PROPOSED
BEST DEMONSTRATED AVAILABLE TECHNOLOGY (BDAT)
BACKGROUND DOCUMENT FOR MERCURY WASTES
U.S. Environmental Protection Agency
Office of Solid Waste
401 M Street, S.W.
Washington, D.C. 20460
Larry Rosengrant, Chief
Treatment Technology Section
Jose' Labiosa
Project Manager
November 1989
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Table of Contents
Section Page
1. INTRODUCTION 1-1
2. INDUSTRIES AFFECTED AND WASTE CHARACTERIZATION 2-1
2.1 Industries Affected and Process Descriptions 2-2
2.1.1 Manufacture of Mercury Batteries 2-5
2.1.2 Chlorine Production by the Mercury Cell Process .... 2-6
2.1.3 Manufacture and Use of Organomercury Fungicides
and Bactericides 2-10
2.2 Waste Characterization 2-11
2.2.1 K071 2-11
2.2.2 K106 2-11
2.2.3 P065 2-17
2.2.4 P092 2-17
2.2.5 U151 2-17
2.2.6 D009 2-18
2.3 Determination of Waste Treatability Groups 2-18
2.3.1 Mercury Nonwastewaters 2-20
2.3.2 Radioactive Wastes Containing Mercury 2-24
2.3.3 Wastewaters 2-25
3. APPLICABLE/DEMONSTRATED TREATMENT TECHNOLOGIES 3-1
3.1 Applicable Treatment Technologies 3-1
3.1.1 Applicable Technologies for Nonwastewaters 3-1
3.1.2 Applicable Technologies for Wastewaters 3-5
3.2 Demonstrated Treatment Technologies 3-7
3.2.1 Demonstrated Technologies for Nonwastewaters 3-7
3.2.2 Demonstrated Technologies for Wastewaters 3-9
4. PERFORMANCE DATA 4-1
4,1 Performance Data for Nonwastewaters 4-1
4.2 Performance Data for Wastewaters 4-2
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Table of Contents (Continued)
Section Page
5. DETERMINATION OF BEST DEMONSTRATED AVAILABLE TECHNOLOGY
(BOAT) 5-1
5.1 BOAT for Nonwastewaters 5-2
5.1.1 Inorganic Mercury Nonwastewaters - High-Mercury
Subcategory 5-2
5.1.2 Inorganic Mercury Nonwastewaters - Low-Mercury
Subcategory 5-5
5.1.3 Organic Mercury Nonwastewaters 5-6
5.1.4 Radioactive Nonwastewaters Containing Mercury 5-6
5.2 BOAT for Wastewaters 5-8
6. SELECTION OF REGULATED CONSTITUENTS 6-1
6.1 Nonwastewaters 6-1
6.2 Wastewaters 6-3
7. CALCULATION OF TREATMENT STANDARDS 7-1
7.1 Nonwastewaters 7-2
7.2 Wastewaters 7-3
8. REFERENCES 8-1
APPENDIX A QUALITY ASSURANCE/QUALITY CONTROL DATA A-l
ii
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LIST OF TABLES
Paee
Table 1-1 Proposed BOAT Treatment Standards for D009
K106, P065, P092, and U151 Wastewaters 1-8
Table 1-2 Proposed BOAT Treatment Standards for K106
and' U151 Nonwastewaters 1-10
Table 1-3 Proposed Revised BDAT Treatment Standards for K071
Nonwastewaters 1-9
Table 1-4 Proposed BDAT Treatment Standards for P065
and P092 Nonwastewaters 1-11
Table 1-5 Proposed BDAT Treatment Standards for D009
Nonwastewaters 1-12
Table 1-6 Proposed BDAT Treatment Standards for D009 and U151
Elemental Mercury Contaminated with Radioactive
Materials 1-13
Table 1-7 Proposed BDAT Treatment Standards for D009 Hydraulic
Oil Contaminated with Mercury and Radioactive
Materials 1-14
Table 2-1 Major Industrial Uses of Mercury 2-4
Table 2-2 Number of Producers of Chlorine Using the Mercury Cell
Process Listed by State 2-7
Table 2-3 Number of Producers of Chlorine Using the Mercury Cell
Process Listed by EPA Region 2-8
Table 2-4 Waste Composition Data for Untreated K106 Wastes 2-12
Table 2-5 Waste Composition Data for D009 Wastes 2-19
Table 4-1 Retorting Performance Data from Thermal Recovery of
Mercuric Sulfide Ores Collected by EPA at Plant A 4-3
Table 4-2 Treatment Performance Data for Retorting of K106
Hydrazine Sludge Submitted by Plant B 4-8
Table 4-3 Treatment Performance Data for Retorting of Mixed
K071/K106 Waste from Literature Source A 4-12
iii
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LIST OF TABLES (Continued)
Page
Table 4-4 Treatment Performance Data for Retorting of K106
Sodium Borohydride Sludge Submitted by Plant C 4-13
Table 4-5 Treatment Performance Data for Stabilization of
K106 Collected by EPA at Plant D ' 4-14
Table 4-6 Performance Data for Sulfide Precipitation Treatment
of K071 Wastewaters Collected by EPA at Plant E 4-16
Table 5-1 Summary of Accuracy Adjustment of Treatment Data for
Total Mercury Generated from Thermal Recovery
Technologies 5-12
Table 5-2 Summary of Accuracy Adjustment of Treatment Data for
Total Mercury in Wastewaters 5-13
Table 7-1 Calculation of Numerical Treatment Standards for
Nonwastewaters 7.7
Table 7-2 Calculation of Expected Performance of Cinnabar Ore
Roasting Process 7-8
Table 7-3 Calculation of Numerical Treatment Standards for
Wastewaters 7.9
Table 7-4 Proposed BDAT Treatment Standards for D009, K106,
P065, P092, and U151 Wastewaters 7-10
Table 7-5 Proposed Revised BDAT Treatment Standards for K071
Nonwastewaters 7-11
Table 7-6 Proposed BDAT Treatment Standards for K106 and U151
Nonwastewatexs 7-12
Table 7-7 Proposed BDAT Treatment Standards for P065 and P092
Nonwastewaters .' 7-13
Table 7-8 Proposed BDAT Treatment Standards for D009
Nonwastewaters 7-14
Table 7-9 Proposed BDAT Treatment Standards for D009 and U151
Elemental Mercury Contaminated with Radioactive
Materials 7-15
iv
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LIST OF TABLES (Continued)
Page
Table 7-9 Proposed BDAT Treatment Standards for D009 Hydraulic
Oil Contaminated with Mercury and Radioactive Materials 7-16
Table A-l Analytical Methods for K071 Wastewaters A-2
Table A-2 Procedures or Equipment Used in Mercury Analysis of
K071 Wastewaters When Alternatives or Equivalents
Are Allowed in the SW-846 Methods A-3
Table A-3 Matrix Spike Recoveries Used to Correct Analytical Data
for K071 Mercury-Containing Wastewaters A-4
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LIST OF FIGURES
Page
Figure 2-1 Mercury Chemicals and Primary Uses 2-3
Figure 2-2 Chlorine Manufacture by the Mercury Cell Process 2-9
vi
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1. INTRODUCTION
Pursuant to section 3004(m) of the Resource Conservation and Recovery
Act (RCRA), enacted as a part of the Hazardous and Solid Waste Amendments
(HSWA) .on November 8, 1984, the Environmental Protection Agency (EPA) is
proposing treatment standards based on best demonstrated available
technology (BOAT) for the following: mercury-containing waste identified
in 40 CFR 261.32 as K106; commercial chemical product wastes identified
in 40 CFR 261.33 as P065, P092, and U151; and wastes identified in 40 CFR
261.24 as exhibiting the characteristic of leachability for mercury
(D009). In addition, the Agency is proposing to revise treatment
standards for K071 nonwastewaters, for which treatment standards were
originally promulgated with the First Third of RCRA hazardous wastes (53
FR 31137, August 17, 1988); the revised treatment standards for this
waste incorporate a total mercury concentration level for K071 wastes
that contain recoverable concentrations of mercury.
Compliance with these treatment standards would be a prerequisite for
the placement of these wastes in units designated as land disposal units
according to 40 CFR Part 268. The effective date of final promulgated
treatment standards for these wastes will be May 8, 1990.
This background document presents the Agency's rationale and
technical support for developing regulatory treatment standards for the
mercury-containing wastes identified above. Section 2 describes the
industries affected by regulation of these wastes, explains the processes
generating these wastes, and presents available waste characterization
data. Section 3 specifies the applicable and demonstrated treatment
technologies for these wastes. Section 4 contains performance data for
the demonstrated technologies, and Section 5 analyzes these performance
data to determine BOAT for each waste. Section 6 presents the rationale
for selection of regulated constituents, and Section 7 presents the
proposed BOAT treatment standards for the regulated constituents selected
for each waste.
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EPA's promulgated methodology for developing BOAT treatment standards
is described in two separate documents: Generic Quality Assurance
Project Plan for Land Disposal Restrictions Program ("BOAT") (USEPA
1988a) and Methodology for Developing BOAT Treatment Standards (USEPA
1989a). The petition process to be followed in requesting a variance
from the BDAT treatment standards is discussed in the methodology
document.
The Agency classifies hazardous wastes as either wastewaters or
nonwastewaters. For the purpose of determining the applicability of the
proposed treatment standards, wastewaters are defined as wastes
if
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 proposed
treatment standards for nonwastewaters.
For all mercury-containing wastewaters for which treatment standards
are being proposed (D009, K106, P065, P092, and U151), the best
demonstrated available technology (BDAT) is chemical precipitation.
Treatment standards are based on the performance of sulfide precipitation
treatment of K071 vastewaters. Some mercury-containing wastewaters may
require more extensive treatment trains in order to treat other metals or
organics that may interfere with the treatment of mercury. Fretreatment
by an oxidation step (with reagents such as hydrogen peroxide or sodium
hypochlorite) or incineration may be necessary to treat the organics in
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"C to 105°C)
in Standard Methods for the Examination of Water and Wastewater,
15th Edition (APHA, AWWA, and WPCF 1985).
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P092 wastewaters and D009 organomercury wastewaters. Pretreatment by
aqueous chemical deactivation or by incineration in specially-designed
thermal treatment units may be necessary to treat reactive constituents
in P065 wastewaters and reactive D009 wastewaters. The treatment
standard for mercury-containing wastewaters is presented in Table 1-1, at
the end of this section.
For D009 wastewaters, EPA is proposing two regulatory options. One
regulatory option would require treatment of these wastes to comply with
a treatment standard that is less than the EP toxic(level for mercury.
The proposed treatment standard (0.030 mg/1, as shown in Table 1-1) is
supported by the performance of chemical precipitation, which has been
determined to be BOAT for K106, U151, P065, and P092 wastewaters. The
second regulatory option would require treatment of these wastes to meet
a treatment level of 0.2 mg/1 (the EP toxicity level for mercury). EPA
is soliciting comments on the merits of each of these approaches.
For nonwastewater forms of K071, K106, U151, and D009 wastes, EPA is
proposing to establish two general mercury subcategories. A total
mercury concentration of 16 mg/kg is proposed to classify these mercury
wastes into one of these two subcategories and to determine compliance
with the proposed treatment standards. The 16 mg/kg cut-off level is
based on the retorting/roasting of K071 and K106 wastes. (See Section 7
for a detailed explanation of the derivation of the 16 mg/kg cut-off
level.)
For nonwastewater forms of K071, K106, U151, and D009 wastes in the
high-mercury subcategory (greater than or equal to 16 mg/kg total
mercury), proposed BDAT treatment standards are based on thermal recovery
of mercury. The proposed treatment standard is expressed as the use of a
thermal recovery technology (roasting or retorting) as a method of
treatment. Thermal recovery treatment technologies provide an overall
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reduction in both toxicity and mobility of mercury in wastes. EPA is
proposing thermal recovery as a treatment method for these wastes to
ensure that the treatment standard achieves the environmental benefits
associated with recycling technologies.
It is likely that residuals from thermal recovery treatment of the
listed mercury wastes will be considered by the Agency to be indigenous
wastes to the thermal recovery process. Hence, these wastes would only
be considered hazardous if they exhibit the characteristic of EF toxicity
for mercury or any other hazardous waste characteristic. Thus, any
nonwastewater residue from retorting of a listed hazardous waste that
exhibits the characteristic of EP toxicity for mercury and has a total
mercury concentration equal to or greater than 16 mg/kg will require
treatment to meet the D009 inorganic nonwastewater treatment standard.
For K106, U151, and D009 wastes in the low-mercury subcategory, BOAT
has been determined to be acid leaching. EPA is proposing to transfer
the performance of acid leaching treatment of K071 wastes to these
inorganic mercury nonwastewaters in the low-mercury subcategory. The
proposed BOAT treatment standard for these wastes is 0.025 mg/1 mercury
as measured by the TCLP leachate. Treatment standards for K106 and U151
nonwastewaters are summarized in Table 1-2.
The Agency is proposing to create a new subcategory for K071 wastes
identified as the K071 high-mercury subcategory (greater than or equal to
16 mg/kg total mercury). Accordingly, EPA is thus proposing to revise
the K071 nonwastewater treatment standard previously promulgated for K071
wastes which now meet the criteria for this* high mercury subcategory.
For K071 nonwastewaters in the high-mercury subcategory, the proposed
treatment standard is retorting or roasting as a method of treatment.
The Agency is also proposing to create a second subcategory for K071
nonwastewaters, identified as the K071 low-mercury subcategory, and is
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retaining the promulgated K071 treatment standard (0.025 mg/1 mercury
based on analysis of a TCLP leachate) for these wastes. Treatment
standards for K071 nonwastewaters are summarized in Table 1-3.
For P092 nonwastewaters, proposed BOAT treatment standards are based
on incineration followed by thermal recovery of mercury from the solid
residuals generated from incineration, provided such residues exceed 16
rag/kg total mercury. For P065 nonwastewaters, the proposed BOAT
treatment standard is incineration in units designed for treatment of
explosive wastes, followed by thermal recovery of mercury from the solid
residuals generated by incineration. The proposed treatment standard for
these wastes is expressed as a technology standard (incineration)
followed by treatment of the wastewater and nonwastewater incineration
residuals (scrubber water and incinerator ash) as inorganic mercury
wastes. Scrubber waters generated from incineration are classified as
P065 and P092 wastewaters by the derived-from rule. For these scrubber
waters EPA is proposing the 0.030 mg/1 wastewater standard which relies
on the same performance data used to develop the existing K071 wastewater
standard. Proposed treatment standards for P065 and P092 nonwastewaters
are shown in Table 1-4.
The proposed BOAT treatment standard for D009 high-mercury
nonwastewaters is a combination of the treatment standards for the
high-mercury inorganic nonwastewaters and the organic mercury
nonwastewaters. EPA has determined that retorting or roasting represent
BOAT for D009 high-mercury nonwastewaters containing elemental mercury or
inorganic mercury compounds. However, D009 wastes may contain
organomercury constituents or may contain mercury contaminated with
organics. Incineration has been determined to be BOAT for organics in
this type of D009 nonwastewater and also for nonwastewater organomercury
constituents. Since incineration cannot destroy mercury, but instead
incineration concentrates mercury in scrubber water or ash to levels not
acceptable for land disposal, the Agency is proposing additional
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requirements for the mercury in these residuals. As a result the
proposed treatment standard for D009 high-mercury nonwastewaters is
expressed as either retorting/roasting or incineration followed by
retorting or roasting of nonwastewater incineration residuals if these
residuals contain recoverable (i.e., greater than 16 mg/kg)
concentrations of mercury.
For D009 low-mercury nonwastewaters, BOAT is acid leaching. The
proposed treatment standard for these wastes is 0.025 mg/1 as measured as
a TCLF leachate concentration. The treatment standard is based on the
transfer of treatment performance data from acid leaching treatment of
K071 wastes. Proposed BOAT treatment standards for D009 nonwastewaters
are summarized in Table 1-5.
Information provided to EPA by the U.S. Department of Energy (DOE)
indicates the generation of two particular mixed radioactive/hazardous
wastes that contain mercury. This information also suggests that the
BDAT technologies and standards proposed for the corresponding
nonradioactive wastes may not be applicable to these mixed wastes. The
Agency has therefore developed alternative treatment standards for these
wastes.
One of the mixed wastes identified is waste elemental mercury
contaminated with radioactive tritium (a radioisotope of hydrogen).
These wastes are often identified as D009 or U151. EPA has determined
that recovery technologies do not represent BDAT for this waste because
the Agency has no data or information that would indicate that these
processes would be able to separate the mercury from the radioactive
material, resulting in recovery of reuseable mercury. EPA has identified
amalgamation with zinc as a technology that provides significant
treatment to these waste in terms of air emissions (thus greatly reducing
the toxicity of these wastes) and also potentially reduces the
leachability of mercury by amalgamation. The proposed BDAT for these
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zeeig
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wastes is amalgamation with zinc, and the proposed treatment standard is
amalgamation with zinc as a method of treatment.
