FINAL
BEST DEMONSTRATED AVAILABLE TECHNOLOGY (BDAT)
BACKGROUND DOCUMENT FOR
BARIUM WASTES
(D005 AND P013)
Larry Rosengrant, Chief
Treatment Technology Section
Rhonda M. Craig
Project Manager
U.S. Environmental Protection Agency
401 M Street, S.W.
Office of Solid Waste
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-W9-006. 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 D005 and P013 wastes. The technical project officer for
the waste was Rhonda M. Craig. 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. James Berkes and Ms. Kathryn Jones, Staff
Engineers; Ms. Justine Alchowiak, Quality Assurance Officer; Ms. Martha
Martin, Technical Editor, and Ms. Sally Gravely, Program Secretary.
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TABLE OF CONTENTS
Page No.
1 . INTRODUCTION AND SUMMARY ................................. 1-1
2 . INDUSTRIES AFFECTED AND WASTE CHARACTERIZATION ........... 2-1
2.1 Industries Affected and Process Descriptions ....... 2-1
2.1.1 Production of Inorganic Barium Compounds .... 2-1
2.1.2 Users of Inorganic Barium Compounds ......... 2-2
2 . 2 Waste Characterization ............................. 2-2
2.3 Determination of Waste Treatability Group ........... 2-3
3. APPLICABLE AND DEMONSTRATED TREATMENT TECHNOLOGIES ....... 3-1
3.1 Applicable Treatment Technologies .................. 3-1
3.1.1 Applicable Technologies for Wastewaters ..... 3-1
3.1.2 Applicable Technologies for Nonwastewaters .. 3-3
3.2 Demonstrated Treatment Technologies ................ 3-5
3.2.1 Demonstrated Technologies for
Wastewaters ................................. 3-5
3.2.2 Demonstrated Technologies for
Nonwastewaters .............................. 3-5
4 . PERFORMANCE DATA
4.1 Performance Data for Wastewaters ................... 4-2
4.2 Performance Data for Nonwastewaters ................ 4-3
5. DETERMINATION OF BEST DEMONSTRATED AVAILABLE
TECHNOLOGY (BOAT) .......... '. ............................. 5-1
5 . 1 Was tewater s ........................................ 5-1
5.2 Nonwastewaters ..................................... 5-1
6 . CALCULATION OF BOAT TREATMENT STANDARDS .................. 6-1
6.1 Wastewaters ........................................ 6-1
6 . 2 Nonwastewaters ..................................... 6-1
ii
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8.
TABLE OF CONTENTS
(continued)
Paee No.
P013
7.1
7.2
7.3
7.4
7.5
Industries Affected
Applicable and Demonstrated Treatment
Technologies
Determination of Best Demonstrated Available
Technology
Selection of Regulated Constituents
Calculation of Proposed Treatment Standard
for P013 Nonwastewaters
REFERENCES
7
7
7
7
7
7
8
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iii
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LIST OF TABLES
Pace No.
Table 1-1 BOAT Treatment Standards for D005 Wastes 1-4
Table 1-2 BOAT Treatment Standards for P013 Wastes 1-4
Table 2-1 Current Manufacturers of Barium Chemicals 2-5
Table 4-1 Performance Data for Barium Wastewaters 4-5
Table 4-2 Performance Data for Stabilization of Barium
Nonwastewaters 4-6
Table 6-1 Calculation of Achievable Treatment Standard
for D005 Nonwastewaters 6-2
Table 6-2 BOAT Treatment Standards for D005 Wastes 6-3
Table 7-1 Calculation of Treatment Standard for P013
Nonwastewaters 7-4
Table 7-2 BOAT Treatment Standards for P013 Wastes 7-5
IV
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1. INTRODUCTION AND SUMMARY
Pursuant to section 3004(m) of the Resource Conservation and Recovery
Act (RCRA) as enacted by the Hazardous and Solid Waste Amendments (HSWA)
on November 8, 1984, the Environmental Protection Agency (EPA) is
proposing treatment standards based on the best demonstrated available
technology (BOAT) for barium in characteristic wastes identified in 40
CFR 261.24 as waste code D005 and for commercial chemical product wastes
identified in 40 CFR 261.33 as waste code P013 - barium cyanide.
Treatment standards for cyanides contained in P013 - barium cyanide were
promulgated in the Final Rule for Second Third Wastes (54 FR 26614, June
23, 1989). Compliance with treatment standards is a prerequisite for
placement of wastes in facilities designated as land disposal units as
defined in 40 CFR 268.2. The effective date of final treatment standards
for barium in D005 and P013 wastes will be August 8, 1990.
This background document presents the Agency's technical support and
rationale for developing regulatory standards for barium-containing
wastes. Sections 2 through 6 present waste-specific information for the
D005 wastes. Section 2 describes the industries affected by the
regulation of D005 wastes, explains the processes generating these
wastes, and presents available waste characterization data. Section 3
specifies the applicable and demonstrated treatment technologies for D005
wastes. Section 4 presents available performance data for the
demonstrated technologies, including data upon which treatment standards
are based. Section 5 contains analyses of the performance data to
determine BOAT, and Section 6 contains the determination of the proposed
treatment standards for the regulated constituent (barium). Section 7
discusses the listed waste P013 - barium cyanide and details the
development of the treatment standard for these wastes.
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The land disposal restrictions program and promulgated BOAT
methodology are more thoroughly described in two additional documents:
Methodology for Developing BOAT Treatment Standards (USEPA 1989a) and
Generic Quality Assurance Project Plan for Land Disposal Restrictions
Program ("BOAT") (USEPA 1988a). The petition process to be followed in
requesting a variance from the treatment standards is discussed in the
methodology document.
Treatment standards are being promulgated for the wastewater and
nonwastewater forms of D005 and P013 wastes. For the purposes of
determining BOAT and developing treatment standards, a wastewater is
defined by the Agency as a waste containing less than 1 percent (weight
basis) total suspended solids* (TSS) and less than 1 percent (weight
basis) total organic carbon (TOG). Wastes not meeting this definition
must comply with the treatment standards for nonwastewaters.
