavior between
arsenic and selenium, EPA believes that vitrification is also
demonstrated to treat selenium wastes.
In addition, commercial plate glass typically contains about
0.3 percent arsenic. Arsenic oxide has been used for years as a fining
agent to remove tiny, dispersed air bubbles and also as a decolorant for
glass. Selenium has also been used as an additive to glass at
concentrations less than 0.3 percent to impart a red coloration to the
glass. In the normal glassmaking process, the arsenic and/or selenium
are blended with the other constituents prior to introduction into the
glassmaking furnace. Glassmaking furnaces are designed to minimize any
arsenic or selenium emissions. EPA believes that some glass formulations
may be similar to some arsenic and selenium nonwastewaters with regard to
either the arsenic or selenium concentrations. The Agency also believes
that the vitrification treatment technology is essentially the same as
that used in glass manufacturing.
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(4) Recycle/Recovery. Recycle/recovery is not currently
demonstrated for treatment of arsenic-bearing nonwastewaters. The Agency
is aware of a copper smelter in Canada that is reviewing the idea of
accepting wastes generated by the wood preserving industry, processing
the waste materials in the smelter, and recovering arsenic trioxide from
the flue gases. The recovered arsenic trioxide would then be sold to
produce the arsenic acid used in the production of wood preservatives.
Furthermore, the Agency has identified one producer of wood preservatives
using arsenic-bearing lead smelter flue dusts containing about 50 percent
arsenic to produce arsenic acid.
Selenium is generally recovered from "anode slimes" containing
approximately 15 percent selenium. Anode slimes refer to the residual
material collected from the bottom of the electrolytic cells during the
refining of copper. Conventional anode slime treatment processes usually
remove copper first, then recover precious metals in the form of an
alloy. Selenium is considered an impurity and is collected as a
by-product. While the recoveries of copper, gold, and silver are about
97 percent, recovery of selenium seldom exceeds 80 percent. Selenium
tends to oxidize and volatilize at fairly low temperatures; consequently,
its evolution during all heat treatment steps distributes this element
over much of the process. In the selenium recovery step, sulfur dioxide
and sulfuric acid are added to the selenium slurry. Elemental selenium
precipitates and is recovered by filtration (Osseo-Asare and Miler 1982).
Because the economic incentive is greater, most of the elemental
selenium present at high concentrations in waste from the photocopying
and electronics industries is currently recycled. Scrap xerographic
materials containing selenium have been exported to Canada and the United
Kingdom for processing to recover selenium. An estimated 200 tons of
selenium metal refined from scrap was imported in 1987. EPA believes
that some D010 wastes resemble the anode slimes and scrap xerographic
materials; therefore, the Agency believes recovery to be demonstrated for
selenium nonwastewaters.
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3.2.2 Demonstrated Technologies for Wastewaters
(1) Chemical precipitation. Chemical precipitation has been
demonstrated for D004 wastewaters containing up to 1,700 ppm arsenic by
the veterinary pharmaceuticals segment of the arsenic chemicals industry
at a facility in Charles City, Iowa (USEPA 1987b). The facility uses a
three-stage precipitation system in which most of the arsenic is removed
from wastewaters as calcium and manganese arsenates. Precipitation with
excess iron salts to form a precipitate containing ferric oxides and
ferric arsenate is used as the final treatment step. Hence, the Agency
believes precipitation to be demonstrated to treat arsenic wastewaters.
Much of the work involving ferric precipitation has been done by the
mining industry to develop methods for treatment of arsenic-bearing
residuals generated by the mining and smelting of arsenic-bearing ores.
The one-stage process of using ferric precipitation alone to remove
arsenic from wastewaters is currently in full-scale use at two Canadian
gold mining operations and hence is demonstrated to treat wastewaters
containing arsenic.
The sulfide precipitation of arsenic is used for wastewater and
product treatment in the phosphorous chemicals segment of the inorganic
chemicals industry and hence is demonstrated to treat wastewaters
containing arsenic.
Chemical precipitation to reduce soluble selenates and selenites to
insoluble elemental selenium is an integral part of the process for the
manufacture of selenium from copper refinery by-products (Elkin 1978) .
The Agency believes the aqueous selenium-containing solution generated by
copper refineries to be more difficult to treat than the D010 selenium
wastewaters because the selenium concentration is expected to be greater
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in the copper refineries aqueous solutions (i.e., approximately 50,000
mg/1) than in the wastewaters (Osseo-Asare and Miler 1982).
Additionally, the Agency knows of one facility using ferrous ions to
precipitate selenium from wastewaters. Therefore, chemical precipitation
is demonstrated to treat selenium wastewaters.
(2) Ion exchange. The Agency has identified at least one facility
using ion exchange to treat D004 wastewaters and therefore believes that
ion exchange is demonstrated to treat arsenic-bearing wastewaters.
Because of the similarity in chemical properties between arsenic and
selenium, the Agency believes that ion exchange is also demonstrated for
selenium.
(3) Carbon adsorption. The Agency has identified at least one
facility using carbon adsorption to treat D004 wastewaters and
consequently believes that it is demonstrated to treat arsenic-bearing
wastewaters. Because of the similarity in chemical properties between
arsenic and selenium, the Agency believes that carbon adsorption is also
demonstrated for selenium.
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4. PERFORMANCE DATA
This section presents the data available to EPA on the performance of
demonstrated technologies in treating the listed wastes. These data are
used elsewhere in this document for determining which technologies
represent BOAT (Section 4), for selecting constituents to be regulated
(Section 5), and for developing treatment standards (Section 6). Eligible
data, in addition to full-scale demonstration data, may include data
developed at research facilities or obtained through other applications at
less than full-scale operation, as long as the technology is demonstrated
in full-scale operation for a similar waste or wastes as defined in
Section 2.
Performance data, to the extent that they are available to EPA,
include the untreated and treated waste concentrations for a given
constituent, values of operating parameters for the treatment technology
that were measured at the time the waste was being treated, the values of
relevant design parameters for the treatment technology, and data on
waste characteristics that affect performance of the treatment technology.
Where data are not available on the treatment of the specific wastes
of concern, the Agency may elect to transfer data on the treatment of a
similar waste or wastes, using a demonstrated technology. To transfer
data from another waste category, EPA must find that the wastes covered
by this background document are no more difficult to treat (based on the
waste characteristics that affect performance of the demonstrated
treatment technology) than the treated wastes from which performance data
are being transferred.
4.1 Performance Data for Nonvastewaters
The Agency reviewed data from literature sources, data generated from
EPA treatment testing, and data submitted to the Agency by industry to
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develop the treatment performance data base for arsenic and selenium
wastes. Some of the industry data were submitted as confidential
business information (CBI). This information could not be presented in
this document, but it is contained in the RCRA CBI docket at EPA. The
performance data presented in the CBI submittals are consistent with the
data findings described in this section.
4.1.1 Incineration Performance Data
Performance data collected by EPA for rotary kiln incineration of
both K101 and K102 are not presented in this document, but can be found
in the best demonstrated available technology (BDAT) background document
for the K101 and K102 low arsenic subcategory (USEPA 1988d). The data
present the analytical results for samples collected during the Agency's
sampling visit at a pilot-scale incineration facility. The results
include analytical data for the untreated K101 and K102 wastes, the
treated K101 and K012 wastes (kiln ash), and the scrubber wastewater.
Performance data for K101 consist of four sample sets of treated and
untreated data. The untreated data show arsenic ranging from 590 to
1950 ppm and 2-nitroaniline in concentrations up to 191,000 ppm. The
scrubber water data show arsenic ranging from 91.7 to 504 mg/1 and
2-nitroaniline less than the detection limit of 0.05 mg/1. The ash data
show arsenic ranging from 244 to 360 ppm total concentration and 0.656 to
0.73 mg/1 in the TCLP leachate. The concentration of 2-nitroaniline is
less than the detection limit of 2.0 mg/kg in the ash residual. The
operating temperature of the kiln ranged from 1625 to 1960°F, and the
afterburner temperature ranged from 1868 to 2019°F.
The performance data for K102 consist of six sample sets of treated
and untreated data. The untreated data show arsenic ranging from 3,060
to 8,320 ppm and 2-nitrophenol ranging from 220 to 870 ppm. The scrubber
water data show arsenic ranging from 341 to 713 mg/1 and 2-nitrophenol
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less than the detection limit of 0.010 mg/1. The ash data show arsenic
ranging from 633 to 1,080 ppm total concentration and 8.69 to 38.3 mg/1
in the TCLP leachate. The concentration of 2-nitrophenol is less than
the detection limit of 1.0 mg/kg in the ash residual. The operating
temperatures of the kiln ranged from 1750 to 2000°F, and the
afterburner temperature ranged from 1868 to 2019°F.
Additional data has been provided to the Agency on incineration of
arsenic wastes, capture of the arsenic by wet scrubbing from vent gases,
subsequent conversion of the captured arsenic to ferric arsenate and
fixation of the arsenate (American NuKEM 1990). This information will be
discussed in Section 4.2.).
4.1.2 Stabilization Performance Data
The Agency has bench-scale stabilization test results for nine
different stabilizing processes. These data are shown in Table 4-1.
Each stabilizing process was performed with three different waste types
(i.e., K031, arsenic sulfide waste, smelter dust). The data show that
before stabilization, the K031 has an arsenic concentration of 533 mg/1
in the EP toxicity leachate, the arsenic sulfide has an arsenic
concentration of 41 mg/1 in the EP toxicity leachate, and the smelter
dust has an arsenic concentration of 6,450 mg/1 in the EP toxicity
leachate.
For the K031 waste, all nine processes show reductions of arsenic
present in the EP toxicity leachate, with the asphalt encapsulation
process achieving the lowest value. For the arsenic sulfide waste, the
leachate results after using cement stabilization, silicate polymer
fixation, clay stabilization, silicate fixation, and polyethylene
encapsulation show an increase of arsenic in the leachate. The urea
formaldehyde resin encapsulation process achieves the lowest arsenic
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3287g
Table 4-1 Stabilization Treatment Performance Data
for Arsenic Wastes
Treatment process
Cement stabilization
Cement stabilization
Cement stabilization
Urea formaldehyde resin
encapsulation
Urea formaldehyde resin
encapsulation
Asphalt encapsulation
Silicate polymer fixation
Clay stabilization
Cement and sod inn
silicate fixation
Silicate fixation
Lime-fly ash stabilization
Polyethylene encapsulation
Waste
type
K031
Arsenic sulf ide
Smelter dust
K031
Arsenic sulf ide
Smelter dust
K031
Arsenic sulf ide
K031
Arsenic sulfide
Smelter dust
Arsenic sulfide
Smelter dust
K031
Arsenic sulfide
Smelter dust
K031
Arsenic sulfide
K031
Arsenic sulfide
Smelter dust
K031
Arsenic sulfide
Smelter dust
K031
Arsenic sulfide
Smelter dust
K031
Arsenic sulfide
Smelter dust
K031
Arsenic sulfide
Arsenic concentration
in EP toxic itv leachate
Untreated Treated
(mg/1) (mg/1)
533
41
6450
533
41
6450
533
41
533
41
6450
41
6450
533
41
6450
533
41
533
41
6450
533
41
6450
533
41
6450
533
41
6450
533
41
102
127
8350
205
46.5
4520
42.3
115
356
5.2
1980
6.7
498
25.3
1.7
61.8
128
162
278
97
6050
74.5
27.3
3860
73.0
43.3
5900
35.8
21.9
780
139
71
Source: JBF Scientific Corp. 1978.
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concentrations in the EP toxicity leachate. In one instance, the smelter
dust shows an increase of arsenic in the EP toxicity leachate using
cement stabilization. The silicate polymer fixation process achieves the
lowest value of arsenic in the EP toxicity leachate for the smelter dust.
The design and operating parameters used to obtain the data in
Table 4-1 varied with the type of waste processed and the fixation agents
used. These are given in detail in the experimental section of that
study report (JBF Scientific Corp. 1978).
The Agency also has data on efforts made to stabilize K031 waste
containing organoarsenic compounds. These data, shown in Table 4-2,
consist of total concentration and the TCLP leachate results for BDAT
list metals present in the untreated waste. The untreated waste was
stabilized with three different binders: cement, lime/fly ash, and kiln
dust. Three separate sample results are presented for each stabilization
binder. In one instance, stabilization of the waste with cement resulted
in an increase in arsenic leachability. The binder-to-waste ratio used
was 2.8 to 1.0.
EPA has stabilization performance data for waste soils containing
organoarsenic compounds. The waste was stabilized using a mixture of
pozzolan, portland cement, and a proprietary material called Superset.
The data in Table 4-3 show the results of two different mixture
combinations. Mix A contains 31.4 percent waste soil, 2.1 percent
Superset, 28.6 percent pozzolan, 28.6 percent portland cement, and 9.3
percent water. The data for Mix A show arsenic present at 268 mg/1 in
the untreated EP toxicity leachate and at 21.2 mg/1 in the treated
leachate. Mix Z contains 52.7 percent waste soil, 1.0 percent Superset,
18.8 percent pozzolan, 8.0 percent portland cement, and 18.5 percent
water. The data for Mix Z show arsenic present in the untreated EP
toxicity leachate at 268 mg/1 and 13.0 mg/1 in the treated leachate.
