Best Demonstrated Available Technology (BDAT) Background Document for Cyanide Wastes: Final


                      FINAL
BEST  DEMONSTRATED AVAILABLE TECHNOLOGY  (BDAT)
       BACKGROUND DOCUMENT  ADDENDUM  FOR

                 CYANIDE WASTES
              Larry Rosengrant, Chief
            Treatment Technology Section
               Monica Chatmon-McEaddy
                  Project Manager
        U.S. Environmental Protection Agency
               Office of Solid Wastes
                 401 M Street, S.W.
               Washington, DC 20460
                     May 1990

-------
                            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 F019 wastewaters and nonwastewaters.   The technical  project
officer for the waste was Ms. Monica Chatmon-McEaddy.   Mr. Steven
Silverman served as legal advisor.

    Versar personnel involved in the preparation of this  document
included Mr. Jerome Strauss, Program Manager;  Ms.  Christel Ackerman,
Staff Engineer and Author; Ms. Justine Alchowiak,  Quality Assurance
Officer; Ms. Martha Martin and Ms. Barbara Malczak,  Technical Editors;
and Ms. Sally Gravely, Program Secretary.

-------
                           TABLE OF CONTENTS


Section                                                           Page No.


1.   Introduction 	     1-1

2.   Industries Affected and Waste Characterization 	     2-1

    2.1  Industries Affected and Process Description 	     2-1
    2.2  Waste Characterization 	     2-3
    2.3  Treatability Groups 	     2-3

3.   Applicable/Demonstrated Treatment Technologies 	     3-1

    3.1  Applicable Treatment Technologies for Cyanide 	     3-1
    3.2  Demonstrated Treatment Technologies for Cyanide 	     3-3

4.   Performance Data Base	     4-1

    4.1  Cyanide Treatment Data 	     4-1
    4.2  BOAT List Metals Treatment Data 	     4-3

       4.2.1  Wastewaters 	     4-3
       4.2.2  Nonwastewaters 	     4-3

5.   Identification of BOAT 	     5-1

    5.1  BOAT for Treatment of Cyanides 	     5-1
    5.2  BOAT for Treatment of Metals 	     5-2

       5.2.1  Wastewaters 	     5-2
       5.2.2  Nonwastewaters 	     5.3

6.   Selection of Regulated Constituents 	     6-1

    6.1  Identification of BOAT List Constituents in F019 	     6-1
    6.2  Constituents Selected for Regulation 	     6-1

7.   Calculation of BOAT Treatment Standards 	     7-1

8.   References 	     8-1

APPENDIX A  Data from Development Document for Effluent
            Limitations Guidelines and Standards for the
            Metal Finishing Point Source Category 	     A-l
                                     ii

-------
                              LIST  OF TABLES
                                                                   Page No.
Table 1-1  BOAT Treatment Standards for F019 	   1-2

Table 2-1  Approximate Major Constituent Analysis of F019 Waste,
           as Generated 	   2-4

Table 2-2  F019 Waste Composition Data 	   2-5

Table 2-3  Summary of Waste Composition Data for F006-F012 Wastes ..   2-6

Table 2-4  F012 Waste Composition Data 	   2-7

Table 4-1  Alkaline Chlorination Data Submitted by Plant C During
           the Public Comment Period 	   4-5

Table 4-2  Wet Air Oxidation Data for Treatment of F019 	   4-19

Table 4-3  Performance Data for UV/Ozonation Treatment of Complexed
           Cyanide F009 Waste 	   4-22

Table 4-4  Chemical Precipitation Treatment Performance Data for
           K062 - EPA-Collected Data 	   4-24

Table 4-5  Treatment Performance Data for Stabilization of F006
           Waste 	   4-35

Table 5-1  Summary of Accuracy Adjustment of Treatment Data for
           Total Cyanide in Electroplating Wastes 	   5-4

Table 5-2  Accuracy-Corrected Performance Data for Chromium in K062
           Wastewaters 	   5-5

Table 5-3  Accuracy-Corrected Performance Data for Chromium in F006
           Nonwastewaters Treated by Stabilization 	   5-6

Table 7-1  Calculation of Wastewater Treatment Standards for Total
           and Amenable Cyanide Based on Alkaline Chlorination 	   7-4

Table 7-2  Calculation of Nonwastewater Treatment Standards for
           Total Cyanide for F006, F007, F008,  and F009 Wastes 	    7-5

Table 7-3  Calculation of BOAT List Metals Treatment Standards for
           F019 	   7-6

Table 7-4  BOAT Treatment Standards for F019 	   7-7
                                     iii

-------
                     1.   INTRODUCTION AND SUMMARY

    This document provides the Agency's rationale and technical support
for selecting the constituents to be regulated in F019 nonwastewaters and
wastewaters and for developing proposed best demonstrated available
technology (BDAT) treatment standards for those regulated constituents.
This document is an addendum to the Best Demonstrated Available
Technology (BDAT) Background Document for Cyanide Wastes (F006-F012),
dated June 1989.  In the Second Third Final Rule (54 FR 26611), the
Agency promulgated a treatment standard for total cyanide in F006 through
F009 nonwastewaters as 590 mg/kg.  While the Agency stated that F019
wastes were different from F006-F009 wastes because the F019 wastes
contained high concentrations of iron-cyanide complexes, review of the
waste characterization data for F006 wastes indicates that many F006
wastes also contain high concentrations of iron-cyanide complexes that
are somewhat similar.  Based on this information, the Agency is
promulgating treatment standards for F019 based on a transfer from F006
wastes.

    According to 40 CFR 261.31, waste code F019 is generated from the
chemical conversion coating process and is listed as "wastewater
treatment sludges from chemical conversion coating of aluminum."  The
waste as generated is typically, by BDAT definition, a nonwastewater
since it usually contains greater than 1 percent total suspended solids
(TSS).  (For the purpose of determining the applicability of the
treatment standards, wastewaters are defined as wastes containing less
than 1 percent (weight basis) total suspended solids and less than
1 percent (weight basis) total organic carbon (TOO).  Wastes not meeting
this definition are nonwastewaters.)

    The Agency has determined that BDAT for both F019 nonwastewaters and
wastewaters is alkaline chlorination for cyanide followed by chemical
                                    1-1
3163g

-------
reduction, precipitation, filtration, and stabilization for metals
(chromium) based on transfer of data from similar wastes.

    Table 1-1 summarizes the proposed treatment standards for F019
nonwastewaters and wastewaters.

    In Section 2 of this document, generation and characterization of
waste code F019 will be discussed.  This waste is generated as a
wastewater treatment sludge from treatment of chromate conversion coating
solutions that contain hexavalent chromium and may also contain dissolved
ferricyanide compounds.  In Section 3, applicable and demonstrated
technologies for cyanide and metals will be discussed.  Applicable
technologies for cyanide were specified on the basis of treatment of
waste conversion coating solutions before generation of the wastewater
treatment sludge, as well as on the basis of applicability to treatment
of cyanide in the sludge.  Section 4 presents the data available to EPA
on treatment of complexed cyanide wastes.  Section 5 identifies the Best
Demonstrated Available Technology (BDAT).  Sections 6 and 7 present
selection of the regulated constituents and the calculation of BDAT
treatment standards, respectively.
                                    1-2
3163g

-------
                Table 1-1  BOAT Treatment Standards for F019
                                 Maximum  for  anv  single  grab  sample
                                    Nonwastewater          Wastewater
                                 Total      TCLP  leachate       Total
                             concentration  concentration   concentration
    Constituent                  (ing/kg)         (mg/1)          (mg/1)
    Cyanide  (amenable)               30           NA               0.86
    Cyanide  (total)                590           NA               1.20

    Chromium  (total)               NA              5.2             0.32
NA - Not applicable.
                                    1-3
3163g

-------
        2.   INDUSTRIES AFFECTED AND WASTE CHARACTERIZATION

    The following waste from chemical conversion coating operations in
the metal finishing industry, defined in 40 CFR 261.31,  is subject to the
land disposal restriction prohibitions of RCRA according to the  schedule
shown in 40 CFR 268.10-11:
    F019: Wastewater treatment sludge from the chemical conversion
          coating of aluminum.
    Section 2.1 describes the industries affected by the  land disposal
restrictions for F019 and presents a description of the chemical
conversion coating process.  Section 2.2 summarizes the available waste
characterization data for this waste code.   The listed wastes F006-F012,
generated from electroplating (common metals electroplating,  anodizing,
chemical etching and milling, and metal cleaning and stripping) and metal
heat treating operations, were addressed in the Best Demonstrated
Available Technology (BOAT) Background Document for Cyanide Wastes  (USEPA
1989c).

2.1      Industries Affected and Process Description

    The listed waste F019 is generated from chemical conversion coating
of aluminum.  Facilities using chemical conversion coating operations are
considered by EPA to be part of the metal finishing industry.  In the
preamble to the Effluent Limitations Guidelines for the Metal Finishing
Industry (48 FR 32482,  July 15, 1983), the Agency identified  13,500
facilities in the metal finishing industry,  which may use any of 46
electroplating and metal finishing unit operations (including
electroplating, heat treating, and chemical conversion coating).

    Users of chemical conversion coating operations generally fall  under
Standard Industrial Classification (SIC) code series 3000, which
comprises fabricated metal products except machinery and  transportation

                                    2-1
31648

-------
equipment; machinery except electrical; electrical and electronic
machinery, equipment, and supplies; transportation equipment; measuring,
analyzing, and controlling instruments; and miscellaneous manufacturing
industries.  Chemical conversion coating operations are found throughout
the country.

    Chemical conversion coating operations include the following metal
finishing processes:  chromating, phosphating, metal coloring, and
passivating.  In chemical conversion coating operations, a portion of the
base metal is converted to a protective film formed by the coating
solution.

    In chromating, aqueous solutions containing hexavalent chromium and
other active organic or inorganic compounds are used to apply a hard
surface coating that is corrosion resistant.  Chromate coatings are
usually applied only to aluminum surfaces, but can also be applied to
galvanized surfaces.  Phosphating and coloring involve formation of
surface metallic phosphates, oxides, or other compounds that impart a
color to the metal while also forming a protective coating.   Phosphate
conversion coatings are primarily used on steel and galvanized surfaces,
but can be applied to aluminum.  Oxide coatings (coloring) are applied
primarily to galvanized surfaces.  Passivating is the formation of a
protective film on metals, particularly stainless steel and copper, by
immersion in acid, cyanide, or aqueous organic chemical solutions.

    Chromating is the most common chemical conversion coating process
used to apply a coating to aluminum parts.  Chromate coatings are applied
from acid solution containing a source of hexavalent chromium (e.g.,
sodium chromate or chromic acid) and a strong oxidant (e.g., hydrofluoric
acid or nitric acid).  Chromate films are formed by the reaction of
hexavalent chromium with the metal surface.  Certain anions, referred to
as "activators," are necessary for the formation of chromate coatings.
Cyanide is used as an activator, usually in the form of ferricyanide
(Fe(CN)g)"  ion.  Other anions commonly used as activators include

                                    2-2

-------
acetates, formates, sulfates, chlorides, fluorides, nitrates, phosphates,
and sulfamate ions (USEPA 1982).

    Following application of chemical conversion coatings, the parts are
usually rinsed in a bath or with a water spray.  Wastewaters could be
generated from chemical conversion coating operations as rinsewaters or
as spent solutions.  These wastes contain hexavalent chromium and may
contain cyanide.  Wastewater treatment sludges generated from treatment
of these wastes are the listed waste F019.

2.2      Waste Characterization

    This section presents the waste characterization data available to
the Agency for F019 waste.  The major constituents of this waste and
their approximate concentrations are summarized in Table 2-1.  Table 2-2
presents the concentrations for BDAT list constituents and other
parameters identified as constituents of F019 wastes.  Waste
characterization data for electroplating waste are provided in Table 2-3.
F012 waste compositional data submitted in the National Survey of
Hazardous Waste Generators are provided in Table 2-4.  Generally, F019
wastes contain no organic BDAT constituents.  Chromium concentrations can
be as high as 10 percent, zinc concentrations several percentage points,
and cyanide up to 4,000 ppm.  Other BDAT metals present include antimony,
arsenic, barium, beryllium, cadmium, copper, lead, mercury, nickel,,
selenium, thallium, and vanadium.

2.3      Treatabilitv Groups

    Since all F019 wastewaters and nonwastewaters are produced from the
chemical conversion coating of aluminum, the Agency has decided that
presentation of the treatment standards on a waste code basis (according
to the wastewater and nonwastewater forms of the waste) provides a
sufficient distinction of the treatability groups.
                                    2-3

-------
             Table 2-1  Approximate Major Constituent Analysis
                        of F019 Waste, as Generated
           Constituent
Concentration (percent)
BOAT list metals:
     Chromium  (total)
     Zinc
     Other BDAT list metals

Cyanide (total)

Other solids (e.g., filter aid)

Water

Total
       <0.1 - 9
       <0.1 - 3
       <0.1 - 0.4

        2 - 35

       65 - 98

         100
                                    2-4
316*6

-------
3l66g
                                                                          Table 2-2  F019 Waste exposition Data
Const ituent/paraneter (units)
BOAT Inorganics Other Than Hetals
Cyanide (total)
Cyanide (amenable)
BOAT Hetals (mg/kg)
j
n Arsenic
Bar iin
Beryllium
Cadvlun
Chromium (hexavalent)
Chromium (total)
Copper
Lead
Mercury
Nickel
Vanadium
Zinc
Other Parameters
Total solids (percent)
Concentration (source)
(1) (2) (2) (3) (4) (4) (4) (4) (4) (4) (4) (4) (4) (4) (4) (4) (4)
(•gAg)
2.470 7.76 3.93 - <0.22 <4 <4 - <0.001 <0.001 0.24 0.12 <0.10 3.824 1.35 <0.08
I 7.76 BO--------------


9.05 ----------------
21.3 --------- .-- -.-.
0.09 ----------------
7.24 0.212 0.288 -<2 - - -- - - --28 - <0.01
3.76 ----- rt> 1989.
    (2)   MR I  1987.
    (3)   AES  1981.
    (4)   Versar 1986.  Capitation of data fro* EPA delistlng petitions.