BOAT for D005 wastewaters is lime precipitation followed by
sedimentation and filtration. EPA recognizes the diversity of wastes
that qualify as hazardous under the D005 classification. Because of this
diversity, EPA has chosen to regulate D005 wastewaters at the
characteristic level of 100 mg/1. EPA believes even the most difficult
to treat D005 wastewaters can be treated to this level.
BOAT for P013 wastewaters is lime precipitation followed by
sedimentation and filtration. These technologies were part of the
treatment train used as BOAT for regulating the cyanide content of P013
(USEPA 1989c).
* The term "total suspended solids" clarifies EPA's previously used
terminology of "total solids" and "filterable solids." Specifically,
the quantity of total suspended solids is measured by Method 209C
.(Total Suspended Solids Dried at 103°C to 105°C) in Standard
Methods for the Examination of Water and Wastewater, 16th Edition
(APHA, AWWA, and WPCF 1985).
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However, EPA is not regulating P013 wastewaters for barium but only
for cyanides (EPA 1989c). EPA believes that the treatment train used to
treat P013 wastewaters for cyanides will effectively reduce the
concentration of barium at the same time.
BOAT for D005 nonwastewaters is stabilization. The data, presented
in Section 4, show that a treatment standard of 52 mg/1 barium is
achievable for nonwastewater TCLP leachates. Acid or water leaching of
D005 nonwastewaters is expected to yield a nonwastewater residual also
capable of the same treatability (and a wastewater residual that would
require treatment by chemical precipitation). However, .there are no data
available to EPA on this form of nonwastewater treatment. Because EPA
recognizes the diversity of wastes that qualify as hazardous under the
D005 classification, EPA has chosen to regulate D005 nonwastewaters at
the characteristic level of 100 mg/1, rather than 52 mg/1 as shown
above. EPA believes even the most difficult to treat D005 nonwastewaters
can be treated to this level.
BOAT for P013 nonwastewaters is stabilization. EPA is promulgating a
treatment standard of 52 mg/1 for barium in P013 nonwastewaters TCLP
leachate based on performance data presented in Section 4. The treatment
standards for D005 and P013 barium wastes are listed in Tables 1-1 and
1-2, respectively.
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Table 1-1 BOAT Treatment Standards for D005 Wastes
Maximum for any single grab sample
Constituent Wastewater Nonwastewater
(mg/1) TCLP (mg/1)
Barium 100 100
Table 1-2 BOAT Treatment Standards for P013 Wastes
Maximum for any single grab sample
Constituent Wastewater Nonwastewater
(mg/1) TCLP (mg/1)
Barium NRa 52
NR - not regulated.
aP013 wastewaters are not being regulated for barium but are being
regulated for cyanides. See the Best Demonstrated Available Technology
(BOAT) Background Document for Cyanide Wastes (USEPA 1989c).
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2. INDUSTRIES AFFECTED AND WASTE CHARACTERIZATION
As defined in 40 CFR 261.24, D005 wastes are wastes that exhibit the
characteristic of EP toxicity for barium. In other words, D005 wastes
have a barium concentration of greater than 100 mg/1, as measured by the
TCLP (Toxicity Characteristic Leaching Procedure), 51 FR 40643, November
7,
1986. Section 2.1 describes the industries affected by the land disposal
restrictions for D005 wastes and describes the processes identified by
EPA that may generate these wastes. Section 2.2 summarizes the available
waste characterization data for D005 wastes. Section 2.3 uses the
Agency's analyses of the sources of D005 wastes and waste composition to
divide D005 wastes into treatability groups.
2.1 Industries Affected and Process Descriptions
The industries affected by the land disposal restrictions for D005
wastes are (1) the inorganic chemicals industry, which produces various
inorganic barium compounds, and (2) industries that use barium compounds
to manufacture various products. The barium compounds manufactured and
used by these industries are discussed below.
2.1.1 Production of Inorganic Barium Compounds
Barium does not occur in its free state in nature. Its compounds are
widely distributed in the earth's crust in igneous rocks, sandstone, and
shale. The major barium minerals are barium sulfate (baryte) and barium
carbonate (witherite). Barium sulfate is mined in the United States to
produce either barium metal or its compounds.
The initially mined barium sulfate is usually reduced to barium
sulfide (also known as black ash) by calcining with coke in a rotary kiln
at temperatures of 1000 to 1250°C in the oxygen-free environment.
The resultant ash is quenched in water to dissolve the barium sulfide to
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provide a 12 to 30 percent solution. The resultant solution may be used
to produce other barium salts such as barium carbonate, barium chloride,
barium nitrate, and barium sulfate. The following are examples of
reactions used to make barium carbonate and barium sulfate, respectively:
BaS + Na?CO, -+ BaCO- + Na~S
BaS + Na2SO, -»• BaSO, + Na2S
The current manufacturers of barium compounds are listed in Table 2-1 at
the end of this section.
2.1.2 Users of Inorganic Barium Compounds
Barium carbonate is the most important and most widely used barium
compound. It is utilized in the manufacture of bricks, in ceramics
manufacture, in oil drilling fluids as "muds" and lubricating compound
precursors, in the precipitation of "synthetic" barium sulfate for
photographic and medicinal end uses, and in the manufacture of glass.
Barium chloride is used in production of pigments and colors. Barium
nitrate is widely used in the pyrotechnics industry for the production of
tracer bullets, flares, and detonators. Other barium compounds are used
as lubricating oils and greases and as metallic soaps. Some of the black
ash is processed to provide barium metal, which is highly reactive and is
used as a "getter" in electronics equipment and vacuum tubes.
2.2 Waste Characterization
The Agency has information from 57 facilities generating D005
wastes. These facilities reported generating 67 D005 waste streams in
1985. This information was obtained from EPA's 1986 National Survey of
Hazardous Waste Generators (the Generator Survey, USEPA 1986b).
Forty-eight of the waste streams generated were nonwastewater forms of
D005; ten of the waste streams generated were wastewaters. For the
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remainder of the waste streams (i.e., nine waste streams), generators
reported that the form of the waste generated was indeterminable. Barium
concentrations reported by facilities were as follows:
Ba Concentration in Waste: No. of Facilities:
50 - 75% 1
25 - 50% 5
10 - 25% 3
1 - 10% 2
0.1-1% 8
500 ppm - 0.1% 2
100 - 500 ppm 13
10 - 100 ppm 5
Unknown 18
Most D005 wastes are generated in inorganic matrices. However,
Generator Survey data indicate that D005 wastes may sometimes be present
in a matrix containing significant quantities of organic constituents
such as F001-F005 spent solvents or waste oils. The levels of organics
reported in D005 waste streams by two facilities were 98 percent and
25 percent, respectively.