The second mixed waste indentified is a waste hydraulic oil
contaminated with mercury and radioactive materials (tritium). EPA
believes that this waste is amenable to incineration, and has thus
determined that incineration reprsents BOAT as it does for the
nonradioactive organic mercury nonwastewaters. However, the Agency is
proposing to modify the nonradioactive organic mercury nonwastewaters
standard for this waste by removing the requirement to recover mercury
from the inorganic residues generated from incineration of this waste.
Alternatively, the Agency is proposing that nonwastewater incineration
residues (incinerator ash and wastewater treatment sludge generated from
treatment of incineration scrubber waters) must comply with a TCLP
mercury standard of 0.025 mg/1 (based on acid leaching as BOAT), and that
incineration scrubber waters must meet the 0.030 mg/1 total concentration
mercury standard proposed for all mercury-containing wastewaters.
Proposed treatment standards for mixed radioactive/hazardous mercury
wastes are presented in Tables 1-6 and 1-7.
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Table 1-1 Proposed BOAT Treatment Standard for D009,
K106, P065, P092, and U151 Wastewaters
Maximum for anv single grab sample
Total composition
Regulated constituent (mg/1)
Mercury 0.030
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Table 1-2 Proposed BOAT Treatment Standards for K106
and U151 Nonwastewaters
High-Mercury Subcategory - Greater than or equal to 16 mg/kg total mercury
ROASTING OR RETORTING AS A METHOD OF TREATMENT
Low-Mercury Subcategory - Less than 16 mg/kg total mercury
Regulated Maximum for anv single erab sample
constituent TCLP (mg/1)
Mercury 0.025
1-9
286U
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Table 1-3 Proposed Revised BDAT Treatment
Standards for K071 Nonwastewaters
High-Mercury Subcategory - Greater than or equal to 16 rag/kg total mercury
ROASTING OR RETORTING AS A METHOD OF TREATMENT
Low-Mercury Subcategory - Less than 16 mg/kg total mercury
Regulated Maximum for any single grab sample
constituent TCLP (mg/1)
Mercury 0.025
1-10
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Table 1-4 Proposed BOAT Treatment Standards for P065
and P092 Nonwastewaters
INCINERATION FOLLOWED BY ROASTING OR RETORTING OF INCINERATOR
NONWASTEWATER RESIDUALS (ASH AND WASTEWATER TREATMENT SLUDGES FROM
TREATMENT OF THE INCINERATOR SCRUBBER WATERS) PROVIDED SUCH RESIDUES
EXCEED 16 MG/KG TOTAL MERCURY CONCENTRATION
P065 wastes must be incinerated in accordance with the requirements of 40
CFR Part 264, Subpart 0, or Part 265, Subpart 0, in specially-designed
incinerators. The incinerator ash residual must be processed for mercury
recovery using a thermal recovery technology if it does not meet the
total composition treatment standard.
P092 wastes must be incinerated in accordance with the requirements of 40
CFR Part 264, Subpart 0, or Part 265, Subpart 0, or burned in boilers or
industrial furnaces in accordance with applicable regulatory standards.
The incinerator ash residual must be processed for mercury recovery using
a thermal recovery technology if it does not meet the total composition
treatment standard.
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Table 1-5 Proposed BOAT Treatment Standards for D009
Nonwastewaters
High-Mercury Subcategory - Greater than or equal to 16 mg/kg total mercury
ROASTING OR RETORTING AS A METHOD OF TREATMENT; OR INCINERATION* AS A
METHOD OF TREATMENT FOLLOWED BY ROASTING OR RETORTING OF THE INCINERATOR
NONWASTEWATER RESIDUES (ASH AND WASTEWATER TREATMENT SLUDGES FROM
TREATMENT OF THE INCINERATOR SCRUBBER WATERS) PROVIDED SUCH RESIDUES
EXCEED 16 MG/KG TOTAL MERCURY CONCENTRATION
a Organic nonwastewater forms of this waste must be incinerated in
accordance with the requirements of 40 CFR Fart 264, Subpart 0, or Part
265, Subpart 0, or burned in boilers or industrial furnaces in
accordance with applicable regulatory standards. Reactive
nonwastewater forms of this waste must be incinerated in accordance with
the requirements of 40 CFR Part 264, Subpart 0, or Part 265, Subpart 0,
in specially-designed incinerators. The incinerator ash residual must
be processed for mercury recovery using a thermal recovery technology if
it does not meet the total composition treatment standard.
Low-Mercury Subcategory - Less than 16 mg/kg total mercury
Regulated Maximum for anv single grab sample
constituent TCLP (mg/1)
Mercury 0.025
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Table 1-6 Proposed BOAT Treatment Standards for D009 and U151
Elemental Mercury Contaminated with Radioactive Materials
AMALGAMATION WITH ZINC AS A METHOD OF TREATMENT
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Table 1-7 Proposed BOAT Treatment Standards for D009 Hydraulic
Oil Contaminated with Mercury and Radioactive Materials
INCINERATION AS A METHOD OF TREATMENT WITH INCINERATOR RESIDUES MEETING
THE FOLLOWING: (1) ASH AND WASTEWATER TREATMENT SLUDGES FROM TREATMENT
OF THE INCINERATOR SCRUBBER WATERS MUST COMPLY WITH A TCLP MERCURY
CONCENTRATION OF 0.025 MG/L; and (2) SCRUBBER WATERS MUST COMPLY WITH A
TOTAL MERCURY CONCENTRATION OF 0.030 MG/L (WASTEWATER STANDARD)
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2. INDUSTRIES AFFECTED AND WASTE CHARACTERIZATION
As discussed in Section 1, those wastes listed in 40 CFR Sections
261.24, 261.32, and 261.33 are subject to the land disposal restriction
provisions of RCRA. This document discusses the mercury-containing
wastes K071, K106, P065, P092, U151, and D009. This section describes
the industries affected by land disposal restrictions for these
mercury-containing wastes and the processes generating the wastes,
summarizes available waste characterization data, and discusses
applicable treatability groups.
Within the industry-specific listing of hazardous wastes in Section
261.32 are the following three wastes generated by the chlorine industry:
K071: Brine purification muds from the mercury cell process in
chlorine production, where separately prepurified brine is not
used.
K073: Chlorinated hydrocarbon waste from the purification step of
the diaphragm cell process using graphite anodes in chlorine
production.
K106: Wastewater treatment sludge from the mercury cell process in
chlorine production.
The listed waste K071 has been regulated previously with the First Third
of restricted wastes. Nonwastewater treatment standards for this waste
are being revised in this document. This background document addresses
the development of treatment standards for K106 and the reproposed
treatment standards for K071 nonwastewaters. The listed waste K073 is
discussed in a separate Third Third background document (USEPA 1989c).
The following wastes are listed in 40 CFR Section 261.33 for mercury:
P065: Mercury fulminate
P092: Phenylmercuric acetate
U151: Mercury
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The U and P wastes of concern (U151, P065, and P092) are generated as
discarded chemical products, off-specification products, container
residues, or contaminated soil, water, or other debris resulting from the
cleanup of leaks or spills of products or off-specification products.
This background document addresses the development of treatment standards
for P065, P092, and U151.
This document also discusses the development of treatment standards
for wastes listed in 40 CFR Section 261.24 as D009. D009 is any waste
that is characteristically hazardous based on the concentration of
mercury in the leachate as determined by the EP Toxicity Leaching
Procedure. D009 wastes can be generated in many different forms by many
different industrial processes.
2.1 Industries Affected and Process Descriptions
Metallic mercury and inorganic and organic mercury compounds are used
in many industries. Figure 2-1 summarizes the manufacturing process
chemistry and end uses of the industrially-important mercury compounds.
Table 2-1 presents the major end users of mercury and their mercury
consumption in 1983.
The largest use of mercury, amounting to 48 percent of all mercury
used in 1983 (the last year for which statistics were available) is in
the manufacture of mercuric oxide batteries, primarily the mercuric
oxide/zinc dry cell. Mercuric oxide is used as the cathode material in
these batteries. Metallic mercury is often amalgamated with other metals
(e.g., silver and zinc) and used as the anode material in batteries. The
production of batteries using mercury and mercuric oxide is discussed in
Section 2.1.1.
The second largest use of mercury, amounting to 16 percent of that
used in 1983, is in the manufacture of chlorine by the mercury cell
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MERCURY BUTTER (MERCURY/IRON AMALGAM) IN SOME
MEPOURV CELL BATTERIES
CHLOl|-*LKAU MERCURY CELL ELECTRODES.
INDUSTRIAL AND CONTROL INSTRUMENTS.
MERCURY VAPOR LAMPS
WIRUM AND SWITCHING DEVICES - ELECTRICAL CONNECTIONS
MERCURY FULMINATE
HolOCNV
MERCURIC
NITRATE
MERCURIC
CHLORIDE
HOMOGENOUS CATALYST
FOR ORGANIC CHEMICALS
NaOH (yellow)
«f
L+N«OH.A
COMPONENT OF
AGRICULTURAL FUNGICIDES
USED AS A PRIMARY
EXPLOSIVE (DETONATOR).
MADE INTO CAPS; NOT
TRANSPORTED OR SOLD
AS THE PURE COMPOUND
BECAUSE IT IS EXPLOSIVE.
MERCURIC
OXIDE
YELLOW
OR RED
MERCURIC OXIDE
BATTERIES (RED)
(PRIMARY ZINC/CARBON
CELL AND OTHERS)
«HCjH,0,
(ACETIC ACID) i
MERCURIC
ACETATE
CATALYSTS. LABORATORY
USES, PHARMACEUTICALS
INORGANIC
ORGANIC
*4CCTC ACID
BENZENE
LMERCURI
ACETATE
OROANOMERCURV
PHENYLMERCURIC
HYDROXIDE
ROPYLUERCURIC
MERCUROCHHOME
PHENVLMERCURIC
OLEATE. OTHERS
PAINT FUNGICIDE
AND BACTERICtDE
(LATEX PAINTS)
ANTISEPTIC PHARMACEUTICALS
KEY:
o
> CHEMICALS
USES
HEAT
FIGURE 2-1. MERCURY CHEMICALS AND PRIMARY USES
2-3
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Table 2-1 Major Industrial Uses of Mercury
Industry
SIC Codes
Amount of
mercury used
(thousands of Ib)
Electrical products
(batteries, lamps, wiring
and switching devices, etc.)
3600
2,050
Chlorine production
Paints
Instruments
(thermometers, manometers,
barometers, etc.)
Dental supplies
Catalysts, miscellaneous
Other
(Pharmaceuticals, pigments,
lab analyses , etc . )
2812
2851
3820
3843
2819, 2869
2833, 2816,
others
612
460
187
121
36.8
270
Reference: U.S. Bureau of Mines 1985.
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process. Metallic mercury is used in this process as the cathode
material in electrolytic cells that decompose a sodium chloride brine
solution into sodium hydroxide and chlorine. This process is discussed
in Section 2.1.2.
The next largest use of mercury is as a fungicide and bactericide in
latex paints. The primary compound used in this application is
phenylmercurie acetate. Other organic mercury compounds are also used.
Phenylmercuric acetate is made from mercuric acetate, as shown in
Figure 2-1.
Other uses of mercury metal are in electrical equipment such as
industrial control instruments, in mercury vapor lamps, in wiring and
switching devices as an electrical connection, and in barometers and
thermometers. Mercury compounds are also used as primary explosives
(mercury fulminate), as homogeneous catalysts (mercuric chloride), as
components of agricultural fungicides (mercurous chloride and mercuric
chloride), and as antiseptic Pharmaceuticals (various organic and
inorganic mercury compounds).
2.1.1 Manufacture of Mercury Batteries
Many batteries contain metallic mercury or mercuric oxide as
components. Mercury cell batteries (mercuric oxide:zinc cells) consist
of a mercuric oxide powder as the cathode, a mercury/zinc amalgam as the
anode, and an alkaline electrolyte solution (usually potassium
hydroxide). Mercuric oxide is also used in other types of batteries as a
cathode material. Both nonwastewaters and wastewaters containing mercury
can be generated from battery manufacturing. Wastewaters containing
mercury can be generated from cleanup of spills of mercuric oxide or
metallic mercury or as water washes of processing equipment.
Nonwastewaters that can be generated include off-specification batteries,
2-5
2862s
-------
spilled or off-specification mercuric oxide, spilled mercury, or
wastewater treatment sludges generated from the treatment of
mercury-containing wastewaters.
2.1.2 Chlorine Production by the Mercury Cell Process
Chlorine is produced primarily from the electrolytic decomposition of
either sodium chloride or potassium chloride, from which the coproducts
are sodium hydroxide (caustic soda) or potassium hydroxide. All of the
caustic soda and potassium hydroxide and 'over 90 percent of the chlorine
produced in the U.S. are made by the electrolytic decomposition of sodium
chloride or potassium chloride. Chlorine is also produced by other
processes, including non-electrolytic oxidation of hydrochloric acid
(HC1), from the production of sodium metal, and from electrolytic
production of magnesium metal from molten magnesium chloride.
Three types of electrolytic cells are in commercial use for the
production of alkalies and chlorine: the mercury cell, the diaphragm
cell, and the membrane cell. The listed wastes K071 and K106 are
generated in chlorine production by the mercury cell process. The Agency
estimates that there are 20 facilities that produce chlorine by the
mercury cell process and may generate K106 waste. EPA also estimates
that 14 of these facilities do not use prepurified salt, and thus also
may generate K071 waste. The locations of these facilities are provided
in Table 2-2, listed by State, and in Table 2-3, listed by EPA Region.
Chlorine producers fall under SIC Code 2812, Alkalies and Chlorine.
In chlorine production by the mercury cell process, a saturated salt
brine solution is prepared by dissolving sodium chloride, usually in the
form of rock salt (although prepurified salt is sometimes used), in the
depleted brine solution recycled from the mercury cells (see
Figure 2-2). The brine is purified (unless prepurified salt is used) by
addition of sodium carbonate and sodium hydroxide to precipitate any
2-6
2862g
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Table 2-2 Number of Producers of Chlorine Using the
Mercury Cell Process Listed by State
Number of Number that do not
State producers use prepurified salt
Alabama (IV) 3 3
Delaware (III) 1 1
Georgia (IV) 2 1
Kentucky (IV) 1 1
Louisiana (VI) 2 1
Maine (I) 1 1
New York (II) 2 1
North Carolina (IV) 1 1
Ohio (V) 1 1
Tennessee (IV) 1 1
Texas (VI) 1 0
Washington (X) 1 1
West Virginia (III) 2 0
Wisconsin (V) 1 1
Total 20 14
Reference: SRI 1989.
2-7
2B62g
-------
Table 2-3 Number of Producers of Chlorine Using the Mercury
Cell Process Listed by EPA Region
Number of Number that do not
EPA Region producers use prepurified salt
I 1 1
II 21
III 3 1
IV 87
V 22
VI 31
Total 20 14
Reference: SRI 1989.
2-8
2662s
-------
PRODUCTION PROCESS
RECYCLED SPENT BRINE
ro
i
50% NaOH
SOLUTION
PURGED BRINE
WASTE TREATMENT PROCESSES
K071
i
K071 ACID
LEACHINO
TREATMENT
PLANT RUNOFF .
AND WASH DOWN
LEACHATE
WASTEWATER
TREATMENT
T
.TREATED
WASTEWATER
TREATED
K071
SOLIDS
WASTEWATER
TREATMENT
SLUDGE
K106
FIGURE 2-2. PROCESSES GENERATING K071 AND K106 WASTES
-------
dissolved impurities. Solids (muds) generated in brine purification are
the listed waste K071. The purified saturated brine is fed to the
mercury cells, where electrolytic decomposition into sodium hydroxide and
chlorine occurs. The chlorine is subsequently purified. If potassium
chloride is used as a feed to the process, potassium hydroxide and
chlorine are produced.
Sources of wastewater from the production of chlorine by the mercury
cell process include (1) brine that is bled from the end boxes of the
mercury cells, (2) wastewater collected from the floor of or basement
below the room containing the mercury cells, generated from periodic
washdown of the cell room floor and equipment, and (3) any other
wastewaters generated by the plant that may contain mercury, including
wastewaters generated during dewatering or treatment of K071 waste.
Treatment of plant process wastewaters by chemical precipitation
generates a wastewater treatment sludge, which is the listed waste K106.
With the exception of one mercury-cell chlorine production facility, K106
is generated by sulfide precipitation. One facility currently uses
hydrazine to treat mercury-contaminated wastewaters; this process
generates a mercurous hydroxide compound. In the past, K106 was
generated by chemical reduction treatment of mercury-contaminated
wastewaters using sodium borohydride, but EPA believes that this compound
is no longer used to treat mercury-contaminated wastewaters generated in
chlorine production by the mercury cell process.
2.1.3 Manufacture and Use of Organomercury Fungicides and Bactericides
The Agency has information that phenylmercuric acetate (P092) and
phenylmercuric oleate are produced by Cosan Chemical in Carlstadt, New
Jersey (SRI 1989). These compounds (and other phenylmercury compounds)
are used as bactericides in latex paint formulations. Phenlymercuric
acetate is manufactured by reaction of mercuric acetate with benzene.