-------
3560g
Table 2-3 Sunnary of Waste Composition Data for F006-F012 Wastes

Const ituent/parameter
Cyanide (as NaCN)
BOAT List Metals
Cadniun
Chromiun
Copper
Lead
Nickel
Zinc
TOTAL BOAT METALS
BOAT Organ ics
Iron
Other Non-BOAT Inorganics
(primarily sodiun carbonate
and/or calciun hydroxide)
Water
Oil and grease

Const i tuent/paraneter
Cyanide (as NaCN)
BOAT List Metals
Cadmiun
Chromiun
Copper
Lead
Nickel
Zinc
TOTAL BOAT METALS
BOAT Organ ics
Iron
Other Non-BDAT Inorganics
(primarily sodiun carbonate
and/or calciun hydroxide)
Water
Oil and grease
Concentration (percent)
F006 F007 F008
<0.1-0.5 5-10 2-10

0-2 0-2 0-2
0-30 <0.1 <0.1
0-3 0-1 0-2
0-3 <0.1 <0.1
0-17 0-2 0-2
0-9 0-2 0-2
<0.1-30 -2 -2
<0.1 <0.1 <0.1

20-40 20-40 35-40

30-80 55-70 55
0-4 <0.1 <0.1
Concentration (percent)
F010 F011 F012
1-4 3-20 <0.1-12

— *0.1 ^0.1
—
-------
3560g
Table 2-4 F012 Waste Composition Data
Concentration (source)
Constituent/parameter (units)
BDAT Inorganics Other Than Metals (mg/kg)
Cyanide (total)
Fluoride
BDAT Metals (mg/kg)
Barium
Cadmium
Chromium (hexavalent)
Chromium (total)
Copper
Lead
Nickel
Silver
Vanadium
Zinc
BOAT Volatile Organ ics (pg/kg)
Acetone
Chloroform
Methylene chloride
Toluene
(1)

21
6.5

98
5.31
-
11
307
28
758
0.73
6.7
54

250
110
11
28
(2) (2) (3) (4)

26.800 8.400 1.500 60.000-65,000
- - - -

- _ - _
<100
350
_
_
500-600
400-500
_
_
_

_
_
- - -
_
BDAT Semivolatile Organ ics (jig/kg)

Bis(2-ethylhexyl) phthalate

PCBs (MgAg)

Aroclor 1254

Non-BDAT Metals (mg/kg)

Iron
Sodium
1.600
35
2.880
1.276
Non-BDAT Inorganics Other Than Metals (mg/kg)
Chloride
Sulfate
992
6,900
2-7
-------
3560g
Table 2-4 (continued)
Constituent/parameter (units)
(1)
Concentration (source)
(2)
(2)
(3)
(4)
Other Parameters

Total solids (X)
Total organic carbon (rag/kg)
Oil and grease (mg/kg)
PH
60.5
540
432
10.5-11.0
- = Not analyzed.

References:
(1) USEPA 1988d.
(2) USEPA 1980.
(3) Environ 1985.
(4) CyanoKEN 1987.
2-8
-------
3. APPLICABLE/DEMONSTRATED TREATMENT TECHNOLOGIES

Section 2 presented waste characterization information showing the
main constituents were BOAT list metals and cyanide. The applicable and
demonstrated treatment technologies for cyanide wastes were discussed in
detail in the original cyanide wastes background document. Alkaline
chlorination treatment for the other metal finishing cyanide wastes
(F006-F012) was found to be demonstrated for F019, based on the treatment
data available to EPA.

Technologies for treatment of BOAT list metals in F019 are also
discussed in the original background document. The applicable and
demonstrated technologies that EPA has identified for metals treatment in
F019 wastes are chemical reduction, chemical precipitation, filtration,
and stabilization.

3.1 Applicable Treatment Technologies for Cyanide

The technologies applicable to treatment of cyanide in F019 wastes
are those technologies that treat cyanide in the complexed form. The
Agency has identified alkaline chlorination, wet air oxidation, and
ultraviolet-light-enhanced ozonation (UV/ozonation) as applicable for
treatment of complexed cyanide in F019 wastes.

Alkaline chlorination is a process that oxidizes ions or compounds to
render them nonhazardous or to make them more amenable to subsequent
removal or destruction processes. The basic principal of alkaline
chlorination is that inorganic cyanides and some dissolved organic
compounds can be chemically oxidized to yield carbon dioxide, water,
salts, and simple organic acids. Species are oxidized by the addition of
a chemical oxidizing agent that is itself reduced.
3-1
3167g
-------
Aqueous cyanide wastes are typically treated in a batch alkaline
chlorination process. Caustic is used to keep the pH alkaline, usually
between 8.5 and 10.0. Cyanide destruction can be carried essentially to
completion within 2-24 hours, depending upon the extent of interfering
conditions.

Wet air oxidation is a high-temperature, high-pressure oxidation
process in which the oxidizing agent is dissolved oxygen. At elevated
temperatures, oxygen is an effective oxidizing agent for wastes
containing organics or oxidizable inorganics such as cyanide. Typical
operating temperatures for the treatment process range from 175 to
325°C (approximately 350 to 620°F). The pressure is maintained
at a level high enough to prevent excessive evaporation of the liquid
phase at the selected operating temperature (typically between 300 and
3,000 psi). At these elevated temperatures and pressures, the solubility
of oxygen in water is dramatically increased, thus providing a strong
driving force for the oxidation reactions.

UV/ozonation is a chemical oxidation process in which the oxidizing
agent is dissolved ozone (supplied as an O^/CK mixture). Ozone is a
much stronger oxidizing agent than oxygen. Because it is very unstable,
however, it must be generated just prior to being fed to the oxidation
reactor. Ozone addition is controlled similarly to the addition of
chlorine in alkaline chlorination. Ultraviolet (UV) light enhances the
rate of the ozone oxidation reaction. Ultraviolet light is supplied by
immersion of UV lamps in the solution. Wet air oxidation and chemical
oxidation (by ozone and other oxidizing agents) are described in the
Treatment Technology Background Document (USEPA 1989b).

Incineration is not considered applicable for treatment of cyanide in
F019 wastes because these wastes are normally generated as inorganic
3-2
3167g
-------
wastewater treatment sludges. EPA would, however, consider incineration
as applicable to treatment of F019 wastes containing significant
concentrations of oil and grease or other organic constituents.

EPA believes, as was detailed in the background document for cyanide
wastes, that the treatment technologies applicable for treatment of
cyanides (especially complexed cyanides) in wastewater treatment sludges
such as F019 are also applicable for treatment of the wastewaters from
which these sludges are generated. In fact, the Agency believes that the
most effective treatment for cyanide in F019 wastes and other wastewater
treatment sludges containing cyanide is to treat the wastewaters for
cyanide by one of the applicable technologies before generation of the
wastewater treatment sludge because the applicable cyanide treatment
technologies discussed above are designed to treat aqueous waste
streams. (Refer to the development of nonwastewater cyanide treatment
standards for F006-F012 as detailed in the BOAT background document for
cyanide wastes (USEPA 1989c).)

3.2 Demonstrated Treatment Technologies for Cyanide

EPA has identified alkaline chlorination, wet air oxidation, and
UV/ozonation as demonstrated treatment technologies for cyanide in F019
wastes. Alkaline chlorination is in commercial use at several facilities
for treatment of electroplating sludges (F006-F009 wastes) containing
organics and cyanides. Ozonation and wet air oxidation are currently
used for treatment of wastes containing organic constituents, and EPA
believes these could be applied commercially to cyanide wastes.
3-3
3167g
-------
4. PERFORMANCE DATA BASE

This section presents the data available to EPA on treatment of
complexed cyanide wastes in wastes similar to F019. Wastes similar to
F019 are wastes that contain cyanide primarily in the complexed form.

4.1 Cyanide Treatment Data

The BOAT background document for cyanide wastes (USEPA 1989c)
presented the data available to the Agency at the time on the treatment
of cyanide wastes. Since promulgation of the Second Third land disposal
restrictions, EPA has reviewed data for alkaline chlorination, wet air
oxidation, and UV/ozonation of various electroplating wastes for
treatment of F019 waste and treatment of a similar waste containing
complexed iron cyanides.

Table 4-1 presents data from alkaline chlorination of various
electroplating wastes consisting of F006, F007, F008, F009, F011, F012,
D002, D003, P029, P030, and P106 wastes. A variety of cyanide-containing
wastes were treated by this alkaline chlorination process. Fourteen
different sample sets are presented. In addition, the Agency's
development of categorical wastewater discharge standards for the Metal
Finishing industry set standards at 0.86 mg/1 for amenable cyanide and
1.2 mg/1 for total cyanide. Data supporting the Metal Finishing cyanide
standards are found in Development Document for Effluent Limitations
Guidelines and Standards for the Metal Finishing Point Source Category
(EPA 440/1-83/091, June 1983, pp. VII-126 to VII-153). These data are
presented in Appendix A.

Table 4-2 presents the results of a bench-scale batch wet air
oxidation treatment test of F019 waste. The waste tested was an F019
filter cake generated at an aluminum conversion coating facility. The
3166g
4-1
-------
waste was slurried with water before wet air oxidation treatment. The
treated wastewater and treated nonwastewater are the residuals generated
following subsequent chemical precipitation and filtration treatment.
The test runs are presented.

Table 4-3 presents the results of bench-scale testing of UV/ozonation
treatment of an F009 waste in which the cyanide content was complexed
cyanide. This waste was collected at an electroplating facility after
destruction of amenable cyanide by alkaline chlorination treatment. EPA
feels that this waste is similar to wastewaters from chemical conversion
coating of aluminum because the cyanide content of both wastes is
primarily in the complexed form. Also, this waste was generated from a
similar process in the metal finishing industry and did not contain
significant concentrations of other oxidizable compounds. UV/ozonation
treatment was applied to eight test runs.

The data in Table 4-3 give the untreated and treated total waste
composition for total cyanide before and after UV/ozonation treatment.
The residuals from UV/ozonation treatment were not treated for metals
removal; therefore, no data are presented for BDAT list metals and no
data are available to indicate how much of the cyanide remaining after
UV/ozonation would be found in either wastewater or nonwastewater
residuals.

4.2 BDAT List Metals Treatment Data

4.2.1 Wastewaters

No performance data are available for treatment of F019 wastewaters
for metals. EPA would expect F019 wastewaters to be similar in waste
characteristics to K062 wastewaters in terms of the type and
concentration of metals present. The K062 wastewaters tested by the
3168g
4-2
-------
Agency had chromium concentrations of up to 7000 mg/1 (see Table 4-4).
F019 wastewaters would be expected to contain lower concentrations of
chromium because they are typically generated by filtering F019
nonwastewaters. The F019 nonwastewaters should have very little
dissolved chromium since the chromium conversion rinses are generally
treated for chromium prior to generating F019 nonwastewaters. Both
wastes are generated from metal finishing processes in which no organics
would be expected to be present. Data for treatment of K062 by chemical
reduction followed by chemical precipitation and filtration are presented
in Table 4-4.

4.2.2 Nonwastewaters

No performance data are available for treatment of metals in F019
nonwastewaters. (Wet air oxidation and UV/ozonation do not treat the
metals in the wastes.) However, data are available for stabilization of
metals in F006 (wastewater treatment sludges from electroplating
operations). Both F019 and F006 are wastewater treatment sludges
generated from metal finishing operations and are expected to have
similar chemical compositions. Treatment data from F006 waste show
chromium present at up to 43,000 mg/kg, which is a level comparable to
that expected to be found in F019 nonwastewaters (see Tables 2-1 and
2-2). Neither waste is expected to contain concentrations of organic
compounds that would affect stabilization treatment. Therefore, the
Agency believes that the F006 treatment data sets represent a level of
treatment performance that can be achieved for metals in F019
nonwastewaters using stabilization. The performance data for
stabilization of F006 appear in Table 4-5.
3168g
4-3
-------
3560g
Table 4-1 Alkaline Chlorination Data Submitted by
Plant C During the Public Comment Period

Sample Set No. la - for Treatment of F007. F008, D003, and P106
Const ituent/parameter
Untreated
waste
(mg/D
Concentration
Treated
wastewater
(mg/D
Treated
nonwastewater
(mg/D
BDAT Inorganics Other Than Metals

Cyanide (total) 71,759

BDAT List Metals
Copper
Nickel
Cadm i urn
Chromium
Lead
Zinc

Non-BDAT List Metals

Iron

Other Parameters
PH
TOC
4,193
136
2,995
323
184
2,319
2.936
11.2
0.95
357
- = Not analyzed.

aBatch consisted of a mixture of liquids and drummed solids including
waste codes F007, F008, 0003, and P106.

Reference: CyanoKEM 1989.
4-4
-------
3560g
Table 4-1 (continued)

Sample Set No. 2a - for Treatment of F009, F012
Const ituent/parameter
Untreated
waste
(tng/1)
Concentration
Treated
wastewater
(mg/1)
Treated
nonwastewater
(mg/1)
BOAT Inorganics Other Than Metals
Cyanide (total)

BOAT List Metals
12.000
0.95
153
Copper
Nickel
Cadmium
Chromium
Lead
Zinc
Non-BDAT List Metals
Iron
Other Parameters
PH
TOC
1.339
4.088
300
592
327
750

6,200

11.0
<2%
- = Not analyzed.

aBatch consisted of a mixture of liquids and drummed solids including
waste codes F009 and F012.

Reference: CyanoKEM 1989.
4-5
-------
3560q
Table 4-1 (continued)
Sample Set No. 3 - for Treatment of F009, D002. D003, and P030
Constituent/parameter
Untreated
waste
(mg/1)
Concentration
Treated
wastewater
(mg/1)
Treated
nonwastewater
(mg/1)
BOAT Inorganics Other Than Metals
Cyanide (total)

BOAT List Metals
17,206
<0.014
351
Copper
Nickel
Cadmium
Chromium
Lead
Zinc
Non-BDAT List Metals
Iron
Other Parameters
pH
TOC
8.400
1.290
7,610
239
129
5,150

5.520

11.2
<2X
- = Not analyzed.

aBatch consisted of a mixture of liquids and drummed solids including
waste codes F009, D002, 0003. and P030.

Reference: CyanoKEM 1989.
4-6
-------
3560a
Table 4-1 (continued)
Sample Set No. 4a - for Treatment of F007, F009. and D002
Constituent/parameter
Untreated
waste
(mg/1)
Concentration
Treated
wastewater
(mg/1)
Treated
nonwastewater
(mg/1)
BOAT Inorganics Other Than Metals
Cyanide (total)

BOAT List Metals
25,936
<0.014
374
Copper
Nickel
Cadmium
Chromium
Lead
Zinc
Non-BDAT List Metals
Iron
Other Parameters
pH
TOC
3.266
7.172
1,482
707
173
2.389

11.917

11.5
<2%
- = Not analyzed.

aBatch consisted of a mixture of liquids and drummed solids including
waste codes F007. F009, and D002.

Reference: CyanoKEM 1989.
4-7
-------
3560g
Table 4-1 (continued)
Sample Set No. 5 - for Treatment of F007, F008. 0003, and P029
Constituent/parameter
Untreated
waste
(mg/1)
Concentration
Treated
wastewater
(mg/D
Treated
nonwastewater
(mg/1)
BOAT Inorganics Other Than Metals
Cyanide (total)

BDAT List Metals
16.914
<0.014
235
Copper
Nickel
Cadmium
Chromium
Lead
Zinc
Non-BDAT List Metals
Iron
Other Parameters
PH
TOC
5.3-13
151
3.412
408
99 -
3.483

3.670

11.0
<2%
- = Not analyzed.

aBatch consisted of a mixture of liquids and drummed solids including
waste codes F007. F008. D003. and P029.

Reference: CyanoKEM 1989.
4-8
-------
3560g
Table 4-1 (continued)
Sample Set No. 6 - for Treatment of F011. F012, D002. and P106
Constituent/parameter
Untreated
waste
(mg/1)
Concentration
Treated
wastewater
(mg/1)
Treated
nonwastewater
(mg/1)
BOAT Inorganics Other Than Metals
Cyanide (total)

BOAT list Metals
59.421
0.028
245
Copper
Nickel
Cadmium
Chromium
Lead
Zinc
Non-BDAT List Metals
Iron
Other Parameters
pH
TOC
922
259
3.223
180
142
5.143

3,810

11.3
<2%
- = Not analyzed.

aBatch consisted of a mixture of liquids and drummed solids including
waste codes F011. F012, 0002, and P106.