2.3 Determination of Waste Treatabilitv Groups
EPA believes that in some cases, wastes with the same waste code but
produced in different processes in an industry, or in different industries,
may not be treatable to similar concentrations using the same technologies.
In such instances, the Agency may subdivide a waste code into several
treatability groups. This is done when the chemical forms of the wastes
are different and the wastes require different treatments or combinations
of treatments. For example, inorganic and organometallic compounds
containing the same metals frequently require different types of treatment.
Based on a careful review of information on the generation of D005
wastes and of available waste characterization data, the Agency determined
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that all D005 wastewaters form a single treatability group. The Agency
also determined the same to be true for D005 nonwastewaters.
The concentration of barium in D005 wastes is dependent on the waste
type, the particular production process employed, and the specifics of the
treatment process used. However, all D005 wastewaters are expected to be
treatable to similar levels by use of the same technologies. In terms of
waste characteristics that affect treatment performance, the Agency
believes that the presence of BOAT list metals will not affect the
treatability of dissolved barium in wastewaters. While high
concentrations of organics in wastewater might affect the performance of
barium treatment. D005 wastewaters are not expected to have high
concentrations of organics, (because EPA's definition of wastewaters
limits total organic carbon to less than 1% by weight).
The Agency also believes that all D005 nonwastewaters are expected to
be treatable to similar levels by use of the same technologies. However,
the Agency recognizes the possibility that D005 nonwastewaters containing
high levels of organics could be generated. The Agency, therefore,
solicited information on whether such wastes actually exist, the
concentration of barium and organics within such wastes, and treatment
data. The Agency found that these wastes do exist, but treatment data
were not submitted. However, incineration has been shown to destroy
organic wastes and would be expected to do so for organobarium
nonwastewaters. If the potential exists for the volatilization of barium
into the gas stream, air pollution control devices would be required.
Incineration of organobarium wastes yields ash and scrubber water
inorganics that can be treated in the same way as their inorganic
barium-containing counterparts. Therefore, the Agency is including
organobarium nonwastewaters in the same treatability group as other
barium-containing nonwastewaters.
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Table 2-1 Current Manufacturers of Barium Chemicals
Manufacturer's name
Manufacturer's
location
Barium compound
name
Barium & Chemicals, Inc,
Steubenville, OH
Procter & Gamble Co.
J.T. Baker, Inc. (sub)
Phillipsburg,' NJ
Barium acetate
Barium bromide
Barium carbonate
Barium chlorate
Barium chloride
Barium chromate
Barium fluoride
Barium hydroxide,
anhydrous
Barium hydroxide,
octahydrate
Barium iodide
Barium nitrate
Barium nitrite
Barium oxalate
Barium oxide
Barium perchlorate
Barium peroxide
Barium silicide
Barium silcofluoride
Barium sulfate,
natural (barytes)
Barium sulfate,
synthetic (blanc fixe)
Barium sulfide
Barium tartrate
Barium acetate
Barium carbonate
Barium chloride
Barium hydroxide,
octahydrate
Barium nitrate
Barium sulfate,
synthetic (blanc fixe)
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Table 2-1 (continued)
Manufacturer's name
Manufacturer's
location
Barium compound
name
Kaisertech Limited
Harshaw/Filtrol Ptrshp.
Chemical Products Corp.
General Electric Corp.
Components/Quartz Mktg.
GTE Corporation
Chem & Metalurgical Div.
G. Frederick Smith
Chemical Company
National Industrial
Chemical Company
Wayne Pigment Corp.
Nuodex Inc.
Hoosier Magnetics, Inc.
Hoosier of New York
Hoosier of Ohio
Solon, OH
Cartersville, GA
Cleveland, OH
Towanda, PA
Columbus, OH
Chicago, IL
Milwaukee, WI
Elizabeth, NJ
Washington, IN
Ogdensburg, NY
Toledo, OH
Barium calcium fluoride
Barium strontium
niobate
Barium carbonate
Barium chloride
Barium sulfide
Barium carbonate
Barium nitrate
Barium titanate
Barium carbonate
Barium phosphate,
dibasic
Barium chloride
Barium diphenylamine
sulfonate
Barium perchlorate
Barium chromate
Barium chromate
Barium 2-ethylhexanoate
Barium ferrite
Barium ferrite
Barium ferrite
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Table 2-1 (continued)
Manufacturer's name
Manufacturer's
location
Barium compound
name
Kaisertech Ltd.
Pennwalt Corp.
Ozark-Mahoning Co.
Deepwater, Inc.
Strem Chemicals Inc.
Union Carbide
Amerchol Corp.
Buckman Laboratories
Croton Corp.
Hummel Chemical Co.
Akzo America, Inc.
Interstab Chemicals
Ferro Corp.
Transelco Division
Electronic Ceramic Matls.
Tarn Ceramics
Cleveland, OH &
Solon, OH
Tulsa, OK
Carson, CA
Newburyport, MA
Edison, NJ
Memphis, TN
South Plainfield, NJ
South Plainfield, NJ
New Brunswick, NJ
Penn Yan, NY
Niagara Falls, NY
Barium fluoride
Barium fluoride
Barium iodate
Barium iodide
Barium isopropoxide
Barium lanolate
Barium metaborate
Barium nitrate
Barium nitrate
Barium oxalate
Barium peroxide
Barium salt of
nonylphenol
Barium stannate
Barium titanate
Barium zirconate
Barium stannate
Barium titanate
Barium zirconate
Barium zirconium
silicate
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Table 2-1 (continued)
Manufacturer's name
Manufacturer's
location
Barium compound
name
The Norac Co., Inc.
Mathe Division
Nuodex, Inc.
Plastic Spec & Technol
Synthetic Products Co.
Witco Corp.,
Organics Division
Chemtech Industries, Inc
Harstan Division
Cyprus Minerals Co.
