FINAL
BEST DEMONSTRATED AVAILABLE TECHNOLOGY
(BDAT) BACKGROUND DOCUMENT FOR
SILVER-CONTAINING WASTES
Larry Rosengrant, Chief
Treatment Technology Section
Monica Chatmon-McEaddy
Project Manager
U.S. Environmental Protection Agency
Office of Solid Waste
401 M Street, S.W.
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 D011, P099 and P104 wastewaters and nonwastewaters. The
technical project officer for the waste was Ms. Monica Chatmon-McEaddy.
Mr. Steven Silverman served as legal advisor.
Versar personnel involved in the preparation of this document included
Mr. Jerome Strauss, Program Manager; Mr. Stephen Schwartz, Assistant
Program Manager; Ms. Christel Ackerman, Principal Investigator and Author;
Ms. Justine Alchowiak, Quality Assurance Officer; Ms. Martha M. Martin,
Technical Editor; and Ms. Sally Gravely, Program Secretary.
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TABLE OF CONTENTS
Section Page No.
1. INTRODUCTION AND SUMMARY 1-1
1.1 D011 Wastes 1-2
1.2 P099 and P104 Wastes 1-3
2. INDUSTRIES AFFECTED AND WASTE CHARACTERIZATION 2-1
2.1 Industries Affected and Process Descriptions 2-1
2.1.1 Production of Silver Chemicals 2-1
2.1.2 Uses of Silver Chemicals 2-2
2.2 Waste Characterization 2-4
3. APPLICABLE AND DEMONSTRATED TREATMENT TECHNOLOGIES 3-1
3.1 Applicable Treatment Technologies 3-1
3.1.1 Treatment Technologies for Nonwastewaters . 3-1
3.1.2 Treatment Technologies for Wastewaters .... 3-2
3.2 Demonstrated Treatment Technologies 3-3
4. PERFORMANCE DATA 4-1
5. DETERMINATION OF BEST DEMONSTRATED AVAILABLE
TECHNOLOGY (BOAT) 5-1
6. DEVELOPMENT OF BOAT TREATMENT STANDARDS 6-1
6.1 BOAT Treatment Standards for Nonwastewaters 6-1
6.2 BOAT Treatment Standards for Wastewaters 6-1
7. P WASTE CODES 7-1
7.1 Industries Affected 7-1
7.2 Applicable and Demonstrated Treatment
Technologies 7-1
7.3 Determination of Best Demonstrated
Available Technology 7-2
7.4 Selection of Regulated Constituents 7-2
7.5 Calculation of Treatment Standards 7-2
8. REFERENCES 8-1
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LIST OF TABLES
Page No.
Table 1-1 BDAT Treatment Standards for D011 1-4
Table 1-2 BDAT Treatment Standards for P099 and P104
Wastewaters 1-5
Table 1-3 BDAT Treatment Standards for P099 and P104
Nonwastewaters 1-5
Table 2-1 U.S. Industrial Distribution of Silver and Its
Compounds 2-3
Table 4-1 EPA Effluent Guidelines and Standards for
Photographic Processing for Silver 4-3
Table 4-2 Treatment Performance Data for Stabilization of
F006 Waste 4-4
Table 4-3 Wastewater Treatment Performance Data for Silver... 4-6
Table 6-1 BDAT Treatment Standards for D011 Nonwastewaters ... 6-2
Table 6-2 BDAT Treatment Standards for D011 Wastewaters 6-2
Table 7-1 BDAT Treatment Standards for P099 and P104
Wastewaters 7-4
Table 7-2 BDAT Treatment Standards for P099 and P104
Nonwastewaters 7-5
Table 7-3 Calculation of Treatment Standard for P099 and P104
Nonwastewaters 7-6
Table 7-4 Calculation of Treatment Standard for P099 and P104
Wastewaters 7-7
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1. INTRODUCTION AND SUMMARY
Pursuant to section 3004(m) of the Hazardous and Solid Waste
Amendments (HSWA), enacted on November 8, 1984, the Environmental
Protection Agency (EPA) is establishing treatment standards based on best
demonstrated available technology (BOAT) for the silver-containing wastes
identified in 40 CFR 261.24 as the waste code D011 and for commercial
chemical product wastes identified in 40 CFR 261.33 as P099 (potassium
silver cyanide) and P104 (silver cyanide). Treatment standards for
cyanide in P099 and P104 wastes were promulgated with the Second Third
land disposal restriction final rule (54 FR 26614, June 23, 1989).
