FINAL
AMENDMENT TO
FINAL BEST DEMONSTRATED AVAILABLE TECHNOLOGY (BOAT)
BACKGROUND DOCUMENT
FOR
ORGANOPHOSPHORUS WASTES
(K036 NONWASTEWATERS)
Richard Kinch
Acting Chief, Waste Treatment Branch
Mary Cunningham
Project Manager
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Solid Waste
401 M Street, S.W.
Washington, D.C. 20460
May 1990
-------
TABLE OF CONTENTS
Page
1.0 INTRODUCTION 1 -1
2.0 AMENDMENT TO SECTION 3 ("APPLICABLE/DEMONSTRATED TREATMENT 2-1
TECHNOLOGIES") OF THE FINAL BACKGROUND DOCUMENT FOR ORGANO-
PHOSPHORUS WASTES (K036)
2.1 Applicable Treatment Technologies 2-1
2.2 Demonstrated Treatment Technologies (Incineration) 2-1
3.0 AMENDMENT TO SECTION 4 ("PERFORMANCE DATA BASE") OF THE FINAL 3-1
BACKGROUND DOCUMENT FOR ORGANOPHOSPHORUS WASTES (K036)
4.0 AMENDMENT TO SECTION 5.1 ("IDENTIFICATION OF BEST DEMONSTRATED 4-1
AVAILABLE TECHNOLOGY FOR K036 NONWASTEWATER") OF THE FINAL
BACKGROUND DOCUMENT FOR ORGANOPHOSPHORUS WASTES (K036)
5.0 AMENDMENT TO SECTION 7 ("DEVELOPMENT OF BOAT TREATMENT STAN- 6-1
DARDS") OF THE FINAL BACKGROUND DOCUMENT FOR ORGANOPHOSPHORUS
WASTES (K036)
6.0 ACKNOWLEDGEMENTS 7 -1
7.0 REFERENCES 8 -1
- i -
-------
LIST OF TABLES
Table No. Title Page
1-1 Proposed BOAT Treatment Standards for K036 1-4
3-1 Rotary Kiln Incineration: EPA-Collected Data 3-3
Sample Set #1
3-2 Rotary Kiln Incineration: EPA-Collected Data 3-4
Sample Set #2
3-3 Rotary Kiln Incineration: EPA-Collected Data 3-5
Sample Set #3
3-4 Rotary Kiln Incineration: EPA-Collected Data 3-6
Sample Set #4
3-5 Rotary Kiln Incineration: EPA-Collected Data 3-7
Sample Set #5
3-6 Rotary Kiln Incineration: EPA-Collected Data 3-8
Sample Set #6
ii
-------
LIST OF FIGURES
Figure No. Title Page
2-1 Liquid Injection Incinerator 2-6
2-2 Rotary Kiln Incinerator 2-7
2-3 Fluidized Bed Incinerator 2-8
2-4 Fixed Hearth Incinerator 2-9
iii
-------
1.0 INTRODUCTION
The United States Environmental Protection Agency (EPA or Agency)
is amending the "Final Best Demonstrated Available Technology (BOAT) Background
Document for Organophosphorus Wastes" (Reference 1) and promulgating as proposed,
revised treatment standards for nonwastewater forms of the listed organophos-
phorus waste stream, K036, promulgated on August 8, 1988 as part of the land
disposal restrictions for the "First Third" list of hazardous wastes.1 No
comments were received on the proposed K036 nonwastewater treatment standards
(see 54 FR 48454, November 22, 1989). K036 is listed in Title 40, Code of
Federal Regulations, Section 261.32 (40 CFR 261.32) as "still bottoms from
toluene reclamation distillation, in the production of disulfoton." The previous
standard of "No Land Disposal" ^as based on an assumption of "No Generation" for
K036 nonwastewaters (Reference 1). Because information received subsequent to
i
promulgation of the standard indicates that K036 indeed may be generated, EPA
is now promulgating numerical standards for nonwastewater forms of K036.2 BOAT
treatment standards for K036 nonwastewaters will be effective no later than May
8, 1990, as part of the "Third Third" rulemaking. On and after the effective
date, compliance with BOAT treatment standards is required under 40 CFR Part 268
for placement of K036 in land disposal units.
These standards were originally promulgated in accordance with the amendments to the Resource Conserva-
tion and Recovery Act (RCRA) of 1976, under the Hazardous and Solid Waste Amendments (HSVIA) of November 8, 1984.
With this authority, the EPA established best demonstrated available technology (BOAT) treatment standards for
the wastes identified in Title 40, Code of Federal Regulations. Section 261.32 (40 CRF 261.32) as K036.
Compliance with these BOAT treatment standards is a prerequisite under 40 CFR Part 268 for placement of K036
in land disposal units.
For wastewater forms of K036, a treatment standard of 0.02S mg/l for disulfoton is based on biological
treatment. This numerical standard was developed from treatment performance data transferred from wastestreams
containing the similar organophosphorous compound, parathion (Reference 1). The Agency is not revising the
treatment standard for K036 wastewater.
1-1
-------
This amendment to the background document for organophosphorus wastes
provides the Agency's rationale and technical support for selecting the regulated
constituent, disulfoton, and for developing the treatment standard for this
constituent.
The numerical standard for nonwastewater forms of K036 is based on
treatment performance data for incineration of K037, presented in the "Final Best
Demonstrated Available Technology (BDAT) Background Document for K037" (Reference
2). K037 is listed in 40 CFR 261.32 as "wastewater treatment sludges from the
production of disulfoton" and its primary constituents are disulfoton, an organo-
phosphorus insecticide, and toluene. Because of the similar origins and composi-
tion of K037 and K036, treatment performance data are being transferred from
incineration of K037 to K036 nonwastewaters for the purpose of developing BDAT
treatment standards. Incineration treatment data for K037 are presented in
Section 3 of this document and indicate substantial treatment of the K037
nonwastewater constituent, disulfoton.
The Agency's legal authority and promulgated methodology for estab-
lishing treatment standards and the petition process necessary for requesting
a variance from the treatment standards are summarized in EPA's Methodology for
Developing BDAT Treatment Standards (Reference 3).