Cyprus Metec Corp.
Pennwalt Corp.
Ozark-Mahoning Co.
Pfizer, Inc
Min, Pig & Mtls. Div.
Whittaker, Clark & Daniels
Lodi, NJ
Piscataway, NJ
Cleveland, OH
Chicago, IL
Brooklyn, NY
Cartersville, GA
Rosiclare, IL
Easton, PA
South Plainfield, NJ
Alex Chemical Co.
Shenandoah, PA
Barium stearate
Barium stearate
Barium stearate
Barium stearate
Barium sulfamate
Barium sulfate,
natural (barytes)
Barium sulfate,
natural (barytes)
Barium sulfate,
natural (barytes)
Barium sulfate,
synthetic (blanc fixe)
Barium sulfate,
natural (barytes)
Barium sulfate,
synthetic (blanc fixe)
Red 53:1 pigment
(Red Lake C, Ba salt)
Red 57 pigment
(Lithol Rubine, Ba salt)
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Table 2-1 (continued)
Manufacturer's name
Manufacturer's
location
Barium compound
name
Allied Signal, Inc.
Ridgeway Color Co. (sub)
Apollo Colors
BASF Corp.
Pigments Business
Chromatic Color Corp.
Die Acquisition Group
Sun Chemical Corp.
Pigments Div.
Hilton Davis Co.
Industrial Color Inc.
Cincinnati, OH
Rockdale, IL
Holland, MI
Elizabethtown, KY
Cincinnati, OH &
Rosebank, NY
Cincinnati, OH
Hoechst Celanese Corp. Coventry, RI
Joliet, IL
Kaisertech Ltd. Louisville, KY
Harshaw/Filtrol Ptrshp
H. Kohnstamm & Co., Inc. Camden, NJ
Red 53:1 pigment
(Red Lake C, Ba salt)
Red 53:1 pigment
(Red Lake C, Ba salt)
Red 57 pigment
(Lithol Rubine, Ba salt)
Red 53:1 pigment
(Red Lake C, Ba salt)
Red 53:1 pigment
(Red Lake C, Ba salt)
Red 53:1 pigment
(Red Lake C, Ba salt)
Red 53:1 pigment
(Red Lake C, Ba salt)
Red 53:1 pigment
(Red Lake C, Ba salt)
Red 53:1 pigment
(Red Lake C, Ba salt)
Red 53:1 pigment
(Red Lake C, Ba salt)
Red 57 pigment
(Lithol Rubine, Ba salt)
Red 53:1 pigment
(Red Lake C, Ba salt)
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Table 2-1 (continued)
Manufacturer's name
Manufacturer's
location
Barium compound
name
Magruder Color Corp
Max Marx Color Corp.
Paul Uhlich & Co., Inc.
Bayer, USA Inc.
Mobay Corp. (sub)
Binney & Smith, Inc,
Heubach Inc.
Industrial Color Inc.
Elizabeth, NJ
Irvington, NJ
Red 53:1 pigment
(Red Lake C, Ba salt)
Red 53:1 pigment
(Red Lake C, Ba salt)
Hastings-on-Hudson, NY Red 53:1 pigment
(Red Lake C, Ba salt)
Haledon, NY
Easton, PA
Newark, NJ
Joliet, IL
Red 57 pigment
(Lithol Rubine, Ba salt)
Red 57 pigment
(Lithol Rubine, Ba salt)
Red 57 pigment
(Lithol Rubine, Ba salt)
Red 57 pigment
(Lithol Rubine, Ba salt)
Reference: SRI 1989.
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3. APPLICABLE AND DEMONSTRATED TREATMENT TECHNOLOGIES
This section identifies the treatment technologies that are
applicable to the wastewater treatability group and to the nonwastewater
group. This section also explains the determination of which, if any, of
the applicable technologies can be considered demonstrated for the
purpose of establishing BOAT.
To be applicable, a technology must be theoretically usable to treat
the waste in question or to treat a waste that is similar in terms of the
parameters that affect treatment selection. 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 1989b).
To be demonstrated, the technology must be employed in full-scale
operation for the treatment of the waste in question or a similar waste.
Technologies available only at pilot- and bench-scale operations are not
considered in identifying demonstrated technologies.
3.1 Applicable Treatment Technologies
The applicable technologies for treatment of barium wastes are those
that could reduce the concentration of barium or reduce the leachability
of barium in the treatment residual.
3.1.1 Applicable Technologies for Wastewaters
Barium wastewaters are typically generated from the inorganic
chemicals industry. The two technologies identified as applicable for
barium wastewaters are chemical precipitation and ion exchange. These
technologies are described below.
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(1) Chemical precipitation. Chemical precipitation typically
involves addition of lime (calcium hydroxide) or caustic (sodium
hydroxide) to the wastewater solution. This results in the precipitation
of barium as barium hydroxide. Barium, however, is usually precipitated
as barium sulfate using sodium sulfate, ferric sulfate, or aluminum
sulfate, or precipitated as barium carbonate at a pH of 10-10.5 with lime
used for pH adjustment. These precipitation techniques are usually used
for barium-containing wastes because barium sulfate and barium carbonate
are the most insoluble barium compounds. Metal salts precipitated from
solution are usually gravity settled and/or filtered. The collected
solids may then be further treated by a technology applicable to
nonwastewaters prior to disposal. The treated wastewater may be further
treated for other components or discharged. Chemical precipitation is
further discussed in the Treatment Technology Background Document (USEPA
1989b).
(2) Ion exchange. This technology is applicable to treatment of
wastewaters containing relatively low concentrations of dissolved
metals. The metal must be in a soluble ionic form in order to be
removed. The waste is passed through a bed of ion exchange resin beads.
The resin adsorbs the soluble ions, thus removing them from solution.
Ion exchange produces both a wastewater residual (from regeneration of
the ion exchange resin) and a nonwastewater residual (the spent ion
exchange resin). The spent regenerate solutions (usually acid solutions)
are more concentrated than the original untreated waste (though much
lower in volume) and must be treated to remove metals by chemical
precipitation followed by filtration if the regenerate solution is not
recyclable. Ion exchange is discussed in detail in the Treatment
Technology Background Document (USEPA 1989b).
