ESTIMATING RELEASES AND
WASTE-TREATMENT EFFICIENCIES FOR THE
TOXIC CHEMICAL RELEASE
INVENTORY FORM
Section 313 of the
Emergency Planning and Community
Right-to-Know Act of 1986
PN 3687-33, 3687-40, 3687-52
Contract No. 68-02-4248
Work Assignment No. P2-10, P2-17 and P3-4
U.S. ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF PESTICIDES AND TOXIC SUBSTANCES
WASHINGTON, D.C. 20460
December 1987
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DISCLAIMER
This document has been reviewed and. approved for
publication by the Office of Toxic Substances, Office of
Pesticides and Toxic Substances, U.S. Environmental
Protection Agency. Mention of trade names or commercial
products does not constitute endorsement or
recommendation for use.
For more information or assistance regarding Toxic
Release Inventory Reporting, call:
Emergency Planning and Community
Right-to-Know Information Hotline
(800) 535-0202 8:30 am - 7:30 PM
(202) 479-2449 (in Washington, DC or Alaska)
or write to:
Emergency Planning and Community
Right-to-Know Information Hotline
US Environmental Protection Agency
401 M Street, SW (OS-120)
Washington, DC 20460
Copies of this document can be obtained by writing
or calling:
Superintendent of Documents
Government Printing Office
Washington, DC 20402-9325
Phone: (202) 783-3238
GPO Stock No. 055-000-00270-3
Price $11.00
or
National Technical Information Service
5285 Port Royal Road
Springfield, VA 22161
Phone: (703) 487-4650
NTIS Accession No. PB 88-210380
Price: $25.95 (paper copy) $6.95 (microfiche)
11
2/28/89
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ERRATA LIST FOR EPA 560/4-88-002
p. 3-14 Example 3-7 illustrates use of an engineering
calculation, not an emission factor, to
estimate releases to air from material
storage.
p. B-4 Center of page under the Claussius-Clapeyron
equation. Grams or pounds should be divided
by molecular weight, not multiplied, to
convert to g-moles.
p. B-8 The vapor pressure for 1,2-Dibromoethane, CAS
No. 106-93-4, should be 11.7 mm Hg instead of
1117 mm Hg.
p. B-12 The vapor pressure of 10 mm Hg at 31° C for sulfuric
acid, CAS No. 7664-93-9, is incorrect. This
value was obtained from the 62nd edition of
the CRC Handbook of Chemistry and Physics. A
more appropriate value is 0.0117 mm Hg at 30°
C for 90% H2SO4 concentrations (Perry's
Chemical Engineering Handbook) or less than
0.001 mm Hg for 93-98% concentrations at
ambient temperature (NIOSH Pocket Guide to
Chemical Hazards).
7-18-88
iii
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CONTENTS
Figures
Tables -
1. Introduction
2. General Principles and Considerations
2.1 Data to be reported
2.2 Sources of wastes/releases
2.3 An overview of the analysis
2.4 Definitions of major approaches
2.5 Some observations on the use of data
2.6 Which approach to use
3. Estimating Releases to Air
3.1 Sources of releases to air and release estimation methods
3.2 Air pollution control equipment and treatment efficiency
Section 3 References
Section 3 Bibliography
4. Estimating Releases in Wastewater
4.1 Sources of wastewater and methods for its disposal
4.2 Calculating releases in wastewater
4.3 Estimating treatment equipment efficiency
Section 4 Bibliography
5. Estimating Releases in Solid, Slurry, and Nonaqueous Liquid
Wastes
5.1 Sources and disposal methods for solid, slurry, and
nonaqueous liquid wastes
5.2 Methods for calculating releases in solid, slurry, and
nonaqueous liquid wastes
5.3 Estimating treatment equipment efficiency
v
vi
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2-1
2-1
2-2
P-3
2-6
2-7
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3-32
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5-9
Section 5 Bibliography
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CONTENTS (continued)
6. Estimating Accidental Releases
6.1 General methods and considerations
6.2 Equations for modeling release wastes
Section 6 Bibliography
7. An Overall Facility Example Release Calculation
7.1 Atmospheric releases
7.2 Wastewater column releases
Appendices
A
B
C
0
E
Wastewater Treatment Efficiency Data
Chemical and Physical Data for the Listed Chemicals
Estimating Atmospheric Releases From Storage of Organic
Liquids
Table of Uncontrolled Fugitive Emission Factors for the
Synthetic Organic Chemicals Manufacturing Industry
Table of Contents of EPA Publication AP-42, Volume I
Page
6-1
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6-2
6-10
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B-l
C-l
D-l
E-l
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Number
3-1
3-2
3-3
7-1
FIGURES
Hypothetical Unit Process Using Chemical X
Percent Reduction Ranges for Add-On Control Devices
Venturi Scrubber Collection Efficiencies
Acrylonitrile Production Process
Page
3-5
3-25
3-31
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vi
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Number.
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3-2
3-3
3-4
3-5
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4-5
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5-3
TABLES
Source Categories for Common Releases to Air
Calculating Loading Losses for Volatile Organic Liquids
Techniques for Controlling Selected Air Pollutants
Optimal Operating Conditions for Flares
Availability of Chemical-Specific Emission Factors for
Various Processes
Typical Wastewater Sources
Methods of Wastewater Disposal
Unit Operations and Processes Used to Treat Wastewater
Development Documents for Effluent Limitation Guidelines
for Selected Categories
EPA Regional Office Libraries
Some Solid, Slurry, and Nonaqueous Wastestream Sources
Summary of Residue Quantities From Pilot-Scale Experi-
mental Study
Unit Operations and Treatment Processes Used to Treat
Solid, Slurry, and Nonaqueous Wastes
Page
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3-13
3-22
3-26
3-36
4-2
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4-30
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vii
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SECTION 1
INTRODUCTION
Under a new Federal law, the Emergency Planning and Community Right-to-
Know Act of 1986, certain chemical manufacturers, processors, and users are
required to report total annual releases of listed toxic chemicals to air,
water, and land. These reporting requirements, which are outlined in Section
313 of Title III of Superfund Amendments and Reauthorization Act of 1986
(SARA), specify that both routine and accidental releases be reported.
The regulations that implement this reporting requirement describe its
applicability in detail. In summary, your facility is subject to the report-
ing requirements if all of the following apply:
0 It has 10 or more full-time employees.
0 It conducts manufacturing operations (i.e., if it is included in
Standard Industrial Classification Codes 20 through 39).
0 It manufactures, processes, or in any other way uses any of the
listed toxic chemicals in amounts greater than the threshold quan-
tities.
The threshold quantities for manufacturers and processors are as follows:
0 75,000 pounds during the 1987 calendar year
0 50,000 pounds during the 1988 calendar year
0 25,000 pounds during the 1989 calendar year and in subsequent years
The threshold quantities for users are as follows:
0 10,000 pounds during the 1987 calendar year and in subsequent years
Each facility must complete and file the Toxic Chemical Release Invento-
ry Reporting Form (hereinafter referred to as "Form") for each listed chemi-
cal or listed Chemical category for which it meets or exceeds the preceding
thresholds. For chemical categories based on metal content (e.g., copper
compounds), releases of the metal, in whatever form, are to be reported (even
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though the thresholds for amounts manufactured, processed, or used are based
on the metal compounds). For other chemical categories (e.g., glycol
ethers), total releases of all members of the category are to be reported.
The Form(s), which are to be filed by July of each year, cover the
preceding calendar year. For example, Form(s) filed by July 1988 will cover
the 1987 calendar year. Facilities are urged to consult the Code of Federal
Regulations (40 CFR Part 372) to determine their legal responsibilities under
Section 313 of Title III of SARA.
This manual provides an overview of the general methods that may be used
to estimate releases subject to the reporting requirements. Examples of the
application of most of the methods discussed are also included. Where possi-
ble, the manual indicates which method is likely to provide the most accurate
estimate. The manual focuses on processes that may be present in facilities
within Standard Industrial Classification Codes 20 through 39. It does not
include methods specific to commercial service establishments, waste sites,
mobile sources9 etc. Sources of additional information on release estimation
are also provided.
This manual is not intended to cover all possible situations; many types
of releases may require case-by-case analysis and simply cannot be covered
herein. Neither is its purpose to describe and/or recommend monitoring/ana-
lytical programs that might be used to generate data for completing the
Form(s). Although no monitoring is required to comply with the reporting re-
quirements, facilities are urged to use monitoring data (which may have been
gathered under other regulatory programs or research efforts) wherever possi-
ble and to initiate the monitoring of waste streams, particularly where esti-
mation techniques may be complex and result in estimates of limited accuracy.
Most users of chemicals subject to the reporting requirements will not
need many of the estimation techniques covered here. In some cases, a single
calculation based on available monitoring data may yield the only release
estimate needed to meet the reporting requirements. In others, a few calcu-
lations based on chemical and/or physical properties may suffice. The U.S.
Environmental Protection Agency (EPA) believes that many affected facilities
will be able to meet the reporting requirements based on methods discussed
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herein. The Agency also recognizes, however, that complex chemical manufac-
turing processes, "unique" uses, and other special situations present diffi-
culties that cannot be covered here. In addition to this manual, EPA is
developing other guidance manuals aimed at some specific industry segments
that process or use many of the listed chemicals. The intent of these man-
uals is to provide industry-specific guidance for estimating toxic emissions.
(Reference numbers will be provided when the documents are available.)
Section 2 of this manual presents an overview of the information that
must be reported and the various types of analyses that a facility can use.
Sections 3, 4, and 5 describe methods specific to estimating air releases,
water releases, and "solid" waste releases, respectively. Section 6 briefly
describes procedures that may be used for estimating accidental releases.
Examples are provided throughout the manual to illustrate sources of informa-
tion, manipulation of data, and calculation procedures. Section 7 presents a
set of examples for estimating overall releases from an individual facility.
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OUTLINE FOR SECTION 2
GENERAL PRINCIPLES AND CONSIDERATIONS
2.1 Data to be Reported
2.2 Sources of Wastes/Releases
2.3 An Overview of the Analysis
2.4 Definitions of Major Approaches
2.5 Some Observations on the Use of Data
2.6 Which Approach to Use
2.6.1 Fugitive Air Emissions
2.6.2 Point Source Air Emissions
2.6.3 Releases to Wastewater
2.6.4 Releases in Solids, Slurries, and Nonaqueous Liquids
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SECTION 2
GENERAL PRINCIPLES AND CONSIDERATIONS
This section briefly describes the data that a facility must report and
discusses information that is necessary for the facility to generate the data
required to complete the Form. If you have not already familiarized yourself
with the Form and the reporting requirements, it would be helpful to do so
before proceeding.
2.1 DATA TO BE REPORTED
Items 5 and 6 in Part III of the Form require the following releases of
the chemical be reported (in pounds per year):
0 To air from fugitive or nonpoint sources
0 To air from stack or point sources
0 To water directly discharged to a receiving stream
0 In wastes that are injected underground
0 To land on site (including landfills, surface impoundments, or
landspreading)
0 To water discharged to a publicly owned treatment works (POTW)
0 In other wastes transferred offsite for treatment or disposal.
Quantities reported on the Form should reflect the amounts of chemical re-
leased after any onsite treatment and are specific to the chemical, metal, or
chemical category subject to reporting. These quantities should not reflect
the total quantity of waste or constituents of the waste that are not subject
to the reporting requirements.
Part III, Item 7, of the Form requires reporting of the percentage by
which any onsite treatment of any wastes containing the listed chemical
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reduces the amount of that chemical in the wastestream (weight percent reduc-
tion). The instructions for the Form specify how to list the treatment
method, by code, and the concentration of the chemical in the waste prior to
treatment.
2.2 SOURCES OF WASTES/RELEASES
All sources of wastes should be considered in estimating releases of a
chemical from your facility. Sources include but are not limited to the
following:
Fugitive air sources
0 Volatilization from open vessels, waste-treatment facilities,
spills, and/or shipping containers
0 Leaks from pumps, valves, and/or flanges
0 Building ventilation systems
Stack or point air sources
Vents from reactors and other process vessels
Storage tarjk vents
Stacks or vents from pollution control devices, incinerators,
etc.
Water sources
Process steps
Pollution control devices
Washings from vessels, containers, etc.
Storm water (if your permit includes storm water sources of a
listed chemical)
Solids, slurries, and nonaqueous liquid sources
o
o
o
o
Filter cakes, and/or filter media
Distillation fractions
Pollution control wastes such as baghouse particulates,
absorber sludges, spent activated carbon, and/or wastewater
treatment sludge
Spent catalysts
Vessel or tank residues (if not included under water sources)
Spills and sweepings
Off-specification product
Spent solvents
Byproducts
Accidental or nonroutine releases should also be included in the release
totals, and are not to be listed separately. The quantities that are to be
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reported in Part III of the Form should be the total of the releases of the
listed chemical from the various individual release points of waste streams
for each medium (i.e., air, water, and land). For example, fugitive air
emissions estimated separately for leaks, open vessels, and spills would be
added and entered under "Fugitive or Nonpoint Air Emissions."
So that consideration of all of the possible points/sources of release
is ensured prior to making the release estimate, it will be useful to prepare
or refer to simplified flow diagrams for those processes involving the listed
chemical; for example, for a polymerization process that uses a listed chemi-
cal, a schematic of the major pieces of equipment in which the polymerization
is carried out, the associated storage vessels, and the treatment steps for
wastes containing the solvent would be helpful in assessing possible release
points/sources. If the chemical is made or used in multiple processes, the
quantities to be reported are the total releases for all processes; a flow
diagram for each process would also be helpful.
2.3 AN OVERVIEW OF THE ANALYSIS
The level of detail of the analysis and the level of effort required
depend on your specific circumstances. Before data needs are described and
before methods are outlined for estimating quantities to be entered on the
Form, it should be noted that many (if not most) processors and users will
have only one or two releases- of a given chemical to report. Further, if
monitoring data are available for that release, simple multiplication of the
concentration of the chemical in the waste by the volume of the waste re-
leased may yield an acceptable estimate.
The following are examples of this "simple" solution:
0 A furniture maker uses a listed solvent in coating furniture. The
solvent evaporates in a drying area, from which it is ducted to a
discharge stack and is then released into the air without treat-
ment. In this case, the release estimate would simply be the
amount of solvent present in the coating(s) purchased (adjusted for
any inventory change). This value would be entered on the Form
under point source emissions to air.
0 A food processor uses an an aqueous cleaning solution that contains
a listed, nonvolatile component to wash down food processing equip-
ment. In this case, the quantity of cleaning solution used multi-
plied by the concentration of the nonvolatile component in the
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cleaning solution would be used as an estimate of the release, say
to a POTW (assuming that it does not undergo treatment prior to
discharge). This amount would be entered in Part III, Item 6.1,
"Discharge to POTW."
0 The manufacture of a chemical compound in solution generates a sol-
id filter cake that is land-filled on site. The filter cake con-
tains a listed chemical. The release of the listed chemical would
be estimated by multiplying the concentration of that chemical in
the filter cake by the quantity of the filter cake landfilled in
the reporting year. This estimate would then be entered in Part
III, Item 5.5, "Releases to Land," with the code D02 for landfills
(these codes can be found in the instructions for completing the
Form).
0 A processor of copper-containing compounds has measured the concen-
tration of copper in wastewater to comply with a water discharge
permit. The copper concentration times the daily volume of waste-
water times the number of days on which discharge occurs yields the
release estimate. This estimate would be entered in Part III, Item
5.3, "Discharge to Water."
*-
In all of the above situations, readily available data on the volume of,
the chemical manufactured, processed, or used and data from the measurement
of the concentration of the chemical in the waste were all that was needed to
estimate a release. Of course, careful scrutiny of the process(es) at the
facility is necessary to ensure that no rources are overlooked. For example,
discarded containers of unused coating or water used to wash a filter press
may be additional sources in the first and third examples, respectively.
The task will be somewhat more complicated when, for example, there are
several waste streams, treatment is used, or wastewater is discharged but the
chemical in the wastewater has not been measured. The following are examples
of slightly more complex situations:
0 A paint formulator incorporates a listed pigment into coatings.
The formulator has determined that there are two sources of release
for the listed pigment: 1) fine solids emitted to air from a mill-
ing step, and 2) solvent cleaning wastes that are sent to an off-
site location for incineration. In this case, total release would
be equal to the amount of pigment used (purchases adjusted for
inventory changes) minus the amount of pigment sold in the product
(the concentration of the pigment in the coating multiplied by the
weight of coating solid). Because two wastes are involved, it is
necessary to apportion the total release between them. It is un-
likely that "fugitive" solids to air will have been measured;
therefore, the best approach may be to estimate the amount of
cleaning waste (perhaps based on the known volume of the waste
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shipped offsite, the concentration of coating in the waste, and the
concentration of the pigment in the coating). The release quantity
in cleaning wastes calculated from these estimates would be entered
in Part II, Item 2, "Transfer to Offsite Location," and could then
be subtracted from the total release estimate to yield the "fugi-
tive air emissions" (which should be entered in Part III, Item
5.1). The code "M50" for "Incineration/Thermal Treatment" would be
entered with the location and address of the off-site incineration
facility.
0 The processor of copper-containing compounds, discussed earlier,
precipitates solids from wastewater generated by the process. In
addition to the discharge mentioned previously, some precipitate is
shipped to a waste broker. This additional copper release may be
estimated by multiplying the volume of waste shipped by the con-
centration of copper in the waste. This release estimate would be
entered in Part II, Item 2. The type of disposal (transfer to a
waste broker) would be indicated by entering the code "M91".
Treatment efficiency may be specified in Part III, Item 7 (Code C09
for chemical precipitation). Treatment efficiency may be calculat-
ed by dividing the amount of copper in solids by the total amount
of copper (the amount of copper in solids plus the amount in the
treated water). The resulting fraction would be multiplied by 100
to obtain a percentage reduction of copper in water resulting from
the treatment (precipitation step). The concentration of copper in
the influent would simply be the total copper in the two "releases"
divided by the wastewater volume. (Alternatively, copper concen-
tration in influent water may have been measured.)
Calculations will be more complicated when a volatile material is made
or used and air emissions must be estimated for leaks, vents, etc., or when
no data are available on water releases and the water comes from several
points in the process.
0 The manufacture of a solvent uses a continuous process that in-
volves a reactor, distilation columns, pumps, compressors, miles of
piping, and hundreds of fittings as well as associated storage
tanks^and pollution control devices. Generally, the air release
points will not have been monitored, and no "emission factor(s)"
for the process will be available to facilitate estimating releases
for the process as a whole (emission factors are discussed further
in Subsection 2.4). Estimates of air releases must then be based
on the other calculation techniques. Section 3 discusses other
calculation techniques and presents a subsection on calculating air
releases.
0 The manufacture of a chemical generates wastewater during the
reaction step. This wastewater is separated for treatment prior to
discharge. Additional wastewaters arising from product washings
and pollution control equipment are all combined in a central
treatment system. The amount of chemical released can be estimated
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by considering the losses from each part of the process and then
using mass balances and engineering calculations (defined in Sub-
section 2.4). Obviously, the larger the number of sources, the
more difficult it will be to estimate the total release.
2.4 DEFINITIONS OF MAJOR APPROACHES
The preceding examples illustrated four basic approaches to estimating
releases after release points have been identified. These approaches are
defined here:
0 Calculations based on measured concentrations of the chemical in a
waste stream and the volume/flow rate of that stream.
0 Mass balance around entire processes or pieces of process equip-
ment. The amount of a chemical leaving a vessel equals the amount
entering. If input and output or "product" streams are known
(based on measured values), a waste stream can be calculated as the
difference between input and product (any accumulation/depletion of
the chemical in the equipment, e.g., by reaction, must also be
accounted for).
0 Emission factors, which (usually) express releases as a ratio of
amount released to process or equipment throughput. Emissions
factors, which are commonly used for air emissions, are based on
the average measured emissions at several facilities in the same
industry.
0 Engineering calculations and/or judgment based on physical/chemical
properties and relationships such as the ideal gas law.
A single release estimate may involve the use of more than one of these
estimation techniques; for example, when a mass balance is used to estimate
the amount of wastewater leaving a process, and water solubility is used to
calculate the maximum amount of chemical in that wastewater.
Estimates may be based on analogy. The emission factor approach relies
heavily on your determination that your process is analogous to the process
for which data were used to derive the factor. The use of any published data
(for example, on the effectiveness of wastewater treatment for a chemical or
on the releases from a papermaking plant) implies that the treatment schemes
of processes are analogous to those you are using. Extreme caution should be
used in the application of an analogy, especially from one facility to anoth-
er.
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2.5 SOME OBSERVATIONS ON THE USE OF DATA
You may be able to estimate a release in several ways based on the
various sets of data that are available. If this is the case, you will have
to make a decision as to which estimate to report based on the expected
accuracy of each. Assuming that equally valid and equally accurate data are
available for each of the preceding approaches, the following caveats should
be noted:
° Data on the actual released waste will generally provide a better
estimate than data on the waste before treatment (to which a treat-
ment efficiency must be applied).
0 Data on the aggregate stream are preferable to data on the several
streams that make up the aggregate.
0 Data on the specific chemical are preferable to data on an
analogue.
0 Data on the chemical for a specific process are preferable to
published data on similar processes. In fact, data on the treat-
ment efficiency for a close analogue chemical treated at a specific
facility will probably provide a better estimate than published
data on the actual chemical, as operating conditions vary greatly
from plant to plant. It may be easier to make a good chemical
analogy based on physical/chemical properties than to make a pro-
cess analogy.
Data (for example, on the concentration of chemical in wastewater) may
be available as a range of measured values. In this case, the average value
of all measurements should be used for data specific to the facility as it
operated in the reporting year, unless it can be demonstrated that some data
points can be disregarded. If operating conditions varied during the year
(e.g., the listed chemical was used periodically or new equipment was in-
stalled at midyear), releases should be estimated for each set of conditions
(e.g., 3 months during which the chemical was used, 9 months during which it
was not), and these values should be added. Representative data taken during
the reporting year should be used. You should, however, consider whether
including data from previous years might improve the estimate because so few
samples are taken each year.
With regard to published data on other processes, the average for
facilities/equipment/operating conditions most closely analogous to the one
in question should be used.
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2.6 WHICH APPROACH TO USE
Selection of the best approach to estimating releases depends on the
circumstances at your facility. Available information on a process may be
the single most important factor in determining how to proceed. This subsec-
tion provides some general guidelines on the most effective approach(es),
assuming that information is available to complete the analysis. It is
organized according to type of release.
2.6.1 Fugitive Air Emissions
Measurement data on fugitive air emissions will rarely be available.
Furthermore, the fugitive emissions from most single sources is small com-
pared with the total volume of chemical handled; therefore, inaccuracies in
measurements of input and output can totally mask the magnitude of the re-
lease if mass balance is attempted (ah exception is the example of all sol-
vent volatilized after application of a coating). For this reason, the use
of emission factors is a major method for estimating fugitive air emissions.
This approach requires the following:
0 A published factor (usually reported as pounds emitted per pound of
chemical processed or pounds emitted per piece of equipment, such
as a valve).
0 The amount'of chemical handled at a facility and/or a count of the
valves, pumps, etc., for which emission factors are available.
Specific emission factors are available for only a few processes as a
whole (see Table 3-5 in Section 3 entitled "Availability of Chemical-Specific
Emission Factors for Various Processes"), and these process-specific factors
can only be applied to processes that are very similar to the one for which
the factor was developed.
Volatilization equations can also be used for open vessels or for
spills. This approach, however, requires that the vapor pressure of the
chemical at the appropriate temperature, its molecular weight, and the open
surface area be known or estimated (see Sections 3 and 6).
2.6.2 Point Source Air Emission
Point-source air emissions are enclosed; thus, such releases are much
more likely to have been measured (as compared with fugitive air emissions)
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This permits calculations based on available data on the concentration and
flow rate of the emission. For example, multiplication of the measured
benzene concentration by the measured flow rate of air through a vent yields
the quantity of benzene being released. Unavailability of analytical tech-
niques for determining airborne concentration of many of the chemicals on the
list limits this approach. When this is the case, total hydrocarbon analysis
can be used to set an upper limit to the estimate.
Emission factors specific to some point sources (e.g., the reactor vent
for ethylene dichloride production) are available and should be used if
monitoring data are not available.
When these approaches are not possible, estimates for point sources must
be based on mass balance calculations or on engineering calculations, design
data, etc. Point sources such as storage tanks will usually require a
calculation based on physical properties of the chemical, the throughput, and
the configuration of the storage tank. (See Section 3 for example of storage
tank release calculations.)
2.6.3 Releases to Wastewater
Many of the listed chemicals for which your facility may.be subject to
reporting requirements may be controlled under Federal, State, and/or local
regulations. Frequently, wastewater discharges will have been monitored. If
this is the case, release can be calculated directly. In fact, your dis-
charge permit and Discharge Monitoring Reports may contain sufficient infor-
mation to support any needed calculations (i.e., concentration of the listed
chemical in the discharge and the wastewater flow rate). Multiplication of
the measured concentration by the measured flow will yield an estimate of the
release.
When monitoring data for the listed chemical are not available at your
facility, the following approaches may be applicable (in approximate order of
preference):
0 Identifying individual process points that contribute to water
discharge, performing a mass balance calculation around each to
determine individual releases, and then totaling them.
0 Conducting a mass balance around the process as a whole. For
example, input of dye equals output on dyed fabric plus output in
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wastewater (individual sources of that water need not be esti-
mated). This approach is most appropriate if the only release of
the listed chemical is through a wastewater stream.
0 Using discharge data on the listed chemical from similar facili-
ties. This approach is particularly useful if the industry has
been studied by EPA's Office of Water Regulations and Standards and
an Effluent Guidelines Background Document containing release
estimates or typical waste stream concentrations for that industry
is available.
2.6.4 Releases in Solids, Slurries, and Nonaqueous Liquids
Some of these wastes may be regulated as hazardous wastes under the
Resource Conservation and Recovery Act (RCRA). Information in the permit and
manifests for disposing of the waste provide a basis for estimating released
quantities of a listed chemical. Frequently, however, the concentration of
individual chemicals that make up a waste will not have been measured. In
this case, the concentration of the listed chemical will have to be deter-
mined, either by measurement or by an estimation method based on mass bal-
ance, engineering calculations, etc.
For nonhazardous wastes in this category, the volume or total weight of
the waste should be readily derivable from shipping records, a count of waste
containers, etc. Again, the important factor to determine is the concentra-
tion of the listed chemical.
Unfortunately, there are no solid waste emission factors and little
published data on concentrations of chemicals in such wastes. When monitor-
ing data are not available for a waste, mass balance and engineering calcula-
tion approaches will be necessary.