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3250g
Table 4-2 Stabilization Treatment Performance Data for K031
45.
i
Stabilized
Untreated K031 waste Test f 1
Constituents
BDAT List Metals
Ant imony
Arsenic
Barium
Beryllium
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Total t
[mg/kg)
• 456
133.000
0.30
ND
375
1.3
14
151
0.17
47
3.1
ND
ND
ND
3.5
TCLP
(mg/D
18:5
5.930
0.081
ND
16
0.025
0.494
5.95
0.0022
1.79
ND
NO
ND
ND
0.217
TCLP
(mg/1)
11.9
6.535
0.5
0.003
1.9
0.12
1.1
1.8
0.0023
1.2
ND
0.02 <
0.09
0.1
0.86
waste using cement
Test 92
TCLP
(mg/1)
12.7
5.334
0.5
0.002
2
0.11
0.86
1.6
0.003
1.2
ND
0.01
0.05
0.11
0.97
Test *3
TCLP
(mg/1)'
»2
5.792
0.42
0.002
2
0.12
0.66
1.4
0.003
1.2
NO
0.01
0.08
0.1
0.68
Stabilized
Test 11
TCLP
(mg/1)
16
4,687
0.25
0.0025
1.9
0.07
ND
7
0.0003
1.4
NO
NO
0.05
0.08
2.4
waste using
Test *2
TCLP
(mg/D
16.1
4.888
0.31
0.003
1.9
0.07
ND
7.1
0.0006
1.3
ND
ND
0.05
0.09
3
lime/fly ash
Test *3
TCLP
(mg/D
16
5.713
0.37
0.002
1.9
0.07
NO
7.5
0.0009
1.3
ND
ND
0.05
0.09
8.8
Stabilized
Test 11
TCLP
(mg/1)
14.8
5.856
0.3
0.002
1.9
0.1
1
3.5
0.0013
1.1
ND
ND
0.08
0.13
1.3
waste using kiln dust
Test tt
TCLP
(mg/D
14.7
5.402
0.31
0.002
1.9
0.09
1.3
3.8
0.003
1.1
ND
ND
0.07
0.13
2.8
Test 13
TCLP
(mg/1)
14.7
5.544
0.33
0.001
1.8
0.08
1.8
3.4
0.002
1-1
ND
ND
0.08
0.12
1.9
Other Parameters
Sulfate 46.600
Chloride 211.000
Oil and grease 191
Total organic carbon (Avg.) 21.100
Operating Data
Binder-to-waste ratio
2.8 2.8 2.8
2.8 2.8
2.8
2.8
2.8 2.8
- = No data available.
ND = Not detected.
Source: USEPA 1988f.
-------
Table 4-3 Stabilization Treatment Performance Data for Proprietary Process
Arsenic concentration
Analysis
Sample
Untreated
Duplicate
Treated
Sample # 1 Duplicate
Mix A
Total composition (rag/kg)
EP-toxicity (cog/1)
TCLP leachate (mg/1)
Additive-to-waste ratio
7,880
268
9,150
263
243
21.2
50
2,140
20.9
78.0
3.3 to 1
Mix Z
Total composition (mg/kg)
EP toxicity (mg/l>
TCLP leachate (mg/1)
Additive-to-waste ratio
7,880
268
9,150
263
243
13.0
109.5
5,640
68.0
288.2
0.6 to 1
- - No data available.
Source: Price 1989.
4-7
2993g
-------
In some instances, the stabilization process may simultaneously occur
as a result of the chemical precipitation process (i.e., the precipitate
may be so insoluble that stabilization is unnecessary). The Agency also
has information on the stability of ferric arsenate precipitates prepared
under different conditions. These data are shown in Table 4-4. Three
different iron-to-arsenic weight ratios were subjected to pH values
ranging from 3.0 to 9.0. In all three cases, the data show that while
ferric arsenate is fairly insoluble at low pH values, its solubility
increases at higher pH levels. These data were obtained using a
simulated waste believed to be similar to arsenate-containing D004
wastes. The changing iron-to-arsenic ratios in the data of Table 3-4
reflect the complex nature of the solids formed in ferric arsenate
precipitation.
Other data that the Agency has received on the stabilization of
ferric arsenate containing residues are shown in Table 4-5. The wastes
treated in this study were first oxidized either chemically with
hypochlorite or thermally with incineration to ensure conversion of the
arsenic to the arsenate form. The arsenate was then converted into
ferric arsenate using a four-fold excess of ferric ion. These results
were obtained from pilot-scale incineration/chemical oxidation tests
using pure arsenic wastes. Ordinarily, the facility blends organoarsenic
compounds with other organics for incineration. For these samples, data
show TCLP levels of below 0.5 ppm for unstabilized ferric arsenate
generated from chemical or thermal treatment of arsenic containing
wastes. Table 4-5 also presents data for three other samples. These
data show TCLP leachate values from ferric arsenate precipitates
stabilized with lime. Information is also provided on alkaline leach
tests run at pH 9.5 on the lime stabilization materials. The alkaline
leachate values in all cases are higher than the acid TCLP leachates,
showing an increased solubility of arsenic in alkaline media.
Nevertheless, leachate levels of below 1.3 mg/1 were seen in all the
alkaline leachates from tests (American NuKEM 1990).
4-8
2993g
-------
Table 4-4 Effect of the pH on the Stability of
Ferric Arsenate Precipitates
Iron-to-arsenic ratio (wt %) pH
Leachate concentration^
3.89 3.0
4.0
5.0
6.0
7.0
8.0
9.0
7.63 3.0
5.0
7.0
9.0
17.1 3.0
4.0
5.0
6.0
7.0
8.0
9.0
Operating conditions
Temperature - 25 °C
Arsenic
0.095
0.080
0.27
1.13
10.3
31
67
0.08
0.27
0.11
15
<0.05
<0.05
<0.05
0.07
0.08
0.09
0.94
Iron
3.9
0.08
<0.05
0.46
6.7
16.6
39.4
2.0
0.17
0.23
2.6
1.5
0.05
<0.05
0.05
0.10
0.21
1.6
Source: Krause and Ettel 1985.
aFrom a water leach test (i.e., not EP or TCLP)
4-9
2993g
-------
Table 4-3 Chemical Treatment and Stabilization of Concentrated Arsenic Stri
Wast* code/ Haste Arsenic (ppn),
description Pretreatnent untreated wast*
Stabilization
technique*
Honwastewater residues
TCLP Alltaline
leachate leachate
(pp.) (ppm)
DOOVarsenic
•ulfide waste
chemical
oxidation
80,000
<0.5
DOOVarsenic
sulXide waste
chemical
oxidation
700.000
<0.5
DOOVarsanic
oxide waste
incineration 750,000
<0.5
DOOVspent
catalyst
chemical
oxidation
280.000
With
0.79
1.2S
P012/reagent
grade
P012/reagent
grade AS203
cbemical
oxidation
chemical
oxidation
750,000
750,000
With Use
With lime
O.SS
<0.05
0.79
0.3*
8 In stabilization experiments, the stabilized materials contained 6 to 10 percent lime with the
balance bains ferric arsenate sludge.
Alkaline leachate tests ore maintained at pfl 9.5 during the extraction and filtration
procedure.
Source: American BuKEM 1990.
4-10
2993g
-------
The data in Table 4-6 present the TCLP leachate results of three
wastewater treatment precipitates generated as a result of treating D004
wastewaters with three different precipitating agents (i.e., ferric
sulfate, calcium hydroxide, and manganese sulfate). The wastewater
performance data are presented in Table 4-7. The ferric arsenate
precipitate has an arsenic total concentration of 9,760 mg/kg and a TCLP
leachate of 0.508 mg/1; the calcium arsenate precipitate has an arsenic
total concentration of 45,200 mg/kg and a TCLP leachate of 2,200 mg/1;
and the manganese arsenate precipitate has an arsenic total concentration
of 47,400 mg/kg and a TCLP leachate of 984 mg/1.
The Agency also has data on EP toxicity test results for precipitates
of lime neutralization sludges, where lime addition is the only treatment
used to remove arsenic from wastewaters. Twenty-one sludge samples were
subjected to the EP toxicity test. The arsenic contents of the samples
ranged from 1,900 to 6,900 mg/kg, and 11 failed the test of 5.0 mg/1 in
the EP toxicity leachate for arsenic. These data are shown in Table 4-8
and were obtained from a copper smelter treating wastewaters containing
inorganic arsenic compounds. The treatment process at that facility
consists of only lime neutralization. No chemical oxidation is performed
so that the precipitates generated are a mixture of calcium arsenite and
calcium arsenate. Calcium arsenate is more soluble than ferric
arsenate. Hence, the method is less satisfactory for treatment of
arsenic wastes.
The Agency has received additional stabilization data obtained on
arsenic-contaminated soil and arsenic sulfide sludge D004 wastes using
proprietary stabilizing agents. These data are shown in Table 4-9. The
data show that with the use of proprietary reagents, some arsenic-bearing
wastes can be successfully stabilized wtihout prior conversion to ferric
arsenate (Solidiwaste Technology 1990).
4-11
2993g
-------
3250g
Table 4-6 Performance Data for the Stability of Calciun Arsenate,
Manganese Arsenate, and Ferric Arsenate Precipitates
Ferric Calciun Manganese
precipitate sludge precipitate sludge precipitate sludge
(K0841 (K0841 (K084)
Constituent (units) Total
TCLP
extract
Total
TCLP
extract
Total
TCLP
extract
BOAT List Metals (ng/kg)
Ant inony
Arsenic
Barium
Beryllium
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
68
9760
1.7
<0.1
9.4
10
37
18
0.93
5.6
0.16
<0.4
<1.0
<3.0
24
<-02
0.508
0.34
<.001
<-003
<.04
.34
<.05
.0002
<0.1
<0.01
<0.004
<0.01
<0.003
1.15
55
45201
23
<0.1
25
3.2
4.4
7.8
2.2
1.6
<0.5
<0.4
<1.0
2.9
1530
0.44
2.200
0.28
•c.OOl
5.12
1.18
.029
<.025
.0047
<0.10
<0.05
<0.004
<0.01
0.043
25.8
36
47400
9.5
<0.1
20
5.3
6.2
12
2.4
9.2
1
1.2
<1.0
2.2
2330
0.067
984
0.319
<0.001
2.64
<0.04
0.026
<0.05
0.008
<0.1
<0.02
0.049
<0.01
<0.03
20
Other Analyses (mg/kg)
TOC
COD
Total Solids (X)
TSS
pH
Ash Content (X)
Sulfate
Chloride
Moisture (X)
156000
109000
23.5
MA
NA
13.8
6080
NA
76.5
12900
9700
25.9
NA
NA
24
641
NA
74.1
75300
65500
26.2
NA
NA
19.9
5220
NA
73.8
NA = Not available.
Source: Alchowiak 1987.