Compliance with treatment standards is a prerequisite for placement of
these wastes in facilities designated as land disposal treatment units
according to 40 CFR Part 268.
This background document presents the Agency's technical support and
rationale for developing regulatory standards for these wastes. Sections
2 through 6 present waste-specific information for the D011 wastes.
Section 2 identifies the number and location of facilities affected by
the land disposal restrictions for D011 wastes, discusses processes
generating these wastes, and presents all available waste characterization
data. Section 3 discusses the technologies used to treat the waste (or
similar wastes), and Section 4 presents available performance data,
including data on which the treatment standards are based. Section 5
explains EPA's determination of BDAT. Promulgated treatment standards
are determined in Section 6. Section 7 discusses associated
silver-containing P-code wastes and details the development of treatment
standards for these wastes.
The BDAT program and promulgated methodology are more thoroughly
described in two additional documents: Methodology for Developing BDAT
Treatment Standards (USEPA 1989a) and the Generic Quality Assurance
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Project Plan for Land Disposal Restrictions Program ("BDAT") (USEPA
1988a). The petition process to be followed in requesting a variance
from the BDAT treatment standards is discussed in the methodology
document.
It is EPA's understanding that relatively few facilities presently
generate D011 wastes. From a partial analysis of responses to EPA's 1986
National Survey of Hazardous Waste Generators, the Agency has identified
35 facilities that generate D011 wastes. These wastes are primarily the
wastewater treatment sludges from the production and use of silver
compounds. For the purpose of BDAT these are usually nonwastewaters. A
wastewater is defined by the Agency as containing less than 1 percent
(weight basis) total suspended solids* and less than 1 percent (weight
basis) total organic carbon (TOG). Wastes not meeting this definition
must comply with the treatment standards for nonwastewaters.
1.1 D011 Wastes
The Agency is promulgating a treatment standard for D011 wastes at
the characteristic level of 5 mg/1. The data available to EPA show that
nonwastewater and wastewater treatment standards of 0.072 mg/1 and
0.29 mg/1, respectively, are achievable. However, EPA recognizes the
diversity of wastes that qualify as hazardous under the D011
classification and is, therefore, promulgating a treatment standard of
5 mg/1 for all D011 wastes.
* The term "total suspended solids" (TSS) 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 to 105°C) in Standard Methods
for the Examination of Water and Wastewater, 15th Edition (APHA, AWWA,
and WPCF 1985).
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1.2 P099 and P104 Wastes
The promulgated BOAT for nonwastewater forms of P099 and P104 is
recovery or stabilization. The Agency realizes that because of its
economic value, silver is usually recovered from wastes where it is
contained at relatively high concentrations. However, the Agency also
realizes that wastes with a silver content of less than about 5 mg/1
(Kodak 1989) or with the silver present at low concentrations in complex
matrices, e.g., organic sludges, may not be suitable for most recovery
technologies.
The data available to EPA show that a treatment standard of
0.072 mg/1 for nonwastewater forms of P099 and P104 is achievable (see
Section 4.0). This treatment standard was promulgated in Second Thirds
final rule.
The data available to EPA show that a treatment standard of 0.29 mg/1
for wastewater forms P099 and P104 is achievable (see Section 4.0).
Therefore, EPA is promulgating a treatment standard of 0.29 mg/1 for
wastewater forms of P099 and P104.
Table 1-2 presents BOAT treatment standards for P099 and P104
wastewaters and Table 1-3 presents BOAT treatment standards for P099 and
P104 nonwastewaters, which were promulgated in the Second Thirds Final
Rule for F006 (USEPA 1988b).
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Table 1-1 BOAT Treatment Standards for D011
Nonwastewaters Wastewaters
Maximum for any Maximum for any
single grab sample single grab sample
Regulated constituent TCLP (mg/1) Total composition (mg/1)
Silver 5.0 5.0
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Table 1-2 BDAT Treatment Standards for P099
and P104 Wastewaters
Maximum (24 hr. composite sample)
Regulated constituent Total concentration
(mg/1)
Silver 0.29
Cyanide (total)* 1.9
Cyanide (amenable)* 0.10
*These constituents were promulgated in the Second Thirds Final Rule.