2-10
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OUTLINE FOR SECTION 3
ESTIMATING RELEASES TO AIR
3.1 Sources of Releases to Air and Release Estimation Methods
3.1.1 Process Vents
3.1.2 Releases From Material Handling, Storage, and Loading
3.1.3 Fugitive Emissions
3.1.4 Releases to Air From Wastewater Treatment and Solid Waste Dis-
posal
3.2 Air Pollution Control Equipment and Treatment Efficiency
3.2.1 Combustion
3.2.2 Adsorption
3.2.3 Absorption
3.2.4 Condensation
3.2.5 Particulate Collection Devices
3-0
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-------
SECTION 3
ESTIMATING RELEASES TO AIR
Air emissions can originate from a wide variety of sources and therefore
are usually not centrally collected before being discharged; as a conse-
quence, each source or category of sources must be evaluated individually to
determine the amount released. Often, releases to air are reduced by the use
of air pollution control devices, and the effectiveness of the control devic-
es must be accounted for in the calculation of the release estimate. This
section provides various methods for estimating releases to air and for
determining the efficiency of pollution control devices. A bibliography of
reports pertaining to releases and efficiency of the various pollution con-
trol devices is provided at the end of this section. These reports present
more specific emission data on various industries.
3.1 SOURCES OF RELEASES TO AIR AND RELEASE ESTIMATION METHODS
Releases to air from industrial processes can be broadly categorized as
follows: point sources, such as stacks and vents, and fugitive sources,
which are not contained or ducted into the atmosphere. Whether a source is
considered a point or fugitive source depends on whether the release is
contained in a duct or stack before it enters the atmosphere. Table 3-1
lists common air emission sources that should be considered when estimating
releases. Examples in the following subsections illustrate the emission
estimation methods described in Section 2 for air emission sources. The
examples presented in this section and throughout the manual are for purposes
of illustration only; they are not meant to predict actual releases.
3.1.1 Process Vents
In general, process vents are the main air exhaust devices in a manufac-
turing or processing operation functioning under normal conditions; however,
emergency venting devices on unit operations, such as relief valves, are also
3-1
-------
TABLE 3-1. SOURCE CATEGORIES FOR COMMON RELEASES TO AIR
00
ro
(1)
Process vents
Reactors
Distillation system
'Vacuum systems
Baghouses or precipi-
tators
Combustion stacks
Blow molding
Spray drying
Curing/drying
Scrubbers/absorbers
Centrifuges
Extrusion operations
Pressure safety valves
Manual ventings
(2)
Secondary sources
Pond evaporation
Cooling tower evaporation
Wastewater treatment
facilities
(3)
Fugitive sources
Flanges/connectors
Valves
Pump seals
Compressor seals
Sample connections
Open-ended lines
Pressure relief
devices (e.g.,
rupture disks)
Lab hoods
Process sampling
Equipment inspection
Equipment cleaning
Equipment maintenance
Blowing out pipelines
Storage piles
(4)
Handling, storage, and loading
Breathing losses
Loading/unloading
Line venting
Packaging/container loading
NOTE: Process vents are usually point sources.
Secondary sources are usually not contained and are considered fugitive sources.
Storage tank emissions are considered as point sources; other loading and unloading releases could
be categorized as either point or fugitive sources, depending on whether the releases are ducted.
-------
grouped under process vents. The methods that can be used to estimate
releases to air from a process vent are discussed here; they include measure-
ment, mass balance, emission factors, engineering calculations, or a combina-
tion of these methods. Several examples are given to illustrate the basic
principles of each technique.
Measurement. Measurement is the most straightforward means of estimat-
ing releases.* The pollutant concentration and flow rate from a process vent
during typical operating conditions, if available, can be used to calculate
releases. Total annual releases are based on the plant operating schedule
for the year.
Example 3-1 - Use of measurement data to estimate releases to air from
a process vent:
Step 1. Assemble data from emission measurement task.
Measurements are taken at the oxychlorination vent of a plant produc-
ing dichloroethylene at its normal operating rate. The vent gas velocity
is measured and an average of 26 ft/s is obtained. The measured average
concentration of dichloroethylene is 0.22 gram/cubic meter (g/m3) after
correction to 70°F. The vent gas temperature is measured to be 200°F. The
diameter of the vent is 1 foot.
Step 2. Calculate volumetric flow of vent gas stream.
The next step in estimating emissions using this information is to
calculate the vent gas flow rate. The product of the velocity and the
stack cross-sectional area will be the actual volumetric flow.
Volumetric flow = Gas velocity x area
Area = 3.14 x (diameter)2/4
Volumetric flow =
x 3.14 (1 ft)2/4
20.41 ft3
second
at 200°F
Step 3. Calculate annual releases.
The dichloroethylene concentration, 0.22 g/m3, was reported at a stan-
dard temperature, 70°F. The actual emission rate is derived by making a
volume correction to account for the difference between standard and actual
Emission measurement is a complex procedure requiring specialized equipment
and personnel trained in chemical analysis and flow measurement. The de-
scription of sampling procedures is beyond the scope of this document. The
EPA emission test procedures for regulated compounds are described in the
Code of Federal Regulations, 40 CFR 60, Appendix A, July 1986.
3-3
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vent gas absolute temperatures and multiplying the concentration by the
vent gas flow rate.
Actual emission rate = Volumetric flow x concentration
= 20.41 ft3
second
0.22 g
2.205 x 10"3 Ib .. 0.028 m3
cubic meter
gram
x (70°F + 460)°R*
(200°F + 460)°R
3600 seconds _ n
hour u'
cubic foot
80 Ib per hour
During this test period, the average plant production was 10 tons of
product per hour. From the calculated mass emission rate, the loss is
0.080 Ib/ton of product (0.80 Ib/h * 10 tons/h). On an annual basis, the
atmospheric release is determined for a production rate of 20,000 tons/year
as follows:
Annual release = 20»;°°rtons x
= 1603 Ib per year
NOTE:
1600 pounds per year.
This calculation assumes that the measured emissions are representa-
tive of the actual emissions at all times. This may not always be the
case. Ideally, using a continuous emission monitor to measure and record
releases would provide the most representative data and provide a basis for
calculating an average concentration.
Gaseous concentrations also are frequently expressec in parts per mil-
lion (ppm) by volume; i.e., a volume of the constituent in a million vol-
umes of vent gas. In this case, the vent gas volume must be multiplied by
the concentration and this value divided by the molar volume** (adjusted to
the vent gas temperature) and multiplied by the compound's molecular weight
to obtain the mass emission rate.
Some vent streams contain large amounts of water vapor (10 to 20 per-
cent by volume), and the actual vent gas rate includes this volume of
vapor. Concentrations of chemicals in the gas, however, are frequently
expressed on a dry basis. For an accurate release rate, the vent gas rate
should be corrected for its moisture content by multiplying by [1 minus the
fraction of water vapor]. The resulting dry volume can then be multiplied
by the chemical's concentration.
**
Absolute temperatures must be used in making volume-temperature correc-
tions based on the ideal gas law. Thus, 460 must be added to degrees
Fahrenheit and 273 to degrees Centigrade to obtain an absolute tempera-
ture expressed in degrees Rankine or Kelvin, respectively.
The molar volume of any gaseous compound is 359 ft /lb-mole at 32°F or
492°R.
3-4
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Mass Balance. As defined in Section 2, mass balance provides a means of
accounting for all the inputs and outputs of a chemical in a process. A mass
balance is useful for estimating releases when measured release data are not
available and when other inlet and output streams are quantified. The
amounts entering and/or leaving a process are either measured or estimated.
A mass balance can be performed on the process as a whole or on a subprocess.
Individual operations within the process usually must be evaluated.
Example 3-2 - Use of a mass balance to estimate releases to air from a
process vent:
Step 1. Draw a diagram, label all streams, and list input and output
values.
Consider a unit process that uses Chemical X to produce a product. In
a year, 10,000 Ib of Chemical X is used to produce 24,000 Ib of a product
containing 25 percent of Chemical X by weight. The input consists of 8000
Ib of purchased Chemical X and 2000 Ib that is collected from recycling.
This process generates 5 tons or 10,000 Ib of solid waste containing 15
percent (1500 Ib) of Chemical X. The only other unit process stream is a
process vent, which emits an unknown amount of Chemical X to the atmo-
sphere. Figure 3-1 presents a schematic of this hypothetical unit process.
PROCESS
VENT
-MASS BALANCE
BOUNDARY
,
CHEMICAL X
INPUT
^
; ^
I
RECYCLE
UNIT
PROCESS
^
r
WASTE
PRODUCT _
Figure 3-1. Hypothetical unit process using Chemical X.
Step 2. Set up equations with input streams equal to ouput streams.
Considering the quantities of Chemical X in all streams that enter or
leave the process, the amount of Chemical X that is lost through the
process vent on an annual basis can be estimated as follows:
Input = Amount purchased (8000 Ib)
Output = Product (24,000 Ib x 25%) + waste (10,000 Ib x 15%) + process
vent loss (unknown)
3-5
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Input = Output
8000 Ib Chemical X = 6000 Ib + 1500 Ib + process vent loss
Process vent loss = 8000 - 6000 - 1500 = 500 Ib Chemical X per year
NOTE;
In this example, suppose that an error of 5 percent was made in the
quantity of materials purchased; i.e., the input of Chemical X into the
process was thought to be 8400 Ib rather than the actual 8000 Ib. Substi-
tuting 8400 Ib of Chemical X into the mass balance equation,yields an air
emission of 900 Ib (i.e., an 80 percent error). This illustrates the
sensitivity of emission estimates based on mass balances to small errors in
raw material and product quantities. Care must be taken to ensure that
accurate values of raw materials and product quantities are available
before a mass balance is used to make release estimates.
Emission Factors. A third technique for estimating air releases from
process vents involves the use of emission factors. One type of emission
factor relates a quantity of a pollutant to some process-related parameter or
measurement. The amount of pollutant per quantity of product is frequently
used.
Example 3-3 - Use of an emission factor to estimate releases to air
from a process vent:
Step 1. Assemble emission factor information from literature.
Hydrofluoric acid is being produced by reacting fluorspar with sul-
furic acid. The emission factor given in EPA Publication AP-421 is 50
pounds of fluoride per ton of acid product. The plant produced 55,000 tons
of acid in the past year.
Step 2. Calculate releases.
In the absence of more accurate information (such as measurement data,
etc.), the uncontrolled fluoride emissions from the process would be calcu-
lated as follows:
tons
= 2,750,000 Ib per year
Based on information in AP-42, the use of a water scrubber to control
releases would reduce emissions to 0.2 Ib of fluorides per ton of acid.
Emissions after control would thus be:
55,000 tons „ 0.2 Ib _
year
ton
= 11,000 Ib per year
3-6
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NOTE:
Releases from other unit processes could be calculated in a similar
manner, and the amounts from all unit processes would be summed to estimate
the total release from the plant. When emission control devices (i.e., air
pollution control devices) are used to reduce emissions, atmospheric re-
leases are estimated by multiplying the uncontrolled emission by the quan-
tity (1 minus the fractional control efficiency).
Many air emission factors are expressed in terms of total volatile or-
ganic compounds (VOC) or particulates rather than a single chemical compound.
Emission factors for VOC's are available in "VOC Emission Factors for the
NAPAP Emission Inventory," EPA 600/7-86-052, December 1986.2 These data can
be used with actual process vent measurements of volatile organics or partic-
ulates to estimate emissions of a specific compound. The "Volatile Organic
o
Compound (VOC) Species Data Manual" • also provides information on numerous
air emission sources, which allows the user to estimate releases of specific
toxic compounds based on the total amount of VOC's emitted from a particular
source. Similarly, the "Receptor Model Source Composition Library" provides
information relating metals emissions to total particulate emissions for
different release sources.
Example 3-4 - Use of emission factors to determine releases of a
specific chemical to air:
Step 1. Assemble emission factor information from literature.
Air emissions from the blast furnace of a primary lead smelting facil-
ity are controlled by a fabric filter system. In Section 7.6 of AP-42
(Primary Lead Smelting), an emission factor for uncontrolled releases of
particulate is given as 361 Ib per ton of lead produced. Also in this
section, a particulate removal efficiency range of 95 to 99 percent is
provided for fabric filter control devices used for primary lead smelting
operations.
Step 2. Calculate particulate releases.
Assuming the fabric filter system is 97 percent efficient, the particulate
emission factor is reduced to:
(1'00 - °'97> x lln leadPapr?oSuceSe = 10'83 1b Paniculate P^ ton of lead
Thus, an annual production of 31,500 tons of lead will result in the
emission of 341,145 Ib of particulate (10.83 x 31,500).
3-7
-------
Step 3. Calculate specific chemical releases.
The "Receptor Model Source Composition Library" is used to determine the
amount of toxic compounds emitted. Source Profile No. 29302 gives a
typical chemical composition for particulate matter sampled downstream of a
fabric filter controlling emissions from a primary lead smelting blast
furnace. Based on this information, annual emissions of individual toxic
compounds can be calculated by multiplying the respective chemical composi-
tion by the total particulate 341,145 Ib/yr. The specific compounds found
according to this data source, their respective percentages of the total
particulate matter, and their resultant annual emissions are summarized
below.
Compound
Percentage of
particulate
Annual
emissions, Ib
Report, Ib
Chromium
Nickel
Copper
Zinc
Cadmium
Lead
0.02
0.06
0.35
15.2
23.1
30.7
68.2
204.7
1,194.0
51,854.0
78,804.5
104,731.5
70
200
1,200
52,000
79,000
105,000
Emission factors have been developed for a number of processes and
pollutants. The bibliography at the end of this section lists literature
sources containing emission factors for some industries. The source of an
emission factor must be carefully evaluated to determine that it is applica-
ble to the process vent in question at your facility. The Journal of the Air
Pollution Control Association deals primarily with the subject of air emis-
sions and controls. Appendix E lists industries for which emission factors
have been published in EPA's Publication AP-42, "Compilation of Air Pollutant
Emission Factors."
Another good source of air emission factors is a series of reports
published by the EPA on locating and estimating emissions for specific toxic
chemicals. Reports for 13 chemicals are currently available. All are listed
in the Bibliography under "U.S. Environmental Protection Agency" and are
identifiable by the number series "EPA 450/4-84-007a through m."
Engineering Calculations. When parameters related to emissions cannot
be directly measured, emissions may be estimated or inferred through en-
gineering calculations and/or measurement of other secondary parameters
(i.e., physical/chemical properties of the materials involved, design in-
formation on the unit operation for which the estimate is being made, or
3-8
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emission information from similar processes). Engineering calculations are
generally used to "fill in" information needed for one of the other emission
estimation methods.
Information derived from equipment design, such as fan curves, vessel
capacities, operating temperatures, and operating pressures, can be used to
estimate gaseous flow rates. Physical/chemical information derived from the
ideal gas law, vapor pressure, and equilibrium relationships can frequently
be applied when estimating gaseous concentrations of a particular compound.
A common approach to calculating the concentration of a compound in the
vapor phase over a liquid is to determine its partial pressure. The partial
pressure of a compound divided by the total pressure of the gas stream is
equal to the mole fraction of the compound (XAG) in the stream. The follow-
ing paragraphs discuss two methods of determining the partial pressure of a
compound in a gas stream at equilibrium. Even though equilibrium may not
occur for the process under consideration at your facility, these methods can
provide approximate results.
In dilute aqueous solutions (i.e., when gases are dissolved in low con-
centrations in water), the partial pressure of the gas above the liquid sur-
face (P.) is equal to the mole fraction of the compound dissolved in the
iiquid (XAL) multiplied by Henry's law constant (H); P. = x,,H. Thus, if the
Henry's Law constant can be estimated or found in the technical literature
for the solution temperature, the partial pressure of a gas above this liquid
can be estimated by multiplying the mole fraction in solution by the constant
H at the solution temperature. This relationship, however, is only valid for
dilute aqueous solutions.
The partial pressure of a compound in the vapor phase over a solution
(organic or aqueous) also may be estimated by multiplying its mole-fraction
in the solution by the vapor pressure it exerts when it is pure; i.e.
PA = xALP° (Raoult's Law)
where P° = vapor pressure of pure liquid
XAL = mo1e fractlon °f tnat liquid in solution
PA = partial pressure exerted by that compound in the vapor phase
over the solution
3-9
-------
This equation is valid only for ideal solutions, however, and should
only be used to make an approximation. At equilibrium, the partial pressure
divided by the total pressure (Pj) will give the mole fraction in the gas
stream.
AG = mole fraction of A in gas phase
Example 3-5 - Use of engineering calculations to estimate releases to
air from a process vent:
Step 1. Assemble process composition information.
A process vessel containing 5 wt. percent A, 15 wt. percent B, and 80
wt. percent C is vented to the atmosphere. The discharge rate through the
vent has been measured at 5 ft3 per minute at 70°F. The process tank is in
service 200 days/yr. At 32°F, 1 Ib-mole of the gas occupies 359 ft3.
Step 2. Calculate composition of vented gas.
Assuming equilibrium between air and liquid in the tank, the emissions
of A are calculated by using the following equations:
wt. % A
MW.
X., = mole fraction. =
ML M wt. % A ^ wt. % B A wt.
MW,
MW
B
MW,
(1)
where MW s molecular weight of compound
wt. % = percent by weight
= x
A
AL
where P° s vapor pressure of A at ambient temperature
(2)
14.7
fraction of A in gaseous phase, X
AG
(3)
Equation 3 calculates the fraction of A in the gaseous phase at standard
temperature and pressure.
Step 3. Calculate annual release.
To calculate the annual release, multiply the following factors:
5 ft3 v 60 min v 24 h 200 operating days
~~ — " " -
v v
x ~mTn~ x *
v
FT" x day" x
yr
_
1477'
3-10
-------
Ib-mole (32°F + 460)°R (MW) Ib . . , . , . .ti .
359 ft» (706F + 460)6R x Ib-mole = pounds of chemical A emitted per year
where Py/14.7 is a correction for the pressure at the vent. PT may be
assumed to be 14.7 in the absence of pressure measurement data!
A combination of the previous methods often can be used to estimate air
releases. The following example demonstrates the combined use of an emission
factor, a mass balance, and an engineering calculation.
Example 3-6 - Use of an emission factor, mass balance, and an engi-
neering calculation to estimate releases to air from a process vent:
Step 1. Layout process and obtain process information.
Perch!oroethylene (PCE).is emitted from open-top vapor degreasing
processes via evaporation. The emission factor for this process has been
determined to be 0.78 Ib per pound of PCE entering the degreaser.5 The PCE
entering the degreaser consists of recycled PCE and fresh PCE makeup.
Spent PCE from the degreaser is sent to solvent recovery, where 75 percent
is estimated to be recovered and subsequently recycled. The 25 percent
that is not recovered is sent offsite for disposal.
Fresh PCE ^
i
1PCE Emissions
Degreaser
Spent PCE ^
Solvent
Recovery
,
Nonrecoverable
PCE
Recycled PCE
To determine how much PCE is emitted from the degreaser, one needs to
determine the pounds of PCE emitted per pound of fresh PCE used; the amount
of fresh PCE used should be ascertainable from the facility's records.
This factor can be calculated if the amount of PCE recycled per pound of
fresh PCE used is known. A mass balance approach can be used to calculate
the necessary emission factor.
Step 2. Set up mass balance around degreaser.
Using a basis of 1 Ib of fresh PCE entering the degreaser and letting
X = pounds of PCE recycled per pound of fresh PCE used, set up a mass
balance around the degreaser. The total amount into the degreaser equals
(1 + X). A material balance around the degreaser is made to determine the
spent PCE rate.
3-11
-------
Input = Output
Fresh + recycled = emissions + spent solvent
(1 + X) = 0.78 (1 + X) + spent solvent
0.22 (1 + X) = spent PCE
Step 3. Set up mass balance around solvent recovery system.
Knowing that 75 percent of the spent PCE is recycled, a mass balance
around the solvent recovery process can be expressed as follows:
Input = Output
Spent = recycled + nonrecoverable
0.22 (1 + X) = 0.75 [0.22 (1 + X)] + nonrecoverable
0.055 + 0.055X = nonrecoverable PCE
Step 4. Set up mass balance around entire process.
An overall mass balance around the entire process can be used to solve
for X:
I
ihb
(Fresh PCE)"
I
I
(PCE Emissions)
Degreaser
0.22 (1 + X)
(Spent PCE)
X (Recycled PCE)
0.055 + 0.055X
(Nonrecover-
able PCE)
Overall Mass
Balance Boundary
Line
Input = Output
Fresh PCE = emissions + nonrecoverable PCE
1 = 0.78 (1 + X) + 0.055 + 0.055X
1 = 0.78 + 0.78X + 0.055 + 0.055X
X = 0.2 Ib of PCE recycled per pound of fresh PCE used
Step 5. The PCE emitted per Ib of fresh PCE can then be calculated.
PCE emissions = 0.78 (1 + X)
= 0.78 (1 + 0.20)
= 0.94 Ib per pound of fresh PCE
Total annual emissions of PCE would be 0.94 times the total amount of
fresh PCE consumed annually.
3.1.2 Releases From Material Handling. Storage, and Loading
Releases of chemicals from material handling, storage, and loading may
result from both breathing and working losses. Breathing losses are due to
3-12
-------
vapor expansion and contraction, which force vapor from a tank or vessel.
Expansion and contraction are caused by temperature and atmospheric pressure
fluctuations. Working losses occur when the tank or vessel is filled or
emptied.
These types of releases are generally estimated by the use of emission
factors and engineering calculations. The U.S. EPA publication "Compilation
of Air Pollutant Emission Factors" (AP-42) provides equations for estimating
air emissions from organic liquid storage and handling operations. These
equations contain factors that depend on tank parameters and service condi-
tions. For convenience, the storage tank equations and factors are provided
in Appendix C. For emissions from loading operations (tank trucks, barges,
etc.), use equations and factors in Table 3-2.
TABLE 3-2. CALCULATING LOADING LOSSES FOR VOLATILE ORGANIC LIQUIDS1
Li =
. 45
SPM
where
L. = release in pounds/1000 gal of liquids loaded
P = liquid vapor pressure, psia (see chemical handbook or
Appendix B)
M - molecular weight (see chemical handbook or Appendix B)
.. T-= liquid temperature, °R (°F + 460)
S = Saturation factor depending on carrier and mode of "
operation as shown below:
Cargo carrier Mode of operation
Tank trucks and tank cars Submerged loading of a clean
. . cargo tank
Splash loading of a clean
cargo tank
Submerged loading: normal
dedicated service
Splash loading: normal dedi-
cated service
Submerged loading: dedicated
vapor balance service
Splash loading: dedicated
vapor balance service
Marine vessels Submerged loading: ships
Submerged loading: barges
S factor
0.50
1.45
0.60
1.45
1.00
1.00
0.2
0.5
3-13
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Example 3-7 - Use of an emission factor to estimate releases to air
from material storage:
Step 1. Assemble tank and product data.
The following calculations are for a 10,000-gallon, white, fixed-roof
tank that holds 1,1,1-trichloroethane at an average temperature of 60°F.
The tank is 10 feet in diameter and 17 feet high. On the average, the tank
is half full and has a throughput of 2000 gallons per month, or 24,000
gallons per year. The average diurnal (day and night) temperature change
is 20°F. Ambient pressure is 1 atmosphere or 14.7 psi. Chemical handbook
data8 show that 1,1,1-trichloroethane has a molecular weight of 133 and a
vapor pressure of 1.6 psi at 60°F. The vapor pressure may be estimated by
plotting temperature against vapor pressures obtained from handbooks and
selecting the pressure at the given temperature.
Step 2. Use Equation 1 for calculating breathing losses from Appendix C:
2.26 x 10"2M,
0.68
(1)
where LR = fixed roof breathing loss (Ib/yr)
MV = molecular weight of vapor in storage tank (Ib/lb mole), see Note
1 in Appendix C
Pfl = average atmospheric pressure at tank location (psia)
A
P
D
H
AT
FP
C
Step 3.
M * 133
- true vapor pressure at bulk liquid conditions (psia), see Note 2
in Appendix C
= tank diameter (ft)
= average vapor space height, including roof volume correction
(ft), see Note 3 in Appendix C
= average ambient diurnal temperature change (°F)
= paint factor (dimensionless), see Table 4.3-1 in Appendix C
= adjustment factor for small diameter tanks (dimensionless), see
Figure 4.3-4 in Appendix C
= product factor (dimensionless), see Note 4 in Appendix C
Calculate each of the factors and insert into Equation 1.
3-14
-------
P. = 14.7 psia
P = 1.6 psia
D = 10 ft
H = (17 ft)(i) since the tank is half full
AT = 20°F
Fp = 1 since tank is white
C = 0.51 obtained from Figure 4.3-4 in Appendix C
KC = 1 since this is an organic liquid (as per Appendix C)
Substituting these values in Equation 1 yields
= 2.26 x
'
(1)
= 262.5 pounds/year
Working losses can be estimated by using Equation 2 in Appendix C.
LW = 2.40 x io
"5
MVPVNKNKC
(2)
where L = fixed roof working loss (Ib/year)
W
= molecular weight of vapor in storage tank (Ib/lb-mole); see
Note 1 to Equation 1 in Appendix C
P = true vapor pressure at bulk liquid temperature (psia); see
Note 2 to Equation 1 in Appendix C
V = tank capacity (gal)
N = number of turnovers per year (dimensionless)
M = Total throughput per year (gal)
Tank capacity, V (gal)
K,, = turnover factor
K« = product factor
3-15
-------
Again, calculate each of the factors and insert into Equation 2:
Mv * 133
P s 1.6 psia
V - 10,000 gallons
N - 24.000 gallons used
~ 10,000-gallon capacity
1 obtained from Figure 4.3-7 in Appendix C
KC = 1 since this is an organic liquid (as per Appendix C)
Substituting these values into Equation 2 yields:
•w
(2.40 x 10-5)(133)(1.6 psia)(10,000 gal Ions) (
122.6 pounds/year
) (i ) ( i )
Total losses due to handling = I_B + LW = 262.5 + 122.6 = 385.1 pounds/year
Report 390 Ib/yr
The density of 1,1,1-trichloroethane is 11.2 pounds per gallon.
Annual throughput is 24,000 gallons or 269,000 pounds. The calculated
annual release is 385 pounds. A mass balance could not determine a 385-
pound loss in 269,000 pounds handled. Consequently, the use of emission
factors is an appropriate method for estimating tank releases.
NOTE:
If the storage tank in the this example contained a mixture of materi-
als A and B, the air releases could be calculated in a similar manner given
the mole fractions of the components in the liquid chase (X., and XB,.) and
the vapor pressure of the pure components (P? and PR). The molecular
weight and vapor pressure used in the calculation of breathing and working
losses would be calculated as:
Molecular weight = MV = (M.) x
(M>
True vapor pressure = P£ = (Pj)(XAL) + (PJS)(XBL)
3-16
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These values would be used in the previous equation to calculate total
emissions. Each component would be released in proportion to its mole
fraction in the gas phase (X
ed as:
and XBC) in the tank, which can be calculat-
XA6~
P° X
PA XAL
The gaseous mole fractions must be converted into weight fraction (in gas
phase) by use of the following equation:
W
XA6MA
AG
XA6 MA + XB6 MB
The weight fraction of component A in the gaseous air emissions can then be
multiplied by the total pounds of emissions per year as previously calcu-
lated.