This amendment to the Final Best Demonstrated Available Technology
(BDAT) Backeround Document for Organophosphorus Wastes presents: 1) a discussion
of incineration as an additional applicable and demonstrated technology for
treating disulfoton, the proposed constituent of concern in K036 nonwastewaters,
2) EPA's determination of incineration as the best demonstrated available tech-
nology for K036 nonwastewaters, and 3) EPA's rationale for transferring treatment
performance data from incineration of K037 to K036 nonwastewater streams. More
1-2
-------
specifically, Section 2 of this document amends Section 3 of the Final SPAT
Background Document for Oreanophosphorus Wastes by adding incineration as an
applicable and demonstrated technology for treating nonwastewater forms of K036.
Section 3 of this document amends Section 4 of the Final BOAT Background Document
for Organophosphorus Wastes by adding treatment performance data for incinera-
tion of K037 to develop treatment standards for K036 nonwastewaters. Section
4 amends Section 5.1, identifying incineration as BOAT for K036 nonwastewaters.
Finally, Section 6 amends Section 7, presenting numerical standards for disulfo-
ton based on treatment performance data for incineration transferred from K037
to K036 nonwastewaters.
To determine the applicability of a treatment standard, wastewaters
are defined as wastes containing less than 1% (weight basis) total suspended
solids3 (TSS) and less than 1% (weight basis) total organic carbon (TOC). Wastes
not meeting this definition are classified as nonwastewaters and must comply with
nonwastewater treatment standards. The numerical treatment standard for disulfo-
ton in K036 nonwastewater is shown in Table 1-1. This treatment standard is
based on the total concentration of disulfoton in the waste for any single grab
sample. The units used for the constituent concentration are mg/kg (parts per
million on a weight-by-weight basis).
The term "total suspended solids" (TSS) clarifies EPA's previously used terminology of "total solids"
and "filterable solids." Specifically, total suspended solids are measured by Method 209C (total suspended
solids dried at 103-105°C) in Standard Methods for the Examination of Water and Wastewater. Sixteenth Edition
(Reference 4).
1-3
-------
TABLE 1-1
BOAT TREATMENT STANDARDS FOR K036
NONWASTEWATERS
(REVISED FROM NO LAND DISPOSAL)
Maximum for Any
Single Grab Sample
BOAT
No.
195
Regulated
Constituent
Disulfoton
Total Concentration
(mg/kg)
0.10
1-4
-------
2.0 AMENDMENT TO SECTION 3 ("APPLICABLE/DEMONSTRATED TREATMENT TECHNOLO-
GIES") OF THE FINAL BACKGROUND DOCUMENT FOR ORGANOPHOSPHORUS WASTES
(K036)
This section discusses incineration as an applicable and demonstrated
technology for the treatment of K036 nonwastewaters. Other technologies already
identified as applicable and demonstrated are discussed in the Organophosphorus
Wastes Background Document (Reference 1). These technologies (for wastewater
forms of organophosphorus wastes) are biological treatment and carbon absorption.
They are not discussed further here.
2.1 Applicable Treatment Technologies
In addition to those technologies already described in the BOAT
Background Document for Organophosphorus Wastes (including K036), the Agency has
identified incineration as an applicable treatment technology for K036 nonwaste-
waters (Reference 1). Incineration destroys organic constituents present in
untreated wastes with high filterable solids. Because K036 nonwastewaters
contain high concentrations of organics and filterable solids, incineration is
applicable for treatment of these wastes. The selection of the treatment
technologies applicable for treating BOAT list organic constituents in K036
nonwastewaters is based on data submitted by industry, current literature
sources, and field testing.
2.2 Demonstrated Treatment Technologies
Incineration is considered to be demonstrated for treatment of K036
nonwastewaters or similar wastes (i.e., high organic content, low water content,
and high filterable solids content). Of the various types of incineration, EPA
believes fluidized bed incineration is demonstrated for K036 nonwastewaters
because it has been used to treat wastes with similar characteristics. The
2-1
-------
Agency knows of at least one facility using fluidized bed incineration for
treatment of wastes similar to K036 nonwastewaters. However, EPA is not aware
of any generator or TSD facility currently using this technology for treatment
of wastes containing K036.
The Agency believes that rotary kiln incineration is also demon-
strated to treat K036 nonwastewaters since it has been shown to effectively treat
wastes that are similar in parameters affecting treatment selection, including
low water content, high organic content, and high solids concentration. EPA
tested rotary kiln incineration to demonstrate treatment of the closely related
wastestream, K037. K037 is defined as "wastewater treatment sludges from the
production of disulfoton" (40 CFR 261.32). K036 and K037 both are derived from
the production of disulfoton and contain this organophosphorus compound as their
primary constituent. The Agency conducted a rotory kiln incineration test on
K037 and treatment performance data collected by EPA from this test are presented
and discussed more fully in Section 3.
The remainder of this section provides information regarding the
applicability of incineration technologies, the underlying principles of opera-
tion, a technology description, waste characteristics that affect performance,
and finally, important design and operating parameters. As appropriate, the
subsections are divided by type of incineration unit.
2.2.1 Applicability and use of this technology
Liquid Injection - Liquid injection is applicable to wastes that have
viscosity values low enough that the waste can be atomized in the combustion
chamber. A range of maximum viscosity values are reported in the scientific
literature, with the lowest being 100 Seybolt Univeral Seconds (SUS) (@100°F) and
the highest being 10,000 SUS. It is important to note that viscosity is temper-
2-2
-------
ature dependent so that while liquid injection may not be applicable to a waste
at ambient conditions, it may be applicable when the waste is heated. Other
factors that affect the use of liquid injection are particle size and the
presence of suspended solids. Both of these waste parameters can cause plugging
of the burner nozzle.
Rotarv kiln/fluidized bed/fixed hearth - These incineration technologies
are applicable to a wide range of hazardous wastes. They can be used on wastes
that contain high or low total organic content, high or low suspended solids,
various viscosity ranges, and a range of other waste parameters. EPA has not
found these technologies to be demonstrated on wastes that are composed essen-
tially of metals with low organic concentrations. In addition, the Agency
expects that some of the high metal content wastes may not be compatible with
existing and future air emission limits without emission controls far more
extensive than currently practiced.
2.2.2 Underlying principles of operation
Liquid injection - The basic operating principle of this incinera-
tion technology is that incoming liquid wastes are volatilized and then addition-
al heat is supplied to the waste to destabilize the chemical bonds. Once the
chemical bonds are broken, these constituents react with oxygen to form carbon
dioxide and water vapor. The energy needed to destabilize the bonds is referred
to as the energy of activation.