Table 1-3 BDAT Treatment Standards for P099 and P104
Nonwastewaters
Maximum for any single grab sample
Regulated constituent TCLP Total concentration
(mg/1) (mg/kg)
Silver 0.072 NA
Cyanide (total)* NA 110
Cyanide (amenable)* NA 9.1
*These constituents were promulgated in the Second Thirds Final Rule.
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2. INDUSTRIES AFFECTED AND WASTE CHARACTERIZATION
The Agency has determined that D011 wastes represent one treatability
group for nonwastewaters and another treatability group for wastewaters
based on their physical and chemical characteristics. As described later
in this report, EPA has examined the sources of the wastes, specific
similarities in waste composition, applicable and demonstrated treatment
technologies, and attainable treatment performance in order to support a
simplified regulatory approach for silver-containing wastes.
2.1 Industries Affected and Process Descriptions
2.1.1 Production of Silver Chemicals
Silver is used in industry in two forms--as the metal and as various
silver compounds. Presently, eight silver compounds are produced in
commercial quantities. These compounds are discussed below.
Silver nitrate represents the largest volume of silver-containing
chemical manufactured. Its production involves digestion of silver in
nitric acid to form a silver nitrate solution that is partially
evaporated and fed to crystallizers to recover silver nitrate crystals.
The mother liquor is recycled. Wastes from this process are in the form
of wastewaters. Treatment of these wastewaters generates silver-contain-
ing residues that are reclaimed when the silver content is high enough.
Other silver salts are produced from the silver nitrate. Silver
chloride, silver bromide, and silver iodide, for example, are produced by
reaction of silver nitrate in solution with sodium chloride, sodium
bromide, or sodium iodide. The insoluble product precipitates from
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solution, is recovered by filtration, and then is washed and dried.
These processes give rise to waterborne wastes, the treatment of which
results in silver-bearing residues. Silver oxide, silver carbonate, and
silver sulfide are made by similar processes involving reaction in
aqueous solution of silver nitrate with sodium hydroxide, sodium
carbonate, or sodium sulfide, respectively. In all cases, the products
precipitate from solution and are then collected by filtration and dried.
Silver cyanide is produced by reaction of sodium cyanide and silver
nitrate in solution under carefully controlled conditions. Again, the
insoluble product precipitates from solution, is collected by filtration,
and then is washed, dried, and packaged. Treatment of the wastewaters
generated by this process yields silver-bearing residues.
2.1.2 Uses of Silver Chemicals
Table 2-1 lists the major uses of silver and its alloys. The largest
use is in the photographic industry, where silver chloride, silver
bromide, and silver iodide are used in the manufacture of photographic
films. Both the manufacture and subsequent processing (developing) of
the films generate a variety of silver-containing nonwastewaters and
wastewaters. Wastewater treatments generate silver-bearing sludges,
which are mostly reclaimed for silver value.
Brazing solders frequently contain silver chloride as a fluxing
agent, and the manufacture and use of these solders generate wastes
containing silver chloride. The production of silver oxide-zinc
batteries gives rise to wastewaters and nonwastewaters containing
silver. The same is true for the production and reclamation of silver
oxide catalysts.
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Table 2-1 U.S. Industrial Distribution of Silver and Its Compounds
Industry
Silver compounds
used
Percent
Photographic film manufacturing
Electrical contacts
Brazing alloys and solders
Sterling silverware
Batteries
Jewelry
Electroplating
Coins and medallions
Catalysts
Dental and medical supplies
Mirrors
Bearings
Other
Nitrate, halides
Metal
Chloride
Metal
Oxide
Metal
Cyanide
Metals
Oxide
Metal
Nitrate
Metal
Metal
41.2
21.6
7.4
6.8
5.3
4.1
3.5
3.5
3.3
1.6
0.5
0.2
1.0
100.0
Source: Lockhart, H.B. 1981.
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Electroplating operations consume considerable quantities of silver
cyanide and complex silver cyanide salts such as potassium silver cyanide.
The listed wastes generated by these operations (F006, F007, F008, and
F009) are discussed in EPA's Best Demonstrated Available Technology (BOAT)
Background Document for F006 (USEPA 1988b) and Best Demonstrated Available
Technology (BOAT) Background Document for Cyanide Wastes (USEPA 1989c).
In the production of mirrors, two separate solutions, one of an
ammonia-complexed silver nitrate and the other containing an organic
compound such as formaldehyde, are reacted on the glass surface to be
coated. A coating of silver forms on the glass surface. The mirror is
then rinsed, and a silicone coating may be applied to protect the
silvered surface. This process generates waterborne wastes containing
silver. Subsequent treatment of the wastewaters generates silver-bearing
residues.