3.1.3 Fugitive Emissions
Fugitive emissions are those emissions that are not released through a
stack, chimney, vent, or other confined vent stream. These releases include
process leaks, evaporation from open processes and spills, and raw material
and product loading and unloading losses. Whenever possible, fugitive emis-
sions should be calculated by the use of data available from direct measure-
ment. Fugitive emissions, however, often have to be estimated by the use of
emission factors or engineering calculations because they are too diffuse
and/or dilute to be measured directly, or they are too small relative to the
amounts of material processed to permit the use of a mass balance. This is
particularly true of hazardous and/or toxic air pollutants. An EPA report
entitled "Hazardous Waste Treatment, Storage, and Disposal Facilities (TSDF)
- Air Emission Models" provides methods for the estimation of emissions from
container loading, storage, and cleaning; waste treatment and disposal opera-
tions; and equipment leaks in the synthetic organic chemical manufacturing
industry.
Uncaptured Process Releases. One basis for estimating process fugitive
releases is the use of plant air measurement data. Health and safety regula-
tions may require measurements of regulated air pollutant concentrations on
3-17
-------
either an absolute or not-to-exceed basis. These data could provide a basis
for determining fugitive emissions. Occupational standards themselves,
however, should not be used to calculate emissions; only actual measurements
taken to ensure compliance with the standards should be used.
Example 3-8 - Use of measurement data to estimate the potential re-
lease to air from an uncaptured process:
Step 1. Determine basis for estimating releases and assemble necessary
data.
Employee exposure to benzene should not exceed 1 ppm as an 8-hour
time-weighted average. A plant has an alarm system that responds to 0.2
ppm benzene and a ventilation system that exhausts 20,000 acfm of room air
at 70°F. If the alarm has not sounded during the course of the year and
the plant operates 24 hours per day, 330 days per year, a conservative
estimation of benzene fugitive releases could be performed as follows:
Step 2. Calculate releases.
Benzene releases per year would be calculated as follows:
20,000 ft3 60 minutes 24 hr 330 days 0.2 ft3 benzene
minute hour day year In6
10" ft" air
= 1900.8 ftw
The density of benzene vapor is 0.2 lb/ft3, and the annual release
would be less than:
1900 ft benzene
year
Qf
ft
Report 380 Ib of benzene/year. This value thus serves as an upper
limit of potential releases.
Leaks in Vessels, Pipes, Valves, etc. The accepted method of estimating
releases from leaks in vessels, pipes, and valves is to use emission factors.
Various factors are available to estimate releases due to leaks in process
streams carrying hydrocarbon vapors, light liquids (more volatile than kero-
sene, i.e., a vapor pressure greater than 0.1 psia at 100°F), or heavy liq-
uids (equal to or less volatile than kerosene). These factors can also be
used to estimate fugitive emissions in other industries that process hydro-
carbon streams.
For convenience, data to estimate releases from leaks are included in
Appendix Tables D-l and-D-2. These data are based on information in EPA
3-18
-------
Publication EPA-450/3-86-002, entitled "Emission Factors For Equipment Leaks
of VOC and HAP." This report addresses fugitive emissions and reductions due
to scheduled operation and maintenance procedures.
The EPA has also published a protocol for use in estimating emissions
from equipment leaks entitled "Protocols for Generating Unit-Specific Emis-
sion Estimates for Equipment Leaks of VOC and HAP." This protocol provides
for the use of EPA's average emission factors, along with equipment component
counts or screening data for calculating fugitive emission rates. The emis-
sion factors used in this approach are based on typical refinery and synthet-
ic organic chemical manufacturing plants.
Example 3-9 - Use of emission factors to estimate releases to air from
leaks in vessels, pipes, and valves:
Step 1. Compile an inventory of fittings and appurtenances that may leak
organic compounds.
A chemical plant uses benzene (a light liquid with a vapor pressure
greater than 2 psia) and has six pipe valves, three open-end valves, four
flanges, two pumps, one compressor, and one pressure-relief valve. The
plant operates 24 hours a day, 250 days a year. Average factors from
Appendix D-l are used to estimate fugitive emissions.
Step 2. Review maintenance schedule and select appropriate emission
factors based on leak rates.
The following calculation uses light liquid service factors and units
of pounds per hour from Appendix D:
(6 x 0.016)
+ (3 x 0.0037)
+ (4 x 0.0018)
+ (2 x 0.11)
+ (1 x 0.5)
+ (1 x 0.23)
(pipe valves)
(open-end valves)
(flanges)
(pumps)
(compressor in vapor service)
(pressure-relief valves in vapor service)
= 1.064 pounds per hour
- 6384
Report 6400 Ib/yr
3-19
-------
NOTE;
In this example, an average value of the emission factors was used.
The factors cover a range, and a higher or lower value might be more appro-
priate if the number of leaks are identified through a leak detection
screening study.
3.1.4 Releases to Air From Wastewater Treatment and Solid Waste
Disposal ~~~
Secondary emissions of volatile compounds to the air may occur from the
onsite treatment of aqueous or solid waste. The bulk of secondary emissions
are estimated to result from the handling, pretreatment, and final treatment
(primarily biological treatment) of aqueous wastes. Other sources include
surface impoundments, landfilling, and incineration of liquid and solid
waste.
Estimating releases of volatile compounds from disposal is complex and
requires detailed knowledge of the compound's parameters and the disposal
procedure. Table A-2 in Appendix A presents data on the fate of some toxic
compounds in secondary wastewater treatment plants, including the percentage
of the compound in the influent that is volatilized to air. These data,
however, should be used only when operating conditions are similar to those
under which the data were derived.
Analytical models have been developed by EPA's Office of Air Quality
Planning and Standards (OAQPS) to estimate emissions of volatile organic
compounds via various pathways from emission sources at hazardous waste
disposal sites. These models are discussed in a draft EPA report entitled
"Hazardous Waste Treatment, Storage, and Disposal Facilities (TSDF) -• Air
Emission Models," dated December 1987. To make reasonable estimates of
volatile releases, one must know which pathways predominate for a given
chemical, type of waste site, and set of meteorological conditions. Models
have been developed for the following emission sources:
0 Nonaerated impoundments (which include quiescent surface impound-
ments and open-top tanks)
0 Aerated impoundments (which include aerated surface impoundments
and aerated tanks)
0 Disposal impoundments (which include nonaerated disposal impound-
ments)
3-20
-------
0 Land treatment
Landfills
Computerized methods for applying these emission models are being devel-
oped by EPA. Models for aerated and nonaerated impoundments, lagoons, land-
fills, wastepiles, and land treatment facilities have been installed in an
integrated spreadsheet program, CHEMDAT4, which allows a user to calculate
the partitioning of volatile compounds among various pathways depending on
the particular parameters of the facility of interest. The EPA report in-
cludes a diskette containing the program for use on an IBM PC and a user's
guide.
3.2 AIR POLLUTION CONTROL EQUIPMENT AND TREATMENT EFFICIENCY
Air pollutants entering an air control device may undergo one or more of
the following: 1) they may be transferred from the air stream to another
medium, 2) they may be modified to a less toxic state, 3) they may be de-
stroyed through combustion and/or dissociation, or 4) they may pass through
untreated. The physical characteristics of the pollutant to. be removed
generally determine which type of control device is used. Table 3-3 presents
a summary of air pollution control techniques used to control some of the
various pollutants of concern.
Estimates of releases to air must take into account, the control equip-
ment efficiency. This efficiency should be based on the amount of pollutant
removed from the air inlet stream of the control device by destruction, by
modification, or by transfer to another medium.
Percent efficiency =
X inlet - X outlet
X inlet
x 100
where X inlet = Total mass of pollutant X flowing to the air inlet of the
control device in a given year
X outlet = Total mass of pollutant X flowing from the air outlet of the
control device in a given year
The amount of pollutant transferred to and subsequently released in another
medium (solid or water) would be included in the releases of that particular
pollutant in that medium.
3-21
-------
TABLE 3-3. TECHNIQUES FOR CONTROLLING SELECTED AIR POLLUTANTS'
Catalytic incineration Thermal incineration Boilers/process heaters5
Flares1
Absorption
co
i
ro
Acrylic acid
Acrylonitrile
Benzene .
Butadiene
Cumene
Ethylene dichloride
Ethylene oxide
Phenol
Acrolein
Acrylonitrile
Ani1i ne
Benzene
Benzyl chloride
Butadiene
Epichlorohydrin
Ethylene dichloride
Formaldehyde
Methyl chloroform
Perchloroethylene/
trichloroethylene
Polychlorinated
bipheyhyls
Toluene
Toluene diisocya-
nate
Vinylidene chloride
Butadiene
Cumene
Ethyl benzene/styrene
Ethylene oxide
Formaldehyde
Phenol
Propylene oxide
Acetaldehyde
Acrolein
Acrylic acid
Acrylonitrile
Ally! chloride
Butadiene ,
Chloromethanes
Chloroprene
Cumene
Ethyl benzene/
styrene
Ethylene oxide
Formaldehyde
Methyl methacrylate
Propylene oxide
Acetaldehyde
Acrylonitrile
Acrylic acid
Ally! chloride
Aniline
Benzene
Benzyl chloride
Butadiene
Carbon tetrachloride
Chlorobenzene
Chloromethanes
Chloroprene
Epichlorohydrin
Ethyl benzene/
styrene
Ethylene dichloride
Ethylene oxide
Methyl chloroform
Perch!oroethylene/
trichloroethylene
Phenol
Phosgene
Propylene/oxide
Vinylidene chloride
Xylene
(continued)
-------
TABLE 3-3 (continued)
Adsorption
Condensation
Fabric filters
Wet scrubbing
Electrostatic
precipitators
Cyclones;
co
i
ro
co
Acrylonitrile
Aniline
Benzene
Carbon tetrachloride/
perch!oroethylene
Chlorobenzene
Chloroform
Ethylene dichloride
Methyl chloroform
Methyl methacrylate
Methylene chloride
Phenol
Naphthalene
Phosgene
Styrene
Toluene
Toluene diisocyanate
Trichloroethylene
Vinyl chloride
Vinylidene chloride
Vinyl chloride
Xylene
Acetaldehyde
Acrylic acid
Acrylonitrile
Allyl chloride
Aniline
Benzene
Benzyl chloride
Butadiene
Carbon tetrachloride
Chlorobenzene ,
Chloromethanes
Chloroprene
Ethylbenzene/sty-
rene
Ethylene dichloride
Ethylene oxide
Formaldehyde
Methyl chloroform
Methyl methacrylate
Perchloroethylene/
trichloroethylene
Phenol
Toluene
Toluene diisocyanate
Vinylidene chloride
Xylene
Cadmium
Chromium
Copper
Nickel
Cadmium
Chlorobenzene
Chromium
Nickel
Toulene
diisocyanate
Cadmi urn
Chromium
Copper
Nickel
Cadmium
Copper
Nickel
Combustion techniques.
Refers to 1,3 butadiene.
Possible control technique.
Chloromethanes include methylene chloride, chloroform, and carbon tetrachloride.
whenever specific information is available.
Individual compound is listed
-------
The best basis for an efficiency estimate is a measurement or test, a
mass balance calculation, or a combination of measurement and mass balance
calculations. If such data are not available, comparison of "controlled" and
"uncontrolled" emission factors for the pollutant (chemical) of concern,
engineering calculations, data on the operating parameters of the control
device, or vendor data and/or guarantees that reflect actual operating condi-
tions may be used. It is important to use data that reflect efficiency
achieved during typical operations, not the theoretical optimum efficiency.
In the absence of typical operating data, treatment efficiency data
cited in the open literature for a similar process may be used as an approxi-
mate guide. Figure 3-2 can be used to help estimate treatment efficiencies
by identifying the expected emission reduction from the application of each
control technique on the basis of the total VOC (volatile organic compound)
concentration in the inlet stream. Without actual source test data for a
specific emission stream and control system, the removal efficiency can be
assumed to equal total VOC removal efficiency if the chemical is a volatile
organic compound (not a particulate, metal, PCB, etc.). For example, up to
95 percent reduction can be achieved for incineration of a gas stream con-
taining 50 ppm styrene. Some potential sources of air efficiency data are
listed in the bibliography at the end of this section. Other potertial
sources of information include air pollution journals. Unfortunately, many
complex variables enter into the calculation of efficiency, and actual mea-
surement is the best way to determine efficiency.
Adsorption, absorption, condensation, particulate collection (cyclones,
fabric filters, electrostatic precipitators, and scrubbers), and combustion
equipment are the major categories of control devices that can be used to
reduce toxic air emissions. Each technique is briefly discussed in the
following subsections.
3.2.1 Combustion
Combustion is widely applicable for control of air emissions of combus-
tible organic compounds. The combustion device can be a thermal or catalytic
incinerator, a boiler or process heater, or a flare. Combustion can destroy
organic pollutants through oxidation, which forms water vapor and carbon
3-24
-------
Thermal Incineration
Catalytic Incineration
T-
Carbon Adsorption
Absorption
Condensation
i i
T k"%
T "
90% _. 95%
T * T
T »50% T »95% T J>9%T
T T T w T
T i^'T >95% T »98%T
T * T * T • T
T ^°% T *80%T »95%
T *- T * T *
• iii iii i i i
10
20
50 100 200 300 500 1,000 2,000 3,000 5,000
Inlet Concentration, VOC (ppmv)
10,000 20,000
Figure 3-2. Percent reduction ranges for add-on control devices.
Represents maximum achievable reduction for the corresponding
inlet concentration.
7
3-25
-------
dioxide. Any other elements in the organic compound will also be emitted as
an oxide or acid gas; e.g., chlorine will be emitted as hydrogen chloride.
Thermal incinerators rely on high temperature, sufficient pollutant
residence time, and adequate turbulence to ensure high destruction efficien-
cies. Catalytic incinerators operate at somewhat lower temperatures as a
catalyst promotes the oxidation. Information on destruction efficiency of
specific organic compounds is limited. Most volatile organic compounds are
rapidly destroyed at temperatures over 1400°F; some compounds, however (e.g.,
halogenated hydrocarbons), require higher temperatures.
While destroying one air pollutant, incineration may create other pollu-
tants that require further treatment for removal from flue gases. For
example, an incinerator that effectively destroys trichloroethylene may
create hydrogen chloride, which is then removed by flue gas scrubbing. The
Toxic Release Inventory Form(s) should indicate the destruction of trichloro-
ethylene and any resulting release, the release of hydrogen chloride, and the
amount of HC1 in any wastewater or slurry resulting from scrubbing.
Waste and purged gaseous organic compounds are also commonly destroyed
by flaring when it is not economical to recover the heat value of the gases,
and the control process upset vent gases. Although flaring is widely
applied, information on the air pollutant destruction efficiencies is
limited. A 98 percent destruction efficiency can be achieved for flares
provided they operate under the conditions listed in Table 3-4.
TABLE 3-4. OPTIMAL OPERATING CONDITIONS FOR FLARES
Type of flare
Steam-assisted
Non-assisted
Exit velocity, V
(ft/sec)
V
60 < V
V
V
60 < V
V
< 60
< Vmax(l)
< 400
< 60
< Vmax(l)
< 400
Heating value, H,- of
gas stream (Btu/scf)
HT >_ 300
300 < HT < 1000
HT > 1000
HT >. 200
200 < HT < 1000
HT > 1000
Air-assisted
V < V
max(2)
300
a Heating value of total gas stream (not Just listed chemical).
3-26
-------
Notes:
V,
= e
max(l)
Vmax(2) = 28'54
[1.424 + 0.00118 (HT)]
or log Vmax(1) = 1.424 + 0.00118 (HT)
°'087 H
HT should be calculated at conditions of 25°C (77°F) and 1 atmosphere (14.7
psia). For information on measurement and calculation of operating exit
velocity and heating value of gas stream, consult 40 CFR 60.18 (July 1986).
Flares with values of less than 300 Btu/scf (steam- or air- assisted flares)
or 200 Btu/scf (nonassisted flares) may or may not achieve 98 percent de-
struction. For example, a steam-assisted flare burning a volatile organic
compound subject to reporting could be considered to have a 98 percent effi-
ciency for that compound if its exit velocity and Btu value of the gas stream
were within one of the three operating conditions listed for this type of
flare. This would allow an estimate of the treatment efficiency in absence
of other data for the compound.
Another combustion technique that may be used as a control device for
toxic air pollutants is to inject the pollutants into process heaters or
boilers. Waste streams may provide supplemental fuel or may even be the
primary fuel in some operations.
3.2.2 Adsorption
In an adsorption process, a pollutant is adsorbed on the surface of the
adsorbent until its capacity is reached. Common adsorbent materials used are
activated carbon, resins, and molecular sieve materials. The adsorbent can
then be regenerated. The pollutant is released in a more concentrated form,
which is recovered or treated by further processing. The particular adsorp-
tion/regeneration process and the pollutant and its associated process para-
meters determine further processing steps, which can include incineration or
condensation and decantation so that the chemical can be recovered for recy-
cling or disposal. Although adsorption is effective in the removal of vari-
ous toxic chemicals from air, the regeneration and further processing steps
may transfer some of the toxic substance to water or to solid waste streams,
which must be considered releases to these media. Typically, the adsorption
capacity increases with the molecular weight of the VOC being adsorbed. In
addition, unsaturated compounds are generally more completely adsorbed than
saturated compounds, and cyclical compounds are more easily adsorbed than
3-27
-------
linearly structured materials. Also, the adsorption capacity is enhanced by
lower operating temperatures and higher concentrations. The VOC's character-
ized by low vapor pressures are more easily adsorbed than those with high
vapor pressures.
3.2.3 Absorption
Absorption as a method of treating an emission is a physical or chemical
process that transfers a component(s) from a gas stream to a liquid. Al-
though often used to recover products or raw materials, absorption can also
serve as an emission control device. In this capacity, absorption has been
used to control alcohols, acids, chlorinated and fluorinated compounds,
aromatics, esters, and aldehydes. Absorption devices can be used separately
or in conjunction with other air pollution control equipment, e.g., to pro-
vide additional pollutant removal after incineration or after condensation.
Liquids are used as the absorbent; therefore, a media transfer of toxic
pollutants can occur. In general, more soluble compounds are removed with
greater efficiency. Liquid-to-gas ratios, liquid temperature, and column
height are also important parameters affecting efficiency.
3.2.4 Condensation
Condensation is used as a control technique for some organic compounds.
It cools the gas stream and transforms the gaseous compound to a liquid.
Like absorption, condensation is one of the primary techniques used for
product recovery; however, it is also used as an air-pollution-control de-
vice. Control of storage and process emissions is a common application.
Condensers are frequently used in series with other control equipment,' in-
cluding absorbers, incinerators, and adsorbers.
3.2.5 Particulate Collection Devices
Electrostatic precipitators (ESP's), fabric filters, wet scrubbers, and
cyclones or mechanical collectors are the four devices commonly used to re-
move particulate matter from air streams. These devices are widely applied
in the metal processing industries, where they control many of the Title III,
Section 313, metals and other solids. Gaseous compounds are not collected by
these devices unless they adsorb on a solid particle or react with water in a
scrubber. Vendors of particulate control equipment, when supplied with
3-28
-------
sufficient data on, flow rates, particle size distribution, etc., will guar- ;
antee the removal efficiency of their equipment. Any process variations that
affect particle size, particle density, and gas velocity, however, will gen-
erally affect the removal efficiency of particulate control devices. In some
applications, the solid particulate collected by these devices is recycled to
a process, in which case they may be considered part of a unit process as op-
posed to air-pollution-control equipment. Otherwise, the collected particu-
late is disposed of and has the .potential to create liquid or solid waste
problems. Collection efficiency can be readily determined through a simple
mass balance if one knows the inlet flow rate and concentration of particu-
late and can measure the amount of material collected by the device. In this
case, the fractional efficiency is equal to the amount collected divided by
the amount entering.
Cyclones/Mechanical Collectors. Cyclones are seldom used as the sole or
primary means of particulate collection, but they often serve as "first
stage" air-cleaning devices that are followed by other methods of particle
collection. Cyclone collection efficiency is probably more susceptible to
changes in particulate characteristics (i.e., process variation) than are
other types of devices. Therefore, care should be taken in the use of design
efficiency to estimate actual operating conditions. Although very little
compound-specific collection data are available, cyclone operation is de-
pendent on physical parameters (particle size, density, velocity) as opposed
to the chemical nature or properties of the material being collected. Thus,
within reason, it may be possible to obtain and transfer efficiency data from
known applications to unknown applications on processes with physically
similar particulate and gas flows.
Fabric Filters. When properly designed and operated, fabric filters or
baghouses are efficient collection devices, even for small particles. Vendor
information is often a good source of collection efficiency information, as
most units are designed for specific applications. As in the case of cy-
clones, fabric filter performance is affected by process variations that
affect the gas stream and by other variables, such as temperature and gas dew
point. The particle collection mechanisms of these filters (like those of
3-29
-------
cyclones) usually depend solely on physical as opposed to chemical prop-
erties; thus, data from known applications may be transferable.
Electrostatic Precipitators. Electrostatic precipitators remove from
gas streams particles that have been electrically charged. They are not used
to collect organic solids because of combustibility potential. Efficiency
data are limited with the exception of ESP's applied to combustion processes.
The collection efficiency of an ESP depends on the physical characteristics
of the particulate and the gas stream, as well as on the electrical resistiv-
ity of the pollutant to be collected. Electrical resistivity, in turn, can
be affected by temperature, which may vary in some processes.
Wet Scrubbers. Wet scrubbers are used to collect organic as well as
inorganic particulate matter and reactive gases. Scrubbers, which often use
water as the scrubbing medium, have the inherent potential of creating re-
leases in the liquid medium. Like some other particulate collection equip-
ment devices, scrubber designs are based on physical parameters, so available
efficiency data may be transferrable. The key factors in scrubber perform-
ance are particle size and scrubber pressure drop. As shown in Figure 3-3
for a venturi-type scrubber, a high particle removal efficiency can be
achieved for larger particles and at higher pressure drops across the device.
3-30
-------
i
£
99.9
99.8
99.5
99
0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Size of Particles (Aerodynamic Mean Diam.), |
2.0
3.0 4.0 5.0
Figure 3-3. Venturi scrubber collection efficiencies.
3-31
-------
SECTION 3 REFERENCES
1. U.S. Environmental Protection Agency. Compilation of Air Pollutant
Emission Factors, Volume I: Stationary Point and Area Sources. Fourth
Edition. AP-42, September 1985. "L '. ,
2. U.S. Environmental Protection Agency. VOC Emission Factors for NAPAP
Emission Inventory. EPA 600/7-86-052, December 1986.
3. U.S. Environmental Protection .Agency. Volatile Organic Compound (VOC)
Species Data Manual. Second Edition. EPA-450/4-80-015.. Research
Triangle Park, North Carolina. 465 pp. 1980.
4. Carl, J. E., et. al., Receptor Model Source Composition Library.
EPA-450/4-85-002. November 1984..
5. U.S. Environmental Protection Agency. Survey of Perch!oroethylene Emis-
sion Sources. EPA-450/3-85-017, June 1985. ,
6. U.S. Environmental Protection Agency. Hazardous/Toxic Air Pollutant
Control Technology, A Literature Review. EPA-600/2-84-194, December
1984.
7. U.S. Environmental Protection Agency, Control Technologies for Hazardous
Air Pollutants. EPA/,625/6-86/014. September 1986.
8. Perry, R. H., and C. H. Chilton. Chemical Engineer's Handbook. Fifth
Edition. New York. McGraw-Hill. 1973.
3-32
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SECTION 3 BIBLIOGRAPHY
Documents 4 through 17 contain detailed information on the certain
process industries, their emission sources, development and use of emission
factors, control devices and their efficiency, as well as qualitative data on
other emission sources. Documents 4 through 16 are chemical-specific, where-
as Document 17 covers mostly VOC's, particulates, and other criteria pollu-
tants. It does have some chemical-specific emission factors.
Document 1 is a compilation summary of chemical-specific emission fac-
tors, which includes a summary of factors found in Documents 4 through 16.
Document 18 is a summary of the criteria pollutant emission factors from
Document 17 and other data sources.
Table 3-5 has been prepared to aid users of this guidance to find infor-
mation on chemical-specific emission factors for their industry. Although
specific chemicals mentioned in the industry categories may not be on the
Section 313 list, the documents cover emissions of listed 313 chemicals from
the process. The industries for which particulate and VOC emission factors
are available in Document 17 are listed in Appendix E. Industries covered by
Document 18 are too numerous to list here, but are similar to those covered
by Document 17.
The NTIS documents can be obtained from:
National Technical Information Service (NTIS)
5285 Port Royal Road
Springfield, Virginia 22161
(703) 487-4650
Document
Preliminary Compilation of Air Pollutant
Emission Factors for Selected Air Toxic Com-
pounds. EPA 450/4-86-OlOa, April 1987
Hydrogen Chloride and Hydrogen Fluoride
Emission Factors for the NAPAP Emission
Inventory. EPA 600/7-85-041, January 1986
NTIS price
as of
NTIS No. June 1987
PB 87-183414 .$13.95
PB 86-134020 $13.95
Ammonia Emission Factors for the NAPAP Emis- PB 87-152336 $13.95
sion Inventory. EPA 600/7-87-001, January
1987
3-33
-------
Docu-
ment
No.
4
5
6
7
S
9
10
11
12
13
14
15
16
17
Document
NTIS price
as of
NTIS No. June 1987
Locating and Estimating Air Emissions from
Sources of:
Acrylonitrile. EPA 450/4-84-007a,
March 1984
Carbon Tetrachloride. EPA 450/4-84-007b,
March 1984
Chloroform. EPA 450/4-84-007C, March 1984
Ethylene Dichloride. EPA 450/4-84-007d,
March 1984
Formaldehyde. EPA 450/4-84-007e, March 1984
Nickel. EPA 450/4-84-007f, March 1984
Chromium. EPA 450/4-84-007g, July 1984
Manganese. EPA 450/4-84-007h, September
1984
Phosgene. EPA 450/4-84-007i, September
1985
Epichlorohydrin. EPA 450/4-84-007j,
September 1985
Vinylidene Chloride. EPA 450/4-84-007k,
September 1985
Ethylene Oxide. EPA 450/4-84-0071,
September 1986
Chlorobenzenes. EPA 450/4-84-007m}
September 1986
Compilation of Air Pollutant Emission Fac-
tors-AP-42, Volume 1. Stationary Point and
Area Sources, Fourth Edition. (Also avail-
able from:
Supt. of Documents
Government Printing Office
Washington, D.C. 20402
(202) 783-3238
6PO Stock No. 055-000-00251-7
Price: $20.00)
PB 84-200609 $13.95
PB 84-200625 $18.95
PB 84-200617 $18.95
PB 84-239193 $13.95
PB 84-200633
PB 84-210988
PB 85-106474
PB 86-117587
$18.95
$18.95
$24.95
$18.95
PB 86-117595 $13.95
PB 86-117603 $13.95
PB 86-117611 $13.95
PB 87-113973 $.13.95
PB 87-189841 $18.95
PB 86-124906 $60.95
3-34
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Docu-
ment
No.
18
19
20
21
22
23
Document
NTIS price
as of
NTIS No. June 1987
24
Supplement A to Fourth Edition of AP-42
Criteria Pollutant Emission Factors for the
1985 NAPAP Emissions Inventory.
EPA 600/7-87-015, May 1987
VOC Species Data Manual. EPA 450/4-80-015,
1980
Receptor Model Source Composition Library.
