FINAL
BEST DEMONSTRATED AVAILABLE TECHNOLOGY (BOAT)
BACKGROUND DOCUMENT FOR
INORGANIC PIGMENT WASTES
Larry Rosengrant, Chief
Treatment Technology Section
Monica Chatmon-McEaddy
Project Manager
U.S. Environmental Protection Agency
Office of Solid Waste
401 M Street, S. W.
Washington, D.C. 20460
May 1990
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ACKNOWLEDGMENTS
This document was prepared for the U.S. Environmental Protection
Agency, Office of Solid Waste, by Versar Inc. under Contract No.
68-W9-0068. Mr. Larry Rosengrant, Chief, Treatment Technology Section,
Waste Treatment Branch, served as the EPA Program Manager during the
preparation of this document and the development of treatment standards
for the inorganic pigment wastes. The technical project officer for the
waste was Ms. Monica Chatmon-McEaddy. Mr. Steven Silverman served as
legal advisor.
Versar personnel involved in the preparation of this document
included Mr. Jerome Strauss, Program Manager; Mr. Stephen Schwartz,
Assistant Program Manager; Mr. Edwin F. Rissmann, Principle Investigator
and Author; Ms. Justine Alchowiak, Quality Assurance Officer;
Ms. Juliet Crumrine, Technical Editor; and the Versar secretarial staff,
Ms. Sally Gravely
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TABLE OF CONTENTS
Section Page No.
1. INTRODUCTION & SUMMARY 1-1
2. INDUSTRY AFFECTED AND WASTE CHARACTERIZATION 2-1
2.1 Industry Affected and Process Description 2-1
2.2 Waste Characterization 2-15
2.3 Determination of Waste Treatability Group 2-20
3. APPLICABLE AND DEMONSTRATED TREATMENT TECHNOLOGIES 3-1
3.1 Applicable Treatment Technologies 3-1
3.1.1 Treatment Technologies for Nonwastewaters 3-1
3.1.2 Treatment Technologies for Wastewaters 3-2
3.2 Demonstrated Treatment Technologies 3-3
3.2.1 Demonstrated Technologies for Nonwastewater 3-3
3.2.2 Demonstrated Technologies for Wastewater 3-5
4. PERFORMANCE DATA 4-1
5. IDENTIFICATION OF BEST DEMONSTRATED AVAILABLE TECHNOLOGY
(BOAT) 5-1
6. SELECTION OF REGULATED CONSTITUENTS 6-1
6.1 Selection of Regulated Constituents for
Nonwastewaters 6-1
6.2 Selection of Regulated Constituents for
Wastewaters 6-2
7. DEVELOPMENT OF BOAT TREATMENT STANDARDS 7-1
8. REFERENCES 8-1
11
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LIST OF TABLES
Page No.
Table 1-1 Treatment Standards for K002, K003, K004, K005, K006
(Anhydrous Chrome Oxide Green) K007 and K008
Nonwastewaters 1-4
Table 1-2 Standards for K006 Generated from Production
of Chrome Oxide Green Nonwastewaters 1-4
Table 1-3 Treatment Standards for K002, K003, K004, K005, K006,
K007, and K008 Wastewaters 1-4
Table 2-1 Present Chrome Pigments Manufacturers That Generate
K002, K003, and K006 Wastes 2-3
Table 2-2 Chrome Pigment Manufacturers That Recycle Wastes or
Wastewaters or Discharge Untreated Wastewaters to
POTW Systems 2-4
Table 2-3 BOAT Metals Concentrations for the Chromate and
Carbonate Sludge Samples 2-16
Table 2-4 Waste Characterization Data for K006 Waste Generated
from Facility Producing Hydrated Chrome Oxide Green
Pigment 2-17
Table 2-5 Estimated Composition of Wastewater Treatment Sludges
from Inorganic Pigments Manufacturing Processes 2-18
Table 2-6 Estimated Composition of Wastewater Treatment Sludges
from Inorganic Pigments Manufacturing Processes 2-19
Table 4-1 BOAT TCLP Metal Values for Untreated Inorganic
Pigment Sludges 4-3
Table 4-2 TCLP Analytical Results for the Treated (Stabilized)
Combined Wastewater Treatment Sludge Samples
K002/K003/K004 4-4
Table 4-3 Stabilization Results for K006 Wastes Generated from
Production of Hydrated Chrome Oxide Green Pigment 4-6
Table 4-4 Performance Data for Untreated and Treated F006
Wastes - Metal Concentrations (ppm) 4-7
111
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LIST OF TABLES
Page No.
Table 4-5 Treatment Performance Data for K062 - EPA-Collected
Data 4-9
Table 4-6 Alkaline Chlorinate Data Submitted by Plant C for
Various Wastes 4-21
Table 4-7 Monitoring and Verification Samples of a Chrome
Pigments Plant 4-29
Table 7-1 BOAT Treatment Standards for K002, K003, K004, K005
K006 (Anhydrous Chrome Oxide Green Subcategory), K007,
and K008 Nonwastewaters 7-3
Table 7-2 BOAT Treatment Standards for K006 (Generated from the
Production of Chrome Oxide Green) Nonwastewaters 7-3
Table 7-3 Treatment Standards for K002, K003, K004, K006
(for Production of both Anhydrous and Hydrated
Chrome Oxide Green) and K008 Wastewaters 7-3
7-4 Treatment Standards for K005 and K007 Wastewaters 7-3
IV
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LIST OF FIGURES
Page No.
Figure 2-1 Chrome Yellow Manufacture 2-6
Figure 2-2 Molybdate Orange Manufacture 2-8
Figure 2-3 Zinc Yellow Pigment Manufacture by the Mineral
Pigments Process 2-9
Figure 2-4 Zinc Yellow Production by the Wayne Pigments Process.. 2-10
Figure 2-5 Hydrated Chrome Oxide Green Manufacture by the
Ammonium Dichromate Process 2-13
Figure 2-6 Hydrated Chrome Oxide Green Manufacture by the Boric
Acid Process 2-14
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1. INTRODUCTION AND SUMMARY
Pursuant to section 3004(m) of the Hazardous and Solid Waste
Amendments (HSWA), enacted on November 8, 1984, the Environmental
Protection Agency (EPA) is establishing treatment standards based on the
best demonstrated available technology (BOAT) for wastewater treatment
sludges from the production of inorganic pigments. These wastes are
identified in 40 CFR 261.32 as K002, K003, K004, K005, K006, K007, and
K008. Compliance with these treatment standards is a prerequisite for
placement of these wastes in facilities designated as land disposal units
according to 40 CFR Part 268. The effective date of these treatment
standards is August 8, 1990.
This background document presents the Agency's technical support and
rationale for developing regulatory standards for these wastes.
Sections 2 through 7 present waste-specific information for the K002,
K003, K004, K005, K006, K007, and K008 wastes. Section 2 presents the
number and location of facilities affected by the land disposal
restrictions, the waste-generating process, and waste characterization
data. Section 3 discusses the technologies used to treat the waste (or
similar wastes), and Section 4 presents available performance data,
including data on which treatment standards are based. Section 5
explains EPA's determination of BOAT, while Section 6 discusses the
selection of constituents to be regulated. . Section 7 explains the
process used for calculation of proposed treatment standards.
The BDAT program and promulgated methodology are more thoroughly
described in two additional documents: Methodology for Developing BDAT
Treatment Standards (USEPA 1988c) and Generic Quality Assurance Project
Plan for the Land Disposal Restrictions Program ("BDAT") (USEPA 1988b).
The petition process to be followed in requesting a variance from the
BDAT treatment standards is discussed in the methodology document.
1-1
2824g
-------
It is EPA's understanding that three facilities presently generate
K002, K003, and K006 (chrome pigment wastes) as defined. These wastes
are the wastewater treatment sludges from the production of chrome
inorganic pigments. A wastewater is defined by the Agency as containing
less than 1 percent (weight basis) total suspended solids and less
than 1 percent (weight basis) total organic carbon (TOC). Wastes not
meeting this definition must comply with the treatment standards for
nonwastewaters. Six facilities manufacture chrome inorganic pigments but
do not generate a listed waste because they either recycle all process
waters and solids or discharge the untreated wastewaters to publicly
owned treatment works (POTWs). In addition, the Agency believes that the
last company generating K005 and K007 ended production of the pigments in
June 1987. The Agency also believes, based on RCRA 3007 Questionnaire
responses, that nonwastewater forms of K004 and K008 are not currently
generated.
The promulgated treatment standards for K002, K003, K004, K005, K006
(from anhydrous chrome oxide green production), K007, and K008
nonwastewaters are based on the performance of chromate reduction,
precipitation with lime and sulfide, and sludge dewatering for K062
wastes. The Agency has based the treatment standard for K006
nonwastewaters generated from the production of hydrated chrome oxide
green pigments on stabilization. The stabilization data were received
from the sole known generator of this waste. The promulgated treatment
standards for K002, K003, K004, K006, and K008 wastewaters are based on
effluent guidelines regulations for the chrome pigments subcategory of
the inorganic chemicals industry.
The term "total suspended solids" (TSS) clarifies EPA's previously
used terminology of "total solids" and "filterable solids."
Specifically, the quantity of total suspended solids is measured by
Method 209c (Total Suspended Solids Dried at 103 to 105°C) in
Standard Methods for the Examination of Water and Wastewater, 16th
Edition (APHA, AWWA, and WPCF 1985).
1-2
2824g
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The Agency is currently not promulgating cyanide treatment standards
for K005 and K007 nonwastewaters. The Agency realizes the problems
involved in the treatment of complex iron cyanides and is further
investigating the issue. The Agency reserves the right to promulgate
cyanide treatment standards for K005 and K007 nonwastewaters at a future
date.
The specific BOAT treatment standards for K002, K003, K004, K005,
K006 (from anhydrous chrome oxide green production), K007, and K008
nonwastewaters are shown in Table 1-1.
The specific BOAT treatment standards for K006 nonwastewaters
generated from the production of chrome oxide green are described in
Table 1-2.
The treatment standards for wastewater forms of K002, K003, K004,
K005, K006, K007, and K008 are based on chemical reduction,
precipitation, and sludge dewatering. The specific treatment standards
for these wastewaters are shown in Tables 1-3 and 1-4. These treatment
standards are being transferred directly from the effluent guideines for
the chrome pigments subcategory of the inorganic chemicals industry.