2.2 Waste Characterization
The Agency has data from EPA's National Survey of Hazardous Waste
Generators (USEPA 1986) on the approximate composition of the types of
D011 wastes currently generated. The nonwastewater forms of D011 contain
from 0.1 up to 100,000 parts per million (ppm) of silver. Other metals
are typically present at comparable concentrations. Most nonwastewaters
contain very low levels of organics. The wastewater forms of D011
contain from 0.1 to 10,000 ppm of silver. Frequently, other metals are
also present. In a few cases, organics may be present at concentrations
up to 1 percent. Cyanides are usually not present because most silver-
cyanide electroplating wastes are reclaimed rather than disposed of.
Most of the facilities reporting D011 wastes in the Generator Survey
were plants producing photographic chemicals, electronics equipment, or
aerospace-related products. The nature of the individual processes
generating the waste streams is quite varied and includes most of the
operations identified as significant consumers of silver salts.
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3. APPLICABLE AND DEMONSTRATED TREATMENT
TECHNOLOGIES
This section identifies the treatment technologies that are
applicable to treatment of these wastes and determines which, if any, of
the applicable technologies can 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 for 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
3.1.1 Treatment Technologies for Nonwastewaters
Two types of technologies are applicable to nonwastewater forms of
D011: silver recovery and stabilization.
(1) Silver recovery technologies. Three types of silver recovery
technologies are in use today: electrolytic recovery, cementation
processes, and high-temperature recovery processes (Lockhart 1981).
Electrolytic recovery involves digestion of the waste to solubilize the
silver present followed by electrolysis of the silver-bearing solution
generated. This is the process most frequently used to recover silver
from photographic film. The silver recovered by electrolysis is generally
sent to precious metals refineries for purification prior to reuse.
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Cementation is an oxidation/reduction process for recovery of
metallic silver. Cementation processes involve initial digestion of the
waste to solubilize the silver. The silver-containing solution is
filtered to remove insoluble residues, and a finely divided non-noble
metal, such as zinc dust, is added. Zinc dissolves in the solution,
replacing the silver, which precipitates as silver metal. The silver
metal is recovered and sent to a precious metal refinery.
Recovery of silver in residues generated by chemical precipitation or
reduction processes also involves an initial digestion of the waste to
solubilize the silver, followed by wastewater treatment as described in
the next section. Residues from the wastewater treatment processes
(nonwastewaters) are collected by filtration and sent to a precious
metals reclaimer, where the impure silver recovered is purified by
high-temperature processes to yield a 99.9 percent purity product. The
reclamation process involves roasting of the silver sulfide filter cake
to thermally convert it to the metal and subsequent refining of the metal.
(2) Stabilization. Residues generated by chemical treatment
processes such as chemical reduction and sulfide precipitation may be
treated for silver recovery as described in Section 3.1.1(1) or
stabilized with lime, cement, or fly ash formulations prior to land
disposal. Stabilization technologies are discussed in the Treatment
Technology Background Document (USEPA 1989b).
3.1.2 Treatment Technologies for Wastewaters
The silver recovery and chemical treatment processes described above
are applicable to wastewaters as well as nonwastewaters. The chemical
treatment processes will either reduce silver salts to the metal for
recovery or precipitate silver as insoluble silver salts such as silver
sulfide or silver chloride.
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(1) Chemical reduction. In chemical reduction technologies, the
waste is treated with a solution containing a reducing agent such as
ferrous salt or sodium bisulfite. The reducing agent reacts with the
soluble silver compounds present to generate elemental silver, which
precipitates from solution. Chemical reduction technologies are
discussed in greater detail in the Treatment Technology Background
Document (USEPA 1989b).
(2) Chemical precipitation. Sulfide precipitation converts
soluble silver salts to insoluble silver sulfide. Chloride compounds may
also be used to remove silver from wastewaters as insoluble silver
chloride. Chemical precipitation technologies are discussed in greater
detail in the Treatment Technology Background Document (USEPA 1989b).
3.2 Demonstrated Treatment Technologies
Silver recovery technologies (e.g., electrolysis, cementation, and
high-temperature recovery) have been in widespread use in the
photographic chemicals and photographic processing industries for over a
decade. A 1977 study, for example, showed extensive use of these
technologies at photographic processing facilities (Haderer and DeFilippi
1977). These technologies were installed primarily for economic reasons
(i.e., to maximize silver recovery and minimize silver losses).