Phenylmercuric acetate can be used as a starting material in the
production of many other phenylmercury compounds.
2-10
2862g
-------
In paint formulation operations, pigments are mixed with solvents,
carriers, and other additives. Phenylmercury compounds are added in very
small quantities (less than 1 percent) as preservatives for latex
paints. Washing of equipment used in paint formulation may result in the
generation of wastes containing organomercury compounds such as
phenylmercuric acetate. These wastes sometimes contain other organic
compounds as well.
2.2 Waste Characterization
2.2.1 K071
K071 characterization data are presented in the BOAT Background
Document for K071 (USEPA 1988b). This waste was found to consist of
primarily inorganic solids and water, with a mercury content of less than
100 ppm as metallic mercury and soluble mercuric chloride.
2.2.2 K106
EPA has waste characterization data for both K106 generated by
sulfide treatment and K106 generated by hydrazine treatment. The
approximate concentrations of the major constituents for both of these
K106 forms were determined from EPA analysis of the waste and other
characterization data and information submitted by industry to EPA. As
summarized in Table 2-4, both forms of K106 are primarily composed of
water and diatomaceous earth filter aid. The K106 generated by sulfide
precipitation contains approximately 4.4 percent mercury, as mercuric
sulfide; the K106 generated by hydrazine treatment contains approximately
0.5 percent mercury, as mercurous hydroxide.
2-11
2862g
-------
2872g
Table 2-4 Waste Composition Data for Untreated K106 Wastes
Constituent
Untreated K106 waste concentration (im/ka)
(a)
(b)
(c)
(c)
(c)
BOAT List Metals
Antisnny
Arsenic
BariuM
Beryl HUB
Cacbilui
ChroBlu*
Copper
Lead
Mercury
Nickel
Selenius
Silver
Thai Hi*
Vanadiui
Zinc
Other Analyses
AlueiiuM
Calcius
Cobalt
Iron
Magnesius
Manganese
Potassium
Sodlui
Tin
Sulflde
Total sol Ids
Total suspended solids
Paint filter test
Diatanceous earth
Water
Sodlui chloride
<3.8 - -
1.1 - - - -
74 - -
<0.1 - - -
Z.3 - - - -
B.3 - - - -
133 - - - -
50 - - - -
25.900 2000 - 150.000 4300 - 17,000 55,000 - 146,000 5000 - 7000
14 - - - -
<5.0 - - - -
131 - - - -
«8.8 - - - -
0.46 - - - -
443 - - -
168 - - -
478 - - - -
1.3 - - - -
833-400 -
132 - - - -
6.5 - - -
7.870 - -
4.120 - - -
<5.5 - - -
- - - -
41.5 - - - -
- - _
Pass - - - -
700.000 - 950,000 800.000 - 950,000
5000 - 20.000 50,000 - 150,000
80.000 - 100.000
Not analyzed.
References:
()
(b)
(c)
USEPA 1988c.
Versar 1986a.
USEPA 1985.
(d) The Chlorine Institute 1988.
2-12
-------
2872g
Table 2-4 (continued)
Untreated K106 waste concentration (m/ka)
Constituent
BOAT List Metals
Ant tony
Arsenic
Barlus
Beryl HUM
CaOBluM
ChroBlue
Copper
Lead
Mercury
Nickel
Selenlua
Silver
ThalliuB
Vanadlua
Zinc
Other Analyses
Alualnus
Calclus
Cobalt
Iron
Nagneslua
Manganese
Potass 1w
Sodlus
Tin
Sulfide
Total solids
Total suspended solids
Paint filter test
DlatosBceous earth
Mater
Sodiua chloride
Chloride
Sulfate
Total organic carbon
Oil and grease
- - Not analyzed.
References: (a) USEPA
Total
<52
52
119
<1.4
15
223
861
456
62.500
138
1.7
12
-
9.0
3940
-
-
-
-
-
-
-
-
-
-
-
-
-
-
50.000
-
-
-
-
-
1988c.
(d)
TOP (en/1)
0.175
<0.076
0.551
<0.004
0.03
0.128
<0.032
1.59
0.045
0.681
<0.05
<0.02
-
<0.016
15.2
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
(d)
Total EP Toxlclty
(-9/1)
-
0.7 0.003
6.0 0.06
2.3
2.3 0.03
4.6 0.024
-
Ill
0.006
1.0 0.045
0.3 0.001
2.8 0.0027
-
-
-
_
_ _
-
- -
-
-
-
-
_ _
-
-
-
-
_
540.000
-
5910
3090
-
9.6
(d)
Total TCLP
<0.005
0.407
175
<1.5
5.0
36
345
135
38.300
260
<0.005
10
<5
<5
128
_
_
-
-
-
-
-
_
_
7.493
_
-
_
_
440.000
_
<60
5.0
_
4495
(-9/1)
<0.005
0.018
0.12
<0.005
<0.01
<0.01
0.07
0.05
2.73
<0.01
<0.005
<0.01
-------
Z872g
Table 2-4 (continued)
Constituent
BOAT List Metals
Antieony
Arsenic
Barius
BeryllliM
Cadelue
Chraslusi
Copper
Lead
Mercury
Nickel
Selenius
Silver
Thallitsi
Vanadius
Zinc
Other Analyses
Alusinus
Calclue
Cobalt
Iron
Magnesius
Manganese
Potassius
Sodiue
Tin
Sulfide
Total solids
Total suspended solids
Paint filter test
DlatcMcaous earth
Hater
Sodiue chloride
Chloride
Sulfate
Total organic carbon
Oil and grease
- Not analyzed.
References: (a) USEPA
Total
<6
8.0
71
<0.2
2.0
70
361
142
161.000
167
<2
4.0
<5
<4
405
-
'
-
-
-
-
-
-
-
1590
-
-
-
-
690.000
-
47,000
19.100
39,600
3400
1988c.
Untreated
(d)
TCLP (eg/1)
<0.06
0.14
0.21
<0.002
<0.005
<0.007
<0.03
<0.05
3.88
1.16
<0.05
<0.005
<0.05
<0.04
3.04
-
-
-
-
-
-
-
-
-
1.2
-
-
-
-
-
-
-
-
-
K108 waste concentration (ma/ka)
(d) (d)
Total EP Toxicity Total EP Toxicity
(9/1) (»9/l)
0.2
3.0 <0.005 0.1 0.01
5.0 <0.03 3.0 2.5
_ -
0.4 <0.005 - 0.01
750 0.6 3.0 0.01
250
4.0 <0.5 100 0.25
20,000 <0.0005 5.000 5.0
34 0.09 100
4.0 <0.005 - 0.05
1.0 <0.007 - 0.1
_ _
_
250
- - -
_ _
- - -
- -
- - -
_
. _
_ _
_ _
<11 - -
_ _
- _
- .
- _
580.000 - 500.000
_ _
- _
- .
- _
22,500
(b) Versar 1986.
(c) USEPA
1985.
2-14
(d) The Chlorine Institute 1988.
-------
2872g
Table 2-4 (continued)
Untreated K106 waste concentration fm/ka)
Constituent (dl _ (dj
Total EP Toxlclty Total EP Toxiclty Total TCLP
(9/D (-9/D
BOAT List Metals
Antimony
Arsenic
BarlM
Beryl Hue
Chraariui - - -
Copper - - _
Lead - - - -
HBrcury 28.347 0.399 4098 2.26 23,004 1.25
Nickel - - - _
Selenlw - - _
Silver - - . _
Thalliui - - . .
VanadtUM - - .
Zinc - - ...
Other Analyses
Aluiinui - - . . _ _
Calciui - _ .
Cobalt - - - .
Iron - - _
Magnesius - _ _
Manganese - _ _
Potass iui - - .
Sodius - ' - -
Tin - - ...
Sulfide - - _
Total solids - . _ _
Total suspended solids - - _ _
Paint filter test - . .
Diatanceous earth - - _
*ter 290.000 - - - 400.000
Sodius chloride - . .
Chloride - . .
Sulfate - - _ .
Total organic carbon - - _
Oil and grease - _
- Not analyzed.
References: (a) USEPA 1988c.
(b) Versar 1986.
(c) USEPA 1985. 2-15
(d) The Chlorine Institute 1988.
-------
2872g
Table 2-4 (continued)
Untreated K106 waste concentration (mo/kg)
Constituent
Total
EP Toxlclty
("g/D
(dl
(dl
Total
EP Toxlclty
(9/1)
Total
EP Toxlclty
("9/D
BOAT List Metals
Antlsnny
Arsenic
Darius
Beryl Hut
Chroilisi
ClNNMr
"I"*"
Hercury
Nickel
Selenlw
Silver
Thai Hi*
Vanadlus
Zinc
<100
1300
<100
<100
400
10.100
<100
<100
<0.005
1.32
<0.01
<0.01
0.05
0.113
<0.005
<0.01
25.000
0.12
<0.01
0.06
O.OB
<0.01
0.55
6.5
2.46
204
90
70
0.012
0.07
0.5
<0.1
1.0
<0.3
Other Analyses
Alinlnus
Calclw
Cobalt
Iron
Nagneslui
Manganese
Potass 1m
Sodlui
Tin
Sulfldt
Total solids
Total suspended solids
Paint filter test
Dlatowceous earth
Hater
Sodlus chloride
Chloride
Sulfate
Total organic carbon
Oil and grease
<0.016
650,000
450.000
1270
- Not analyzed.
References: (a) USEPA 198Bc.
(b) Versar 1986.
(c) USEPA 1985.
(d) The Chlorine Institute 1988.
2-16
-------
2.2.3 P065
The Agency does not have data or information on the characterization
or treatment of P065 wastes. Analysis of the 1986 National Survey of
Treatment, Storage, Disposal, and Recycling Facilities (TSDR Survey,
USEPA 1986a) and the 1986 National Survey of Hazardous Waste Generators
(Generator Survey, USEPA 1986b) data bases indicates that no facilities
generated or treated P065 wastes in 1986. As of 1984, the U.S. Army
reported that mercury fulminate is no longer used by the U.S. military as
an initiating compound in explosives because of poor stability (U.S. Army
1984).
2.2.4 P092
The Agency has no data on the composition of P092 (phenylmercurie
acetate) wastes. However, EPA does have data from the one manufacturer
identified in Section 2.1.3 on the composition of a wastewater generated
in production of this chemical (a D009 waste). Characterization data for
this waste are presented in Table 2-5. EPA expects phenylmercuric
acetate to be the primary constituent of P092 wastes.
2.2.5 U151
EPA has data from the Generator Survey on the composition of U151
wastes (USEPA 1986b). These data show that of the U151 wastes that are
reported as a single waste code (i.e., not mixed with other listed or
characteristic wastes), a majority have mercury concentrations greater
than 50 percent. EPA expects that the principal constituent of most U151
wastes is metallic mercury.
2-17
2862s
-------
2.2.6 D009
Characterization data for D009 wastes generated in the organomercury
chemicals and battery manufacturing industries are presented in
Table 2-5. EPA also has data from the Generator Survey on the
composition of D009 wastes (USEPA 1986b). These data show that D009
wastes may contain organic compounds (usually when mixed with solvent
wastes). Also, some wastes generated in the production of organomercury
compounds for fungicide/bactericide and pharmaceutical uses and generated
in organic chemicals manufacturing where mercuric chloride catalyst is
used may contain mercury in an organic waste matrix. The mercury
concentrations of D009 wastes range from less than 1 ppra to greater than
75 percent. From these Generator Survey data, the Agency concludes that
the characteristics of D009 wastes are extremely diverse, depending on
the industry and process generating the waste, and therefore that D009
wastes may have similar characteristics to any of the other mercury waste
groups.
2.3 Determination of Waste Treatabilitv Groups
EPA has evaluated the characteristics of the K-, P-, D-, and U-code
mercury wastes and the processes generating these wastes to determine
whether any wastes or groups of wastes can be treated to similar levels
using the same technology. If so, these wastes could be classified as a
single treatability group.
In some cases, wastes classified under the same waste code (e.g.,
wastewater and nonwastewater forms of the same waste) may not be
treatable to the same concentrations using the same technology or may
require different treatment technologies. For example, characteristic
wastes (i.e., D-code wastes) may have the same waste code but be
generated in different processes in a specific industry or in different
industries. This can result in the wastes having different waste
2-18
2862s
-------
2872g
Table 2-5 Waste Composition Data for D009 Wastes
Untreated 0009 Waste Concentration (units)
(a) (bl
Total Total TCLP Total TCLP
Constituent (ng/1) (ng/kg) («9/l) ("9Ag) (mg/D
BOAT List Metals
Antimony - <2.4 <0.024 <2.4 <0.024
Arsenic - <1.0 <0.01 <1.0 <0.01
BariuB - 0.36 0.006 42 1.1
Beryllium - <0.1 <0.001 <0.1 <0.001
CaoiiuH - <0.5 <0.005 6.8 0.306
ChromiuH (total) - 4.8 <0.004 5.0 <0.004
Copper - 2.1 0.024 73 0.128
Lead - <0.5 0.016 6.6 0.062
Mercury 100-1.000 974.000* 1.490 27.200 1.83
Nickel - 2.8 <0.01 11 0.116
Selenium -
-------
characteristics, such that the wastes may not be treatable to similar
concentrations using the same technology. In these instances, the Agency
may subdivide waste codes into several treatability groups. EPA expects
the chemical forms of some D-code wastes, in particular, to be different
and to clearly require different treatments or combinations of
treatments. For example, inorganic and organometallic compounds
containing the same metal frequently require different types of treatment.
The treatability groups defined by the Agency for the mercury wastes
K071, K106, P065, P092, U151, and D009 are discussed in the following
subsections. As discussed above, D009 wastes can be generated in many
different forms and are expected to comprise more than one treatability
group. However, some of the D009 waste groups identified have similar
treatability characteristics to one of the K, U, or P waste groups. Some
subcategories of D009 wastes have thus been combined with the similar K-,
U-, or P-code waste or wastes into treatability groups.
2.3.1 Mercury Nonwastewaters
Based on the available waste characterization data, the chemical and
physical behavior of mercury compounds upon treatment, and the
performance of treatment technologies identified as BOAT, EPA has
determined that all mercury nonwastewaters can be narrowed down to two
treatability groups: (1) the high mercury group and (2) the low mercury
group.
EPA lacks data to define the nature and characteristics of all wastes
in these groups. However, the available data suggest that most mercury
nonwastewaters that are currently being roasted/retorted contain
inorganic mercury. These same data suggest that nonwastewater derived
from the treatment of organomercury wastes can also be retorted. Other
mercury wastes, however, such as mercury fulminate (P065), may require
2-20
2862«
-------
pretreatment, such as incineration, or chemical treatment, to convert the
wastes to a form more amenable to recovery/recycling.
In absence of other characterization data that can further define
those nonwastewaters amenable to roasting/retorting, EPA is proposing
16 rag/kg as a cut-off level to define the high and low mercury
treatability groups. Derivation of this cut-off level is discussed in
Section 7.2. Inorganic and organic mercury nonwastewater members of
these two treatability groups are discussed below.
(1) Inorganic mercury nonwastewaters. EPA has identified certain
wastes as inorganic mercury nonwastewaters. These wastes are expected to
contain mercury in the metallic form or as inorganic mercury compounds
and are not expected to contain significant concentrations of organic
compounds. These wastes include waste codes K071, K106, U151, and D009
wastes. P065 (mercury fulminate) wastes and D009 wastes that may be
explosive or reactive are discussed under organic mercury nonwastewaters.
Mercury fulminate dissociates in water to mercury ions and cyanate ions,
and therefore is chemically more similar to inorganic mercury compounds
than to organomercury compounds. P065 and other reactive mercury wastes
will, however, be discussed with the organic mercury wastes, because
similar technologies (e.g., incineration) are expected to result in
similar treatment for these wastes.
Inorganic mercury nonwastewaters (K071, K106, U151, and D009 wastes)
are amenable to mercury recovery technologies because the mercury is
present in the elemental form or as inorganic mercury compounds.
However, these wastes have been shown to sometimes contain as little as 1
ppm or less total mercury. Therefore, not all wastes in this
treatability group may be amenable to treatment by thermal mercury
recovery technologies. Hence, EPA has divided these wastes into the two
above mentioned treatability groups: the high-mercury treatability group
2-21
2662s.
-------
and the low-mercury treatability group. This reflects the applicability
of mercury recovery technologies to only mercury nonwastewaters
containing recoverable concentrations of mercury.
K106 wastes, as generated, contain from 0.5 percent to 16 percent
mercury, normally (except for one known generator) in the form of
mercuric sulfide (see Table 2-4). Sulfide-containing residuals from
wastewater treatment may also be classified as D009 wastes or (by the
derived from rule) as K071, U151, P065, or P092.
Mercuric sulfide has the highest decomposition temperature of any of
the common mercury compounds (Weast 1977). Because decomposition is the
first step in the volatilization of mercury compounds in mercury
recovery, these wastes are expected to be the most difficult from which
to recover mercury.