1-3
2824g
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Table 1-1 BOAT Treatment Standards for K002, K003, K004, K005, K006
(Anhydrous Chrome Oxide Green), K007, and K008 Nonwastewaters
Constituent TCLP Concentration in mg/1
Chromium (total) 0.094
Lead (total) 0.37
Table 1-2 BOAT Treatment Standards for K006 Generated from Production
of Hydrated Chrome Oxide Green Nonwastewaters
Constituent TCLP Concentration mg/1
Chromium (total) .5.2,)
Table 1-3 Treatment Standards for K002, K003, K004, K006
(Anhydrous and Hydrated), and K008 Wastewaters
Wastewater Concentration in mg/1
30-day
Constituent average 24-hour maximum
Chromium (total) 1.2
Lead (total) 1.4
1-4
28248
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Table 1-4 BOAT Treatment Standards for K005 and K007
(Uastewaters)
Regulated Constituent
Total Concentration in (mg/1)
30-day average 24-hour maximum
Chromium (Total)
Lead (Tp.t.alJtx^^^
Cyanides (Total) )
T
1-5
2824g
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2. INDUSTRY AFFECTED AND WASTE CHARACTERIZATION
Wastes listed as K002, K003, K004, K005, K006, and K007 are
generated as the wastewater treatment sludges from the production of
inorganic pigments. Under 40 CFR 261.32, wastes identified as K002,
K003, K004, K005, K006, and K007 are specifically listed as follows:
K002: Wastewater treatment sludge from the production of chrome
yellow and orange pigments.
K003: Wastewater treatment sludge from the production of molybdate
orange pigments.
K004: Wastewater treatment sludge from the production of zinc yellow
pigment.
K005: Wastewater treatment sludge from the production of chrome
green pigments.
K006: Wastewater treatment sludge from the production of chrome
oxide green pigments (anhydrous and hydrated).
K007: Wastewater treatment sludge from the production of iron blue
pigments.
K008: Oven residues from the production of chrome oxide green
pigments.
The waste K008 is identified as oven residues from the production of
chrome oxide green pigments. The Agency has determined that these listed
wastes represent a single broad treatability group based on their similar
physical and chemical characteristics. As described later in this
section, EPA has examined the sources of the wastes, the specific
similarities in the waste composition, applicable and demonstrated
treatment technologies, and attainable treatment performance in order to
support a simplified regulatory approach for these inorganic wastes.
2.1 Industry Affected and Process Description
The four-digit Standard Industrial Classification (SIC) code
associated with the production of inorganic pigments is 2816. These
pigments are used extensively in paints, printing ink, floor covering
2-1
2833g
-------
products, and paper. In addition, they may also be used in ceramics,
cement, and asphalt roofing.
The Agency believes that two facilities generate both K002 and K003,
and two facilities generate K006. This information was obtained from
3,007 questionnaire responses from the industry. It is the Agency's
understanding that one chrome oxide green manufacturing facility that
generates a K006 waste produces only hydrated chrome oxide green; the
second facility, which recycles all wastes,* manufactures anhydrous
chrome oxide green. Based on available information, the Agency also
believes that the last company in the United States to generate K005 and
K007 ended production in June 1987. Table 2-1 lists the names and
locations of the current known generators of K002, K003, and K006; the
treatment and disposal methods used at these facilities; and the
approximate product production levels achieved.
The Agency also identified those facilities that manufacture
inorganic pigments but do not generate wastewater treatment sludges.
These six facilities either discharge their untreated wastewaters to an
NPDES regulated system (i.e., exempted from RCRA regulations) or recycle
their solids by blending them with product for subsequent sale.
Table 2-2 identifies these facilities.
Below are descriptions of the five pigment manufacturing processes
that EPA identified as generating K002, K003, K004, K005, K006, and K007.
2.1.1 K002
Chrome yellow and orange pigments (lead chromate) are produced by
reacting sodium dichromate, caustic soda, and lead nitrate as follows.
First, lead oxide or elemental lead is dissolved in nitric acid to
Neither facility generates any K008 wastes.
2-2
2833g
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Table 2-1 Present Chrome Pigment Manufacturers That Generate
K002. K003. and K006 Wastes
Products Manufactured
Chrome Molybdate Chrome
Plant Location yellow orange oxide green
Pfizer Lehigh Gap. PA (2)
Harshaw Filtrol Louisville. KY (2) (2)
Heubach Newark, NJ (1) (1)
(1) Listed waste generated and sold for feedstock to lead smelter.
(2) Listed waste generated and land disposed offsite.
A = >5.000 TRY
8 = <5.000 TPY
Total product Wastes
production volumes generated
B K006
A K002. K003
A K002, K003
Source: 3007 Questionnaire responses and telephone conversations with facilities to clarify responses (10/87 - 1/88).
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3646g-3
Table 2-2 Chrome Pigment Manufacturers That Recycle Wastes or Wastewaters or
Discharge Untreated Wastewaters to POTW Systems
Plant
NJZ Colors
KiKuchi Color
Products Manufactured
Chrome
yellow and Molybdate Chrome Zinc
Location orange orange oxide green yellow
Brooklyn. NY X X
Patterson. NJ X
Reason for
no waste
generation
Discharge to POTV
Discharge to POTV
American Chrome Corpus Christ 1, TX
and Chemical
NL Chemicals
St. Louis, MO
Wayne Pigments Milwaukee. WI X
Mineral Pigments Beltsville. MD
Total reuse of waste
generated
Total process water
recycle
Discharge to POTW
Consumptive use of
wastewater to
produce a byproduct
Source: 3007 Questionnaire responses and telephone conversations with facilities to clarify
responses (10/87 - 1/88).
2-4
-------
generate a lead nitrate solution. This solution is then mixed with an
alkaline solution of sodium dichromate. The reaction that occurs can be
written as follows:
2NaOH + 2Pb(N03>2 -» 2PbCr04 + 4NaNC>3
Lead chromate (a hexavalent species) is formed as a precipitate and
is recovered by filtration, then washed, dried, milled, and packaged.
The filtrate and wash waters, containing lead and hexavalent chromium
compounds, are sent to a wastewater treatment facility. Figure 2-1
presents a general schematic of a typical lead chromate production and
waste treatment process.
2.1.2 K003
Molybdate orange pigment is made by the coprecipitation of lead
chromate (PbCrO,) and lead molybdate (PbMoO,). Molybdic oxide is
first dissolved in aqueous sodium hydroxide, then sodium chromate is
added. This solution is mixed with a solution of lead oxide in nitric
acid. The product, a mixture of lead chromate and lead molybdate,
precipitates from solution.
The precipitate (lead chromate and lead molybdate) is collected by
filtration, then washed, dried, milled, and packaged. The filtrate
contains unreacted sodium chromate and sodium molybdate, lead ions, and
some suspended particulates of unrecovered products. This wastewater
stream is usually sent to a wastewater treatment facility. The
wastewater treatment sludge produced is the listed waste K003.
Figure 2-2 presents a general schematic of a typical molybdate orange
production and waste treatment process.
2-5
2833g
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en
PbO
LEAD OXIDE
WATER
HN03
NITRIC ACID
NaOH
SODIUM
HYDROXIDE
WATER
DISSOLVING
SODIUM
DICHROMATE
DISSOLVING
MIXING
AND
DEVELOPMENT
WATER
I
FILTRATION
AND
WASHING
I
WASTE-
WATER
TREATMENT
DRYING,
MILLING.
AND
PACKAGING
PRODUCT
! I
SOLIDS LIQUID
K002 EFFLUENT
FIGURE 2-1 CHROME YELLOW MANUFACTURE
-------
1
-J
MOLVBDIC O
M
H,0 ^
WATER
"
IE/
r-i i-»"
•0> I I H.o
Pb0 "HO,
ID OXIDE NITRIC At
4
STIC
A
H
:ID
SODIUM
CHROMATE
NA|Cio4 r~
IftK
TANK
-
-w«
••
, ^
TER
HIKER
•
WATER
1
fit VBAWlflftl
HOLDING .
TAI1H * AHD
IAHK WA8IIINO
1 1
CHEMICAL TREATMENT
1
8LUDQE SEPARATION
1 1
SOLIDS LIQUID
(K001) EFFLUENT
OR VINO.
» MILLIHO. ^ pBoniirr
^ AND ^ PRODUCT
PACKAOINO
FIGURE 22 MOLYDDATE ORANGE MANUFACTURE
-------
2.1.3 K004
Zinc yellow pigments are produced by two methods. In the first
method, chromic acid solution is reacted with zinc oxide or zinc
carbonate. The product precipitates from solution and is collected by
filtration, then washed, dried, and packaged. The spent process liquor
and wastewaters are combined and forwarded to a second process, where
barium carbonate is added. Barium chromate precipitates, is collected by
filtration, is washed, dried, packaged, and then sold. The spent process
and wash waters from this second process are combined and used to prepare
the chromic acid solutions for the zinc yellow process at the one
facility using this process so that no wastewaters are generated, and no
K004 wastewater treatment sludges are produced. Figure 2-3 is a diagram
of the process.
The second process for zinc yellow pigment products involves reaction
of a solution of potassium dichromate with an added zinc salt, such as
the nitrate or chloride. The product precipitates from solution. The
reaction equation is:
2K2Cr207 + 4ZnCl2 + 6H20 --->
4ZnO • K20 • 4Cr03 • 3H20 (zinc yellow) + 2KC1 + 6HC1.
The precipitate is then collected by filtration, washed, dried, and
packaged. The spent process liquors and wash waters are combined and
released to a local POTW. Figure 2-4 shows the process diagram. This
facility also does not currently generate K004 waste but would do so if
the process wastewaters were treated onsite prior to discharge.
2.1.4 K005
Chrome green pigments are no longer manufactured in the United
States. These pigments are mixtures of chrome yellow and iron blue (iron
2-8
2833S
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CHROMIC
ACID
ZINC OXIDE
OR
ZINC CARBONATE
1
SOLUTION
MAKEUP
1
WATER
REACTION
TANK
1
FILTRATION
AND WASHING
BARIUM
CARBONATE
1
DRYING
AND PACKAGING
ZINC YELLOW
PIGMENT
PROCESS
WASTE
WATER
REACTION
TANK
SPENT
PROCESS WATER
WATER
FILTRATION
DRYING
AND PACKAGING
BARIUM
CHROMATE
PRODUCT
FIGURE 2-3 ZINC YELLOW PIGMENT MANUFACTURE BY THE MINERAL PIGMENTS PROCESS
-------
WATER
POTASSIUM
DICHROMATE
SOLUTION
MAKEUP
WATER
I
ZINC CHLORIDE
SOLUTION
MAKEUP
MIX
TANK
WATER
i
FILTRATION
AND WASHING
DRYING
AND PACKAGING
PROCESS
WASTEWATER
TO POTW
PRODUCT
ZINC
YELLOW
FIGURE 2-4 ZINC YELLOW PRODUCTION BY THE WAYNE PIGMENTS PROCESS
-------
ferrocyanide) . They include a wide variety of hues, from very light to
very dark green. Chrome green is produced by mechanically mixing aqueous
dispersions of chrome yellow and iron blue pigments.