Rotary kiln and fixed hearth - There are two distinct principles
of operation for these incineration technologies, one for each of the chambers
involved. In the primary chamber, energy in the form of heat is transferred to
the waste to achieve volatilization of the various organic waste constituents.
During this volatilization process, some of the organic constituents will oxidize
2-3
-------
to carbon dioxide and water vapor. In the secondary chamber, additional heat
is supplied to overcome the energy requirements needed to destabilize the
chemical bonds and allow the constituents to react with excess oxygen to form
carbon dioxide and water vapor. The principle of operation for the secondary
chamber is similar to that of liquid injection.
Fluidized bed - The principle of operation for this incineration
technology is somewhat different from that for rotary kiln and fixed hearth
incineration in that the fluidized bed incinerator contains fluidizing sand and
a freeboard section above the sand. The purpose of the fluidized bed is to both
volatilize the waste and combust the waste. Destruction of the waste organics
can be accomplished to a better degree in the primary chamber of a fluidized bed
incinerator than that of a rotary kiln or fixed hearth incinerator because of;
1) improved heat transfer from fluidization of the waste using forced air and,
2) the fact that the fluidization process provides sufficient oxygen and turbu-
lence to convert the organics to carbon dioxide and water vapor. The freeboard
generally does not have an afterburner; however, additional time is provided for
conversion of the organic constituents to carbon dioxide, water vapor, and
hydrochloric acid if chlorine is present in the waste.
2.2.3 Description of incineration technologies
Liquid injection - The liquid injection system is capable of
incinerating a wide range of gases and liquids. The combustion system has a
simple design with virtually no moving parts. A burner or nozzle atomizes the
liquid wastes and injects it into the combustion chamber where it burns in the
presence of air or oxygen. A forced draft system supplies the combustion chamber
with air to provide oxygen for combustion and turbulence for mixing. The
combustion chamber is usually a cylinder lined with refractory (i.e., heat
2-4
-------
resistant) brick and can be fired horizontally, vertically upward, or vertically
downward. Figure 2-1 illustrates a liquid injection incineration system.
Rotary kiln - A rotary kiln is a slowly rotating, refractory lined
cylinder that is mounted at a slight incline from the horizontal (see Figure 2-
2). Solid wastes enter at the high end of the kiln, and liquid or gaseous wastes
enter through atomizing nozzles in the kiln or after burner section. Rotation
of the kiln exposes the solids to the heat, vaporizes them, and allows them to
combust by mixing with air. The rotation also causes the ash to move to the
lower end of the kiln where it can be removed. Rotary kiln systems usually have
a secondary combustion chamber or afterburner following the kiln for further
combustion of the volatilized components of solid wastes.
Fluidized bed - A fluidized bed incinerator consists of a column
containing inert particles such as sand, which is referred to as the bed. Air,
driven by a blower, enters the bottom of the bed to fluidize the sand. Air
passage through the bed promotes rapid and uniform mixing of the injected waste
material within the fluidized bed. The fluidized bed has an extremely high heat
capacity (approximately three times that of flue gas at the same temperature),
thereby providing a large heat reservoir. The injected waste reaches ignition
temperature quickly and transfers the heat of combustion back to the bed.
Continued bed agitation by the fluidizing air allows larger particles to remain
suspended in the combustion zone. (See Figure 2-3)
Fixed hearth - Fixed hearth incinerators, also called controlled
air or starved air incinerators, are another major technology used for hazardous
waste incineration. Fixed hearth incineration is a two-stage combustion process
(see Figure 2-4). Waste is ram-fed into the first stage, or primary chamber,
2-5
-------
Water
Auxiliary
Fuel
Liquid
or
Gaseous
Waste
Injection
Burner
Air
Burner
Primary
Combustion
Chamber
Afterburner
(Secondary
Combustion
Chamber)
Spray
Chamber
Gas to Air
Pollution
Control
Horizontally
Fired Liquid
Injection
Incinerator
Ash
Water
Figure 2—1. Liquid Injection Incinerator
-------
Gas to
Air Pollution
Control
Auliliary
Fuel
Solid
Waste
Influent
Combustion
Gases
Liquid or
Gaseous
Waste
Injection
Ash
Figure 2-2. Rotary Kiln Incinerator
-------
Waste
Injection
Burner
Freeboard
Sand Bed
Gas to Air
Pollution
Control
Make—up Sand
Air
I
Ash
Figure 2-3. Fluidized Bed Incinerator
-------
Air
Waste
Injection
Burner
Air
L
Gas to Air
Pollution
Control
Primary
Combustion
Chamber
Grate
T
Ash
Secondary
Combustion
Chamber
t
Auliliary
Fuel
2—Stage Fixed
Hearth
Incinerator
Figure 2-4. Fixed Hearth Incinerator
-------
and burned at less than stoichiometric conditions. The resultant smoke and
pyrolysis products, consisting primarily of volatile hydrocarbons and carbon
monoxide, along with the additional air is injected to complete the combustion.
This two-stage process generally yields low stack particulate and carbon monoxide
(CO) emissions. The primary chamber combustion reactions and combustion gas are
maintained at low levels by the starved air conditions so that particulate
entrainment and carryover are minimized.
Air pollution controls - Following incineration of hazardous wastes,
combustion gases are generally further treated in an air pollution control
system. The presence of chlorine or other halogens in the waste requires a
scrubbing or absorption step to remove HC1 and other halo-acids from the combus-
tion gases. Ash in the waste is not destroyed in the combustion process.
Depending on its composition, ash will either exit as bottom ash, at the dis-
charge end of a kiln or hearth for example, or as particulate matter (fly ash)
suspended in the combustion gas stream. Particulate emissions from most hazard-
ous waste combustion systems generally have particle diameters less than one
micron and require high efficiency collection devices to minimize air emissions.
Scrubber systems provide an additional buffer against accidental releases of
incompletely destroyed waste products due to poor combustion efficiency or
combustion upsets, such as flame outs.
2.2.4 Waste characteristics affecting performance (WCAP)
(a) Liquid injection - In determining whether liquid injection is
likely to achieve the same level of performance on an untested waste as a
previously tested waste, the Agency will compare dissociation bond energies of
the constituents in the untested and tested wastes. This parameter is being used
as a surrogate indicator of activation energy which, as discussed previously,
2-10
-------
destabilizes molecular bonds. In theory, the bond dissociation energy would be
equal to the activation energy; however, in practice this is not always the case.