Other inoragnic wastes contain mercury either in the elemental form
or as nonsulfide compounds. These wastes are expected to be more easily
treatable by mercury recovery technologies than are the mercuric sulfide
wastes.
K106 nonwastewaters are generated at one mercury cell chlor-alkali
facility by treatment of wastewaters using hydrazine as a reducing agent
to precipitate mercury as mercuric hydroxide and metallic mercury. The
sludges generated from filtration of this wastewater would be expected to
contain mercury and mercury oxide or hydroxide compounds.
K071 wastes contain relatively low concentrations of mercury (up to
77 mg/1, USEPA 1988b) in an inorganic waste matrix. Because K071 is
generated from the brine purification step in chlorine production by the
mercury cell process, this waste is expected to contain mercury either as
metallic mercury or as soluble mercuric chloride.
2-22
2862g
-------
U151 nonwastewaters and some D009 nonwastewaters also contain
elemental mercury or inorganic mercury compounds as the primary
constituent. The Agency's data on the composition of U151 wastes
(summarized in Section 2.2) indicate that the majority of these wastes,
when not mixed with other wastes, are composed of greater than 50 percent
mercury. D009 wastes containing mercury or nonsulfide inorganic mercury
compounds as the major constituent would also be expected to be treatable
to similar levels using the same technologies as U151 wastes, K071
wastes, and nonsulfide K106 wastes.
(2) Organic mercury nonwastevaters. These wastes comprise P065
nonwastewaters and P092 nonwastewaters, as well as some D009
nonwastewaters. The Agency expects some D009 nonwastewaters to contain
organomercury compounds or mercury in an organic waste matrix. These
wastes may be generated from paint formulation, from the manufacture of
organomercury Pharmaceuticals, and from the use of homogeneous mercury
catalysts in the production of organic chemicals. Because of the
presence of organomercury compounds (such as phenylmercuric acetate) or
organic compounds in the waste, these wastes may require pretreatment
(such as incineration) prior to being treated by the same technologies as
D009 nonwastewaters containing only inorganic mercury compounds.
P065 wastes and D009 wastes containing explosive mercury compounds
may require specially designed incinerators for treatment. EPA has no
data on the composition of P065 wastes, but expects mercury fulminate to
be the major constituent. Mercury fulminate and mercury azide, both
extremely explosive compounds used as explosive initiators, may also be
the major constituent of some D009 wastes. The Agency expects that both
nonwastewater and wastewater forms of these wastes will be treatable to
similar levels as other inorganic nonwastewaters and wastewaters after-
treatment of these wastes to remove the reactivity hazard.
2-23
2B62s
-------
2.3.2 Radioactive Wastes Containing Mercury
Information provided to EPA by the United States Department of Energy
(DOE) indicates the generation of two particular mixed
radioactive/hazardous wastes that contain mercury. Treatment
technologies applicable to other mercury-containing nonwastewaters may
not be applicable to treatment of these wastes. The Agency, therefore,
has established two separate treatability groups for radioactive wastes
containing mercury, which are discussed below.
In the nuclear industry, elemental mercury found in vacuum pumps.
manometers, and other instruments may be contaminated with radioactive
tritium (a radioisotype of hydrogen). These wastes are often identified
as D009 or U1S1. The Agency has no data or information indicating that
recovery processes applicable to treatment of other inorganic mercury
nonwastewaters would be able to separate the mercury from the radioactive
material and recover reusable mercury. These wastes thus represent a
separate treatability group from other inorganic high-mercury
nonwastewaters.
The DOE also indicated the generation of a hydraulic oil contaminated
with mercury and tritium. This waste is expected to be similar to the
organic mercury nonwastewaters identified in Section 2.3.2 above in that
the organic components of the waste would have to be treated before the
mercury could be treated effectively. Treatment of this waste may be
different from the other organic nonwastewaters, however, because recovery
technologies may not be applicable for treatment of the nonwastewater
residuals generated from incineration because reusable (i.e., nonradio-
active) mercury may not be recoverable from these residuals. Radioactive
hydraulic oils containing mercury thus represent a separate treatability
group from other organic mercury nonwastewaters.
2-24
2862s
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2.3.3 Wastewaters
EPA has determined that all mercury-containing wastewaters (K106,
U151, P065, P092, and D009 wastewaters) represent a single treatability
group. Treatment standards for K071 wastewaters were promulgated with
the First Third of RCRA-listed hazardous wastes (53 FR 31137, August 17,
1988) and are not being proposed for revision. K106 wastewaters are
generated from treatment of K106 wastes (e.g., as scrubber waters from
thermal treatment methods). EPA has no data on the composition of K106,
U151, or D009 wastewaters. However, the Agency expects K106 wastewaters
to contain only the major constituents, which are mercury and non-BDAT
list inorganics, reported for K106 wastes as generated (as shown in
Table 2-4). EPA expects K106 and U151 wastewaters to contain suspended
or dissolved metallic mercury or soluble inorganic mercury compounds
(e.g., mercuric chloride). D009 wastewaters containing suspended or
dissolved metallic mercury or soluble inorganic mercury compounds would
also be included in this treatability group because dissolved or
suspended inorganic D009 mercury compounds are expected to be amenable to
treatment by the same technologies as are applicable for treatment of
K071 and K106 wastewaters.
EPA has no data on P092 wastewaters, but expects these wastes to
contain phenylmercuric acetate, a soluble organomercury compound, as a
major constituent. As discussed in Section 2.1.3, EPA also expects D009
wastes generated from the paint formulation industry to contain
phenylmercury compounds in an organic or inorganic waste matrix. Other
D009 wastes, as generated, may be mixed with solvent constituents (USEPA
1986b). These wastewaters may require more extensive treatment trains
(e.g., chemical oxidation with reagents such as hypochlorite or hydrogen
peroxide) in order to treat organics that may interfere with the
treatment of mercury. However, this currently lacks information that
indicates that these wastes cannot be treated to similar levels as
inorganic mercury wastewaters.
2-25
2862»
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3. APPLICABLE/DEMONSTRATED TREATMENT TECHNOLOGIES
In the previous section, discussions of the industries and processes
generating mercury-containing wastes and major constituent analyses of
these wastes were presented. Nine treatability groups were identified
for the mercury-containing wastes. This section describes the applicable
and demonstrated treatment technologies for treatment of these wastes.
The technologies that are considered applicable to the treatment of
mercury-containing wastes are technologies that treat BOAT list metals by
reducing their concentration and/or their leachability in the waste and
technologies that treat the organic compounds or organomercury compounds
found in these wastes (so that the mercury content can subsequently be
treated). Discussions of these treatment technologies can be found in
EPA's Treatment Technology Background Document (USEPA 1989b).
3.1 Applicable Treatment Technologies
Based on the waste characteristics discussed in the previous section,
the technologies applicable for treatment of mercury-containing wastes
are those that reduce the concentration of BOAT list metals in the
treated residual and/or reduce the leachability of these metals in the
treated residual. Because organic mercury wastes (P065 wastes, P092
wastes, and some forms of D009 wastes) may contain organic mercury
compounds or mercury compounds in an organic waste matrix), treatment
technologies that are applicable to these wastes must also be able to
free the mercury from its organic bond so that subsequent mercury
treatment is effective.
3.1.1 Applicable Technologies for Nonwastewaters
The Agency has identified thermal mercury recovery processes, the
acid leaching process, and stabilization as applicable for treatment of
nonwastewaters containing metallic mercury and/or inorganic mercury
3-1
26631
-------
compounds. Incineration and chemical oxidation have been identified as
applicable for treatment of nonwastewaters containing organomercury
compounds or mercury in an organic waste matrix. Aqueous chemical
deactivation and incineration in units specially designed for treatment
of explosive wastes have been identified as applicable treatment
technologies for treatment of reactive mercury-containing nonwastewaters.
Absorption technologies have been identified as applicable for treatment
of spilled metallic mercury wastes.
(1) Thermal mercury recovery processes. Thermal mercury recovery
processes volatilize mercury from the waste at high temperatures and then
condense and collect it as the pure metal, reducing the mercury
concentration in the treatment residual compared to that in the untreated
waste. Thermal recovery processes for mercury include retorting,
roasting, distillation processes (vacuum distillation or batch steam
distillation), and thermal processes recovering mercury from concentrated
mercury ores.
Retorting and roasting processes can be operated as batch processes
in a closed vessel or continuously in a furnace. In retorting processes,
waste is heated and mercury vaporizes and is collected in a condenser.
The vessel is usually kept either at a slightly negative pressure or
under a strong vacuum. Air is not introduced from outside the vessel.
Roasting processes are usually operated continuously, but may be operated
in batch. In roasting, air is supplied to the system as a source of
oxygen to enable decomposition of some mercury compounds. Retorting and
high-temperature metals recovery technologies are discussed further in
the Treatment Technology Background Document (USEPA 1989b).
Distillation technologies are applicable to treatment of wastes
containing high concentrations of metallic mercury (such as U151). The
residuals from distillation technologies are a high-purity mercury as the
"overhead" product and the remaining solid residual as the "bottoms."
Distillation processes are also discussed in the Treatment Technology
Background Document.
3-2
2863|
-------
The thermal process recovering mercury from concentrated mercury ores
is very similar to continuous retorting. This process is used by one
facility in the U.S. in a continuous multiple -hearth furnace. All four
thermal mercury recovery processes discussed above may generate a
wastewater from air pollution control equipment that may contain mercury.
(2) Acid leaching process. Acid leaching solubilizes low
concentrations of mercury in wastes, reducing the concentration of
mercury in the nonwastewater treatment residual. The acid leaching
process used for treatment of K071 wastes involves a chemical oxidation
step followed by a step combining sludge dewatering and acid washing.
This process generates an acid leachate (wastewater) that contains the
mercury in soluble ionic form and requires treatment by chemical
precipitation. Acid leaching is described in Che Treatment Technology
Background Document (US EPA 1989b) .
(3) Stabilization. Stabilization is applicable for treatment of
nonwastewater s containing BDAT list metals in an inorganic waste matrix.
Stabilization treatment involves mixing the waste with a binding agent
that is designed to reduce the leachability of metals from the waste.
Common stabilization technologies are discussed in detail in the
Treatment Technology Background Document (USEFA 1989b) .
Incineration. Incineration is applicable to treatment of
wastes containing organic and organometallic constituents. Treatment
using incineration technologies will destroy the organic constituents of
the waste. As a consequence of destruction of the organics, incineration
will break the organic -metal bond in the organometallic waste
constituents. The metallic part of the organometallic constituents in
the waste as well as any metals present in a mixed metal/organic waste
will remain in the residual (ash) generated, be removed from the gases
exiting the incinerator by the air pollution control equipment; or remain
in the gases exiting the incineration system. Incineration technologies
3-3
28638
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are described in the Treatment Technology Background Document (USEPA
1989b). Technologies demonstrated for removal of mercury vapors, sulfur
dioxide, and other gaseous air pollutants are discussed in Appendix B.
(5) Chemical oxidation of oreanomercurv compounds. Chemical
oxidation is applicable to the treatment of wastes containing
organomercury constituents (such as phenylraercurie acetate, P092).
Chemical oxidation treatment of organomercury compounds involves addition
of a chemical oxidizing agent such as chlorine, hypochlorite,
permanganate, or ozone in an aqueous reaction medium. Chemical oxidation
results in the breaking of the organic-mercury chemical bond, thereby
generating a residual from which the organic contaminant can either be
destroyed (by further oxidation or incineration) or recovered (by
distillation). Chemical oxidation is discussed in the Treatment
Technology Background Document (USEPA 1989b). The inorganic mercury
wastewaters resulting from chemical oxidation treatment can be treated by
one of the technologies identified in Section 3.1.2 as applicable for
wastewaters containing inorganic mercury compounds.
(6) Aqueous chemical deactlvatlon. Aqueous chemical deactivation
is applicable for treatment of wastes containing reactive mercury
constituents (such as mercury fulminate, P065). Aqueous chemical
deactivation involves careful dissolution of explosive solids in water,
combined with oxidation treatment of the dissolved waste. In the case of
mercury fulminate (mercuric cyanate), the dissolved cyanate ions can be
chemically oxidized completely to carbon dioxide and nitrogen using
strong aqueous oxidizing agents such as sodium hypochlorite. The
chemical reaction of mercury fulminate with sodium thiosulfate
(Na2S20_), recommended by the Army as the proper chemical
deactivating agent (U.S. Army 1984), forms thiocyanate as follows:
Hg(OCN)2 + 2Na2S203 - HgS04 + Na2S04 + 2NaSCN
3-4
2B63g
-------
(7) Absorption of elemental mercury. Several methods have been
developed to handle spills of liquid metallic mercury. These methods
involve absorption of mercury with several agents. Calcium polysulfide
and flowers of sulfur are the most common mercury absorbents used, and
elemental zinc powder is also used.
Because of the high vapor pressure associated with elemental mercury
in the liquid form, the predominant safety concern with elemental mercury
wastes is air emissions. In absorption of liquid mercury with zinc dust,
elemental zinc powder is applied to areas that have been contaminated
with mercury. The visible droplets of liquid mercury are physically
collected in a separate step before application of the zinc. The zinc is
dampened with dilute sulfuric acid (5 to 10 percent) until a paste is
formed. This paste is then collected for disposal. The mercury forms an
amalgam with the zinc, providing a significant reduction in air emissions
of mercury (Easton 1988). EPA prefers this procedure over the
conventional spill cleanup procedures involving addition of calcium
polysulfide or flowers of sulfur because use of zinc results in lower air
emissions of mercury.
3.1.2 Applicable Technologies for Wastewaters
(1) Chemical precipitation and chemical reduction. EPA has
identified chemical precipitation and chemical reduction, both followed
by filtration, as applicable to treatment of mercury-containing
wastewaters with high concentrations of inorganic mercury compounds.
Chemical precipitation followed by filtration removes BOAT list metals
and concentrates them in the wastewater treatment sludge. Chemical
reduction (with reagents such as sodium borohydride) reduces mercury to
the metallic state. The reduction step is then followed by filtration to
remove mercury and other solids.
3-5
2663s
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The applicability of chemical precipitation and chemical reduction
technologies depends to some extent on the form of mercury in the waste
(e.g., dissolved ionic, pure metal, and insoluble ionic). Mercury in the
dissolved ionic form (soluble mercuric compounds, for example) may be
reduced to the pure metal by the borohydride reduction process, while
this process may not be effective in treatment of the insoluble mercury
compounds. The borohydride process cannot remove the small amount of
metallic mercury that is soluble in water. Chemical oxidation treatment
may be required to oxidize metallic mercury to soluble ionic mercury
prior to chemical precipitation treatment. Chemical precipitation,
chemical reduction, and chemical oxidation technologies are discussed in
the Treatment Technology Background Document (USEPA 1989b). The solids
produced as a residual from chemical reduction processes are, in general,
easier to treat by high-temperature metals recovery methods than are the
solids produced in chemical precipitation treatment because they contain
mercury in its elemental form rather than as mercuric sulfide.
(2) Chemical oxidation of orcanomercurv constituents. EPA has
identified chemical oxidation followed by chemical precipitation and
filtration as an applicable technology for wastewaters containing
organomercury constituents. Chemical oxidation breaks the bonds between
the mercury and the organic components of these constituents, as
discussed in Section 3.1.1(5). Chemical precipitation then treats the
mercury in the inorganic form.
(3) Carbon adsorption and ion exchange. Two other technologies,
carbon adsorption and ion exchange, are also applicable to treatment of
wastewaters containing relatively low concentrations of dissolved
o
mercury. The mercury must be in the soluble mercuric (Hg ) form in
order to be removed by these technologies (Rosenzweig 1975, lamnartino
1975). Thus, these technologies may require pretreatment by chemical
oxidation to solubilize any insoluble inorganic mercury. Carbon
3-6
2863(
-------
adsorption will also remove mercury from wastes containing dissolved
organomercury compounds.
Carbon adsorption and ion exchange produce both a wastewater residual
(from regeneration of the ion exchange resin or activated carbon bed) and
a nonwastewater residual (the spent carbon or ion exchange resin, when
these are exhausted and must be discarded). The waste regenerant
solutions (usually acid solutions) are more concentrated than the
original waste treated and must usually be treated for mercury removal by
chemical precipitation followed by filtration if these regenerant
solutions are not recyclable to the process originally generating the
waste. Spent carbon can be incinerated (if mercury emissions are
controlled) or processed in a retort to recover residual mercury. The
spent resins may also be processed by retorting to recover residual
mercury. Carbon adsorption and ion exchange technologies are discussed
in the Treatment Technology Background Document (USEPA 1989b).
3.2 Demonstrated Treatment Technologies
Section 3.1 described applicable technologies for treatment of
mercury wastes. This section identifies, for nonwastewaters and
wastewaters, those of the applicable technologies that are demonstrated
in terms of the waste treatability groups that were discussed in
Section 2.3. To be demonstrated, a technology must be in full-scale use
to treat either the waste in question or a similar material.