The resulting pigment suspensions are then filtered, dried, ground,
blended, and packaged. When the sole facility known to be producing
chrome green pigment was operating, the filtrate, which contains
unrecovered particulates of chrome yellow and iron blue pigments , was
sent to wastewater treatment for removal of suspended particulates prior
to release under NPDES permit. The removed particulates were the K005
waste. This production facility closed permanently in 1987.
2.1.5 K006
Chrome oxide green pigments are produced at two facilities by two
different processes.
The first process, which produces anhydrous chromic oxide, employs
the thermal decomposition of ammonium dichromate. Sodium dichromate
solution and ammonium sulfate are mixed together; this mixing results in
a solid mass consisting of ammonium dichromate and sodium sulfate
decahydrate
This mixture is then heated in a kiln to a temperature above
500°C. The ammonium dichromate decomposes according to the following
reaction:
The reacted material is recovered from the kiln and leached with
water. The sodium sulfate dissolves out of the product mass, and the
leached product is then recovered by filtration, washed, dried, and
packaged. The sodium sulfate-containing wastewater is treated to reduce
2-11
2833g
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any hexavalent chromium compounds present and then is filtered prior to
discharge. The K006 waste stream is the filter cake generated from this
process, which is collected, reclaimed in a second calciner, and recycled
by blending with the product.
In the second process, which manufactures hydrated chrome oxide green
pigment, sodium dichromate is reacted with boric acid as follows:
8(>2.
The raw materials are blended in a mixer, then heated in an oven at
550°C. Oven residues, which contain hexavalent and trivalent
chromium, are washed out of the oven and sent to a wastewater treatment
unit. .The reacted material is slurried with water and filtered. The
filtered solids are washed, dried, ground, screened, and packaged. The
filtrate and wash water are also sent to wastewater treatment where
chemical treatment of the wastewater with sodium bisulfite and lime
neutralization in series followed by filtration generates the listed
waste K006. Figures 2-5 and 2-6 present schematics of the two types of
chrome oxide green manufacturing and waste treatment processes.
2.1.6 K007
Iron blue pigments are produced by the reaction of sodium
ferrocyanide with an aqueous solution of iron sulfate and ammonium
sulfate. The precipitate formed is separated and oxidized with sodium
chlorate or sodium chromate, a hexavalent chromium compound, to form iron
blues.
The final product is then collected by filtration, washed, dried,
milled, and packaged.
2-12
2833g
-------
rv)
i
NijCrO4
SODIUM CHROMATE
NA2CR207 fc
SODIUM DICHROMATE SOLUTION
H,304 ^
SULFURIC ACID
-------
r\>
i
WATER
WATER
WATER
WATER
NijCrjOr
SODIUM DICHROMATE '
H3BOj .
BORIC ACID
BLENDER
1 I
OVEN
WASTE-
WATERS'
WASTEWATER
TREATMENT
8OLIQ3 LIQUID
K006 EFFLUENT
SLURRY
TANK
WASH
FILTER
WASTEWATERS
DRYER
GRIND.
SCREEN.
AND
PACKAGE
•PRODUCT
FIGURE 2-6 HYDRATED CHROME OXIDE GREEN MANUFACTURE BY THE BORIC ACID PROCESS
-------
The wastewaters contain all of the chemicals used in the process,
along with some unrecovered product. Subsequent treatment of the
wastewaters generates a sludge containing complex iron cyanides. This
sludge is considered the listed waste K007. EPA believes that the last
facility producing iron blues in the United States closed permanently in
June 1987.
2.1.7 K008
The two processes described previously as the sources of generation
of K006 waste are the potential generators of K008 wastes if the reaction
kiln or oven is cleaned by dry methods. Presently, both K006 generation
facilities employ wet cleaning methods. The wastewater generated is
combined with other process wastewaters prior to treatment. The
wastewater treatment sludges generated as a result of this waste
treatment become K006. They contain all of the chromium values that
would have been removed from the kiln or oven as dry solids had dry
cleanout methods been used.
2.2 Waste Characterization
Waste characterization data for waste codes K002, K003, K004, K005,
K006, K007, and K008 are provided below. Tables 2-3 and 2-4 contain
waste characterization data obtained by the Agency for two plants
generating a mixed K002, K003, and K004 wastewater treatment sludge.
Table 2-5 shows waste characterization data for the K006 waste generated
from the one facility producing hydrated chrome oxide green. Table 2-6
presents data for the major contaminants in wastes K002, K003, K004,
K005, K006, K007, and K008 along with their approximate concentrations
from the original listing documents. No data are presently available for
characterization of wastewater forms of K002, K003, K004, K005, K006,
K007, or K008. These wastewaters would consist of leachates from
landfills containing these pigment wastes or filtrates from dewatering
nonwastewater sludges.
2-15
28338
-------
3646g-7
Table 2-3 Waste Characterization of Data for Mixed K002, K003, and £004
BOAT constituent
(ppnO
Ant imony
Arsenic
Barium
Beryllium
Cadmium
Chromium (T)
Copper
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
Total cyanide
Sulfide
Other constituents
K002/K003
Yellow chromate sludge
NO
NO
530
NO
NO
108.000
NO
670,000
0.27
NO
NO
NO
NO
NO
290
NO
NA
balance
Mixture of
K002. K003, and K004
carbonate sludge
NO
NO
NO
NO
NO
850
NO
750,000
NO
NO
NO
NO
NO
NO
85,000
NO
NA
balance
K002/K003
Orange chromate sludge
NO
NO
700
NO
NO
74,000
NO
610,000
NO
NO
NO
NO
NO
NO
710
NO
NO
ba lance
NO =-Not detected.
NA = Not analyzed.
Source: USEPA 1987.
2-16
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3348g
Table 2-4 Waste Characterization Data for a Mixed K002/K003
Waste Generated at a Chrome Pigments Production Facility
Constituent
Total composition (kg/kg)
Sample 1 Sample 2
EP-Toxicity leachate (mg/1)
Sample 1 Sample 2 Sample 3 Sample 4
Cadmium
Chromium
Lead
Zinc
Barium
Water
Total Solids
1.476
61.800
54,700
2,400
1 , 093
393,000
607,000 602,000
18 0.98 3.75 3.81
13 <.01 <0.1 <0.1
64.5 <.01 308 150
-
-
.
Sample 1 was obtained on April 25, 1988 and Sample 2 was obtained on March 3, 1989.
Samples 3 and 4 were obtained on unspecified dates in August and September, 1988,
respectively.
Source: Engelhard 1989.
2-17
-------
3646g-l
Table 2-5 Waste Characterization Data for K006 Waste Generated
from Facility Producing Hydrated Chrome Oxide Green Pigment
Constituent
Arsenic
Barium
Cadmium
Chromium
Lead
Mercury
Selenium
Silver
Concentration
(dry weight
<2.0
<20
<0.6
81,000
9.7
<0.6
<2.0
<0.6
(mg/kg)
basis)
Source: Pfizer Inc. Coimunication to EPA, June 22, 1989; Comment # LD12-00063.
2-18
-------
3646g-2
Table 2-6 Estimated Composition of Wastewater Treatment Sludges from Inorganic
Pigments Manufacturing Processes
Sludge source
Estimated contaminants in sludge
K002
Production of chrome yellow and
orange pigments
K003
Production of molybdate orange pigments
K004
Production of zinc yellow pigments
K005
Production of chrome green pigments
K006
Production of anhydrous chrome oxide
green pigments
K.006
Production of hydrated chrome oxide
green pigments
K007
Production of iron blue pigments
K008
Production of chrome oxide green
pigments
30,000 ppm PbCrO^ lead chromate
10,400 ppm CrIOHjj chromium hydroxide
2,500 ppm Pb(OH)2 lead hydroxide
20,000 ppm PbCr04 -PbMo04 (molybdate orange)
10,000 ppm Cr(OH)3 chromium hydroxide
2,500 ppm Pb(OH). lead hydroxide
20,000 zinc yellow pigment
48,000 chromic hydroxide
5,000 ppm PbCr04Fe (NH4) [Fe(CN)g]
22,000 ppm Cr(OH)j chromium hydroxide
66,000 ppm Cr(OH)j chromium hydroxide
25,000 ppm Fe4(Fe(CN)6)3 ferric ferrocyanide
10,000 chromium oxides
Source: USEPA 1980a.
2-19
-------
2.3 Determination of Waste Treatabilitv Group
In some cases EPA believes that wastes with different waste codes
produced in similar processes in an industry or in similar industries,
can be treated to similar concentrations by using the same technologies.
In these instances, the Agency may combine the codes into a single
treatability group. Based on careful review of the generators of
inorganic pigments and available waste characterization data, the Agency
has determined that wastes K002, K003, K004, K005, K006, K007, and K008
represent a single treatability group. The concentration and type of
metal constituents in the various wastes are dependent upon the waste
type, the particular production process employed, and the specifics of
the treatment process. Also, the presence of minor constituents such as
boron may depend on the exact process used. However, all the wastes
contain similar constituents and are expected to be treatable to similar
levels by using the same technology for metals. The same complex
cyanides are present in two of the wastes, K005 and K007, and are
treatable by cyanide destruction processes such as alkaline chloromate.
Lead and/or chromium are present in K002, K003, K004, K006, and K008
wastes.
With respect to wastes K005 and K007, EPA has determined that the
pigments from which these wastes were generated are no longer produced in
the United States. However, some firms could wish to produce these
pigments again at some future date.
Process changes occurring in the last decade have eliminated the
generation of K008 nonwastewaters from the manufacture of both hydrated
and anhydrous chrome oxide green pigments. Dry cleaning of ovens and
kilns has been eliminated. Presently, washout waters from oven or kiln
cleaning are combined with other chrome oxide green process wastewaters
and treated to generate a K006 waste.
2-20
2833g
-------
Wastewater treatment sludges from the production of zinc yellow
pigment (K004) are not generated at either of the two facilities
producing this product. One facility sends its untreated wastewater to a
POTW for treatment. The second plant uses a new process chemistry and is
thereby able to recycle all wastewater and to generate a co-product
barium chromate pigment for sale. Both of these wastewater management
methods could change in future years because of changes in POTW
regulations and demand for barium chromate.
Another reason for grouping all of the waste codes into a single
treatability group is that inorganic pigments plants often produce more
than one of the chrome pigments. These facilities have wastewater
treatment systems, which manage the wastewaters generated by all of the
individual processes operated. As a result, the wastewater treatment,
sludges produced can be a mixture of K002, K003, K004, K005, K006, and
K007, which vary in composition with the production schedules for the
individual pigments produced.
2-21
2833g
-------
3. APPLICABLE AND DEMONSTRATED TREATMENT TECHNOLOGIES
Section 2 established a single treatability group for the management
of K002, K003, K004, K005, K006, K007, and K008 wastes. This section
identifies the treatment technologies that are applicable to this group
and determines which, if any, of the applicable technologies can be
considered demonstrated for the purpose of establishing BOAT.