Chemical reduction, chemical precipitation, and stabilization are
demonstrated technologies that have been in full-scale use for many years
in industry. In fact, effluent limitations guidelines for several
segments of the inorganic chemicals industry are based on the use of
chemical reduction and chemical precipitation technologies (USEPA 1982).
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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 5). 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 3.
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 that were measured at the
time the waste was being treated, values of relevant design parameters
for the treatment technology, and data on waste characteristics that
affect the 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.
The Agency has data on the effectiveness of recovery technologies
in those industries using silver salts, such as the photographic
processing industries. Most of these data have been accumulated from
earlier Agency studies aimed at developing effluent limitations
guidelines for the photographic industry (USEPA 1976). The data
basically show that with the use of one or more of the silver recovery
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systems, photographic processing plants could meet the 1977 effluent
limitations guidelines for silver (as a time-weighted average) of
0.45 mg/1 in their wastewaters. Table 4-1 presents a summary of the
silver standard for photographic processing.
The Agency also has extensive data on the use of chemical
precipitation and stabilization of the waste F006. These data are
included in Table 4-2.
Additional wastewater treatment data, primarily from EPA's Office
of Water, have been analyzed for the development of concentration-based
treatment standards for and other wastewaters. These data are presented
in Table 4-3. Available data from the Office of Water's Industrial
Technology Division (ITD) and the Hazardous Waste Engineering Research
Laboratory (WERL) data bases were used, and a treatment standard of
0.29 mg/1 for P099 and P104 wastewaters was calculated. Further
information on these data, including the sources of the data and the
treatment technologies used, can be found in the preamble to the proposed
rule and in the Best Demonstrated Available Technology (BOAT) Background
Document for Wastewaters Containing BOAT List Constituents (USEPA 1989d).
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Table 4-1 EPA Effluent Guidelines and Standards for
Photographic Processing for Silver
Plant No.
32
33
34
Raw waste load average
Raw waste load
concentration (mg/1)
Type of
operation
Color
(0.013)
Color
Color
Influent concentration
Raw waste load
Silver
kg/1000 raz
(lbs/1000 ft2(mg/1)
32
33
Black and white
Black and white
0.10
(0.02)
0.08
(0.016)
0.06
0.05
(0.011)
0.08
(0.016)
0.07
(0.015)-
0.45
Plant 32 - black and white not included in raw waste load average.
Source: USEPA 1976.
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Table 4-2 Treatment Performance Data for Stabilization of F006 Waste
Concentration
Constituent
Untreated waste Treated waste - TCLP (nut/1)
Total TCLP Binder-to-waste ratio3
(mg/kg) (mg/l) 0.2 0.5 1.0 1.5
Sample Set #1
(Source-unknown)
Silver
Oil and grease
TOC
2.3
1,520
14,600
0.01
0.03
NR
NR
NR
Sample Set #2
(Source-auto parts
manufacturing)
Silver
Oil and grease
TOC
6.62
60
1,500
0.14
0.03
0.05
NR
NR
Sample Set #3
(Source-aircraft over-
hauling facility)
Silver
Oil and grease
TOC
39.0
37,000
137,000
0.02
0.20
0.05
NR
NR
Sample Set #4
(Source-aerospace manufacturing-
mixture of F006 & F007)
Silver 6.26
Oil and grease 3,870
TOC 6,280
1.64
NR
NR
0.09
0.15
Sample Set #5
(Source-zinc plating)
Silver 9.05
Oil and grease 1,150
TOC 21,200
0.16
0.03
0.04
NR
NR
Sample Set #6
(Source-unknown)
Silver
Oil and grease
TOC
5.28
20,300
28,600
0.08
0.04
0.06
NR
NR
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Table 4-2 (continued)
Constituent
Concentration
Untreated waste
Total
(ing/kg)
TCLP
(mg/1)
Treated waste - TCLP (mg/1)
a
Binder-to-waste ratio'
0.2 0.5 1.0 1.5
Sample Set #7
(Source-small engine
manufacturing)
Silver
Oil and grease
TOC
4.08
2,770
6,550
0.12
0.03
0.05
NR
m
Sample Set #8
(Source-circuit board
manufacturing )
Silver
Oil and grease
TOC
12.5
130
550
0.05
0.03
0.05
NR
NR
Sample Set Y>9
(Source-unknown)
Silver
Oil and grease
TOC
8.11
30
10,700
0.31
0.03
0.05
NR
NR
Sample Set #10
(Source-unknown)
Silver
Oil and grease
TOC
19.1 <0.01
1,430
5,960
<0.01 <0.01 NR NR
-
— — _ _
Not applicable.