4-12
-------
Table 4-7 Precipitation Treatment Performance Data for DOM Vastewaters
Sample Set fl
I
I—'
co
Calcium hydroxide precipitation
Constituents (units)
BOAT List Hetals (mq/1)
Ant imony
Arsenic
Cadmium
Lead
Mercury
Zinc
Other Analyses (mg/1)
Total solids
Total dissolved solids
Total suspended solids
Chemical oxygen demand
Total organic carbon
untreated
waste
tank 11
2.9
1.260
3.98
2.98
0.036
1.22
75.800
54.400
96
2.84
0.45
Effluent
waste from
tank tl
1.13
160
0.479
<0.05
0.026
0.061
52.700
49.800
84
1.310
392
Untreated
waste
tank 12
3.74
826
2.99
0.044
0.019
0.473
38.400
37.300
84
836
240
Effluent
waste from
tank *2
0.838
388
1.34
<0.05
0.0064
0.047
44.900
40.700
293
809
217
Manganese sulfate
Influent
<0.64
143
0.476
0.0053
0.0049
0.047
44.600
40.000
68
972
351
precipitation
Effluent
<0.64
16.3
<0.080
0.0063
0.0057
0.0059
43.000
42.700
18
972
245
Ferric sulfate
Influent
<0.64
23.4
0.259
<0.05
0.0086
0.178
42.400
41.500
151
972
245
precipitation
Effluent
<0.64
0.58
<0.08
0.012
0.00049
0.789
42.300
40.500
30
787
201
Operating Parameters
pH
4.04
12.34
10.94
12.18
12.01
7.02
7.42
3.79
-------
3250g
I
1-1
4*
Table 4-7 (continued)
Sample Set 12
Calcium hydroxide precipitation
Constituents (units)
BOAT List Metals (mq/1)
Antimony
Arsen ic
Cadmium
Lead
Mercury
Zinc
Other Analyses (mq/1)
Total solids
Total dissolved solids
Total suspended solids
Chemical oxygen demand
Total organic carbon
untreated
waste
tank f 1
1.46
960
3.08
<0.05
0.142
0.749
39.600
39.300
96
1.39
0.401
Effluent
waste from
tank fl
1.07
105
0.422
0.007
0.123
0.082
36.700
59.000
63
1.250
358
Untreated
waste
tank 12
1.09
427
1.09
0.075
0.076
1.0
11.700
11.100
334
724
221
Effluent
waste from
tank 12
<0.64
67.3
0.242
0.0077
0.047
<0.04
12.300
12.200
14
—
~
Manganese sulfate
Influent
0.7
147
0.324
<0.005
0.038
0.097
36.500
35,800
418
1.030
322
precipitation
Effluent
<0.64
10.5
<0.08
0.013
0.0069
<0.04
37.500
35.800
70
773
226
Ferric sulfate
Influent
<0.64
35.9
0.092
<0.05
0.0094
0.097
48.500
35.800
344
980
258
precipitation
Effluent
<0.64
0.247
<0.08
0.011
0.0038
0.900
35.700
36.000
83
692
186
Operating Parameters
pH
2.17
11.96
7.06
12.82
11.8
8.06
7.6
4.17
-------
I
I—•
en
Table 4-7 (continued)
Sample Set «
Calcium hydroxide precipitation
Constituents (units)
BOAT List Metals trnq/1)
Ant imony
Arsenic
Cadmium
Lead
Mercury
Zinc
Other Analyses (mq/D
Total solids
Total dissolved solids
Total suspended solids
Chemical oxygen demand
Total organic carbon
Untreated
waste
tank f 1
4.11
706
2.59
0.078
0.19
1.17
22.300
22.100
117
1.590
532
Effluent
waste from
tank 11
2.04
279
0.73
0.063
0.114
0.059
24.900
20.400
52
1.410
450
Untreated
waste
tank f 2
0.914
1.280
3.25
0.279
0.112
0.617
61.400
72.500
26
1.180
213
Effluent
waste from
tank 12
<0.64
142
0.416
<0.005
0.051
0.047
56.600
57.000
161
1.250
170
Manganese sulfate
Influent
1.09
205
0.552
<0.005
0.044
0.082
18.700
17.800
128
1.130
341
precipitation
Effluent
0.671
6.02
<0.080
<0.005
<0.026
<0.04
23.100
20.700
8
515
129
Ferric sulfate
Influent
0.695
15.0
<0.08
0.0092
0.028
0.04
21.200
21.500
97
750
145
precipitation
Effluent
<0.64
0.163
<0.08
0.014
0.017
0.699
21.400
20.900
23
442
116
Operating Parameters
pH
7.61
12.31
2.01
12.09
12.41
7.34
7.17
4.0
-------
3250g
Table 4-7 (continued)
Sample Set *4
Calcium hydroxide precipitation
Constituents (units)
BOAT List Metals (mq/D
Antimony
Arsenic
Cadmium
Lead
^ Mercury
^ Zinc
CTi
Other Analyses (mq/1)
Total solids
Total dissolved solids
Total suspended solids
Chemical oxygen demand
Total organic carbon
Untreated
waste
tank *1
3.16
399
0.977
<0.05
0.04
0.636
17.400
14.500
161
1.990
667
Effluent
waste from
tank 1 1
0.908
112
0.201
<0.05
0.016
<0.04
17.500
15.000
7
1.730
554
Untreated
waste
tank 12
1.59
1.340
2.86
0.478
0.076
0.21
62.800
62.200
48
1.190
232
Effluent
waste from
tank f 2
0.963
500
0.953
0.0064
0.058
0.04
62.000
59.100
180
932
196
Manganese sulfate
Influent
<0.64
125
0.201
0.014
0.022
0.056
36.900
37.200
184
1.230
330
precipitation
Effluent
<0.64
22.4
<0.08
<0.005
0.0041
0.051
37.200
36.500
48
1.070
233
Ferric sulfate
Influent
<0.64
26.5
<0.08
<0.02
0.011
0.05
36.800
37.400
39
992
264
precipitation
Effluent
<0.64
0.204
<0.08
<0.05
0.0023
0.712
36.400
36.500
69
823
207
Operating Parameters
PH
12.12
12.85
6.46
11.84
12.35
7.49
7.49
4.12
-------
Table 4-7 (continued)
Sample Set 15
Calciun hydroxide precipitation
Constituents (units)
BOAT List Metals (mq/1)
Ant imony
Arsenic
Cadmium
Lead
Hercury
Zinc
Other Analyses (mq/11
Total solids
Total dissolved solids
Total suspended solids
Chemical oxygen demand
Total organic carbon
Operating Parameters
pH
Untreated
waste
tank *1
3.41
717
1.5
0.197
0.139
0.974
30.100
29.800
128
940
194
6.97
Effluent
waste from
tank 11
2.26
60.5
0.134
<0.01
0.051
<0.04
27.900
28.100
193
833
225
11.86
Untreated
waste
tank f 2
0.64
1.670
3.64
0.371
3.4
0.164
84.700
83.800
178
3.250
107
1.79
Effluent
waste from
tank *2
<0.64
174
0.32
0.014
0.0027
0.07
38.200
33.800
82
982
270
12.02
Manganese sulfate
Influent
1.36
302
0.447
<0.005
0.046
0.056
42.600
41.600
423
1.050
301
11.93
precipitation
Effluent
<0.64
15.3
<0.08
<0.005
<0.02
<0.04
44.300
44.200
56
843
178
7.02
Ferric sulfate
Influent
0.698
107
0.106
<0.05
0.041
0.098
44.300
44.100
601
1.110
203
7.34
precipitation
Effluent
<0.64
0.224
<0.08
<0.025
0.00073
1.92
58.900
44.000
70
651
140
3.91
- = No analysis performed.
Source: USEPA 1987b.
-------
Table 4-8 EP-Toxicity Testing of Calcium Arsenate and
and Arsenite-Containing Precipitates
Sample
1
2
3
4
5
6
7
8
9
9M
10
11
12
13
14
15
16
17
18
19
20
Arsenic
total
concentration
(mg/kg)
4400
3500
3100
4300
3200
3300
5500
3400
3500
2700
3400
1900
3200
3300
4400
4700
4800
6900
5500
5200
6500
Arsenic
EP toxicity
leachate
(mg/D
25.4
2.6
2.6
6.0
2.0
2.7
3.4
6.5
7.7
9.6
5.2
0.2
0.3
0.4
3.9
20.5
3.0
17.6
9.5
14.6
74.5
Source: BP Minerals America 1988.
2993g
4-18
-------
Table 4-9 Stabilization of Arsenic-Contaminated
Soils and Arsenic Sulfide Sludge
Amounts utilized in stabilization mixtures (Erams)
Constituent Sample la Sample 2a Sample 3a Sample 4a
Desien Criteria Composition
1.
2.
3.
4.
5.
6.
7.
8.
Waste
Sulfuric
Ca(OH)2
acid
100.
.
-
0
100
.
-
.0
B-l reagent
Water
URRICHEM
Class C
Portland
fly ash
cement
38.
6.
67.
-
0
0
0
45
7
75
-
.0
.5
.0
100
2
-
10
64
8
100
-
.0
.0
.0
.0
.0
.0
100.
-
20.
-
41.
7.
133.
66.
0
8
7
5
3
7
TOTAL 211.0 227.5 284.0 370.0
Design Crtieria Operating Variables
Original pH of waste 7.5 7.5 7.5 1.5
Initial pH of mixb 8.0 8.0 4.5 6.0
Final pH of mix 9.0 8.5 8.0 11.0
Volume expansion0 40% 53% 100% 80%
TCLP (mg/1) 0.26 0.17 0.11 0.08
Results
Untreated waste composition
arsenic mg/1
TCLP - stabilized waste
arsenic mg/1
2,430
0.26
2,430
0.17
2,430
0.11
35,000
0.18
a Samples 1, 2, and 3 were arsenic-contaminated soil having 2,430 ppm of
arsenic in the oxide form. Sample 4 was arsenic-contaminated sludge having
35,000 ppm of arsenic in the sulfide form.
The values were measured before adding the fly ash and cement to the mix.
c The values have been adjusted based on the field experience.
Source: Solidiwaste Technology 1990.
4-19
2993s
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The Agency has also received other data on stabilization of arsenic -
contaminated soils using a number of proprietary stabilization mixtures.
The data show total arsenic present in the raw wastes and TCLP leachate
values from the stabilized solids. No TCLP values were given for the
untreated wastes. Concentrations of arsenic in the untreated wastes
range from 6.5 to 602 ppm arsenic. Levels of arsenic in the TCLP
leachates from the treated waste ranged from 0.112 to 22.2 mg/1. Ratios
of binder to waste ranged from 0.8 thru 2 to 1 (Hazardous Waste Treatment
Council 1989).
The Agency has received data on the stabilization of selenium-
containing mineral processing wastes believed to be similar to D010
wastes. These data are shown in Table 4-10. The TCLP leachate value
obtained on the untreated waste was 3.75 mg/1. Stabilization with four
different proprietary stabilization mixtures gave TCLP leachate values
ranging from 0.154 to 1.80 mg/1, showing that at least some stabilizing
agents will immobilize selenium (Hazardous Waste Treatment Council
1989). The data were obtained using different mixtures of proprietary
additives to treat the same waste.
Data on the stabilization of soil samples spiked with selenium
sulfide and selenium dioxide (U204) were also provided to the Agency.
However, these studies were laboratory-scale studies on synthetic
samples, which may differ considerably from real industrial wastes. Data
on stabilization for a single sample of pure selenium dioxide were also
provided. The TCLP value of the leachate from this sample was 30 mg/1
selenium, and the stabilizing agents were not identified.
The Agency also has data on EP toxicity test results for precipitates
of lime neutralization sludges, where lime addition is the only treatment
used to remove selenium from wastewaters. Twenty-one sludge samples were
subjected to the EP toxicity test. The selenium ranged from 10 to
329 mg/kg, and eight samples failed the test of 1.0 mg/1 in the EP
4-20
2993g
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Table 4-10 Stabilization of Selenium-Containing
Mineral Processing Waste
Parameter Value
TCLP leachate untreated waste 3.75 mg/1 selenium
TCLP leachate stabilized waste:3
Stabilized mixture #1 0.154 mg/1 selenium
Stabilized mixture #2 0.372 mg/1 selenium
Stabilized mixture #3 1.80 mg/1 selenium
Stabilized mixture #4 0.370 mg/1 selenium
a Proprietary stabilization mixtures.
Source: Hazardous Waste Treatment Council 1989.
4-21
2993g
-------
toxicity leachate for selenium. These data, shown in Table 4-11, were
obtained from copper smelter treating wastewaters containing inorganic
selenium compounds.
4.1.3 Vitrification Performance Data
The Agency has data on the slag vitrification of arsenic. Arsenic
oxide (AS20,) in flue dust was converted to calcium arsenate (Ca-(AsO,)2)
by low-temperature (i.e., 400°C) roasting of mixtures of the dust and
pelletized lime in the air. The resulting calcined mixture was dissolved
in molten iron silicate slag at temperatures up to 1290°C without
volatilization of arsenic oxides. The dissolution process was
accomplished by adding the roasted flue dust to molten slag immediately
after tapping the slag. These results show that arsenic oxide, if
converted to a nonvolatile arsenic salt (i.e., ferric or calcium
arsenate), can be successfully vitrified in slag. Calcium arsenate is
reported not to volatilize below 1,250°C (Twidwell and Mehta 1985).
The data are presented in Table 4-12. These data consist of 14 separate
data points, with arsenic concentration in the slag ranging from 0.3 to
23.5 percent and the EP toxicity leachate containing 0.007 to 1.8 mg/1
(Twidwell and Mehta 1985). A slag containing over 20 percent arsenic
will not greatly increase the volume of material land disposed because of
the higher density of the slag.
The Agency also has data on the EP toxicity testing of glass samples
prepared by the vitrification of waste in a furnace in which arsenic and
other EP-toxic metals were incorporated into the formulation used to
produce the glass. This information, provided in Table 4-13, shows that
the metals have low leachability in the glass matrix. These data consist
of five different samples that were obtained from evaluation of the glass
vitrification process. The data are for leachate results using the EP
toxicity test.
4-22
2993g
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Table 4-11 EP Toxicity Testing of Calcium Arsenate-Containing and
Calcium Selenate-Containing Precipitates
Sample
1
2
3
4
5
6
7
8
9
9M
10
11
12
13
14
15
16
17
18
19
20
Selenium
total
concentration
(mg/1)
<10
20
<10
<10
<10
<10
<10
<10
<10
<10
<10
20
28
28
24
74
18
127
182
121
329
Selenium in
EP toxicity
leachate
(mg/1)
2.44
.40
1.27
1.13
.48
.91
.87
.50
.60
.86
.45
0.04
0.20
0.20
0.90
3.00
0.84
3.04
2.20
2.19
7.57
Source: BP Minerals America 1988.
4-23
2993g
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Table 4-12 Vitrification Treatment Performance
Data for Slags Containing Arsenic
Arsenic
(wt % vitrified
in slag)
0.3
0.54
0.77
2.1
3.3
5.2
9.0
9.1
12.4
13.7
16.4
19.4
20.7
23.5
Arsenic in EP toxicity leachate
(mg/1)
0.007
0.016
0.047
0.448
0.421
0.902
0.337
0.415
0.115
0.308
0.377
0.802
0.846
1.791
Source: Twidwell and Mehta 1985.
4-24
2993g
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Table 4-13 Vitrification/Glass ification Treatment Performance Data
Sample Set 11
Total EP
composition toxicity
of glass leachate
Constituent (mg/kg) (mg/1)
Arsenic
Barium 2.500 <0.2
Chromium 7.200 <0.1
Lead - <0.02
Sample Set 12
Total EP
composition toxicity
of glass leachate
(mg/kg) (mg/1)
2.500 <0.2
7.200 <0.1
<0.02
Sample
Total
compos i t i on
of glass
(mg/kg)
1.230
2.900
0.65
Set §3
EP
toxicity
leachate
(mg/D
0.9
0.08
1.1
Sample
Total
composition
of glass
(mg/kg)
2.000
-
-
Set f 4
EP
toxicity
leachate
(mg/D
<0.2
<0.1
<0.02
Sample
Total
composition
of glass
(mg/kg)
17
3.700
11.000
-
Set 15
EP
toxicity
leachate
(mg/1)
<0.005
1.2
0.03
<0.1
r!o Source: Chapman 1989.
in
-------
Data on vitrification of D004 arsenic sulfide wastes have also been
provided to the Agency and are presented in Table 4-14. All samples of
waste vitrified were arsenic sulfide-containing purification sludges from
phosphoric acid production and contained from 2 to 3 percent arsenic
sulfide. The balance of the wastes consisted of filter aids, such as
Celite or attapulgus clay used as a filter medium. These results were
obtained from laboratory- and pilot-scale testing of a recently patented
process for vitrifying arsenic sulfide-containing wastes (Rhone-Poulenc
1990).