EPA 450/4-85-002, November 1984
Emission Factors for Equipment Leaks of VOC
and HAP. EPA 450/3-86-002, January 1986
Evaluation of Control Technologies for Haz-
ardous Air Pollutants, Volume I, Technical
Report. EPA 600/7-86-009a, 1986
Hazardous Waste Treatment, Storage, and
Disposal Facilities (TSDF) - Air Emission
Models. U.S. EPA Office of Air Quality
Planning and Standards, Emission Standards
Division (MD-13), Research Triangle Park,
North Carolina 27711. Phone (919) 541-5671
Protocols for Generating Unit-Specific
Emission Estimates for Equipment Leaks of
VOC and HAP. U.S. EPA Office of Air Quality
Planning and Standards, December 1987.
David Markwodt, Chemicals and Petroleum
Branch (MD-13), Research Triangle Park,
North Carolina 27711. Phone (919) 541-5411
PB 87-150959 $36.95
PB 87-198735 $24.95
PB 81-119455 $36.95
PB 85-228823 $30.95
PB 86-171527 $13.95
PB 86-167020 $30.95
Not available
from NTIS
3-35
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TABLE 3-5. AVAILABILITY OF CHEMICAL-SPECIFIC EMISSION FACTORS
FOR VARIOUS PROCESSES
Industry/process
No. for
chemical-specific
emission factor
CHEMICAL PROCESS INDUSTRY
Ammonia synthesis
Petroleum refineries
Coke manufacture
Sodium dichromate manufacture
Chromic acid manufacture
Acrylonitrile manufacture
Fluorocarbon 22 manufacture
Methane chlorination process
Ethylene oxide manufacture
Pesticide manufacture
Perch!oroethylene manufacture
Ethylene dichloride manufacture
Vinyl chloride monomer manufacture
Methyl chloroform manufacture
Ethylene amines manufacture
Trichloroethylene manufacture
Vinylidene chloride manufacture
Ethyl chloride manufacture
Carbon tetrachloride manufacture
Fluorocarbon 11 and 12 manufacture
Pharmaceutical manufacture
Chlorobenzene manufacture
Dye/pigment manufacture
3,4-Dichloroaniline manufacture
Chlorinated solvent manufacture
Caprolactam manufacture
Phenol manufacture
Propylene oxide manufacture
Hydrogen chloride manufacture
Hydrogen fluoride manufacture
Formaldehyde manufacture
Hexamethylene tetramine manufacture
Pentaerythritol manufacture
1,4-Butanediol manufacture
Trimethylol propane manufacture
Phthalic anhydride manufacture
Solid urea manufacture
Phosgene manufacture
Toluene diisocyanate manufacture
Substituted phenyl urea manufacture
Epichlorohydrin manufacture
3, 17
1, 3, 8
3, 9, 17
1, 9
1, 9
1, 4
1, 6
1, 6
1, 15
1, 16
1, 5, 6, 7, 14
1, 5, 6, 7
1, 7
1, 7
1, 7
5, 6, 7, 14
7, 14
1, 7
1, 5
1, 5
1, 5, 16
1, 16
1, 16
1, 16
1, 16
1
1
2
2, 17
2, 17
1, 8
1, 8
1, 8
1, 8
1, 8
1, 8
1, 8, 17
1, 12
1, 12
1, 12
1, 13
(continued)
3-36
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TABLE 3-5 (continued)
Industry/process
No. for
chemical-specific
emission factor
CHEMICAL PROCESS INDUSTRY (continued)
Batch process using epichlorohydrin as
feedstock
Adi pic acid manufacture
Carbon black manufacture
Chlorine manufacture
Phosphoric acid manufacture
Sulfuric acid manufacture
Lead alky! compound manufacture
Maleic anhydride manufacture
Ammonium nitrate manufacture
Ammonium sulfate manufacture
Manganese chemicals manufacture
Polysulfide rubber production
Vinylidene chloride polymerization plants
Formaldehyde resin production
Polyacetal resin production
Polycarbonate production
Epoxy resin production
METALLURGICAL INDUSTRY
Nickel production
Nickel ore mining and smelting
Nickel matte refining
Steel production
Ferrous and nonferrous metals production
Chromite ore refining
Ferrochrome plants
Cast iron production
Nonferrous alloy production
Primary lead smelting
Beryllium alloy stamping, drawing, molding
Beryllium metal fabrication
Gray iron production
Zinc smelting
Copper smelting
Cadmium refining
Secondary lead smelting
Steel scrap
Primary aluminum production
Primary mercury ore processing
1, 13
17, 18
17
1, 17
17
17
17
17
17
17
1, 11
1, 7
1, 14
1, 8
1, 8
1, 12
1, 13
1, 9
1, 9
1, 9
1, 9, 10, 11
1, 9
1, 10
1, 10
1, 11
1
1
1
1
1, 17
1
1, 17
1
1, 17
1
1, 2, 17
1
(continued)
3-37
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TABLE 3-5 (continued)
Industry/process
No. for
chemical-specific
emission factor
METALLURGICAL INDUSTRY (continued)
Secondary mercury processing 1
Metallurgical vanadium processing 1
Manganese ore beneficiation, transport, 11
storage
Manganese ferroalloy production 1, 11
Manganese metal and manganese oxide production 1, 11
Iron and steel foundries
Lead type production 17
FOOD AND AGRICULTURAL INDUSTRY
Cropland spreading of livestock wastes 3
Beef cattle feed lots 3, 17
Fertilizer manufacture and use 3
Grain fumigation 1, 5, 7
Phosphate fertilizer production 2, 17
Fish processing plants- 17
MINERAL PRODUCT INDUSTRY
Cement plants 1, 9, 11
Refractory industry 1, 10
Asbestos milling, processing 1, 10
Glass production 1
Ceramics 1
Brick manufacture 17
Glass fiber manufacture 17
Frit smelting 17
Lead glass manufacture 17
Asphalt concrete plant 17
Hot mix asphalt plant 1, 8
MISCELLANEOUS INDUSTRY/PROCESS
Integrated circuit board manufacture 1, 8
Battery manufacture 1, 9, 17
Functional fluids use 16
Textile dyeing 16
Vapor decreasing 1
Conveyorized decreasing 1
Photoresist stripping 1
(continued)
3-38
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TABLE 3-5 (continued)
Industry/process
No. for
chemical-specific
emission factor
MISCELLANEOUS INDUSTRY/PROCESS (continued)
Cooling water systems
Loading/storage of gasoline
Use of epoxy resins
Tank and drum solvent cleaning
Burning cotton ginning waste
Waste treatment, storage, and disposal
Wastewater treatment operations
Explosives manufacturing
Can soldering (lead)
Lead cable covering
Ammunition manufacture
1, 6, 9, 10
1, 7
1, 13
17
1
1, 11
1, 16
17
17
17
17
3-39
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OUTLINE FOR SECTION 4
ESTIMATING RELEASES IN WASTEWATER
4.1 Sources of Wastewater and Methods for its Disposal
4.1.1 Direct Discharge to Surface Waters
4.1.2 Discharge to a Publicly Owned Treatment Works
4.1.3 Underground Injection
4.1.4 Surface Impoundments
4.1.5 Land Treatment
4.2 Calculating Releases From Wastewater
4.2.1 Direct Measurement
4.2.2 Wastewater Release Calculations by Mass Balance
4.2.3 Emission Calculations Using Release Data From Other Facilities in
Same Industry
4.2.4 Engineering Estimates
4.3 Estimating Treatment Equipment Efficiency
4-0
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SECTION 4
ESTIMATING RELEASES IN WASTEWATER
At most facilities, wastewater from individual process sources is cen-
trally collected and discharged from one point. This greatly simplifies the
task of estimating releases of toxic materials to water because it decreases
to one or a few the number of discharge streams for which releases must be
estimated. Nevertheless, in some situations it may be necessary to estimate
releases in wastewater from individual sources.
A facility that discharges or has the potential to discharge water
containing toxic and/or hazardous wastes probably operates under the terms of
Federal, State, and/or local permits. The permit(s) usually require measure-
ments of the water volume and analyses of some generalized wastewater parame-
ters [e.g., biological oxygen demand (BOD) and total suspended solids (TSS)].
Occasionally, releases for which the permit requires analyses and those
subject to reporting will be similar. In these instances, releases can
be calculated by straightforward multiplication of the volume of wastewater
released by the concentration of the chemical released. The permit(s) also
often require that the wastewater be treated before its discharge to minimize
releases.
The following subsections present some of the various sources of waste-
water and methods of wastewater disposal. Also discussed are methods for
calculating releases of compounds subject to reporting in wastewater and
estimating efficiencies of wastewater treatment devices.
4.1 SOURCES OF WASTEWATER AND METHODS FOR ITS DISPOSAL
Releases of toxic chemicals can originate from a wide variety of waste-
water sources. Table 4-1 lists some of the more common sources and processes
that generate wastewater. Unlike air emissions, wastewater from individual
4-1
-------
sources in a facility are usually centrally collected and combined for dis-
charge at one or a few points. Methods of wastewater disposal are presented
in Table 4-2 and are discussed briefly in the following subsections.
TABLE 4-1. TYPICAL WASTEWATER SOURCES
Untreated process wastewater
Miscellaneous untreated wastewater - equipment washdown,
steam jet condensate, cooling water
Decantates or filtrates
Cleaning wastes
Steam stripping wastes
Acid leaching solutions
Spent plating, stripping, or cleaning baths
Spent scrubber, absorber, or quench liquid
Off-spec, discarded products or feedstock
Distillation side cuts
Cyclone or centrifuge wastes
Spills, leaks, vessel overflows
TABLE 4-2. METHODS OF WASTEWATER DISPOSAL
Direct discharge to surface waters
Discharge to a publicly owned treatment works
Underground injection
Surface impoundments
Land treatment
4.1.1 Direct Discharge to Surface Waters
Many facilities discharge wastewater directly to nearby bodies of water;
this action requires a National Pollutant Discharge Elimination System
(NPDES) permit. The permit usually requires monitoring of the wastewater
discharge flow and the concentrations of various constituents within the
4-2
-------
wastewater (usually generalized constituents such as BOD and TSS). Mon-
itoring is usually not required for most of the individual chemicals or
compounds. When such monitoring is required, wastewater flow rate and con-
centration data collected for the NPDES permit can be used to calculate
wastewater releases directly.
4.1.2 Discharge to a Publicly Owned Treatment Works (POTW)
Many facilities discharge their wastewater to POTW's. In some cases, a
POTW may require pretreatment of wastewater and/or monitoring of the flow
rate and the concentration of various constituents. If a POTW requires
monitoring of a chemical or compound subject to reporting, releases of that
chemical or compound in the wastewater can be calculated by multiplying the
reported concentration by the flow rate. On the Toxic Chemical Release
Inventory Form, discharge to a POTW is considered a transfer to an offsite
location.
4.1.3 Underground Injection
In some situations, wastewater containing hazardous and/or toxic wastes
may be injected beneath the earth's surface in locations where it is unlikely
to contaminate ground water. Injection operations are usually controlled by
RCRA permitting procedures that require maintaining records of the volumes
and analyses of the wastes injected. From this information, quantities of
listed chemicals and/or compounds that are disposed of in this manner can be
directly calculated.
4.1.4 Surface Impoundments
A surface impoundment is a natural topographic depression, man-made
excavation, or diked area formed primarily of earthen materials (although it
may be lined with man-made materials), which is designed to hold an accumula-
tion of liquid wastes or wastes containing free liquids. Examples of surface
impoundments are holding, storage, settling, and elevation pits, ponds, and
lagoons. If the pit, pond, or lagoon is intended for storage or holding
without discharge, it is considered to be a surface impoundment used as a
final disposal method under Section 313 Reporting. The operation of surface
impoundments is usually controlled by RCRA permits, which require maintaining
records of the volume and concentration of hazardous wastes disposed of.
4-3
-------
This information can be used for direct calculation of the quantity of a
listed chemical and/or compound disposed of in this manner. This disposal
method is considered a release to land; however, listed chemicals in the
impoundment may be released to air by volatilization, collected as sludge and
removed, or biodegraded. Any releases from the impoundment should be ac-
counted for in release totals to air, water, land, or offsite disposal.
4.1.5 Land Treatment
Land treatment is a disposal method in which wastewater is applied onto
or incorporated into soil. These operations are usually controlled by RCRA
permits with conditions that regulate the volumes of wastewater to be
treated, the concentrations of hazardous and/or toxic materials it contains,
and the frequency of land application, and also require a ground-water
monitoring program. This information can be used to calculate the quantity
of a listed chemical and/or compound disposed of in this manner. Chemicals
and/or compounds in the wastewater are released to the soil or to air (by
volatilization). On the Toxic Chemical Release Inventory Form, this disposal
method is considered a "release to land."
4.2 CALCULATING RELEASES IN WASTEWATER
Quantities of listed chemicals and/or compounds released to the environ-
ment in wastewater can be calculated by summing the releases from individual
operations or by determining releases from a central wastewater discharge
point (if available). The latter method is preferred because it involves the
direct measurement or estimation of the flow of the discharge stream, and the
concentrations of chemicals and/or compounds it contains. The following sub-
sections describe the use of direct measurement, mass balance, release data
from other facilities in the industry, and engineering calculations to esti-
mate releases of listed chemicals and/or compounds in wastewater. No general
compilation of emission factors is available for release in wastewater as it
is for releases to air; however, in some instances, information from other
facilities in the industry can be applied to estimate releases in wastewater.
4.2.1 Direct Measurement
Direct measurement can be used to calculate releases in wastewater from
individual processes or from a central discharge point. This method involves
4-4
-------
multiplying the. wastewater flow rate by the concentration of the chemical or
compound of concern. The following two items describe direct measurement of
wastewater releases based on average measured values and multiple measured
values, respectively.
Releases Based on Total Annual Volume and Average Measured Concentra-
tion. If a wastewater stream has a relatively constant daily flow rate and
the measured concentrations of listed the chemicals and/or compounds in the
stream do not vary greatly or are well characterized, average values for flow
rate and concentration can be used to calculate releases.
Example 4-1 - Use of direct measurement to estimate releases in waste-
water:
Step 1. Gather process information and monitoring data.
A stream containing an average acetaldehyde concentration of 500
milligrams per liter is sent to an onsite treatment system at a rate, of 5
gal/min. The stream leaving the treatment system at 5 gal/min contains 25
milligrams of acetaldehyde per liter. If the plant operates 24 hours per
day, 330 days per year, the quantity of acetaldehyde entering and leaving
the treatment system can be calculated, assuming no net loss of water or
acetaldehyde by evaporation to air. Also, the treatment system efficiency
can be calculated.
Step 2. Calculate the quantity of acetaldehyde entering and leaving the
system.
\/rti, Q 5 gal v 60 min 24 h 330 days _ 2.376 million gal
volume - minute x hour x dgy x yeay, year
Into svstPm- 2.376 million gal 500 mg 3.78 liters 1 Ib
into system. year x mer x gallon x 453j000 mg
= 9913.11 Ib
year
c™m c,,c+.Qm. 2.376 million gal 25 mg 3.78 liters 1 Ib
From system: - — - x ^^ x gallon - x 453j000 mg
= 495.66 Ib
year
Step 3. Calculate treatment system efficiency.
Treatment system efficiency:
Report 95%.
95.66
9913.11
x 100 = 94.99%
4-5
-------
Releases Based on Calculated Annual Volume and Average Concentration
From Scheduled Periodic Water Analyses. Even though a facility has regularly
scheduled wastewater sampling and analyses to determine flow rates and toxic
pollutant concentrations before and after treatment, both flow rates and
concentrations may vary considerably. Daily release rates are calculated by
multiplying the flow rate times the concentration. These daily emission
rates can be averaged to yield an annual release rate if the sample timing
and frequency accurately represent the discharge.
Example 4-2 - Use of direct measurement to estimate releases in waste-
water:
Step 1. Gather wastewater flow and concentration data from NPDES permit.
The NPDES Permit of a leather tanning facility requires daily monitor-
ing of wastewater flow volume and biweekly analysis of a daily composite
sample of this discharge for total chromium. The total chromium analytical
results for the year are presented below.
Step 2. Calculate releases for those days in which a chromium analysis was
performed.
The total chromium releases (in pounds per day) to water for a given
day at this facility are calculated by multiplying the daily flow (in
million gallons per day) by the total chromium concentration (in micrograms
per liter) times a conversion factor (8.34 x 10"3).
Discharge
flow rate,
106 gal/day
0.415
0.394
0.417
0.440
0.364
0.340
0.457
0.424
0.463
0.414
0.476
Total chromium,
iter
918
700
815
683
787
840
865
643
958
681
680
Releases,
Ib/day
3,
2,
2,
2.
2,
2,
3,
177
300
834
506
389
382
297
2.274
3.699
2.351
2.699
(continued)
4-6
-------
Discharge
flow rate,
106 gal /day
0.431
0.369
0.392
0.323
0.302
0.358
0.322
0.330
0.322
0.408
0.442
0.356
0.390
0.423
0.487
Step 3. Calculate annual
Based on an average
days of discharge during
water is:
2.435
day
Total chromium,
iig/liter
627
807
729
964
722
566
510
630
630
652
649
695
758
658
970
Average
releases.
Releases,
Ib/day
2.254
2.484
2.383
2.597
1.818
1.690
1.370
1.734
1.692
2.218
2.392
2.063
2.465
2.321
3.940
2.435
daily release of 2.44 Ib over the year and 250
the year, the yearly total
Ib 250 days -.„ ,.
x year fc09 IL per
chromium discharged to
year
Report 610 Ib per year.
Permit requirements or detection limits of analytical procedures (par-
ticularly after treatment) may produce an analytical result, such as the
concentration of a toxic and/or hazardous pollutant, expressed as less than a
certain value. For example, a copper concentration may be reported as less
than 5 micrograms per liter (5 parts per billion). In this case, a common
practice is to use a value of one-half the detection limit in calculating an
average concentration. Based on the data set available, this may or may not
be the best procedure for evaluating results. Any procedure used must take
into account the number of analyses available, the distribution of data, and
the detection limit.
4-7
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Example 4-3 - Use of direct measurement ,to estimate releases in waste-
water:
Step 1. Gather analytical results and determine average value.
The results of 10 copper analyses are expressed in micrograms per
liter:
6
10
<5
<5
<5
<5
<5
<5
<5
8
The average concentration is -1(6) * 1(10) ^1(8) + 7(5/2) = 4.2 micrograms
= 4.2 x 10 grams per liter
Step 2. Determine annual releases.
For an annual flow of 37.8 million liters (10 million gallons), the average
discharge would be 4.2 x 10~6 grams/liter x 37.8 x 106 liters/year = 159
grams/year or 0.35 Ib/year.
4.2.2 Wastewater Release Calculationsby Mass Balance
Wastewater releases from individual processes or a central discharge
point can be estimated by the use of mass balances; however, care must be
exercised because it is not always clear to which medium (air, water, or
solid waste) the release occurs. In some cases, the contaminants in the
Wastewater volatilize and result in an air release, not a water release.
During wastewater treatment, many contaminants settle out of the wastewater
and are disposed of as solid waste. Also, as discussed previously, when mass
balances are applied to very large operations, they are susceptible to' large
errors in release estimates as a result of even small errors in raw material
or finished product quantities.
Example 4-4 - Use of a mass balance to estimate releases in waste-
water:
Step 1. Gather purchasing and inventory data.
A plant buys 20,000 gal (75,800 liters) per year of a water-based
cleaner that contains 0.5 Ib/gal (60 g/liter) of 1,1,1-trichloroethane as
an emulsion. No material is recovered and year-beginning and year-ending
inventories are both 1000 gallons.
4-8
-------
Step 2. Calculate annual releases.
Assume all trichloroethane is discharged into the plant wastewater and
none evaporates into the air.
If the plant wastewater undergoes treatment before discharge, releases
would equal 10,000 Ib/year multiplied by [1 minus the treatment efficiency]
for trichloroethane. The quantity of trichloroethane removed during treat-
ment is equal to the sum of the quantities volatilized to air, partitioned
to sludge (solid waste), and chemically transformed or destroyed.
Example 4-5 - Use of a mass balance to estimate releases in waste-
water:
Step 1. Gather production data.
A plant processes 220,000 Ib per year of scrap containing an average
of 12 percent silver. The plant recovers 26,000 Ib of 100 percent silver
metal.
Step 2. Calculate annual releases.
Emissions = Material In - Material Recovered
220,000 Ib scrap x ^^scrap^ = 26'400 lb Sllver
26,400 Ib silver in scrap - 26,000 Ib silver recovered
= 400 lb discharged yearly
Again, any treatment of plant wastewater would result in a release
adjusted for the treatment removal efficiency for silver.
4.2.3 Release Calculations Using Release Data From Other Facilities
in the Same Industry
The wastewater bibliography at the end of this section lists some possi-
ble sources of information on wastewater emission and treatment for various
processes and industries. This listing, which was compiled from a literature
search of wastewater emissions and treatment efficiencies, is provided as a
starting point for finding documented wastewater information concerning simi-
lar processes and industries. It does not represent a complete listing of
available sources and those presented may not contain information pertaining
to many of the listed toxic chemicals.
A listing of EPA development documents for effluent limitation guide-
lines and standards for particular industries is attached to the wastewater
4-9
-------
bibliography. These documents, which contain measured data on specific
compounds (primarily the 129 priority pollutants) discharged by a particular
industry, may serve as a source of emission data. A facility should use only
data for operations and treatment methods similar to its own. These docu-
ments may not give direct emission factors, but they can provide other useful
information, such as estimates of wastewater concentrations for specific
chemicals.
In lieu of these documents, emission factors based on production or
process throughput may be derived from information available in the technical
literature or based on manufacturers' or vendors' data for a similar process.
Information also may be available through trade and industrial organizations
and associations.
In addition, technical journals sometimes contain information applicable
to one's particular process or industry. The following journals deal with
wastewater and wastewater treatment:
o
o
o
o
o
o
o
o
Water Engineering and Management
Journal of the Water Pollution Control Federation
Water Technology
Journal of the Environmental Engineering Division, ASCE
Environmental Science and Technology
Pollution Engineering
Effluent and Water Treatment Journal
Chemical Engineering
Because each individual processing or manufacturing facility is unique,
great care must be taken when applying emission factors to ensure that the
conditions under which the factor was developed apply to the facility in
question.
4.2.4 Engineering Estimates
Estimates in lieu of direct measurements would not generally satisfy
wastewater discharge permit requirements for any hazardous and/or toxic
material. The permit would require monitoring and analyses that provide a
basis for estimating releases.
Engineering estimates could be used, however, to calculate releases in
wastewater from individual unit operations. Physical and chemical properties
of the listed chemicals and/or compounds, such as water solubility, could be
4-10
-------
used as a basis for estimating releases directly or in conjunction with one
of the other release-estimation methods. Also, equipment parameters (e.g.,
pump flow capacity) could be used to estimate wastewater flow rates.
The solubility of most compounds in water is known, and this value can
serve as a basis for the upper limit concentration of a chemical present in a
wastewater stream; however, temperature, pressure, pH, and the presence of
other compounds will affect solubility.
Measurement of a secondary or generalized parameter can also be used in
an engineering estimate of releases in wastewater. Typically, the only mea-
surements that can be used to calculate releases are those representing the
particular chemical or compound of concern. In some situations, however, the
concentration of a particular chemical in a wastewater can be related to gen-
eralized parameters, such as BOD, chemical oxygen demand (COD), or pH. For
example, the wastewater generated from a particular process is known to con-
tain only phenol, and a relationship has been established that indicates that
the wastewater contains an average of 0.4 milligram per liter of phenol for
every milligram per liter of COD. Based on this relationship, the concentra-
tion of phenol in the wastewater can be estimated by measuring the COD. A
word of caution: if the wastewater contains other compounds that will influ-
ence the measurement of the generalized parameter, the relationship between
the chemical of concern and the generalized parameter will vary. Under these
circumstances, this estimation technique cannot be used.
The pH parameter can be used to estimate the concentration of an acid or
base if it is known that the acid or base is the only compound in the waste-
water affecting pH; however, this situation is rare. When it does occur, the
acid or base disassociation constant can be used with the pH measurement to
calculate the concentration of the acid or base in solution. The reader is
urged to consult a general chemistry textbook for details of this calcula-
tion.
Example 4-6 - Use of engineering calculations to estimate releases in
wastewater:
Step 1. Diagram process.
In the production of ethylene dichloride (EDC) by the oxygen process
(oxychlorination), a decanter is used to separate EDC from H20 formed
4-11
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during the reaction step. The decanted H20 stream is then discharged to a
POTW along with wastewater from the entire facility.
Step 2. Make engineering assumptions to estimate chemical concentration in
process streams.
To estimate the quantity of EDC emitted to the POTW from this particu-
lar operation, the following engineering calculations will be used to
develop a mass balance around the decanter:
0 Engineering calculation: The reaction stoichiometry dictates
that equal molar portions of EDC and water are contained in the
stream entering the decanter (Stream No. 1). As such, the com-
position of Stream No. 1 is known.
1 mole EDC = 97 grams; 1 mole H20 = 18 grams
1 mole EDC + 1 mole H20 = 115 grams
EDC weight percentage - ff^ 9rams x 10° = 86 Percent
0 Engineering calculation: The solubility of EDC in water is 0.869
gram per 100 grams. Assuming equilibrium in the decanter, this
solubility represents the concentration of EDC in the wastewater
stream (Stream No. 2). Also, the solubility of water in EDC is
0.160 gram per 100 grams. This solubility represents the concen-
tration of H20 in the EDC product stream (Stream No. 3).
Step 3. Perform mass balance around the process.
This facility is known to produce 185,000 Mg/year (megagrams per year)
of EDC. By combining this with the engineering calculations above, the
following mass balance can be performed.
Stream No. 1
Equal-molar ratio of H20 and EDC, which
yields 86% EDC and 14% H20.
Stream No. 2
(waste)
Wastewater con-
taining EDC at
0.869 g/100 grams of
water, which equals a
weight percentage of
0.869.
Decanter
Stream No. 3
(product)
185,000 Mg/yr EDC plus an unknown
quality of H20. The collection of
H20 contains 0.160 g of water per
100 g of EDC, which equals a weight
percentage of 0.16.
4-12
-------
Mass Balance:
Total: Stream No. 1 (Mg/yr) = Stream No. 2 (Mg/yr) + Stream No. 3 (Mg/yr)
From the EDC production rate, it is known that:
Stream No. 3 = 185,000 Mg EDC/yr + X Mg H20/yr
The quantity of H20 in Stream No. 3 is determined by using the
solubility of H20 in EDC:
- 0.160 gram H,0
100 grams EDC
185.000 Mg EDC
year
10° grams EDC
1 Mg EDC
= 296 x
10° grams H,0 = 296 Mg H,0
year
year
.*. Stream No. 3 =
The total mass balance can be written as:
Eq. A: Stream No. 1 (Mg/yr) = Stream No. 2 (Mg/yr)
+ 185,296 (Mg/yr)
EDC: Eq. B: (0.86) Stream No. 1 = (0.00869) Stream No. 2 + 185,000
Eg. B n p. (0.00869) Stream No. 2 + 185,000 (Mg/yr)
Eq. A U>BD Stream No. 2 + 185,296 (Mg/yr)
Solving for Stream No. 2 = 30,125 Mg/yr.