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3.1.2 Applicable Technologies for Nonwastewaters
Barium nonwastewaters typically are generated as inorganic solids and
sludges from treatment of wastewaters, or as ash or slag from thermal
processes such as incineration or metallurgical processes. The
technologies that are applicable to barium nonwastewaters are
stabilization, chemical precipitation, leaching with acid or water, and
incineration. These technologies are described below.
(1) Stabilization technologies. Stabilization treatment
technologies are designed to reduce the leachability of metals in the
treated waste compared to that in the untreated waste. These
technologies require mixing the waste with lime, fly ash mixtures,
cement, concrete mixtures or other formulations (both proprietary and
nonproprietary). Water is then added, and the mixture sets into a solid
mass. Stabilization technologies are discussed in detail in the
Treatment Technology Background Document (USEPA 1989b).
(2) Chemical precipitation. Chemical precipitation technologies
are normally used to treat wastewaters. They may also be used, however,
to treat suspensions of solids in water. Such suspensions may meet the
definition of nonwastewaters (i.e., greater than 1 percent total
suspended solids). These technologies were previously discussed in
Section 3.1.1 on wastewaters.
(3) Leaching Processes. Leaching is the removal of a soluble
fraction, in the form of a solution, from an insoluble, permeable solid
phase with which the soluble phase is associated. A liquid leaching
agent is mixed with the nonwastewater to dissolve the soluble fraction.
The leaching agent may be acid or water, but they both operate using the
same principle. Acid or water leaching can often be applied to wastes
containing hazardous metals (Green 1984).
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(4) Incineration. Incineration is a destruction technology used
for organic or organometallic nonwastewaters, in which energy, in the
form of heat, is transferred to the waste to destabilize chemical bonds
and destroy hazardous organic constituents. In a fluidized bed
incinerator, waste is injected into the fluidized bed material (generally
sand and/or incinerator ash), where it is heated to its ignition
temperature. Heat energy from the combustion reaction is then
transferred back to the fluidized bed. Ash is removed periodically
during operation and during bed change-outs.
In a rotary kiln incinerator, wastes are fed into the elevated end of
the kiln. The rotation of the kiln mixes the wastes with hot gases,
heating the wastes to ignition temperature. Ash is removed from the
lower end of the kiln. Combustion gases from the kiln enter the
afterburner for complete destruction of waste constituents. Other wastes
may be injected into the afterburner for treatment.
In a liquid injection incinerator, atomized liquid wastes are
injected into the incinerator. In general, only wastes with low ash
content are amenable to liquid injection incineration; therefore, this
technology generally does not generate an ash residual.
Combustion gases from any incinerator are fed to a scrubber system to
cool and to remove entrained particulates and acid gases. With the
exception of liquid injection incineration, two residuals are generated
by incineration processes: ash and scrubber water.
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3.2 Demonstrated Treatment Technologies
3.2.1 Demonstrated Technologies for Wastewaters
Chemical precipitation. This technology has been demonstrated on a
commercial basis to treat a wide variety of wastewaters containing metal
constituents, such as the listed waste K062. K062 contains relatively
high concentrations of metals such as cadmium and lead. Although the
K062 waste did not have barium, chemical precipitation is universally
applied to all forms of metal-containing wastewaters. The use of
chemical precipitation to treat K062 wastewaters is described in the K062
background document (USEPA 1988f).
3.2.2 Demonstrated Technologies for Nonwastewaters
(1) Stabilization. The use of stabilization to treat barium
wastes has been demonstrated (HWTC 1989a, 1989b). Relatively high
concentrations of barium have been treated by stabilization using
proprietary reagents. This technology has been demonstrated on a
commercial basis to treat metal-bearing wastes such as the listed wastes
K061 and F006. These wastes contain relatively high concentrations of
metals such as cadmium and lead. The use of stabilization to treat these
wastes is described in the K061 background document (USEPA 1988b) and the
F006 background document (USEPA 1988c).
(2) Chemical precipitation. As previously discussed, chemical
precipitation technologies are normally used to treat wastewaters. They
may be used, however, to treat suspensions of solids in water. These
technologies are discussed further in the wastewater Section 3.2.1.
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(3) Leaching Processes. While there are no data available to EPA
on acid or water leaching of D005 nonwastewaters , acid or water leaching
has been demonstrated on wastes in solid or slurry form containing
hazardous metals (USEPA 1989b) .
Incineration. This technology is demonstrated for treatment
of many hazardous wastes containing both organic and metal constituents.
Incineration for organobarium wastes yields ash (nonwastewater residue)
and scrubber water (wastewater) containing inorganic barium. These
residues can be treated like other nonwastewaters and wastewaters
described above.
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4. PERFORMANCE DATA
This section presents relevant data on the performance of
demonstrated technologies in treating listed wastes containing barium in
concentrations expected to be found in D005 wastes. These data are used
elsewhere in this document for determining which technologies represent
BOAT (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 as defined in
Section 3.
Performance data that are required for determining treatment
standards include the untreated and treated waste concentrations for a
given constituent, the values of operating parameters that were measured
at the time the waste was being treated, the values of relevant design
parameters for the treatment technology, and data on waste
characteristics that affect performance of the treatment technology.
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.
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4.1 Performance Data for Wastevaters
The reference manual Industrial Wastewater Treatment Technology
(Patterson 1985) contains performance data on the treatment of barium
wastes. The technologies used for barium treatment include chemical
precipitation of barium as barium sulfate, barium carbonate, and barium
hydroxide, as well as treatment by ion exchange. The concentration of
barium in the untreated wastes ranged from 2,100 mg/1 to 0.5 mg/1.
Percent removal ranged from 11 to >99 percent. The waste containing
2,100 mg/1 of barium was the only waste containing barium above the EP
toxicity level of 100 mg/1. Treatment by sulfate precipitation reduced
the barium concentration in this waste to 1.78 mg/1.