NR
Results of tests at this binder-to-waste ratio were not reported.
•Binder-to-waste ratio
weight of binder material
weight of waste
Oil and grease and total organic carbon (TOC) have been identified by EPA as
waste characteristics that affect the performance of stabilization.
""Circuit board manufacturing waste is not in its entirety defined as F006;
however, an integral part of the manufacturing operation is electroplating.
Treatment residuals generated from treatment of these electroplating wastes are
F006.
Source: CWM 1987.
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Table 4-3 Hastewater Treatment Performance Data for Silver
Technology
AL
AS
AS
As
As
AS
As
AS
AS
AS
AS
AS
AS
AS
AS
AS
AS
L+Sed
L+Sed+Fil
Pt+Sed
Sed+Fil
TF
TF
TF
TF
Technology
size
Full
Full
Full
Full
Full
Full
Full
Full
Full
Full
Full
Full
Full
Full
Full
Full
Full
Full
Full
Full
Full
Full
Full
Full
Full
Facility
IB
97 SB
IB
20 IB
IB
IB
IB
IB
IB
IB
IB
IB
IB
IB
IB
IB
IB
IB
IB
IB
IB
Detection Range
limit Influent
(ppb) concentration
0-100
0-100
0-100
0-100
0-100
0-100
0-100
0-100
0-100
0-100
0-100
0-100
0-100
0-100
0-100
0-100
0-100
4700
4700
10 0-600000
0-100
0-100
0-100
0-100
No. of
Data
points
6
6
35
6
6
6
6
6
6
6
6
6
6
6
6
6
21
6
6
6
6
Average
Effluent Recovery
concentration (X)
2.000
15.000
2.000
1.000
5.000
2.000
3.000
1.000
1.000
1.000
5.000
3.000
5.000
2.000
3.000
5.000
1.000
100.000
70.000
96.000
50.000
2.000
7.000
S.OOO
3.000
Removal
(X)
60.00
50.00
94.10
86.00
50.00
78.00
87.00
88.00
86.00
80.00
71.00
85.00
67.00
90.50
81.00
72.00
90.90
90.00
63.00
47.00
73.00
Reference
HERL
WERL
WERL
WERL
HERL
HERL
HERL
HERL
HERL
HERL
HERL
HERL
HERL
HERL
HERL
HERL
HERL
ITD-CMDB
ITD-CMDB
ITD-MF
ITD-CMDB
HERL
HERL
HERL
HERL
Source: USEPA 1989d.
3654g
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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 nonwastewater and wastewater
forms of D011.
To determine BDAT, the Agency examines all available performance data
on technologies that are identified as demonstrated to determine (using
statistical techniques) 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 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 found to be not
available, then the next best technology is evaluated, and so on.
The most desirable waste management technology is one that results in
no residual streams or a residual stream with no hazardous properties.
In this instance, silver recovery eliminates the D011 waste streams in
many cases. This is especially true for wastewaters, where most if not
all of the silver can be recovered from these waste streams as metal.
For nonwastewater forms of D011, recovery technologies also reduce the
concentrations of silver present in wastes to be land disposed.
The Agency realizes, however, that not all nonwastewater and
wastewater forms of D011 may be readily amenable to recovery processes.
Silver may be present in refractory solid matrices from which it cannot
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be easily extracted, or it may be present in solution in the form of
complex ions that cannot easily be treated by recovery processes. For
nonwastewater forms of D011 wastes from which silver cannot be recovered,
the best technology has been determined to be stabilization, based on
data on stabilization of wastewater treatment sludges (F006) with
significant concentrations of leachable silver (up to 1.64 mg/1 in the
untreated waste TCLP leachate). Stabilization has been shown to reduce
the leachability of silver in these wastes. Accordingly, the Agency has
determined that either recovery or stabilization represents BOAT for
nonwastewater forms of D011.
For wastewaters where silver recovery is not viable, chemical
treatment is the best technological treatment option. Chemical treatment
(either chemical reduction or chemical precipitation) removes soluble
silver salts either as the metal or as insoluble silver compounds. EPA
has data that show that chemical precipitation followed by filtration is
used for treatment of most D011 wastewaters from which silver is not
recovered and that the use of this technology results in the generation
of wastewater residuals in which the silver concentration is
substantially reduced from the concentration in the untreated waste.