Reference: CyanoKEM 1989.
4-9
-------
3560g
Table 4-1 (continued)
Sample Set No. 7a - for Treatment of F007 and F009
Const ituent/parameter
Untreated
waste
(mg/1)
Concentration
Treated
wastewater
(mg/1)
Treated
nonwastewater
(mg/1)
BOAT Inorganics Other Than Metals

Cyanide (total) 31,994

BDAT List Metals
Copper
Nickel
Cadmium
Chromium
Lead
Zinc

Non-BDAT List Metals

Iron

Other Parameters

pH
TOC
15,739
1,897
944
100
124
3,187
403
11.2
0.028
169
- = Not analyzed.

aBatch consisted of a mixture of liquids and drummed solids including
waste codes F007 and F009.

Reference: CyanoKEM 1989.
4-10
-------
3560g
Table 4-1 (continued)

Sample Set No. 8 - for Treatment of F007
Const ituent/parameter
Untreated
waste
(mg/1)
Concentration
Treated
wastewater
(mg/1)
Treated
nonwastewater
(mg/1)
BOAT Inorganics Other Than Metals
Cyanide (total)

BOAT List Metals
41.900
<0.014
189
Copper
Nickel
Cadmium
Chromium
Lead
Zinc
Non-BDAT List Metals
Iron
Other Parameters
pH
TOC
19.510
2 . 683
1,350
100
138
4,708
498
11.5
<2%
- = Not analyzed.
Reference: CyanoKEM 1989.
4-11
-------
3560g
Table 4-1 (continued)

Sample Set No. 9a - for Treatment of F006, F009. FOIL
0002, and D003
Const ituent/parameter
Untreated
waste
(mg/1)
Concentration
Treated
wastewater
(mg/1)
Treated
nonwastewater
(mg/1)
BOAT Inorganics Other Than Metals

Cyanide (total) 18,882

BOAT List Metals
Copper
Nickel
Cadmium
Chromium
Lead
Zinc
Non-BDAT List Metals

Iron

Other Parameters

pH
TOC
11,654
1,925
792
3,658
289
5.357
6.713
10.3
<0.014
106.3
- = Not analyzed.

aBatch consisted of a mixture of liquids and drummed solids including
waste codes F006. F009, FOIL DOQ2, and D003.

Reference: CyanoKEM 1989.
4-12
-------
3560g
Table 4-1 (continued)

Sample Set No. 10a - for Treatment of F006 and F012
Const ituent/parameter
Untreated
waste
(mg/1)
Concentration
Treated
wastewater
(mg/1)
Treated
nonwastewater
(mg/1)
BDAT Inorganics Other Than Metals
Cyanide (total)

BDAT List Metals
1.270
0.17
143
Copper
Nickel
Cadmium
Chromium
Lead
Zinc
Non-BDAT List Metals
Iron
Other Parameters
PH
TOC
2,319
6.739
1.903
14,079
662
19,163

7.786

10.0
<2%
- = Not analyzed.

aBatch consisted of a mixture of liquids and drummed solids including
waste codes F006 and F012.

Reference: CyanoKEM 1989.
4-13
-------
3560g
Table 4-1 (continued)
Sample Set No. lla - for Treatment of F007, F009. D002.
P029. and P030
Const ituent/parameter
Untreated
waste
(mg/1)
Concentration
Treated
wastewater
(mg/1)
Treated
nonwastewater
(mg/1)
BOAT Inorganics Other Than Metals
Cyanide (total)

BOAT List Metals
22.820
1.16
114.1
Copper
Nickel
Cadmium
Chromium
Lead
Zinc
Non-BDAT List Metals
Iron
Other Parameters
PH
TOC
7,910
450
3.109
<100
124
4.695

832

11.2
<2%
- = Not analyzed.

aBatch consisted of a mixture of liquids and drummed solids including
waste codes F007, F009. D002. P029, and P030.

Reference: CyanoKEM 1989.
4-14
-------
3560g
Table 4-1 (continued)
Sample Set No. 12 - for Treatment of F007, F009, F012. and 0003
Const ituent/parameter
Untreated
waste
(mg/1)
Concentration
Treated
wastewater
(mg/1)
Treated
nonwastewater
(mg/1)
BOAT Inorganics Other Than Metals
Cyanide (total)

BOAT List Metals

Copper
Nickel
Cadmium
Chromium
Lead
Zinc
Non-BDAT List Metals

Iron

Other Parameters

PH
TOC
12.085
8.165
138
128

105
325
248
10.7
<0.014
252.4
- = Not analyzed.

aBatch consisted of a mixture of liquids and drummed solids including
waste codes F007. F009. F012, and D003.

Reference: CyanoKEM 1989.
4-15
-------
3560g
Table 4-1 (continued)

Sample Set No. 13 - for Treatment of 0002
Const ituent/parameter
Untreated
waste
(mg/1)
Concentrat ion
Treated
wastewater
(mg/1)
Treated
nonwastewater
(rag/1)
BDAT Inorganics Other Than Metals
Cyanide (total)

BDAT List Metals
10,902
- = Not analyzed.

Reference: CyanoKEM 1989.
0.07
203.1
Copper
Nickel
Cadmium
Chromium
Lead
Zinc
Non-BDAT List Metals
Iron
Other Parameters
pH
TOC
355
160
7,050
120
125
9,940

1.530

11.8
<2%
4-16
-------
3560g
Table 4-1 (continued)
Sample Set No. 14a - for Treatment of F009. FOIL 0002, and D003
Untreated
waste
Const ituent/parameter
Concentration
Treated
wastewater
(mg/D
Treated
nonwastewater
(mg/1)
BDAT Inorganics Other Than Metals
Cyanide (total)

BDAT List Metals
16.010
0.07
94.4
Copper
Nickel
Cadmium
Chromium
Lead
Zinc
Non-BDAT List Metals
Iron
Other Parameters
pH
TOC
6.272
223
4 . 063
133
124
6.012

3.511

11.5
<2%
- = Not analyzed.

Batch consisted of a mixture of liquids and drummed solids including
waste codes F009, FOIL 0002. and 0003.

Reference: CyanoKEM 1989.
4-17
-------
3221g
Table 4-2 Wet Air Oxidation Data for Treatment of F019

Sample Set #1

Concentration
Const ituent/parameter
Untreated
waste
(wg/D
Treated
wastewater
(mg/1)
Treated filter
cake
(mg/kg)
BOAT Inorganics Other Than Metals

Cyanide (amenable) 241
Cyanide (total) 293
Fluoride 38.9
Sulfide <1.0
BOAT List Metals

Ant imony
Arsenic
Barium
Beryllium
Cadmium
Chromium (total)
Copper
Lead
Mercury
Nickel
Selenium
Thallium
Vanadium
Zinc
<0.005
0.08
2.7
0.007
2.1
1,230
0.36
14.7
0.00035
0.88
0.05
<0.14
0.31
4,900
Non-BDAT List Metals

Iron 190

Other Parameters (units)
5.0
5.07
24.7
COD (mg/1)
pH (-)
10,500
8.54
<0.005
0.13
0.21
<0.001
0.013
1.9
0.053
0.003
0.0011
0.007
0.25
0.0095
0.006
4.6
0.13
1,750
7.95
22.9
22.9
0.17
465
114
138
0.32
102
72,800
48.7
816
<0.02
46
<20
<5
<0.5
261,000
12,000
Design and Operating Parameters

Parameter (units) Design value Operating value
Oxidation Temperature (*C) NA
Time at Temperature (min) 60
200
60
- = Not analyzed.
NA = Not applicable.
Reference: Zimpro 1988.
4-18
-------
3221g
Table 4-2 (continued)

Sample Set #2
Concentration
Untreated

Constituent/parameter
waste
(mg/1)
Treated
wastewater
(mg/1)
Treated filter
cake
(mg/kg)
BOAT Inorganics Other Than Metals
Cyanide (amenable)
Cyanide (total)
Fluoride
Sulfide
BOAT List Metals
Antimony
Arsenic
Barium
Beryllium
Cadmium
Chromium (total) 1,
Copper
Lead
Mercury
Nickel
Selenium
Thallium
Vanadium
Zinc 4,
Non-BOAT List Metals
Iron
Other Parameters (units)
COD (mg/1) 10.
pH (-)
241
293
38.9
<1.0

<0.005
0.08
2.7
0.007
2.1
230
0.36
14.7
0.00035
0.68
0.05
<0.14
0.31
900

190

500
8.54
<0.02
0.058
30.9
<1.0

<0.005
0.22
0.35
<0.001
0.007
1.9
0.046
0.008
0.001
0.011
<0.005
0.005
<0.005
4.6

0.08

3,040
7.90
142
142
0.15
-

460
135
145
0.29
99
68.600
34
586
<0.02
43
<20
<5
<0.5
257.000

11.000

-
-
Desian and Operating Parameters
Parameter (units)
Oxidation Temperature (*C)
Time at Temperature (min)
Design
NA
60
value Operating
240
60
value

- = Not analyzed.
NA = Not applicable.
Reference: Zimpro 1988.
4-19
-------
3221g
Table 4-2 (continued)

Sample Set 13
Concentration
Untreated

Constituent/parameter
waste
(nig/1)
Treated Treated filter
wastewater
(mg/1)
cake
(mg/kg)
BOAT Inorganics Other Than Metals
Cyanide (amenable)
Cyanide (total)
Fluoride
Sulfide
BOAT List Metals
Ant imony
Arsenic
Barium
Beryllium
Cadmium
Chromium (total) 1,
Copper
Lead
Mercury
Nickel
Selenium
Thallium
Vanadium
Zinc 4,
Non-BDAT List Metals
Iron
Other Parameters (units)
COD (mg/1) 10,
pH (-)
241
293
38.9
<1.0

<0.005
0.08
2.7
0:007
2.1
230
0.36
14.7
0.00035
0.88
0.05
<0.14
0.31
900

190

500
8.54
<0.02
0.133
38.9
<1.0

<0.005
<0.005
0.77
<0.01
<0.04
24
0.12
0.916
0.0008
0.21
<0.005
0.005
<0.05
15.2

0.08

2,120
7.8
18
18
0.23
-

469
109
166
0.32
105
74,100
66
584
<0.02
48
<20
<5.0
<0.5
279.000

15,200

-
~
Desiqn and Ooeratina Parameters
Parameter (units)
Oxidation Temperature (*C)
Time at Temperature (min)
Design
NA
60
value Operating
280
60
value

- = Not analyzed.
NA = Not applicable.
Reference: Zimpro 1988.
4-20
-------
3221g
Table 4-3 Performance Data for UV/Ozonation Treatment
of Complexecl Cyanide F009 Waste
Concentration
Untreated waste Treated waste
Constituent (mg/1) (mg/1)
Sample Set Ho. 1
Cyanide (total) 61 53

Sample Set No. 2
Cyanide (total) 61 53

Sample Set No. 3
Cyanide (total) 61 36

Sample Set No. 4
Cyanide (total) 61 49

Sample Set No. 5
Cyanide (total) 61 37

Sample Set Ho. 6
Cyanide (total) 61 63

Sample Set No. 7
Cyanide (total) 61 25

Sample Set No. 8
Cyanide (total) 1.355 1.170
4-21
-------
IZZla
Table 4-3 (continued)
Design and operating parameters:
Design
Operating value
Parameter
UV output (watts)
Temperature ("C)
Ozone concentration (wt ")
Gas flow rate (1/min)
Time (hr)
ro pH
value3
5.0
60-68
>3.0
0.5
1
8 or 10-12
SS#1
1.9
40-65
3.5
0.5
1
10.5-11.8
SS#2
3.5
63-66
3.0
0.5
1
10.6
SS#3
5.0
62-66
3.0
0.5
I
10.4
SSI4
5.0
22-27
3.0-3.1
0.5
1.1
10.8-11.3
SSI5
5.0
66
3.0
0.2-0.5
1.1
8.0
SS#6
5.0
66
0
0
1
8.0
SS#7
0
62-68
3.0
0.5
1
8.0
SS#8
5.0
66
2.5-4.0
0.25-0.5
1
8.0
aDesign values were varied for each sample set to determine the effect of these variables on the treated waste cyanide concentration.

Reference: 1ITRI 1989.
-------
3221g
Table 4-4 Chemical Precipitation Treatment Performance Data
for K062 - EPA-Collected Data

Sample Set #1
Constituent
Arsenic
Cadmium
Chromium (hexavalent)
Chromium (total)
Copper
Lead
Nickel
Zinc

Untreated
K062 waste
(mg/1)
Sample no.
801
3
<5
I
1800
865
<10
3200
<2
Design and
Design
Untreated
K062 waste
(mg/1)
Sample no.
802
<1
<5
1
7000
306
<10
2600
<2
Operating Parameters
value
Untreated
waste
composite3
(mg/1)
Sample no.
805
<1
13
893
2581
138
64
471
116

Operating
Treated
waste
(wastewater)
(mg/1)
Sample no.
806
<0.1
<0.5
0.011
0.12
0.21
<0.01
0.33
0.125

value
PH
8-10
I = Color interference.

aThe untreated waste composite is a mixture of the untreated K062 waste streams
shown on this table, along with other non-K062 waste streams.

Reference: USEPA 1988b.
4-23
-------
3221g
Table 4-4 (continued)

Sample Set #2

Constituent
Arsenic
Cadmium
Chromium (hexavalent)
Chromium (total)
Copper
Lead
Nickel
Zinc

Untreated
K062 waste
(mg/1)
Sample no.
801
3
<5
I
1800
865
<10
3200
<2
Design and
Design
Untreated
Untreated waste
K062 waste composite9
(mg/1) (mg/1)
Sample no. Sample no.
802 813
<1
<5 10
I 807
7000 2279
306 133
<10 54
2600 470
<2 4
Operating Parameters
Treated
waste
(wastewater)
(mg/1)
Sample no.
814
<0.1
<0.5
0.12
0.19
0.15
<0.01
0.33
0.115

value Operating value
8-10
I = Color interference.

aThe untreated waste composite is a mixture of the untreated K062 waste streams
shown on this table, along with other non-K062 waste streams.

Reference: USEPA 1988b.
4-24
-------
3221g
Table 4-4 (continued)

Sample Set #3

Constituent
Arsenic
Cadmium
Chromium (hexavalent)
Chromium (total)
Copper
Lead
Nickel
Zinc

Untreated
K062 waste
(mg/1)
Sample no.
817
3
<5
1
1700
425
<10
100310
7
Design and
Design

Untreated
K062 waste
(mg/1)
Sample no.
802
<1
<5
I
7000
306
<10
2600
<2
Operating Parameters
value
Untreated
waste
composite3
(mg/1)
Sample no.
821
<1
5
775
1990
133
<10
16330
3.9

Operating
Treated
waste
(wastewater)
(mg/1)
Sample no,
822
<0.1
<0.5
1
0.20
0.21
<0.01
0.33
0.140

value
pH
8-10
10
I = Color interference.

aThe untreated waste composite is a mixture of the untreated K062 waste streams
shown on this table, along with other non-K062 waste streams.

Reference: USEPA 1988b.
4-25
-------
3221g
Table 4-4 (continued)

Sample Set #4

Constituent
Arsenic
Cadmium
Chromium (hexavalent)
Chromium (total)
Copper
Lead
Nickel
Zinc

Untreated
K062 waste
(mg/D
Sample no.
827
2
<5
1
142
42
<10
650
3
Design

Untreated
K062 waste
(mg/1)
Sample no.
802
<1
<5
I
7000
306
<10
2600
<2
and Operating

Untreated
K062 waste
(mg/1)
Sample no.
817
3
5
I
1700
425
<10
41000
7
Parameters
Untreated
waste
composite3
(mg/1)
Sample no.
829
<1
<5
0.6
556
88
<10
6610
84

Treated
waste
(wastewater)
(mg/1)
Sample no.
830
-I
<0.5
0.042
0.10
0.07
<0.01
0.33
1.62

Design value

8-10
Operating value

9
! = Color interference.

aThe untreated waste composite is a mixture of the untreated K062 waste streams shown on this
table, along with other non-K062 waste streams.