The poorest barium removal was 11 percent, but the untreated waste
concentration contained a small concentration of barium. Other
information available from the literature (Kirkpatrick 1978, Versar 1980)
also indicates that barium may be chemically precipitated as barium
sulfate or barium carbonate. Chemical precipitation as sulfate or
carbonate is an effective treatment for barium because of the relative
insolubility of barium sulfate in water and weak acids, and barium
carbonate in water. The solubilities of some barium compounds are
presented below:
Solubility in Water Temperature
Compound Name (mg/1) ( °C)
Barium Acetate 588,000 0
Barium Formate 262,000 0
Barium Carbonate 20 20
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Solubility in Water Temperature
Compound Name (mE/1) (°C)
Barium Chloride 317,000 0
Barium Bromide 922,000 0
Barium Iodide 170,000 0
Barium Hydroxide 17,000 0
Barium Nitrate 50,000 0
Barium Sulfate 3.36 50
Barium Hydrosulfide 326,000 0
Barium Sulfite 197 20
Sources: Kirkpatrick 1978, Weast 1977.
Additional wastewater data, primarily from EPA's Office of Water,
were analyzed. Average influent and effluent concentrations were given.
For two similar chemical precipitation technologies, these data show
treatment from 2.8 mg/1 to 42 mg/1 for one technology and from 2.8 mg/1
to 0.28 mg/1 for the other technology, both technologies being a
combination of sedimentation, lime precipitation, and filtration.
Further information on these data, including the sources of the data and
the treatment technologies used, can be found in the Best Demonstrated
Available Technology (BOAT) Background Document for Wastewaters
Containing BOAT List Constituents (USEPA 1990), and these data are
presented in Table 4-1 at the end of this section.
4.2 Performance Data for Nonwastewaters
The Agency believes that the data discussed in Section 4.1 for
treatment of wastewaters by chemical precipitation as sulfate or
carbonate also apply to D005 nonwastewaters; i.e., precipitates of barium
sulfate and carbonate are so insoluble that they are likely not to
require additional treatment.
Stabilization data were submitted in comments on the proposed
treatment standard (HWTC 1989a, 1989b). The performance data are
presented in Table 4-2. The reagents are proprietary.
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Stabilization data were also received from commenters (Tricil 1989,
Waste Management, Inc. (WMI) 1989, and Vision-Ease 1989). These data
were not used in calculating the treatment standard because no untreated
waste concentrations were included that correspond to the treated
values. For Tricil the data showed treatment values of 0.4 to 2.18 mg/1
EP for the treated waste; for WMI, values of 0.26 to 561 mg/1 for TCLP
for the treated waste; and for Vision-Ease, values of 3.2 to 150 mg/1 EP
for the treated waste. All three commenters used stabilization as a
method of treatment.
EPA's methodology for developing treatment standards requires that
untreated concentrations of hazardous constituents be reported in order
to determine whether treatment actually occurred (USEPA 1989a).
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Table 4-1 Performance Data for Barium Wastewaters
Range Average
influent effluent
Technology concentration concentration
Technology size (ppb) (ppb)
Lime Precipitation Full 2800 420.00
and
Sedimentation
Lime Precipitation Full 2800 280.00
and
Sedimentation and
Filtration
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Table 4-2 Performance Data for Stabilization of
Barium Nonwastewaters
Accuracy-Adjusted3
Untreated TCLP (mg/1) Stabilized TCLP (mg/1) Stabilized TCLP (mg/1)
353
2.38
353
2.38
353
2.38
12
1
19
1
6
0
.32
.01
.8
.14
.22
.883
14.49
1.19
23.29
1.34
7.32
1.04
Accuracy-adjusted by dividing stabilized TCLP concentration by the
recovery value of 0.85. Recovery values of 85-115 percent were
obtained by matrix spike recovery (USEPA 1989a). The lowest value
was used.
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5. DETERMINATION OF BEST DEMONSTRATED
AVAILABLE TECHNOLOGY (BOAT)
This section presents the Agency's rationale for determining best
demonstrated available technology (BDAT) for D005 wastewaters and
nonwastewaters.
To determine BDAT, the Agency examines all available performance data
on demonstrated technologies to determine (using statistical techniques)
whether one or more of the technologies perform significantly better than
the others. The technology that performs best on a particular waste or
waste treatability group is then evaluated to determine whether it is
"available." To be available, the technology must (1) be commercially
available to any generator and (2) provide "substantial" treatment of the
waste, as determined through evaluation of accuracy-adjusted data. In
determining whether treatment is substantial, EPA may consider data on
the performance of a waste similar to the waste in question, provided
that the similar waste is at least as difficult to treat. If the best
technology is not available, then the next best technology is evaluated,
and so on.
5.1 Wastewaters
For D005 wastewaters, the Agency has identified lime precipitation
followed by sedimentation and filtration as the "best" treatment. The
selection of this treatment is based on the performance data on chemical
precipitation from EPA's Office of Water, as discussed in Section 4.
5.2 Nonwastewaters
For D005 nonwastewaters, the Agency has identified stabilization as
the "best" treatment. The selection of stabilization is based on
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performance data on stabilization as a demonstrated technology. These
data are discussed in Section 4.
EPA has determined that the best demonstrated technologies specified
above for the D005 treatability groups (i.e., lime precipitation followed
by sedimentation and filtration for wastewaters; stabilization for
nonwastewaters) are commercially available and provide substantial
treatment. Hence, these technologies represent BOAT for D005 wastewaters
and nonwastewaters, respectively.
EPA has determined that the BDAT for treatment of D005 organobarium
wastes is incineration (a demonstrated technology for the destruction of
organics) followed by stabilization or leaching of the residual ash.
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6. CALCULATION OF BOAT TREATMENT STANDARDS
In this section, wastewater and nonwastewater D005 treatment
standards, based on the performance of the applicable BOAT, are developed.
6.1 Wastewaters
The BOAT for D005 wastewaters is lime precipitation followed by
sedimentation and filtration. EPA recognizes, however, the diversity of
wastes that qualify as hazardous under the D005 classification. Because
of this diversity, EPA has chosen to regulate D005 wastewaters at the
characteristic level of 100 mg/1. EPA believes even the most difficult
to treat D005 wastewaters can be treated to this level.
6.2 Nonwastewaters
The BOAT for D005 nonwastewaters is stabilization. The available
data, which are presented in Section 4, show that a treatment standard of
52 mg/1 is achievable for nonwastewater in TCLP leachates. The
calculation of the standard is presented as Table 6-1. EPA does not
believe that these data--which are very sparse--adequately represent the
diversity of wastes covered by the characteristic. Because of this
diversity, EPA has chosen to regulate D005 nonwastewaters at the
characteristic level of 100 mg/1 (see Table 6-2). EPA believes even the
most difficult to treat D005 nonwastewaters can be treated to this level.