Step 4. Calculate total annual releases.
Therefore EDC emissions to the wastewater equal
(30,125 Mg/yr) x (0.00869) = 262 Mg/yr
262 Mg/yr x 103 Kg/Mg x 2.2 Ib/Kg = 576,400 Ib/year
Report 576,000 Ib/year.
Example 4-7 - Use of engineering calculations to estimate releases in
wastewater:
Step 1. Gather process information and analytical data.
Ethyl acrylate is used to make a water-soluble acrylic polymer in a
batch process. The polymerization reactor is cleaned after each batch, and
some unreacted ethyl acrylate is released in wastewater. The reactor
4-13
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volume is 10,000 gallons, and eight batches are processed per day for 250
days per year. Based on laboratory analyses, it is known that the reactor
product mixture contains 1.2 percent ethyl acrylate and has an approximate
specific gravity of 1.02.
Step 2. Using an engineering assumption, calculate annual releases from
the process.
Based on a study of equipment cleaning practices, the amount of resi-
due left in tanks after emptying can be estimated as 1 percent.* The
amount of ethyl acrylate released to the wastewater through cleaning resi-
due from the reactor can be estimated as follows:
8 batches 250 days 10,000 gallons 8.34 Ib H,0
3ay* year x Eaten"x 1 gallon
x 1.02 Ib reactor product 0.010 Ib residue
1.00 Ib H20x 1 Ib reactor product
0.012 Ib ethyl acrylate _
1. Ib residue
20,416 Ib ethyl acrylate
year
Step 3. Calculate total annual releases from the entire facility.
The wastewater from this activity is treated along with the wastewater
for the entire facility before discharge. It is estimated that an addi-
tional 10,000 pounds of ethyl acrylate is discharged to the wastewater from
other sources in the facility. If the wastewater treatment process pro-
vides 80 percent removal of ethyl acrylate, the yearly discharge of ethyl
acrylate from the facility to water would be:
r20.416 Ib
L year
10.000 Ib
year
•] x
rlOO-80-.
L 100 -'
= 6083
Ib
year
Report 6100 Ib/year.
From "Releases During Cleaning of Equipment." Prepared by PEI Associ-
ates, Inc., for the U.S. Environmental Protection Agency Office of Pesti-
cides and Toxic Substances, Washington, D.C. Contract No. 68-02-4248.
June 30, 1986. The reactor product mixture in this example would have a
relatively high viscosity. For lower-viscosity materials, a table is
presented in Section 5 (Table 5-2), which relates residue quantities to
the capacity of tanks and drums based on unloading method, vessel materi-
al, and bulk fluid material. If the information in Table 5-2 dannot be
applied to a particular situation or material, 1.0 percent is a common
estimate for residue quantities.
4-14
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Example 4-8 - Use of engineering calculations to estimate releases in
wastewater:
In batch dyeing processes for textiles or leather, unexhausted dye is
released during the draining of the dye batch and subsequent rinsings of
the fabric or leather. An estimate of the amount of dye released to waste-
water can be made if the degree of exhaustion for the particular dye is
known. It is best to use exhaustion data as measured for the dye under
actual plant operating conditions, but in the absence of such data, litera-
ture values (or manufacturers data) could be utilized. The type of fabric
being dyed, the dyeing temperatures, and other operating parameters may
greatly influence the degree of exhaustion and should be taken into account
when using exhaustion data from other sources. An example for calculating
releases for a dye with the use of exhaustion data is as follows:
Step 1. Gather production information and process data from similar
operations at other facilities
A facility consumed approximately 37,000 Ib/yr of 30 percent active
C.I. Disperse Yellow 3 dye in the paddle-dyeing of nylon carpets. The
following is a list of exhaustion data for various substrates collected
from dye manufacturers:
Dye Temperature and Exhaust Data for C.I. Disperse Yellow 3
Substrate
Dyeing
Temperature, °F
Degree of
Exhaustion, %
Nylon carpet
Nylon hosiery
Acetate linings
190-212
180-205
160-190
80-90
75-90
68-90
Step 2. Calculate annual releases.
Total yearly releases can be calculated by assuming that all the un-
exhausted dye is released in wastewater.
37,000 Ib dye formulation 0.30 active dye (1-0.80) fraction of dye
per year formulation not exhausted on fabric
= 2220 Ib C.I. Disperse Yellow 3 released per year
Report 2200 Ib/year.
If the wastewater is treated before being discharged from the facility,
emissions would be reduced by a factor equal to the treatment efficiency
for the dye in wastewater.
4-15
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4.3 ESTIMATING TREATMENT EQUIPMENT EFFICIENCY
Toxic pollutants entering a wastewater treatment device may undergo one
or more of the following fates: 1) transfer from the wastewater stream to
another media (air or land), 2) modification to a less toxic state by chemi-
cal reaction, 3) destruction through biodegredation or chemical reaction, or
4) passing through untreated. Any releases of listed chemicals and/or com-
pounds to air or land (via sludge disposal) resulting from the treatment of
wastewater must be accounted for in the total quantity of releases to those
media. Care must be taken to ensure that the quantity released to another
medium is not also counted into the total quantity released to water.
Table 4-3 lists some wastewater unit operations.
Wastewater treatment efficiency is based on the amount of a contaminant
removed from the wastewater stream, either by destruction or modification of
the pollutant or fay transfer to another medium (air or solid).
Percentage efficiency = X 1n1f.:iL°Ut1et x 100
A 1nIGt
where X inlet s total mass of pollutant X flowing to the wastewater
treatment system in a given year
X outlet = total mass of pollutant X flowing from the wastewater
treatment system in a given year
For toxic metals, release estimates and treatment efficiencies must be re-
ported on the basis of the mass of the parent metal. For acids and bases,
treatment efficiency is calculated based on the amount of acid or base neu-
tralized.
Wastewater treatment systems are often made up of multiple-unit opera-
tions. In these instances, each unit operation in the system used to treat a
particular chemical should be listed on Form R, and the boxes for sequential
treatment marked. The range of influent concentration should only be pro-
vided for the first unit in the treatment sequence. Also, only the overall
system treatment efficiency should be estimated. The efficiency of the sys-
tem should be reported in the space provided for the last step of the system.
For example, if acetone is present in a facility's wastewater that is treated
by settling/clarification followed by aerobic biological treatment, portions
of the acetone will be removed during both steps of the treatment sequence.
4-16
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TABLE 4-3. UNIT OPERATIONS AND PROCESSES USED TO TREAT WASTEWATER
i. Chemical oxidation
Cyanide oxidation—alkaline chlorination
Cyanide oxidation—Electrochemical
Cyanide oxidation—Other
General oxidation (including disinfection)—chlorination
General oxidation (including disinfection)—ozonation
General oxidation (including disinfection)—other
ii. Chemical precipitation (pH adjustment, flocculation, and settling)
Chemical precipitation—lime or sodium hydroxide
Chemical precipitation—sulfide
Chemical precipitation—other
i i i. Chromium reduction
iv. Complexed metals treatment (other than pH adjustment)
v. Emulsion breaking
Emulsion breaking—thermal
Emulsion breaking—chemical
Emulsion breaking—other
vi. Adsorption
Carbon adsorption
Ion exchange
Resin adsorption
Other adsorption
vii. Stripping
Air stripping
Steam stripping
Other stripping
viii. Filtration
ix. Air flotation
x. Settling/clarification and oil skimming
xi. Biological treatment
Aerobic
Anaerobic
Facultative
Other
xii. Other wastewater treatment
Wet air oxidation
Neutralization
Equalization
Reverse osmosis (other than for recovery/reuse)
4-17
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On the Toxic Chemical Release Inventory Reporting Form for acetone, both
treatment codes should be entered separately, and the sequential treatment
box should be checked for both. The acetone influent concentration range
should be entered with the settling/clarification treatment method. The
overall system treatment efficiency should be entered with the aerobic bio-
logical treatment method.
The efficiency of removing or destroying a specific compound varies
widely depending on the design and operation of a system (e.g., retention
time, inlet loading, biological activity). The best method for calculating
treatment efficiency for an individual compound is by direct measurement of
the treatment device's influent and effluent streams. A combination of
measurement data and mass balances can be used to make reliable estimates
based on actual operating conditions.
In lieu of operating data, it is best to refer to the EPA Development
Documents for Effluent Limitation Guidelines for the facility's particular
industry, which was discussed in Subsection 4.2.3. The next best source is
information from the literature on treatment systems similar to those at the
given facility (see Subsection 4.2.3). Obviously, the operating conditions
under which the efficiency information was derived for a particular treatment
system would have to be similar to those at the given facility.
Table A-l in Appendix A contains numerous citations of wastewater treat-
ment efficiency for specific compounds based on the wastewater stream. The
data in this table were compiled and summarized from a literature search on
pilot- and full-scale treatment systems.* The data in this table should be
used with an awareness and understanding of test conditions involved. Facil-
ities should use the removal data for a treatment system whose conditions are
similar (type of waste, chemical concentration, suspended solids concentra-
tion, residence time) to the facility's own wastewater treatment system.
"Estimation of Removal of Organic Chemicals During Wastewater Treatment,
Draft Final Report," Versar Inc. Prepared for U.S. Environmental Protec-
tion Agency, Exposure Evaluation Division, Office of Toxic Substances,
Washington, D.C. EPA Contract No. 68-02-3968, Task 867.148. September
30, 1986.
4-18
-------
Table A-2 In Appendix A also presents wastewater treatment efficiencies
for a number of chemicals; however, this information applies only to second-
ary biological wastewater treatment systems receiving relatively low concen-
trations of the particular toxic pollutant (= 500 parts per billion). It
provides educated estimates on pollutant fate in the treatment system (i.e.,
volatilized to air, particularly to sludge, or biodegraded) from "Report to
Congress on the Discharge of Hazardous Waste to Publicly-Owned Treatment
Works."
Tables A-l and A-2 do not have information on all of the chemicals sub-
ject to reporting. These tables should be used only when efficiency informa-
tion cannot be obtained through any of the methods described above.
The following subsections describe briefly the general wastewater treat-
*t
ment methods presented in Table 4-3.
Chemical Oxidation. Chemical oxidation is a process that oxidizes
compounds or ions to render them nonhazardous or to make them more amenable
to subsequent removal or destruction processes. Species are oxidized by the
addition of a chemical oxidizing agent that is itself reduced. Treatment
efficiency is measured by dividing the quantity of a particular contaminant
chemically modified by the quantity entering the process.
Chemical Precipitation. Chemical precipitation is a physicochemical
process in which a dissolved contaminant is transformed into an insoluble
solid to facilitate its subseqent removal from the liquid phase by sedimen-
tation or filtration. The process usually involves 1) adjustment of pH to
shift the chemical equilibrium to a point that no longer favors solubility;
2) addition of the chemical precipitant; and 3) flocculation, in which pre-
cipitate particles agglomerate into larger particles. Treatment efficiency
is calculated by dividing the quantity of a particular contaminant removed
from the wastewater by the quantity entering the process.
"Briefing: Technologies Applicable to Hazardous Waste," Metcalf and Eddy,
Inc. Prepared for U.S. Environmental Protection Agency, Office of Research
and Development, Cincinnati, Ohio. May 1985.
"Remedial Action at Waste Disposal Sites," (Revised), EPA/625/6-85/006,
U.S. Environmental Protection Agency, Office of Research and Development,
Hazardous Waste Engineering Laboratory, Cincinnati, Ohio. October 1985.
4-19
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Chromium Reduction. Chemical reduction, which involves the transfer of
reactive electrons from one compound to another, is used either to render
compounds nontoxic or to enable compounds to undergo chemical destruction or
physical removal. Metals, in particular hexavalent chromium, are reduced
through the addition of a compatible reducing agent (for examples reduced
sulfur compounds). Specific solution pH and agitation requirements must be
met to ensure successful chemical reduction. Treatment efficiency is calcu-
lated by dividing the quantity of a particular contaminant chemically modi-
fied by the quantity entering the process.
Adsorption. Adsorption is the adherence of one substance to the surface
of another by physical and chemical processes. Treatment of wastestreams by
adsorption is essentially a process of transferring and concentrating contam-
inants (the adsorbate) from one medium (liquid or gas) to another (the ad-
sorbent). The most commonly used adsorbent is activated carbon. Other
adsorbents include specially manufactured resins. Ion exchange is a process
whereby the toxic ions are removed from the aqueous waste by being exchanged
with relatively harmless ions held by the ion exchange material. In each of
these processes, treatment is achieved by transfer of contaminant compounds
from wastewater to a solid phase. Treatment efficiency is measured by divid-
ing the quantity of a particular contaminant removed from the wastewater by
the quantity entering the process.
Stripping. Air stripping is a mass transfer process in which volatile
contaminants in wastewater are transferred to gas streams. Typically, a
wastewater stream will flow countercurrently to a forced air stream in a
packed tower to maximize the transfer of volatile materials. The gas stream
subsequently requires treatment before emission to the atmosphere.
Steam stripping essentially involves removing volatile constituents from
an aqueous stream by steam heat. The volatile constituents are concentrated
in a vapor or liquid solution that usually requires further treatment. In
both steam and air stripping, pollutants are transferred from the wastewater
to a gaseous or liquid stream, and efficiency is measured by dividing the
quantity of particular constituents removed from the wastewater stream by the
quantity entering the process.
4-20
-------
Filtration. Filtration is a physical process whereby suspended solids
are removed from solution by forcing the fluid through a porous medium.
Granular media filtration is typically used for treating wastewater streams.
The filter medium consists of a bed of granular particles (typically sand or
sand with anthracite or coal). The bed is contained within a basin and is
supported by an underdrain system that allows the filtered liquid to be drawn
off while the filter media is retained in place. As water laden with sus-
pended solids passes through the bed of filter medium, the particles become
trapped on top of and within the bed.
Removal of toxic constituents in the wastewater is confined to the
quantity of toxic constituents in the form of filterable suspended solids.
The efficiency of the process is measured by dividing the mass of a particu-
lar chemical removed from the wastewater stream by the mass of that chemical
entering the process.
Air Flotation. Air flotation is a gravity separation process in which
the attachment of fine air bubbles to suspended solids or oils decreases the
effective density of the material and thereby enhances gravity separation.
Treatment efficiency is calculated by dividing the quantity of the contami-
nant removed from the wastewater by the quantity entering the process.
Settling/Clarification and Oil Skimming. Gravity separation is widely
used as a waste treatment process for the removal of settleable suspended
solids, oil and grease, and other material heavier or lighter than the carry-
ing fluid (usually water). Grit chambers, clarifiers, American Petroleum
Institute (API) separators, inclined plate settlers, and corrugated plate
interceptors (CPI) are common forms of gravity separation devices used in
wastewater treatment. Treatment efficiency is calculated by dividing the
quantity of a particular contaminant removed from the wastewater by the
quantity entering the process.
Biological Treatment. The function of biological treatment is to remove
organic matter from the wastestream through microbial degradation. The most
prevalent form of biological treatment is aerobic, i.e., in the presence of
dissolved oxygen. In anaerobic treatment, biological degradation takes place
in the absence of dissolved oxygen; in facultative treatment, biological deg-
radation occurs with or without dissolved oxygen. In all of these processes,
4-21
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contaminants are either destroyed, transferred to solid phase, or volatilized
to air. Efficiency is measured by dividing the quantity of a particular con-
taminant removed from the wastewater (or destroyed) by the quantity entering
the process.
Other Wastewater Treatment. Wet air oxidation is the aqueous-phase
oxidation of dissolved or suspended organic or inorganic substances at ele-
vated temperature (177° to 315°C) and pressure (300 to 3000 psi). Removal of
the contaminants is accomplished by destruction. Neutralization involves
combining either an acid or a base with wastewater to adjust liquid pH to ac-
ceptable levels. Acid and bases in the wastewater are chemically transformed
during the process. Equalization is the method of controlling the concentra-
tion or "strength" of a wastewater before entering subsequent processes.
Contaminants are neither destroyed nor removed, and as such, treatment effi-
ciency is zero. Reverse osmosis is used to separate water from inorganic
salts and some relatively high-molecular-weight organics. Pressure (typical-
ly 200 to 1200 psi) is used to force water from a solution through a semi-
permeable barrier (membrane) that will pass only certain components of a
solution (the permeate) but is impermeable to most dissolved solids (both
inorganic and organic).
4-22
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SECTION 4 BIBLIOGRAPHY
Cleland, J. G., G. L. Kingsbury, R. C. Sims, and J. B. White. 1977.
Multimedia Environmental Goals for Environmental Assessment, Volumes 1 and 2.
EPA-600/7-77-136b. U.S. Environmental Protection Agency, Research Triangle
Park, North Carolina. 366 pp.
Hossain, S. M., P. F. Cilicone, A. B. Cherry, and J. Wasylenko, Jr. 1979.
Applicability of Coke Plant Control Technologies to Coal Conversion.
EPA-600/7-79-184. U.S. Environmental Protection Agency, Research Triangle
Park, North Carolina. 212 pp.
Lebowitz, H. E., S. S. Tarn, G. R. Smithson, Jr., H. Nack, and J. H. Oxley.
1975. Potentially Hazardous Emissions from the Extraction and Processing of
Coal and Oil. EPA-650/2-75-038. U.S. Environmental Protection Agency,
Research Triangle Park, North Carolina. 162 pp.
U.S. Environmental Protection Agency. 1980. Proceedings: First Symposium
on Iron and Steel Pollution Abatement Technology, Chicago, Illinois, October
30-Hovember 1, 1979. EPA-600/9-80-012. Research Triangle Park, North
Carolina. 513 pp.
U.S. Environmental Protection Agency. 1983. Health Assessment Document for
Toluene. EPA-600/8-82-008f. Research Triangle Park, North Carolina.
427 pp.
U.S. Environmental Protection Agency. 1985. Technical Support Document for
Water Quality-Based Toxics Control. EPA-440-4-85-032. Washington, D.C.
4-23
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EPA DEVELOPMENT DOCUMENTS FOR EFFLUENT LIMITATION GUIDELINES
The following list of development documents for effluent limitation
guidelines (Table 4-4) is available from NTIS or the Government Printing
Office if referenced by the appropriate number.
Requests can be submitted to:
National Technical Information Service (NTIS)
5285 Port Royal Road
Springfield, Virginia 22161
Order Desk Telephone Number: (703) 487-4650
NTIS Accession Number is required when ordering
NTIS Information Telephone Number: (703) 487-4600
Supt. of Documents
Government Printing Office
Washington, D.C. 20402
(202) 783-3238
All development documents are available for review and inspection at the
EPA Regional Office Libraries listed in Table 4-5.
4-24
-------
TABLE 4-4. DEVELOPMENT DOCUMENTS FOR EFFLUENT LIMITATION GUIDELINES FOR SELECTED CATEGORIES4
ro
en
Industrial point
source category
Aluminum forming
Asbestos manufac-
turing
Battery manufac-
turing
Builders' paper
and board mills
Canned and pre-
served fruits and
vegetables
Canned and pre-
served seafood
processing
Subcategory
Aluminum forming
Building, construction, and
paper
Textile, friction materials,
and sealing devices
Battery manufacturing
Pulp, paper and paperboard,
and builders' paper and board
mills
Apple, citrus, and potato
processing
Catfish, crab, and shrimp
Fishmeal, salmon, bottom fish,
EPA publication
document No. NTIS accession No.
EPA 440/1-84/073
Vol. I
Vol. II
EPA 440/l-74/017a
EPA 440/l-74/035a
EPA 440/1-84/067
Vol. I
Vol. II
EPA 440/1-82/025
EPA 440/l-74/027a
EPA 440/l-74/020a
EPA 440/l-75/041a
PB84-244425
PB84-244433
PB238320/6
PB240860/7
PB85-121507
PB85-121515
PB83-163949
PB238649/8
PB238614/2
PB256840/0
GPO stock No.
-
5501-00827
-
-
-
5501-00790
5501-00920
„
sardine, herring, clsm,
oyster, scsllop, snd sbslone
Cement nranufsctur- Cement manufacturing
EPA 440/1-74/0053
PB238610/0
5501-00866
inq
(continued)
-------
TABLE 4-4 (continued)
cr>
Industrial point
source category
Coil coating
Copper forming
Dairy products
processing
Electroplating and
metal finishing
Ferroalloy
Fertilizer manu-
facturing
Glass manufactur-
ing
Grain mills
Subcategory
Coil coating, Phase I
Coil coating. Phase I! - can-
making
Copper
Dairy products processing
Copper, nickel, chrome, and
zinc
Electroplating - pretreatment
Metal finishing
Smelting and slag processing
Basic fertilizer chemicals
Formulated fertilizer
Pressed and blown glass
Insulation fiberglass
Flat glass
Grain processing
Animal feed, breakfast cereal,
EPA publication
document No. NTIS accession No.
EPA 440/1-82/071
EPA 440/1-83/071
EPA 440/1-84/074
EPA 440/l-74/021a
EPA 440/l-74/003a
EPA 440/1-79/003
EPA 440/1-83/091
EPA 440/1-74/0083
EPA 440/1-74/Olla
EPA 440/l-75/042a
EPA 440/l-75-034a
EPA 440/1-74/OOlb
EPA 440/1-77/OOlc
EPA 440/l-74/028a
EPA 440/1-74/0393
PB83-205542
PB84-198647
PB84-192459
PB238835/3
PB238834/AS
PB80-196488
PB84-115989
PB238650/AS
PB238652/AS
PB240863/AS
PB256854/1
PB238078/0
PB238-907/0
PB238316/4
PB240861/5
GPO Stock No.
-
-
-
5501-00898
5501-00816
-
-
5501-00780
5501-00868
5501-01006
5501-01036
5501-00781
5501-00814
5501-00844
5501-01007
and wheat
(continued)
-------
TABLE 4-4 (continued)
-p>
ro
Industrial point
source category
Inorganic chemi-
cals manufacturing
Iron and steel
manufacturing
Leather tanning
Meat products and
rendering
Metal finishing
Metal molding and
Subcategory
Inorganic chemicals Phase I
Inorganic chemicals Phase II
Iron and steel
Volume I
Volume II
Volume III
Volume IV
Volume V
Volume VI
Leather tanning
Red meat processing
Renderer
Metal finishing
Metal molding and casting
EPA publication
document No.
EPA 440/1-82/007
EPA 440/1-84/007
EPA 440/1-82/024
EPA 440/1-82/024
EPA 440/1-82/024
EPA 440/1-82/024
EPA 440/1-82/024
EPA 440/1-82/024
EPA 440/1-82/024
EPA 440/1-82/016
EPA 440/l-74/012a
EPA 440/l-74/031d
EPA 440/1-83/091
EPA 440/1-85/070
NTIS accession No. 6PO stock No.
PB82-265612
PB85-156446/XAB
PB82-240425a
PB82-240433b
PB82-240441C
PB82-240458d
PB82-240466e
PB82-240474f
PB83-172593
PB238836/AS 5501-00843
PB253572/2
PB84- 115989
PB86-161452/XAB
casting (foundries)
Nonferrous metals
forming
Nonferrous metals
manufacturing
Nonferrous metals forming
Bauxite refining - aluminum
segment
EPA 440/l-84/019b
Vol. I
Vol. II
Vol. Ill
EPA 440/1-74/019C
PB83/228296
PB83/228304
PB83/228312
PB238463/4
5501-00116
(continued)
-------
TABLE 4-4 (continued)
Industrial point
source category
Subcategory
EPA publication
document No. NTIS accession No. GPO stock No.
ro
oo
Nonferrous metals
manufacturing
(continued)
Organic chemical
manufacturing and
plastics and syn-
thetic fibers
Petroleum refining
Pharmaceuticals
Phosphate manu-
facturing
Porcelain enamel-
ing
Pulp, paper, and
paperboard
Primary aluminum smelting -
aluminum segment
Secondary aluminum smelting -
aluminum segment
Organic chemicals manufactur-
ing and plastics and synthet-
ic fibers
Petroleum refining
Pharmaceutical
Phosphorus-derived chemicals
Other non-fertilizer chemicals
Porcelain enameling
Unbleached kraft and semi-
chemical pulp
Pulp, paper and paperboard,
and builders' paper and board
mills
Rubber processing Tire and synthetic
Fabricated and reclaimed
rubber
EPA 440/l-74/019d
EPA 440/l-74/019e
PB240859/9
PB238464/2
EPA 440/1-87-009 Available from NTIS
after publication
(1/87)
EPA 440/1-82/014
EPA 440/1-83/084
EPA 440/l-74/006a
EPA 440/1-75/043
EPA 440/1-82/072
EPA 440/l-74/025a
EPA 440/1-82/025
EPA 440/l-74/013a
.EPA-440/l-74/030a
PB83-172569
PB84-180066
PB241018/1
PB238833/AS
PB83-163949
PB238609/2
PB241916/6
5501-00817
5501-00819
5503-00078
5501-00885
5501-01016
(continued)
-------
TABLE 4-4 (continued)
Industrial point
source category
Subcategory
EPA publication
document No. NTIS accession No. 6PO stock No.
ro
10
Soaps and deter- Soaps and detergents
gents
Sugar processing Beet sugar
Cane sugar refining
Textile mills man- Textile mills
ufacturing
Timber products Wood furniture and fixtures
processing
Timber products processing
EPA 440/1-74/0183
EPA 440/1-81/023
PB238613/4
EPA 440/l-74/002b PB238462/6
EPA 440/1-74/002C PB238147/3
EPA 440/1-82/022 PB83-116871
EPA 440/1-74/0333
PB81-227282
5501-00867
5501-00117
5501-00826
This list includes only "final" development documents for effluent limitations guidelines. For many
industries, these documents are in the draft or propossl stsge.
-------
TABLE 4-5. EPA REGIONAL OFFICE LIBRARIES
Library
Environmental Protection Agency, Region I
John F. Kennedy Federal Bldg.
Boston, MA 02203
Library
Environmental Protection Agency, Region II
26 Federal Plaza
New York, NY 10278
Diane M. McCrary, Librarian
Environmental Protection Agency, Region III
Sixth & Walnut Streets - Curtis Bldg.
Philadelphia, PA 19106
Library
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OUTLINE FOR SECTION 5
ESTIMATING RELEASES IN SOLID, SLURRY, AND NONAQUEOUS LIQUID WASTES
5.1 Sources and Disposal Methods for Solid, Slurry, and NonAqueous Liquid
Wastes
5.1.1 Landfilling
5.1.2 Land treatment
5.1.3 Underground injection
5.1.4 Surface impoundments
5.2 Methods for Calculating Releases in Solid, Slurry, and NonAqueous
Liquid Wastes
5.3 Estimating Treatment Equipment Efficiency
5.3.1 Incineration
5.3.2 Reuse as fuel
5.3.3 Solidification
5.3.4 Recovery of solvents and other organic chemicals
5.3.5 Recovery of metals
5.3.6 Sludge dewatering operations
5-0
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SECTION 5
ESTIMATING RELEASES IN SOLID, SLURRY, AND NONAQUEOUS LIQUID WASTES
In the context of section 313 reporting requirements, the terms solid,
slurry, and nonaqueous liquid refer to those wastes which are not gaseous
waste or wastewater. Where a waste is a mixture of water and organic liquid,
it is considered a wastewater unless the organic content exceeds 50 percent.