To be applicable, a technology must be usable to treat the waste in
question or to treat a waste that is similar in terms of the parameters
that affect treatment selection. (For detailed descriptions of the
technologies applicable for these wastes, or for wastes judged to be
similar, see EPA's Treatment Technology Background Document (USEPA
1988d)). To be demonstrated, the technology must be employed in
full-scale operation for the treatment of the waste in question or a
similar waste.
3.1 Applicable Treatment Technologies
3.1.1 Treatment Technologies for Nonwastewaters
Initial data gathering on the treatment of these wastes included
review of the technical literature, review of RCRA 3007 Questionnaires,
and contacts with industry representatives. As a result of these
efforts, EPA has identified three technologies as potentially applicable
for treatment of these wastes. These technologies are stabilization,
high temperature metals recovery (HTMR), and reuse/recycle.
With respect to nonwastewaters, stabilization reduces the
leachability of the metals, HTMR reduces both the total concentration and
the leachability of the metals through the production of slag, and
product reuse/recycle eliminates the waste stream entirely.
3-1
28348
-------
The Agency believes that stabilization with prior chemical treatment
can be used to treat inorganic pigment wastes; this belief is based on
the chemical and physical similarity of these wastes to F006 (wastewater
treatment sludges from electroplating operations) and also the similarity
of the untreated pigment production wastewaters to the waste K062 (waste
pickle liquor). Also, the Agency is of the opinion that HTMR can be used
to treat K002 and K003 because of the chemical and physical similarities
of these wastes to K061 (electric arc furnace dust); all are solid wastes
with a high metal content.
Stabilization and high-temperature metals recovery are discussed
fully in the F006 Background Document (USEPA 1988a) and in the Treatment
Technology Background Document (USEPA 1988d). Product reuse/recycle
involves the elimination of the nonwastewater streams by reuse in the
manufacture of another product or recycle of all nonwastewater process
residuals in the production cycle.
The Agency believes that the wastes K004 and K008 ara similar to
K002, K003, and K006 with respect to concentrations of specific toxic
metals present because K004 and K008 contain comparable concentra- tions
of chromates. Therefore K004 and K008 nonwastewaters can be managed by
the same technologies as K002, K003, K004, and K006. The Agency also
believes, based on the data in Table 2-6, that the wastes K005 and K007
will contain complex cyanides and chromates. The wastes F006 and F007
contain comparable forms and higher concentrations of cyanides and
chromates and hence should be more difficult to treat than the K005 and
K007 wastes.
3.1.2 Treatment Technoloeies for Wastevaters
Wastewater forms of K002, K003, K004, K005, K006, K007, and K008
consist primarily of leachates from monofills or filtrates from
dewatering of waste sludges. All of these wastes were originally
3-2
-------
generated by treatment of process wastewaters from the production of the
chrome and iron blue colors. As a result, the leachates are expected to
contain those constituents originally removed from the wastewaters [i.e.,
chromium, lead, and complex cyanides). The treatments, first discussed
in the Development Document for Effluent Limitations Guidelines (i.e.,
Best Available Technology Economically Achievable (BATEA)), New Source
Performance Standards and Pretreatment Standards for the Inorganic
Chemicals Manufacturing Point Source Category (USEPA 1982), were chemical
reduction and hydroxide and lime precipitation. These technologies are
also discussed in more detail in the Treatment Technology
Background Document (USEPA 1988d).
3.2 Demonstrated Treatment Technologies
3.2.1 Demonstrated Technologies for Nonvastewaters
Of the above-mentioned applicable technologies, all have been
demonstrated on the pigment production wastes or similar wastes.
Stabilization has been demonstrated on F006 wastes (wastewater treatment
sludges from electroplating operations) and on K061 wastes (electric arc
furnace dust). HTMR has been demonstrated on K061. Chemical reduction
has also been demonstrated on K062 waste pickle liquor from iron and
steel manufacturing. The sole generator of K006 wastes has provided
stabilization data to the Agency on wastes generated by the production of
hydrated chrome oxide green pigments. The Agency has data from a
facility that is recycling, in conjunction with HTMR, for a mixed
K002/K003 waste, and also has stabilization data for this waste.
Finally, the Agency is aware of a facility that recycles its solids
(K006) resulting from the manufacture of anhydrous chrome oxide green.
Product reuse/recycle of mixed K002/K003 involves the addition of
lead salts to the process wastewater; the lead salts act as a
precipitating agent and raise the lead content of the sludge. The sludge
3-3
283tg
-------
is subsequently sold to a lead smelter to be used as a feedstock
substitute for the smelter's raw material (lead-bearing scrap
materials). This sludge consists primarily of lead chromate and lead
carbonate, which occur in nature as the lead-bearing minerals crocoite
and cerussite, respectively.
According to information supplied to the Agency, the recycle of K006
nonwastewaters from production of anhydrous chrome oxide green pigment
results in the reduction of BDAT metals in the wastewater residuals
generated from the production of chrome oxide green. Solids from the
wastewater treatment system are recycled back to the production process
for inclusion in the finished product. The solids are chemically
identical to the product chrome oxide green.
The Agency, however, believes these reuse/recycle technologies may
be plant- and product-grade-specific and hence not applicable to all
potential generators of K006 nonwastewaters. The Agency also
acknowledges that reuse and recycle are demonstrated for some K002 and
K003 nonwastewaters but also feels that these technologies may only be
applicable only under certain specialized conditions. The Agency notes
that processing of the wastes at lead smelters may generate residues
requiring treatment and disposal. It appears that K006 wastes originating
from the production of hydrated chrome oxide green may not be easily
recycled because of their low chromium content. Therefore, based on
analysis of data available on the stabilized K006 waste from this source,
stabilization is a treatment technology that is applicable in this case.
K002 and K003 wastes will vary in their TCLP toxic metal content,
depending on the wastewater treatment methods used. Two facilities
presently generate mixed K002 and K003 wastes. One facility generates a
sludge containing lead chromate and lead carbonate which it then sells to
a lead smelter; this is the waste whose composition was given in
3-4
283<.g
-------
Table 2-3. The second facility treats its wastewater with ferrous
sulfate and lime in series to generate a waste containing considerable
amounts of iron oxides and hydroxide, trivalent chromium hydroxide, and
sparingly soluble lead salts, which have much lower lead content.
Because recycle of this waste may be problematic, the Agency considers
that chemical reduction of chromate followed by precipitation and
filtration in series is an applicable treatment train for this type of
K002 and K003 waste.
Treatment of cyanides by alkaline chlorination has been demonstrated
for F007 wastes. However, the cyanides present in K005 and K007 are
complex iron cyanides, which may be more difficult to treat. Therefore,
the Agency is further evaluating whether alkaline chlorination is truly
applicable to K005 and K007 nonwastewaters.
3.2.2 Demonstrated Technologies for Vastewater
The use of chromate reduction, cyanide oxidation, and chemical
precipitation technologies by the inorganic pigments industry is
discussed in detail in the Development Document for Effluent Limitations
Guidelines, New Source Performance Standards and Pretreatment Standards
for the Inorganic Chemicals Manufacturing Point Source Category (USEPA
1982) . Extensive documentation is presented on the use of these
technologies by the pigments industry and on the results normally
obtained with these technologies. The techniques discussed in detail
include chemical reduction of chromates with bisulfite, ferrous ion, and
sulfide; alkaline chlorination for cyanide oxidation; lime and sulfide
precipitation for metals removal; and filtration.
3-5
28348
-------
4. PERFORMANCE DATA
This section presents the data available to EPA on the performance
of demonstrated technologies in treating the listed wastes. These data
are used elsewhere in this document for determining which technologies
represent BOAT (Section 5), for selecting constituents to be regulated
(Section 6), and for developing treatment standards (Section 7).
Eligible data, in addition to full-scale demonstration data, may include
data developed at research facilities or obtained through other
applications at less than full-scale operation, as long as the technology
is demonstrated in full-scale operation for a similar waste or wastes as
defined in Section 3.
Performance data, to the extent that they are available to EPA,
include the untreated and treated waste concentrations for a given
constituent, values of operating parameters for the treatment technology
that were measured at the time the waste was being treated, values of
relevant design parameters for the treatment technology, and data on
waste characteristics that affect performance of the treatment technology.
Where data are not available on the treatment of the specific wastes
of concern, the Agency may elect to transfer data on the treatment of a
similar waste or wastes, using a demonstrated technology. To transfer
data from another waste category, EPA must find that the wastes covered
by this background document are no more difficult to treat (based on the
waste characteristics that affect performance of the demonstrated
treatment technology) than the treated wastes from which performance data
are being transferred.
The Agency has stabilization data for a mixed untreated and treated
K002/K003/K004 waste generated from a wastewater treatment system that
4-1
2835«
-------
does not utilize hexavalent chromium reduction. This waste was
obtained from a facility that produced chrome yellow, molybdate orange,
and zinc yellow pigments in 1985 and 1986. The facility phased out
production of zinc yellow in early 1987, but still produces the other two
pigments. The untreated leachate data are presented in Table 4-1 and the
treated leachate data are presented in Table 4-2. The Agency also has
received data from the one facility producing hydrated chrome oxide green
pigment. Table 4-3 shows the results of TCLP tests conducted on five
samples of stabilized K006 wastes from the one facility.
The Agency does not have data on stabilization of the K002/K003
wastes generated from the facility using ferrous sulfate treatment of its
process wastewaters. However, the Agency expects that this waste will
behave similar to both F006 and treated K062 wastes with respect to
stabilization because the same constituents are present at comparable
levels. Data on stabilization of F006 wastes are in the F006 Background
Document (USEPA 1988a). A summary of these data is presented in Table
4-4. Data on the treatment and subsequent lime stabilization of K062
wastes are presented in the K062 background document (USEPA 1988f).
Table 4-5 shows a summary of the K062 treatment data. With respect
to reuse/recycle, the Agency has documentation from three facilities
recycling K002, K003, and/or K006 nonwastewaters and has noted the
special circumstances accompanying use of these technologies.
The Agency does not have cyanide treatment data for K005 and K007
nonwastewaters; however, the Agency has a considerable volume of
treatment information on various cyanide-containing wastes. These
Use of chromate reduction technologies will convert any chromates
present to trivalent chromium hydroxide. Chromates are generally
soluble. Trivalent chromium hydroxide, however, is essentially
insoluble, and thus more easily managed by stabilization.
4-2
2835g
-------
3646g-B
Table 4-1 BOAT TCLP Metal Values for Untreated Inorganic Pigment Sludges
BOAT constituent
K002/K003
Yellow chranate sludge
(mg/1)
K002/K003/K004
Carbonate sludge
K002/K003
Orange chrcmate sludge
(mg/D
Arsenic
Barium
Cadmium
Chromium (TOT)
Lead
Mercury
Selenium
Silver
NO
NO
NO
1.2
320
NO
NO
NO
NO
0.09
0.047
1.3
5400
NO
NO
NO
NO
NO
NO
2.7
1600
NO
NO
NO
ND = None detected at practical quant 1tat ion limit.