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Table 6-1 Calculation of Achievable Treatment Standard for
D005 Nonwastewaters
Accuracy-adjusted Mean of
treated waste accuracy-adjusted
concentrations3 concentrations Treatment
(mg/1) (mg/1) Variability standard
Constituent (TCLP) (TCLP) factor (mg/1)
Barium 14.49b 15.03 3.5 52
Data were adjusted by dividing the treated waste concentration by the
recovery value of 0.85. Recovery values of 85-115 percent were found
by matrix spike recovery (USEPA 1989a). The lowest value was used.
Only those data sets where the untreated TCLP concentrations are
above the characteristic level of 100 mg/1 were used in the
calculation of the treatment standard.
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Table 6-2 BOAT Treatment Standards for D005 Wastes
Maximum for any single grab sample
Constituent Wastewater Nonwastewater
(mg/1) TCLP/mg/1)
Barium 100 100
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7. P013
This section addresses regulation of the only P waste that is listed
for barium. This waste, P013 - barium cyanide, is identified in 40 CFR
261.33 as "discarded commercial chemical products, off-specification
species, container residues, and spill residues thereof." Treatment
standards for cyanides in P013 wastes were promulgated in the Final Rule
for Second Third Wastes (54 FR 26614, June 23, 1989). Detailed
information on the development of cyanide treatment standards for P013
wastes is found in the BOAT Background Document for Cyanide Wastes (USEPA
1989c) . This section addresses only the development of a treatment
standard for barium in P013 wastes.
7.1 Industries Affected
Barium cyanide is prepared by the reaction of barium hydroxide with
hydrocyanic acid in water followed by low-temperature evaporation under
vacuum (Jenks 1978). Barium cyanide is used in the metallurgy and
electroplating industries (Hawley 1981). Additional information on the
industries affected by the land disposal restrictions for barium wastes
is presented in Section 2.1.
7.2 Applicable and Demonstrated Treatment Technologies
The treatment technologies described in Section 3 as being applicable
and demonstrated for D005 barium wastes are also considered to be
applicable and demonstrated for P013. EPA has no data suggesting that
other treatment technologies are applicable or demonstrated for P013
wastes.
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7.3 Determination of Best Demonstrated Available Technology
The Generator Survey data base listed barium concentrations from
10-100 ppm to 50-75 percent (USEPA 1986b). The concentrations of barium
in barium cyanide fit within this range and therefore could show similar
treatabilities.
EPA believes that P013 wastes, as commonly generated, are similar to
D005 wastes. Therefore, the Agency expects P013 wastes to be generated
as wastewaters or to be easily dissolvable in water prior to treatment.
The solubility in water of barium cyanide is 800 g/1 (Weast 1977).
Because barium cyanide is very water soluble, the Agency believes that
the best way to treat nonwastewater forms of P013 is to dissolve them in
water (if they are not already dissolved) and then treat them by a
technology applicable to wastewaters.
The Agency has identified lime precipitation followed by sedimenta-
tion and filtration as the "best" treatment for P013 wastewaters. These
technologies were part of the treatment train used as BOAT for regulating
the cyanide content of P013 (USEPA 1989c). However, EPA is not
regulating P013 wastewaters for barium but only for cyanides (USEPA
1989c). EPA believes that the treatment train used to treat P013
wastewaters for cyanides will effectively reduce the concentration of
barium at the same time.
For P013 nonwastewaters, the Agency has identified stabilization as
the "best" treatment. EPA has also determined that the best demonstrated
technologies specified above for P013 wastewaters and nonwastewaters are
commercially available and provide substantial treatment. Hence, these
technologies represent BDAT for P013 wastewaters and nonwastewaters.
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7.4 Selection of Regulated Constituents
EPA is not regulating for barium in P013 wastewaters, only for
cyanides. Treatment standards for cyanides in P013 wastes were
promulgated in the Final Rule for Second Third Wastes (54 FR 26614
June 23, 1989). Barium and cyanides are the only BOAT list constituents
that the Agency expects to find in the wastes on a regular basis (unless
these wastes are mixed with other listed hazardous wastes, in which case
other treatment standards would also apply). Note that barium and
cyanides are the only Appendix VIII constituents for which P013 wastes
are listed.
7.5 Calculation of Proposed Treatment Standards
P013 wastewaters are being regulated for cyanide but are not being
regulated for barium (USEPA 1989c). The Agency has identified lime
precipitation followed by sedimentation and filtration as the "best"
treatment for P013 wastewaters. These technologies were part of the
treatment train used as BOAT for regulating the cyanide content of P013
(USEPA 1989c). However, EPA is not regulating P013 wastewaters for
barium but only for cyanides. EPA believes that the treatment train used
to treat P013 wastewaters for cyanides will effectively reduce the
concentration of barium at the same time.
For P013 nonwastewaters, the Agency believes that stabilization is
BOAT. The treatment standard for P013 nonwastewaters is calculated in
Table 7-1. The treatment standard for P013 nonwastewaters is presented
in Table 7-2. Stabilization data have been transferred from D005
nonwastewaters to P013 nonwastewaters because of the expected
similarities of both wastes (after cyanide treatment). EPA has no data
suggesting that another standard would be applicable.
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7.19.2.4
Table 7-1 Calculation of Achievable Treatment Standard for
D005 Nonwastewaters
Accuracy-adjusted Mean of
treated waste accuracy-adjusted
concentrationsa concentrations Treatment
(mg/1) (mg/1) Variability standard
Constituent (TCLP) (TCLP) factor (mg/1)
Barium 14.49b 15.03 3.5 52
Data were adjusted by dividing the treated waste concentration by the
recovery value of 0.85. Recovery values of 85-115 percent were found
by matrix spike recovery (USEPA 1989a). The lowest value was used.
Only those data sets where the untreated TCLP concentrations are
above the characteristic level of 100 mg/1 were used in the
calculation of the treatment standard.