Other energy effects (e.g., bond vibration, intermediate formation, and bond
interaction) may have a significant influence on activation energy.
Because of the shortcomings of bond energies in estimating activation
energy, EPA analyzed other waste characteristic parameters to determine whether
these parameters would provide a better basis for transferring treatment stan-
dards from an untested waste to a tested waste. These parameters include heat
of combustion, heat of formation, use of available kinetic data to predict
activation energies, and general structural class. All of these were rejected
for reasons provided below.
The heat of combustion measures only the difference in energy of the
products and reactants, it does not provide information on the transition state
(i.e., the energy input needed to initiate the reaction). Heat of formation is
used as a tool to predict whether reactions are likely to proceed; however, there
are a significant number of hazardous constituents for which these data are not
available. Use of kinetic data were rejected because these data are limited and
could not be used to calculate free energy values (delta G) for the wide range
of hazardous constituents to be addressed by this rule. Finally, EPA decided
not to use structural classes because the Agency believes that evaluation of bond
dissociation energies allows for a more direct determination of whether a consti-
tuent will be destabilized.
(b) Rotary kiln/fluidized bed/fixed hearth - Unlike injection, these
incineration technologies also generate a residual ash. Accordingly, in deter-
mining whether these technologies are likely to achieve the same level of perfor-
mance on an untested waste as on a previously tested waste, EPA would need to
2-11
-------
examine the waste characteristics that affect volatilization of organics from
the waste, as well as destruction of the organics, once volatilized. Relative
to volatilization, EPA will examine thermal conductivity of the entire waste and
boiling point of the various constituents. As with liquid injection, EPA will
examine bond energies in determining whether treatment standards for scrubber
water residuals can be transferred from a tested waste to an untested waste.
Below is a discussion of how EPA arrived at thermal conductivity and boiling
point as the best method to assess volatilization of organics from the waste;
the discussion relative to bond energies is the same for these technologies as
for liquid injection and will not be repeated here.
(i) Thermal conductivity. Consistent with the underlying principles
of incineration, a major factor with regard to whether a particular constituent
will volatilize is the transfer of heat through the waste. In the case of rotary
kiln, fluidized bed, and fixed hearth incineration, heat is transferred through
the waste 'by three mechanisms; radiation, convection, and conduction. For a
given incinerator, heat transferred through various wastes by radiation is more
a function of the design and type of incinerator than of the waste being treated.
Accordingly, the type of waste treated will have a minimal impact on the amount
of heat transferred by radiation. With regard to convection, EPA also believes
that the type of heat transfer will generally be more a function of the type and
design of the incinerator than of the waste itself. However, EPA is examining
particle size as a waste characteristic that may significantly impact the amount
of heat transferred to a waste by convection and thus impact volatilization of
the various organic compounds. The final type of heat transfer, conduction, is
the one that EPA believes will have the greatest impact on volatilization of
organic constituents. To measure this characteristic, EPA will use thermal
2-12
-------
conductivity; an explanation of this parameter, as well as how it can be
measured, is provided below.
Heat flow by conduction is proportional to the temperature gradient
across the material. The proportionality constant is a property of the material
and is referred to as the thermal conductivity. (Note: The analytical method
that EPA has identified for measurement of thermal conductivity is named "Guard-
ed, Comparative, Longitudinal Heat Flow Technique,"). In theory, thermal conduc-
tivity would always provide a good indication of whether a constituent in an
untested waste would be treated to the same extent in the primary incinerator
chamber as the same constituent in a previously tested waste.
In practice, thermal conductivity has some limitations in assessing
the transferability of treatment standards; however, EPA has not identified a
parameter that can provide a better indication of heat transfer characteristics
of a waste. Below is a discussion of both the limitations associated with
thermal conductivity and other parameters considered.
Thermal conductivity measurements, as part of a treatability compari-
son for two different wastes through a single incinerator, are most meaningful
when applied to wastes that are homogeneous (i.e., major constituents are essen-
tially the same). As wastes exhibit greater degrees of nonhomogeneity (e.g.,
significant concentrations of metals in soil) , then thermal conductivity becomes
less accurate in predicting treatability because the measurement essentially
reflects heat flow through regions having the greatest conductivity (i.e., the
path of least resistance) and not heat flow through all parts of the waste.
Btu value, specific heat, and ash content were also considered for
predicting heat transfer characteristics. These parameters can no better account
for nonhomogeneity than can thermal conductivity; additionally, they are not
2-13
-------
directly related to heat transfer characteristics. Therefore, these parameters
do not provide a better indication of heat transfer that will occur in any
specific waste.
(ii) Boiling point. Once heat is transferred to a constituent within
a waste, removal of this constituent from the waste will depend on its volatil-
ity. EPA is using boiling point as a surrogate for the volatility of a consti-
tuent. Compounds with lower boiling points have higher vapor pressures and,
therefore, would be more likely to vaporize. The Agency recognizes that this
parameter does not take into consideration the impact of other compounds in the
waste on the boiling point of a constituent in a mixture; however, the Agency
is not aware of a better measure of volatility that can easily be determined.
2.2.5 Incineration design and operating parameters
(a) Liquid injection. For a liquid injection unit, EPA's analysis
of whether the unit is well-designed will focus on (1) the likelihood that
sufficient energy is provided to the waste to overcome the activation level for
breaking molecular bonds and (2) whether sufficient oxygen is present to convert
the waste constituents to carbon dioxide and water vapor. The specific design
parameters that the Agency will evaluate to assess whether these conditions are
met are temperature, excess oxygen, and residence time. Below is a discussion
of why EPA believes these parameters to be important, as well as a discussion
of how these parameters will be monitored during operation.
(i) Temperature. Temperature is important in that it provides an
indirect measure of the energy available (i.e., Btu/hr) to overcome the activa-
tion energy of waste constituents. As the design temperature increases, it is
more likely that the molecular bonds will be destabilized and the reaction
2-14
-------
completed.
The temperature is normally controlled automatically through the use
of instrumentation which senses the temperature and automatically adjusts the
amount of fuel and/or waste being fed. The temperature signal transmitted to
the controller can be simultaneously transmitted to a recording device, referred
to as a strip chart, and thereby continuously recorded. To fully assess the
operation of the unit, it is important to know not only the exact location in
the incinerator where the temperature is being monitored but also the location
of the design temperature.