EPA has data for the in situ vitrification of a waste contaminated
with arsenic and organochlorine pesticides. The data show total arsenic
concentrations up to 4.4 percent in the untreated waste. The treatment
process achieves a 99.99 percent destruction removal efficiency for the
organics, and the glass produced has 0.91 mg/1 arsenic in the TCLP
leachate. The vitrification process operated at temperatures of
approximately 1200°C. The system used has air pollution control
equipment to remove any arsenic that volatilizes during treatment
(Timmons 1989). The waste treated was a mixture of K031 and other
pesticide wastes.
4.2 Performance Data for Wastewaters
The Agency performed an onsite sampling and analysis test at a
facility in Charles City, Iowa, to help develop treatment standards for
arsenic present in wastewaters. The wastewater treatment process at the
site consisted of a three-stage chemical precipitation process whereby
calcium arsenate was precipitated in the first stage, manganese arsenate
was precipitated in the second stage, and ferric arsenate was precipitated
in the third stage. The data consist of five sample sets of untreated
and treated results for each stage of the chemical precipitation process.
4-26
2993g
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Table 4-14 Vitrification Glass Samples Using Arsenic
Sulfide-Containing Sludge
Sample l.D.
EP toxicity extract
arsenic levels
(ppm)
TCLP extract
arsenic levels
(ppm)
Experimental Data:
R-P
5129
WW2
WW2, 2
WW2, 1.5
WW2, 1.0
<0.5
0.5
NA
NA
NA
NA
NA
NA
0.8
1.0
<0.5
2.5 (±
0.5)
Other Operating Parameters:
Percent of arsenic in unvitrified
waste
Volume reduction on
vitrification
2.0 to 2.5 weight percent
70 percent
NA - Not available.
Notes:
1. All samples were crushed to approximately 1/4 inch or less for
testing.
2. Method Detection Limit 0.5 ppm As.
Source: Rhone-Poulenc 1990.
4-27
2993g
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The untreated D004 wastewater generally contained concentrations up to
1,700 mg/1 of arsenic. Five samples taken of the effluent from the
ferric treatment process revealed arsenic values ranging from 0.163 to
0.580 mg/1 arsenic. These data are presented in Table 4-7.
Characterization and solubility data for the precipitates are shown in
Table 4-6.
The data in Table 4-15 show the correlation between the molar ratio
of iron to arsenic and the treatment performance of the ferric arsenate
precipitation process for arsenic removal. The data show that as the
amount of the ferric precipitating agent, in this case ferric sulfate, is
increased, more arsenic can be removed from the wastewaters. The
material studied was a simulated mining waste similar to D004.
Data on treatment of wastewaters from wet scrubbing of incinerator
vent gases to remove arsenic oxides prior to venting have also been made
available to the Agency and are shown in Table 4-16. The scrubber waters
were treated in series with chemical oxidation followed by addition of
ferric salts to precipitate ferric arsenate (American NuKEM 1990). The
data show residual arsenic levels in the treated wastewaters at or below
0.6 mg/1 in all cases. The wastes treated were D004 and P011.
The Agency has data on the use of the ferrous ion to reduce low
levels of selenate ion to selenium in wastewaters. These data consist of
five sample sets of untreated and treated results. The data are shown in
Table 4-17.
Limited information on treatment and recovery of selenium-bearing
wastewaters in the copper industry similar to D010 wastewaters have been
made available to the Agency. Selenium can be precipitated in elemental
form from solution by treatment with hydrogen sulfide at pH 2. The
products formed are elemental selenium and elemental sulfur, both of
which precipitate from solution (ASARCO 1990). The sulfur dioxide
4-28
2993g
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Table 4-15 Ferric Arsenate Precipitation Treatment
Performance Data for Different Iron-to-Arsenic Ratios
Influent arsenic Effluent arsenic
concentration concentration Molar Fe/As ratio
(mg/1) (mg/1) used in precipitation
7492
7492
7492
7492
7492
Operating conditions:
310
26
2.1
0.23
<0.05
1.0
2.0
4.0
8.0
16.0
pH - 5
Source: Krause and Ettel 1985.
4-29
2993g
-------
Table 4-16 Incineration/Scrubber Water Treatment for Arsenic
Arsenic, ppm Arsenic, mg/1 Arsenic, mg/1
input waste untreated treated
Waste code to incinerator scrubber water scrubber water
P011/D004
P011
P011/D004
D004/a
512
832
961
1200
83.7
69.6
80.0
-
0.4
0.6
0.5
<0.2
aluminum
chloride
contaminated
with arsenic
a Results of chemical oxidation/precipitation batch run.
Source: American NuKEM 1990.
4-30
2993g
-------
Table 4-17 Selenium Removal from Wastewaters
by Chemical Reduction with Ferrous Ion
Selenium concentration (ue/1)
Sample Untreated Treated
1 90
2 85
3 80
4 81
5 79
Source: Murphy 1989.
4-31
29B3g
-------
reduction process is used to recover selenium from concentrated aqueous
solutions containing selenates and selenites. For example, in the ASARCO
copper refinery in Amarillo, Texas, sulfur dioxide treatment of selenium-
containing process water is conducted at below pH 3.0. The influent
selenium levels are 80,000 mg/1 selenium as selenite and 10,000 to
20,000 mg/1 selenium as selenate. The effluent process stream contains
50 to 500 mg/1 selenium. No further treatment of this in-process stream
is used because longer retention times for the reduction reaction would
be needed to recover the additional amounts of product. This stream is
then further processed to recover other metal values such as silver (King
1990). The Agency also has received data from a commercial treatment
facility that indicates that, to comply with their wastewater discharge
permit requirements, selenium levels in the plant effluent must be kept
below 1.0 mg/1. This facility reported that the use of chemical
reduction followed by ferrite coprecipitation in series is a method for
achieving these permit requirements (American NuKEM 1990). The
discharged stream at this plant contains less than 1 mg/1 selenium. All
of these data demonstrate that selenium can be removed from waterborne
solutions down to below characteristic levels by stepwise treatment.
4-32
2993g
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5. DETERMINATION OF BEST DEMONSTRATED
AVAILABLE TECHNOLOGY (BDAT)
This section presents the Agency's rationale for determining best
demonstrated available technology (BDAT) for the various arsenic- and
selenium-containing hazardous wastes. To determine BDAT, the Agency
examines all available performance data on technologies that are
identified as demonstrated to determine whether one or more of the
technologies performs significantly better than the others. The
technology that performs best on a particular waste or waste treatability
groups is then evaluated to determine whether it is "available." To be
available, a technology must (1) be commercially available to any
generator and (2) provide "substantial" treatment of the waste, as
determined by evaluation of analytical accuracy-adjusted data. In
determining whether treatment is substantial, EPA may consider data on
the performance of a waste similar to the waste in question provided that
the similar waste is at least as difficult to treat.
5.1 Nonwastevaters
Consistent with EPA's methodology for determining BDAT as summarized
above, the Agency evaluated all the information and performance data to
determine the "best" performing technology. The demonstrated technologies
for arsenic and selenium nonwastewaters are incineration, stabilization,
and vitrification. Additionally, recycle/recovery is demonstrated for
selenium nonwastewaters.
5.1.1 Arsenic Nonwastewaters
The Agency examined the performance data for incineration, but
concluded that incineration is not "best" because it destroys only
organic contaminants, but not arsenic. The arsenic in ash or scrubber
5-1
299*8
-------
water is likely to require additional treatment. Thus, incineration
alone cannot be considered BOAT.
Next, the Agency reviewed the stabilization data and determined that
stabilization is not considered "best" for arsenic-containing wastes.
EPA made this determination because the performance data appear
inconsistent from waste to waste, possibly because the arsenite and
arsenate salts of common metals generally have relatively high
solubilities in water under alkaline conditions. For example, arsenic
pentasulfide and ferric arsenate are fairly insoluble in acidic or
neutral aqueous solutions. However, both solubilities increase
substantially at pH values above 9.0; hence, stabilization with alkaline
materials such as lime and cement alone is undesirable. As a result,
binders such as plastics may prove useful, but the Agency has data only
on a few wastes treated by these methods. Stabilization technologies
also have the disadvantage of increasing the amount of waste requiring
disposal. Binder-to-waste ratios of from 1.5 thru 3 to 1 are required.
The Agency also examined the stability of arsenic compound
precipitates and concluded that the ferric arsenate coprecipitate is the
most stable, but still leaches and may require further treatment. It
should be mentioned that when using ferric coprecipitation, the sludge
volume generated is generally larger than when using other precipitates.
Generally, ratios of iron to arsenic required for complete treatment
range from 4 thru 17 to 1, and this greatly increases the volumes of
waste requiring disposal (and may even constitute dilution rather than
treatment). Other arsenates, such as calcium arsenate, have also been
examined by the Agency as alternatives. However, these materials all
have significantly higher solubilities than that of ferric arsenate.
Furthermore, some of these salts react with carbon dioxide in the air to
form calcium carbonate and soluble arsenic compounds (Robins 1981).
5-2
2994g
-------
The vitrification process is capable of managing a wide variety of
arsenic wastes. At the temperatures at which the vitrification process
is normally operable (1100 to 1400°C), organoarsenic compounds will
be combusted to arsenic oxide, carbon dioxide, and water. The arsenic
oxide formed will react with the other glass-forming constituents and
become immobilized in the glass formed. Inorganic compounds alone or
inorganic compounds mixed with organic materials can likewise be
vitrified.
Based on the above analysis, glass or slag vitrification is
considered the "best" technology for arsenic-containing wastes.
Furthermore, treatment of arsenic using vitrification is substantial. It
has been shown that arsenic can be vitrified into slag at concentrations
of up to 24 percent arsenic and that the slag so generated will pass the
EP toxicity test for arsenic.
The Agency has identified one commercial waste vitrification facility
and has determined that the vitrification process units are currently
available for purchase. Consequently, EPA believes vitrification is
available.
The Agency also believes that treatment using vitrification achieves
reductions of hazardous constituents that are substantial and that
vitrification is commercially available. Furthermore, at least in some
cases, vitrification can result in a substantial volume reduction for the
residues being land disposed. For arsenic sulfide wastes, a 70 percent
volume reduction has been achieved with vitrification (Rhone Poulenc
1990). For all these reasons, the Agency feels that vitrification
represents BOAT for arsenic nonwastewaters.
5-3
2994g
-------
5.1.2 Selenium Nonwastewaters
The Agency also examined the available stabilization data base for
selenium-containing wastes and found that at least some of the wastes can
be stabilized. The data show reductions of selenium in the leachate of
the stabilized waste.
The Agency believes that treatment using vitrification achieves
substantial reductions of hazardous constituents and that it is
commercially available; therefore, vitrification represents BOAT for
arsenic nonwastewaters. Since selenium has chemical properties very
similar to those of arsenic, the Agency also believes that vitrification
is an available treatment technology for selenium nonwastewaters.
However, the Agency currently does not have vitrification data on any
specific selenium wastes. Therefore, the Agency feels that stabilization
is currently the only commercially proven technology for selenium wastes.
According to information available to the Agency, most nonwastewater
forms of selenium-containing wastes that have high concentrations of
selenium are currently reprocessed. However, the various recycle/recovery
technologies may not be viable for generators of wastes containing fairly
low concentrations of selenium compounds. For this reason, the Agency is
not considering recycle/recovery as BDAT for selenium. Nevertheless,
recycle and reuse are encouraged where viable.
5.2 Wastewaters
EPA has identified chemical precipitation, ion exchange, and carbon
adsorption as demonstrated to treat arsenic-containing and selenium-
containing wastewaters. However, chemical precipitation is the only
demonstrated technology for which the Agency has data.
5-4
299*8
-------
5.2.1 Arsenic Wastewaters
The Agency has no reason to believe that ion exchange or carbon
adsorption could improve the level of performance; therefore, chemical
precipitation is the "best" performing technology for wastewater forms of
arsenic-bearing wastes. Data available to the Agency indicate that iron
arsenate precipitation alone or in combination with other precipitation
methods is capable of removing arsenic from wastewaters down to well
below the characteristic concentration level (5 mg/1).
The Agency determination of substantial treatment is based on
reductions of arsenic from 1,670 mg/1 in the untreated wastewaters to
0.224 mg/1 in the treated wastewaters. EPA believes that the reductions
of hazardous constituents are substantial and that chemical precipitation
is available to treat arsenic wastewaters because it is commercially
available; therefore, chemical precipitation represents BOAT for arsenic
wastewaters.
5.2.2 Selenium Wastewaters
EPA believes chemical precipitation to be the "best" performing
technology for wastewater forms of selenium-bearing wastes. Data and
information available to the Agency indicate that wastewater forms of
selenium-containing wastes can be reduced with hydrogen sulfide or sulfur
dioxide to precipitate elemental selenium or can be precipitated with
ferrous ion. Since no data were submitted for ion exchange or carbon
adsorption, the Agency has no reason to believe that these technologies
could improve the level of performance.