Source: USEPA 1987.
4-3
-------
3646g-l
Table 4-2 TCLP Analytical Results for the Treated (Stabilized)
Combined Wastewater Treatment Sludge Samples K002/K003/K004
Treated waste (cement binder)
Antimony
Arsenic
Barium
Beryllium
Cadm 1 urn
Chromium (Total)
Copper
Lead
Mercury
Nickel
Selenium
Silver
Thai 1 ium
Vanadium
Zinc
A
mq/1
NO
NO
0.2
NO
NO
9.9
NO
0.13
NO
NO
NO
NO
NO
NO
0.094
TCLP samole number
B
ma/1
NO
NO
0.26
NO
NO
1.9
NO
0.16
NO
NO
NO
NO
NO
NO
0.24
C
mq/1
NO
NO
0.47
NO
NO
NO
NO
1.34
NO
NO
NO
NO
NO
NO
NO
KiIn dust binder
Ant imony
Arsenic
Barium
Beryl 1 ium
Cadmium
Chromium (Total)
Copper
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
NO
NO
0.088
NO
NO
39.1
NO
6.6
NO
NO
NO
NO
NO
NO
2.3
NO
NO
0.024
NO
NO
1.6
NO
13.5
NO
NO
NO
NO
NO
NO
1.7
NO
NO
0.18
NO
NO
NO
NO
1.5
NO
NO
NO
NO
NO
NO
NO
4-4
-------
3646g-l
Table 4-2 (continued)
Treated waste (lime flvash binder)
Antimony
Arsenic
Barium
Beryllium
Cadmium
Chromium (Total)
Copper
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
A
ma/1
NO
ND
0.14
ND
ND
45.4
ND
6.3
ND
ND
NO
NO
ND
NO
2.6
TCLP samole number
B
ma/1
NO
ND
0.055
NO
ND
4.5
ND
14
ND
ND
ND
ND
NO
ND
2.1
C
ma/1
NO
ND
0.16
ND
NO
NO
ND
73.4
ND
ND
NO
ND
ND
NO
0.96
Note: Wastes A, B, and C were three individual samples of mixed K002/K003/K004 wastes
of the same composition.
NO = Not detected.
Source: USEPA 1987.
4-5
-------
3646g-l
Table 4-3 Stabilization Test Results for K006 Wastes Generated
from Production of Chrome Oxide Green Pigment
TCLP extract
Test number total chromium
(ppm)
1 0.95
2 0.26
3 0.89
4 4.25
5 1.08
TCLP extract
hexavalent chromium
(ppm)
0.53
<0.02
<0.02
0.33
0.23
Source: Pfizer Inc. 1989.
4-6
-------
3611g
Table 4-4 Performance Data for Untreated and Treated F006 Wastes
Metal Concentrations (ppm)
Source
Unknown
Unstabi lized
As received
TCLP
Stabilized
TCLP
Autopart manufacture
Unstabi 1 ized
As received
TCLP
Stabi lized
TCLP
TCLP
Aircraft overhaul facility
Unstabi 1 ized
As received
TCLP
Stabilized
TCLP
TCLP
\
Zinc plating
Unstabi lized
As received
TCLP
Stabi lized
TCLP
TCLP
Unknown
Unstabi lized
As received
TCLP
Stabilized
TCLP
TCLP
Mix*
Ratio Barium Cadmium Chromium Copper
0.2
31.3 755 7030
2.21 0.76 368
0.2 0.50 0.40 5.4
0.5 0.01 0.39 0.25
85.5 67.3 716
1.41 1.13 0.43
0.2 0.33 0.06 0.08
0.5 0.31 0.02 0.20
1.31 1510
0.02 4.62
0.2 0.01 0.30
1.0 0.23 <0.01 0.15
14.3 720 12200 160
0.38 23.6 25.3 1.14
0.2 0.31 3.23 0.25 0.20
0.5 0..73 0.01 0.30 0.27
Lead
409
10.7
0.40
0.36
257
2.26
0.30
0.41
88.5
0.45
0.30
0.21
52
0.45
0.24
0.34
Nickel
435
0.71
0.04
989
22.7
1.5
0.03
259
1.1
0.23
0.15
374
0.52
0.10
0.02
701
9.78
0.53
0.03
Silver
6.62
0.14
0.03
0.05
38.9
0.20
0.20
0.05
9.05
0.16
0.03
0.03
5.28
0.08
0.04
0.04
Zinc
1560
0.16
0.03
4020
219
36.9
0.01
631
5.41
0.05
0.03
90200
2030
32
0.01
35900
867
3.4
0.04
-------
3611g
Table 4-4 (continued)
Source
Small engine manufacture
Unstabilized
As received
TCLP
Stabilized
TCLP
TCLP
Circuit board manufacture
Unstabilized
As received
TCLP
Stabi lized
TCLP
TCLP
i
oo
Unknown
Unstabilized
As received
TCLP
Stabilized
TCLP
TCLP
Unknown
Unstabilized
As received
TCLP
Stabilized
TCLP
TCLP
Mix*
Ratio Barium Cadmium . Chromium Copper
7.28 3100 1220
0.3 38.7 31.7
0.2 0.02 0.21 0.21
0.5 0.01 0.38 0.29
5.39 42900 10600
0.06 360 8.69
0.2 0.01 3.0 0.40
0.5 0.01 1.21 0.42
15.3 5.81 17600
0.53 0.18 483
0.2 0.32 0.01 0.50
0.5 0.27 0.01 0.32
19.2 27400
0.28 16.9
0.2 0.19 3.18
0.5 0.08 0.46
Lead
113
3.37
0.30
0.36
156
1.0
0.30
0.38
1.69
4.22
0.31
0.37
24500
50.2
2.39
0.27
Nickel
19400
730
16.5
0.04
13000
152
0.40
0.10
23700
644
15.7
0.04
5730
16.1
1.09
0.02
Silver Zinc
4.08 27800
0.12 1200
0.03 36.3
0.06 0.03
12.5 120
0.05 0.62
0.03 0.02
0.05 0.02
8.11 15700
0.31 650
0.03 4.54
0.05 0.02
322
1.29
0.07
<0.01
*Mix ratio
weight of reagent
weight of waste
Source: USEPA 1988(a).
-------
3611g
Table 4-5 Treatment Performance Data for
K062 - EPA-Collected Data
Sample Set #1
Constituent
Arsenic
Chromium (hexavalent)
Chromium (total)
Copper
Lead
Nickel
Zinc
Untreated
K062 waste
(mg/1)
Sample no.
801
3
I
1800
865
<10
3200
<2
Design
Untreated
K062 waste
(mg/1)
Sample no.
802
<1
I
7000
306
<10
2600
<2
Design
value
Untreated
waste
composite3
(mg/1)
Sample no.
805
<1
893
2581
138
64
471
116
and Operating
Treated
waste
(wastewater)
(mg/1)
Sample no.
806
<0.1
0.011
0.12
0.21
<0.01
0.33
0.125
Data
Treated waste K062
(nonwastewater)
Total TCLP
(mg/kg) (mg/1)
Sample no.
807 807
<1
1.43
7300
380
2800
1400
1300
<0.010
-
<0.050
-
<0.10
-
-
Operating value
PH
8-10
1 = Color interference.
- = Not analyzed.
aThe untreated waste composite is a mixture of the untreated K.062 waste streams shown on this table, along with other
non-K062 waste streams.
Source: USEPA (1988f).
4-9
-------
3611g
Table 4-5 (continued)
Sample Set #2
Constituent
Arsenic
Chromium (hexavalent)
Chromium (total)
Copper
Lead
Nickel
Zinc
Untreated
K062 waste
(mg/1)
Sample no.
801
3
I
1800
865
<10
3200
<2
Design
Untreated
K062 waste
(mg/1)
Sample no.
802
<1
I
7000
306
<10
2600
<2
Design
value
Untreated
waste
composite3
(mg/1)
Sample no.
813
<1
807
2279
133
54
470
4
and Operating
Treated
waste
(wastewater)
(mg/1)
Sample no.
814
<0.1
0.12
0.19
0.15
<0.01
0.33
0.115
Data
Treated waste K062
Total TCLP
(mg/kg) (mg/1)
Sample no.
815 815
1
1.04
7400
400
1200
1200
2100
<0.010
-
<0.050
-
<0.10
-
-
Operating value
PH
8-10
I = Color interference.
- = Not analyzed.
aThe untreated waste composite is a mixture of the untreated K062 waste streams shown on this table, along with other
non-K062 waste streams.
Source: USEPA (1988f).
4-10
-------
3611g
Table 4-5 (continued)
Sample Set #3
Constituent
Arsenic
Chromium (hexavalent)
Chromium (total)
Copper
Lead
Nickel
Zinc
Untreated
K062 waste
(mg/1)
Sample no.
817
3
I
1700
425
<10
100310
7
Desiqn
Untreated
K062 waste
(mg/1)
Sample no.
802
<1
1
7000
306
.10
2600
<2
Design
value
Untreated
waste
composite3
(mg/1)
Sample no.
821
<1
775
1990
133
<10
16330
3.9
and Operating
Treated
waste
(wastewater)
(mg/1)
Sample no.
822
<0.1
I
0.20
0.21
<0.01
0.33
0.140
Data
Treated waste
Total
(mg/kg)
K062
TCLP
(mg/1)
Sample no.
823
2
1
4000
445
118
3900
112
823
0.012
-
<0.050
-
<0.10
-
-
Operating value
pH
8-10
10
I = Color interference.
- = Not analyzed.
aThe untreated waste composite is a mixture of the untreated K062 waste streams shown on this table, along with other
non-K062 waste streams.
Source: USEPA (1988f).
4-11
-------
3611g
Table 4-5 (continued)
Constituent
Arsenic
Chromium (hexavalent)
Chromium (total)
Copper
Lead
Nickel
Zinc
Untreated
K062 waste
(mg/1)
Sample no.
827
2
1
142
42
<10
650
3
Sample Set #4
Untreated Untreated
K062 waste K062 waste
(mg/1) (mg/1)
Sample no. Sample no.
802 817
<1 3
I I
7000 1700
306 425
<10 <10
2600 41000
<2 7
Design and Operating
Untreated
waste
composite3
(mg/1)
Sample no.
829
<1
0.6
556
88
<10
6610
84
Data
Treated
waste
(wastewater)
(mg/1)
Sample no.
830
<1
0.042
0.10
0.07
<0.01
0.33
1.62
Treated waste K062
Total TCLP
(mg/kg) (mg/1)
Sample no.
831 831
2
0.92
2400
292
99
2700
1200
0.015
-
0.068
-
<0.10
-
-
.PH
Design value
8-10
Operating value
9
I = Color interference.