(ii) Excess oxygen. It is important that the incinerator contain
oxygen in excess of the stoichiometric amount necessary to convert the organic
compounds to carbon dioxide and water vapor. If insufficient oxygen is present,
then destabilized waste constituents could recombine to the same or other BOAT
list organic compounds and potentially cause the scrubber water to contain higher
concentrations of BOAT list constituents than would be the case for a well-
operated unit.
In practice, the amount of oxygen fed to the incinerator is control-
led by continuous sampling and analysis of the stack gas. If the amount of
oxygen drops below the design value, then the analyzer transmits a signal to the
valve controlling the air supply and thereby increases the flow of oxygen to the
afterburner. The analyzer simultaneously transmits a signal to a recording
device so that the amount of excess oxygen can be continuously recorded. Again,
as with temperature, it is important to know the location from which the
combustion gas is being sampled.
(iii) Carbon monoxide. Carbon monoxide is an important operating
parameter because it provides an indication of the extent to which the waste
2-15
-------
organic constituents are being converted to carbon dioxide and water vapor. An
increase in the carbon monoxide level indicates that greater amounts of organic
waste constituents are unreacted or partially reacted. Increased carbon monoxide
levels can result from insufficient excess oxygen, insufficient turbulence in
the combustion zone, or insufficient residence time.
(iv) Waste feed rate. The waste feed rate is important to monitor
because it is correlated to the residence time. The residence time is associated
with a specific Btu energy value of the feed and a specific volume of combustion
gas generated. Prior to incineration, the Btu value of the waste is determined
through the use of a laboratory device known as a bomb calorimeter. The volume
of combustion gas generated from the waste to be incinerated is determined from
an analysis referred to as an ultimate analysis. This analysis determines the
amount of elemental constituents present, which include carbon, hydrogen, sulfur,
oxygen, nitrogen, and halogens. Using this analysis plus the total amount of
air added, one can calculate the volume of combustion gas. After both the Btu
content and the expected combustion gas volume have been determined, the feed
rate can be fixed at the desired residence time. Continuous monitoring of the
feed rate will determine whether the unit was operated at a rate corresponding
to the designed residence time.
(b) Rotary kiln. For this incineration type, EPA will examine both
the primary and secondary chamber when evaluating the design of a particular
incinerator. Relative to the primary chamber, EPA's assessment of design will
focus on whether sufficient energy is likely to be provided to the waste to
volatilize the waste constituents. For the secondary chamber, analogous to the
sole liquid injection incineration chamber, EPA will examine the same parameters
discussed previously under liquid injection incineration. These parameters will
2-16
-------
not be discussed again here.
The particular design parameters to be evaluated for the primary
chamber are kiln temperature, residence time, and revolutions per minute. Below
is a discussion of why EPA believes these parameters to be important, as well
as a discussion of how these parameters will be monitored during operation.
(i) Temperature. The primary chamber temperature is important, in
that it provides an indirect measure of the energy input (i.e., Btu/hr) that is
available for heating the waste. The higher the temperature is designed to be
in a given kiln, the more likely it is that the constituents will volatilize.
As discussed earlier under "Liquid injection," temperature should be continuously
monitored and recorded. Additionally, it is important to know the location of
the temperature sensing device in the kiln.
(ii) Residence time. This parameter is important in that it affects
whether sufficient heat is transferred to a particular constituent in order for
volatilization to occur. As the time that the waste is in the kiln is increased,
a greater quantity of heat is transferred to the hazardous waste constituents.
The residence time will be a function of the specific configuration of the rotary
kiln including the length and diameter of the kiln, the waste feed rate, and
the rate of rotation.
(iii) Revolutions per minute (RPM). This parameter provides an
indication of the turbulence that occurs in the primary chamber of a rotary kiln.
As the turbulence increases, the quantity of heat transferred to the waste would
also be expected to increase. However, as the RFM value increases, the residence
time decreases, resulting in a reduction of the quantity of heat transferred to
the waste, This parameter needs to be carefully evaluated because it provides
a balance between turbulence and residence time.
2-17
-------
(c) Fluidized bed. As discussed previously, in the section on
"Underlying principles of operation," the primary chamber accounts for almost
all of the conversion of organic wastes to carbon dioxide, water vapor, and acid
gas if halogens are present. The secondary chamber will generally provide
additional residence time for thermal oxidation of the waste constituents.
Relative to the primary chamber, the parameters that the Agency will examine in
assessing the effectiveness of the design are temperature, residence time, and
bed pressure differential. The first two were discussed under rotary kiln and
will not be discussed here. The last, bed pressure differential, is important
in that it provides an indication of the amount of turbulence and therefore,
indirectly, the amount of heat supplied to the waste. In general, as the
pressure drop increases, both the turbulence and heat supplied increase. The
pressure drop through the bed should be continuously monitored and recorded to
ensure that the design value is achieved.
(d) Fixed hearth. The design considerations for this incineration
unit are similar to those for a rotary kiln except that rate of rotation (i.e. ,
RPMs) is not an applicable design parameter. For the primary chamber of this
unit, the parameters that the Agency will examine in assessing how well the unit
is designed are the same as those discussed under rotary kiln; for the secondary
chamber (i.e., afterburner), the design and operating parameters of concern are
the same as those previously discussed under "Liquid injection."
2-18
-------
3.0 AMENDMENT TO SECTION 4 ("PERFORMANCE DATA BASE") OF THE FINAL
BACKGROUND DOCUMENT FOR ORGANOPHOSPHORUS WASTES (K036)
This section presents the data available on the performance of incin-
eration in treating K037. K037 has been judged to be similar to the waste stream
subject to this amendment, K036. The incineration data presented in this section
are used later in this document in determining which technologies represent BOAT,
in selecting constituents to be regulated, and in developing treatment standards
for K036.
Treatment performance data, to the extent that they are available
to EPA, include concentrations for a given constituent in the untreated and
treated waste, the values of operating parameters that were measured at the time
the waste was being treated, and the values of relevant design parameters for
the treatment technology.
Where data are not available on treatment performance for the
specific wastes of concern, the Agency may elect to transfer performance data
from a demonstrated technology that treats a similar waste or wastes. To
transfer data from another waste category, EPA must determine that the wastes
covered by this (amended) background document are no more difficult to treat
(based on the waste characteristics that affect performance of the demonstrated
treatment technology) than the treated wastes from which performance data are
being transferred.