The Agency's determination of substantial treatment is based on
reductions of selenium from levels that are expected to be as high as
100,000 mg/1 (King 1990) to levels of less than 1 mg/1. EPA believes
5-5
299<.g
-------
that the reductions of hazardous constituents are substantial and that
chemical precipitation is available to treat selenium wastewaters because
it is commercially available; therefore, chemical precipitation
represents BDAT for selenium wastewaters.
5-6
2994g
-------
6. SELECTION OF REGULATED CONSTITUENTS
For the characteristic wastes (i.e., D004 and D010), the Agency
cannot accurately determine all constituents that may be present in every
waste. All D004 wastes contain arsenic and all D010 wastes contain
selenium, but the wastes are diverse with respect to other constituents
that may be present, such as organics and cyanide. Therefore, the Agency
has determined that D004 will be regulated for arsenic and D010 will be
regulated for selenium.
The K101 and K102 (low-arsenic subcategory) nonwastewater treatment
standards for a number of metal and organic constituents were promulgated
as part of the First Third regulations in August 1988. BOAT for the
development of the original performance standards was incineration.
Arsenic standards were not established at that time because EPA could not
determine BOAT for the arsenic present in K101 and K102. The Agency is
proposing to develop an arsenic performance standard based on the
performance of vitrification for the nonwastewater forms of K101 and
K102. Because the vitrification process operates at temperatures of
approximately 2300°F and the incineration process used to treat K101
and K102 wastes operated at temperatures of less than 2000°F,
vitrification should result in destruction of the organics present in the
waste. However, the vitrification units may need to be equipped with
afterburners to ensure that any organic constituents are destroyed. For
this reason, the Agency feels that regulation of the same organic
constituents that were selected for regulation in August 1988 is still
valid. Other metal constituents present in the wastes will be
incorporated into the slag or glass matrix along with the arsenic.
Consequently, the Agency believes the other metals present in the K101
and K102 wastes will be controlled by the regulation of arsenic.
6-1
299Sg
-------
The wastes designated by codes K031 and K084 were originally listed
by the Agency because of their arsenic content; however, the K031 and
K084 wastes also may contain some organic compounds. The Agency has no
performance data for the thermal destruction of organics present in K031
and K084 wastes, but believes that the organics present will be combusted
at the operating temperatures of the vitrification processes. Any ash
generated will be incorporated into the glass or slag matrix, along with
the arsenic present. As a result, the Agency feels that regulation of
the arsenic alone is sufficient to ensure proper treatment of other
constituents that may be present in K031 and K084.
For all of the P and U constituents, methods to analyze the listed
compounds in treatment residuals are not currently available. Although
the Agency recognizes that these compounds exist, and that the
manufacturers may have methods to verify their purity and determine their
product specifications, there are no EFA-approved analytical procedures
to ascertain trace quantities of these chemicals in the raw sample or in
the residues from treatment. Consequently, EPA will use arsenic as a
surrogate for arsenic acid (P010), arsenic trioxide (P011), arsenic
pentoxide (P012), dichlorophenyl arsine (P036), diethyl arsine (P038),
and cacodylic acid (U136). The Agency will use selenium for a surrogate
for selenourea (P103), thallium selenite (P114), selenium dioxide (U204),
and selenium disulfide (U205). Thallium selenite (P114) is also
regulated for thallium. The development of the thallium standard is
discussed in Best Demonstrated Available Technology (BDAT) for P and U
Thallium Wastes (USEPA 1990).
6-2
2995g
-------
7. CALCULATION OF BOAT TREATMENT STANDARDS
In this section, the performance levels of the best technologies for
treatment of the arsenic and selenium wastes are calculated. For
nonwastewaters, this calculation is based on the treatment data presented
in Table 4-12 for vitrification. For wastewater, this calculation is
based on the treatment data in Table 4-15 for chemical precipitation.
For a more detailed description of how the Agency calculates treatment
standards, refer to Methodology for Developing BOAT Treatment Standards
(USEPA 1988c). Appendix B presents the analytical methods and quality
assurance/quality control (QA/QC) data used to calculate the treatment
performance standards.
7.1 Arsenic Nonwastewaters
The Agency has limited data representing TCLP leachate concentrations
from arsenic-containing residuals from vitrification of arsenic sulfide
wastes only. EPA also has performance data for vitrification of an
arsenic-containing slag and for vitrification of arsenic sulfide-
containing wastes. The slag data consist of 14 points, with one data
point showing an arsenic concentration of 23.5 percent in the vitrified
slag leachates at 1.8 mg/1 based on the EP toxicity test. The Agency
feels that the EP data represent the more difficult waste to treat since
the arsenic content (up to 23.5 percent) is much higher than that
normally encountered with arsenic sulfide sludges (2 to 2.5 percent).
EPA would expect the same level of performance to be achieved in the
residuals from vitrification of D004, K031, K084, K101, K102, P010, P011,
P012, P036, P038, and U136 because for most of these wastes the untreated
arsenic concentrations are less than 23.5 percent. In addition, the
Agency believes that the organic and organometallic bonds present in some
of these wastes will be destroyed by the high temperature at which the
vitrification processes operate.
7-1
3033S
-------
7.1.1 D004, K031, K084, P010, P011, P012, P036, P038, and U136
Nonwastevaters
For D004 nonwastewaters, EPA is promulgating the characteristic level
of 5.0 mg/1 arsenic as the treatment standard. The Agency has taken this
approach because most data indicate that treatment below the
characteristic level is achievable and because of the concern for the
resulting potential regulatory disruptions that would be created by
establishing a standard slightly higher than the characteristic level.
Furthermore, the Agency believes that persons will normally try to ensure
that their waste no longer exhibits a characteristic in order to have
less expensive subtitle 0 disposal. Also, these technologies cannot
easily be "turned off" at precisely the characteristic level.
EPA calculated the treatment standard for arsenic nonwastewaters
based on the leachate data point of 1.8 mg/1 for the matrix containing
23.6 percent arsenic. Analytical recovery data transferred from the
Agency's analysis of K102 incinerator ash (which had the appearance of a
slag) were used to adjust the value for analytical accuracy. The
adjusted value was multiplied by a variability factor of 2.8, and a
concentration-based treatment standard for arsenic of 5.6 mg/1 in the
leachate (measured by the EP toxicity test) was calculated. This
calculation is shown in Table 7-1.
The Agency is transferring the concentration-based treatment standard
of 5.6 mg/1 in the EP toxicity leachate arsenic to K031, K084, P010,
P011, P012, P036, P038, and U136 nonwastewaters, primarily because of the
similarities in total arsenic concentrations anticipated in these wastes
when compared to the 23.5 percent total arsenic that was vitrified (i.e.,
the basis of the 5.6 mg/1 standard). For example, waste characterization
data indicate total arsenic concentrations of 0.1 to 18 percent for K031
and 10 to 25 percent for K084, with theoretical arsenic content in the U
and P wastes ranging from approximately 25 percent total arsenic in P036
7-2
3033g
-------
Table 7-1 Calculation of Treatawnt Standards for Arsenic
Average Treatoent
treated standard
AccuracT-corrected concentration waste Variability (ms/1)
Seaple Saaple Saople Sample Ssaple concentration factor (average
BDAT constituent Set #1 Set *2 Set #3 Set #4 Set *5 (s«/l) (VP) z VF)
BonwBBtewater
Arsenic 2.0 - - - - 2.0 2.8 5.6
EP leachate (s«/l)
Hastewater
Arsenic (n»/l) O.S80 0.247 0.163 0.204 0.224 0.284 2.78 0.70
- - Bo data available.
7-3
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to a maximum of 75 percent in P011. While some of these U and P wastes
may contain percent levels of arsenic greater than the amount in the
untreated waste used to develop the treatment standard (i.e., 23.5
percent), the Agency believes that the arsenic contents in these wastes
are similar enough to transfer this standard. In addition, for such
wastes, the Agency believes that more glass-forming reagents can be added
to the molten slag/waste mixture during the vitrification process in
order to achieve the promulgated treatment standard. Based on EPA's
analysis of additional vitrification data, the Agency believes that the
performance of the vitrification technology and analytic variability of
treatment residues will not change significantly for different
arsenic-containing wastes; thus, this transfer is legitimate.
Since the vitrification performance data that EPA used to develop the
nonwastewater treatment standards for arsenic were EP toxicity leachate
data, the Agency has based the nonwastewater standards on the arsenic
concentration in the EP leachate. However, since the Agency has some
information that appears to indicate that the TCLP test is more
aggressive than the EP test for determining arsenic leachability, the
Agency is establishing that if a waste does not achieve the arsenic
nonwastewater standard based on analysis of a TCLP extract but achieves
the standard based on analysis of an EP extract, the waste is considered
to be in compliance with the arsenic nonwastewater standard. Thus, a
facility can use the TCLP test to demonstrate compliance for D004, K031,
K084, K101, K102, P010, P011, P012, P036, P038, and U136 nonwastewaters.
The Agency is aware that some arsenic wastes are generated at
concentrations greater than 90 percent total arsenic. To treat these
wastes, the Agency believes that more glass-forming reagents could be
added to the molten slag/waste mixture and that the same treatment
performance could be achieved by the vitrification process.
7-4
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7.1.2 K101 and K102 Nonwastewaters
The Agency is changing the nonwastewater standards for K101 and K102
promulgated on August 17, 1988, by eliminating the low- and high-level
arsenic subcategories and by establishing a concentration-based
treatment standard for arsenic of 5.6 mg/1 in the EP leachate. This
standard is based on the performance of vitrification.
The organics performance standards based on the detection limits will
not change. The Agency believes that the organic constituents present in
these wastes would be destroyed to nondetectable levels by the high
temperatures at which vitrification processes operate (temperatures
comparable to those of incineration).
7.2 Arsenic Wastevaters
7.2.1 D004 Arsenic Vastewaters
The Agency has data on precipitation of arsenic using lime followed
by manganese and ferric sulfate in a three-stage alkaline process from
wastewaters identified as D004 by the veterinary pharmaceutical industry.
The Agency believes that these data represent a matrix that is very
difficult to treat since it consists of a mixture of organic and
inorganic compounds, including organoarsenicals and inorganic arsenic
compounds in concentrations up to 1,600 ppm. According to these data,
concentrations of arsenic in the treated wastewaters are as low as
0.16 mg/1.
Some arsenic wastewaters, such as those from wood preserving
operations, may require more extensive treatment trains in order to treat
hexavalent chromium, other metals, and organics, which could possibly
interfere with the treatment of the arsenic. A reduction step for
7-5
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hexavalent chromium and an oxidation step (with reagents such as hydrogen
peroxide or hypochlorite) may be necessary to treat the organics. In
addition, complexed organometallies that may be present will probably
have to be oxidized or otherwise removed prior to conversion of the
metals to their proper valence state for further metal treatment by
precipitation. Hexafluoroarsenates also are known to present treatment
problems in that they are not readily converted into ferric arsenate.
These more complex inorganic forms of arsenic occur in the wastewaters of
at least one fluorine production facility. As a result, there appear to
be some types of D004 wastewaters that may present more difficult
treatment problems than wastewaters from the veterinary Pharmaceuticals
industry.
The veterinary pharmaceutical data available to EPA show that a
treatment standard of 0.79 mg/1 is achievable for D004 wastewaters.
However, EPA recognizes the diversity of wastes that qualify as hazardous
under the D004 classification. Because of this diversity, EPA has chosen
to regulate D004 wastewaters at 5.0 mg/1. This numerical value
represents the level at which the wastewaters are defined by EPA
according to 40 CFR 261.3 as hazardous. Information and data available
to the Agency indicate that even the most difficult to treat D004 wastes
can be treated to this level, a level below which the wastewaters will be
rendered nonhazardous.
7.2.2 K031, K084, P010, P011, P012, P036, P038, and U136 Wastewaters
EPA believes that the data collected for D004 wastewaters generated
by the veterinary Pharmaceuticals industry represent data on a waste that
is more difficult to treat than wastewater forms of K031, K084, P010,
P011, P012, P036, P038, and U136 for the reasons stated below. These
wastes are typically generated as nonwastewaters. Therefore, wastewater
forms of these wastes are expected to be generated from accidental
7-6
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spills, leachate collection, or the treatment process itself. It is
expected that these untreated K, U, and P wastewaters generally will be
more dilute than the untreated D004 wastewaters from veterinary
Pharmaceuticals plants tested by the Agency. None of these wastes are
expected to contain more difficult to treat ions such as
hexafluoroarsenates.
Based on the performance data for precipitation of D004 wastewaters,
the Agency has calculated a concentration-based treatment standard of
0.79 mg/1 for arsenic. The calculation of the treatment standard is
shown in Table 7-1 using accuracy-corrected data. The Agency is
transferring the treatment performance for precipitation of D004 to K031,
K084, P010, P011, P012, P036, P038, and U136 wastewaters. This is a
reasonable approach given that (1) the D004 wastewater that was tested by
the Agency contained organoarsenicals similar in structure to those
contained in K031, K084, P036, P038, and U136; (2) the D004 wastewater
also contained inorganic arsenic compounds similar to those contained in
K031, K084, P010, P011, and P012; (3) the untreated wastewater forms of
these wastes are expected to be more dilute than the untreated D004
wastewater; and (4) the performance data demonstrate that the arsenic in
the D004 wastewater can effectively be removed.