- = Not analyzed.
aThe untreated waste composite is a mixture of the untreated K062 waste streams shown on this table, along with other
non-K062 waste streams.
Source: USEPA (1988f).
4-12
-------
3611g
Table 4-5 (continued)
Constituent
Arsenic
Chromium (hexavalent)
Chromium (total)
Copper
Lead
Nickel
Zinc
Untreated
K062 waste
(mg/1)
Sample no.
801
3
I
1800
865
<10
3200
<2
Sample Set #5
Untreated . Untreated
K062 waste K062 waste
(mg/1) (mg/1)
Sample no. Sample no.
802 817
<1 3
I I
7000 1700
306 425
•<10
2600 41000
<2 7
Untreated
waste
composite3
(mg/1)
Sample no.
837
<1
917
2236
91
18
1414
71
Treated
waste
(wastewater)
(mg/1)
Sample no.
838
<0.1
0.058
0.11
180.14
0.01
0.31
0.125
Treated waste K062
Total TCLP
(mg/kg) (mg/1)
Sample no.
839 839
1
0.741
11500
375
525
3300
410
<0.010
-
<0.050
-
<0.10
-
-
Design and Operating Data
Design
va lue Operating
value
PH
8-10
1 = Color interference.
- = Not analyzed.
aThe untreated waste composite is a mixture of the untreated K062 waste streams shown on this table, along with other
non-K062 waste streams.
Source: USEPA (1988f).
4-13
-------
3611g
Table 4-5 (continued)
Sample Set 16
Constituent
Arsenic
Chromium (hexavalent)
Chromium (total)
Copper
Lead
Nickel
Zinc
Untreated
K062 waste
(mg/1)
Sample no.
801
3
'I
1800
865
<10
3200
<2
Design
Untreated
K.062 waste
(mg/1)
Sample no.
802
<1
I
7000
306
<10
2600
<2
Design
value
Untreated
waste
composite3
(mg/1)
Sample no.
845
<1
734
2548
149
<10
588
4
and Operating
Treated
waste
(wastewater)
(mg/1)
Sample no.
846
<0.1
I
0.10
0.12
<0.01
0.33
0.095
Data
Treated waste K062
Total TCLP
(mg/kg) (mg/1)
Sample no.
847 847
1
1.775
10000
432
42
1600
68
<0.010
-
<0.050
-
<0.10
-
-
Operating value
8-10
I = Color interference.
- = Not analyzed.
aThe untreated waste composite is a mixture of the untreated K062 waste streams shown on this table, along with other
non-K062 waste streams.
Source: USEPA (1988f).
4-14
-------
3611g
Table 4-5 (continued)
Sample Set 17
Constituent
Arsenic
Chromium (hexavalent)
Chromium (total)
Copper
Lead
Nickel
Zinc
Untreated
K062 waste
(mg/D
Sample no.
801
3
I
1800
865
<10
3200
<2
Oes iqn
Untreated
K062 waste
(mg/1)
Sample no.
802
<1
1
7000
306
<10
2600
<2
Design
value
Untreated
waste
composite3
(mg/1)
Sample no.
853
<1
769
2314
72
108
426
171
and Operating
Treated
waste
(wastewater)
(mg/1)
Sample no.
854
<0.1
0.12
0.12
0.16
<0.01
0.40
0.115
Data
Treated waste K062
Total TCLP
(mg/kg) (mg/1)
Sample no.
855 855
1
I
16300
330
375
1700
375
<0.010
-
<0.050
-
<0.10
-
-
Operating value
pH
8-10
1 = Color interference.
- = Not analyzed.
aThe untreated waste composite is a mixture of the untreated K062 waste streams shown on this table, along with other
non-K062 waste streams.
Source: USEPA (1988f).
4-15
-------
3611g
Table 4-5 (continued)
Sample Set #8
Constituent
Arsenic
Chromium (hexavalent)
Chromium (total)
Copper
Lead
Nickel
Zinc
Untreated
K062 waste
(mg/1)
Sample no.
859
<1
0.220
15
151
<10
90
7
Design
Untreated
K062 waste
(mg/1)
Sample no.
801
3
I
1800
865
<10
3200
9
Design
value
Untreated
waste
composite3
(mg/1)
Sample no.
861
<1
0.13
831
217
212
669
151
and Operating
Treated
waste
(wastewater)
(mg/1)
Sample no.
862
<0.1
<0.01
0.15
0.16
<0.01
0.36
0.130
Data
Treated waste K062
Total TCLP
(mg/kg) (mg/1)
Sample no.
863 863
4
0.116
2800
638
300
2600
420
0.011
-
<0.050
-
<0.10
-
-
Operating value
PH
8-10
I = Color interference.
- = Not analyzed.
aThe untreated waste composite is a mixture of the untreated K062 waste streams shown on this table, along with other
non-K062 waste streams.
Source: USEPA (1988f).
4-16
-------
3611g
Table 4-5 (continued)
Sample Set 19
Constituent
Arsenic
Chromium (hexavalent)
Chromium (total)
Copper
Lead
Nickel
Zinc
-
Untreated
K.062 waste
(mg/D
Sample no.
867
<0.1
0.079
6
5
«1
4
0.4
Untreated
K062 waste
(mg/D
Sample no.
801
3
I
1800
865
<10
3200
<2
Design
Untreated
K062 waste
(mg/1)
Sample no.
802
<1
I
7000
306
<10
2600
<2
and Operating
Untreated
waste
composite3
(mg/1)
Sample no.
869
.1
0.07
939
225
<10
940
5
Data
Treated
waste
(wastewater)
(mg/1)
Sample no.
870
<0.1
0.041
0.10
0.08
<0.01
0.33
0.06
Treated waste
Total
(mg/kg)
K062
TCLP
(mg/1)
Sample no.
871
3
I
3400
775
85
3500
150
871
0.011
-
<0.050
-
<0.10
-
-
pH
Design value
8-10
Operating value
10
I = Color interference.
- = Not analyzed.
aThe untreated waste composite is a mixture of the untreated £062 waste streams shown on this table, along with other
non-K.062 waste streams.
Source: USEPA (1988f).
4-17
-------
3611g
Table 4-5 (continued)
Sample Set #10
Constituent
Arsenic
Chromium (hexavalent)
Chromium (total)
Copper
Lead
Nickel
Zinc
Untreated
K062 waste
(mg/D
Sample no.
801
<3
I
1800
865
<10
3200
<2
Design value
Untreated
waste
composite3
(mg/1)
Sample no.
885
<1
0.08
395
191
<10
712
5
Design and
Treated
waste
(wastewater)
(mg/1)
Sample no.
862
<0.10
0.106
0.12
0.14
<0.01
0.33
0.070
Operating Data
Operating
Treated waste K062
Total TCLP
(mg/kg) (mg/1)
Sample no.
863 863
5
. 0.078
4400
758
28
4700
43
value
0.016
-
<0.050
-
<0.10
-
-
pH
8-10
I = Color interference.
- = Not analyzed.
aThe untreated waste composite is a mixture of the untreated K062 waste streams shown on this table, along with other
non-K062 waste streams.
Source: USEPA (1988f).
4-18
-------
3611g
Table 4-5 (continued)
Sample Set #11
Constituent
Arsenic
Chromium (hexavalent)
Chromium (total)
Copper
Lead
Nickel
Zinc
Untreated
K062 waste
(mg/D
Sample no.
801
3
I
1800
865
<10
3200
<2
Desiqn
Untreated
K062 waste
(mg/1)
Sample no.
859
<1
0.220
15
151
<10
90
7
Design
value
Untreated
waste
composite9
(mg/1)
Sample no.
893
<1
0.30
617
137
136
382
135
and Operating
Treated
waste
(wastewater)
(mg/1)
Sample no.
894
<0.10
<0.01
0.18
0.24
<0.01
0.39
0.100
Data
Treated waste K062
Total TCLP
(mg/kg) (mg/1)
Sample no.
895 895
3
1.240
2100
388
200
1600
325
<0.010
-
<0.050
-
<0.10
-
-
Operating value
pH
8-10
I = Color interference.
- = Ndt analyzed.
aThe untreated waste composite is a mixture of the untreated K062 waste streams shown on this table, along with other
non-K062 waste streams.
Source: USEPA (1988f).
4-19
-------
wastes, like those from the chrome pigments industry also contain high
levels of toxic metals. Table 4-6 shows alkaline chlorination data for a
variety of metal- and cyanide-containing wastes (USEPA 1989). The data
show substantial treatment for cyanides. However, the Agency realizes
that complex iron cyanides may be more difficult to treat than cyanides
normally present in F007 nonwastewaters. The Agency is currently further
evaluating this question with the aim of determining whether any of the
treatment technologies for cyanide wastes are truly applicable to K005
and K007 nonwastewaters.
The Agency also has a considerable amount of wastewater treatment
data, applicable to wastewater forms of K002, K003, K004, K005, K006,
K007, and K008 which are presented in the Development Document for
Effluent Limitations Guidelines for the inorganic chemicals industry
(USEPA 1982). These data show the results achievable using various
methods for reduction of hexavalent chromium and precipitation of
trivalent chromium and lead from wastewaters. The data also show the
results of treatment for simple and complex cyanides. Table 4-7 shows
data obtained by sampling of a chrome pigments production facility as
presented in the Effluent Guidelines Development Document (USEPA 1982).
The wastewater treatment system used at the facility included
equalization, reduction of hexavalent chromium lime addition to
precipitate metals, sedimentation, biological oxidation, and filtration
prior to discharge (USEPA 1982).
The data in Table 4-7 were obtained at a facility that at the time
produced a variety of chrome pigments, iron blue and chrome green. These
data were only a part of the data base EPA used to develop the Effluent
Guidelines.
4-20
2835g
-------
3611g
Table 4-6 Alkaline Chlorination Data Submitted by Plant C
for Various Wastes
Sample Set Ho. la - for Treatment of 0003 and F007
Const i tuent/parameter
Concentration (units)
Untreated
waste
Treated
wastewater
(mg/D
BOAT Inorganics Other Than Metals
Cyanide (amenable)
Cyanide (total)
BOAT List Metals
60.000
Cadmium
Chromium (total)
Copper
Lead
Nickel
Zinc
Non-BDAT List Metals
Iron
117
<100
4,000
<100
1.500
1.800
1,700
-
-
-
-
-
-
-
Note: Design and operating parameters are as follows:
Parameter Design value Operating value
Alkaline chlorination reactor pH 12.5-13.0 12.9
Retention time for alkaline 2-6 hr minimum 96 hr
chlorination
ORP for alkaline chlorination >200 roV 380 mV
- = Not analyzed.
aBatch consisted of a mixture of waste codes 0003 and F007.
Actual retention time is based on a "not detected" result for the
analysis of the waste for amenable cyanide.
Source: USEPA (1989).