Accordingly, the Agency has determined that chemical precipitation
followed by filtration represents BOAT for D011 wastewaters.
EPA has determined that the best demonstrated technologies specified
above for the D011 treatability groups (i.e., recovery or chemical
precipitation followed by sedimentation and filtration for wastewaters
and recovery or stabilization for nonwastewaters) are also commercially
available and provide substantial treatment. Hence, these technologies
represent BOAT for D011 wastewaters and nonwastewaters.
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6. DEVELOPMENT OF BOAT TREATMENT STANDARDS
In Section 5, the Agency chose the best demonstrated available
technologies for both nonwastewaters and wastewaters based on the
treatment data available to the Agency. In this section, BOAT treatment
standards are verified based on the performance of these technologies.
Silver is selected as the only regulated constituent because it is the
only constituent for which this waste is listed. If D011 wastes are
mixed with other listed or characteristic hazardous wastes and thus
contain other constituents, other treatment standards also apply.
The Agency bases treatment standards for regulated constituents on
the performance of well-designed and well-operated BDAT treatment
systems. These standards must account for analytical limitations in
available performance data and must be adjusted for variabilities related
to treatment, sampling, and analytical techniques and procedures.
6.1 BDAT Treatment Standards for Nonwastewaters
EPA recognizes the diversity of wastes that qualify as hazardous
under the D011 classification. Because of this diversity, EPA has chosen
to regulate D011 nonwastewaters at the characteristic level of 5 mg/1 in
the TCLP leachate. Data available show that the characteristic level can
be met.
6.2 BDAT Treatment Standards for Wastewaters
EPA recognizes the diversity of wastes that qualify as hazardous
under the D011 classification. Because of this diversity, EPA has chosen
to regulate D011 wastewaters at the characteristic level of 5 mg/1 in the
TCLP leachate.
Tables 6-1 and 6-2 show the promulgated treatment standards for D011
nonwastewasters and wastewaters, respectively.
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Table 6-1 BOAT Treatment Standards for D011
Nonwastewaters
Maximum for any
single grab sample
Regulated Constituent TCLP (mg/1)
Silver 5.0
Table 6-2 BDAT Treatment Standards for D011
Wastewaters
Maximum for any
single grab sample
Regulated constituent Total composition (mg/1)
Silver 5.0
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7. P WASTE CODES
This section addresses regulation of P-code wastes that are listed
for silver. These wastes, P099 (potassium silver cyanide) and P104
(silver cyanide), are identified in 40 CFR 261.33 as "discarded
commercial chemical products, off-specification species, container
residues, and spill residues thereof." Treatment standards for cyanide
in P099 and P104 wastes were promulgated with the Second Third Land
Disposal Restrictions Final Rule (54 FR 26614, June 23, 1989). Therefore,
this section will address only the development of a treatment standard
for silver in P099 and P104 wastes. Detailed information on the
development of cyanide treatment standards for P099 and P104 wastes is
included in the Best Demonstrated Available Technology (BOAT) Background
Document for Cyanide Wastes (USEPA 1989c).
7.1 Industries Affected
Silver cyanide is prepared by the reaction of silver nitrate and
sodium cyanide under carefully controlled conditions. Potassium silver
cyanide is prepared by reacting silver nitrate with potassium cyanide.
Silver cyanide and potassium silver cyanide are used in the metal
finishing industry in electroplating operations as a source of soluble
silver. Additional information on the industries affected by the land
disposal restrictions for silver 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 D011 silver wastes are also considered to be
applicable and demonstrated for P099 and P104 wastes. EPA has no data
suggesting that other treatment technologies are applicable or
demonstrated for silver in P099 and P104 wastes.
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7.3 Determination of Best Demonstrated Available Technology
Silver cyanide is a relatively insoluble compound (approximately 0.2
ppm silver). Therefore, these wastes will be generated primarily as
nonwastewaters. However, these wastes may have to be dissolved in order
to treat them for cyanide by aqueous chemical oxidation treatment methods.
Based on performance data on the treatment of silver-containing
wastes, as presented in Section 4, the Agency has identified chemical
precipitation followed by sedimentation and filtration as the "best"
treatment for P099 and P104 wastewaters. For P099 and P104
nonwastewaters, the Agency has identified recovery or stabilization as
the "best" treatment.