7.2.3 K101 and K102 Vastewaters
The treatment standards for K101 and K102 wastewaters were
promulgated on August 17, 1988 (53 FR 31170). These standards were based
on the same D004 wastewater treatment data used to establish arsenic
standards for other K, U, and P wastes. In the process of reevaluating
the D004 wastewater treatment data, to determine their applicability for
other arsenic wastewaters, the Agency found an error in the operation of
the system used to develop standards for the metal constituents in K101
and K102 wastewaters. The Agency determined that the sand and gravel
7-7
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filter was not properly operated based on an increase in the average
total suspended solids (TSS) content from 55 to 64 mg/1. Therefore, the
Agency is amending the wastewater standards for the metal constituents
(arsenic, cadmium, lead, and mercury) in K101 and K102. The new
treatment standards are 0.79 mg/1 for arsenic, 0.24 mg/1 for cadmium,
0.17 mg/1 for lead, and 0.082 mg/1 for mercury. These new standards are
based on the same chemical precipitation process used to calculate the
standards on August 17, 1988 (53 FR 31170), but using a different point
in the process. That is, the data representing the wastewater before the
wastewater flows through the sand and gravel filter are used instead of
the data representing the wastewater contents after filtration.
Calculation of the new metals treatment standards is shown in Table 7-2
at the end of the section. The Agency, however, is not changing the
standards for the organics present in K101 and K102 wastewaters since
these data are based on treatment using a resin adsorption technology
located after the filtration unit.
7.3 Selenium Nonwastewaters D010. P103. P114. U204. and U205
The Agency has no treatment performance data for vitrification of
selenium nonwastewaters. However, the Agency does have data on the
stabilization of selenium nonwastewaters. The BOAT treatment standards
for D010, P103, P114, U204, and U205 nonwastewaters were determined using
the data from Table 4-10 and adjusting for accuracy using a recovery
factor of 85 percent and multiplying the corrected average value of
0.796 mg/1 by a variability factor of 7.15. This calculation, shown in
Table 7-3, yielded a treatment standard of 5.70 mg/1 in the TCLP leachate
for D010, P103, P114, U204, and U205 nonwastewaters. This standard was
transferred to the U and P code wastes because the Agency believes wastes
containing low levels (i.e., below 1,000 ppm) of selenium are most
representative of wastes requiring stabilization and not recovery.
Because this treatment standard (5.7 mg/1 based on TCLP leachate) is
7-8
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Table 7-2 Calculation of Hetal Treatment Performance Standards
for K101 and K102 Haatewaters
Accuracy-corrected concentration
BOAT constituent
Arsenic
Cadnitzo
Laud
Mercury
Sonple
Sat #1
0.580
0.085
0.060
0.00052
Sample
Set *2
0.247
0.08S
0.060
0.00*
Sonple
Set f 3
0.183
0.085
0.060
0.018
Saople Sanple
Set #4 Set #5
0.204 0.224
0.085 0.085
0.060 0.060
0.0024 0.0077
Average
treated
vast* Variability
concentration factor
(•g/1) (VF)
0.284 2.78
0.085 2.8
0.060 2.8
0.0065 12.6
Treatment
standard
(«*/!)
(average
z VF)
0.79
0.24
0.17
0.082
Table 7-3 Calculation of Treatment Standards for Seleniw Banwastewaters
Accuracr-corrected concentration
SoBDle SesDle Sonpls Sonpla
BOAT constituent Sat 41 Sat #2 Sat 43 Set #4
Average Traatavnt
treated standaxa
waste Variability (•*/!)
concentration factor (overage
(a«/l) (VF) x VF)
Seleniun
0.182 0.440 2.124 0.437
0.796
7.15
5.70
"The data in Table 4-10 were corrected using a spike recovery factor of 85 percent.
Expressed as ••»«••• for any single grab sample in TCLF laachate (•«/!).
7-9
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above the level of leachable selenium that defines the waste as D010
(1.0 mg/1 based on TCLP toxicity), wastes that are generated at a level
between 5.7 mg/1 based on TCLP leachate and 1.0 mg/1 based on TCLP
toxicity would meet the treatment standards, but are still considered
hazardous wastes. Therefore, they must be land disposed in a Subtitle C
facility.
7.4 Selenium Wastewaters D010. P103. P114. U204. and U205
The Agency has limited treatment performance data for chemical
precipitation of selenium wastewaters believed to be more difficult to
treat than D010 because of their high selenium concentrations. EPA
recognizes the diversity of wastes that qualify as hazardous under the
D010 classification; consequently, EPA has chosen to regulate D010
wastewaters at 1.0 mg/1. These numerical values represent the levels at
which D010 wastes are defined by EPA as hazardous according to
40 CFR 261.3. EPA believes even the most difficult to treat D010 wastes
can be treated to this level.
Because the Agency believes these data represent treatment of the
most difficult to treat selenium wastewaters, the Agency is transferring
the treatment performance of chemical precipitation of the high-
concentration selenium wastewater to the treatment performance of P103,
P114, U204, and U205 wastewaters.
7-10
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-------
8. REFERENCES
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Engineering, on analytical data for familiarization samples for
Fermenta and Salsburg. June 25, 1989.
American NuKEM. 1990. Letter submission of data on arsenic treatment to
U.S. Environmental Protection Agency. February 1990. Comment Nos.
LD1200044 and LD12L0031.
Anderson, C. 1984. A survey of roasting techniques to volatilize
arsenic and antimony for copper smelter flue dust. A thesis submitted
to the Department of Metallurgy and Mineral Processing Engineering at
Montana College of Mineral Science and Technology in partial
fulfillment of the requirements for the degree of Master of Science in
Metallurgical Engineering. Montana College of Mineral Science and
Technology, Butte, Montana.
Arratia, J. 1985. Optimization of lime roasting-segregation treatment
of flue dust. A thesis submitted to the Department of Metallurgy and
Mineral Processing Engineering at Montana College of Mineral Science
and Technology in partial fulfillment of the requirements for the
degree of Master of Science in Metallurgical Engineering. Montana
College of Mineral Science and Technology, Butte, Montana.
ASARCO. 1990. Letter submission of data on selenium to U.S.
Environmental Protection Agency. January 1990.
Bhattacharyya, Jumawan, and Grieves. 1979. Separation of toxic heavy
metals by sulfide precipitation. Separation Science and Technology
14(5): 441-452.
Bhattacharyya, Jumanwan, Sun, Sund-Hagelburg and Schwitzgebel. 1981.
Precipitation of heavy metals with sodium sulfide: bench-scale and
full-scale experimental results. Chemical Engineering Progress
77:31-37.
Bhattacharyya, Sund-Hagelburg, Schwitzgebel, Blythe, and Craig. 1980.
Removal of heavy metals, arsenic, and fluoride from smelter effluents
by sulfide-lime precipitation. Proceedings: Industrial Waste
Symposium at Las Vegas, Nevada.
Blaskovich, S. 1982. Elemental distribution of lime-roasted lead
smelter speiss in a copper matte-slag system. A thesis submitted to
the Department of Metallurgy and Mineral Processing Engineering at
Montana College of Mineral Science and Technology in partial
fulfillment of the requirements for the degree of Master of Science in
Metallurgical Engineering. Montana College of Mineral Science and
Technology, Butte, Montana.
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BP Minerals America. 1988. Letter of submission of data for the Magna,
Utah, Bingham Canyon copper smelter to U.S. Environmental Protection
Agency, December 7, 1988.
Chapman, C. 1989. Letter submission of data on glass vitrification from
Battelle Northwest Laboratories to U.S. Environmental Protection
Agency, April 1989.
Comba, P. 1987. Removal of arsenic from process and wastewater
solutions. A thesis submitted to the Department of Metallurgy and
Mineral Processing Engineering at Montana College of Mineral Science
and Technology in partial fulfillment of the requirements for the
degree of Master of Science in Metallurgical Engineering. Montana
College of Mineral Science and Technology, Butte, Montana.
Elkin, E.M. 1978. Selenium. In Kirk-Othmer encyclopedia of chemical
technology, Vol. 20, pp. 575-601. New York: John Wiley Interscience.
Environ Corp. 1985. Characterization of waste streams listed in 40 CFR
Section 261, waste profiles. Prepared for Characterization and
Assessment Division, U.S. Environmental Protection Agency, by Environ
Corp., Washington, D.C.
Freeman, H. 1985. Innovative thermal hazardous organic waste processes.
Park Ridge, New Jersey: Noyes Data Corp.
Ghosh, M.M. 1987. Adsorption of inorganic arsenic and organoarsenicals
on hydrons oxides. In Metals specialization, separation, and recovery,
eds. J.W. Patterson and R. Passeno, pp. 499-526. Chelsea, Mich. Lewis
Publishing Company.
Hazardous Waste Treatment Council. 1989. Data submission on
stabilization of wastes to U.S. Environmental Protection Agency.
December 22, 1989. Comment No. LD1200050.
JBF Scientific Corp. 1978. Stabilization, testing and disposal of
arsenic containing wastes. Contract no. 68-03-2503, final report for
Municipal Environmental Research Laboratory, Office of Research and
Development. Cincinnati, Ohio: U.S. Environmental Protection Agency.
King, M., ASARCO, Inc. 1989. Letter to E. Rissmann on production
volumes of selenium compounds. June 16, 1989.
King, M., ASARCO, Inc. 1990. Telephone conversation with E. Rissmann on
production of selenium. February 8, 1990.
Kirk Othmer. 1979. Encyclopedia of chemical technology. 3rd ed.
New York: Wiley.
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Krause, E., and Ettel, V.A. 1985. Ferric arsenate compounds: Are they
environmentally safe? Solubilities of basic ferric arsenates. Paper
presented at the 15th Annual Hydrometallurgical Meeting of the Canadian
Institute of Mining, Vancouver, Canada, August 18-22, 1985.
Loebenstein, R. 1989. Mineral commodity summaries. McGraw-Hill
encyclopedia of science and technology. New York: McGraw-Hill Book
Company.
McGraw-Hill. 1982. McGraw-Hill encyclopedia of science and technology.
New York: McGraw-Hill Book Company.
Mellor, J.W. 1946. A comprehensive treatise on inorganic and
theoretical chemistry, Vol. 10, pp. 697-700. London, UK: Longmans
Green.
Munehori, M., Aurio, T., and Inowe, Y. 1979. Simultaneous removal of
hazardous metals from wastewaters and disposal of the resulting
sludge. Paper presented before the Division of Environmental
Chemistry, American Chemical Society, Honolulu, Hawaii, April 1-6, 1979.
Murphy, A.P. 1989. Ferrous ion reduction of selenate to selenium.
Journal of the Water Pollution Control Federation 61(3):361-362.
Oppelt, Blaney, and Kemer, eds. Performance and costs of alternatives
to land disposal of hazardous waste. Presented at an APCA International
Specialty Conference.
Osseo-Asare, K., and Miler, J.D. 1982. Hydrometallurgy research,
development and plant practice. Warrendale, Pennsylvania: The
Metallurgical Society of AIME.
Patterson, J. 1985. Industrial wastewater treatment technology.
Boston, Mass.: Buttenwork Publishers.
Penberthy, H.L. 1981. Method and apparatus for converting hazardous
material to a relatively harmless condition, U.S. Patent 4,299,611.
Phelps Dodge Corp. 1989. Data submittal by letter from Phelps Dodge
Corp., El Paso, Texas, to U.S. Environmental Protection Agency on
treatment of selenium-bearing wastes.
Price. 1989. Letter to Jim Berlow, U.S. Environmental Protection
Agency, Office of Solid Waste, on stabilization treatment
data for the Crystal Chemical Site, Houston, Texas, October 4, 1989.
Rhone-Poulenc. 1990. Letter submission of data on arsenic
vitrification to U.S. Environmental Protection Agency, January 1990,
Comment No. LD1200207.
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Robins, R.G. 1981. Metallurgical Transactions, Volume 13, pp. 103-109.
Roset, G. 1982. The influence of experimental variables on the
elemental distribution of lime-roasted smelter dusts in a copper matte-
slag system. A thesis submitted to the Department of Metallurgy and
Mineral Processing Engineering at Montana College of Mineral Science
and Technology in partial fulfillment of the requirements for the
degree of Master of Science in Metallurgical Engineering. Montana
College of Mineral Science and Technology, Butte, Montana.
Solidiwaste Technology. 1990. Letter submission of data on arsenic
stabilization to U.S. Environmental Protection Agency, February 1990,
Comment No. LD1200061.
SRI. 1988. Stanford Research Institute. 1988 Directory of chemical
producers - United States of America. Menlo Park, California:
Stanford Research Institute.
Stern, A., ed. 1977. Nonferrous metallurgical operations. In Air
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Timmons, D. 1989. Letter submission of data on in situ vitri-
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Protection Agency, Office of Solid Waste, October 19, 1989.
Tooley, F. 1984. The handbook of glass manufacture. 3rd ed. ,
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297-303.
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8-4
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USEPA. 1987b. U.S. Environmental Protection Agency, Office of Solid
Waste. Onsite engineering report for D004, Salsbury Laboratories,
Charles City, Iowa. Washington, D.C.: U.S. Environmental Protection
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USEPA. 1987c. U.S. Environmental Protection Agency, Office of Solid
Waste. Computer printout; data on total volume of waste generated
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November 24, 1987. Washington, D.C.: U.S. Environmental Protection
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USEPA. 1988a. U.S. Environmental Protection Agency, Office of Solid
Waste. Onsite engineering report, John Zink, Tulsa, Oklahoma, for K101
and K102. Washington, D.C.: U.S. Environmental Protection Agency.