Treatment standards for K037, based on incineration, were promulgated
in the First Third Final Rule (53 FR 31174, August 17, 1988). K036 and K037 both
have similar chemical composition and physical characteristics. Both derive
from .the same manufacturing process operated in the single U.S. facility produc-
ing disulfoton and, therefore, have the same primary constituent, disulfoton.
3-1
-------
Consequently, treatment performance data for incineration of K037 nonwastewater
are being transferred to K036 nonwastewater.
The Agency collected six data sets for untreated and treated K037
to characterize treatment of K037 nonwastewater using an EPA in-house rotary kiln
treatment system. Treatment of K037 resulted in the generation of two treatment
residuals: ash and scrubber water. Tables 3-1 through 3-6 present the six data
sets of total waste concentration analyses for K037 nonwastewater samples, and
the design and operating data for the treatment system. All six sets of inciner-
ation data indicate that concentrations of disulfoton may be reduced from greater
than 10% to below detection levels in the ash and scrubber water treatment resid-
uals. Furthermore, all the data sets also show treatment of the other organic
BOAT list constituents detected in the untreated wastes to nondetectible concen-
trations in the treatment residuals, as shown by the operating data taken during
collection of the samples. The Agency has no reason to believe that the treat-
ment system was not well-designed and well-operated.
3-2
-------
Table 3-1 Rotary Kiln Incineration
EPA-Collected Data
Sample Set *1
ANALYTICAL DATA:
BOAT
Reference
No.
43
70
155
156
157
158
159
160
161
163
166
167
168
195
BOAT list
constituent
Toluene
Bis(2-ethylhexyl )phthalate
Arsenic
Barium
Beryllium
Cadmium
Chromium
Copper
Lead
Nickel
Thallium
Vanadium
Zinc
Oisulfoton
Treated
Untreated Treated waste Scrubber
waste waste TCLP water
(mq/kq) (ma/kg) (mq/l) (uq/l)
640
<250
3.1
26
<0.5
3.9
70
24
28
130
<2.5
8
190
171,000
<10
<2.0
10
150
0.54
2.1
80
610
54
110
<2.5
82
290
<0.0335
NA
NA
<0.01
<0.045
<0.005
<0.015
0.079
3.3
0.029
0.20
<0.015
0.93
0.64
NA
<10
<50
0.10
0.91
<0.005
0.059
0.15
4.7
6.6
0.10
<0.015
<0.1
16
<1.00
DESIGN AND OPERATING DATA:
Design value
Operating value
Kiln
Temperature
Revolutions per minute
Afterburner
Temperature
Excess oxygen
Carbon monoxide
1832°F
0.2 rpm
2200°F
6-8X
<1000 ppm
1778-1818°F
0.2 rpm
2043-2063°F
8X
<1 ppm
NA • Not Applicable.
Reference: USEPA 1987. Omit* Engineering Report for K037 (Reference 5).
3-3
-------
Table 3-2 Rotary Kiln Incineration
EPA-Collected Data
Sample Set *2
ANALYTICAL DATA:
BOAT
Reference BOAT list
Mo. constituent
43
70
155
156
157
158
159
160
161
163
166
167
168
195
Toluene
Bis(2-ethylhexyl)phthalate
Arsenic
Barium
Beryllium
Cadmium
Chromium
Copper
Lead
Nickel
Thallium
Vanadium
Zinc
Disulfoton
Untreated
waste
(mg/kg)
530
<250
2.4
39
<0.5
3.9
73
12
12
90
<2.5
7
89
104,000
Treated
Treated waste
waste TCLP
(mg/kg) (mg/l)
<10
<2.0
5.0
140
0.51
<2.0
93
940
66
110
<2.5
80
330
<0.0335
NA
NA
<0.01
<0.045
<0.005
<0.015
0.22
10
0.013
0.58
<0.015
1.8
0.45
NA
Scrubber
water
(ug/l)
<10
<50
0.26
0.19
<0.005
0.062
0.21
4.7
11
<0.1
<0.015
<0.1
4.2
<1.00
DESIGN AND OPERATING DATA:
Design value
Operating value
Kiln
Temperature 1832°F
Revolutions per minute 0.2 rpm
Afterburner
Temperature
Excess oxygen
Carbon monoxide
2200°F
6-8X
<1000 ppm
1778-1818°F
0.2 rpm
2043-2063°F
8X
<1 ppm
NA - Not Applicable.
Reference: USEPA 1987. Onsite Engineering Report for K037 (Reference 5).
3-4
-------
Table 3-3 Rotary Kiln Incineration
EPA-Collected Data
Sample Set *3
ANALYTICAL DATA:
BOAT
Reference BOAT list
No. constituent
43
70
155
156
157
158
159
160
161
163
166
167
168
195
Toluene
Bis(2-ethylhexyl)phthalate
Arsenic
Barium
Beryllium
Cadmium
Chromium
Copper
Lead
Nickel
Thallium
Vanadium
Zinc
Oisulfoton
Untreated
waste
(ma/kg)
1,300
<250
<2.0
18
<0.5
3.8
43
7.0
5.6
46
<2.5
7
110
246,000
Treated
Treated waste
waste TCLP
(mg/kg) (mg/l)
<10
<2.0
25
130
<0.5
<2.0
100
630
25
180
<2.5
61
840
<0.0335
NA
NA
0.022
0.049
<0.005
<0.015
0.13
1.1
<0.01
0.19
<0.015
0.97
0.75
NA
Scrubber
water
(ug/l)
<10
<50
0.22
0.22
<0.005
0.073
0.19
3.9
9.6
<0.1
<0.015
<0.1
2.7
<1.00
DESIGN AND OPERATING DATA:
Design value
Operating value
Kiln
Temperature 1832°F
Revolutions per minute 0.2 rpm
Afterburner
Temperature
Excess oxygen
Carbon monoxide
2200p4op1F
6-8X
<1000 ppm
1778-1818°F
0.2 rpm
2043-2063°F
8X
<1 ppm
NA • Not Applicable.
Reference: USEPA 1987. Onsite Engineering Report for K037 (Reference 5).