Slurries containing water should be reported as solids if they contain appre-
ciable amounts of settleable or dissolved solids such that the viscosity or
density of the waste is considerably different from that of process waste-
water. Throughout this document, "solid/slurry waste" refers to all solid,
slurry, and nonaqueous liquid wastes.
Solid/slurry wastes originate from a wide variety of sources. Based on
the physical and chemical characteristics of a particular solid waste, it can
be treated and disposed of either individually by source or mixed with other
wastes from a facility. Treatment and disposal can take place on site or at
an approved off-site facility.
For a number of the listed toxic chemicals, generation, storage,
transportation, treatment, and disposal of wastes are subject to RCRA regula-
tions. The RCRA reporting requirements such as permits, manifests, and
biennial reports can serve as a valuable source of information for the'
estimation of releases in solid/slurry wastes. In this section, sources and
disposal methods for solid/slurry wastes are presented, along with associated
release estimation techniques. Treatment methods and efficiencies are also
discussed.
5.1 SOURCES AND DISPOSAL METHODS FOR SOLID, SLURRY, AND NONAQUEOUS LIQUID
WASTES
Table 5-1 presents some generalized sources of solid/slurry wastes, and
the following subsections describe disposal methods for these wastes. In
5-1
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TABLE 5-1. SOME SOLID, SLURRY, AND NONAQUEOUS WASTESTREAM SOURCES
Spent solvents
Heavy ends - distillation residues
Heavy ends - miscellaneous
Light ends - condensable
Steam stripping wastes
Acid leaching solutions
Spent plating, stripping, or cleaning baths
Off-spec, discarded products or feedstock
Distillation side cuts
Residue in containers, liners, drums, cans, cleaning rags, gloves
Spills, leaks, vessel overflows
Precipitates or filtration residues
Spent activated carbon or other adsorber
Spent ion-exchange resins
Spent catalyst
Scrap metal
Solid scrap from finishing or trimming operations
Untreated solid waste
Equipment cleaning sludge (tank bottoms, heat exchangers)
Oven residue
Wastewater treatment sludges - biological
Wastewater treatment sludges - other
Treated organics
Treated solids
Oily waste from treated wastewater
5-2
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most circumstances involving the disposal of the chemicals subject to report-
ing, these disposal methods will be controlled by RCRA permitting procedures.
Therefore, quantities of the listed chemicals disposed of by these methods
have the potential of being calculated directly from the information obtained
for the permit. Incineration is not discussed as a disposal method because
(for purposes of this report) it is included in treatment methods (see Sub-
section 5.3). Sometimes, solid/slurry wastes are discharged in wastewater
(either to an onsite wastewater treatment facility or a POTW). In this
instance, these wastes would be reported as part of the releases to water
after accounting for any onsite removal.
5.1.1 Landfill ing
Typically, the ultimate disposal method for solid wastes is landfilling.
Any waste generating free liquids (based on EPA's "paint filter test") must
be disposed of in some other fashion besides landfilling. For onsite land-
fills, volatilization of toxic chemicals from the landfill must be accounted
for as a separate emission to air (see Section 3.1.4).
5.1.2 Land Treatment ;
Land treatment is a disposal method in which waste is applied onto or
incorporated into soil. This disposal method is considered a release to
land, but volatilization of toxic chemicals into air from this source must be
accounted for.
5.1.3 Underground Injection
Analogous to underground injection of wastewater, "pumpabie" solid/slur-
ry wastes containing hazardous and/or toxic chemicals may be injected beneath
the earth's surface, where they are unlikely to contaminate ground water.
5.1.4 Surface Impoundments
A surface impoundment is a natural topographic depression, man-made ex-
cavation, or diked area formed primarily of earthen materials (although some
may be lined with man-made materials), which is designed to hold an accumula-
tion of liquid wastes or wastes containing free liquids. Examples of surface
5-3
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impoundments are holding, storage, settling, and elevation pits; ponds; and
lagoons. If the pit, pond, or lagoon is intended for storage or holding
without discharge, it is considered to be a surface impoundment used as a
final disposal method under Section 313 reporting. This disposal method is
considered a release to land; however, listed chemicals in the impoundment
may be released to air by volatilization, collected as sludge and removed, or
biodegraded.
5.2 METHODS FOR CALCULATING RELEASES IN SOLID, SLURRY, AND NONAQUEOUS
LIQUID WASTES
Combinations of direct measurement, mass balance, and engineering calcu-
lations may be used to estimate environmental releases of listed chemicals
from the disposal of solid/slurry wastes. A general compilation of emission
factors for these wastes is not available. However, some emission factors
may be found in trade journals and the literature for specific industries.
The bibliography at the end of this section presents some potentially helpful
references on solid and slurry wastes. This bibliography was developed from
a literature search of solid/slurry waste emissions and treatment efficien-
cies. It is not a complete listing of available references on the subject
and those listed may not contain information pertaining to all of the listed
chemicals. Other potential sources of information include journals (such as
Waste Age and World Wastes) that deal primarily with the subject of solid/
slurry wastes.
The quantity of solid waste generated can be estimated from shipping
invoices if the waste is sent offsite. Quantities can also be estimated by
keeping track of the drums or tanks filled with waste prior to disposal.
For plants subject to the RCRA regulations (40 CFR Part 261 et seq.),
the quantities of waste and its fate will have been reported on hazardous
waste manifests. Generators of hazardous waste that ship their waste offsite
will have completed biennial reports on EPA Form 8700-13A. The amount of
waste disposed of each year is reported on this form, but its exact composi-
tion may not be known. Specific constituents in the waste may be available
from chemical analyses performed to determine the hazardous nature of the
5-4
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waste. These analyses may be performed by the generator or an offsite facil-
ity accepting the waste. The following examples illustrate the calculations
for estimating annual releases.
Example 5-1 - Use of direct measurement to estimate releases in
solid/slurry:
Spent degreasing sludges are disposed of by shipping to an off-site
waste treatment facility. The specific release of methylene chloride can
be estimated as follows.
Step 1. Gather information from RCRA permit.
From EPA Form 8700-13A, the quantity of waste identified by hazardous
waste Number F001 is recorded as 50,000 gallons per year. The receiver of
this waste has analyzed each shipment and determined that the methylene
chloride content averages 10 percent by weight.
Step 2. Calculate annual releases.
The methylene chloride release (to off-site disposal) is calculated by
multiplying the volume shipped by its density (8.5 Ib/gal determined by
weighing a known volume of waste) and by the weight percent of methylene
chloride.
50.000 gal x
year
Report 43,000 Ib/year.
8.5 Ib x 10% =
gallon
42.500 Ib
year
Example 5-2 - Use of direct measurement to estimate releases in
solid/slurry:
Step 1. Gather information on quantity and concentration of solid/slurry
waste.
During the year, an electroplater shipped 7500 gallons of waste solu-
tion to a hazardous waste treatment, storage, and disposal facility (TSDF).
The electroplater1 s analyses showed that the wastes contained an average of
87.4 grams of cyanide per liter of solution before treatment.
Step 2. Calculate annual releases.
Cyanide shipped to TSDF:
"00
Report 5500 Ib/year.
=2.481,067.5
or
5-5
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Example 5-3 - Use of a combination of measurement, mass balance, and
an engineering calculation to estimate releases in solid/slurry:
Step 1. Gather process and analytic information.
A tannery utilizes a filter press to dewater raw sludge from its
wastewater treatment plant. The dewatered sludge is disposed of in an on-
site landfill. Liquid filtrate from the filtering operation is recircu-
lated to the wastewater treatment process. Several analyses for chromium
have been made on the dewatered sludge and have yielded an average value of
100 mg total chromium/kg sludge. The quantity of dewatered sludge disposed
multi- plied by this concentration will yield the quantity of chromium
released to land from this source.
To calculate the quantity of dewatered sludge sent to the landfill, an
engineering estimate and mass balance will be used. Moisture measurements
of the raw and dewatered sludge show that these streams contain an average
of 95 and 53 percent H20 by weight, respectively.
RAW SLUDGE
95% H20 -
5% SOLIDS
FILTER PRESS
FILTRATE
100% H,0
DEWATERED SLUDGE
53% H20
47% SOLIDS
Step 2. Make an engineering assumption to estimate the quantity of fil-
trate from the filter press.
It is known that the filter press has a filtration area of 100 ft2 and
operates an average of 10 hours per day, 5 days per week, and 50 Weeks per
year. When designing the filter press, a filtration rate of 10 gal/h per
ft2 of filtration area was used. With this information, the total amount
of filtrate produced by the filter press can be estimated.
inn -F+-2 v 10 gal filtrate v 10 hours 5 days 50 weeks 8.34 Ib water
i.UU T U X « X XX X i
hour ' ft day week yr 1 gal of water
- 20.85 x 106 Ib filtrate
yr
Step 3. Perform a mass balance around the process.
A mass balance can then be performed around the filter press to find
the quantity of dewatered sludge produced per year.
5-6
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Total mass balance: (raw sludge) = (dewatered sludge) + (filtrate)
Eq. 1: Raw sludge = dewatered sludge + 20.85 x 10 l_b
yr
Solids mass balance: Eq. 2: (0.05)(raw sludge) = (0.47)(dewatered
sludge)
Eg. .2 . n 05 - (0.47)(dewatered sludge)
Eq< l ' (dewatered sludge) + 20.85 x 106 Ib/yr
;. dewatered sludge = 2.482 x 106 Ib
Step 4. Calculate annual releases.
To calculate the amount of chromium discharged to land:
100 mg total chromium _ 100 mg total chromium 100 Ib total chromium
1 kg dewatered sludge 106 mg dewatered sludge 106 Ib dewatered sludge
100 Ib Cr 2.482 x 106 Ib dewatered sludge
/\
106 Ib dewatered sludge yr
248.2 Ib Cr
Report 250 Ib Cr/yr.
Example 5-4 - Use of an engineering calculation to estimate
solid/slurry:
Step 1. Gather process information.
A semiconductor production facility uses 1,1,1-trichloroethane (1,1,1-
TCE) to degrease semiconductors. The solvent is pumped into degrees ing
units from 55-gallon steel drums when needed. The empty drums are sent to
an offsite drum cleaning facility for reclamation.
Step 2. Use an engineering estimate of the quantity of residue left in
each drum.
To estimate the quantity of 1,1,1-trichloroethane sent to the drum
cleaning facility as residue in the drums, the information in Table 5-2 can
be utilized. This table provides results from experimentation on residue
quantities left in drums and tanks when emptied. Results are presented as
the mass percent of the vessel capacity, and are categorized based on
unloading method, vessel material, and bulk fluid material properties
(i.e., viscosity and surface tension).
5-7
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TABLE 5-2. SUMMARY OF RESIDUE QUANTITIES FROM PILOT-SCALE EXPERIMENTAL STUDYa'b
(wt. percent of drum capacity)
en
i
oo
Unloading
method
Pumping
Pumping
Pouring
Pouring
Gravity drain
Gravity drain
Gravity drain
Material
Vessel type
Steel drum
Plastic drum
Bung-top steel drum
Open-top steel drum
Slope-bottom steel
tank
Dish-bottom steel tank
Dish-bottom glass-
lined tank
Value
Range
Mean
Range
Mean
Range
Mean
Range
Mean
Range
Mean
Range
Mean
Range
Mean
c
Kerosene
1.93 - 3.08
2.48
1.69 - 4.08
2.61
0.244 - 0.472
0.404
0.032 - 0.080
0.054
0.020 - 0.039
0.033
0.031 - 0.042
0.038
0.024 - 0.049
0.040
Waterd
1.84 - 2.61
2.29
2.54 - 4.67
3.28
0.266 - 0.458
0.403
0.026 - 0.039
0.034
0.016 - 0.024
0.019
0.033 - 0.034
0.034
0.020 - 0.040
0.033
Motor oil6
1.97 - 2.23
2.06
1.70 - 3.48
2.30
0.677 - 0.787
0.737
0.328 - 0.368
0.350
0.100 - 0.121
0.111
0.133 - 0.191
0.161
0.112 - 0.134
0.127
Surfactant.*
solution
3.06
3.06
Not
available
0.485
0.485
0.089
0.089
0.048
0.048
0.058
0.058
0.040
0.040
From "Releases During Cleaning of Equipment." Prepared by PEI Associates, Inc., for the U.S.
Environmental Protection Agency Office of Pesticides and Toxic Substances, Washington, D.C. Contract No.
68-02-4248. June 30, 1986. ;
The values listed in this table should only be applied to similar vessel types, unloading methods, and
bulk fluid materials. At viscosities greater than 200 centipoise, the residue quantities can rise
dramatically and the information on this table is not applicable.
For kerosene, viscosity = 5 centipoise, surface tension = 29.3 dynes/cm2.
For water, viscosity = 4 centipoise, surface tension = 77.3 dynes/cm2.
For motor oil, viscosity = 97 centipoise, surface tension = 34.5 dynes/cm2.
For surfactant solution viscosity = 3 centipoise, surface tension = 31.4 dynes/cm2.
-------
In this example, steel drums were pumped empty; of the four materials
tested, 1,1,1-trichloroethane most resembles kerosene. As such, it can be
estimated that each empty drum contains approximately 2.48 percent of the
1,1,1-trichloroethane in the drum.
Step 3. Calculate annual releases.
The yearly quantity of 1,1,1-trichloroethane sent to the drum reclaim-
er would be estimated as follows based on the use of 1.3249 as the specific
gravity of 1,1,1-trichloroethane relative to H20 at 1.00.
100 drums 55 gal 8.34 Ib H,0 1.3249 Ib 1,1,1-trichloroethane
year drum x galx Ib H20
x 0.0248 Tb residue. _ 15Q7 lb of uj.trichloroethane residue per year
Report 1500 Ib of 1,1,1-trichloroethane residue per year.
5.3 ESTIMATING TREATMENT EQUIPMENT EFFICIENCY
Toxic pollutants entering a solid/slurry waste treatment device will
undergo one or more of the following fates: 1) transfer to a different
media, 2) destruction through combustion, biodegredation, or chemical
reaction, 3) modification to a less toxic state, 4) fixed in place or
concentrated in the same waste media by transformation of the solid/slurry
matrix, or 5) pass through untreated. In some instances, treatment is not
provided to solid/slurry wastes before disposal. Table 5-3 presents a list
of various solid/slurry waste treatment processes.
Efficiency for solid/slurry waste treatment devices is based on the
amount of a contaminant removed from the solid/slurry waste, either through
destruction, modification by chemical reaction, or transfer to air or water.
X inlet - X outlet
Percent efficiency
X inlet
x 100
where X inlet = total mass of pollutant entering the solid/slurry treatment
system in a given year
X outlet = total mass of pollutant leaving the solid/slurry treatment
system in a given year
The amount of a pollutant transferred and subsequently released to
another media must be included with the total releases for that particular
5-9
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TABLE 5-3. UNIT OPERATIONS AND TREATMENT PROCESSES USED
TO TREAT SOLID, SLURRY, AND NONAQUEOUS WASTES
Incineration/thermal treatment
Liquid injection
Rotary kiln with liquid injection unit
Other rotary kiln
Two stage
Fixed hearth
Multiple hearth
Fluidized bed
Infra-red
Fume/vapor
Pyrolytic destructor
Wet air oxidation
Thermal drying/dewatering
Other incineration/thermal treatment
Reuse as fuel
Industrial kiln
Industrial furnace
Boiler
Fuel blending
Other
Solidification
Cement processes (including silicates)
Other pozzolanic processes (including silicates)
Asphaltic processes
Thermoplastic techniques
Other solidification processes
Recovery of solvents and other organic chemicals
Fractionation
Batch still distillation
Solvent extraction
Thin film evaporation
Other solvent recovery
Recovery of metals
Electrolytic metal recovery
Ion exchange (for metals recovery)
Reverse osmosis (for metals recovery)
Solvent extraction (for metals recovery)
Other metals recovery
Sludge dewatering operations
5-10
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pollutant in that media. Of course this amount should be subtracted from the
quantity of the pollutant released as a solid/slurry waste. Release esti-
mates and treatment efficiencies for toxic metals must be based on quantities
of parent metal.
The best method of estimating treatment efficiency is direct measurement
of the inlet and outlet streams. Measurement of treatment efficiency may
also be necessary for RCRA reporting requirements. The next best method
would involve the use of a mass balance along with measurement of a secondary
parameter. In lieu of these methods, efficiency estimates in the literature
may be used provided that the cited treatment system is similar to the opera-
tion for which the estimate is being made.
Solid/slurry waste treatment devices usually fall within one of six cat-
egories (incineration, reuse as fuel, solidification, recovery of solvents,
recovery of metals, and dewatering), based on the predominant method of con-
taminant removal. Frequently however, a solid/slurry waste treatment device
will not fall into one of these categories and will more closely resemble a
wastewater treatment process (see Section 4.3). The treatment process
reported on the Toxic Chemical Release Inventory Form should most closely
resemble the treatment process at the facility, regardless of how it may be
categorized in this report.
The following subsections provide a brief description of each of the six
categories of solid/slurry waste treatment devices.*
5.3.1 Incineration
Incineration is a controlled oxidation destruction process that uses
combustion to destroy wastes with oxygen by converting the wastes to carbon
dioxide, water, and other combustion products. The specific products of
incineration (combustion) vary depending on the type of wastes that are
burned. Typically, controls are required to reduce transfer of contaminants
to the air. The efficiency of the incinerator should be based on the quanti-
ty of the compound in the input solid/slurry waste stream and the quantity of
the compound in the ash.
5.3.2 Reuse as Fuel
Reuse as fuel involves the use of combustible organic wastes as substi-
tutes or supplements for conventional fuels that are burned in industrial
5-11
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processes. As in incineration, the organic waste is destroyed in flame com-
bustion yielding essentially carbon dioxide and water. The efficiency of
treatment through reuse as a fuel should be calculated as with incinerators.
5.3.3 Solidification
Solidification/stabilization is used to reduce the mobility of pollu-
tants in the environment and thereby make disposal safer. Materials are
mixed with wastes to immobilize the waste constituents chemically and physi-
cally. The process is usually applied to concentrated waste solids, sludges,
and slurries; however, liquid wastes may also be treated. Separate tech-
niques are usually applied to the solidification/stabilization of organic and
inorganic wastes; however, several processes are available to immobilize both
organic and inorganic pollutants with the same processes. In most of these
treatment methods, the toxic component of the waste is neither destroyed nor
transferred to a different media. Therefore, treatment efficiency as defined
has no meaning for these processes and should be reported as zero on the
Toxic Chemical Release Inventory Form.
5.3.4 Recovery of Solvents and Other Organic Chemicals
These treatment methods generally involve the separation of a particular
organic compound or group of organic compounds from a dilute liquid waste
stream. Removal is based on differences in physical properties (usually
boiling point) between the desired product and the bulk of the waste stream.
The recovered product is in nearly pure form, which enables it to be reused;
whereas the original waste stream is depleted of its toxic component. Effi-
ciency is based on the amount of the toxic component removed from the main
input-output waste stream.
5.3.5 Recovery of Metals
Treatment processes for metals recovery use a combination of physical
separation and chemical reaction methods to extract metals from a waste
stream for reuse or disposal. Efficiency of these processes is based on the
removal of the toxic metals from the main input-output waste stream.
Hazardous Waste, HW-122B, Background Document for Solvents to Support 40
CFR Part 268 Land Disposal Restrictions (Volume II). Analysis of Treatment
and Recycling Technologies for Solvents and Determination of Best...,
Pope-Reid Associates, Inc. EPA Contract No. 68-01-6892, January 1986.
5-12
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5.3.6 Sludge Dewatering Operations
Dewatering operations are used to remove excess liquid from solid/slurry
wastes. The liquid portion of the waste is separated from the solid by grav-
ity settling, centrifugation, or filtration. Toxic chemicals in the waste
entering the process exit in the liquid filtrate stream, remain in the dewat-
ered solid, or both. For reporting purposes, treatment efficiency is based
on the difference between the quantity of material entering the process and
the quantity leaving in the dewatered solid. Because the goal of a dewater-
ing process is usually volume reduction of the waste, efficiencies calculated
in this manner may be low.
5-13
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SECTION 5 BIBLIOGRAPHY
Anonymous, Hazardous Waste Disposal and the Printing Industry, published by
Youngblood Publishing Co., Ltd., Wi11owdale, Ontario, Canada, 1986.
Assessment of Fluidized-Bed Combustion Solid Wastes for Land Disposal.
Volume 1. Final Report. PB85-175867/REB, 85-02, PC A12/MF A01
Assessment of Volatile Organic Emissions from a Petroleum Refinery Land
Treatment Site. 1986. Pub. in Proceedings of the National Conference on
Hazardous Wastes and Hazardous Materials, Atlanta, Georgia, March 4-6.
Sponsored by U.S. Environmental Protection Agency, Cincinnati, Ohio.
Cleland, J. G., G. L. Kingsbury, R. C. Sims, and J. B. White. 1977. Multi-
media Environmental Goals for Environmental Assessment, Volumes 1 and 2.
EPA-600/7-77-136b. U.S. Environmental Protection Agency, Research Triangle
Park, North Carolina. 366 pp.
Hazardous Waste, HW-19, Engineering Handbook for Hazardous Waste Incinera-
tion, Monsanto Research Corporation, EPA No. SW^-889, PG:487, NTIS: PB81-
248163, September 1981.
Hazardous Waste, HW-25, Guide to the Disposal of Chemically Stabilized and
Solidified Waste (Revised Edition), U.S. Army Engineer Waterways Experiment
Station, EPA No. SW-872, PG:127, September 1982.
Hazardous Waste, HW-122A, Background Document for Solvents land Disposal
Restrictions (Volume 1), Pope-Reid Associates, Inc., EPA Contract No.
68-01-6892, November 20, 1985.
Hazardous Waste, HW-122B, Background Document for Solvents to Support 40 CFR
Part 268 Land Disposal Restrictions (Volume II). Analysis of Treatment and
Recycling Technologies for Solvents and Determination of Best...9 Pope-Reid
Associates, Inc. EPA Contract No. 68-01-6892, January 1986.
Hazardous Waste, HW-122C, Background Document for Solvents to Support 40 CFR
Part 268, Land Disposal Restrictions (Volume III). Solvent Waste Volumes and
Characteristics, Required Treatmen and Recycling Capacity,..., Pope-Reid
Associates, Inc., EPA Contract No. 68-01-6892, January 1986.
Hazardous Waste Tank Failure (HWTF) and Release Model: Description of Meth-
odology, Appendices A, B, C, D, and E. PB86-192945/REB, 86-02, PC A99/MF A01
Hazardous Waste Treatment Research - U.S. Environmental Protection Agency,
PB85-176667/REB, 85-03, PC A02/MF A01
Hossain, S. M., P. F. Cilicone, A. B. Cherry, and J. Wasylenko, Jr. 1979.
Applicability of Coke Plant Control Technologies to Coal Conversion.
EPA-600/7-79-184. U.S. Environmental Protection Agency, Research Triangle
Park, North Carolina. 212 pp.
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Lebowitz, H. E., S. S. Tarn, G. R. Smithson, Jr., H. Nack, and J. H. Oxley.
1975. Potentially Hazardous Emissions from the Extraction and Processing of
Coal and Oil. EPA-650/2-75-038. U.S. Environmental Protection Agency,
Research Triangle Park, North Carolina. 162 pp.
Metry, A. A. The Handbook of Hazardous Waste Management, Technomic
Publishing Company, Inc. West Port, Connecticut. 1980.
Stabilization/Solidification of Hazardous Waste, PB86-156312/REB, 86-02 PC
A02/MF A01
Treatment Technologies for Hazardous Wastes, Part 3, Treatment Technologies
for Corrosive Hazardous Wastes. PB86-224565/REB, 86-04, PC A02/MF A01
U.S. Environmental Protection Agency. 1986. Best Demonstrated Available
Technology (BOAT) Background Document for F001-F005 Spent Solvents. EPA/530-
SW-86-056.
U.S. Environmental Protection Agency. 1980. Proceedings: First Symposium
on Iron and Steel Pollution Abatement Technology, Chicago, Illinois, October
30-November 1, 1979. EPA-600/9-80-012. Research Triangle Park, North
Carolina. 513 pp.
Wilhelmi, A. R., and P. V. Knopp. 1979. Wet Air Oxidation: An Alternative
to Incineration. Chemical Engineering Progress, 75(8):45-52.
5-15
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OUTLINE FOR SECTION 6
ESTIMATING ACCIDENTAL RELEASES
6.1 General Methods and Considerations
6.2 Equations for Modeling Release Rates
6.2.1 Liquid Discharge
6.2.2 Fraction of Discharge Flashed
6.2.3 Vaporization Model
6.2.4 Two-Phase Discharge
6.2.5 Gas Discharge
6-0
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SECTION 6
ESTIMATING ACCIDENTAL RELEASES
In fulfillment of Section 313, Title III, reporting requirements, acci-
dental releases of a listed chemical into the environment should be included
in the release totals reported on the Form; they should not be listed sepa-
rately. Accidental releases from a facility may be the result of spills,
vessel overflows, tank overpressures, pipe ruptures, etc. Other regulations,
such as Section 304 of Title III, CERCLA, or the Clean Water Act, may require
the reporting of quantities of these releases, and these same data can also
be used for Section 313 reporting purposes.
6.1 GENERAL METHODS AND CONSIDERATIONS
Because the volume of a spill or accidental discharge cannot always be
measured easily, engineering judgment must be used to determine the best
method for making the most accurate estimate. In lieu of direct measurement,
a mass balance method could be used in some cases to estimate the amount of a
chemical spill or leak; this would involve evaluating the difference in ves-
sel inventory before and after the discharge occurred. Alternatively, equa-
tions in Section 6.2 can be used to calculate the release from an opening in
the equipment containing the chemical, provided the area of the opening and
physical properties of the material within the system are known. Users .
should try to calculate these types of releases by the best means available
to obtain the most accurate estimate.
Spills should be reported as a release to water if, for example, the
spilled chemical is washed down the sewer or into the waste treatment system
after accounting for removal in treatment. If the spill is absorbed onto
some material and landfilled, it should be reported as a release to land.
Volatilization of the chemical may take place as it is discharged from equip-
ment and/or after it is discharged to the ground. Equations are presented in
6-1
-------
Section 6.2 to estimate the amount volatilized in either case. The amount
volatilized should be included in any totals for fugitive air emissions
reported on the Form, and this amount should be subtracted from the total
spill to arrive at an amount, if any, disposed of in water or on land.
Spilled liquid chemical may completely evaporate to air; therefore, the
entire amount of this accidental release would be reported as a fugitive air
emission.
6.2 EQUATIONS FOR MODELING RELEASE RATES
The methods described in this section were originally developed for the
calculation of rates of chemical release for use in dispersion modeling to
determine downwind concentrations. They provide a generation rate, which
must then be multiplied by the duration of the release to yield the quantity
released. The circumstances under which each method applies are described.