USEPA. 1988b. U.S. Environmental Protection Agency, Office of Solid
Waste. Generic quality assurance project plan for the land disposal
restrictions program ("BOAT"). Washington, D.C.: U.S. Environmental
Protection Agency.
USEPA. 1988c. U.S. Environmental Protection Agency. Office of Solid
Waste. Methodology for developing BDAT treatment standards.
Washington, D.C.: U.S. Environmental Protection Agency.
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Waste. Best demonstrated available technology (BDAT) background
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U.S. Environmental Protection Agency.
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Waste. Treatment technology background document. Washington, D.C.:
U.S. Environmental Protection Agency.
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K031 at U.S. Army Corps of Engineers Waterways Experiement Station
Vicksburg, Mississippi. Washington, D.C.: U.S. Environmental
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codes containing arsenic or selenium listing constituents from the 1986
Generator Survey data base. Retrieved August 7, 1989. Washington,
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Generator Survey data base. Retrieved October 5, 1989. Washington,
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Cleveland, Ohio: CRC Press.
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APPENDIX A
HIGH-TEMPERATURE STABILIZATION TECHNOLOGIES
-------
A. HIGH-TEMPERATURE STABILIZATION TECHNOLOGIES
A.I Applicability
High•temperature stabilization technologies include glass and slag
vitrification and elevated-temperature calcination processes.
Vitrification processes involve dissolving of the waste at high
temperatures into glass or a glasslike matrix. Calcination involves
merely heating of the material at high temperatures.
High-temperature vitrification is applicable to nonwastewaters
containing arsenic* or other EP-toxic metal constituents that are
relatively nonvolatile at the temperatures at which the process is
operated. It is also applicable to many wastes containing organometallic
compounds, where the organic portion of the compound can be completely
oxidized at process operating conditions.
The process is not applicable to volatile metallic compounds or to
wastes containing high levels of constituents that will interfere with
the vitrification process. High levels of chlorides and other halogen
salts should be avoided in the wastes being processed because they
interfere with glassmaking processes and cause corrosion problems.
Calcination processes are applicable to inorganic wastes that do not
contain volatile constituents.
* Volatile arsenic compounds are generally converted to nonvolatile
arsenate salts such as calcium arsenate prior to use of this process.
In ordinary glassmaking, arsenic volatilization problems are minimized
by adding arsenic as arsenate salts.
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A.2 Underlying Principles of Operation
The basic principles of operation for high-temperature stabilization
technologies are dependent on the technology used. In glass and slag
vitrification processes, the waste constituents become chemically bonded
inside a glasslike matrix in many cases. In all instances, the waste
becomes surrounded by a glass matrix. This acts to immobilize the waste
constituents and to retard or prevent their reintroduction into the
environment. Arsenates are converted to silicoarsenates, and other
metals are converted to silicates.
High-temperature calcination processes remove water of hydration from
the toxic metal-bearing solids, convert hydroxides present to oxides, and
sinter the material, reducing its surface area to a minimum. Conversion
of hydroxides to oxides and minimization of available surface area retard
surface reactions that would reintroduce the material into the
environment. Calcination may also be accompanied by chemical reaction if
a material such as lime is blended with the waste before it is heated.
For example, lime will react with arsenic oxides at high temperatures to
form calcium arsenate, and this material will then be sintered at
elevated temperatures. Brief descriptions of each of the high-tempera-
ture processes are given below.
A.2.1 Glass Vitrification
In the glass vitrification process, the waste and normal glassmaking
constituents are first blended together and then fed to a glassmaking
furnace, where the mixed feed materials are introduced into a pool of
molten glass. The feed materials then react with each other to form
additional molten glass, in which particles of the waste material become
dissolved or suspended. The molten glass is subsequently cooled. As it
cools, it solidifies into a solid mass that contains the dissolved and/or
A-2
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suspended waste constituents. Entrapment and chemical bonding within the
glass matrix render the waste constituents unavailable for reaction.
A.2.2 Slag Vitrification
Slag vitrification differs from glass vitrification in that finely
ground slag from metal-refining processes and waste are premixed and fed
to the same type of furnace as that used for glassmaking. The slag
liquifies at the process temperature (1100 to 1200°C), and the waste
constituents either dissolve or become suspended in the molten slag.
Subsequent cooling of the slag causes it to solidify, trapping the waste
inside a glasslike matrix and rendering it unavailable for chemical
reaction or migration into the environment.
A.2.3 High-Temperature Calcination
In the high-temperature calcination process, the waste is heated in a
furnace or kiln to between 400 and 800°C. In some instances, the
waste may be blended with lime prior to heating. In those cases,
chemical reaction may occur during the calcining process. Water present
as either free water or water of hydration is evaporated, and hydroxides
present are thermally decomposed to the corresponding oxides and water
vapor. At the high temperatures, the surface area of the dehydrated
material is decreased by thermal sintering. Conversion of hydroxides to
oxides and substantial loss of surface area render the material less
reactive in the environment and lower the leachability of EP toxic metals
present. In general, the higher the calcination temperatures used, the
more complete is the loss of water and the greater is the accompanying
loss of surface area, resulting in lower leachability potential.
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A.3 Description of the High-Temperature Stabilization Processes
This section discusses three types of high-temperature stabilization
processes, which differ considerably from each other. Individual process
descriptions are given in the following subsections.
A.3.1 Glass Vitrification
Soda ash, lime, silica, boron oxide, and other glassmaking
constituents are first blended with the waste to be treated. The amount
of waste added to the blend is dependent on the waste composition.
Different metal oxides have differing solubility limits in glass
matrices. The blended waste and glass raw material mixture is then fed
to a conventional, heated glass electric furnace.
The introduced material typically is added through a port at the top
of the furnace and falls into a pool of molten glass. The glass
constituents dissolve in the molten glass and form additional glass.
Molten glass is periodically withdrawn from the bottom of the furnace and
cooled. This material then solidifies on cooling into solid blocks of
glasslike material. Organics present in the feed mixture undergo
combustion at the normal operating temperatures of 1100 to 1400°C and
are fully oxidized to carbon dioxide and water vapor.
The top of the furnace is normally cooled so that volatile materials,
such as arsenic oxides, that are present in the feed mixtures condense on
the cooled surface and fall back into the melt, where they can undergo
chemical reaction to form silicoarsenates involved in the glassmaking
process. Most of the arsenic used in making glass by this method is
present as salts such as calcium arsenate. This approach was introduced
into the glass industry to minimize fugitive arsenic losses.
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Gases, such as carbon dioxide, that are liberated during the
glassmaking process exit the furnace through the top and are generally
wet-scrubbed prior to reentering the atmosphere.
A.3.2 Slag Vitrification
The slag vitrification process is basically similar to glass
vitrification except that granulated slag, instead of the normal
glassmaking constituents, is blended with the waste for feed to the
system. A pool of liquid slag is present in the furnace, and the blended
raw material mix typically is introduced at the top of the furnace and
falls into this molten slag. The granulated slag-waste mixture liquifies
to form additional slag. Slag is periodically withdrawn from the slag
pool and cooled into blocks.
The type of furnace used for glass vitrification can also be used for
slag vitrification. The operating parameters are similar.
A.3.3 High-Temperature Calcination
In the high-temperature calcination process, wastes containing
inorganic compounds are fed to ovens or kilns, where they are heated to
high temperatures (i.e., 500 to 900°C) to drive off water of
hydration and to convert hydroxides present to the corresponding oxides.
This process is primarily applicable to inorganic wastes that contain
nonvolatile constituents.
The waste is heated in the oven or kiln to the desired temperature,
moisture and water of hydration are driven off, and, at the 500 to
900°C temperature range, hydroxides decompose to the corresponding
oxides and water vapor. The high-temperature treatment also
significantly reduces the surface areas of the oxides formed by
A-5
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sintering, thereby reducing the reactivity of the material. After the
waste material has been calcined at an elevated temperature, it is
withdrawn from the oven or kiln, cooled, and either land disposed or
forwarded to another process such as stabilization for further treatment.
A.4 Waste Characteristics Affecting Performance (WCAPs)
The waste characteristics affecting performance are different for the
two vitrification processes and the calcination process. Accordingly,
they are discussed separately in the following subsections.
A.4.1 Waste Characteristics Affecting Performance of Vitrification
Processes
In determining whether vitrification will achieve the same level of
performance on an untested waste as on a previously tested waste, and
whether performance levels can be transferred, EPA examines the following
waste characteristics that affect performance of the vitrification
processes: (1) organic content of the waste, (2) concentrations of
specific metal ions in the waste, (3) concentrations of compounds in the
waste that interfere with the glassmaking process, and (4) moisture
content of the waste.
(1) Organic content. At process operating temperatures (1100 to
1400°C), organics are combusted to carbon dioxide, water, and other
gaseous products. The combustion process liberates heat, reducing the
external energy requirements for the process.
The amount of heat liberated by combustion is a function of the Btu
value of the waste. The Btu content merely changes the energy input
needs for the process and does not affect waste treatment performance.
The amount of material that may not oxidize completely is a function of
the organic halogen content of the waste. The presence of these
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halogenated organics does impact process performance because sodium
chloride has a low solubility in glass. The presence of high chlorides
results in a porous glass that is undesirable. If the halogenated
organic content of an untested waste is the same as or less than that
present in an already tested waste, the system should achieve the same
performance for organic destruction.
(2) Concentrations of specific metal ions. Most metal oxides
have solubility limits in glass matrices. Hence, their concentration
determines the amount of glass-forming materials or slag with which they
must be reacted in this process to generate a nonleaching slag or glass.
The solubility limits of most common metal oxides and salts in glass are
found in the Handbook of Glass Manufacture and other treatises on glass
production. Oxides for which extensive solubility information is
available are alumina, antimony oxide, arsenic oxides, barium oxide,
cadmium oxide, chromium oxides, copper oxides, cobalt oxides, iron
oxides, lead oxides, manganese oxides, nickel oxides, selenium oxides,
tin oxides, and zinc oxides. Analysis for individual metal
concentrations in the waste can be performed according to EPA-approved
methods. If the concentrations of specific metals in an untested waste
are less than those in a tested waste, then the same ratio of slag or
glass raw materials to waste may be used for vitrification purposes. If,
however, the concentration of metal is greater than that in the tested
waste, a different formulation must be used.
(3) Concentrations of deleterious materials. Some waste
constituents, such as chlorides, fluorides, and sulfates, interfere with
the vitrification process if present at high levels. These salts have
limited solubilities in glass; therefore, when they are present,
additional glass-forming raw materials must be added to compensate for
their presence. The solubility limits of various salts in glasses are
discussed in references on glass production such as the Handbook of Glass
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Manufacture. Generally, if the concentrations of such materials in an
untested waste are lower than those in a tested waste, then the same
ratio of glass-forming constituents to waste may be used. Reducing
agents such as carbon or ferrous salts reduce arsenates and selenates to
lower valence compounds that are more volatile. These properties should
not be present when vitrifying arsenic or selenium.
(4) Moisture content. Materials fed to the vitrification
process should be reasonably dry (i.e., contain less than 5 percent free
moisture). If a waste has excess moisture above this level, it should be
thermally dried before it is blended with glass-forming materials, as it
may react violently when introduced to the molten glass or slag pool.
A.4.2 Waste Characteristics Affecting Performance of High-Temperature
Calcination
In determining whether high-temperature calcination will achieve the
same level of performance on an untested waste as on a previously tested
waste, and whether performance levels can be transferred, EPA examines
the following waste characteristics that impact the performance of the
high-temperature calcination process: (1) the organic content of the
waste, (2) the moisture content of the waste, and (3) the inorganic
composition of the waste. These characteristics are discussed below.
(1) Organic content. Calcination temperatures normally used are
too low to initiate combustion of some types of organic compounds.
However, they are high enough to cause volatilization of organics, which
have to be removed from process off-gases. For these reasons, the
presence of significant levels of organics is undesirable but can be
handled with appropriate air pollution controls. Organics, per se, do
not interfere with the conversion of oxides to hydroxides or with
sintering processes. Afterburners may be required on vitrification units
A-8
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managing high organic content wastes to insure complete combustion of the
organics present.
(2) Moisture content. Excess water that has to be removed from
the waste by heating increases the amount of time needed to bring the
waste to the calcination temperature. For this reason, wastes with high
moisture content should be dewatered prior to the use of this process.
(3) Inorganic composition. Calcination temperatures are
normally selected based on the temperatures at which hydroxides are
thermally decomposed to the corresponding oxides and water vapor. To
select an optimum operating temperature, the approximate composition of
the waste should be known.
A few toxic metal oxides have fairly low volatilization
temperatures. Arsenic oxide, selenium dioxide, and mercuric oxide all
volatilize below 500°C. High-temperature calcination should not be
used for wastes that contain these volatile constituents unless they are
blended with materials such as lime, which will react with them before
they can vaporize. Nonvolatile arsenic compounds such as ferric and
calcium arsenates may be calcined without concern for vaporization of
material.
A.5 Design and Operating Parameters
The design and operating parameters for the vitrification processes
are similar to each other, but differ considerably from those for
high-temperature calcination. The following subsections discuss these
two technologies separately.