Reference: USEPA 1988b.
4-26
-------
3221g
Table 4-4 (continued)

Sample Set #5
Constituent
Arsenic
Cadmium
Chromium (hexavalent)
Chromium (total)
Copper
Lead
Nickel
Zinc

Untreated Untreated
K062 waste K062 waste
(mg/1) (mg/1)
Sample no. Sample no.
801 802
3 <1
<5 <5
I 1
1800 7000
865 306
<10 <10
3200 2600
<2 <2
Design and Operating
Design value
Untreated
K062 waste
(mg/1)
Sample no.
817
3
5
I
1700
425
<10
41000
7
Parameters
Operating
Untreated
waste
composite9
(mg/1)
Sample no.
837
<1
<5
917
2236
91
18
1414
71

value
Treated
waste
(wastewater)
(mg/1)
Sample no.
838
<0.1
<0.5
0.058
0.11
0.14
0.01
0.31
0.125

PH
8-10
I = Color interference.

aThe untreated waste composite is a mixture of the untreated K062 waste streams shown on this
table, along with other non-K062 waste streams.

Reference: USEPA 1988b.
4-27
-------
322ig
Table 4-4 (continued)

Sample Set #6

Constituent
Arsenic
Cadmium
Chromium (hexavalent)
Chromium (total)
Copper
Lead
Nickel
Z1nc

Untreated
K062 waste
(mg/1)
Sample no.
801
3
<5
I
1800
865
<10
3200
<2
Design and
Design

Untreated
K062 waste
(mg/1)
Sample no.
802
<1
<5
I
7000
306
<10
2600
<2
Operating Parameters
value
Untreated
waste
composite3
(mg/1)
Sample no.
845
<1
<5
734
2548
149
<10
588
4

Operating
Treated
waste
(wastewater)
(mg/1)
Sample no.
846
<0.1
<0.5
I
0.10
0.12
<0.01
0.33
0.095

value
pH
8-10
1 = Color interference.

aThe untreated waste composite is a mixture of the untreated K062 waste streams
shown on this table, along with other non-K062 waste streams.

Reference: USEPA 1988b.
4-28
-------
3221g
Table 4-4 (continued)

Sample Set #7

Constituent
Arsenic
Cadmium
Chromium (hexavalent)
Chromium (total)
Copper
Lead
Nickel
Zinc

Untreated
K062 waste
(mg/1)
Sample no.
801
3
<5
I
1800
865
<10
3200
<2
Design and
Design

Untreated
K062 waste
(mg/1)
Sample no.
802
<1
•=5
1
7000
306
<10
2600
<2
Operating Parameters
value
Untreated
waste
composite3
(mg/1)
Sample no.
853
<1
10
769
2314
72
108
426
171

Operating
Treated
waste
(wastewater)
(mg/1)
Sample no.
854
<0.1
<0.5
0.12
0.12
0.16
<0.01
0.40
0.115

value
PH
8-10
1 = Color interference.

aThe untreated waste composite is a mixture of the untreated K062 waste streams
shown on this table, along with other non-K062 waste streams.

Reference: USEPA 1988b.
4-29
-------
3Z21g
Table 4-4 (continued)

Sample Set #8

Constituent
Arsenic
Cadmium
Chromium (hexavalent)
Chromium (total)
Copper
Lead
Nickel
Zinc

Untreated
K062 waste
(mg/1)
Sample no.
859
<1
<5
0.220
15
151
<10
90
7
Design and
Design

Untreated
K062 waste
(mg/1)
Sample no.
801
3
<5
1
1800
865
<10
3200
9
Operating Parameters
value
Untreated
waste
composite3
(mg/1)
Sample no.
861
<1
<5
0.13
831
217
212
669
151

Operating
Treated
waste
(wastewater)
(mg/1)
Sample no.
862
<0.1
<0.5
<0.01
0.15
0.16
<0.01
0.36
0.13

value
pH
8-10
1 = Color interference.

aThe untreated waste composite is o mixture of the untreated K062 waste streams
shown on this table, along with other non-K062 waste streams.

Reference: USEPA 1988b.
4-30
-------
3221g
Table 4-4 (continued)

Sample Set #9

Constituent
Arsenic
Cadmium
Chromium (hexavalent)
Chromium (total)
Copper
Lead
Nickel
Zinc

Untreated
K062 waste
(mg/1)
Sample no.
867
<0.1
<0.5
0.079
6
5
<1
4
0.4
Design

Untreated
K062 waste
(mg/1)
Sample no.
801
3
<5
I
1800
865
<10
3200
<2
and Operating

Untreated
K062 waste
(mg/1)
Sample no.
802
<1
<5
I
7000
306
<10
2600
<2
Parameters
Untreated
waste
composite3
(mg/1)
Sample no.
869
<1
<5
0.07
939
225
<10
940
5

Treated
waste
(wastewater)
(mg/1)
Sample no.
870
--0.1
,0.5
0.041
0.10
0.08
<0.01
0.33
0.06

pH
Design value

8-10
Operating value

10
I = Color interference.

aThe untreated waste composite is ? mixture of the untreated K062 waste streams shown on
this table, along with other non-K062 waste streams.

Reference: USEPA 19881).
4-31
-------
3221g
Table 4-4 (continued)

Sample Set #10
Untreated
Untreated waste
K062 waste composite9
(mg/1) (mg/1)
Sample no. Sample no.
Constituent 801 885
Arsenic <3 <1
Cadmium <5 <5
Chromium (hexavalent) I 0.08
Chromium (total) 1800 395
Copper 865 191
Lead <10 <10
Nickel 3200 712
Zinc <2 5
Treated
waste
(wastewater)
(mg/1)
Sample no.
862
<0.10
<0.5
0.106
0.12
0.14
<0.01
0.33
0.070
Design and Operating Parameters
Design value
Operating value
8-10
I = Color interference.

aThe untreated waste composite is a mixture of the untreated K062 waste streams
shown on this table, along with other non-K062 waste streams.

Reference: USEPA 1988b.
4-32
-------
3221g
Table 4-4 (continued)

Sample Set #11

Constituent
Arsenic
Cadmium
Chromium (hexavalent)
Chromium (total)
Copper
Lead
Nickel
Zinc

Untreated
K062 waste
(mg/1)
Sample no.
801
3
<5
I
1800
865
<10
3300
<2
Design and
Design

Untreated
K062 waste
(mg/1)
Sample no.
859
<1
<5
0.220
15
151
<10
90
7
Operating Parameters
value
Untreated
waste
composite3
(mg/1)
Sample no.
893
<1
23
0.30
617
137
136
382
135

Operating
Treated
waste
(wastewater)
(mg/1)
Sample no.
894
<0.10
<5
<0.01
0.18
0.24
<0.01
0.39
0.100

value
pH
8-10
I = Color interference.

aThe untreated waste composite is a mixture of the untreated K062 waste streams
shown on this table, along with other non-K062 waste streams.

Reference: USEPA 1988b.
4-33
-------
3041g
Table 4-5 Treatment Performance Data for Stabilization of F006 Waste
Oil and
grease TOC Mix
Source (mg/kg) (mg/kg) ratio9
Unknown
Unstabilized
As received 1.520 14,600
TCLP
Stabilized
TCLP 0.2
Auto parts manufacturing
Unstabilized
As received 60 1.500
TCLP
Stabilized
TCLP 0.2
TCLP 0.5
Aircraft overhauling
facility
Unstabilized
As received 37.000 137.000
TCLP
Stabilized
TCLP 0.2
TCLP 0.5
Aerospace manufacturing
(mixture of
F006 & F007)
Unstabilized
As received 3.870 8.280
TCLP
Stabilized
TCLP 1-0
TCLP 1-5
Metal concentrations (DOT)
Arsenic Barium

36.4
<0.01 0.08

<0.01 0.12

21.6
<0.01 0.32

<0.01 0.50
<0.01 0.42

85.5
0.01 1.41

<0.01 0.33
<0.01 0.31

0.74
<0.01 0.83

<0.01 0.52
<0.01 1.18
Cadmium

1.3
0.01

0.01

31.3
2.21

0.50
0.01

67.3
1.13

0.06
0.02

1.69
0.66

<0.01
0.01
Chromium

1270
0.34

0.51

755
0.76

0.40
0.39

716
0.43

0.08
0.20

12.9
7.58

0.40
0.34
Copper

40.2
0.15

0.20

7030
368

5.4
0.25

693
1.33

1.64
1.84

18.5
4.12

0.23
0.19
Lead

35.5
0.26

0.30

409
10.7

0.40
0.36

25.7
0.26

0.03
0.41

11.4
6.86

0.20
0.36
Mercury Nickel Selenium

435
<0.001 0.71 <0.01

<0.001 0.04 0.06

989
<0.001 22.7 <0.01

<0.001 1.5 0.06
<0.001 0.03 0.11

259
<0.001 1.1 <0.01

<0.001 0.23 0.07
<0.001 0.15 0.11

234
0.003 158 <0.01

<0.001 4.35 0.17
<0.001 2.47 0.20
Silver

2.3
0.01

0.03

6.62
0.14

0.03
0.05

39
0.02

0.20
0.05

6.26
1.64

0.09
0.15
Zinc

1560
0.16

0.03

4020
219

36.9
0.01

631
5.41

0.05
0.03

8.86
2.28

0.05
0.03
-------
Table 4-5 (Continued)
Source
Zinc plating
Unstabilized
As receiuved
TCLP
Stabilized
TCLP
TCLP
Unknown
Unstabilized
As received
TCLP
Stabilized
TCLP
"T TCLP
CO
in
Small engine
manufacturing
Unstabilized
As received
TCLP
Stabilized
TCLP
TCLP
Circuit board
manufacturing
Unstabilized
As received
TCLP
Stabilized
TCLP
TCLP
Oil and
arease TOC Mix
(mg/kg) (mg/kg) ratio9 Arsenic Barium

1.150 21.200 - 17.2
0.84

0.2 <0.01 0.20
0.5 <0.01 0.23

20,300 28.600 - 14.3
<0.01 0.38

0.2 <0.01 0.31
0.5 <0.01 0.19

2.770 6.550 - 24.5
<0.01 0.07

0.2 <0.01 0.30
0.5 <0.01 0.33

130 550 - 12.6
<0.01 0.04

0.2 <0.01 0.04
0.5 <0.01 0.14
Metal concentrations lorn)
Cadmium

1.30
0.22

0.01
0.01

720
23.6

3.23
0.01

7.28
0.3

0.02
0.01

5.39
0.05

0.01
0.01
Chromium

110
0.18

0.23
0.30

12.200
25.3

0.25
0.38

3.100
38.7

0.21
0.76

42.900
380

3.0
1.21
Copper

1.510
4.6

0.30
0.27

160
1.14

0.20
0.29

1.220
31.7

0.21
0.20

10.600
8.69

0.40
0.42
Lead

88.5
0.45

0.30
0.34

52
0.45

0.24
0.36

113
3.37

0.30
0.36

156
1.0

0.30
0.38
Mercury Nickel Selenium

37
<0.001 0.52

<0.001 0.10 0.08
<0.001 0.02 0.14

701
<0.001 9.78 <0.01

<0.001 0.53 0.04
<0.001 0.04 0.09

19.400
0.003 730 <0.01

<0.001 16.5 0.05
<0.001 0.05 0.11

13,000
<0.001 15? <0.01

<0.001 0.40 0.04
<0.001 0.10 0.07
Silver

9.05
0.16

0.03
0.04

5.28
0.08

0.04
0.06

4.08
0.12

0.03
0.05

12.5
0.05

0.03
0.05
Zinc

90.200
2.030

32
0.04

35.900
867

3.4
0.03

27.800
1.200

36.3
0.04

120
0.62

0.02
0.01
-------
304 Ig
Table 4-5 (Continued)
Source
Unknown
Unstabilized
As received
TCLP
Stabilized
TCLP
TCLP
Unknown
Unstabilized
As received
TCLP
^ Stabilized
i, TCLP
°* TCLP
Oil and
grease TOC Mix
(ing/kg) (tug/kg) ratio3 Arsenic Barium

30 10.700 - 15.3
<0.01 0.53

0.2 <0.01 0.32
0.5 <0.01 0.27

1.430 5.960 - 19.2
0.88 0.28

0.2 <0.02 0.19
0.5 <0.02 0.08
Metal concentrations (DOT)
Cadmium

5.81
0.18

0.01
0.01

5.04
0.01

<0.01
<0.01
Chromium

47.9
0.04

0.10
0.2

644
0.01

0.03
0.21
Copper

17.600
483

0.50
0.32

28.400 24.
16.9

3.18
0.46
Lead

169
4.22

0.31
0.37

500
50.2

2.39
0.27
Mercury Nickel Selenium

23.700
<0.001 644 <0.01

<0.001 15.7 0.07
<0.001 0.04 0.07

5.730
<0.001 16.1 <0.45

<0.001 1.09 <0.01
<0.001 0.02 <0.01
Silver

8.11
0.31

0.03
0.05

19.1
<0.01

<0.01
<0.01
Zinc

15.700
650

4.54
0.02

322
1.29

0.07
<0.01
Mix ratio
weight of reagent
weight of waste
bCircuit board manufacturing waste is not in its entirety defined as F006; however, an integral part of the manufacturing operation is electroplating.
Treatment residuals generated from treatment of these electroplating wastes are F006.

Reference: CVM 1987.
-------
5. IDENTIFICATION OF THE BEST DEMONSTRATED
AVAILABLE TECHNOLOGY (BDAT)
This section presents the rationale for the determination of best
demonstrated available technology (BDAT) for treatment of F019 wastes.
For both cyanide and metals treatment, the Agency examined all of the
available data for the demonstrated technologies to determine whether one
of the technologies performed significantly better than the others.
Next, the "best" performing treatment technology was evaluated to
determine whether the resulting treatment is available. To be
"available," a technology (1) must provide substantial treatment and
(2) must be commercially available to the affected industry. If the best
demonstrated technology is "available," then this technology represents
BDAT.

5.1 BDAT for Treatment of Cyanide

Section 4 presents data for treatment of various electroplating
wastes by alkaline chlorination followed by filtration (Table 4-1).
These data show significant reduction in the concentrations of amenable
and total cyanide.

The Agency believes that this process is likely to incorporate repeti-
tive treatment for the concentrated cyanide wastes, i.e., greater than
30,000 ppm of total cyanides. This belief is based on information
received from a commercial treatment facility (CyanoKEM 1989). The fact
that repetitive treatment is necessary does not call into question the
achievability of the cyanide standard by one-step alkaline chlorination
processes. It only reflects that the wastes may be heavily concentrated
with cyanide and complexing metals. Normal chemical conversion wastes
contain much lower concentrations of these cyanides. Also, the Agency
notes that if F019 wastewater treatment sludges at chemical conversion
3217g
5-1
-------
facilities do not meet the cyanide treatment standards, these wastes can
be held in a holding tank and resolubilized and treated again by the
plant's alkaline chlorination system. Most important, all existing data
(public comments to this rulemaking and the Agency's review of the
Generator Survey data, which corroborates the information in the public
comments) show that the final cyanide treatment standard is being
achieved by over 90 percent of the industry by performance of existing
treatment systems.