3.2.1 Demonstrated Technologies for Nonwastewaters
Retorting, roasting, batch distillation technologies, and thermal
treatment of mercury ores are all demonstrated for treatment of
nonwastewaters containing mercury as the metal or as inorganic mercury
compounds. Incineration has been identified as demonstrated for
3-7
2863g
-------
treatment of nonwastewaters containing organomercury constituents or
containing inorganic mercury in an organic waste matrix. Incineration in
specially-designed units has been identified as demonstrated for
explosive mercury nonwastewaters.
Retorting was used in the past to treat K106 at two mercury cell
chlor-alkali facilities and to treat a mixture of K071 and K106 at
another facility. EPA is not aware of any facilities currently retorting
K106 sulfide wastes. However, a thermal treatment process similar to
retorting is presently being used at one facility for recovery of mercury
from ores consisting primarily of mercuric sulfide (cinnabar). These
ores are concentrated to approximately 70 to 75 percent mercury prior to
retorting (from 3 percent in the unprocessed ores). As shown in
Table 2-4, the concentration of mercury in nonwastewater K106 generated
by sulfide treatment averages 4.4 percent, and the concentration of
mercury on K106 generated by hydrazine treatment is 0.5 percent. The
processed mercury ores are much more concentrated in mercury (as mercury
sulfide) than either form of K106. Hence, the Agency believes that the
mercury ores are much more difficult to treat than K106. As a
consequence, the Agency considers retorting to be demonstrated for K106
and other sulfide-containing nonwastewaters.
Retorting is also demonstrated at two additional facilities for
treatment of nonsulfide-containing mercury nonwastewaters. U151 wastes
and inorganic D009 wastes such as mercury lamps, debris, contaminated
equipment, and mercury cell batteries are routinely treated by retorting,
vacuum or scrap metal distillation, and a thermal proprietary process.
Incineration is demonstrated for many RCRA-listed hazardous wastes
that contain BOAT list metals (such as K048-52 and K087). EPA believes
incineration is currently used for treatment of organomercury wastes such
as spent mercury catalysts from organic chemicals production, paint
3-8
2863s
-------
sludges, or organomercury lab packs. Incineration in specially-designed
units has been identified as a demonstrated technology for many D001
reactive wastes (USEPA 1989e), including some wastes that contain metals
as well as organics. The U.S. Army recommends this technology for
treatment of mercury fulminate (P065) wastes (U.S. Array 1984).
Absorption of mercury is a common method of cleanup of spilled
mercury. Although not a conventional treatment technology, this
technology is expected to provide some treatment for radioactive metallic
mercury wastes, for which mercury recovery technologies may not be
applicable.
Stabilization was identified as potentially applicable for treatment
of K106 nonwastewaters. Stabilization typically binds BDAT list metals
into a solid in a form that is more resistant to leaching than the metals
in the untreated waste. EPA's testing of cement, kiln dust, and lime/fly
ash stabilization for treatment of K106 nonwastewaters generated by
sulfide precipitation indicates that the technology did not provide
effective treatment. Based on this testing, EPA has concluded that these
types of stabilization do not appear to be demonstrated for this form of
K106. The stabilization data collected by EPA are summarized in
Section 4. EPA recognizes, however, that the ineffectiveness of
stabilization treatment of K106 in this EPA test may have resulted from
the fact that the mercury present in the K106 waste tested was in a form
that already had a low teachability for mercury. It is possible that
stabilization may be applicable for treatment of other similar wastes if
mercury is present in a more leachable form in untreated K106 or in other
similar wastes. Other stabilizing agents, such as proprietary asphalt or
silicate agents, may also be applicable but have not been tested for
treatment of K106 or other mercury wastes.
3-9
-------
3.2.2 Demonstrated Technologies for Wastewaters
Chemical precipitation followed by filtration has been demonstrated
for treatment of K071 wastewater. EPA does not have characterization
data on K106 wastewaters generated from retorting of K106. However, EPA
does have data on wastewaters generated from air pollution control
devices from the roasting of mercuric sulfide ores to recover metallic
mercury. The Agency believes that these wastewaters (K106 wastewaters
and wastewaters produced from mercuric sulfide ore processing) are
similar to the K071 and other mercury-contaminated wastewaters currently
treated by chemical precipitation (see Table 4-4) because they are
expected to contain mercury as the major BOAT list constituent and are
not expected to contain concentrations of organic compounds that would
affect treatment by chemical precipitation. The concentration of mercury
in the wastewaters for which the Agency has treatment data ranges from
23.7 to 77.2 mg/1. The ore roasting air pollution control wastewaters
contained mercury up to 9.6 ppm (see Table 4-1). EPA would not expect
the K106 wastewater generated from retorting to be more difficult to
treat than the waste tested by the Agency because they are expected to
have concentrations of mercury similar to that of the ore roasting air
pollution control wastewaters generated in EPA testing of mercuric
sulfide ore roasting. Chemical precipitation followed by filtration of
mercury-containing wastewaters is used at 19 or more facilities.
Ion exchange is demonstrated at many facilities in Europe for
treatment of wastewaters generated from the mercury cell chlor-alkali
process. Activated carbon adsorption is also used at several facilities
for treatment of inorganic mercury-containing wastewaters.
Therefore, the Agency believes that chemical precipitation, ion
exchange, and carbon adsorption are all applicable and demonstrated for
treatment of wastewaters generated from thermal treatment of K106
3-10
2863s
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wastewaters and for Che treatment of wastewaters generated from the
management of other mercury-containing treatment sludge wastes.
Chemical oxidation is demonstrated for treatment of wastewaters
containing mercury at concentrations up to 1,000 mg/1 (as phenylmercuric
acetate) at one facility that manufactures this compound. Therefore,
this technology is demonstrated for treatment of organic and
organometallic mercury wastewaters. Chemical oxidation technologies are
also demonstrated for treatment of wastewaters containing oxidizable
inorganic constituents (such as cyanide or cyanate) (USEPA 1989f).
As discussed in Section 3.2.1, incineration in specially-designed
units is demonstrated for explosive mercury nonwastewaters. This
technology is also recommended by the Army for treatment of mercury
fulminate wastewaters, as well as aqueous chemical deactivation by
chemical oxidation. Chemical oxidation is also demonstrated for many
wastewaters containing organics or oxidizable inorganics (such as
cyanate).
3-11
2863s
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4. PERFORMANCE DATA
4.1 Performance Data for Nonwastewaters
For treatment of inorganic mercury-containing nonwastewaters, EPA has
treatment performance data as described below. EPA collected 5 sets of
treatment data from a thermal mercury recovery system that processes
mercuric sulfide ores for mercury recovery. These data, presented in
Table 4-1, show total composition, TCLP, and EP leachate data for both
the untreated mercury ores and the treated nonwastewater furnace residue
and also data for the wastewaters generated from the air pollution
control devices. Also presented are design and operating data associated
with each sample set.
Plant B submitted 4 sets of performance data for retorting treatment
data of K106 hydrazine sludge, presented in Table 4-2. These data
include total and EP leachate concentration of mercury in the untreated
waste and data for mercury and the other EP metals in the treated
nonwastewater residual, as well as design and operating data associated
with each sample set.
Table 4-3 presents two sets of performance data on retorting
treatment of a combined K071/K106 waste. These data show total mercury
concentration for each test in the untreated waste and a range of total
mercury concentrations for the treated nonwastewater residual, as well as
design and operating data for each sample set.
Plant D submitted seven sets of performance data for retorting of a
K106 sludge generated by sodium borohydride reduction and filtration.
These data, presented in Table 4-4, show total mercury concentration of
the untreated waste and total and EP leachate mercury concentrations for
the treated nonwastewater residual. No design or oprating data were
included.
4-1
2864g
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Table 4-5 presents data collected by EPA on stabilization of K106
wastes. These data show the total and TCLP BDAT list metal
concentrations for the untreated waste and the TCLP concentration for the
treated waste. Three binding agents (lime/fly ash, kiln dust, and
cement) were tested. The table presents the results of the test for kiln
dust, which was the most successful of the three binding agents in terms
of reduction of the TCLP leachate concentration for mercury. Both lime/
fly ash and cement stabilization resulted in a significant increase in
mercury TCLP leachate concentration in the treated waste compared to that
in the untreated waste.
Data were presented in the BDAT background document for K071 (USEPA
1988b) on acid leaching treatment of K071 wastes. These data included
both EPA-collected data and data submitted by industry.
4.2 Performance Data for Wastewaters
The Agency collected three data sets of untreated and treated data
for treatment of K071 wastewater in a sulfide precipitation and
filtration treatment system. The treatment performance data for K071
wastewaters are presented in Table 4-4.
EPA does not have analytical data on K106 wastewaters as generated
from retorting operations. EPA believes that the K106 wastewaters
generated would be similar in chemical and physical characteristics to
wastewaters generated in treatment of K071 waste by acid leaching and
other mercury-containing wastewaters.
The Agency does have data characterizing the wastewater generated
from air pollution control at the facility at which mercuric sulfide ores
were processed. These wastewaters contained up to 9.4 mg/1 mercury and
are similar in composition to K071 wastewaters.
4-2
2864g
-------
2872g
Table 4-1 Ore Roasting Performance Data fron Thermal Recovery of
Mercuric Sulfide Ores Collected by EPA at Plant A.
Sample Set No. 1
Untreated waste
Constituent
Antimony
Arsenic
Barium
Beryllium
Caomium
Chromium (total)
Copper
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Total
(g/kg)
330
290
13
0.15
3.4
2.8
8.2
3.1
625.000
<1.0
3.6
2.8
6.2
5.4
50
Tap
(9/1)
0.82
0.41
0.69
<0.001
<0.005
<0.003
0.012
<0.05
0.26
<0.01
<0.005
<0.004
0.03
<0.003
0.33
EP leachate
(g/D
.
0.33
0.19
-
0.007
0.009
-
<0.028
0.10
-
<0.005
<0.004
-
-
Treated nonwastewater
Total
(g/kg)
1.170
960
77
0.39
5.0
5.2
23
5.8
45
2.0
<0.5
7.6
<1.0
27
94
TCLP
(3/1)
0.47
7.3
0.21
0.0013
0.051
<0.003
<0.003
<0.005
<0.0002
<0.01
<0.05
<0.004
<0.01
0.012
0.17
EP leachate
(g/D
.
4.54
0.14
-
0.037
<0.003
-
<0.028
<0.0002
-
<0.05
<0.004
-
-
Air pollution
control wastewater
Total (mg/1)
3.23
0.023
0.007
-------
2872g
Table 4-1 (continued)
Simple Set No. 2
Untreated waste
Constituent
Ant tony
Arsenic
Barlun
Beryl HIM
CadBlui
CnraiuB (total)
Copper
Lead
Total
(g/kg)
360
280
12
0.13
2.7
3.1
8.4
3.2
Mercury 738,000
Nickel
Seleniun
Silver
Tnalllin
Vanadiuii
Zinc
Note: Design and
Parameter
<1.0
2.8
2.6
5.6
5.1
49
operating
TCLP
(9/D
0.79
0.44
0.72
<0.001
0.006
0.004
0.013
<0.005
0.42
<0.01
<0.005
<0.004
0.03
<0.003
0.34
parameters
EP leachate
(g/D
_
0.33
0.14
-
<0.005
<0.003
-
<0.028
0.087
-
<0.005
<0.004
-
-
are as folloi
Design value
Treated norwastewater
Total
(g/kg)
2.270
1,290
66
0.43
7.4
5.8
26
10
42.4
3.5
<0.5
8.6
<1.0
24
120
is:
TCLP
(g/D
4.1
18.7
0.18
<0.001
0.15
<0.003
<0.003
<0.005
0.00047
<0.01
<0.05
<0.004
<0.01
0.021
0.26
EP leachate
(g/D
.
10.6
0.21
-
0.095
<0.003
-
<0.028
<0.0002
-
<0.05
<0.004
-
-
Air pollution
control wastewatef.
Total (mg/1)
5.76
0.032
0.011
<0.002
<0.004
<0.007
<0.003
0.017
8.52
<0.013
<0.005
<0.003
0.029
<0.003
0.042
Operating value
Temperature of
K furnace hearth CF)
Te^ierature of
« furnace hearth (*F)
Ore concentrate
feed rate (Ib/hr)
1350-1450
1450-1550
1000-1300
1440-1510
1540-1580
1370
- - Not analyzed
Reference: USEPA 1989g.
4-4
-------
2872g
Table 4-1 (continued)
Sample Set No. 3
Untreated waste
Constituent
Ant tony
Arsenic
Barium
Beryl HUB
Cadmium
Chromium (total)
Copper
Lead
Mercury 640
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Total
(gAg)
320
270
12
0.12
2.8
3.5
9.0
3.0
,000
1.2
5.5
3.5
5.1
5.2
52
TCLP
(S/l)
0.82
0.44
1.03
<0.001
0.008
0.006
0.014
<0.005
1.44
<0.01
<0.005
<0.004
0.031
<0.003
0.64
EP leachate
(9/1)
0.36
0.13
-
0.008
<0.003
-
<0.028
0.078
-
<0.005
<0.004
-
-
Treated nonwastewater
Total
(«9/kg)
1,920
1.220
70
0.45
7.1
5.6
32
7.0
36
3.6
<0.5
10
<1.0
30
140
TCLP
(9/1)
0.94
12
0.18
<0.001
0.091
<0.003
<0.003
<0.005
<0.0002
<0.01
<0.05
<0.004
<0.01
<0.003
0.073
EP leachate
(9/D
.
1.1
0.13
-
0.014
<0.003
-
<0.028
<0.0002
-
<0.05
<0.004
-
-
Air pollution
control wastewater
Total (mg/1)
2.73
0.029
0.010
<0.002
<0.004
<0.007
<0.003
0.013
4.14
<0.013
<0.005
<0.003
0.027
<0.003
0.032
Note: Design and operating parameters are as follows:
Parameter Design value Operating value
Temperature of
#2 furnace hearth (*F)
Temperature of
*4 furnace hearth CF)
Ore concentrate
feed rate Mb/hr)
1350-1450
1450-1550
1000-1300
1480
1570
1370
- - Not analyzed
Reference: USEPA 1989g.
4-5
-------
2872g
Table 4-1 (continued)
Sanple Set No. 4
Untreated waste
Constituent
Antiamy
Arsenic
Barlui
Beryl HUB
Cactaiu*
ChroBlui (total)
Copper
Lead
Total
(g/kg)
350
300
14
0.16
3.3
3.7
9.0
3.3
Mercury 473.000
Nickel
Selenium
Silver
Thai HUB
Vanadiw
Zinc
Not*: Design and
Parameter
1.0
1.2
3.2
5.1
5.8
51
operating
TCLP
(9/1)
0.84
0.42
0.77
<0.001
0.006
0.006
0.010
0.006
3.8
<0.01
<0.005
<0.004
0.037
<0.003
0.41
parameters
EP leachate
(g/D
0.36
0.14
-
-------
2872g
Table 4-1 (continued)
Saqile Set No. 5
Untreated waste
Constituent
Antiamy
Arsenic
BariM
Beryl HIM
CadMiM
ChroBiuM (total)
Copper
Lead
Mercury
Nickel
Seleniu*
Silver
Thallium
Vanadiui
Zinc
Total
(gAg)
340
300
14
0.15
3.0
3.1
8.7
f 3.1
600,000
1.3
2.3
3.2
5.1
5.6
50
TCLP
(9/1)
0.90
0.41
0.76
<0.001
<0.005
0.005
0.013
0.007
1.7
<0.01
<0.005
<0.004
0.026
<0.003
0.38
EP leachate
(9/1)
.
0.36
0.14
-
<0.005
<0.003
-
<0.028
0.093
-
<0.005
<0.004
-
-
Treated nonwastewater
Total
(«g/kg)
2.310
1.250
71
0.37
7.S
5.9
30.8
7.4
11
3.1
<0.5
9.5
<1.0
29
140
TCLP
(9/1)
15
18
0.16
<0.001
0.13
<0.003
<0.003
<0.005
0.006
<0.01
<0.025
<0.004
<0.01
0.004
0.24
EP leachate
(9/D
.
4.7
0.12
-
0.042
-
-
<0.028
<0.0002
-
<0.05
<0.004
-
-
Air pollution
control wastewater
Total (mg/1)
4.64
0.037
0.012
<0.002
<0.004
<0.007
<0.003
0.018
5.48
<0.013
<0.005
<0.003
0.043
<0.003
0.042
Note: Design and operating parameters are as follows:
Parameter Design value Operating value
Temperature of
il furnace hearth CF)
Temperature of
14 furnace hearth CF)
Ore concentrate
feed rate (Ib/hr)
1350-1450
1450-1550
1000-1300
1490
1560-1580
1370
- - Not analyzed
Reference: USEPA 1989g.
4-7
-------
2872g
Table 4-2 Treatment Performance Data for Retorting of K106 Hydrazine
Sludge Submitted by Plant B
Sample Set No. 1
Constituent
Arsenic
BariM
CadMiM
Chroniui
Lead
Nercury
Nickel
Seleniin
Silver
Untreated
waste
Total EP leachate
(gAg)
-
-
-
-
4.300
-
-
~
(«9/D
-
-
-
-
4.8
-
-
Treated
Total
(9A9)
2.5
48
3.0
38
56
100
39
<0.6
6.5
nonwastewater
EP leachate
(ng/D
0.033
0.070
0.016
<0.005
<0.06
6.0017
0.090
<0.005
<0.007
Note: Design and operating parameters are as follows:
Parameter Design value Operating value
Retort temperature (*F) 1000 1000
- - Not analyzed
Reference: Occidental Cheatcal 1987.