-------
3611g
Table 4-6 (continued)
Sample Set No. 2a - for Nixed F006-F012, P030
Const ituent/parameter
Concentration (units)
Untreated
waste
(mg/D
Treated
wastewater
BOAT Inorganics Other Than Metals
Cyanide (amenable)
Cyanide (total) 11.400
BOAT List Metals
Cadmium 25
Chromium (total) 1,300
Copper 3,400
Lead . 250
Nickel 7.300
Zinc 18.500
Non-BDAT List Metals
Iron 3,000
Note: Design and operating parameters are as follows:
Parameter Design value
Operating value
Alkaline chlorination reactor pH 12.5-13.0 12.45
Retention time for alkaline 2-6 hr minimum1* 24 hr
chlorination
ORP for alkaline chlorination >200 mV 345 mV
- = Not analyzed.
aBatch consisted of a mixture of liquids and drummed solids including
waste codes F006. F007, F008, F009. F011. F012. and P030.
Actual retention time is based on a "not detected" result for the
analysis of the waste for amenable cyanide.
Source: USEPA (1989).
4-22
-------
3611g
Table 4-6 (continued)
Sample Set No. 3a - for Treatment of F007
Const ituent/parameter
Concentration (units)
Untreated
waste
(rag/D
Treated
wastewater
(mg/D
BOAT Inorganics Other Than Metals
Cyanide (amenable)
Cyanide (total)
BOAT List Metals
100
Cadmium
Chromium (total)
Copper
Lead
Nickel
Zinc
Non-BDAT List Metals
Iron
-
780
440
<100
1.740
<100
470
Note: Design and operating parameters are as follows:
Parameter Design value
Operating value
Alkaline chlorination reactor pH 12.5-13.0 12.65
Retention time for alkaline 2-6 hr minimum 5.5 hr
chlorination
ORP for alkaline chlorination >200 mV 350 mV
- = Not analyzed.
aBatch was waste code F007.
Actual retention time is based on a "not detected" result for the
analysis of the waste for amenable cyanide.
Source: USEPA (1989).
4-Z3
-------
3611g
Table 4-6 (continued)
Sample Set No. 4 - for Treatment of D003
Concentration (units)
Const ituent/parameter
Untreated
waste
(rog/1)
Treated
wastewater
(mg/D
BOAT Inorganics Other Than Metals
Cyanide (amenable)
Cyanide (total) 13,000
BOAT List Hetals
Caomium
Chromium (total)
Copper <100
Lead
Nickel <100
Zinc
Non-BDAT List Metals
Iron 320
Note: Design and operating parameters are as follows:
Parameter Design value Operating value
Alkaline chlor1nation reactor pH 12.5-13.0 11.8
Retention time for alkaline 2-6 hr minimum 2 hr
chlorination
ORP for alkaline chlorination >200 mV 520 mV
- = Not analyzed.
aBatch consisted of solid sodium and potassium cyanide salts of
130,000 ppm cyanide concentration (D003).
bActual retention time is based on a "not detected" result for the
analysis of the waste for amenable cyanide.
Source: USEPA (1989).
4-24
-------
3611g
Table 4-6 (continued)
Sample Set No. 5a - for Treatment of F009
Const ituent/parameter
Concentration (units)
Untreated
waste
(mg/D
Treated
wastewater
to/D
BOAT Inorganics Other Than Metals
Cyanide (amenable)
Cyanide (total)
BOAT list Hetals
27.200
Cadmium
Chromium (total)
Copper
Lead
Nickel
Zinc
Non-BDAT List Hetals
Iron
-
-
270
-
1,050
3.070
3,320
Note: Design and operating parameters are as follows:
Parameter Design value
Operating value
Alkaline chlorination reactor pH 12.5-13.0 12.6
Retention time for alkaline 2-6 hr minimum 20 hr
chlorination
OAP for alkaline chlorination >200 mV 460 mV
Not analyzed.
tested was F009.
Actual retention time is based on a "not detected** result for the
analysis of the waste for amenable cyanide.
Source: USEPA (1969).
4-25
-------
3611g
Table 4-6 (continued)
Sample Set No. 6a - for Treatment of F011 and D002
Const ituent/parameter
Concentration (units)
Untreated
waste
(mg/D
Treated
wastewater
(mg/D
BOAT Inorganics Other Than Metals
Cyanide (amenable)
Cyanide (total) 6.000
BOAT List Metals
Cadmium
Chromium (total)
Copper
Lead
Nickel
Zinc 11,000
Non-BOAT List Metals
Iran 4,000
Note: Design and operating parameters are as follows:
Parameter Design value Operating value
Alkaline chlorination reactor pH 12.5-13.0 12.8
Retention time for alkaline 2-6 hr minimum 48 hr
chlorination
ORP for alkaline chlorination >200 mV 424 mV
- = Not analyzed.
aBatch consisted of a mixture of F011 and 0002.
Actual retention time is based on a "not detected" result for the
analysis of the waste for amenable cyanide.
Source: USEPA (1989).
4-26
-------
3611g
Table 4-6 (continued)
Sample Set No. 7a - for Treatment of F009
Concentration (units)
Const ituent/parameter
Untreated
waste
(mg/D
Treated
wastewater
(mg/1)
BOAT Inorganics Other Than Metals
Cyanide (amenable)
Cyanide (total) 30,000
BOAT List Metals
Cadmium
Chromium (total)
Copper
Lead
Nickel
Zinc 19.250
Non-BDAT List Metals
Iron
Note: Design and operating parameters are as follows:
Parameter Design value Operating value
Alkaline chlorination reactor pH 12.5-13.0 12.8
Retention time for alkaline 2-6 hr minimum 12 hr
chlorination
ORP for alkaline chlorination >200 mV 400 mV
- - Not analyzed.
aBatch consisted of a mixture of F009 (zinc plating waste) and a waste
hypochlorite solution.
Actual retention time is based on a "not detected" result for the
analysis of the waste for amenable cyanide.
Source: USEPA (1989).
4-27
-------
3611g
Table 4-6 (continued)
Sample Set No. 8a - for Treatment of F007
Const ituent/parameter
Concentration (units)
Untreated
waste
(mg/1)
Treated
wastewater
(mg/1)
BOAT Inorganics Other Than Metals
Cyanide (amenable)
Cyanide (total)
BOAT List Metals
6,000
Cadmium
Chromium (total)
Copper
Lead
Nickel
Zinc
Non-BDAT List Metals
Iron
-
<100
1,500
-
-
580
490
Note: Design and operating parameters are as follows:
Parameter Design value
Operating value
Alkaline chlorination reactor pH 12.5-13.0 12.9
Retention time for alkaline 2-6 hr minimum 8 hr
chlorination
ORP for alkaline chlorination >200 mV 380 mV
Not analyzed.
aBatch was F007 waste.
Actual retention time is based on a "not detected" result for the
analysis of the waste for amenable cyanide.
Source: USEPA (1989).
4-28
-------
3611g
Table 4-7. Monitoring and Verification Sampling of a Chrome Pigments Plant
Verification Sampling:*
Pollutant
Total Suspended Solids. TSS
Chromium, CR
+6
Chromium VI, Cr
Iron. FE
Lead, Pb
Zinc, Zn
Cyanide, CN
Cyanide (Free)
Antimony, Sb
Cadmium, Cd
Copper, Cu
Nickel, Ni
Monitoring Data - Treated Effluent
Total Suspended Solids, TSS
+6
Chromium VI, Cr
Chromium, Cr
Copper, Cu
Lead, Pb
Zinc, Zn
Cyanide (Free), CN
Cyanide (Total), CN
Arsenic
Caotaium
Mercury
Influent
mg/1 kg/kkg
780 78
78 7.8
<0.01 <0.001
49 4.9
15.2 1.52
4.2 0.42
5.1 0.51
<0.94 <0.094
0.74 0.074
0.90 0.090
3.56 0.36
0.017 0.0017
Avfl
Concent
11.2
0.11
0.44
0.13
0.41
0.044
<0.012
0.12
0.08
0.08
<0.001
mg/1
3.9
0.32
<0.03
0.30
0.11
0.058
<0.066
<0.011
0.30
0.0084
0.04
<0.024
30 day Ava
ration (mg/1)
23.5
0.3
0.73
0.25
0.87
0.075
0.044
0.31
0.16
0.12
0.0017
Effluent
kg/kkg
0.39
0.032
<0.003
0.03
0.011
0.0058
< 0.0066
<0.0011
0.030
0.00084
0.004
<0.0024
Waste Load (Aval
(kg/kkg)
1.92
0.018
0.074
0.023
0.069
0.0072
0.0019
0.019
0.0125
0.013
0.00007
•The average flow from the facility is 153 m /kkg.
Source: USEPA (1982).
4-29
-------
5. DETERMINATION OF BEST DEMONSTRATED
AVAILABLE TECHNOLOGY (BOAT)
This section presents the Agency's rationale for determining best
demonstrated available technology (BOAT) for K002, K003, K004, K005,
K006, K007, and K008 nonwastewaters and wastewaters. EPA notes, however,
that this applies only to wastes from current management, and not to
materials such as leachate, contaminated environmental media, or other
residues derived from historic management of these wastes.
To determine BOAT, the Agency examines all available performance data
on technologies that are identified as demonstrated to determine (using
statistical techniques) whether one or more of the technologies performs
significantly better than the others. The technology that performs "best"
on a particular waste or waste treatability group is then evaluated to
determine whether it is "available." To be available the technology must
(1) be commercially available to any generator and (2) provide
"substantial" treatment of the waste, as determined through evaluation of
accuracy-adjusted data. In determining whether treatment is substantial,
EPA may consider data on the performance of a waste similar to the waste
in question provided that the similar waste is at least as difficult to
treat. If the best technology is found to be not available, then the
next best technology is evaluated, and so on.
Chemical reduction of chromates, followed by chemical precipitation
and stabilization of the precipitated solids has been determined to be
the most viable treatment method for K006 nonwastewaters. The waste does
not contain significant levels of lead or zinc, which could be recovered,
and the levels of chromium present are far too low to make the material
useful either as recycled material or as a feedstock to a process using
chrome ore.
5-1
2836g
-------
Chemical reduction of chromates followed by chemical precipitation
and stabilization of the precipitated solids has been determined to be
the most viable treatment technology for K002 and K003 nonwastewaters.
Such wastes will contain relatively low levels of lead and will also
contain high levels of calcium, making them undesirable for high-
temperature treatment processes that might recover the lead.
Presently, there are two plants that generate K002/K003
nonwastewaters. The one facility that sends its lead-rich waste to a
smelter does not use chromate reduction as part of its wastewater
treatment train. As a result, this waste contains lead chromate.