As presented, the equations apply only for release of the pure compound, not
for mixtures of chemicals. Estimating the release of a chemical in a mixture
will require adjustments in the equation.
6.2.1 Liquid Discharge
For releases of liquids in enclosed systems that are refrigerated, are
subject to a hydrostatic liquid head or internal pressure in excess of ambient
atmospheric pressure, or are liquified gases, the liquid rate of discharge
from an opening in the vessel can be estimated by using a model based on the
Bernoulli flow equation. This model can also be used to analyze bottom pipe
failures close to vessels containing saturated liquid under pressure, P,.
This method assumes an incompressible flow through the opening and makes no
allowances for the time dependency of the discharge as the pressure of liquid
head falls.
i
W = Cd ADe
288 g (Pi - Pj
+ 2gh
where
W = discharge rate, Ib/second
6-2
-------
Cd = discharge coefficient, dimensionless for nozzles and orifices (may
be available from vendor or manufacturer)
C. may be available from the equipment vendor or manufacturer, can
be calculated by standard chemical engineering methods (see Perry's
Chemical Engineering Handbook), or can be istimated by using:
C. = 0.97 nozzle type safety relief valves
C . = 0.81 openings on rupture discs
C. =f 0.8 leakage from pipes connected to vessels
Cd = 0.6 (conservative figure) used for hole in vessel
A = discharge area, ft2
De = density of liquid at conditions (T,Pj) of discharge, lb/ft3
g = gravitational constant, 32.17 Ib-ft/lb force-second2
Pj = absolute pressure of system, gauge pressure plus atmospheric, psia
Pa = atmospheric pressure, psia (can assume 14.7 psia)
h = hydrostatic head pressure due to elevation or liquid depth, ft
(if hydrostatic pressure already included in P,, then set h = 0)
To estimate the release of chemicals in a mixture, use the density of
the mixture in the equation (instead of the density of the chemical), and
then multiply the amount of mixture released by the weight fraction of the
chemical of interest.
6.2.2 Fraction of Discharge Flashed
When a release of liquified gas or superheated liquid occurs, a portion
of the discharge may flash immediately to form a vapor. The following equa-
tion calculates the fraction that will flash when the discharge contacts
ambient air. If this fraction is less than 1, further dilution of the liquid
spray with ambient air is necessary to complete vaporization of the remaining
cold liquid; however, if F is greater than 1, the liquid has evaporated
completely before reaching atmospheric pressure.
vap
= C
pl (T1 - Tb)/Hvap
6-3
-------
where
H
vap
Si
Ti
vap
fraction of fluid vaporized, dimensionless
heat capacity of liquid at a constant pressure at temperature
of system, Btu/1b-°F
temperature of liquid in system, °F
boiling point of liquid at atmospheric pressure, °F
heat of vaporization, Btu/lb
This fraction can be multiplied by the generation rate obtained with
equations in Subsection 6.2.1 (liquid discharge) or Subsection 6.2.4 (two-
phase discharge) to obtain the quantity of chemical emitted to air as it is
being discharged.
For a chemical in a mixture, use the boiling point and heat capacity of
the chemical as before. The system temperature will be the same for all the
chemicals in the mixture. Multiply the fraction flashed by the release rate
calculated according to instructions for mixtures in Section 6.2.1.
6.2.3 Vaporization Model
A liquid c'lemical that is spilled onto the ground may spread out over an
area, vaporize, and thus result in an air emission. A vaporization model
developed by Clements can be used to estimate the rate of evaporation if the
size (area) of the spill is known or can be estimated. This is a simple
vaporization model, but other available spill models (TRC 1986) are more
complex and may require more input data.
MKAP°
where
W
M
A
P°
W =
vapor generation rate, Ib/second
molecular weight of chemical
area of spill, ft2
vapor pressure of chemical, psia, at temperature T, [can assume
25°C (77°F) if not known] i
R = universal gas constant, 10.73 psia-ft3/°R-lb mole
6-4
-------
T.| = temperature of liquid spilled, °R = °F + 460
K = gas-phase mass transfer coefficient, ft/second
]2/3
K = 0.00438 (U)°-78[
3.1 x
where D = diffusion coefficient for chemical in air, ft2/second
U = Windspeed, miles/h
Diffusion coefficients can be found in chemical handbooks, usually in
cm /second (converted to ft/second by multiplying cm2/second by 1.08 x
•
If D is not available, use the following equation instead to calculate
10'3).
K.
K = 0.00438 (U)0-78
1/3
ft/second
For a chemical in a spilled mixture, use the partial pressure, P., for
the chemical instead of the chemical's vapor pressure. See Section 3.1.1 to
calculate P.; M and K remain chemical specific parameters.
6.2.4 Two-Phase Discha-ge
This method, which is based on the Fauske/Cude method, involves calcu-
lating the rate of discharge from two-phase (liquid-gas) critical flows. It
is applicable to releases of saturated liquids stored under pressure at a
temperature above the normal boiling point, and it is valid only if the
calculated fraction of liquid flashing (see Section 6.2.2) is less than 1.
This method assumes that the two phases (as discharged) are homogeneous and
in mutual equilibrium. A simple empirical method, it yields approximate
solutions. Alternative methods are requfred for more complex situations.
The accuracy of this method is questionable for discharges involving long
lengths of pipe where two-phase flow may develop within the line.
Two-phase critical flows can occur in failures of connections to the
vapor space of vessels containing superheated liquids under pressure. They
can also occur in failures of pipework containing superheated liquids remote
from the vessel, where a fully developed critical flow would be established.
Critical flow exists when velocity of the fluid attains sonic velocity, which
can be determined by calculating the critical pressure ratio and using the
6-5
-------
criteria presented in Subsection 6.2.5. Alternatively, the critical pressure
can be assumed to be 55 percent of the system pressure, P (World Bank 1985).
W = ACd [288 Dm (?l - PC)] , Ib/second
where
W = generation rate
A = discharge area of opening, ft2
C. = discharge coefficient, dimensionless (see Subsection 6.2.1)
P_ = critical pressure (P = 0.55P, for critical flow), psia
c c
P, = absolute pressure, gauge plus atmospheric, psia
g - 32.17 lb/sec2
Dm = mean density of the two-phase mixture, lb/ft2
F..._ , F.
where
F = fraction of discharge vaporized (see Subsection 6.2.2), except
P values of C , T. , and H shoulc. be at system pressure, not
atmosphericppressure p
D s density of vapor at system temperature and pressure, lb/ft3
D, = density of liquid at system temperature and pressure, lb/ft3
D can be estimated by:
P1 M
RT1
where ,
= Dv,
10.73 Ib - psia
" ' °R - ft3
M = molecular weight
For a chemical in a mixture, the calculations are more complicated, but
they can be performed with sufficient information and extra effort. The
release rate of the mixture should first be calculated and then this value
should be multiplied by the weight fraction of chemical in the mixture. To
6-6
-------
obtain the release rate of the mixture, use average molecular weight, M »
to calculate vapor density:
where
M
avg
M
XBG MB
= molecular weight of chemical I
= gas phase mole fraction of chemical I
IL
VIG
where Pj = vapor pressure of chemical I at system pressure,
Xj. = liquid phase mole fraction
P, = system pressure, psia
See Section 3.1.1 to calculate XIL from liquid-phase weight fractions.
D, should be density of liquid mixture. Fraction vaporized should be
calculated as follows:
vap
where
fract1onA FvapA
wt' fraction
B
fracl FvaPj
F = fraction of chemical I vaporized using C , Tb, H
for chemical at the system temperature and pressure
6.2.5 Gas Discharge
This method can be used to calculate discharge rates for gases from
sources under pressure and assumes reversible adiabatic behavior. Ideal gas
behavior is a reasonable assumption for all cases but very high (near criti-
cal) pressures.
The ratio of specific heats, k, is calculated as follows:
k = CP/Cv
where
C = heat capacity at constant pressure
C = heat capacity at constant volume
(Specific units are not important
but need to be the same for both.)
6-7
-------
Critical pressure, P , is calculated as follows to estimate critical
\*
ratio, P_/P, and P is then calculated by multiplying P. by the ratio.
C C X
k
where
P, = absolute system pressure, psia = gauge + atmospheric (14.7) pressure
(or relief valve set pressure can be used if actual pressure is not
known)
k = Cp/Cv
The critical pressure ratio is the largest ratio of downstream pressure
to upstream pressure capable of producing sonic velocity. Critical flow will
usually exist for most gases and vapor discharging through a safety valve or
orifice.
First, it must be determined if flow is critical:
If P2 < PC> flow is critical (sonic)
If P2 > PC» flow 1S subcritical (subsonic)
P2 - absolute pressure of downstream discharge flow, psia
(for discharge to atmosphere, it is assumed to be 14.7 psia).
For critical flow:
W = 735 Cd A G P]
where
W
A
.
G
generation rate, Ib/h
discharge area, in.2
discharge coefficient, dimensionless (see Subsection 6.2.1)
gas constant, determined from k
G= 520
, - absolute pressure upstream of discharge opening, psia
(if unknown, relief device set pressure should be used).
6-8
-------
M = molecular weight of chemical, Ib/lb-mole
R = universal gas constants 10.73 psia-ft3/°R tb-mole
T = absolute temperature at inlet of discharge opening, °R = °F + 460
(system temperature)
For subcritical flow:
W = 735 Cd A
Mk
RT (k-1)
Definitions for the parameters are the same as for critical flow.
For a chemical in a mixture, values of C , C , and M will have to be
averaged by summing the product of each chemical property by its weight
fraction in the gas. (See calculation for M in Section 6.2.4.) The
calculated release rate of the mixture in pounds/hour should then be multi-
plied by the weight fraction of the chemical of interest.
6-9
-------
SECTION 6 BIBLIOGRAPHY
Perry, R. H., and Chilton, C. H. (Consultant and Advisor). 1973. (Perry's)
Chemical Engineering Handbook, Fifth Edition. McGraw-Hill, New York.
Rose, R. S. (Dow Chemical Co.) 1987. Emission Estimates/Emission Factors
Paper presented at Chemical Manufacturers Association (CMA) Air Toxics
Policy Implementation Workshop, Atlanta, GA, Jan 13-14, 1987.
TRC, Environmental Consultants, Inc. 1986. Evaluation and Assessment of
Models for Emergency Response Planning. TRC Project No. 3088-R31.
800 Connecticut Blvd., East Hartford, CT 06108.
U.S. Environmental Protection Agency. 1983. A Manual for the Preparation
of Engineering Assessments. Chemical Engineering Branch, Office of
Toxic Substances, Washington, DC.
World Bank. 1985. Manual of Industrial Hazard Assessment Techniques
World Bank, Office of Environmental and Scientific Affairs, London,
England.
6-10
-------
OUTLINE FOR SECTION 7
AN OVERALL FACILITY EXAMPLE RELEASE CALCULATION
7.1 Atmospheric Releases
7.2 Wastewater Column Releases
7-0
-------
-------
SECTION 7
AN OVERALL FACILITY EXAMPLE RELEASE CALCULATION
This section presents an example illustrating the procedures used to
estimate releases. The example involves a complex manufacturing process for
producing acrylonitrile, which has air and water waste streams. Several
methods of estimating the releases are shown.
This complex manufacturing process (illustrated in Figure 7-1) produces
three listed chemicals: acrylonitrile (AN), acetonitrile, and hydrogen
cyanide. It also uses ammonia as a raw material and sulfuric acid as a
quenching aid, and produces ammonium sulfate as a byproduct. Separate toxic
chemical release forms would be completed for each of these compounds. In
this example, only the main product (AN) is discussed. Only routine releases
occurring during normal operation are considered here; however, estimates of
Startup releases and any accidental releases would normally be included.
7.1 ATMOSPHERIC RELEASES
7.1.1 Absorber Vent B
Releases from this vent contain nitrogen, oxygen, unreacted propylene,
other organic impurities present in the propylene feed, carbon monoxide,
carbon dioxide, water, and small amounts of AN. Hydrogen cyanide and aceton-
itrile are other toxic compounds in this stream. This vent stream may be
sent to a fume incinerator prior to discharge to the atmosphere.
Problem: Estimate AN emissions from the absorber Vent B.
Available data:
0 Vent gas flow rate is 80,000 cubic feet per minute (measured) at
100°F and 1 atmosphere.
0 Moisture content is 7 percent by volume (measured).
0 AN concentration is 8 parts per million by volume on a dry basis
(measured).
7-1
-------
-s to
o c:
3 3
m
cn o
i o
00 3
-P> -••
I r*
§ 2-
•o
2 -S
O) O
-S Q.
O C
3- O
rt-
vo o
03 3
o
o
n>
)
©
^ — I
V
^ — -
Qn)
*^^r
C?y
\ t
^ *
©
-------
0 Annual operating hours equal 7000, based on the operating log.
Step 1: Calculate annual volume of gas discharged 80,000 ft3/min x 60
min/h x 7000 hours/yr = 3.36 x 1010 ft3/yr.
Step 2: Calculate annual AN volume discharged on dry basis.
3.36 x 1010 ft3 gas/year x 8 x 10"6 parts AN/parts gas
x (1 - 0.07) to correct to dry basis
x (70°F + 460)°R/(100°F + 460) °R to correct volume to 70°F
= 236,592 ft3 AN per year . - ....
Step 3: Calculate pounds of AN per year.
236,600 ft3 x 53.06 Ib/lb-mole (molecular weight of AN)
* 387 ft3/lb-mole (the volume occupied by a Ib-mole of gas
at standard conditions)
= 32,438 Ib/yr
If the vent stream is controlled by a device such as a fume incinerator,
use outlet measurements to estimate releases. If no monitoring data are
available, apply a control efficiency based on design data for the incinera-
tor to the value calculated in the example. > .
* ' V-- 'L'
7.1.2 Product Recovery Column Vents, C, E, F, 6, and H"''
Gaseous releases from the recovery column, light-ends column, product
column, and the acetonitrile column are frequently tied together and vented
to a flare. The fact that these streams are combined makes it possible to
measure one flow and its concentration. Releases after the flare can only be
estimated, however, because quantitative measurements cannot be made in the
flare exhaust. ,
Problem: Estimate AN emissions from Vents C, E, F, 6, and H.
Available data:
0 The emission factor for all column vents is 5 g/kg of product
(equivalent to 5 lb/1000 Ib), based on published data in EPA
publication 450/4-84-007a.
0 350 million Ib of AN was produced, based on your operating logs
or product inventory data.
Step 1: Caled?ate AN emissions
5 Ib emission/1000 Ib production x 350 x 106 Ib/yr production
= 1.75 x 106 Ib/yr
7-3
-------
As an example of a control device applied to an air emission, assume that a
flare is used with a destruction efficiency of 98 percent. Actual releases
are:
1.75 x 106 Ib/yr x (1 - 0.98)
= 35,000 Ib/yr
The alternative of performing mass balances around the columns would be
very difficult because of the number of streams involved. Several input and
output values, each with an associated error, would be involved to estimate
what is a relatively small release value compared with the process stream.
7.1.3 Storage Tank Releases
Releases of AN from storage tanks and loading operations depend pri-
marily on the quantities handled and the number, size, and type of tanks.
Release estimates are calculated according to procedures provided in EPA
Publication AP-42, Section 4.3 (Appendix C).
Problem: Estimate annual AN releases from storage tanks.
Approach: Because monitoring data are not available, use equations pre-
sented in EPA Publication AP-42, Section 4.3.2. Here it is
assumed that a fixed-roof tank is used. For floating-roof
tanks, which are commonly used, other equations in this section
of AP-42 should be ured.
Equation for breathing loss:
0.68
= 0.0226 x
p _ p
M
D1'73 x H°'51 x AT0'50 x FpCKc
A
P
D
H
AT
= fixed-roof breathing loss, Ib/yr
- molecular weight of vapor in storage tank, Ib/lb-mole
* average atmospheric pressure at tank location, psia
s true vapor pressure at bulk liquid conditions, psia
= tank diameter, ft
= average vapor space height, including roof volume correction, ft
= average ambient diurnal temperature change, °F
- paint factor, dimension!ess
7-4
-------
C = adjustment factor for small diameter tanks, dimensionless
KP = product factor, dimensionless
To complete the calculation in this example:
Mu = 53.6 for acrylonitrile (see Appendix B)
V ,
P = 2.4 at 80°F (see Appendix B or standard chemical reference)
D = 30 ft for your tank (measured)
H = 6 f t for your tank (estimated)
Fp = 1.15 for a white tank in poor condition (see Appendix C)
C = 0.89 for a small tank (Appendix C)
1C = 1.0 for acrylonitrile (Appendix C)
Inserting these values into the equation for Lg produces the following
result:
LB = 1,635 Ib/year
For 20 tanks of this size and type, uncontrolled releases due to
breathing losses would be: .
20 x 1635 = 32,700 Ib/year
Report 33,000 Ib/year .
If scrubbers are used to reduce these emissions by 95 percent, the
controlled releases would be:
32.700 1b „ 100 - 95 _
year
100
= 1600 Ib/year
Problem: Estimate release due to working losses during tank filling.
Approach: Because monitoring data are not available, use equations in
AP-42, Section 4.3.2. (See also Appendix C.)
The storage tank working losses can be estimated by the following
equation:
Lw = 2.4 x 10
-5
MVPVN KN Kc
V = tank volume (gal) = 100,000
7-5
-------
where L^ s fixed roof tank working losses, Ib/yr
N = turnovers per year = annual throughput * tank capacity & 25
Kj. - turnover factor = 1.0 (from Figure 4.3-7 in AP-42)
Other factors are the same as in the preceding LB equation.
Lw = 2.4 x 10"5 x 53 x 2.4 x 100,000 x 20 x 1.0 x 1.0.
~ 6106 Ib per year
For 20 tanks, total annual releases would be:
20 x 6106 = 122,120 Ib per year (without emission controls)
Working losses are reduced by using scrubbers on the tank vents or by
using floating-roof tanks. With a scrubber operating at 95 percent effi-
ciency, the final release would be:
122.120 Ib „ 100 - 95 _
year
100
= 6105 Ib per year
7.1.4 Other Fugitive Releases
Emissions from loading operations and from leaks in valves, flanges,
pumps, etc., also contribute to the overall annual AN release.
Problem: Estimate emissions from loading operations and from leaks in
valves, flanges, pumps, etc.
Available data: Plant loading 51 x 106 gal/year
P = liquid vapor pressure = 2.4 psia
M = molecular weight = 53.6
T = liquid temperature (°F + 460°) = 540°R
Approach: Loading releases are estimated by the equations and data in
AP-42, Section 4.4.
LL = 12.46 SPM
L, = releases in lb/1000 gal of liquid loaded
S s Saturation factor (use 0.6 for submerged fill into tank truck or
rail car)
LL = 12.46 x 0.6 x 2'4540bj^6 = 1.78 Ib per 1000 gal
7-6
-------
Total loading releases would be:
x 51,000,000 gal = ~90,828 Ib per year
The use of vapor balance loading would greatly reduce these releases.
Leaks from valves, flanges, pumps, etc. can be estimated from factors
developed for the synthetic organic manufacturing processes (see Appendix
D). The number of fittings in the plant and the service (i.e., gas, liq-
uid, etc.) of each fitting must be known to make this estimate.
Available data:
Equipment
25 pumps in light-liquid service
500 pipeline valves in light-liquid service
100 pipeline valves in gas-vapor service
50 safety-relief valves in gas-vapor service
Approach: Use the following emission factors from Appendix D and multiply
times the number of fittings associated with the factor.
Emission factor,
Ib/h per fitting
0.11
0.016
0.012
0.23
Fitting type
Pumps in light liquid service
Valves in light liquid service
Valves in gas service
Safety valves in gas service
The total AN releases are the sum of these separate leaks, or:
25 (0.11) + 500 (0.016) + 100 (0.012) + 50 (0.23) = 23.45 Ib per hour
For 7000 hours of operation per year, annual releases would be:
7000 h „ 23.45 Ib _
year
hour
= "164,150 Ib per year
A good maintenance and inspection program would greatly reduce these
average releases. If you have data on your leak rates, these data should
be used.
7.1.5 Atmospheric Release Summary for AN
The following is a listing summarizing atmospheric releases of AN.
7-7
-------
Process
Absorber
Recovery columns after flare
Storage (1635 + 6105)
Loading
Leaks
Estimated total annual release of
AN during normal operations
7.2 WASTEWATER COLUMN RELEASES
Stack
releases. Ib/yr
32,438
35,000
7,740
Fugitive
releases, Ib/yr
90,828
164,150
or
75,178
75,000 Ib/yr
(stack)
254,978
255,000 Ib/yr
(fugitive)
Liquid discharge from the wastewater column contains small amounts of AN
in addition to cyanide, sulfates, ammonia, and acetonitrile, which generally
would go to wastewater treatment. Estimates of releases after treatment
should be based on effluent measurements, if available. In the absence of
such data, the amount of AN released can be estimated by calculating the
amount of AN influent to treatment and then applying the efficiency of the
treatment.
Problem: Estimate wastewater releases of AN
Approach: Measured flow data are available prior to treatment and will be
used to calculate annual releases of AN. A treatment efficiency
will then be applied to estimate actual plant releases.
0 Average discharge flow = 500 gallons/min
0 AN concentration = 150 parts per million by weight
0 Annual operating hours = 7000
The AN releases to a wastewater treatment system are calculated by
multiplying the flow by the concentration and the duration of release.
Note that the density of water is 8.32 Ib/gal at 70°F.
500 gal 8.32 Ib 150 parts 60 min 7000 h
minute gallon 10b parts hour year
per year
The treatment efficiency can be estimated based on published data for
similar treatment at the appropriate influent concentration. As shown in
Appendix D, AN can be reduced by 99.1 percent for an initial concentration
7-8
-------
of 110 mg/liter (ppm) by the use of activated sludge treatment. Releases
to surface water would then be:
262.000 Ib to treatment (100 - 99.1) = 235g lb
year 100 H
or 2400 Ib/year
7-9
-------
-------
APPENDIX A
WASTEWATER TREATMENT EFFICIENCY DATA
A-l
-------
Appendix A contains tables of information that allow the estimation of
wastewater treatment efficiency for selected processes and compounds. The
information provided should only be used when no other method of wastewater
treatment efficiency is available. Extreme care must be taken to ensure that
the data are applied only to systems operating under conditions similar to
those used to develop the efficiency estimates.
Table A-l contains numerous citations of wastewater treatment efficiency
for specific compounds based on the type of treatment and source of the
wastewater stream. The data in this table were compiled and summarized from
a literature search in "Estimation of Removal of Organic Chemicals During
Wastewater Treatment," Draft Final Report, Versar, Inc., prepared for the
U.S. EPA, Exposure Evaluation Division, Office of Toxic Substances, Washington,
D.C., EPA Contract No. 68-02-3968, Task 807.148, September 30, 1986. The
original data are from research conducted on pilot- and full-scale treatment
systems.
Data in the table should be used with an awareness and understanding of
test conditions involved.,
0 Tests with the same chemical performed at different temperatures
often showed thermally dependent differences in removal, with
higher percentage removal values at higher temperatures.
0 Longer retention times usually result in a higher rate of removal.
0 Aeration often results in greater removal for various reasons:
more agitation causes more contact between chemicals and cells;
aeration adds more oxygen to the wastewater system, and oxidative
microbial processes proceed more rapidly at higher oxygen levels;
many of the organic compounds reviewed in the Summary Table are
volatile, and aeration of the wastewater will accelerate the rate
of chemical transport from the aqueous to the atmospheric compart-
ment.
It is suggested that the user consult the references cited in Table A-l.
A-2
-------
Facilities should use the removal data for a treatment system that has
similar conditions (type of waste, chemical concentration, suspended solids
concentration, and residence time) to the facility's own wastewater treatment
system.
Table A-2 also presents wastewater treatment efficiencies for a number
of chemicals. This information, however, applies only to secondary biological
wastewater treatment systems receiving relatively low concentrations of the
particular toxic pollutant (approximately 500 parts per billion). It pro-
vides educated estimates on pollutant fate in the treatment system (i.e.,
volatilized to air, partitioned to sludge, or biodegraded) extracted from
"Report to Congress on the Discharge of Hazardous Wastes to Publicly Owned
Treatment Works," EPA/530-SW-86-004 (February 1986). ...
A-3
-------
TABLE A-l. SELECTED WASTEWATER TREATMENT REMOVAL EFFICIENCIES
Chemical
Acetone
Acroleln
Acrylonitrile
Aniline
Anthracene
Anthracene
Anthracene
Anthracene
Benzene
Benzene
Benzene
Benzene
Benzene
Benzidine
Butylbenzyl phthalate
Butylbenzyl phthalate
Carbon TetracKtor-ide
J> Carbon Tetrachloride
1 Carbon Tetrachloride
** Carbon Tetrachloride
Carbon Tetrachloride
Carbon Tetrachloride (3)
Chlorobenzene
Chlorobenzene
Chlorobenzene
Chlorobenzene
Chlorobenzene
Chloroform
Chloroform
Chloroform
Chloroform
Chloroform
Chloroform
Chloroform
Chloroform
Chloroform
Chlorophenol.m
Di (2-ethylhexyl) phthalate (1)
Di (2-ethylhexyl) phthalate (1)
Di (2-ethylhexyl) phthalate (1)
Percent |
Removal |
73.0
>85.7
99.1
>99
>96.0
>99.0
98.0
97.0
99.40
>99
>99
99.90
>75.00
0.00
>95.5
96.0
100.00
98.70
93.0
>99
51.0
99.90
99.80
97.60
74.00
97.80
>99
>93.60
65.0
85.0
99.40
0-91
>97
86.00
99.90
57-70
99.90
>96.9
50-69
88.60
Waste Strem
Domestic Uasteuater
Synthetic Wasteuater
Petroleum Refinery Waste
Coke processing plant
Coke processing plant
Coke processing plant
Municipal Sewage
Coke Plant Effluent
Raw Wastewater
Ind/domestic Wasteuater
Domestic Wasteuater
Paper/Petrochemical Wastes
Domestic Wasteuater
Municipal Seuage
Industrial Wastewaters
NR
Pulp waste
Raw Wastewater
Acid waste
Ind/domestic uastewater
NR
Dyestuff Hanufact Waste
Domestic/Ind. Wasteuater
Dyestuff Hanufact Waste
Raw Wastewater
Domestic Wasteuater
Pulp waste
Acid uaste
NR
Primary Domestic Sewage
Raw Wastewater
Ind/domestic uasteuater
Industrial Wasteuaters
Paper/Petrochemical Wastes
Domestic Wasteuater
Industrial Wasteuaters
Trickling Filter Effl
Initial
Chen Cone
700 ug/l
110 mg/l
7.2 ug/l
85 ug/l
15 ug/l
50 ug/l
5 ug/l
6.1-9.8 mg/l
73 ug/l
2.2 mg/l
4 ug/l
4 ug/l
21-24 ug/l
50 ug/l
1-2 ug/l
50-200 ug/l
NR
60 ug/l
NR
2.2 mg/l
50-200 ug/l
0.55 mg/l
NR
0.55 mg/l
197 ug/l
6-140 ug/l
NR
NR
50-200 ug/l
0-10 ug/l
137 ug/l
2.2 mg/l
30-36 ug/l
0.9 ug/l
21-66 ug/l
32-36 ug/l
NR
Treatment
Activated Sludge
Bio/Act Carbon
Activated Sludge
Activated Sludge
Activated sludge
Activated sludge
Activated sludge
Plug Flow A.S.