4-8
-------
2872g
Table 4-2 (continued)
Swple Set No. 2
Constituent
Arsenic
Barlwi
CadilUM
Chraiw
Lead
Mercury
Nickel
Seleniu*
Silver
Untreated waste
Total EP leachate
(g/kg) (»g/l)
-
-
-
-
5.500 5.3
-
-
- -
Treated
Total
(g/kg)
2.7
44
2.8
35
99
90
35
<0.6
8.3
nonwastewater
EP leachate
(9/1)
0.030
0.11
0.013
<0.005
<0.06
0.0024
0.11
<0.005
<0.007
Note: Design and operating parameters are as follows:
Parameter Design value Operating value
Retort temperature (*F) 1000 1000
- - Not analyzed
Reference: Occidental Chemical 1987.
4-9
-------
Z87Zg
Table 4-2 (continued)
Set No. 3
Constituent
Arsenic
Barlw
Cadiiui
Chrofliui
Lead
Mercury
Nickel
Selenium
Silver
Untreated waste
Total EP leachate
(g/kg) («g/l)
.
-
-
-
-
2,500 5.6
-
-
-
Treated
Total
(9/kg)
1.1
45
3.9
68
85
47
42
<0.6
9.9
nomtastexater
EP leachate
(g/D
0.021
0.13
0.012
<0.005
<0.06
0.0005
0.13
<0.005
<0.007
Note: Design and operating parameters are as folio
Paraneter Design value
Operating value
Retort te^wrature (*F)
1000
1000
- - Not analyzed
Reference: Occidental Conical 1987.
4-10
-------
Z872g
Table 4-2 (continued)
Sample Set No. 4
Constituent
Arsenic
Barium
Cadmium
Chromium
Lead
Mercury
Nickel
Selenium
Silver
Untreated waste Treated
Total EP leachate Total
(mg/kg) (mg/1) (mg/kg)
1.0
40
4.6
53
71
2,000 5.8 41
33
<0.6
9.5
nonwastexater
EP leachate
(g/D
0.021
0.14
0.015
-------
2872g
Table 4-3 Treatment Performance Data for Retorting of Mixed K071/K106
Waste froi Literature Source A
Untreated waste
Constituent Total concentration
(PP-)
Sanole Set Mo. 1
Mercury 345
Sample Set Nor 2
Mercury 255
Sanole Set No. 3
Mercury 290
Sample Set No. 4
Mercury 438
Sanole Set No. 5
Mercury 370
Treated waste
Total concentration
(PP»)
0.5 - 0.8
1.6 - 3.1
1.7 - 2.6
2 - 7.2
1.6
Note: Design and operating parameters are as follows:
Par-Meter
Operating value
Design value SSfl SS« SStt SS*4 SS*5
Haste feed rate (Ib/hr) 300-700
Retort te^erature (*F) 1200-1400
540 560 580 450 680
1400 1250 1350 1350 1386
Reference: Perry 1974.
4-12
-------
2872g
Table 4-4 Treatment Performance Data for Retorting of K106
Sodiun Borohydride Sludge Submitted by Plant C
Constituent
Sarnie Set No. 1
Mercury
Sanole Set No. 2
Mercury
Samle Set No. 3
Mercury
Samle Set No. 4
Mercury
Samle Set No. 5
Mercury
Mercury
Samle Set No. 7
Mercury
Untreated waste
Total
("9/kg)
50.000*
50.000*
50,000*
50.000*
50.000*
50.000*
50.000*
Treated nonwastewater
Total EP Toxicity
(mg/kg) (wg/1)
0.5 - 10b <0.0005
0.5 - lit* <0.0005
0.5 - 10b <0.0005
0.5 - 10** 0.0082
0.5 - 10* 0.0056
0.5 - 10b 0.0036
0.5 - 10b <0.0005
*0nly an approximate value Mas given for the untreated waste Mercury
concentration.
bOnly one range was given for the treated waste total Mercury concentration.
Reference: IMC 1982.
4-13
-------
2872g
Table 4-5 Treatment Perforaance Data for Stabilization of K106
Collected by EPA at Plant D
Untreated waste
Constituent
BOAT list Metals
Arsenic
BariuH
CadMiia
ChroMiu*
Copper
Lead
Mercury
Nickel
Silver
VanadiM
Zinc
Total
(PP»)
1.1
74
2.3
6.3
133
50
25.900
14
131
0.46
443
TCLP
(9/1)
<0.01
0.74
0.02
<0.01
<0.02
0.13
0.01
0.15
<0.02
<0.01
1.7
Treated nonwastexater
TCLP
("9/D
<0.004
0.326
<0.003
<0.02
<0.003
<0.006
0.0096
<0.025
0.007
<0.007
<0.013
Sanple Set K
Constituent
BOAT list metals
Arsenic
Barlun
CadMiui
ChroBlui
Capper
Lead
Mercury
Nickel
Silver
VanadiuM
Z1nc
Untreated
Total
(PP»)
1.1
74
Z.3
6.3
133
50
25.900
14
131
0.46
443
waste
rap
(9/1)
<0.01
0.74
0.02
<0.01
<0.02
0.13
0.01
0.15
<0.02
<0.01
1.7
Treated nonwastexater
TCLP
(9/1)
<0.004
0.362
0.004
<0.02
<0.003
<0.0076
0.023
<0.025
<0.006
<0.007
<0.013
Reference: USEPA 1988c.
4-14
-------
28729
Table 4-5 (continued)
Sanple Set «
Constituent
Untreated waste
Total
(pp»)
Treated nonwastewater
TCLP
(g/D
BPAT Hat Metals
Arsenic
Bariu*
CadHiiM
Chraiui
Copper
Lead
Mercury
Nickel
Silver
VanadiuM
Zinc
1.1
74
2.3
6.3
133
50
25.900
14
131
0.46
443
<0.01
0.74
0.02
<0.01
<0.02
0.13
0.01
0.15
<0.02
<0.01
1.7
<0.004
0.355
<0.003
<0.02
0.005
<0.006
0.0093
0.027
<0.006
<0.007
<0.013
Reference: USEPA 1988c.
4-15
-------
28729
Table 4-6 Performance Data for Sulfide Precipitation Treatment of £071 Wastewaters Collected by EPA at Plant E
ANALYTICAL DATA:
.
BOAT list constituent
Arsenic
Bariw
CadriiM
Qtrmiim
Copper
Lead
Mercury
Nickel
Silver
Vanadiui
Zinc
DESIGN AND OPERATING
Parameter
Excess sulf ide
Sawle
Untreated
wastewater
(9/D
<0.2
0.248
<0.03
<0.06
0.097
<0.66
23.7
0.157
0.148
<0.04
0.615
PARAMETERS:
Set §1
Treated
wastewater
(9/D
<0.2
0.103
<0.06
0.553
<0.16
<1.32
0.028
0.275
<0.1
<0.08
0.047
Sawle
Untreated
wastewater
(9/D
<0.1
0.226
<0.06
0.189
<0.16
<1.32
9.25
<0.26
0.1
<0.08
0.88
Set 12
Treated
wastewater
(9/D
<0.1
0.158
<0.06
<0.12
<0.16
<1.32
0.027
<0.26
<0.1
<0.08
<0.04
Sawle Set «
Untreated
wastewater
(9/D
<0.1
0.293
<0.06
<0.12
<0.16
<1.32
77.2
<0.26
0.12
<0.08
0.535
Treated
wastewater
(9/D
<0.1
0.144
<0.06
<0.12
<0.16
<1.32
0.028
<0.26
<0.1
<0.08
0.064
Filter cake
Total
(g/kg)
1.1
74
2.3
6.3
133
50
25.900
14
131
0.46
443
(1(1061*
Tap
(9/D
<0.01
0.74
0.02
<0.01
<0.02
0.13
0.01
0.15
<0.02
<0.01
1.7
Ooeratina values
Design value
>40«g/l
Sa*>le Set f 1
85«g/l
Sample Set 12
101 *g/l
Sample
..
Set *3
^1
"Only one saiple was collected of the filter cake (K106).
Reference: USEPA 1988b.
-------
5. IDENTIFICATION OF BEST DEMONSTRATED AVAILABLE TECHNOLOGY
(BOAT)
This section presents the rationale for the determination of best
demonstrated available technology (BDAT) for mercury-containing
nonwastewaters and wastewaters. To determine BDAT, the Agency examines
all available performance data for the technologies that are identified
as demonstrated for each treatability group to determine whether one of
these technologies performs significantly better than the others. All
performance data used for determination of best technology must first be
adjusted for accuracy, as discussed in EPA's publication Methodology for
Developing BDAT Treatment Standards (USEPA 1989a).* BDAT must be
specifically defined for all streams associated with the management of
the listed waste or wastes; this includes the original waste as well as
any residual waste streams created by the treatment process.
The technology that performs best on a particular waste or waste
subcategory is then evaluated to determine whether it is "available." To
be available, the technology must (1) be commercially available to any
generator and (2) provide "substantial" treatment of the waste, as
determined through evaluation of accuracy-adjusted data. In determining
whether a technology is available, EPA may consider data on the
performance of a waste similar to the waste in question, provided that
the similar waste is at least as difficult to treat.
Accuracy adjustment accounts for the ability of an analytical technique
to recover a particular constituent from the waste in a particular
test. The recovery of a constituent is determined by spiking a sample
with a known amount of the target constituent and then comparing the
result of analysis of the spiked sample with the result from the
unspiked sample.
5-1
2865s
-------
5.1 BOAT for Nonwastewaters
EPA reviewed the available treatment performance data for
mercury-containing wastes presented in Section 4 to determine whether
they represent the operation of well-designed and well-operated systems
and whether sufficient quality assurance/quality control (QA/QC) data
were collected to assess the accuracy of the treated waste analyses.
Identification of BOAT for nonwastewaters is discussed below for each
treatability group.
5.1.1 Inorganic Mercury Nonwastewaters - High-Mercury Subcategory
EPA has identified several thermal mercury recovery technologies,
including retorting, roasting, batch vacuum or steam distillation, and a
proprietary process as demonstrated technologies for inorganic mercury
nonwastewaters in the high-mercury subcategory. The Agency has also
identified thermal processing of mercuric sulfide (cinnabar) ores as a
technology that is used to recover mercury from wastes more difficult to
treat than most inorganic mercury wastes because of the higher mercury
content in these ores than in mercuric sulfide-containing wastes for
which EPA has waste composition data (see Section 3.2.1).
For treatment of wastes in which mercury is present as metallic
mercury or as inorganic mercury compounds, the Agency has data from four
tests as follows:
Five sets of performance data (presented in Table 4-1) from
recovery of mercury from cinnabar ores by a thermal treatment
process that is very similar to retorting waste treatment
processes.
Four sets of performance data from retorting of K106 generated
by hydrazine treatment of mercury-containing wastewaters
(presented in Table 4-2),
5-2
2865|
-------
Five sets of performance data from retorting of a mixed
K071/K106 waste (presented in Table 4-3) which contained 95
percent K071 and 5 percent K106 sulfide sludge, and
Seven sets of performance data from retorting of K106 generated
by borohydride reduction treatment (presented in Table 4-4).
The treatment data presented in Table 4-1 include total composition
TCLP leachate, and EP leachate data for both the untreated waste and the
treated nonwastewater residual as well as total composition data for the
air pollution control wastewaters (primarily SO,, scrubber waters).
QA/QC information was also provided. The data presented in Table 4-2
include total and EP Toxicity procedure leachate concentrations for
mercury and the other EP metals for the treated nonwastewater as well as
design and operating information. QA/QC information (analytical
recoveries) was also provided with these data. The data in Table 4-3
include a range of total mercury concentrations in the treated
nonwastewater for each test, as well as design and operating data. EPA
considered the highest value of the range in each test as the value that
represented treatment performance for that test. No analytical QA/QC
data were provided. However, from the detail of the analytical method
provided in the report, EPA believes that the data were adjusted for
analytical recovery before presentation in the report. The data in Table
4-3 present the EP leachate mercury concentration for each sample set for
the treated nonwastewater but only a range of total mercury
concentrations for the seven sample sets. No QA/QC data were provided.
The data in Table 4-4 were not used in determination of "best"
performance because only a range (i.e., two data points) was given, and
no operating or QA/QC data were given for the test. However, this data
set indicates that similar performance was achieved in retorting of the
K106 borohydride sludge as was achieved in retorting of the mixed
K071/K106 sludge.
5-3
28658
-------
The treatment performance data presented in Table 4-1 were adjusted
for analytical recovery to take into account analytical interferences
associated with the chemical makeup of the treated waste samples. In the
QA/QC test for analytical recovery, EPA first analyzes a waste for a
constituent and then adds a known amount (i.e., a spike) of the same
constituent to the waste material and reanalyzes the sample for that
constituent. The difference between the total amount detected after
spiking and the concentration detected in the unspiked sample divided by
the amount of spike added is the recovery value. (If recovery tests are
run in duplicate, EPA uses the lower recovery value.) The reciprocal of
the recovery multiplied by the analytical value obtained during
performance testing is the accuracy-corrected value used in comparing
treatment effectiveness and subsequently in calculating treatment
standards. Percent recovery values for constituents detected in the
mercury ores tested are presented in Appendix A. The accuracy-adjustment
of performance data for total mercury for thermal processing of mercury
ores is detailed in Table 5-1.
EPA also adjusted the data presented in Table 4-2 for accuracy.
These calculations are summarized in Table 5-1, along with the treatment
data from Table 4-3. The three data sets for total mercury concentration
summarized in Table 5-1 were compared using EPA's analysis of variance
(ANOVA) procedure. The ANOVA is described in the methodology document
(USEPA 1989a). A comparison of the accuracy-adjusted treatment data
presented in Table 5-1 for total mercury composition indicates that the
retorting performance data for treatment of the mixed K071/K106 sludge
represents better treatment than the data from retorting of the K106
hydrazine sludge and from thermal recovery of mercury from cinnabar
ores.
The design and operating data provided in Table 4-1 show that the
thermal ore processing system was well operated during the test. Even
though the total composition mercury data from this test show higher
5-4
28B3«
-------
mercury concentrations in the residual from thermal ore processing than
for the K071/K106 retorting test, the EP Toxicity procedure and TCLP
leachates from the ore processing residuals show that mercury leaches
from these residuals at very low levels. The range of TCLP leachate
concentrations for mercury in these residuals, reported in Table 4-1, is
0.0002 to 0.006 mg/1 (ppm). The EPA leachate concentrations reported for
mercury in the same table are all below 0.0002 mg/1 (ppm).
The design and operating data presented in Table 4-2 for the K106
hydrazine sludge indicate that this retorting test was performed at a
much lower temperature (1000'F versus 1250-1400°F) than was the
test of the mixed K071/K106 wastes. This could account for the poorer
treatment performance in this test.
Based on the data presented for thermal treatment of mercury wastes
in Table 5-1, retorting for recovery of mercury has been determined to be
the best technology for treatment of inorganic mercury nonwastewaters.
All of the treatment data for thermal mercury recovery processes
presented in Section 4 show that substantial treatment is achieved based
on the reduction in total, TCLP, and EP leachate mercury concentrations
in the treated nonwastewater compared to that in the untreated waste.
The thermal ore processing technology is used at the one U.S. mine that
is known to process mercury ores. Similar technologies (retorting and
roasting) are used or have been used at several chlor-alkali facilities
in the U.S. and in Europe to process mercury wastewater treatment
sludges. Therefore, thermal recovery of mercury is available and thus
has been determined to be BOAT for inorganic mercury nonwastewaters.
5.1.2 Inorganic Mercury Nonwastewaters - Low-Mercury Subcategory
EPA has identified acid leaching as the only demonstrated treatment
technology for inorganic mercury nonwastewaters with total mercury
5-5
26638
-------
concentrations too low to be amenable to recovery by thermal recovery
technologies (i.e., the low-mercury subcategory). Evaluation of these
data for proper system design and operation and calculation of
accuracy-adjusted treatment data are included in the BOAT background
document for K071 (USEPA 1988b).
5.1.3 Organic Mercury Nonwastewaters
EPA has identified incineration as the only demonstrated technology
for treatment of mercury-containing nonwastewaters that contain
organomercury constituents (such as phenylmercuric acetate) or that
contain mercury in an organic waste matrix. No data are available to the
Agency on incineration of organic mercury nonwastewaters. However,
incineration data for a mixed K048/K051 waste that contained an organolead
compound (tetraethyl lead) in an organic waste matrix showed that
organics were destroyed in the resulting incinerator ash and scrubber
waters and the lead was concentrated in these two residual waste
matrices. EPA expects the same to happen for incineration of organic
mercury nonwastewaters. Therefore, incineration has been determined to
be BDAT for P065, P092, and D009 organic mercury nonwastewaters followed
by treatment of the ash and scrubber water residuals by the BOAT
specified for inorganic high-mercury nonwastewaters and mercury-containing
wastewaters in Sections 5.1.1 and 5.2, respectively.