Section 4 also presents data for treatment of F019 by wet air
oxidation followed by filtration (Table 4-2). These data show
significant reduction in the concentrations of amenable and total cyanide
in both the wastewater filtrate and the nonwastewater filter cake
generated. However, different analytical methods were used to analyze
for amenable cyanide: Method 9012 in Test Methods for Evaluating Solid
Waste, SW-846 and Method 412F in "Standard Methods for Examination of
Water and Wastewater," 16th Edition. In addition, dilution values of the
samples cannot be explained with available data.

Table 4-3 presents data on UV/ozonation treatment of an F009 waste
that was generated following alkaline chlorination treatment and thus had
a high concentration of complexed cyanide. However, the UV/ozonation
treatment data were not directly comparable to the wet air oxidation data
because the "treated waste" data do not reflect settling and/or
filtration to separate solids and generate wastewater and nonwastewater
residuals. Therefore, these data were not considered "best" in further
development of the BOAT treatment standards for F019 wastes.

EPA has no other data for treatment of cyanide in F019 wastes or
similar wastes; therefore, the Agency has determined that alkaline
chlorination represents "best" treatment for cyanide in F019 wastes.
Alkaline chlorination is "available" because it is a commercially
3217g
5-2
-------
available technology, used throughout industry, and it provides
substantial treatment. Therefore, alkaline chlorination represents BDAT
for cyanide in F019 waste (both nonwastewaters and wastewaters). A
summary of the accuracy adjustment of treatment data for total cyanide in
electroplating wastes is presented in Table 5-1 (at the end of this
section).

5.2 BDAT for Treatment of Metals

Treatment of F019 wastes for cyanide destruction by alkaline
chlorination generates both wastewater and nonwastewater residuals that
are likely to require further treatment for BDAT list metals.

5.2.1 Wastewaters

No treatment data are available for treatment of metals in F019 waste-
waters. EPA does, however, have treatment data for wastes (K062) believed
to be similar to F019 wastewaters in terms of the type and concentration
of BDAT list metals present and in terms of waste characteristics affect-
ing treatment performance (as discussed in Section 4.2.1). These treat-
ment data are based on chemical reduction followed by chemical precipita-
tion and filtration. The Agency determined that the treatment performance
data for K062 represented a well-designed, well-operated treatment system
(see Table 5-2).

The treatment data for chemical reduction followed by chemical
precipitation and filtration have been determined to represent "best"
treatment, based on evaluation of all data available to the Agency for
treatment of wastewaters containing high concentrations of chromium at
the time of promulgation of the First Third land disposal restrictions
(USEPA 1988b). Since that time, EPA has found no data on treatment of
chromium-containing wastewaters by the BDAT technology for K062 or by any
3217g
5-3
-------
other technology. This technology is "available" because it provides
substantial treatment of BDAT list metals and the individual processes
are each commercially available. Therefore, chemical reduction of
hexavalent chromium followed by chemical precipitation and filtration
represents BDAT for BDAT list metals in F019 wastewaters.

5.2.2 Nonwastewaters

No treatment data are available to the Agency for treatment of metals
in F019 nonwastewaters. EPA does, however, have stabilization data for
metal-containing nonwastewater treatment sludges (F006) believed to be
similar to F019 nonwastewaters generated as a residual following cyanide
treatment (as discussed in Section 4.2.2). The Agency determined that
the treatment performance data for F006 stabilization represent a
well-designed and well-operated treatment system (USEPA 1988a).

The stabilization data for F006 show TCLP chromium concentration is
reduced from up to 360 mg/1 in the untreated waste down to less than
1.5 mg/1 in the stabilized waste (see Table 5-3).

The Agency has no reason to believe that the use of other processes
could improve the level of performance achieved by stabilization.
Therefore, stabilization is "best." This treatment system is "available"
because the components of the treatment system are commercially available
and provide substantial treatment'. Therefore, stabilization represents
BDAT for BDAT list metals in F019 wastewater treatment sludges and also
in the nonwastewater residuals from treatment of F019 by wet air
oxidation followed by chemical reduction, chemical precipitation, and
filtration. The accuracy-corrected performance data used to develop
metals treatment standards for F019 are presented in Tables 5-2 and 5-3.
3217g
5-4
-------
Table 5-1 Summary of Accuracy Adjustment of Treatment Data
for Total Cyanide In Electroplating Wastes
Untreated
waste
concentration
(mg/1)
Alkaline
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Measured
treated waste
concentration
(mg/1)
Percent
recovery for Accuracy-
matrix correction
spike test factor
Accuracy-
adjusted
concentration
(mg/1)
Chlorination
Set No.
Set No.
Set No.
Set No.
Set No.
Set No.
Set No.
Set No.
Set No.
Set No.
Set No.
Set No.
Set No.
1
2
3
4
5
6
7
8
9
10
12
13
14
71
12
17
25
16
59
31
41
18
1
12
10
16
,759
,000
,206
,936
,914
.421
,994
,900
,882
,270
,085
,902
,010
0.
0.
<0.
<0.
<0.
0.
0.
<0.
<0.
0.
<0.
0.
0.
95
95
014
014
014
028
028
014
014
17
014
070
070
94
94
94
94
94
94
94
94
94
94
94
94
94
1
1
1
1
1
1
1
1
1
1
1
1
1
.06
.06
.06
.06
.06
.06
.06
.06
.06
.06
.06
.06
.06
1.
1.
<0.
•cO.
<0.
0.
0.
<0.
<0.
0.
<0.
0.
0.
01
01
015
015
015
030
030
015
015
18
015
074
074
5-5
-------
2390g
Table 5-2 Accuracy-Corrected Performance Data for
Chromium in K062 Vastewaters

Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample

Set
Set
Set
Set
Set
Set
Set
Set
Set
Set
Set

No.
No.
No.
No.
No.
No.
No.
No.
No.
No.
No.

1
2
3
4
5
6
7
B
9
10
11
Untreated
waste
composite9
(«J/D
2581
2279
1990
556
2236
2548
2314
831
939
395
617
Treated
waste Percent
(mg/1) recovery**
0
0
0
0
0
0
0
0
0
0
0
.12 68
.12
.20
.10
.11
.10
.12
.15
.10
.12
.18
Corrected
Correction value
factor (mg/D
1.47 0
0
0
0
0
0
0
0
0
0
0
.1764
.1764
.294
.147
.162
.147
.1764
.2205
.147
.1764
.2646
aThe untreated waste composite is a mixture of the untreated IC062 waste streams shown on this
table, along with other non-K062 waste streams.
nhe percent recovery has been taken from Table 7-14 of the Onsite Engineering Report from
Horsehead Resource Development Company (USEPA 1987).

Reference: USEPA 1988b.
5-6
-------
2390g
Table 5-3 Accuracy-Corrected Performance Data for
Chromiun in F006 Nonwastewaters Treatment by Stabilization
Source
Untreated Untreated
waste waste
concentration concentration
Mix as received (TCLP)
Accuracy-adjusted
treated waste
concentration (TCLP)
ratio
a
(ng/D
(«J/D
Auto part manufacturing
Aircraft overhauling
Unknown
Small engine Manufacturing
Circuit board manufacturing
0.5
0.2
0.5
0.5
0.5
755
716
12.200
3.100
42.900
0.76
0.43
25.3
38.7
360
0.45
0.09
0.44
0.89
1.41
ix ratio =
weight of reagent
weight of waste
Source: USEPA 1988a.
5-7
-------
6. SELECTION OF REGULATED CONSTITUENTS

As discussed in EPA's Methodology for Developing BOAT Treatment:
Standards (USEPA 1989a), the Agency has developed a list of BOAT
hazardous constituents from which the constituents to be regulated are
selected. EPA may revise this list as additional data and information
become available. The list is divided into the following categories:
volatile organics, semivolatile organics, metals, inorganics other than
metals, organochlorine pesticides, phenoxyacetic acid herbicides,
organophosphorus insecticides, PCBs, and dioxins and furans.

This section describes the process used to select the constituents to
be regulated. The process involves developing a list of potential
regulated constituents and then eliminating those constituents that would
not be treated by the chosen BDAT or that would be controlled by
regulation of other constituents in the waste.

6.1 Identification of BDAT List Constituents in F019

As discussed in Sections 2 and 4, the Agency has characterization
data and performance data for the treatment of F019. These data have
been used to determine which BDAT list constituents may be present in the
waste and thus which ones are potential candidates for regulation. These
constituents are amenable and total cyanides, fluoride, sulfide,
antimony, arsenic, barium, beryllium, cadmium, total chromium, copper,
lead, mercury, nickel, selenium, thallium, vanadium, and zinc.

6.2 Constituents Selected for Regulation

Based on the characterization and performance data for F019 presented
in Sections 2 and 4, the Agency is proposing to regulate total cyanide,
amenable cyanide, and total chromium. EPA is not regulating copper and
3218g
6-1
-------
zinc for the wastes in this subcategory because these constituents are
not listed in Appendix VIII of 40 CFR Part 261 as elemental constituents
but rather as specific compounds (i.e., copper cyanide, zinc phosphide,
and zinc cyanide). In any case, treatment of the other BDAT list metals
by chemical precipitation and/or stabilization will also reduce leachate
concentrations of both of these metals in wastewater and nonwastewater
treatment residuals. Based on EPA's knowledge of the chemical conversion
coating process, the Agency would not expect any other BDAT list
constituents to be commonly found in these wastes at treatable
concentrations. The only other BDAT list constituents expected to be
present in F019 would be other BDAT list metals. These constituents are
expected to be found, if at all, at much lower concentrations than
chromium. Nickel and zinc were detected at greater than 1,000 ppm in two
of the F019 wastes for which characterization data were given. These
metals, when detected in F019 waste, are expected to be treated by a
well-designed and well-operated BDAT treatment system for both
nonwastewaters and wastewaters.
3218g
6-2
-------
7. CALCULATION OF BOAT TREATMENT STANDARDS

This section presents the calculation of the BOAT treatment standards
for the regulated constituents determined in Section 6. As discussed in
the Methodology for Developing BOAT Treatment Standards (USEPA 1989a),
the following steps were taken to derive the BDAT treatment standards for
F019.

The Agency evaluated the compositional similarities between F019
wastewaters and nonwastewaters and F006-F009 wastewaters. The
similarities included composition, concentration, and treatability.
Based on these similarities, the Agency is promulgating treatment
standards for amenable and total cyanide in F019 wastewaters and
nonwastewaters based on the performance of alkaline chlorination
treatment of electroplating wastes. For wastewaters the extensive data
used in the development of Metal Finishing categorical wastewater
discharge standards was used as the basis for BDAT. Because of
analytical difficulties in analyzing for amenable cyanides in F019
nonwastewaters, the amenable cyanide treatment standards for
nonwastewaters are based on 5 percent of the total cyanide standard.
Based on the data available to the Agency, it was determined that the
precision of the SW-846, Method 9010, for amenable cyanide is 5 percent
of the total cyanide concentration. The basis for this estimate is
discussed in "Standard Methods for the Examination of Water and
Wastewater" in which the precision for the analytical method is estimated
to be 5 percent. Since the "Standard Methods for the Examination of
Water and Wastewater" procedure is essentially identical to the precision
of SW-846, Method 9010, EPA believes that the 5 percent value is
transferrable to the analysis performed using SW-846, Method 9010. The
data used in the development of treatment standards for these wastes
represent the performance of well-designed, well-operated treatment
systems.
3219g
7-1
-------
For BOAT list metal constituents, the treatment standards for
nonwastewaters are based on transfer of performance data from
stabilization of F006 wastewater treatment sludges and the treatment
standards for wastewaters are based on transfer of performance data from
treatment of K062 wastes by chemical reduction followed by chemical
precipitation and filtration. It was previously determined in the
associated background documents (USEPA 1988a, USEPA 1988b) that the data
used in development of treatment standards for these wastes represented
the performance of well-designed, well-operated treatment systems.

As described in the methodology, analytical accuracy-corrected
constituent concentrations were calculated for all regulated BDAT list
constituents. An arithmetic average of concentration levels for each
constituent and a variability factor for each constituent were then
determined. The variability factor represents the variability inherent
in the treatment process and the sampling and analytical methods.
Variability factors are calculated based on the treatment data for each
of the regulated constituents. The general methodology for calculating
variability factors is presented in Appendix A of the methodology
document.

The BDAT treatment standard for each constituent to be regulated in
this rulemaking was determined by multiplying the average accuracy-
corrected total composition by the appropriate variability factor, with
the exception of cyanide in wastewaters where the standards were
transferred from Metal Finishing categorical wastewater discharge
standards. These data are presented in Appendix A. The calculations of
the treatment standards for F019 wastewaters and nonwastewaters and
chromium are presented in Tables 7-1, 7-2, and 7-3, respectively. The
treatment standards are shown in Table 7-4.
3219g
7-2
-------
3560g
Table 7-1 Calculation of Wastewater Treatment Standards for
Total and Amenable Cyanide
Regulated
constituent
Cyanide (total)
Cyanide (amenable)
Mean effluent
concentration
(mg/1)
0.16
0.06
Variability
factor
6.68
14.31
Treatment
standard
(mg/1) )
1.20
0.86
Standards transferred from Metal Finishing:
CN.T CN.A

Mean effluent concentration (mg/1) 0.18 0.06
Variability factors 6.68 14.31
Treatment standard (mg/1) 1.20 0.86
7-3
-------
2390g
Table 7-2 Calculation of Nonwastewater Treatment Standards for Total
Cyanide for F006. F007. F008. and F009 Wastes Based on
Generation of F006 Waste by a Well-Operated Treatment
Process Consisting of Alkaline Chlorination, Chemical
Precipitation, Filtration, and Sludge Dewatering
Regulated
constituent (units)
Accuracy-adjusted
treated waste
concentration8
Mean treated
Haste
concentration
Variability
factor (VF)
Treatment
standard (total
composition)
Nonwastexater (ma/kg):
Cyanide (total)
Cyanide (amenable)
390.11 242.9 2.4
166.56
383.68
408.0
256.5
267.43
185.01
206.78
116.02
156.11
124.54
275.58
221.83
b
590
30
aTo calculate the treatment standard for amenable cyanides, the Agency has taken into account
the precision of the analytical methods for cyanide analysis based on performance of alkaline
chlorination.
Because of analytical difficulties in analyzing for amenable cyanides in F019 wastewaters and
nonwastewaters. the amenable cyanide treatment standards are based on 5 percent of the total
cyanide standard. Based on the data available to the Agency, it MS determined that the
precision of the SW-846. Method 9010 for amenable cyanide is 5 percent of the total cyanide
concentration. The basis for this estimate is discussed in "Standard Methods for the Examination
of Water and Wastewater" in which the precision for the analytical method is estimated to be
5 percent. Since the "Standard Methods for the Examination of Water and Wastewater" procedure is
essentially identical to the precision of SW-846. Method 9010. EPA believes that the 5 percent
value is transferable to the analysis performed using SW-846, Method 9010.
7-4
-------
Table 7-3 Calculation of BOAT List Metals Treatment Standards for F019
Arithmetic average of Treatment
corrected treatment Variability standard
values (mgAg) factor (mg/kg)
Wastevater

Chromium (total)

Nonwastewater

Chromium (total)
0.19
0.66
1.69
7.94
0.32
5.2
3219g
7-5
-------
Table 7-4 BDAT Treatment Standards for F019
Maximum for anv single erab sample
Nonwastewater Wastewater
Total TCLP leachate Total
concentration concentration concentration
Constituent (mg/kg) (mg/1) (mg/1)

Cyanide (amenable) 30 NA .086
Cyanide (total) 590 NA 1.20

Chromium (total) NA 5.2 0.32
NA - Not applicable.
3219g
7-6
-------
8. REFERENCES
AES. 1981. American Electroplaters' Society. Electroplating wastewater
sludge characterization. Prepared for U.S. Environmental Protection
Agency, Industrial Environmental Research Laboratory, Cincinnati,
Ohio. Prepared by American Electroplaters' Society, Inc., Winter Park,
Fla. EPA-600/2-81-064. NTIS PB81-190928.