Tables 4-1 and 4-2 show that this waste, when stabilized with alkaline
materials, sometimes shows unacceptable chromium levels in TCLP
leachates. The waste generated by the second facility is the result of a
treatment process that reduces all hexavalent chromium compounds to
trivalent chromium hydroxide. The waste from this second facility should
behave like the sludges from K062 treatment, i.e., wastes from wastewater
treatments that included chromium reduction. Such K062 sludges, when
stabilized, showed TCLP leachate levels for chromium and lead well below
characteristic levels, as is evidenced by data presented in the K062
Background Document (USEPA 1988f) .
Also, stabilization has been determined by the Agency to be BOAT for
the waste K046, wastewater treatment sludge from the production of lead-
based initiating compounds, which contains high levels of lead (USEPA
1988e).
The wastes K002, K003, K004, K005, K006, K007, and K008 are expected
to contain chromium as a hazardous constituent. Some of the wastes, for
example, K002, K003, and K005, will also contain lead. As a result,
chemical treatment for chromate reduction followed by stabilization of
the solids generated should also be applicable to these wastes.
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Nonwastewater forms of K005 and K007 are expected to contain complex
cyanides based on the data in Table 2-6. However, the two pigments,
chrome green and iron blue, whose production results in the generation of
these wastes, are no longer believed to be produced in the United
States. As a result, the Agency does not have cyanide treatment data on
K005 or K007 nonwastewaters. The Agency does, however, have data on
several proven treatment technologies for the oxidation of free cyanide.
Data for treatment of cyanide and metal-containing wastes are shown in
Table 4-6. The Agency believes that alkaline chlorination technology may
be applicable to K005 and K007 wastes because total cyanides are present
in K005 and K007 wastes at concentrations comparable to those observed in
wastes shown in Table 4-6. The Agency realizes that complex iron
cyanides are more difficult to treat than other cyanide complexes present
in these nonwastewaters and is, therefore, studying this issue further.
K005 and K007 nonwastewaters also contain hexavalent chromium compounds.
Reduction of hexavalent chromium to trivalent form and subsequent
precipitation of the trivalent chromium with lime are part of the overall
treatment process for K062 wastes.
Treatment of wastewater forms of K002, K003, K004, K005, K006, K007,
and K008 by chemical treatment and precipitation for metals and
biological treatment or chemical oxidation for cyanides will convert
wastewater forms of these wastes into nonwastewater forms. These
residuals are expected to be of highly variable composition. The
facility from which the effluent guidelines data shown in Table 4-7 were
derived used a treatment system that first removed the metals and then
biologically oxidized dissolved cyanides.
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6. SELECTION OF REGULATED CONSTITUENTS
6.1 Selection of Regulated Constituents for Nonvastevaters
The constituents of concern in nonwastewater forms of K002 and K003
are lead and chromium. In Section 2.2, data on composition of these
waste stream's indicate that lead and chromium are the only BDAT list
constituents present at significant levels. Additional data, also in
Section 2.2, show that chromium is the only BDAT list constituent present
at treatable levels in nonwastewater forms of K004 and K006.
Data available from the original listing documents for the wastes
K005, K007, and K008, which are not currently generated, indicate that
chromium and cyanide are the constituents of concern in K005. Cyanide is
the only constituent of concern in K007, and chromium is the sole
constituent of concern in K008.
As was discussed earlier in Sections 2.2 and 2.3, many plants
produce more than one of the inorganic pigments and use or have used
common wastewater treatment systems for management of wastewaters from
these production operations. As a result, many of the nonwastewater
forms of the wastes K002, K003, K004, K005, K006 (from anhydrous chrome
oxide green production), K007, and K008 would be mixtures of these
wastes. For this reason, the Agency is proposing that the constituents
of concern for these wastes are chromium and lead. The Agency is not
proposing cyanides as a regulated constituent for K005 and K007
nonwastewaters at this time. Complex iron cyanides, which are present in
these wastes, are more difficult to treat than simple oxides, and further
study of this issue is needed. The Agency is reserving the right to
modify treatment standards to include cyanide treatments for K005 and
K007 at a future date.
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For K006 generated from the production of hydrated chrome oxide
green, only chromium is proposed as the constituent of concern. The sole
production facility for this pigment has only produced this one pigment
in its history of operation and does not mix this production waste with
the wastes from the manufacture of other pigments. Therefore, for this
nonwastewater, chromium is the only constituent of concern.
6.2 Selection of Regulated Constituents for Wastevaters
In Sections 2 and 3 of this background document, the nature of the
wastewater forms of K002, K003, K004, K005, K006, K007, and K008 were
discussed. These wastewaters arise basically from two sources:
leachates from landfills containing these wastes, and wastewaters arising
from the treatment of one or more of these wastes as generated
nonwastewaters. These wastewaters have the potential, as a result, to
contain all of the constituents of concern present in the nonwastewater
forms of K002, K003, K004, K005, K006, K007, and K008. For this reason,
the Agency is regulating lead and chromium in these wastewaters, as it
did for the nonwastewaters. In addition, the Agency is regulating
cyanide in K005 and K007 wastewater because it is being regulated as part
of the effluent limitations guidelines for the chrome pigments
subcategory of the inorganic chemicals industry (USEPA 1982)
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7. CALCULATION OF BOAT TREATMENT STANDARDS
The Agency is establishing a treatment standard based on chemical
treatment and subsequent stabilization in the nonwastewater forms of
K002, K003, K004, K005, K006 (from anhydrous chrome oxide green
production), K007, and K008. EPA is transferring standards from the
listed waste K062 nonwastewaters, which contain similar concentrations of
lead and chromium. The specific treatment technologies involved are
chromate reduction and lime and/or sulfide precipitation. The Agency is
presently not promulgating treatment standards for complex cyanides in
K005 and K007 nonwastewaters because problems in the treatment of complex
iron cyanides need further study. The Agency reserves the right to
modify the treatment standards for K005 and K007 nonwastewaters in the
future to include cyanide treatment standards. The BOAT treatment
standards for K002, K003, K004, K005, K006 (from anhydrous chrome oxide
green), K007, and K008 nonwastewaters are as in Table 7-1.
In the case of K006 generated from the production of hydrated chrome
oxide green pigment, the Agency is proposing a standard based on
stabilization and transferred from the use of this technology with the
listed waste F006. This waste will contain boron compounds which could
render it more difficult to stabilize. However, data supplied by the
facility (see Table 4-3) indicate that such a standard can be met. The
BOAT treatment standards for K006 from production of hydrated chrome
oxide green are shown in Table 7-2.
For the wastewater forms of K002, K003, K004, K005, K006, K007, and
K008, the Agency is transferring the treatment standards directly from
the Effluent Guidelines Limitations for the chrome pigments subcategory
of the Inorganic Chemical Industry (USEPA 1982), because wastewater forms
of these wastes should closely resemble the wastewaters generated by the
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inorganic pigments industry. The treatment standards for K002, K003,
K004, K006, and K008 wastewaters are listed in Table 7-3. Table 7-4
shows the treatment standards for K005 and K007 wastewaters.
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3611g
Table 7-1 BOAT Treatment Standards for K002. K003. K004,
K005, K006 (Anhydrous Chrome Oxide Green Subcategory),
K007. and K008 Nonwastewaters
Constituent TCLP concentration (rog/1)
Chromium (total) 0.094
Lead (total) 0.37
Table 7-2. BOAT Treatment Standards for K006 (Generated from
the Production of Chrome Oxide Green) Nonwastewaters
Constituent TCLP concentration (ma/1)
s^~-
Chromium (total) (3.2
Table 7-3. Treatment Standards for K002, K003. K004. K006
(for Production of Both Anhydrous and Hydrated
Chrome Oxide Green) and K008 Wastewaters
Constituent Wastewater concentration (mg/1)
30-dav average 24-hour maximum
Lead (total) 1.2
Chromium (total) 1.4 3.4
Table 7-4. Treatment Standards for K005 and K007 Uastenaters
Regulated Constituent Total concentration (mg/1)
30-dav average 24-hour maximum
Chromium (total) 1.2
:ead (.tota 1)—-=^-—.^
7-3
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8. REFERENCES
APHA, AWWA, and WPCF. 1985. American Public Health Association,
American Water Works Association, and Water Pollution Control
Federation. Standard methods for the examination of water and
wastewater. 16th ed. Washington, D.C.: American Public Health
Association.
Engelhard Corporation. 1989. Letter submission of data to USEPA,
Englehard Corporation, Menlo Park, New Jersey.
Pfizer Materials Science Products. 1989. Letter submission of data
to USEPA, Pfizer Materials Science Products. Easton, Pennsylvania.
USEPA. 1980a. U.S. Environmental Protection Agency, Office of Solid
Waste. Background document for the Resource Conservation and Recovery
Act, Subtitle C--identification and listing of hazardous waste.
Washington, D.C.: U.S. Environmental Protection Agency.
USEPA. 1980b. U.S. Environmental Protection Agency, Industrial
Environmental Research Laboratory. Multi-media assessment of the
inorganic chemicals industry, Volume II. Cincinnati, Ohio: U.S.
Environmental Protection Agency.
USEPA. 1982. Development Document for Effluent Limitations Guidelines
(BATEA), New Source Performance Standards and Pretreatment Standards
for the Inorganic Chemicals Manufacturing Point Source Category,
Washington, D.C.: U.S. Environmental Protection Agency.
USEPA. 1987. U.S. Environmental Protection Agency, Office of Solid
Waste. Onsite engineering report of stabilization of wastewater
treatment sludge from the production of inorganic pigments.
Washington, D.C.: U.S. Environmental Protection Agency.
USEPA. 1988a. U.S. Environmental Protection Agency, Office of Solid
Waste. Best demonstrated available technology (BOAT) background
document for F006. Washington, D.C.: U.S. Environmental Protection
Agency.
USEPA. 1988b. U.S. Environmental Protection Agency, Office of Solid
Waste. Generic quality assurance project plan for the Land Disposal
Restrictions Program ("BOAT"). Washington, D.C.: U.S. Environmental
Protection Agency.
USEPA. 1988c. U.S. Environmental Protection Agency, Office of Solid
Waste. Methodology for developing BOAT treatment standards.
Washington, D.C.: U.S. Environmental Protection Agency.
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USEPA. 1988d. U.S. Environmental Protection Agency, Office of Solid
Waste. Treatment technology background document. Washington, D.C.:
U.S. Environmental Protection Agency.
USEPA. 1988e. U.S. Environmental Protection Agency, Office of Solid
Waste. Best Demonstrated Available Technology (BOAT) background docu-
ment for K046. Washington, D.C.: U.S. Environmental Protection Agency.
USEPA. 1988f. U.S. Environmental Protection Agency, Office of Solid
Waste. Best Demonstrated Available Technology (BOAT) background docu-
ment for K062. Washington, D.C.: U.S. Environmental Protection Agency.
USEPA. 1989. U.S. Environmental Protection Agency, Office of Solid
Waste. Best Demonstrated Available Technology (BOAT) background docu-
ment for F007. Washington, D.C.: U.S. Environmental Protection Agency.
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