5.1.4 Nonwastevaters Containing Radioactive Materials
In Section 2.3.4, EPA discussed two subcategories of nonwastewaters
containing reactive materials that have been reported to be generated by
DOE. These were described as metallic mercury-containing radioactive
materials and waste hydraulic oil contaminated with metallic mercury and
radioactive materials.
5-6
2865g
-------
The Agency has no data or information to indicate that thermal
mercury recovery processes that are demonstrated for treatment of
inorganic high-mercury nonwastewaters would be able to separate the
mercury from the radioactive material (tritium) that is the contaminant
in the metallic mercury waste generated by DOE. Thus, the Agency
believes that technologies demonstrated for these wastes are the
absorption technologies discussed in Section 3.1.1(7). Common absorbants
used are zinc dust, calcium disulfide, and flowers of sulfur. EPA
prefers amalgamation with zinc over conventional spill cleanup procedures
involving addition of calcium polysulfide or flowers of sulfur because
use of zinc results in lower air emissions of mercury.
The Agency currently has no information on whether this procedure
will reduce the overall leachability of mercury. However, the Agency has
determined that this procedure does provide significant treatment due to
the decrease in air emissions, the change in mobility from liquid mercury
to a paste-like solid, and the potential reduction in leachability due to
the amalgamation with the zinc. Based on this information, the general
lack of treatment data, the lack of alternative technologies, and the
unique handling problems associated with the radioactivity, the Agency
has determined that amalamation with zinc represents the best technology
for treatment of elemental mercury wastes contaminated with radioactive
materials.
EPA feels that incineration, which is demonstrated for treatment of
nonradioactive organic mercury nonwastewaters, is also demonstrated for
treatment of waste hydraulic oil contaminated with mercury and
radioactive materials (tritium). However, EPA does not expect recovery
technologies to be applicable to the treatment of nonwastewater residuals
generated from incineration treatment of this waste. Therefore, the best
technology for treatment of the inroganic low-mercury nonwastewaters,
acid leaching, is also BOAT for treatment of the nonwastewater residuals
generated from incineration of this waste.
5-7
2865g
-------
5.2 BOAT for Wastevaters
EPA has identified chemical precipitation followed by filtration,
carbon adsorption, and ion exchange as demonstrated technologies for
treatment of mercury-containing wastewaters where the mercury constituent
is inorganic. EPA has identified chemical oxidation followed by chemical
precipitation and filtration, incineration, ion exchange, and carbon
adsorption as demonstrated technologies for the treatment of wastewaters
containing organomercury constituents or inorganic mercury in an organic
waste matrix.
As discussed in Section 4, EPA does not have treatment data for
wastewaters generated from retorting. However, EPA does have chemical
precipitation treatment data for K071 mercury-containing wastewaters,
presented in Table 4-6. The Agency has determined that these wastewaters
are at least as difficult to treat as wastewaters generated from
retorting because the concentrations of mercury and other metals are
similar and neither waste contains significant concentrations of any
interfering substances. These wastewaters are also expected to be at
least as difficult to treat as other mercury-containing wastewaters that
would be classified as D009 wastes because of the relatively high
concentration of mercury in the K071 wastewaters and because the Agency
has no data indicating that D009 wastewaters are routinely generated
containing significant concentrations of constituents (such as oil and
grease) that would affect performance of chemical precipitation
treatment. This technology substantially reduces the concentration of
mercury in wastewaters, as noted in Table 4-6, where untreated mercury
concentrations of as much as 77 mg/1 are treated to 0.028 mg/1.
EPA has no data on the demonstrated adsorption technologies (ion
exchange and carbon adsorption). However, when these technologies are
used, a regenerant solution is produced that is either recycled or must
5-8
28658
-------
be treated by chemical precipitation. Therefore, the chemical
precipitation treatment standard would ultimately apply to wastewaters
generated by these technologies.
Data collected by the Agency on treatment of K071 wastewater by
sulfide precipitation and filtration are shown in Table 4-6. Operating
data collected during treatment of this waste show that these data
represent the performance of a well-designed, well-operated treatment
system. EPA adjusted the data values based on the analytical recovery
values in order to take into account analytical interferences associated
with the chemical makeup of the treated sample. Accuracy adjustment of
mercury concentrations for these treatment data is detailed in
Table 5-2. The analytical recovery values used in these calculations are
presented Appendix A.
EPA's determination of substantial treatment is based on the observed
reduction in total mercury concentration from 77.2 ppm to 0.028 ppm in
the K071 mercury-containing wastewaters considered by EPA to be similar
to other inorganic mercury-containing wastewaters.
The Agency believes that this reduction in the concentration of
hazardous constituents is substantial and that sulfide precipitation
followed by filtration is available to treat these wastes because it is a
common commercially available wastewater treatment technology.
Therefore, sulfide precipitation followed by filtration represents BDAT
for these wastewaters.
The Agency does not have data on the effectiveness of chemical
oxidation treatment of wastewaters contaminated with organics or
organomercury compounds followed by chemical precipitation and filtration
to enable it to compare this treatment to the performance of sulfide
precipitation treatment of inorganic mercury wastewaters. Lacking these
data, EPA has determined that chemical precipitation is also the best
5-9
2865g
-------
technology for the treatment of organic mercury wastewaters. Incineration
may be required as a pretreatment method for organometallic wastes to
destroy the organics and concentrate the metals in the residual ash or
the incineration scrubber waters. Resulting scrubber waters would be
expected to be free of organics; therefore, mercury in these wastewaters
is then expected to be able to be treated by chemical precipitation with
similar effectiveness as treatment of inorganic mercury wastewaters.
Chemical oxidation may also be effective as a pretreatment method for
organics prior to chemical precipitation.
EFA has no data on the demonstrated adsorption technologies (ion
exchange and carbon adsorption), but these technologies ultimately
generate a residual (the spent carbon or ion exchange resin) that must be
thermally processed (incinerated or retorted) to recover mercury. (In
the cases where the mercury is adsorbed as an organomercury compound,
incineration may be the only thermal treatment option.) Therefore,
either retorting/roasting or incineration are ultimately the best
technologies for treatment of nonwastewater residuals generated by these
treatment technologies, and the incineration treatment standard also
applies to nonwastewater residuals generated from the use of these
technologies to treat organic mercury wastewaters.
No data are available on the treatment of P065 wastewaters or D009
reactive mercury wastewaters by the demonstrated technologies (aqueous
chemical deactivation and incineration) identified in Section 3.2.2.
However, based on the demonstrated effectiveness of incineration of other
explosive and reactive D001 wastes (USEFA 1989e), the Agency has
determined that BOAT for the explosive mercury nonwastewaters
(incineration in specially-designed units) followed by treatment of
scrubber waters produced from incineration by the BDAT for inorganic
mercury wastewaters (chemical precipitation followed by filtration) is
BDAT for explosive mercury wastewaters (P065 and explosive D009
5-10
286S&
-------
wastewaters). The determination is based on the same reasons as were
discussed in Section 5.1.4 for explosive mercury nonwastewaters and in
Section 5.2.1 for inorganic mercury wastewaters.
2865g
-------
2872g
Table 5-1 Sunmary of Accuracy Adjustment of Treatment Data for Total Mercury
Generated from Thermal Recovery Technologies
Untreated
waste
concentration
(mgAg)
Measured
treated waste
concentration
(mg/kg)
Percent
recovery for
treated waste
matrix
Accuracy
correction
factor
Accuracy-
adjusted
concentration
(mg/kg)
Thermal Treatment of Mercuric Sulfide Ores
Sample Set No. 1 625,000
Sample Set No. 2 738.000
Sample Set No. 3 640,000
Sample Set No. 4 473.000
Sample Set No. 5 600,000
Retorting of K106 Hvdrazine Sludge
45
42.4
36
23
11
113
113
113
113
113
1.0
1.0
1.0
1.0
1.0
45
42.4
36
23
11
1
Sample Set No.
Sample Set No. 2
Sample Set No. 3
Sample Set No. 4
4,300
5.500
2,500
2.000
Retorting of Mixed H071/K106
100
90
47
41
89
1.12
1.12
1.12
1.12
112
101
53
46
Sample
Sample
Sample
Sample
Sample
Set
Set
Set
Set
Set
No.
No.
No.
No.
No.
1
2
3
4
5
345
255
290
438
370
NA
HA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0
3
2
7
1
.8
.1
.6
.2
.6
NA - Not available. Data from Literature Source A (Perry 1974), as presented in Table 4-3,
are assumed to have been corrected for accuracy of the analytical method.
5-12
-------
3402g
Table 5-2 Summary of Accuracy Adjustment of Treatment Data
for Total Mercury in Wastewaters
Chemical
Sample
Sample
Sample
Untreated
waste
concentration
(ng/D
Precipitation
Set No. 1 23.7
Set No. 2 9.25
Set No. 3 77.2
Measured
treated waste
concentration
(mg/1)
0.028
0.027
0.028
Percent
recovery for
treated waste
matrix
95
95
95
Accuracy
correction
factor
1.05
1.05
1.05
Accuracy-
adjusted
concentration
(ag/1)
0.029S
0.0284
0.0295
-------
6. SELECTION OF REGULATED CONSTITUENTS
In Section 5, the best demonstrated available technology (BOAT) was
determined for each waste treatability group for the mercury-containing
wastes K071, K106, U151, P065, P092, and D009. This section describes
the selection of constituents to be regulated for each waste code. The
selected constituents must be present in the untreated waste at concentra-
tions that are treatable by the chosen BOAT discussed in Section 5.
6.1 Nonvastevaters
In the EPA treatment test of thermal processing of mercuric sulfide
ores, the Agency analyzed the untreated ore samples for BDAT list metals
and BDAT list organic compounds, as well as for total organic carbon
(TOC). No treatable concentrations of organic compounds were detected in
these samples. Thus, these ores are similar to the K106 mercuric.sulfide
sludge wastes as generated (see Table 2-4).
The mercuric sulfide ores sampled by EPA were not analyzed for
certain compounds on the BDAT list (specifically organochlorine
pesticides, phenoxyacetic acid herbicides, organophosphorus insecticides,
PCBs, and dioxins and furans) because the Agency is not aware of any
in-process source of these constituents and would therefore not expect
any of these constituents to be present at treatable concentrations. Two
inorganics other than metals on the BDAT list (fluoride and cyanide) were
not analyzed. Even though these constituents were not analyzed, EPA
would not expect fluoride or cyanide to be present at treatable
concentrations in the wastes tested.
The K106 hydrazine sludge treated at Plant B was analyzed only for
the eight EP characteristic metals (arsenic, barium, cadmium, chromium,
lead, mercury, selenium, and silver). None of the metals other than
mercury were detected at treatable concentrations in this K106 waste.
6-1
2866S
-------
Results of retorting treatment of the mixed K071/K106 sludge reported in
Literature Source A (see Table 4-3) prsented only total mercury
concentrations. However, no treatable concentrations of other BOAT list
constituents were expected to be detected for this waste. Results of
retorting of K106 at Plant C (presented in Table 4-4) also only reported
mercury concentrations. No other BOAT list constituents were expected to
be present at treatable concentrations in this waste.
Upon analysis of data on characaterization and treatment of K071 and
K106 wastes generated in the mercury cell chlor-alkali process and
available information about this process, EPA concludes that mercury is
the only BOAT list constituent expected to be routinely present in wastes
from this process. Thus, the Agency has determined that mercury is the
only regulated constituent for K106 and for the reproposal of treatment
standards for K071 nonwastewaters. Mercury was previously selected (in
the Fir^t Third regulations) as the only regulated constituent for K071
nonwastewaters and wastewaters (USEPA 1988b).
For P065, P092, and U151, mercury is expected to be the only BDAT
list metal constituent of the waste (unless the wastes are mixed with
other listed or characteristic hazardous wastes, in which case other
treatment standards would also apply). P092 is also expected to contain
organic constituents (benzene, in particular). Mercury has been selected
as the only regulated constituent for these U- and P-code mercury-
containing wastes. No data are available to EPA on the treatment of
organics in P092 wastes. However, the Agency expects the organic
constituents of P092 to be destroyed by incineration of P092 wastes,
which is required as a method of treatment. EPA also expects that the
fulminate constituent of P065 (mercury fulminate) and the reactive
constituents of 0009 reactive wastes will be destroyed by incineration,
which is required as a method of treatment for organic mercury wastes.
Incineration also removes the reactivity characteristic associated with
these wastes.
6-2
2866ft
-------
Mercury has also been selected as the only constituent for regulation
for D009 wastes. EPA does not have sufficient characterization data for
D009 wastes to determine whether these wastes commonly contain other BOAT
list constituents at treatable concentrations. If these wastes contain
organic constituents, EPA believes that these constituents will be
destroyed by incineration, which is a required method of treatment for
organic D009 nonwastewaters.
6.2 Wastewaters
EPA does not have data on the composition or treatment of K106
wastewaters generated from retorting. However, EPA does have data that
indicate that mercury is the only BOAT constituent present in wastewaters
generated from recovery of mercury from mercuric sulfide ores in a
multiple-hearth furnace (see Table 4-1). Thus, EPA would not expect any
BOAT constituent other than mercury to be present in treatable quantities
in the K106 wastewater for reasons already presented in the discussion of
nonwastewaters. Mercury has therefore been selected as the only
regulated constituent for K106 wastewaters.
Mercury has been selected as the only regulated constituent in P065,
P092, U151, and D009 wastewaters. Mercury is the only constituent for
which these wastes are listed and is the only BDAT list constituent
expected to be present in these wastes, with the following exceptions:
If these wastes are mixed with other listed or characteristic
hazardous wastes, other appropriate treatment standards would also
apply.
For P092 and organic D009 wastes, organic constituents will be
present; incineration is required as a method of treatment for
these organics.
For P065 (which may be reactive) and reactive D009 wastes,
incineration is required as a method of treatment for the
reactivity characteristic of these wastes.
6-3
2666g
-------
7. CALCULATION OF TREATMENT STANDARDS
This section presents the calculation of the proposed numerical
treatment standards for K071, K106, P065, P092, U151, and D009 wastes
using the treatment data presented for the best demonstrated available
technologies, as determined in Section 5. In Section 6, mercury was
selected as the only regulated constituent for both nonwastewater and
wastewater forms of the wastes.
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.
BDAT standards are determined for each constituent by multiplying the
arithmetic mean of accuracy-adjusted constituent concentrations detected
in treated waste by a "variability factor" specific to each constituent
for each treatment technology defined as BDAT. Accuracy adjustment of
performance data has been discussed in Section 5 in relation to defining
BDAT. Variability factors account for normal variations in the
performance of a particular technology over time. They are designed to
reflect the 99th percentile level of performance that the technology
achieves in commercial operation. (For more information on the
principles of calculating variability factors, see EPA's publication
Methodology for Developing BDAT Treatment Standards (USEPA 1989a).)
Details on the calculation of variability factors for mercury-containing
nonwastewaters and wastewaters are presented in this section.
Where EPA has identified BDAT for a particular waste, but because of
data limitations or for some other compelling reason cannot define
specific numerical treatment standards for that waste, the Agency can
7-1
2867g
-------
require the use of that treatment process as a technology standard. The
rationale for specifying technology standards for certain mercury wastes
or waste groups, either in lieu of or in addition to numerical treatment
standards, is also discussed in this section.
7.1 Wastewaters
EPA collected three sets of untreated and treated K071 wastewater
data from one facility using sulfide precipitation followed by
filtration. The following steps were taken to derive the numerical BOAT
treatment standards for wastewaters:
Accuracy-corrected constituent concentations were calculated for
mercury. These calculations are presented in Table 5-2.
The Agency evaluated the data collected from the sulfide
precipitation treatment system to determine whether any of the
data represented poor design or poor operation. The available
design and operating data show that all three data sets collected
from the Agency testing for wastewater represent the performance
of a well-designed, well-operated system.
An arithmetic average concentration level and a variability
factor were determined for the BOAT list constituent (i.e.,
mercury) regulated in this waste.
The BDAT treatment standard for mercury was determined by
multiplying the average accuracy-corrected total concentration by
the variability factor, which has been calculated to be 1.05.
Table 7-1 summarizes the calculation of the numerical treatment
standards for mercury-containing wastewaters. It was determined in
Section 5 that incineration may be necessary as a pretreatment step for
organic or reactive mercury wastewaters. However, no treatment data are
available for treatment of wastewaters containing organomercury
constituents or mercury and organic constituents. EPA is thus not
requiring the use of incineration as a treatment technology standard for
organic mercury wastewaters. EPA expects the incineration scrubber water
residual generated from treatment of organomercury wastewaters to be free
7-2
2867B
-------
of organics and thus no more difficult to treat than inorganic mercury
wastewaters. Table 7-4 presents proposed BOAT treatment standards for
all mercury-containing wastewaters.