CWM. 1987. Chemical Waste Management. Technical report no. 87-117,
Stabilization treatment of metal-containing wastes. September 22,
1987. Chemical Waste Management, 150 West 137th Street, Riverdale, IL.

CyanoKEM. 1987. Public comment submitted in response to EPA proposed
California disposal restriction levels, August 12, 1987. EPA RCRA
Docket No. F-87-LDR6-FFFFF. Washington, D.C.: U.S. Environmental
Protection Agency.

CyanoKEM. 1989. Public comment submitted in response to EPA proposed
land disposal restrictions for Second Third scheduled wastes. Janu-
ary 11, 1989. EPA RCRA Docket No. F-89-LD12-FFFFP. Washington, DC:
U.S. Environmental Protection Agency.

Environ. 1985. Characterization of waste streams listed in 40 CFR
Section 261, waste profiles, Vols. I and II. Prepared for Waste
Identification Branch. Characterization and Assessment Division,
Office of Solid Waste, U.S. Environmental Protection Agency.
Washington, D.C.: U.S. Environmental Protection Agency.

Hazardous Waste Treatment Council. 1990. Public comment and data
submitted in response to EPA proposed land disposal restrictions for
Third Third wastes. January 1990. EPA RCRA Docket No. LD12-00032.
Washington, D.C.: U.S. Environmental Protection Agency.

IITRI. 1989. Illinois Institute of Technology Research Institute.
0-j/UV treatment of electroplating wastewater containing complex
cyanides. IITRI C06699-1. Chicago: IIT Research Institute.

MRI. 1987. Midwest Research Institute. Analytical data report for six
facilities included in the electroplating sampling and analysis
program. Draft final report for Office of Solid Waste, Contract no.
68-01-7287. Washington, D.C.: U.S. Environmental Protection Agency.

PEL 1989. PEI Associates, Inc. Quality assurance project plan:
Ultraviolet light/ozonation of cyanide-bearing wastewaters from
electroplating operations. Contract No. 68-03-3389, Revision 2.
Prepared for U.S. Environmental Protection Agency, Office of Research
and Development. Cincinnati, Ohio: U.S. Environmental Protection
Agency.
32208
8-1
-------
USEPA. 1980. U.S. Environmental Protection Agency, Office of Solid
Waste. RCRA listing background document. Washington, D.C.: U.S.
Environmental Protection Agency.

USEPA. 1982. U.S. Environmental Protection Agency, Office of Water.
Development document (final) for effluent limitations guidelines and
standards for the coil coating point source category (Phase I).
EPA-440/1-82-071. Washington, D.C.: U.S. Environmental Protection
Agency.

USEPA. 1983. U.S. Environmental Protection Agency, Office of Water.
Development document (final) for effluent limitations guidelines and
new source performance standards for the metal finishing point source
category. EPA-440/1-83-091. Washington, D.C.: U.S. Environmental
Protection Agency.

USEPA. 1987. U.S. Environmental Protection Agency, Office of Solid
Waste. Onsite engineering report of treatment technology performance
and operation for Horsehead Resource Development Company for K061.
Washington, D.C.: U.S. Environmental Protection Agency.

USEPA. 1988a. U.S. Environmental Protection Agency, Office of Solid
Waste. Best demonstrated available technology (BDAT) background
document for F006. 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 K062. Washington, D.C.: U.S. Environmental Protection
Agency.

USEPA. 1988c. U.S. Environmental Protection Agency, Office of Solid
Waste. Onsite engineering report of treatment technology performance
and operation for wet air oxidation of F007 at Zimpro/Passavant, Inc.,
in Rothschild, Wisconsin. Washington, D.C.: U.S. Environmental
Protection Agency.

USEPA. 1988d. U.S. Environmental Protection Agency, Office of Solid
Waste. Onsite engineering report of treatment technology performance
and operation for Woodward Governor Corporation, Rockford, IL.
Washington, D.C.: U.S. Environmental Protection Agency.

USEPA. 1989a. U.S. Environmental Protection Agency, Office of Solid
Waste. Methodology for developing BDAT treatment standards.
Washington, D.C.: U.S. Environmental Protection Agency.

USEPA. 1989b. U.S. Environmental Protection Agency, Office of Solid
Waste. Treatment technology background document. Washington, D.C.:
U.S. Environmental Protection Agency.
3220g
8-2
-------
USEPA. 1989c. U.S. Environmental Protection Agency, Office of Solid
Waste. Best demonstrated available technology (BOAT) background
document for cyanide wastes. Washington, D.C.: U.S. Environmental
Protection Agency.

Versar Inc. 1986. Summary of available waste composition data from
review of literature and data bases for use in treatment technology
application and evaluation for "California list" waste streams. Draft
report prepared under Contract no. 68-01-7053 for U.S. Environmental
Protection Agency, Office of Solid Waste. Washington, D.C.: U.S.
Environmental Protection Agency.

Zimpro. 1988. Zimpro Passavant. Final report for the pilot plant
demonstration study on wet air oxidation of F007 electroplating cyanide
wastes for PEI Associates. 21-0094/93.0. June 1988. Zimpro
Passavant. Rothschild, WI.
32208
8-3
-------
APPENDIX A
3668g
-------
TREATMENT OF CYANIDE WASTES - SINGLE OPTION

INTRODUCTION

This subsection describes the technique recommended for cyanide
treatment, discusses the mean cyanide concentrations found,
identifies the recommended daily maximum and monthly maximum
average concentrations for cyanide and presents alternative
treatments for the destruction of cyanide.

The following paragraphs describe the chlorine oxidation
technique recommended for the treatment of cyanide bearing
wastes.

RECOMMENDED TREATMENT TECHNIQUE

Oxidation By Chlorination

Cyanides are introduced as metal salts for plating and conver-
sion coating or are active components in plating and cleaning
baths. Cyanide is generally destroyed by oxidation.

Chlorine is used primarily as an oxidizing agent in industrial
waste treatment to destroy cyanide. Chlorine can be used in
the elemental or hypochlorite form. This classic procedure
can be illustrated by the following two step chemical reaction:

1. C12 + NaCN + 2NaOH = NaCNO + 2NaCl + H20

2. 3C12 + 6NaOH + 2NaCNO - 2NaHC03 + N2 + 6NaCl 4- 2H2O

The reaction presented as equation(2) for the oxidation of
cyanate is the final step in the oxidation of cyanide. A
complete system for the alkaline chlorination of cyanide is
shown in Figure 7-25.

The cyanide waste flow is treated by the alkaline chlorination
process for oxidation of cyanides to carbon dioxide and nitrogen,
The equipment often consists of an equalization tank followed
by two reaction tanks, although the reaction can be carried
out in a single tank. Each tank has an electronic recorder-
controller to maintain required conditions with respect to pH
and oxidation-reduction potential (ORP). In the first reaction
tank, conditions are adjusted to oxidize cyanides to cyanates.
To effect the reaction, chlorine is metered to the reaction
tank as required to maintain the ORP in the range of 350 to
400 millivolts, and 50% aqueous caustic soda is added to
maintain a pH range of 9.5 to 10. In the second reaction
tank, conditions are maintained to oxidize cyanate to carbon
dioxide and nitrogen. The desirable ORP and pH for this
reaction are 600 millivolts and a pH of 8.0. Each of the
reaction tanks is equipped with a propeller agitator designed
to provide approximately one turnover per minute. Treatment
by the batch process is accomplished by using two tanks, one
A-l
-------
HAW WASTE
l\>
CAUSTIC
SODA

PH 1 — 1 1
CONTROLLER 1 L_.
1— 1-J <

1
1
1
)__..
^r^

|
1
_^

WATER CONTAINING

CHUORINE >
\

1
1

CAUSTIC
BOOA

CVANATE

Dr |— 1 PH
—I 1 CONTHOUL.CH
1

1 1
r-,, r,.,_r-^- , . .1 - rxJ..— ...
i
•
cdo

|^ TREATED
WASTE

REACTION TANK
CHLORINATOR
REACTION TANK
FIGURE 7-25

TREATMENT OF CYANIDE WASTE BY ALKALINE CHLORI NATION
-------
for collection of waste over a specified time period, and one
tank for the treatment of an accumulated batch. If dumps of
concentrated wastes are frequent, another tank may be required
to equalize the flow to the treatment tank. When the holding
tank is full, the liquid is transferred to the reaction tank
for treatment. After treatment, the supernatant is discharged
and the sludges are collected for removal and ultimate disposal.

Application

The oxidation of cyanide waste by chlorine is a classic process
and is found in most plants using cyanide. This process is
capable of achieving efficiencies of 99 percent or greater and
effluent levels that are nondetectable. Chlorine has also
been used to oxidize phenols, but use of chlorine dioxide for
this purpose is much preferred because formation of toxic
chlorophenols is avoided.

Some advantages of chlorine oxidation for handling process
effluents are operation at ambient temperature, suitability
for automatic control, and low cost. Some disadvantages of
chlorine oxidation for treatment of process effluents are that
toxic, volatile intermediate reaction products must be con-
trolled by careful pH adjustment, chemical interference is
possible in the treatment of mixed wastes, and a potentially
hazardous situation exists when chlorine gas is stored and
handled.

Performance

Performance for cyanide oxidation was determined by evaluating
the amenable cyanide effluent data from visited plants. Amenable
cyanide was evaluated because treatment for cyanide is almost ex-
clusively performed by alkaline chlorination. This form of
treatment focuses upon oxidizing the cyanide which is amenable
to chlorination.

Amenable cyanide data from visited plants are listed in Table 7-52
The table has the following four columns:

1. ID Number - The identification number of the visited plant.
Duplicate numbers indicate different sampling days at the
same plant.

2. Effluent Concentration - The measured concentration of the
final effluent after treatment. At this point, cyanide
wastes are mixed with other wastewaters.

3. Dilution Factor - This number represents the amount of
dilution of the cyanide raw waste stream by other raw
waste streams and is determined by dividing the total
effluent stream flow by the cyanide stream flow.

4. Adjusted Cyanide Effluent Concentration - These concentra-
tions are calculated by multiplying the effluent cyanide
concentrations by the dilution factor applicable in each
individual case.

A-3
-------
The data contained in Table 7-52 were arranged in the following
manner:

1. For each plant data set (CN.) the concentrations
were listed in decending orcfer.

2. The plant data sets were listed in ascending order
using the first value in each plant data set as the
basis for ordering (the first value in each plant
data set represents the highest concentration).

Ordering the data in this fashion facilitates identification of
poorly operated treatment systems. As illustrated in the table.
a break occurs between plant 20080 and 04045. The highest con-
centration at plant 20080 is 0.416 mg/l and at plant 04045 the
highest concentration is 2.2 mg/l. Since alkaline chlorination
is capable of reducing amenable cyanide concentrations to levels
approximating zero, plants listed after plant 20080 exhibit poor
control and excessive effluent concentrations. These plants have
been deleted from the data base used to determine performance for
cyanide oxidation.

Table 7-53 presents amenable cyanide data after deletions to
remove plants with poorly operated treatment systems. The entire
plant data set (both CNA and CNT) was deleted if any cyanide
amenable concentration for that plant exceeded the breakpoint
between 0.416 mg/l and 2.2 mg/l. Plants which were deleted
from both the amenable and total cyanide data bases are listed in
Table 7-54.

Total cyanide data (after deleting the plants listed in Table
7-54) are presented in Table 7-55. These data correspond to the
amenable cyanide data remaining in the data base from which
performance is determined. In Table 7-55 two data points. 105.0
mg/l and 5.69 mg/l were deleted from the calculation of the
mean effluent concentration for total cyanide. The 105.0 mg/l
was deleted because it was a high outlier although the
corresponding cyanide amenable value did not indicate a high
level. The 5.69 mg/l was deleted as a high outlier and because
there was no corresponding cyanide amenable value. Plant data
sets which were deleted from the total cyanide data base are
listed in Table 7-56.

The edited data sets (presented in Tables 7-53 and 7-55) were
used to determine performance for cyanide oxidation. The adjusted
mean effluent concentrations from the edited data base are presented
below.
Adjusted Mean
Parameter Effluent Concentration (mg/l,)

Cyanide, Total 0.18
Cyanide, Amenable 0.06
A-4
-------
TABLE 7-52
AMENABLE CYANIDE DATA BASE
PLANT ID
12065
21051

38051
06075

36623

19050
20079

05021

20078

15070

33073

09026

CN.EFFLUENT
CONCENTRATION (mg/1)
0
0
0
0
0
0.005
0.005
0.005
0.005
0.005
0.005
0.005
0.005
0.005
0.005
0.005
0.005
0.005
0.005
0.005
0.01
0.005
0.005
0.005
0.005
0.005
0.02
0.005
0.005
0.027
0.008
0.06
0.01
0.005
DILUTION
FACTOR
10.0
1.0
1.0
1.0
19.9
5.0
4.8
5.1
4.9
4.3
6.2
7.9
6.2
6.1
5.6
5.0
4.8
8.0
4.8
4.8
6.6
7.4
7.0
6.9
5.7
5.6
3.4
2.8
2.5
5.5
5.1
2.6
2.4
3.8
ADJUSTED CN.
CONCENTRATrCN (mg/1)
0
0
0
0
0
0.025
0.024
0.025
0.024
0.021
0.031
0.039
0.031
0.030
0.028
0.025
0.024
0.04
0.024
0.024
0.066
0.037
0.035
0.034
0.029
0.028
0.068
0.014
0.012
0.147
0.041
0.156
0.024
0.021
A-5
-------
TABLE 7-52(CON'T)
AMENABLE CYANIDE DATA BASE
PLANT ID

31021

33024

20080
04045
06089
36041
06381
06085
20082
06084
CN.EFFLUENT
CONCENTRATION (mg/1)

0.05
0.05
0.05

0.04

0.104
0.005
0.005
0.005
0.005

2.2
1.0
0.25

1.14
0.285
0.163

0.4
0.1
0.1

0.751
0.089
0.096

1.08
0.56
0.06

3.0
1.08
0.945
0.625
0.056
0.034

1.97
DILUTION ADJUSTED CN
FACTOR CONCENTRATION (mg/1)

3.2 0.16
3.2 0.16
3.0 0.150

5.1 0.204
4.0
5.8
4.5
4.5
4.5
1.0
1.0
1.0
3.5
3.0
2.9
10.4
11.5
10.1
6.5
8.7
6.3
5.0
4.8
5.4
1.8
2.1
2.0
2.1
2.0
2.0
0.416
0.029
0.023
0.023
0.023
2.2
1.1
0.25
3.99
0.855
0.478
4.16
1.15
1.01
4.88
0.733
0.609
5.4
2.69
0.323
5.4
2.23
1.88
1.32
0.147
0.064
3.6
7.19
A-6
-------
TABLE 7-52(CON'T)
AMENABLE CYANIDE DATA BASE
PLANT ID
20081