3-5
-------
Table 3-4 Rotary Kiln Incineration
EPA-Collected Data
Sample Set *4
ANALYTICAL DATA:
BOAT
Reference BOAT list
No. constituent
43
70
155
156
157
158
159
160
161
163
166
167
168
195
Toluene
8is(2-ethylhexyl)phthalate
Arsenic
Barium
Beryllium
Cadmium
Chromium
Copper
Lead
Nickel
Thallium
Vanadium
Zinc
Disulfoton
Untreated
waste
(mg/kg)
630
<250
<2.0
28
<0.5
5.3
85
21
22
120
<2.5
9
180
186,000
Treated
Treated waste
waste TCLP
(mg/kg) (mq/l)
<10
<2.0
15
150
<0.5
<2.0
110
460
15
160
<2.5
78
620
<0.0335
NA
NA
<0.01
0.075
<0.005
<0.015
0.074
3.0
0.017
0.24
<0.015
1.1
2.7
NA
Scrubber
water •
(uq/l)
<10
<50
0.23
0.18
<0.005
0.063
0.090
4.0
4.0
<0.1
<0.015
<0.1
0.97
<1.00
DESIGN AND OPERATING DATA:
Design value
Operating value
Kiln
Temperature 1832°F
Revolutions per minute 0.2 rpm
Afterburner
Temperature
Excess oxygen
Carbon monoxide
2200°F
6-8X
<1000 ppm
1830-1897°F
0.2 rpm
2043-2063°F
8X
<1 ppm
NA - Not Applicable.
Reference: USEPA 1987. Onsite Engineering Report for K037 (Reference 5).
3-6
-------
Table 3-5 Rotary Kiln Incineration
EPA-Collected Data
Sample Set 05
ANALYTICAL DATA:
BOAT
Reference BOAT list
No. constituent
43
70
155
156
157
158
159
160
161
163
166
167
168
195
Toluene
Bis(2-ethylhexyl)phthalate
Arsenic
Barium
Beryllium
Cadmium
Chromium
Copper
Lead
Nickel
Thallium
Vanadium
Zinc
Disulfoton
Untreated
waste
(ma/kg)
201
<250
<2.0
22
<0.5
3.3
50
15
12
61
<2.5
10
110
181,000
Treated
Treated waste
waste TCLP
(ma/kg) (mg/l)
<10
<2.0
5.0
140
<0.5
<2.0
88
380
15
110
<2.5
77
450
<0.0335
NA
NA
<0.01
1.1
<0.005
<0.015
0.26
4.3
0.021
0.41
<0.015
1.8
4.8
NA
Scrubber
water
(ug/l)
<10
<50
0.29
0.30
<0.005
0.11
0.13
6.2
6.8
<0.1
0.02
<0.1
1.7
<1.00
DESIGN AND OPERATING DATA:
Design value
Operating value
Kiln
Temperature
Revolutions per minute
Afterburner
Temperature
Excess oxygen
Carbon monoxide
1832°F
0.2 rpm
2200°F
6-8X
<1000 ppm
1830-1897°F
0.2 rpm
2043-2063°F
8X
<1 ppm
NA - Not Applicable.
Reference: USEPA 1987. Onsite Engineering Report for K037 (Reference 5).
3-7
-------
Table 3-6 Rotary Kiln Incineration
EPA-Collected Data
Sample Set #6
ANALYTICAL DATA:
BOAT
Reference BOAT list
No. constituent
43
70
155
156
157
158
159
160
161
163
166
167
168
195
Toluene
Bis(2-ethylhexyl)phthalate
Arsenic
Barium
Beryllium
Cadmium
Chromium
Copper
Lead
Nickel
Thallium
Vanadium
Zinc
Disulfoton
Untreated
waste
(mg/ka)
2000
500
<2.0
33
<0.5
10
93
16
8.2
120
<2.5
8
120
192,000
Treated
Treated waste
waste TCLP
(mg/kg) (ma/ I)
<10
<2.0
20
170
0.71
<2.0
87
240
20
110
<2.5
88
330
<0.0335
NA
NA
<0.01
0.1
<0.005
<0.015
<0.045
0.15
<0.01
0.59
<0.015
0.25
0.16
NA
Scrubber
water
(ug/l)
<10
<50
0.45
0.39
<0.005
0.16
0.17
6.3
11
' 0.11
0.02
<0.1
2.3
<1.00
DESIGN AND OPERATING DATA:
Design value
Operating value
Kiln
Temperature
Revolutions per minute
Afterburner
Temperature
Excess oxygen
Carbon monoxide
1832°F
0.2 rpm
2200°F
6-8X
<1000 ppm
1830-1897°F
0.2 rpm
2043- 2063° F
8X
<1 ppm
NA - Not Applicable.
Reference: USEPA 1987. Onsite Engineering Report for K037 (Reference 5).
3-8
-------
4.0 AMENDMENT TO SECTION 5.1 ("IDENTIFICATION OF BEST DEMONSTRATED AVAIL-
ABLE TECHNOLOGY FOR K036 NONWASTEWATER") OF THE FINAL BACKGROUND
DOCUMENT FOR ORGANOPHOSPHORUS WASTES (K036)
This section presents the rationale for selecting incineration as
the best, demonstrated, and available technology (BOAT) for K036 nonwastewater.
For a treatment technology to be identified as BOAT, the treatment performance
data are first screened to determine whether they represent a well-designed and
well-operated treatment system, whether sufficient analytical quality assurance
and quality control measures were employed to ensure the accuracy of the data,
and whether the appropriate measures of performance were used to assess the
performance of the particular treatment technology. If performance data are to
be transferred from one wastestreara to another (i.e., from K037 to K036 in this
case), the wastestream upon which the performance data was derived is addition-
ally evaluated for similarity to that of the subject wastestream. Preceding
sections have already established the similar characteristics of K036 and K037,
including a commonality of primary constituents and derivation from a single
process.
The treatment performance data and the design and operating data
collected during the test of rotary kiln incineration of K037 were reviewed for
the points described above. The appropriate measure of performance (total
constituent concentration) was used to assess the treatment system. Additional-
ly, the Agency has no reason to believe that this treatment system is not well
designed and well-operated, or that insufficient analytical quality assurance
and quality control measures were employed in generating treatment performance
data. The data collected during the incineration test show a reduction in
concentrations of disulfoton, the primary constituent of K037 nonwastewaters,
4-1
-------
to below detection levels. Thus, incineration is considered demonstrated for
K037 nonwastewaters.