7.2 Nonwastewaters
In Section 5, the retorting performance data of a mixed K071/K106
waste were determined to represent the performance of the BOAT for
inorganic mercury nonwastewaters containing high concentrations of
mercury (the high-mercury subcategory). Acid leaching was determined to
be BOAT for inorganic mercury nonwastewaters in the low-mercury
subcategory. The retorting performance data from K071/K106 were used to
determine a level of mercury that would classify a waste as either a
high-mercury waste or a low-mercury waste. The following steps were
taken to derive the total mercury concentration used to distinguish
between subcategories for inorganic mercury nonwastewaters.
Accuracy-corrected constituent concentrations for these data
were presented in the original report of treatment system
performance. The accuracy-adjusted data are presented in Table
5-1.
The Agency evaluated the data collected from the retorting
treatment system to determine whether any of the data represent
poor design or poor operation. The available design and operating
data indicate that all five sets of data represent the performance
of a well-designed, well-operated system.
An arithmetic average concentration level and a variability
factor were determined for the BOAT list constituent (i.e.,
mercury) regulated in this waste.
The 16 mg/kg cutoff level was determined by multiplying the
average accuracy-corrected total mercury concentration by the
variability factor.
This 16 mg/kg level represents the anticipated performance of
retorting or roasting treatment of mercury wastes based on the best data
7-3
2867g
-------
available to the Agency. Data from the thermal processing of cinnabar
ores were analyzed in the same way as the K071/K106 performance data to
determine the performance level that could be expected from roasting/
retorting of these ores (see Table 7-2). These calculations suggest that
mercury sulfide-containing wastes with untreated mercury concentrations
as high as those in the ores (over 50 percent by weight) would yield
higher mercury concentrations (over 100 mg/kg) when roasted or retorted.
However, an analysis of the performance data from the thermal processing
of cinnabar ores suggests that none of the residues resulting from the
retorting or roasting of mercury sulfide-containing wastes are likely to
leach mercury at greater than 0.2 mg/1 when tested by either the TCLP or
the EP Toxicity procedures. The processed cinnabar ores that were
roasted/retorted had well over 50 percent mercury. EPA believes that
this concentration is much higher than in typical mercury wastes and that
the K071/K106 wastes that were roasted/retorted are more representative.
Hence, EPA is proposing that 16 mg/kg total mercury concentration level,
based on the treatment of the K071/K106 wastes, to identify those
mercury-containing wastes amenable to mercury recovery by retorting or
roasting.
For the purpose of this rule, K071, K106, U151, and D009 wastes
containing greater than or equal to 16 mg/kg total mercury are classified
as high-mercury subcategory wastes. Similarly, K071, K106, U151, and
D009 wastes containing less than 16 mg/kg total mercury are classified as
low-mercury subcategory wastes.
Table 7-3 summarizes the calculation of the 16 mg/kg cutoff level
between high-mercury wastes and low-mercury wastes for inorganic mercury
nonwastewaters.
The inorganic mercury nonwastewaters in the high-mercury subcategory
waste must be processed for mercury recovery using a thermal recovery
technology. This is required as a technology treatment standard. The
7-4
2867g
-------
residual nonwastewater from recovery is considered indigenous to the
process; therefore, the derived-from rule does not apply to this
residual. However, this residual must still be further treated by a
thermal mercury recovery technology if it is EP toxic for mercury and is
classified as a D009 high-mercury subcategory waste (i.e., greater than
16 mg/kg total mercury concentration).
Incineration was selected in Section 5 as BOAT for organic mercury
nonwastewaters (P065, P092, and organic D009 wastes). However, no
incineration performance data are available for treatment of these wastes
or wastes containing similar concentrations of mercury and organic
constituents. Therefore, EPA is requiring the use of incineration as a
treatment technology for these wastes. The Agency is also proposing
technology-based treatment standards for treatment of nonwastewater
incineration residuals (incinerator ash and wastewater treatment sludges
generated from treatment of scrubber waters). EPA believes that the
incineration residuals generated from treatment of the organomercury
wastes will be free of organics and thus no more difficult to treat than
inorganic mercury nonwastewaters and wastewaters.
Tables 7-5 through 7-8 present treatment standards for K071, K016,
U151, P065, P042, and D009 nonwastewaters.
In Section 5, amalgamation with zinc was selected as BOAT for the
radioactive elemental mercury wastes. No performance data are available
on this treatment process. Therefore, EPA has established amalgamation
with zinc, as described in Section 3.1.1(7), as a technology-based
treatment standard for these wastes. The treatment standard is shown in
Table 7-9.
Incineration was determined to be BOAT for hydraulic waste oils
contaminated with mercury and radioactive materials. EPA has no data on
the performance of incineration for treatment of these wastes, but
7-5
2867g
-------
expects incineration to destroy the organic content of the waste. EPA
has therefore established standards based on treatment of the residuals
generated from incineration treatment of these wastes. EPA expects these
incineration residuals (incineration ash and scrubber waters) to be no
more difficult to treat than low-mercury nonwastewaters and K071 mercury-
containing wastewaters, respectively. The Agency is therefore transfer-
ring performance of acid leaching treatment for K071 nonwaste- waters to
the treatment of the incinerator ash residues from incineration of this
waste and transferring the performance of chemical precipitation of K071
wastewaters to the treatment of scrubber waters generated from incinera-
tion. The proposed treatment standard for hydraulic oils contaminated
with mercury and radioactive materials is shown in Table 7-10.
7-6
2867g
-------
3402g
Table 7-1 Calculation of Numerical Treatment Standards for Wastewaters
Accuracy-adjusted Mean
treated waste treated waste Variability Treatment
Constituent concentrations9 concentration factor standard
Wastewater
Hercury (rog/1) 0.0295 0.029 1.05 0.03
0.0284
0.0295
a See Table 5-2.
7-7
-------
Table 7-2 Calculation of Expected Performance of Cinnabar
Ore Roasting Process
Regulated
constituent
Accuracy adjusted3
treated waste
concentration
(mg/kg)
Mean treated
waste Variability Expected
concentration factor performance
(mg/kg) (mg/kg)
Mercury (total)
(mg/kg)
45
42.4
36
23
11
31.5
3.49
110
aSee Table 5-1.
7-8
2867g
-------
3402g
Table 7-3 Calculation of Numerical Treatment Standards for Nonwastewaters
Regulated
constituent
Accuracy-adjusted
treated waste
concentration8
Mean treated
waste Variability
concentration factor
Treatment
standard
Nonwastewater
Mercury (total) (rag/kg)
0.8
3.1
2.6
7.2
1.6
3.1
5.15
16
See Table 5-1.
7-9
-------
Table 7-4 Proposed BOAT Treatment Standard for D009,
K106, P065, P092, and U151 Wastewaters
Regulated constituent
Maximum for anv single grab sample
Total composition
(mg/1)
Mercury
0.030
2867g
7-10
-------
Table 7-5 Proposed Revised BDAT Treatment
Standards for K071 Nonwastewaters
High-Mercury Subcategory - Greater than or Equal to 16 mg/kg total mercury
ROASTING OR RETORTING AS A METHOD OF TREATMENT
Low-Mercury Subcategory - Less than 16/mg/kg total mercury
Regulated Maximum for anv single grab sample
constituent TCLP (mg/1)
Mercury 0.025
7-11
28678
-------
Table 7-6 Proposed BDAT Treatment Standards for K106
and U151 Nonwastewaters
High-Mercury Subcategory - Greater than or equal to 16 mg/kg total mercury
ROASTING OR RETORTING AS A METHOD OF TREATMENT
Low-Mercury Subcategory - Less than 16/mg/kg total mercury
Regulated Maximum for anv single grab sample
constituent TCLP (mg/1)
Mercury 0.025
7-12
2867g
-------
Table 7-7 Proposed BOAT Treatment Standards for P065
and P092 Nonwastewaters
INCINERATION FOLLOWED BY ROASTING OR RETORTING OF INCINERATOR
NONWASTEWATER RESIDUALS (ASH AND WASTEWATER TREATMENT SLUDGES FROM
TREATMENT OF THE INCINERATOR SCRUBBER WATERS) PROVIDED SUCH RESIDUES
EXCEED 16 MG/KG TOTAL MERCURY CONCENTRATION
P065 wastes must be incinerated in accordance with the requirements of 40
CFR Part 264, Subpart 0, or Part 265, Subpart 0, in specially-designed
incinerators. The incinerator ash residual must be processed for mercury
recovery using a thermal recovery technology if it does not meet the
total composition treatment standard.
P092 wastes must be incinerated in accordance with the requirements of 40
CFR Part 264, Subpart 0, or Part 265, Subpart 0, or burned in boilers or
industrial furnaces in accordance with applicable regulatory standards.
The incinerator ash residual must be processed for mercury recovery using
a thermal recovery technology if it does not meet the total composition
treatment standard.
7-13
2867g
-------
Table 7-8 Proposed BDAT Treatment Standards for D009
Nonwastewaters
High-Mercury Subcategory - Greater than or equal to 16 mg/kg total mercury
ROASTING OR RETORTING AS A METHOD OF TREATMENT; OR INCINERATIONa AS A
METHOD OF TREATMENT FOLLOWED BY ROASTING OR RETORTING OF THE INCINERATOR
NONWASTEWATER RESIDUES (ASH AND WASTEWATER TREATMENT SLUDGES FROM
TREATMENT OF THE INCINERATOR SCRUBBER WATERS) PROVIDED SUCH RESIDUES
EXCEED 16 MG/KG TOTAL MERCURY CONCENTRATION
a Organic nonwastewater forms of this waste must be incinerated in
accordance with the requirements of 40 CFR Part 264, Subpart 0, or Part
265, Subpart 0, or burned in boilers or industrial furnaces in
accordance with applicable regulatory standards. Reactive
nonwastewater forms of this waste must be incinerated in accordance with
the requirements of 40 CFR Part 264, Subpart 0, or Part 265, Subpart 0,
in specially-designed incinerators. The incinerator ash residual must
be processed for mercury recovery using a thermal recovery technology if
it does not meet the total composition treatment standard.
Low-Mercury Subcategory - Less than 16/mg/kg total mercury
Regulated Maximum for anv single grab sample
constituent TCLP (mg/1)
Mercury 0.025
7-14
2867g
-------
Table 7-9 Proposed BOAT Treatment Standards for D009 and U151
Elemental Mercury Contaminated with Radioactive Materials
AMALGAMATION WITH ZINC AS A METHOD OF TREATMENT
7-15
2867g
-------
Table 7-10 Proposed BOAT Treatment Standards for D009 Hydraulic
Oil Contaminated with Mercury and Radioactive Materials
INCINERATION AS A METHOD OF TREATMENT WITH INCINERATOR RESIDUES MEETING
THE FOLLOWING: (1) ASH AND WASTEWATER TREATMENT SLUDGES FROM TREATMENT
OF THE INCINERATOR SCRUBBER WATERS MUST COMPLY WITH A TCLP MERCURY
CONCENTRATION OF 0.025 MG/L; and (2) SCRUBBER WATERS MUST COMPLY WITH A
TOTAL MERCURY CONCENTRATION OF 0.030 MG/L (WASTEWATER STANDARD)
7-16
2867g
-------
8. REFERENCES
APHA, AWWA, and WPCF. 1985. Americal 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.
Chlorine Institute. 1988. Waste characterization data for K106 wastes,
submitted to Office of Solid Waste. Washington, D.C.: U.S.
Environmental Protection Agency.
Cosan Chemical Corporation. 1989. Response dated April 13, 1989, to
waste questionnaire dated March 9, 1989. Submitted to Office of Solid
Waste. Washington, D.C.: U.S. Environmental Protection Agency.
lammartino, N.R. 1975. Mercury cleanup routes - II. Chem. Eng. 82(3):
36-37.
IMC. 1982. 'International Minerals and Chemical Corporation. Delisting
petition no. 0321. Submitted by International Minerals and Chemical
Corporation, Electrochemicals Division, Orrington, Maine. Submitted to
Office of Solid Waste. Washington, D.C.: U.S. Environmental
Protection Agency.
Occidential Chemical Corporation. 1987. Delisting petition for
inorganic waste stream K106: wastewater treatment sludge. Submitted
by Occidental Chemical Corporation, Muscle Shoals plant, Sheffield,
Alabama. Submitted to Office of Solid Waste. Washington, D.C.: U.S.
Environmental Protection Agency.
Perry, R. 1974. Mercury recovery from contaminated waste water and
sludges. EPA 660/2-74-086. National Environmental Research Center.
Project 12040 HDU. Corvallis, Oregon: U.S. Environmental Protection
Agency.
Rosenzweig, M.D. 1975. Mercury cleanup routes - I. Chem. Eng. 82(2):
60-61.
SRI. 1989. Stanford Research Institute. 1989 directory of chemical
producers, United States of America. Menlo Park, California: Stanford
Research Institute.
U.S. Army. 1984. Military explosives. Department of the Army Technical
Manual TM 9-1300-214, as revised January 30, 1987. Washington, D.C.:
Headquarters, Department of the Army.
U.S. Bureau of Mines. 1985. Mercury: A chapter from mineral facts and
problems, 1985 edition. Preprint from Bulletin 675. Washington, D.C.:
U.S. Department of the Interior.
8-1
33S4g
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USEPA. 1985. U.S. Environmental Protection Agency, Office of Solid
Waste. Characterization of waste streams listed in 40 CFR Section
261: Waste profiles, Volume II. Final report, prepared for Waste
Identification Branch, Characterization and Assessment Division, Office
of Solid Waste. Washington, D.C.: U.S. Environmental Protection
Agency.
USEPA. 1986a. U.S. Environmental Protection Agency, Office of Solid
Waste. 1986 national survey of hazardous waste treatment, storage,
disposal, and recycling facilities. Washington, D.C.: U.S.
Environmental Protection Agency.
USEPA. 1986b. U.S. Environmental Protection Agency, Office of Solid
Waste. 1986 national survey of hazardous waste generators.
Washington, D.C.: U.S. Environmental Protection Agency.
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Waste. Generic quality assurance project 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 (BDAT) background
document for K071. Washington, D.C.: U.S. Environmental Protection
Agency.
USEPA. 1988c. U.S. Environmental Protection Agency, Office of Solid
Waste. Onsite engineering report for Waterways Experiment Station for
K106. Draft report. 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
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U.S. Environmental Protection Agency.
USEPA. 1989c. U.S. Environmental Protection Agency, Office of Solid
Waste. Proposed best demonstrated available technology (BDAT)
background document for K073. Washington, D.C.: U.S. Environmental
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8-2
335
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8-3
33S4g
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APPENDIX A
QUALITY ASSURANCE/QUALITY CONTROL DATA
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APPENDIX A QUALITY ASSURANCE/QUALITY CONTROL DATA
A.I Analytical Methods
The analytical methods used for analysis of the regulated
constituents identified in Section 5 are listed in Table A-l. SW-846
methods (EPA's Test Methods for Evaluating Solid Waste:
Physical/Chemical Methods. SW-846. Third Edition, November 1986) are used
in most cases, except for the TCLP extraction procedure (published in 51
FR 40643, November 7, 1986, as Appendix I to Part 268 - Hazardous Waste
Management System; Land Disposal Restrictions; Final Rule).
Specific procedures or equipment used for preparing or analyzing the
regulated constituents when alternatives or equivalents are allowed by
SW-846 are listed in Table A-2.
A.2 Accuracy Determination
The accuracy determination for a pollutant is based on the matrix
spike recovery values. The accuracy correction factors were determined
in accordance with the general methodology (see USEPA 1989a). For
example, for most BDAT list metals, actual spike recovery data were
obtained for each individual TCLP sample and the lowest value was used to
calculate the accuracy corrected value. Table A-3 presents the matrix
spike recoveries and the accuracy correction factor used to correct the
concentration of mercury in K071 mercury-containing wastewaters.
A-l
2869g
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2872g
Table A-l Analytical Methods
Analysis/Methods Method
Mercury in Liquid Waste (Manual Cold-Vapor Technique) 7470
Mercury In Solid or Son sol Id Waste (Manual Cold-Vapor 7471
Technique)
TCLP 40 CFR Part
268.
Appendix I
A-2
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2872g
Table A-2 Deviations from SW-846
Deviation from
Analysis Method SW-846 Specification SW-846 Method
[TO BE COMPLETED]
A-3
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2872g
Table A-3 Matrix Spike Recoveries Used to Correct Analytical Data for K071
Mercury-Containing Uastewaters and Untreated K106 TCLP Extract
Sample Set 16 Saaple Set 16 Duplicate Accuracy
BOAT Original amount Spike added Spike result Percent Spike added Spike result Percent correction
constituent found (ug/1) (ug/1) (ug/1) recovery8 (ug/1) (ug/1) recovery9 factor1*
Mercury 1.6 4.0 5.4 95 4.0 5.5 98 1.05
DC « Hot calculable.
Percent Recovery = [(Spike Result - Original A*ount)/Spike Added].
Accuracy Correction Factor = 100/Percent Recovery (using the lowest percent recovery value).
Reference: USEPA. 1988a. Table 6-16.
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