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Table 7-2 BOAT Treatment Standard for P013 Wastes
Maximum for any single grab sample
Constituent Wastewater Nonwastewater
(mg/1) TCLP (mg/1)
Barium NRa 52
NR = Not regulated.
aP013 wastewaters are not being regulated for barium but are being
regulated for cyanides. See the Best Demonstrated Available Technology
(BOAT) Background Document for Cyanide Wastes (USEPA 1989c).
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8. REFERENCES
APHA, AWWA, and WPCF. 1985. American Public Health Association, American
Water Works Association, and Water Pollution Control Federation.
Standard methods for the examination of water and wastewater. 16th
ed. Washington, D.C.: American Public Health Association.
CWM. 1987. Chemical Waste Management. Technical report no. 87-117:
Stabilization treatment of selected metal-containing wastes. Chemical
Waste Management, 150 West 137th Street, Riverdale, IL.
Ethyl Corp. 1989. Letter commenting on proposed rule for barium. EPA
Docket number (LD12-00184).
Green. 1984. Perry's chemical engineer's handbook. 6th ed.
pp. 19-49. New York: McGraw-Hill.
Hawley, G.G. 1981. The condensed chemical dictionary. 10th ed. New
York: Van Nostrand Reinhold Company, Inc.
HWTC. 1989a. Hazardous Waste Treatment Council. Data submission on
barium. EPA Docket No. LD12-00050.
HWTC. 1989b. Hazardous Waste Treatment Council. Data submission on
barium. EPA Docket No. LD12-00067.
Jenks, W.R. 1978. Cyanides. In Kirk Othmer encyclopedia of chemical
technology. Vol. 7, p. 334. New York: John Wiley and Sons.
Kirkpatrick, T. 1978. Barium compounds. In Kirk Othmer encyclopedia of
chemical technology. Vol. 3, pp.463-479. New York: John Wiley and
Sons.
Lubrizol. 1989. Letter commenting on proposed rule for barium. EPA
Docket No. LD12-00184.
Patterson, J.W. 1985. Industrial wastewater treatment technology.
2nd ed. Stoneham, Mass.: Butterworth Publishers.
SRI. 1989. SRI International. 1989 directory of chemical
producers, United States of America. Menlo Park, Calif.: SRI
International.
Tricil. 1989. Data submission on barium. EPA Docket No.
LD12-00094.
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USEPA. 1982. U.S. Environmental Protection Agency. Development
document for effluent limitations guidelines (BATEA). New source
performance standards and pretreatment standards for the inorganic
chemicals manufacturing point source category. Washington, D.C.: U.S.
Environmental Protection Agency.
USEPA. 1986a. 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. 1986b. U.S. Environmental Protection Agency, Office of Solid
Waste. National survey of hazardous waste generators. OMB No.
2050-0075. Washington, D.C.: U.S. Environmental Protection Agency.
USEPA. 1986c. U.S. Environmental Protection Agency, Office of Solid
Waste. National survey of hazardous waste treatment, storage,
disposal, and recycling facilities. OMB No. 2050-0070. Washington,
D.C.: U.S. Environmental Protection Agency.
USEPA. 1987a. U.S. Environmental Protection Agency. Onsite engineering
report for Horsehead Resource Development Company for K061. Draft
report. Washington, D.C.: U.S. Environmental Protection Agency.
USEPA. 1987b. U.S. Environmental Protection Agency. Onsite engineering
report for stabilization of F024 wastes. Washington, D.C.: U.S.
Environmental Protection Agency.
USEPA. 1988a. U.S. Environmental Protection Agency, Office of Solid
Waste. Generic quality assurance plan for Land Disposal Restrictions
Program ("BOAT"). Washington, D.C.: U.S. Environmental Protection
Agency.
USEPA. 1988b. U.S. Environmental Protection Agency, Office of Solid
Waste. Best demonstrated available technology (BOAT) background
document for K061. Washington, D.C.: U.S. Environmental Protection
Agency.
USEPA. 1988c. U.S. Environmental Protection Agency, Office of Solid
Waste. Best demonstrated available technology (BOAT) background
document for F006. Washington, D.C.: U.S. Environmental Protection
Agency.
USEPA. 1988d. U.S. Environmental Protection Agency, Office of Solid
Waste. Best demonstrated available technology (BOAT) background
document for K048-K052. Washington, D.C.: U.S. Environmental
Protection Agency.
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USEPA. 1988e. U.S. Environmental Protection Agency, Office of Solid
Waste. Best demonstrated available technology (BOAT) background
document for K086. Washington, D.C.: U.S. Environmental Protection
Agency.
USEPA. 1988f. U.S. Environmental Protection Agency, Office of Solid
Waste. Best demonstrated available technology (BOAT) background
document for K062. Washington, D.C.: U.S. Environmental Protection
Agency.
USEPA. 1989a. U.S. Environmental Protection Agency, Office of Solid
Waste. Methodology for developing BDAT treatment standards.
Washington, D.C.: U.S. Environmental Protection Agency.
USEPA. 1989b. U.S. Environmental Protection Agency, Office of Solid
Waste. Treatment technology background document. Washington, D.C.:
U.S. Environmental Protection Agency.
USEPA. 1989c. U.S. Environmental Protection Agency, Office of Solid
Waste. Best demonstrated available technology (BDAT) background
document for cyanide wastes. Washington, D.C.: U.S. Environmental
Protection Agency.
USEPA. 1990. U.S. Environmental Protection Agency, Office of Solid
Waste. Best demonstrated available technology (BDAT) background
document for wastewaters containing BDAT list constituents. Washington
D.C.: U.S. Environmental Protection Agency.
Versar Inc. 1980. Multimedia assessment of the Inorganic Chemicals
Industry. Task 4, Contract No. 68-03-2604. Final report for the
Industrial Environmental Research Laboratory, Vol. 3. Cincinnati,
Ohio: U.S. Environmental Protection Agency.
Vision-Ease. 1989. Data submission on barium. EPA Docket No.
LD12-00213.
Weast, R.C., ed. 1977. CRC handbook of chemistry and physics. 58th
ed. Cleveland: CRC Press Inc.
WMI. 1989. Waste Management, Inc. Data submission on barium. EPA
Docket No. LD12-00159.
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