11103

02033
20077

06090
20086

06037

21066

GNAEFFLUENT
CONCENTRATION (mg/1)
0.49
0.348
0.075
0.017
0.005
0.005
3.37
2.91
4.2
3.0
2.1
0.78
0.1
0.005
0.005
5.27
5.25
0.36
0.005
11.6
0.408
0.122
11.75
6.57
8.83
DILUTION
FACTOR
15.6
16.3
17.6
17.7
15.9
14.4
3.0
2.4
2.6
5.9
7.8
9.7
6.5
9.7
7.1
4.3
4.5
4.5
4.5
6.4
6.4
6.4
7.4
10.2
4.7
ADJUSTED CN
CONCENTRATION (mg/1)
7.64
5.68
1.32
0.3
0.079
0.072
10.0
6.98
11.1
17.7
16.4
7.58
0.65
0.049
0.036
22.5
23.6
1.62
0.023
73.7
2.59
0.775
86.9
66.9
41.5
A-7
-------
TABLE 7-53
DATA USED FOR AMENABLE CYANIDE PERFORMANCE
PLANT ID
12065
21051

38051
06075

36623

19050
20079

05021

20078

15070

33073

09026

CNAEFFLUENT
CONCENTRATION (mg/1)
0
0
0
0
0
0.005
0.005
0.005
0.005
0.005
0.005
0.005
0.005
0.005
0.005
0.005
0.005
0.005
0.005
0.005
0.01
0.005
0.005
0.005
0.005
0.005
0.02
0.005
0.005
0.027
0.008
0.06
0.01
0.005
DILUTION
FACTOR
10.0
1.0
1.0
1.0
19.9
5.0
4.8
5.1
4.9
4.3
6.2
7.9
6.2
6.1
5.6
5.0
4.8
8.0
4.8
4.8
6.6
7.4
7.0
6.9
5.7
5.6
3.4
2.8
2.5
5.5
5.1
2.6
2.4
3.8
ADJUSTED CN.
CONCENTRATION (mg/1)
0
0
0
0
0
0.025
0.024
0.025
0.024
0.021
0.031
0.039
0.031
0.030
0.028
0.025
0.024
0.04
0.024
0.024
0.066
0.037
0.035
0.034
0.029
0.028
0.068
0.014
0.012
0.147
0.041
0.156
0.024
0.021
-------
TABLE 7-53(CON'T)
DATA USED FOR AMENABLE CYANIDE PERFORMANCE
CN.EFFLUENT DILUTION
PLANT ID CONCENTRATION (mg/1) FACTOR

31021 0.05 3.2
0.05 3.2
0.05 3.0

33024 0.04 5.1

20080 0.104 4.0
0.005 5.8
0.005 4.5
0.005 4.5
0.005 4.5
ADJUSTED CN.
CONCENTRATION (mg/1)

0.16
0.16
0.150

0.204

0.416
0.029
0.023
0.023
0.023
A-9
-------
TABLE 7-54
PLANTS DELETED FRCM CYANIDE DATA BASE
DUE TO POOR PERFORMANCE
04045
06089
36041
06381
06085
20082
06084
20081
11103
02033
20077
06090
20086
06037
21066
A-10
-------
TABLE 7-55
DATA USED FDR TOTAL CYANIDE PERFORMANCE

PLANT ID
12065
21051

38051
06075

36623

19050
20079

05021

20078

20080

CN_, EFFLUENT
CONCENTRATION (mg/1)
0.014
0
0
0
0
0.005
0.005
0.014
0.01
0.02
0.033
0.005
0.005
0.005
0.005
0.005
0.02
21.0
0.005
0.005
0.007
0.005
0.005
0.005
0.005
0.01
0.04
0.005
0.005
0.005
0.005
0.1
0.111
1.23
DILUTION
FACTOR
10
1.0
1.0
1.0
19.9
4.8
5.0
4.8
4.3
4.9
5.1
6.2
4.8
6.1
6.2
7.9
5.6
5.0
4.8
4.8
8.0
5.6
5.7
7.0
7.4
6.9
6.6
4.5
4.5
4.5
5.8
4.1
4.0
4.6
ADJUSTED OL
CONCENTRATION (mg/1)
0.14
0
0
0
0
0.024
0.025
0.067
0.043
0.098
0.167
0.031
0.024
0.031
0.031
0.039
0.112
105.*
0.024
0.024
0.056
0.028
0.029
0.035
0.037
0.069
0.266
0.023
0.023
0.023
0.029
0.41
0.444
5.69*
* Not used in calculation of mean effluent concentration.
A-ll
-------
TABLE 7-55(CON'T)
DATA USED FOR TOTAL CYANIDE PERFORMANCE
CN_ EFFLUENT DILUTION
PLANT ID COlfcENTRATION (mg/1) FACTOR

15070 0.02 2.5
0.03 3.4
0.29 2.8

33073 0.013 5.5
0.129 5.1
0.254 5.5

09026 0.03 2.4
0.02 3.8
0.08 2.6

31021 0.16 3.2
0.16 3.2
0.35 3.1

33024 0.04 5.1
ADJUSTED CN_
CONCENTRATION (mg/1)

0.05
0.102
0.818

0.071
0.66
1.39

0.072
0.076
0.208

0.512
0.512
1.1

0.204
A-12
-------
PLANT DATA
TABLE 7-56
FROM TOTAL CYANIDE DATA BASE
PLANT ID

02033

04045

06037

06084

06085

06089

06090

06381

11103

20077
CN_ EFFLUENT
OOteENTRATION (mq/ll

10.0

6.4
8.7
15.2

0.53
0.591
12.6

0.027
0.435
2.8

0.96
0.92
1.8

0.285
0.428
2.42

2.81
6.73
10.8

0.089
0.25
0.981

10.0
9.37

0.005
1.5
2.5
3.0
2.5
2.4
DILUTION
FACTOR

2.6

1.0
1.0
1.0

6.3
6.3
6.4

2.9
4.3
3.6

4.8
5.4
5.0

2.9
3.0
3.5

4.3
4.3
4.3

8.7
6.3
6.5

2.4
3.0

7.1
9.7
6.5
5.9
7.8
9.7
ADJUSTED CN
CONCENTRATION

26.0

6.4
8.7
15.2

3.37
3.75
80.6

0.078
1.86
10.2

4.61
4.95
9.0

0.835
1.28
8.47

12.1
28.7
46.1

0.773
1.58
6.38

24.0
28.1

0.036
14.6
16.2
17.7
19.5
23.3
A-13
-------
TABLE 7-56(CON'T)
PLANT DATA DELETED FROM TOTAL CYANIDE DATA BASE
PLANT ID

20081
20082
20086
21066
36041
CN EFFLUENT DILUTION
CONCENTRATION (mg/1) FACTOR

0.035 17.7
0.023 14.4
0.068 15.9
0.911 17.6
1.16 16.3
3.82 15.6

0.034 2.0
0.635 2.1
0.722 2.0
0.945 2.0
3.09 1.8
3.31 2.1

0.73 4.5
1.13 4.5
5.25 4.5

16.38 4.7
12.15 10.2
20.65 7.4

0.25 11.5
0.4 10.1
0.6 10.4
ADJUSTED CN
CONCENTRATION (mg/1)

0.618
0.331
1.08
16.0
19.0
59.6

0.068
1,
1.
1,
5,
34
47
88
63
6.85

3.28
5.08
23.6

76.9
123.9
152.8

2.87
4.04
6.24
A-14
-------
Self-monitoring data for total cyanide and amenable cyanide are
shown in Table 7-57. For each plant, this table shows the number
of data points, the mean effluent concentration, and the
calculated variability factors plus the total number of points.
the overall mean effluent concentration, and the median.
variability factors.

CNT CNA

Mean Effluent Concentration (rag/1) 0.18 0.06
Variability Factors (Daily/10-day) 6.68/3.61 14.31/5.31
Daily Maximum Concentration (rag/I) 1.20 0.86
Maximum Monthly Average Concentration (mg/t) 0.65 0.32

The percent of plants with cyanide levels below the cyanide daily
maximum effluent concentration limitations are as follows:

EPA Sampled Plants Self-Monitoring Self-Monitoring
Parameter Daily Maximum Data Daily Max. Data 10-Day Ave.

Cyanide. Total 97.8 79.2 62.9
Cyanide. Amenable 100.0 92.8 78

The percent compliance for the self-monitoring data for the
cyanide total daily maximum and for the cyanide total and cyanide
amenable 10-day averages is relatively low compared to the EPA
samples plants. When examining the EPA sampled data, the Agency
excluded numerous plants that had high cyanide levels after
correcting for dilution. Apparently many plants are relying on
dilution of treated cyanide wastes rather than performing
alkaline chlprination to its capability. Self-monitoring data
are insufficient to examine the adequacy of the treatment system
because both cyanide amenable and cyanide total results are
generally not available for the same plants. Two plants have
both cyanide amenable and cyanide total values; however, the
cyanide amenable results are indicative of inadequate treatment.
This appears to indicate that there is a need for additional
control of cyanide by many of the plants that submitted
self-monitoring data. This is illustrated in Table 7-58 which
shows the adjusted mean and maximum concentrations for cyanide
total and cyanide amenable for plants with self- monitoring data
for which dilution factors were available.

Demonstration Status

The oxidation of cyanide wastes by chlorine is a widely used
process in plants using cyanide in cleaning and plating baths.
There has been recent attention to developing chlorine dioxide
generators and bromine chloride generators. A problem that
has been encountered is that the generators produce not only
the bromine chloride and chlorine dioxide gas, but chlorine
gas is also formed simultaneously. Both of these gases are
extremely unstable, corrosive, and have low vapor pressure,
which results in handling difficulties. These generators are
in the development stages and as advances are made in their
design, they may become competitive with chlorine.

Oxidation by chlorine is used in 206 plants in the present
data base, and these are identified in Table 7-59.

A-15
-------
TABLE 7-57

EFFLUENT TOTAL CYANIDE SELF-MONITORING PERFORMANCE DATA
FOR PLANTS WITH OPTION 1 SYSTEMS
Plant ID

1067
3043
6051
6107
11008
11125
15193
20080
20082
31021
36082
44045
47025

OVERALL
Number
OF Points

230
89
L3
10
179
54
12
268
246
119
121
50
138
Mean Effluent
Concentration
0.041
0.154
0.07
2.20
0.09
1.21
0.053
0.001
0.132
0.533
0.043
0.008
0.057
Variability Factor
Daily 10-Day
1.92
10.02

25.01
6.10
3.64
3.23

7.25
11.16
4.23

7.92
1.46
4.75
4.15
1.35
3.68

3.55
7.67
3.33
7.68
2.57
1529(Total) 0.156(Mean) 6.68(Median) 3.61(Median)
EFFLUENT AMENABLE CYANIDE SELF-MONITORING PERFORMANCE DATA
FOR PLANTS WITH OPTION 1 SYSTEMS
Plant ID

31021
38223
47025

OVERALL
Number
OF Points

28
235
243
Mean Effluent
Concentration
(mq/U

0.196
0.0004
0.007
Variability Factor
Daily 10-Day
14.32
,18
,31
,77
529(Total) 0.016(Mean) 14.31(Median) 5.31(Median)
A-16
-------
TABLE 7-58

ADJUSTED EFFLUENT TOTAL CYANIDE SELF-MONITORING DATA
Plant ID

3043
11008
11125
15193
20080
20082
31021
36082
44045
47025
Number
OF Points

89
179
54
12
268
246
119
121
50
138
Adjusted
CN,T Mean
Concentration
(ma/n

0.57
0.35
10.11
1.75
0.01
0.66
1.48
0.21
0.83
2.26
LIMITATION COMPARISON
0.18 (EPA Sample
Data Mean)
Adjusted
CN,T Maximum
Daily Concentration
(ma/t)
3.11
8.40
33.32
5.33
0.46
7.0
15.29
5.0
15.0
12.32

1.20 (Daily Max.)
ADJUSTED EFFLUENT AMENABLE CYANIDE SELF-MONITORING DATA
plant ID

31021
38223
47025
Number
OF Points

28
235
243
Adjusted
CN,T Mean
Concentration
(mg/t)

0.54
0.06
0.28
LIMITATION COMPARISON
0.06 (EPA Sample
Data Mean)
Adjusted
CN,T Maximum
Daily Concentration
(ma/ft)
3.89
1.43
6.80

0.86 (Daily Max.)
A-17
-------
TABLE 7-59
METAL FINISHING PLANTS EMPLOYING CYANIDE OXIDATION
••' 007
„• *• V v
11067
J L W ^
j!068
02033
.12037
20240
03042
03043
04045
04076
04114
04178
04199
04124
04227
04236
04263
04277
04279
04182
05021
05029
05033
06002
06006
06037
06050
06051
06052
06053
06002
06072
06073
06075
06079
06078
06079
06081
06084
06085
06087
06089
06090
06094
06101
06107
06111
06113
06115
06119
06120
06122
06124
06129
06141
06146
06147
06152
06358
06360
06381
06679
08004
08008
08074
09026
09060
10020
11008
11096
11098
11103
11125
11118
11174
11177
11184
12005
12065
12078
12087
12709
13033
13034
13039
13040
15042
15045
15047
15048
15070
15193
16033
16035
18050
18055
18534
19050
19051
19063
19069
19084
19090
19099
19102
19104
20001
20005
20017
20073
20077
20078
20079
20080
20081
20082
20084
20086
20087
20158
20162
20172
20243
20708
21003
21062
21066
21074
21078
22028
22656
23039
23059
23061
23074
23076
23337
25001
25030
25031
27044
27046
28082
28105
30011
30022
30090
30096
30097
30109
30111
30162
30967
31021
31037
31040
31047
31070
33024
33043
33065
33070
33071
33073
33113
33120
33137
33146
33184
33187
33275
34041
34042
35061
35963
36036
36040
36041
36082
36083
36084
36090
36091
36102
36112
36113
36151
36154
36156
36623
37042
38031
38038
38051
38223
40037
40047
41116
42830
43052
44037
44040
44045
45035
47005
47025
A-18
-------
ALTERNATIVE CYANIDE TREATMENT TECHNIQUES

Alternative treatment techniques for the destruction of cyanide
include oxidation by ozone, ozone with ultraviolet radiation
(oxyphotolysis), hydrogen peroxide and electrolytic oxidation.
These techniques are presented in the following paragraphs.

Oxidation By_ Ozonation

Ozone may be produced by several methods, but the silent
electrical discharge method is predominant in the field. The
silent electrical discharge process produces ozone by passing
oxygen or.air between electrodes separated by an insulating
material. The electrodes are usually stainless steel or
aluminum. The dielectric or insulating material is usually
glass. The gap or air space between electrodes or dielectrics
must be uniform and is usually on the order of 0.100 to 0.125
inches. The voltage applied is 20,000 volts or more, and a
single phase current is applied to the high tension electrode.

Ozone is approximately ten times more soluble than oxygen on a
weight basis in water, although the amount that can be effi-
ciently dissolved is still slight. Ozone's solubility is
proportional to its partial pressure and also depends on the
total pressure on the system. It should be noted, however,
that it is the oxidizable contaminant in the water that deter-
mines the quantity of ozone needed to oxidize the contaminants
present. A complete ozonation system is represented in Figure
7-26.