An available treatment technology is one that (1) is not a proprie-
tary or patented process that cannot be purchased or licensed from the proprietor
(i.e., it must be commercially available), and (2) substantially diminishes the
toxicity of the waste or substantially reduces the likelihood of migration of
hazardous constituents from the waste. The technology that is demonstrated for
treatment of K037, incineration, is considered to be commercially available and
to provide substantial treatment of the waste. Therefore, incineration has been
judged to be "available."
Incineration performance data for K037 are the only source of inform-
ation currently available to the Agency for treatment of disulfoton or any other
organophosphorus constituent in nonwastewaters. In the absence of performance
data for treatment of disulfoton in similar wastes by technologies other than
incineration, the Agency considers incineration to be best demonstrated available
technology for the similar disulfoton-containing nonwastewater of K036.
4-2
-------
5.0 AMENDMENT TO SECTION 7 ("DEVELOPMENT OF BOAT TREATMENT STANDARDS")
OF THE FINAL BACKGROUND DOCUMENT FOR ORGANOPHOSPHORUS WASTES (K036)
Concentration-based treatment standards for disulfoton in K036 non-
wastewaters were developed based on performance data transferred from incinera-
tion treatment of K037. Disulfoton was treated to concentrations below detection
levels in K037 as shown in Section 3.0 of this document. The detection limit
was 0.0335 mg/kg in K037 incinerator ash. A treatment standard for disulfocon
in K036 nonwastewater was calculated by multiplying the accuracy-corrected detec-
tion limit by a variability factor, as described below.
First, the detection limit was corrected for accuracy as follows.
(1) The lowest matrix spike recovery was determined for the waste constituent.
The lowest matrix spike recovery for disulfoton in K037 incinerator ash was 91%
(see table 5-1). (2) An accuracy correction factor of 1.10 was determined for
disulfoton by dividing 100 by the lowest matrix spike recovery for that consti-
tuent. (3) The disulfoton detection limit was corrected by multiplying the
detection limit by the accuracy correction factor, yielding a value of 0.0368
mg/kg.
Second, a variability factor was derived. The variability factor
accounts for the variability inherent in treatment system performance, treatment
residual collection, and analysis of the samples of treated waste. A variability
factor could not be calculated for disulfoton since it was not detected in the
incinerator ash residual. Therefore, a variability factor of 2.8 was used to
account for this inherent variability, as discussed in the Methodology for
Developing Treatment Standards (Reference 3) (see Table 5-2).
To reiterate, when numerical standards are derived for BOAT List
constituents that are regulated, they are calculated by multiplying the accuracy-
5-1
-------
corrected detection limit by the variability factor. Therefore, the accuracy-
corrected detection limit (0.0368 mg/kg), multiplied by the variability factor
(1.10), which yields the treatment standard of 0.10 mg disulfoton per kilogram
of residual ash (0.10 mg/kg). The use of other technologies is not precluded
to achieve this concentration-based treatment standard.
5-2
-------
Table 5-1 Matrix Spike Recoveries for K037 Treated Solids - EPA-Collected Data
BOAT
constituent
Original
amount
found
(ua/1)
Sanmle Set *5
Spike
Added
(UR/K)
Spike
result
(UK/l)
Percent
recovery
Sacnole Set IS
Spike
added
Spike
result
(UK/ I)
Duollcate
Percent
recoverr(a)
Accuracy
correction
factor(b)
Dlsulfoton <0.007 0.173 0.157 91 0.173 0.16* 95 1.10
NO - Hot calculable because the only values available were the spike amount and the percent recovery.
(a)Percent recovery - [(spike result - original amount)/spIke added].
(b)Accuracy correction factor • 100/percent recovery (using the lowest percent recovery value).
Reference: USEPA 1987. Onslte Engineering Report for K037.
Table 5-2 Proposed Regulated Constituents and Proposed Calculated Treatment Standards for K037
Average Treatment
Accuracy-corrected concentration treated Variability standard
Constituent Sample Sample Sample Sample Sample Sample waste factor (average
Matrix (units) set fl set »2 set »3 set »* set *5 set 06 concentration (VF) x VF)
Nonwaste- Dlsulfoton 0.0368 0.0368 0.0368 0.0368 0.0368 0.0368 0.0368 2.8 0.10
waters (rag/kg)
5-3
-------
6.0 ACKNOWLEDGEMENTS
This document was prepared for the U.S. Environmental Protection
Agency, Office of Solid Waste, by Radian Corporation under Contract No. 68-W9-
0072. This document was prepared under the direction of Mr. Richard Kinch,
Acting Chief, Waste Treatment Branch; Mr. Larry Rosengrant, Chief, Treatment
Technology Section; and Mr. Jerry Vorbach, Project Officer. Ms. Mary Cunningham
served as the project manager for K036 regulatory development.
The following personnel from Radian Corporation were involved in
preparing this document: Mr. John Williams, Program Manager, Ms. Lori Stoll,
Project Director, and the Radian engineering team, Ms. Debra Falatko and Mr.
Steven Cragg.
6-1
-------
7.0 REFERENCES
1. U.S. EPA. 1989. U.S. Environmental Protection Agency, Office of Solid
Waste. Best Demonstrated Available Technology (BOAT) Background Document
for Organophosphorus Wastes. June, 1989. Washington, D.C.: U.S. Environ-
mental Protection Agency.
2. U.S. EPA. 1988. U.S. Environmental Protection Agency, Office of Solid
Waste. Best Demonstrated Available Technology (BOAT) Background Document
for K037. August, 1988. Washington, D.C.: U.S. Environmental Protection
Agency.
3. U.S. EPA. 1989. U.S. Environmental Protection Agency, Office of Solid
Waste. MethodoloEV for Developing BOAT Treatment Standards. June, 1989.
Washington, D.C.: U.S. Environmental Protection Agency.
4. American Public Health Association, American Waterworks Association, and
the Water Pollution Control Federation. 1985. Standard Methods for the
Examination of Water and Wastewater. Sixteenth Edition. Washington, D.C.,
American Public Health Association.
5. U.S. EPA. 1987. U.S. Environmental Protection Agency, Onsite Engineering
Report of Treatment Technology Performance and Operation for Incineration
of K037 Waste at the Combustion Research Facility. Draft report. Washing-
ton, D.C. : U.S. Environmental Protection Agency.
7-1
------- |