EPA has also determined that the best demonstrated technologies
specified above for P099 and P104 wastewaters and nonwastewaters are
commercially available and provide substantial treatment. Hence, these
technologies represent BOAT for P099 and P104 wastewaters and
nonwastewaters.
7.4 Selection of Regulated Constituents
EPA is promulgating a treatment standard for silver in P099 and P104
wastes. Silver and cyanide are the only Appendix VIII constituents for
which P099 and P104 wastes are listed, and they 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).
7.5 Calculation of Treatment Standards
The Agency is promulgating recovery or stabilization as BOAT for P099
and P104 wastewaters. The Agency is also promulgating a treatment
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standard for silver based on the performance of chemical precipitation
followed by sedimentation and filtration. The calculation of this
treatment standard is presented in the Best Demonstrated Available
Technology (BOAT) Background Document for Wastewaters Containing BOAT
List Constituents (USEPA 1989d). The promulgated treatment standard for
P099 and P104 wastewaters is summarized in Table 7-1, and the calculation
of this standard is shown in Table 7-3.
For P099 and P104 nonwastewaters, the Agency is promulgating recovery
or stabilization as BOAT for these wastes. The promulgated treatment
standard is based on the performance of stabilization for F006 wastes.
This treatment standard is summarized in Table 7-2, and the calculation
of this standard is shown in Table 7-4.
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Table 7-1 BOAT Treatment Standards for P099
and F104 Wastewaters
Maximum for any 24-hour
composite sample
Regulated Constituent Total composition (mg/1)
Silver 0.29
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Table 7-2 BOAT Treatment Standards for P099 and
P104 Nonwastewaters
Maximum for any
single grab sample
Regulated Constituent TCLP (mg/1)
Silver* 0.072
*This constituent was promulgated in the Second Thirds Final Rule.
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Table 7-3 Calculation of Treatment Standard for
P099 and P104 Wastewaters
Regulated
constituent
Average
effluent
concentration
(ppb)
Accuracy
correction
factor
Variability
factor
BOAT
Treatment
standard
(ppb)
Silver
100
70
96
50
70
NA
4.1
290
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Table 7-4 Calculation of Treatment Standard for
P099 and P104 Nonwastewaters
Accuracy-adjusted Mean treated
treated waste waste Treatment
leachate leachate standard
concentration concentration Variability (TCLP)
Regulated (mg/1) (mg/1) factor (VF)a (mg/1)
constituent (1) (2) (3) (4) - (2)x(3)
Silver
0.03
0.09
0.03
0.03
0.03
0.03
0.04 1.8 0.072
aSee Methodology Document (USEPA 1989a) for details of the method of
calculation of variability factor.
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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. Stabilization treatment of
selected metal-containing wastes. Technical note 87-117. September
1987. Riverdale, IL: Chemical Waste Management.
Haderer, P.A., and DeFilippi, J.A. 1977. Reducing photoprocessing
wastes through reuse and recycling. Industrial Photography. June
1977, pp.22-45.
Kodak. 1989. Public comment submitted in response to EPA proposed land
disposal restrictions for Third Third Scheduled Wastes. January 1989.
EPA RCRA Docket No. LD12-00176. Washington, D.C.: U.S. Environmental
Protection Agency.
Lockhart, H.B. 1981. Silver compounds. In Kirk Othmer encyclopedia of
chemical technology, Vol. 21, pp. 16-32. New York: John
Wiley-Interscience.
Stanford Research Institute. 1989. Directory of chemical producers,
United States of America. Menlo Park, California: Stanford Research
Institute.
USEPA. 1976. U.S. Environmental Protection Agency, Office of Water.
Development document for effluent limitations guidelines and new source
performance standards for the photographic processing subcategory of
the photographic point source category. Washington, D.C.: U.S.
Environmental Protection Agency.
USEPA. 1982. U.S. Environmental Protection Agency, Office of Water.
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. 1986. U.S. Environmental Protection Agency, Office of Solid
Waste. National survey of hazardous waste generators.
Washington, D.C.: U.S. Environmental Protection Agency.
USEPA. 1988a. U.S. Environmental Protection Agency, Office of Solid
Waste. Generic quality assurance project plan for land-disposal
restrictions program ("BOAT"). Washington, D.C.: U.S. Environmental
Protection Agency.
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USEPA. 1988b. 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. 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. 1989d. 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.
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