Thorough distribution of ozone in the water under treatment is
extremely important for high efficiency of the process. There
are four methods of mixing ozone with water; these ares (1)
diffusers, (2) negative or positive pressure injection, (3) packed
columns whereby ozone-containing air or oxygen is distributed
throughout the water, and (4) atomizing the aqueous solution into
a gaseous atmosphere containing ozone.

Application

Ozonation has been applied commercially for oxidation of
cyanides, phenolic chemicals, and organo-metal complexes. It
is used commercially with good results to treat photoprocessing
wastewaters. Divalent iron hexacyanato complexes (spent bleach)
are oxidized to the trivalent form with ozone and reused for
bleaching purposes. Ozone is used to oxidize cyanides in other
industrial wastewaters and to oxidize phenols and dyes to a
variety of colorless, nontoxic products.
A-19
-------
CONTROLS
OZONE
GENERATOR
ORV AIR
OZONE
REACTION
TANK
RAW WASTE .
TREATED
WASTE
FIGURE 7-26

TYPICAL OZONATION PLANT FOR WASTE TREATMENT
A-20
-------
Oxidation of cyanide to cyanate is illustrated below:

CN"1 + 03 = CNO"1 + 02

Continued exposure to ozone will convert the cyanate formed to
carbon dioxide and ammonia if the reaction is allowed to
proceed;•however, this is not economically practical, and
cyanate can be economically decomposed by biological oxidation
at neutral pH.

Ozone oxidation of cyanide to cyanate requires 1.8 to 2.0
pounds of ozone per pound of CN~ and complete oxidation requires
4.6 to 5.0 pounds of ozone per pound of CN". Zinc, copper,
and nickel cyanides are easily destroyed to a nondetectable
level, but cobalt cyanide is resistant to ozone treatment.

The first commercial plant using ozone in the treatment of
cyanide waste was installed by a manufacturer of aircraft.
This plant is capable of generating 54.4 Kg (120 pounds) of
ozone per day. The concentration of ozone used in the treatment
is approximately 20 mg/1. In this process the cyanate is
hydrolyzed to CO2 and NH,. The final effluent from this
process passes into a lagoon. Because of an increase in waste
flow the original installation has been expanded to produce
162.3 Kg (360 pounds) of ozone per day.

Some advantages of ozone oxidation for handling process effluents
are that it is well suited to automatic control, on-site,
generation eliminates treatment chemical procurement and
storage problems, reaction products are not chlorinated organics,
and no dissolved solids are added in the treatment step.
Ozone in the presence of ultraviolet radiation or other pro-
moters such as hydrogen peroxide and ultrasound shows promise
of reducing reaction time and improving ozone utilization.
Some limitations of the process are high capital expense, possible
chemical interference in the treatment of mixed wastes,, and
an energy requirement of 15 to 22 kwh per kilogram of ozone
generated. Cyanide is not economically oxidized beyond the
cyanate form.

Performance

An electroplating plant (ID 30022) that serves the electronics
industry plates gold, silver, copper, and nickel. Ozone was
selected for treatment of cyanide bearing waste, and the
results were as follows:

A. Optimum operating conditions were determined to be 1 to
1.5 moles of ozone/mole CN at a pH of 9.0-9.5 in the
ozone contactor.

B. It was established that ozone dosage is the most criti-
cal operating parameter, with 1.0 to 1.5 moles 03/mole
CN found to be optimum at low CN concentrations (20 mg/1)
and 1.8 to 2.8 moles 0^/mole CN at levels greater than
40 mg/1. J

A-21
-------
C. Cost data based on plant experience were obtained.
Treatment operating cost was $1.43/100 gallons of
influent cyanide bearing waste water and $1.03/1000
gallons total waste water. Total capital costs were
$66,613 for this installation but are estimated at
$51,200 for an optimized, non-research installation.

D. The results of three days of sampling are shown below:
Parameter

Cyanide, Total
Cyanide, Amenable

Demonstration Status
PLANT ID 30022 (ing/I)

Day 1 Day 2

In Out In Out
Day 3

In Out
1.4
1.4
.113
.110
.30
.30
.039
.039
2.4
2.389
,096
.096
Ozone is useful for application to cyanide destruction. There
are at least two units presently in operation in the country
(Plant ID'S 14062 and 30022), and additional units are planned.
There are numerous orders for industrial ozonation cyanide
treatment systems pending.

Ozone is useful in the destruction of wastewaters containing
phenolic materials, and there are several installations in
operation in the United States.

Research and development activities within the photographic
industry have established that ozone is capable of treating
some compounds that are produced as waste products. Solutions
of key ingredients in photographic products were composed and
treated with ozone under laboratory conditions to determine
the treatability of these solutions. It was found that some
of these solutions were oxidized almost completely by ozona-
tion and some were oxidized that were difficult to treat by
conventional methods. Ozone breaks down certain developer
components that biodegrade slowly, including color developing
agents, pheniodone, and hydroxylamine sulfate. Developing
agents, thiocyanate ions, and formate ions degrade more com-
pletely with ozone than when exposed to biological degradation.
Thiosulfate, sulfite, formalin, benzyl alcohol, hydroquinone,
maleic acid, and ethylene glycol can be degraded to a more or
less equal degree with either biological treatment or ozone.
Silver thiosulfate complexes were also treated with ozone
resulting in significant recovery of the silver present in
solution. Ozone for regeneration of iron cyanide photoprocessing
bleach and treatment of thiosulfate, hydroquinone, and other
chemicals is currently being utilized by the photoprocessing
industry. There are 40 to 50 installations of this nature
in use at the present time.
A-22
-------
Oxidation By^ Ozonation With UV Radiation

One of the modifications of the ozonation process is the
simultaneous application of ultraviolet light and ozone for
the treatment of wastewater, including treatment of halo-
genated organics. The combined action of these two forms
produces reactions by photolysis, photosensitization, hydroxyla-
tion, oxygenation and oxidation. The process is unique because
several reactions and reaction species are active simultaneously.

Ozonation is facilitated by ultraviolet absorption because
both the ozone and the reactant molecules are raised to a
higher energy state so that they react more rapidly. The energy
and reaction intermediates created by the introduction of
both ultraviolet radiation and ozone greatly reduce the amount
of ozone required compared with a system that utilizes ozone
alone to achieve the same level of treament. Figure 7-27 shows
a three-stage UV/ozone system.

A typical process configuration employs three single stage
reactors. Each reactor is a closed system which is illuminated
with ultraviolet lamps placed in the reactors, and the ozone
gas is sparged into the solution from the bottom of the tank.
The ozone dosage rate requires 2.6 pounds of ozone per pound
of chlorinated aromatic. The ultraviolet power is on the
order of five watts of useful ultraviolet light per gallon of
reactor volume. Operation of the system is at ambient tempera-
ture and the residence time per reaction stage is about 24
minutes. Thorough mixing is necessary and the requirement for
this particular system is 20 horsepower per 1000 gallons of
reactor volume in quadrant baffled reaction stages. A system
to treat mixed cyanides requires pretreatment that involves
chemical coagulation, sedimentation, clarification, equalization,
and pH adjustment. Pretreatment is followed by a single stage
reactor, where constituents with low refractory indices are
oxidized. This may be followed by a second, multi-stage reactor
which handles constituents with higher refractory indices.
Staging in this manner reduces the ultimate reactor volume
required for efficient treatment.

Application

The ozonation/UV radiation process was developed primarily for
cyanide treatment in the metal finishing and color photo-
processing areas, and it has been successfully applied to
mixed cyanides and organics from organic chemicals manufactur-
ing processes. The process is particularly useful for treatment
of complexed cyanides such as ferricyanide, copper cyanide and
nickel cyanide, which are resistant to ozone alone, but readily
oxidized by ozone with UV radiation.
A-23
-------
MIXER,

WASTEWATER
FEED
TANK

1
F
S1
SE
ST
T
S
1

„
in
h
I
RST O
'AGE 3
>
3
V.

(A
h
:OND 5
XGE 3
>
3
m
H
HIRD (j
TAGE j
>
3

HH L
PUMP
TREATED WATER
S

u,
r _ EXHAUST

c
n
1

a
u_

1
1 1

™
^m

GAS

TEMPERATURE
CONTROL
PH MONITORING

— TEMPERATURE
— CONTROL
— PH MONITORING

TEMPERATURE
— CONTROL
— PH MONITORING

OZONE

OZONE
GENERATOR
FIGURE 7-27

UV/OZONATION

A-24
-------
Performance

For mixed metal cyanide wastes, consistent reduction in total
cyanide concentration to less than 0.1 mg/1 is claimed.
Metals are converted to oxides, and halogenated organics are
destroyed. TOC and COD concentrations are reduced to less
than 1 mg/1.

Demonstration Status

A full scale unit to treat metal complexed cyanides has been
installed in Oklahoma, while a large American chemical company
in France has installed an on-line unit for the treatment of
cyanides and organics and a similar design is scheduled for
installation by the same company in the United States. There
are also two other units known to be in service, one for
treating mixed cyanides and the other for treatment -of copper
cyanide.

Oxidation By_ Hydrogen Peroxide

The hydrogen peroxide oxidation treatment process treats both
the cyanide and metals in cyanide wastewaters containing zinc
or cadmium. In this process, cyanide rinse waters are heated
to 49-54°C (120-130°) to break the cyanide complex, and the pH
is adjusted to 10.5-11.8. Formalin (37% formaldehyde) is
added, while the tank is vigorously agitated. After 2-5
minutes, a proprietary formulation (41% hydrogen peroxide
with a catalyst and additives) is likewise added. After an
hour of mixing, the reaction is complete. The cyanide is
converted to cyanate and the metals are precipitated as
oxides or hydroxides. The metals are then removed from
solution by either settling or filtration.

The chemical reactions which take place are as follows:

CN + HCHO + H20 = HOCH2CN + OH*

The hydrogen peroxide converts cyanide to cyanate in a single
step:

CN + H202 = NCO + H20

The formaldehyde also acts as a reducer, combining with the
cyanide ions:

Zn(CN)4~2 + 4 HCHO + 4H20 = 4 HOCH2CN + 4 OH" + Zn+2

The metals subsequently react with the hydroxyl ions formed
and precipitate as hydroxides or oxides:

Zn+2 + 2 OH" = ZnO + H.,0

The main pieces of equipment required for this process are two
holding tanks. These tanks must be equipped with heaters and

A-25
-------
air spargers or mechanical stirrers. These tanks may be used
in a batch or continuous fashion with one tank being used for
treatment while the other is being filled. A settling tank or
a filter is needed to concentrate the precipitate.

Application

The hydrogen peroxide oxidation process is applicable to
cyanide bearing wastewaters, especially those from cyanide
zinc and cyanide cadmium electroplating. The process has been
used on photographic wastes to recover silver and oxidize
toxic compounds such as cyanides, phenols and "hypo" (sodium
thiosulfate pentahydrate). Additions of hydrogen peroxide are
made regularly at a large wastewater treatment plant to control
odors and minimize pipe corrosion by oxidizing hydrogen sulfide,

Chemical costs are similar to those for alkaline chlorination
and lower than those for treatment with hypochlorite, and all
free cyanide reacts and is completely oxidized to the less
toxic cyanate state. In addition, metals precipitate and
settle quickly, and they are recoverable in many instances.
However, the process requires energy expenditures to heat the
wastewater prior to treatment. Furthermore, the addition of
formaldehyde results in treated wastewater having relatively
high BOD values. Although cyanates are much less toxic than
cyanide, there is not complete acceptance of the harmlessness
of cyanates.

Performance

In terms of waste reduction performance, this process is
capable of reducing the cyanide level to less than 0.1 mg/1
and the zinc or cadmium to less than 1.0 mg/1.

Demonstration Status

This treatment process was introduced in 1971 and is being
used in several facilities.

Peroxide oxidation is used in three plants in the present data
base: 08061, 21058, and 30009.

Electrochemical Cyanide Oxidation

Electrochemical cyanide oxidation is used to reduce free
cyanide and cyanate levels in industrial wastewaters. In this
process, wastewater is accumulated in a storage tank and then
pumped to a reactor where an applied DC potential oxidizes the
cyanide to nitrogen, carbon dioxide and trace amounts of
ammonia. The gases generated are vented to the atmosphere.
The oxidation reaction is accomplished if concentrations are
not greater than 1000 mg/1. If reaction time is critical, the
process can be accelerated by augmenting the system with a
chemical (hypochlorite) treatment as long as the cyanide

A-26
-------
concentration level is less than 200 mg/1. The process equip-
ment consists of a reactor, a power supply, a storage tank and
a pump.

Another electrochemical oxidation system employs a low voltage
anode with a metallic oxide coating. Upon application of an
electrical potential several oxidation reactions occur at the
anode. These reactions include the oxidation of chloride (from
common salt) to chlorine or hypochlorite and the formation of
ozone, as well as direct oxidation at the anode. Although
untested on cyanide-bearing wastewaters, this system shows
good potential in that area.

Application

The electrochemical cyanide oxidation system has been used
commercially only for heat treating applications; however, it
should be equally appropriate for other cyanide bearing wastes.
Its application for plating and photographic process wastewaters
is still in the development stage. The process can also be
applied to the electrochemical oxidation of nitrite to nitrate.

Electrochemical cyanide oxidation has the advantage of low
operating costs with moderate capital investment, relative to
alternative processes. There is no requirement for chemicals,
thereby eliminating both their storage and control, and there
is no need to dilute or pretreat the wastewater as the process
is most efficient at high cyanide concentration levels.
However, the process is less efficient than chemical destruc-
tion at cyanide concentrations less than 100 mg/1, and it is
relatively slow when not accelerated by addition of treatment
chemicals. Moreover, it will not work well in the presence of
sulfates.

Performance

Performance has been demonstrated on a commercial scale and
shown to result in a reduction in the cyanide concentration
level from 3500 mg/1 to less than 1.0 mg/1 in 160 hours. The
process emits no noticeable odor with adequate ventilation.

Demonstration Status

There is currently a unit in operation which is handling the
cyanide bearing wastewater generated by a heat treating opera-
tion. The manufacturer claims that there is a potential for
future use of the process in both the electroplating and
photographic industries. However, despite a variety of experi-
mental programs, industry has not been enthusiastic about the
electrolytic approach to cyanide oxidation.

Electrochemical cyanide oxidation is used at plants 04224,
18534, 19002, and 30080.

A-27
-------
Chemical Precipitation

Chemical precipitation is a classic waste treatment process
for metals removal as described under the "Treatment of Common
Metal Wastes" heading. The precipitation of cyanide can be
accomplished by treatment with ferrous sulfate. This preci-
pitates the cyanide as a ferrocyanide, which can be removed in
a subsequent sedimentation step. Waste streams with a total
cyanide content of 2 mg/1 or above have an expected waste
reduction of 1.5 to 2'orders of magnitude. These expectations
are substantiated by the following results from plant 01057:

CONCENTRATION OF TOTAL CYANIDE (mg/1)

Raw Waste Final Effluent

2.57 0.024
2.42 0.015
3.28 0.032

Evaporation

Evaporation is another recovery alternative applicable to
cyanide process baths such as copper cyanide, zinc cyanide,
and cadmium cyanide and was described in detail for common
metals removal.
A-28
-------