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A.5.1 Design and Operating Parameters for Vitrification Processes
In assessing the effectiveness of the design and operation of a
vitrification system, EPA examines the following parameters: (1) the
composition of the vitrifying agent, (2) the operating temperature,
(3) the residence time, and (4) the vitrification furnace design.
(1) Composition of the vitrifying agent. Slag and various
glassmaking formulations are used as vitrifying agents. The choice of
the vitrifying agent is determined by the solubility of the waste
constituents to be vitrified. Different inorganic oxides have differing
solubilities in various glass matrices.
For slags, the presence of carbon or other reducing agents is
undesirable when vitrifying arsenic-bearing or selenium-bearing wastes.
Carbon or ferrous salts in the slag reduce arsenates in the waste to
arsenic trioxide, which has a low volatilization temperature. Likewise,
these same reducing agents reduce selenates to elemental selenium, which
also has a low volatilization temperature. When slags are used for
vitrifying arsenic-bearing and selenium-bearing wastes, EPA monitors the
composition of the granulated slags to ensure that they do not contain
significant concentrations of carbon or ferrous salts.
In glass vitrification, various glassmaking formulations can be
used. EPA examines the proposed formulations to ensure that the toxic
metal ion concentrations of the final product do not exceed solubility
limits. Hence, EPA examines the material balances based on waste
composition and glassmaking additives and the published solubility limits
for metal oxides in various glasses to ensure that the vitrified product
is indeed a glass containing the solubilized toxic waste constituents.
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(2) Operating temperature. Vitrification furnaces, are normally
operated in the 1100 to 1400°C range. The exact operating temperature
is usually selected based on the desired composition of the final product.
Furnaces are normally equipped with automatic temperature control systems.
EPA examines the basis of choice for operating temperatures and the
nature and physical condition of the temperature monitoring and control
equipment to ensure that the system is being properly operated.
(3) Residence time. Sufficient time must be allowed for the
materials added to glass furnaces to reach operating temperatures and
then undergo the chemical reactions needed to produce glasses. Residence
times are normally on the order of 1 to 2 hours for processes operated at
1100 to 1200°C. For glasses or slags requiring slightly higher
temperatures, slightly longer residence times are usually selected. EPA
examines the basis for the facility's choice of residence times to ensure
that the system is well operated.
(4) Vitrification furnace design. Vitrification furnaces
normally incorporate the following design features:
• Withdrawal of the product in liquid form from the base of the
furnace.
• Maintenance of a liquid pool of product in the furnace.
• Addition of product constituent mix at the top of the furnace.
• Design of the top area of the furnace in a manner that allows
for cooling of this area. (This is important because volatile
constituents of the input feed may vaporize from the melt. The
cool top area allows these constituents to condense and fall back
into the melt.)
• Presence and proper operation of an air emissions control
afterburners and scrubbing system to manage vent gas emissions
from the system such as hydrogen chloride vapors from combustion
of any chlorinated organics present.
A-ll
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EPA examines the furnaces to be used for waste vitrification to
ensure that the design features mentioned above are present, since they
are important for proper operation of the systems.
A.5.2 Design and Operating Parameters for High-Temperature Calcination
Systems
In assessing the effectiveness of the design and operation of a
high-temperature calcination process, EPA examines the following
parameters: (1) operating temperature, (2) residence time, and (3) air
emission control units in place on the ovens or kilns used.
(1) Operating temperatures. Calcination temperatures of from
500 to 900°C have been used in practice. The calcination temperature
selected is generally a temperature above which metal hydroxides present
will decompose to the corresponding oxides. Data on decomposition
temperatures of some metal hydroxides are given in Table A-l. The
temperature chosen is normally high enough to cause extensive sintering
(surface area loss) of the oxides formed, while at the same time not
volatilizing these materials. EPA examines the technical basis for
selection of the calcining temperature to determine whether the system is
properly operated. EPA also examines the temperature monitoring and
control systems in place to determine whether they are properly operated
and reliable.
Table A-l Metal Hydroxide Decomposition Temperatures
Metal hydroxide Decomposition temperature (°C)
Cadmium hydroxide 300
Chromic acid 400
Lead hydroxide 145
Nickel hydroxide 230
Zinc hydroxide 125
Source: Weast 1977.
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(2) Residence time. Calcination is generally a batch process,
and sufficient time must be allowed for samples to be brought to the
operating temperature. Residence times of several hours are normally
used to minimize the effects of heat-up time. EPA examines the technical
basis for the choice of residence time to ensure that sufficient heating
at the required temperature is allowed to complete the dehydration and
sintering processes. Residence time is a function of the time needed to
bring the calcination furnace or kiln to the desired temperature and the
time needed to complete the dehydration and sintering processes at the
selected temperature.
(3) Air emissions control systems. During the calcination
process, water vapor is driven off as it is formed by the decomposition
of hydroxides present in the waste. These hot gases exit the calcination
furnace or kiln as they are formed. Some particulates of the waste
material and organics present in the waste may become entrained in these
vent gases; therefore, for air pollution control purposes, the
calcination units must be equipped with wet or dry particulate collection
systems that are properly designed and operated when processing inorganic
wastes. If wastes containing organics are processed by high temperature
calcination, the calcination furnaces need to be equipped with
afterburners to combust organic vapors emitted. EPA examines the design
basis, physical condition, and maintenance of these air emissions control
units to determine whether they are properly designed, maintained, and
operated when processing inorganic wastes. If wastes containing organics
are processed by high temperature calcination, the calcination furnaces
need to be equipped with afterburners to combust organic vapors emitted.
EPA also examines the system of management in use for handling and
subsequent treatment of the collected particulates to ensure that these
finely divided waste particles are properly managed.
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A.6 References
Penberthy, L. 1984. Electric melting of glass. In Handbook of glass
manufacture, Vol. I, pp. 387-399. New York: Ashlee Publishing Co.
Penberthy, L. 1981. Method and apparatus for converting hazardous
material to a relatively harmless condition. U.S. Patent 4299.611.
November 10, 1981.
Steitz, W.R., Hibscher, C.W., and Mattocks, G.R. 1984. Electric melting
of glass. In Handbook of glass manufacture, Vol. I, pp. 400-428.
New York: Ashlee Publishing Co.
Tooley, F.V. 1984. Raw materials. In Handbook of glass manufacture,
Vol. I, pp. 19-56. New York: Ashlee Publishing Co.
Twidwell, L.G., and Mehta, A.K. 1985. Disposal of arsenic bearing
copper smelter flue dust. In Nuclear and chemical waste management,
Vol. 5, pp. 297-303. Butte, Montana: Montana College of Mineral
Science and Technology.
Weast, R.C., ed. 1977. Handbook of chemistry and physics, 58th ed.
Cleveland, Ohio: CRC Press.
A-14
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APPENDIX B
ANALYTICAL METHODS AND
QUALITY ASSURANCE/QUALITY CONTROL DATA
-------
B. ANALYTICAL METHODS AND QUALITY ASSURANCE/QUALITY CONTROL DATA
The analytical methods used for analysis of arsenic and selenium are
listed in Table B-l. SW-846 methods (EPA's Test Methods for Evaluation
of Solid Waste; Physical/Chemical Methods, SW-846, Third Edition,
November 1986) are used in most cases for determining total constituent
concentrations. Leachate concentrations were determined using the
Extraction Procedure (EP) Toxicity Test method in SW-846.
In some instances, SW-846 allows for the use of alternative or
equivalent procedures or equipment. The specific procedures or equipment
used for analysis of metal compounds is shown in Table B-2.
All concentrations for the regulated constituents are corrected to
account for analytical interference associated with the chemical makeup
of the waste matrix. The correction factor for a constituent is based on
the matrix spike recovery values. Table B-3 presents the matrix spike
recoveries used to determine the correction factor for the EPA-collected
D004 wastewater data.
Since no matrix spike recovery values were available for the slag
vitrification data, matrix spike recovery values for a similar
nonwastewater (i.e., K102 ash TCLP extract) matrix have been used to
correct the slag vitrification data. The recoveries used to correct the
arsenic slag vitrification EP-Tox leachate metal concentrations are shown
in Table B-4. The recoveries used to correct the selenium stabilization
data as given in Table B-5.
B-l
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Table B-l Analytical Methods for Regulated Constituents
Regulated constituent
Analytical method
Method number
Reference
Arsenic
Arsenic
Extraction procedure tozicity test method
Acid digestion of aqueous samples and
1310
3010
1
1
extracts for total metals for analysis by
flame atomic absorption spectroscopy (AA)
or inductively coupled plasma atomic
emission spectroscopy (ICF)
Acid digestion of aqueous samples and
extracts for total metals for analysis by
furnace atomic absorption spectroscopy (AA)
Acid digestion of sediments, sludges, and
soils
3020
30SO
Selenium
Acid digestion for metals
Inductively coupled plasma atomic emission
spectroscopy
Selenium (AA, furnace technique)
3060
6010
7740
1 - USEPA 1986.
2 - USEPA 1982.
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Table B-2 Specific Procedures or Equipment Used in Preparation for Analysis of Metals
When Alternatives or Equivalents Are Allowed in the SW-846 Methods
Analysis
SW-846
method
Equipment
Alternative or equivalent
allowed by SW-846 methods
Specific procedures or
equipment used
Inductively coupled plasma
atomic emission spectroscopy
6010
Jarrell Ash 1140
Operate equipment following
instructions provided by
instrument's manufacturer.
For operation with organic
solvents, auxiliary argon gas
inlet is recommended.
Equipment operated using
procedures specified in the
Jarrell Ash (JA) 1140
Operator's Manual.
Auxiliary argon gas was not
required for sample matrix.
Metals by furnace AA
co
i
co
7841 (1) Perk in Elmer 5000 II
7740 (2) Perk in Elmer 5000 12
7421 • (3) Perk in Elmer 5000 13
(4) Perk in Elmer 2580
Operate equipment following
instructions provided by
instrument's manufacturer.
Equipment operated using
procedures specified in (1) the
Perkin Elmer 3030 Instruction
Manual. (2) the Perkin Elmer
Model 5000 Instruction Manual,
and (3) the Perkin Elmer 2580
Instruction Manual.
For background correction,
use either continuous
correction or alternatives,
e.g., Zeeman correction.
Background detection was
used. Continuous correction
on Models 2380 and 5000 12
and Zeeman on Model 3030 and
5000 fl.
If samples contain a large
amount of organic material,
they should be oxidized by
conventional acid digestion
before being analyzed.
Samples were prepared using
acid digestion procedures from
SW-846.
Source: USEPA 1987b.
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Table B-3 Matrix Spike Recoveries for Treated D004 Waste
BOAT constituent
Metals
Arsenic
Cadmium
Lead
Mercury
Source: USEPA 1987b.
CO
.p. a = Percent Recovery =
Original amount
found
Ug/i)
782
<80
<5
0.86
([(Spike Result -
Spike added
Ug/l)
2.000
500
25
5
Original Amount) /Spike
Sample Set 1 1 Sample Set Duplicate 1
Spike result Percent Spike added Spike result Percent Accuracy
(
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Table B-4 Matrix Spike Recoveries Used to Calculate Correction Factors
for the Slag Vitrification EP-Tox Leachate Value
BOAT constituent
Original sample
Ug/D
Spike added
Ug/i)
Sample fl
Spike result Percent
(»ig/l) recovery3
Sample Set Duplicate 1
Spike result
(cg/D
Percent
recovery3
Accuracy
Correction
factor6
Arsenic
17,100
10.000
26.100
90
26.100
90
1.11
3 Percent recovery = [(Spike Result - Original AmountJ/Spike Amount] x 100.
Accuracy Correction Factor = 100/Percent Recovery (using the lowest percent recovery values).
Source: USEPA 1988a.
Table B-5 Matrix Spike Recoveries Used to Calculate Correction Factors
for the Selenium Stabilization TCLP Leachate Value
CD
in
BOAT constituent
Selenium
Sample I
1
2
3
4
Uncorrected
Value
(mg/D
0.154
0.372
1.80
0.370
Corrected
Value
(mg/l)a
0.182
0.440
2.124
0.437
Source: Hazardous Waste Treatment Council. 1989
3 Data submitted contained statement that spike recovery ranged from 85 to 115 percent on QC samples run
in addition to waste samples. A spike recovery factor of 85 percent was used to derive corrected
values. The corrected value shown is the raw data value divided by 0.85.
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REFERENCES
Hazardous Waste Treatment Council 1989, Data submission on stabilization
of wastes, December 22, 1989, Comment No. LD1200050.
USEPA. 1982. U.S. Environmental Protection Agency, Office of Solid Waste
and Emergency Response. Test methods for evaluating solid waste. 2nd
ed. Washington, D.C.: U.S. Environmental Protection Agency.
USEPA. 1986. U.S. Environmental Protection Agency, Office of Solid
Waste and Emergency Response. Test methods for evaluating solid waste
(SW-846). 3rd ed. Washington, D.C.: U.S. Environmental Protection
Agency.
USEPA. 1987. U.S. Environmental Protection Agency, Office of Solid
Waste. Onsite engineering report for D004, Salsbury Laboratories,
Charles City, Iowa. Washington, D.C.: U.S. Environmental Protection
Agency.
USEPA. 1988. U.S. Environmental Protection Agency, Office of Solid
Waste. Onsite engineering report, John Zink, Tulsa, Oklahoma, for K101
and K102. Washington, D.C.: U.S. Environmental Protection Agency.
B-6
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