Activated sludge
Activated Sludge
Activated Sludge
Deep Shaft-Biological
Bio/Act Carbon
Activated Sludge
Bio/Act Carbon
Plug Flow A.S.
Activated Sludge
Activated Sludge
Two stage bio.
Aeration Basin
Activated sludge
Deep Shaft-Biological
Activated Sludge
Activated Sludge
Secondary Treatment
Activated Sludge
Aeration Basin
Bio/Act Carbon
Tuo stage bio.
Activated sludge
Activated Sludge
Activated Sludge
Aeration Basin
Activated Sludge
Deep Shaft-Biological
Activated Sludge
Activated Sludge
Bio/Act Carbon
Activated Sludge
Secondary Treatment
Scale
Pilot
Pilot
Full
Full
Full
Full
Pilot
Pilot
Pilot
Pilot
Pilot
Pilot
Full
Pilot
Pilot
Full
Pilot
Full
Pilot
Pilot
Pilot
Pilot
Full
Full
Full
Pilot
Pilot
Full
Pilot
Pilot
Full
Pilot
Pilot
Pilot
Full
Full
Pilot
Full
Full
Tetip
C
NR
NR
NR
MR
N'R
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
[ NR
Susp Solids
Cone
MR
16,300 mg/l
NR
38 mg/l
NR
NR
NR
430 mg/l
NR
45 mg/l
2900 mg/l
140 kg/day
16,300 mg/l
NR
16,300 mg/l
430 mg/l
931 mg/l
NR
NR
2900 mg/l
NR
NR
KR
216 g/cu m
NR
216 g/cu in
2900 mg/l
16,300 mg/l
NR
NR
NR
97 mg/l
2900 mg/l
NR
140 kg/day
931 mg/l
104-19,811 kg/day
16,300 mg/l
931 mg/l
NR
Hydraulic !
Res. Time
8 hrs
?
NR
NR
NR
NR
NR
7 days
SRT=5 days
NR
7.5 hr
30 min
?
NR
?
7 days
NR
NR
12.0 hr
7.5 hr
8.0 hr
30 min
NR
KR
NR
NR
7.5 hr
?
12.0 hr
8.0 hr
NR
NR
7.5 hr
8 hrs
30 min
NR
NR
?
NR
NR
Acclimtlon
NR
NR
4 weeks
NR
NR
HR
NR
NR
NR
NR
NR
?
NR
?
NR
NR
NR
NR
NR
NR
NR
?
NR
NR
None
NR
NR
NR
NR
HR
NR
NR
NR
NR
?
HR
?
NR
NR
None
Reference
Kincennon et at, no date
Cormack and Hsu, 1983
Ktncannon et. al, 1983
Snider and Manning, 1982
Walters and Luthy, 1984
Walters and Luthy, 1984
Walters and Luthy, 1984
Petrasek et al, 1983
Bishop, 1982
Osantouski and Hendriks, no date
Petrasek et. al.,1983b
SCS Engineering, 1979
Cormack and Hsu, 1983
SCS Engineering, 1979
Cormack and Hsu, 1983
Petrasek et al, 1983a
Feiler, 1979
Bishop, 1982
Leuenberger et al. 1985.
Petrasek et al.,1983b
Kincannon et al., no date
SCS Engineering, 1979
Bishop, 1982
Keinath, 1984
McCarty and Reinhard, 1980
Keinath, 1984
Petrasek et al.,1983b
Cormack and Hsu, 1983
Leuenberger et al. 1985.
Kincannon et al., no date
Bishop, 1982
Feiler, 1979
Petrasek et al.,1983b
Kincannon et al, no date
SCS Engineering, 1979
Feiler, 1979
SCS Engineering, 1979
Cormack and Hsu, 1983
Feiler, 1979
McCarty and Reinhard, 1980
(continued)
-------
TABLE A-l (continued)
Chemical
Di (2-ethylhexyl) phthalate (1)
Di (2-ethylhexyl) phthalate (1)
Di (2-ethylhexyl) phthalate (1)
Dibutylphthalate, n
Dibutylphthalate, n
Dibutylphthalate, n
Dibutylphthalate, n
Dichlorobenzene (1,2-)
Dichlorobenzene (1,2-)
Dichlorobenzene (1,3-)
Dichlorobenzene (1,3-)
Dichlorobenzene (1,3-)
Dichlorobenzene (1,3-)
Oichlorobenzene (1,4-)
Dichlorobenzene (1,4-)
Dichlorobenzene (1,4-)
;> Dichlorobenzene (1,4-)
1 Dichlorobenzene (1,4-)
*•" Dichlorobromomethane (5)
Dichlorobromomethane (5)
Dichloroethane (1,2-)
Dichloroethylene (1,1-)
Dichloroethylene (1,1-)
Dichloromethane (6)
Dichloromethane (6)
Dichloromethane (6)
Dichloromethane (6)
Dichloromethane (6)
Dichloromethane (6)
Dichloromethane (6)
Dichloromethane (6)
Dichlorophenol (2,4-)
Dichloropropane (1,2-)
Dichloropropane (1,2-)
Dichloropropylene (4)
Dichloropropylene (4)
Diethyl phthalate
Diethyl phthalate
Diethyl phthalate
Diisobutyl phthalate
Percent
Removal
62.00
79.0
55.00
55.00
94.0
>91.5
83.0
98.80
>97.00
99.20
98.50
93.30
88.00
99.00
96.60
>99.00
99.70
99.60
>99
95.70
>94.00
<99.5
>99
93.10
12.0
91.30
>97
98.90
0-91
>96.6
90.60
27.0
>98
96.10
97.50
97.80
50.00
97.0
>66.7
74.50
Waste Stream
Domestic/Ind. Wastewater
Municipal Sewage
Paper/Petrochemical Wastes
Domestic/Ind. Wastewater
Municipal Sewage
Domestic Wastewater
Municipal Sewage
Trickling Filter Effl
Domestic/Ind. Wastewater
Dyestuff Manufact Waste
Trickling Filter Effl
Dyestuff Manufact Waste
Domestic/Ind. Wastewater
Trickling Filter Effl
Dyestuff Manufact Waste
Domestic/Ind. Uastewater
Dyestuff Manufact Waste
Dyestuff Manufact Waste
Raw Wastewater
NR
Domestic Wastewater
NR
Raw Wastewater
Dyestuff Manufact Waste
Dyestuff Manufact Waste
Raw Wastewater
NR
Industrial Wasteuaters
Domestic Wastewater
Trickling Filter Effl
Pulp waste
Raw Wastewater
NR
Dyestuff Manufact Waste
Dyestuff Manufact Waste
Paper/Petrochemical Wastes
Municipal Sewage
Domestic Wastewater
Trickling Filter Effl
Initial
Chem Cone
NR
50 ug/l
2 ug/l
NR
50 ug/l
9-15 ug/l
50 ug/l
NR
NR
0.42 mg/l
NR
18 ug/l
NR
NR
0.8 mg/l
NR
3.2 mg/l
68 ug/l
89 ug/l
50-200 ug/l
33-710 ug/l
50-200 ug/l
79 ug/l
5.5 ug/l
5.5 ug/l
118 ug/l
50-200 ug/l
6-14 ug/l
1-62 mg/l
NR
NR
309 ug/l
50-200 ug/l
0.1 mg/l
0.13 mg/l
6 ug/l
50 ug/l
2-4 ug/l
| NR
Treatment
Secondary Treatment
Plug Flow A.S.
Activated Sludge
Secondary Treatment
Plug Flow A.S.
Bio/Act Carbon
Plug Flow A.S.
Secondary Treatment
Secondary Treatment
Activated Sludge
Secondary Treatment
Activated Sludge
Secondary Treatment
Secondary Treatment
Activated Sludge
Secondary Treatment
Activated Sludge
Activated Sludge
Aeration Basin
Activated Sludge
Bio/Act Carbon
Activated Sludge
Aeration Basin
Activated Sludge
Activated Sludge
Activated Sludge
Aeration Basin
Activated Sludge
Activated Sludge
Bio/Act Carbon
Secondary Treatment
Two stage bio.
Aeration Basin
Activated Sludge
Activated Sludge
Activated Sludge
Activated Sludge
Plug Flow A.S.
Bio/Act Carbon
Secondary Treatment
Scale
Full
Pilot
Full
Full
Pilot
Pilot
Pilot
Full
Full
Full
Full
Full
Full
Full
Full
Full
Full
Full
Pilot
Pilot
Pilot
Pilot
Pilot
Full
Pilot
Full
Pilot
Pilot
Full
Pilot
Full
Full
Pilot
Pilot
Full
Full
Full
Pilot
Pilot
Full
Temp
C
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
Hfl
NR
NR
NR
Susp Solids
Cone
NR
430 mg/l
NR
NR
430 mg/l
16,300 mg/l
430 mg/l
NR
NR
850 g/cu m
NR
213 g/cu m
NR
NR
850 g/cu m
NR
216 g/cu m
213 g/cu m
2900 mg/l
NR
16,300 mg/l
NR
2900 mg/l
216 g/cu m
HR
216 g/cu m
2900 mg/l
NR
931 ng/l
16,300 mg/l
NR
NR
2900 mg/l
NR
213 g/cu m
213 g/cu m
NR
430 mg/l
16,300 mg/l
NR
Hydraulic |
Res. Time
NR
7 days
NR
NR
7 days
7 days
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
7.5 hr
NR
?
NR
7.5 hr
NR
8 hrs
NR
7.5 hr
NR
NR
?
NR
12.0 hr
7.5 hr-
NR
NR
NR
NR
7 days
?
NR
Acclimation
None
NR
None
NR
NR
NR
None
None
NR
None
NR
None
None
NR
None
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
None
NR
NR
NR
NR
NR
?
NR
NR
None
Reference
McCarty and Reinhard, 1980
Petrasek et al, 1983a
SCS Engineering, 1979
McCarty and Reinhard, 1980
Petrasek et al, 1983a
Cormack and Hsu, 1983
Petrasek et al, 1983a
McCarty and Reinhard, 1980
McCarty and Reinhard, 1980
Keinath, 1984
McCarty and Reinhard, 1980
Keinath, 1984
McCarty and Reinhard, 1980
Mccarty and Reinhard, 1980
Keinath, 1984
McCarty and Reinhard, 1980
Keinath, 1984
Keinath, 1984
Petrasek et al.,1983b
Bishop, 1982
Cormack and Hsu, 1983
Bishop, 1982
Petrasek et al.,1983b
Keinath, 1984
Kincannon et al, no date
Keinath, 1984
Petrasek et al.,1983b
Bishop, 1982
Feiler, 1979
Cormack and Hsu, 1983
Mccarty and Reinhard, 1980
Leuenberger et al. 1985.
Petrasek et al.,1983b
Bishop, 1982
Keinath, 1984
Keinath, 1984
SCS Engineering, 1979
Petrasek et al, 1983a
Cormack and Hsu, 1983
McCarty and Reinhard, 1980
(continued)
-------
TABLE A-l (continued)
Chemical
Dliiobutyl phthalate
Dimethyl phthalate
Dimethyl phthalate
Dimethyl phthalate
Dimethyl phthalate
Dimethyl phthalate
Dlmethylphenol (2,4)
Dlmethylphetwl (2,4-)
Dinitrophenol (2,4-)
Dinitrophenol (2,4-)
Dinitrophenol (2,4-)
Dinitrotoluene (2,4-)
Dinitrotoluene (2,4-)
Dinitrotoluene (2,4-)
Dinitrotoluene (2,4-)
[> Diphenylhydrazine
1 Diphenylhydrazine (1,2-)
°* Ethyl Benzene
Ethyl Benzene, n
Ethylbenzene
Ethylbenzene
Ethylbenzene
Ethylbenzene
Ethylbenzene
Ethylbenzene
Heptachlor
Hexach lorocyc 1 opentadi ene
Isopropanol
Lindane
Undone
Naphthalene
Naphthalene
Naphthalene
Naphthalene
Naphthalene
Naphthalene
Naphthalene
Naphthalene
Naphthalene
Naphthalene
Percent
Removal
93.00
98.0
89.40
95.00
50.00
97.0
98.9
99.90
84.40
63.00
26.40
95.0
95.0
99.90
99.90
99.0
28.00
>90
>90
88.90
>99
72.00
97.90
0.0
77-99
93.0
99.90
70.0
67.00
45.0
2.50
50.00
>99.0
>54.2
>99.2
>99
75.00
99.0
99.0
94.70
Waste Stream
Domestic/Ind. Wastewater
Municipal Sewage
Trickling Filter Effl
Domestic/Ind. Wastewater
Paper/Petrochemical Wastes
Municipal Sewage
Paper/Petrochemical Wastes
Dyestuff Hanufact Waste
Synthetic Wastewater
Dyestuff Hanufact Waste
Petrochemical
Petrochemical
Paper/Petrochemical Wastes
Paper/Petrochemical Wastes
Paper/Petrochemical Wastes
Petroleum refinery wastes
Petroleun refinery wastes
Raw Wastewater
Domestic/Ind. Wastewater
Trickling Filter Effl
Ind. Uastewater
Municipal Sewage
Paper/Petrochemical Wastes
Domestic/Ind. Wastewater
Municipal Sewage
Dyestuff Hanufact Waste
Paper/Petrochemical Wastes
Coke processing plant
Domestic Uastewater
Dyestuff Hanufact Waste
Petroleum Refinery Waste
Domestic/Ind. Wastewater
Coke processing plant
Municipal Sewage
Trickling Filter Effl
iran*x*mrxv**i
Initial
Chen Cone
NR
50ug/l
NR
NR
2og/l
6 us/I
50 ug/l
15ug/l
2.7 mg/l
130 mg/l
5.3 mg/l
8 ug/l
8 ug/l
390 ug/l
390 ug/l
73 ug/l
341 ug/l
5 ug/l
82 ug/l
NR
NR
30-36 ug/l
50 ug/l
113 ug/l
NR
50 ug/l
4 ug/l
4 ug/l
560 ug/l
2-3 ug/l
0.12 mg/l
NR
69 ug/l
50 ug/l
NR
l9ra«X«»BB«mBM*TO*s«z»m
Treatment
Secondary Treatment
Plug Flow A.S.
Secondary Treatment
Secondary Treatment
Activated Sludge
Anaerob/aerob basins
Plug Flow A.S.
Activated Sludge
Activated Sludge
Activated Sludge
Activated Sludge
Anaerob/aerob basins
Anaerob/aerob basins
Activated Sludge
Activated Sludge •
Anaerob/aerob basins
Activated Sludge
Activated sludge/AC
Activated sludge/AC
Activated sludge
Activated Sludge
Secondary Treatment
Secondary Treatment
Activated Sludge
Activated Sludge
Plug Flow A.S.
Activated Sludge
Activated Sludge
Secondary Treatment
Plug Flow A.S.
Activated Sludge
Activated Sludge
Activated sludge
Bio/Act Carbon
Activated Sludge
Activated Sludge
Secondary Treatment
Activated sludge
Plug Flow A.S.
Secondary Treatment
n»B«**»a
Scale
Full
Pilot
Full
Full
Full
Full
Pilot
Full
Full
Full
Full
Full
Full
Full
Full
Full
Full
Full
Pilot
Pilot
Full
Full
Pilot
Full
Pilot
Full
Pilot
Full
Pilot
Full
Full
Full
Pilot
Full
Full
Full
Full
Pilot
Full
i«n>
-------
TABLE A-l (continued)
Chemical
Naphthalene
Nitrobenzene
Nitrobenzene
Nitrophenol (2->
Nitrophenol <2->
Nitrophenol (2->
Nitrophenol, p
N,N-Dimethylaniline
Pentachlorophenol
Pentachlorophenol
Pentachlorophenol
Pentach I oropheno I
Pentachlorophenol
Pentachlorophenol
Phenol
Phenol
Phenol
Phenol
Phenol
Phenol
Phenol
Phenol
Phenol
Phenol
Phenol
Phenol
Phenol
Phenol
Phenol
Phenol
Phenol
Phenol
Phenol
Phenol
Phenol
Phenol
Phenol
Phenol
Phenol
Phenol
Percent
Removal
>99.0
99.60
74.00
14.30
99.90
99.90
92.80
89.00
26.0
81.0
40.00
58.00
35.00
>96.4
91.00
94.60
95.30
90.60
95.90
90.70
98.20
95.0
86.30
93.30
96.70
>86.7
90.70
0-5
90.80
75.30
98.00
94.10
76.20
81.30
99.00
97.40
80.20
82.70
80.20
86.20
Waste Stream
Coke processing plant
Dyestuff Manufact Waste
Dyestuff Manufact Waste
Dyestuff Manufact Waste
Paper/Petrochemical Wastes
Dyestuff Hanufact Waste
Dyestuff Hanufact Waste
Petroleum Refinery Waste
Pulp waste
Wood Preserving Effluent
Wood Preserving Effluent
Wood Preserving Effluent
Domestic Wastewater
Indust. Creosote Waste
Refinery Wastes
Refinery Wastes
Refinery Wastes
Dyestuff Hanufact Waste
Refinery Wastes
Refinery Wastes
Municipal Sewage
Refinery Wastes
Refinery Wastes
Refinery Wastes
Dyestuff Hanufact Waste
Refinery Wastes
Ind. Wastewater
Refinery Wastes
Refinery Wastes
Paper Hill/Petrochemical
Refinery Wastes
Refinery Wastes
Refinery Wastes
Refinery Wastes
Refinery Wastes
Refinery Wastes
Refinery Wastes
Refinery Wastes
Initial
Chem Cone
180 ug/l
0.66 mg/l
0.35 mg/l
7.7 ug/l
9 ug/l
9 ug/l
0.46 mg/l
NR
5.5 mg/l
3.6 mg/l
5.5 mg/l
28 ug/l
47 mg/l
21.2 mg/l
16.2 mg/l
21.2 mg/l
3.2 mg/l
22.7 mg/l
18.5 mg/l
50 ug/l
19.9 mg/l
13.5 mg/l
19.6 mg/l
0.150 mg/l
21 .2 mg/l
13-19 ug/l
20.3 mg/l
0.02-97 mg/ml
21.2 mg/l
20.6 mg/l
20.3 mg/l
39.6 mg/l
21.2 mg/l
21.2 mg/l
21.6 mg/l
24.8 mg/l
24.5 mg/l
Treatment
Activated sludge
Activated Sludge
Activated Sludge
Activated Sludge
Activated Sludge
Activated Sludge
Activated Sludge
Activated Sludge
Two stage bio.
Plug-flow A.S.
Activated Sludge
Activated Sludge
Activated Sludge
Bio/Act Carbon
Hicrob Treat. Tower
Aerated Lagoon
Cont Activated Sludge
Aerated Lagoon
Activated Sludge
Cont Activated Sludge
Cont Activated Sludge
Plug Flow A.S.
Cont Activated Sludge
Cont Activated Sludge
Cont Activated Sludge
Activated Sludge
Aerated Lagoon
Activated Sludge
Batch Activated Sludge
Cont Activated Sludge
Activated sludge
Aerated Lagoon
Cont Activated Sludge
Cont Activated Sludge
Seq Batch Reactor
Aerated Lagoon
Cont Activated Sludge
Cont Activated Sludge
Cont Activated Sludge
Cont Activated Sludge
_____
Scale
Full
Full
Full
Full
Full
Full
Full
Full
Full
Pilot
Pilot
Pilot
Pilot
Pilot
Full
Full
Full
Full
Full
Full
Full
Pilot
Full
Full
Full
Full
Full
Full
Full
Full
Full
Full
Full
Full
Full
Full
Full
Full
Full
Temp
C
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
25.00
26.00
27.00
NR
>10
NR
6.00
MR
NR
6.00
6.00
NR
6.00
6.00
6.00
NR
NR
NR
NR
6.00
NR
NR
6.00
6.00
24-26
NR
6.00
6.00
6.00
6.00
a -a a -—
Susp Solids
Cone
NR
213 g/cu m
216 g/cu m
51 g/ cu m
NR
104-19,811 kg/day
850 g/cu m
38 mg/l
NR
430 mg/l
69 mg/l
69 mg/l
69 mg/l
16,300 mg/l
116 mg/l
227 mg/l
NR
285 mg/l
850 g/cu m
NR
NR
430 mg/l
NR
NR
NR
213 g/cu m
250 mg/l
931 mg/l
NR
NR
NR
245 mg/l
NR
NR
' NR
265 mg/l
NR
NR
NR
NR
Hydraulic
Res. Time
NR
NR
NR
NR
NR
NR
NR
NR
12.0 hr
7 days
NR
NR
NR
7
NR
12 days
7 hr
1 day
NR
7 hr
7 hr
7 days
7 hr
7 hr
7 hr
NR
3 days
NR
10 hr
7 hr
NR
10 days
7 hr
7 hr
8-9 days
10 days
7 hr
7 hr
7 hr
7 hr
.____ ___« — ._
Acclimation
NR
NR
NR
NR
7
1
NR
NR
NR
7
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
>NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
• NR
NR
NR
NR
Reference
Walters and Luthy, 1984
Keinath, 1984
Keinath, 1984
Keinath, 1984
SCS Engineering, 1979
SCS Engineering, 1979
Keinath, 1984
Snider and Manning, 1982
Leuenberger et al. 1985.
Petrasek et al, 1983a
Jank and Fowlie, no date
Jank and Fowlie, no date
Jank and Fowlie, no date
Cormack and Hsu, 1983
Vela and Ralston, 1978
Mahmud and Thanh, no date
Mahmud and Thanh, no date
Mahmud and Thanh, no date
Keinath, 1984
Hahmud and Thanh, no date
Mahmud and Thanh, no date
Petrasek et al, 1983a
Mahmud and Thanh, no date
Hahmud and Thanh, no date
Hahmud and Thanh, no date
Keinath, 1984
Hahmud and Thanh, no date
Feiler, 1979
Mahmud and Thanh, no date
Mahmud and Thanh, no date
SCS Engineering, 1979
Hahmud and Thanh, no date
Hahmud and Thanh, no date
Hahmud and Thanh, no date
Herzbrun et al, 1985
Hahmud and Thanh, no date
Hahmud and Thanh, no date
Hahmud and Thanh, no date
Hahmud and Thanh, no date
Hahmud and Thanh, no date
(continued)
-------
TABLE A-l (continued)
Chemical
Phenol
Phenol
Phenol
Phenol
Phenol
Phenol
Phenol
Phenol
Phenol
Phenol
Phenol
Phenol
Phenol
Phenol
Phenol
Phenol
Phenol
Phenol
Phenol
Pyridine
Pyridine
Styrene, C3
Tetrachloroethane
Tetrachloroethane (1,1,2,2-)
Tetrach loroethy lene
Tetrachloroethylene
Tetrach loroethy lene
Tetrach loroethy lene
Tetrach loroethylene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Percent
Removal
88.60
92.80
80.30
>96.4
99.90
93.70
99.90
96.30
88.30
85.40
26.00
93.50
>99
94.30
>99
94.60
81.40
90-100
>99
65.00
46.00
>99
50.0
99.90
>75.0
9.00
91.70
27.00
83-98
99.10
99.70
83.10
88.10
96.20
51-100
99.90
>97.4
24.00
99.00
>90
Uaste Strean
Refinery Uastes
Refinery Uastes
Refinery Uastes
Domestic Uasteuater
Ind/domestic uasteuater
Refinery Uastes
Dyestuff Hanufact Uaste
Refinery Uastes
Refinery Uastes
Refinery Uastes
Paper/Petrochemical Uastes
Refinery Uastes
Uood Preserving Effluent
Refinery Uastes
Uood Preserving Effluent
Refinery Uastes
Refinery Uastes
Coke Plant Effluent
Uood Preserving Effluent
Aqueous Solution
Aqueous Solution
Petroleun Refinery Uaste
Pulp waste
Ind/domestic uasteuater
Domestic Uasteuater
Trickling Filter Effl
Domestic/Ind. Uasteuater
Industrial Uasteuaters
Dyestuff Hanufact Uaste
Dyestuff Manufact Uaste
Dyestuff Hanufact Uaste
Dyestuff Hanufact Uaste
Dyestuff Hanufact Uaste
Ind. Uasteuater
Ind/domestic uasteuater
Domestic Uasteuater
Dyestuff Hanufact Uaste
Dyestuff Hanufact Uaste
Petroleim refinery uastes
Initial
Chen Cone
23 mg/l
21.2 mg/l
20.2 mg/l
19-66 ug/l
2.2 mg/l
21.2 mg/l
4.9 mg/l
18.8 mg/l
25.7 mg/l
20.3 mg/l
8 ug/l
21.2 mg/l
0.16 mg/l
21.2 mg/l
0.16 mg/l
21.2 mg/l
18.1 mg/l
655 mg/l
0.65 mg/l
NR
NR
NR
2.2 mg/l
4 ug/l
NR
NR
53-57 ug/l
0.8 mg/l
3.6-4 mg/l
0.16 mg/l
0.16 mg/l
7.8 mg/l
18-23 ug/l
2.2 mg/l
14-110 ug/l
7.4 mg/l
0.78 mg/l
Treatment
Cont Activated Sludge
Aerated Lagoon
Cont Activated Sludge
Bio/Act Carbon
Deep Shaft-Biological
Aerated Lagoon
Activated Sludge
Cont Activated Sludge
Cont Activated Sludge
Cont Activated Sludge
Activated Sludge
Aerated Lagoon
Activated Sludge
Aerated Lagoon
Activated Sludge
Aerated Lagoon
Cont Activated Sludge
Activated Sludge
Activated Sludge
AFNOR T 90-302 Test
AFNOR T 90-302 Test
Activated Sludge
Two stage bio.
Deep Shaft-Biological
Bio/Act Carbon
Activated Sludge
Secondary Treatment
Secondary Treatment
Activated Sludge
Activated Sludge
Activated Sludge
Activated Sludge
Activated Sludge
Activated Sludge
Activated Sludge
Deep Shaft-Biological
Bio/Act Carbon
Activated Sludge
Activated Sludge
Activated sludge/AC
B»va*xaun
Scale
Full
Full
Full
Pilot
Pilot
Full
Full
Full
Full
Full
Full
Full
Pilot
Full
Pilot
Full
Full
Pilot
Pilot
Lab
Lab
Full
Full
Pilot
Pilot
Pilot
Full
Full
Full
Full
Full
Full
Full
Full
Full
Pilot
Pilot
Full
Full
Full
nt»a««i«»a
Temp
C
6.00
NR
6.00
NR
NR
NR
NR
6.00
6.00
6.00
NR
NR
27.00
NR
26.00
NR
6.00
NR
25.00
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
Susp Solids
Cone
NR
290 mg/l
NR
16.300 mg/l
140 kg/day
260 mg/l
51 g/ cu m
HR
HR
HR
104-19,811 kg/day
282 mg/l
69 mg/l
265 rog/l
69 mg/l
260 mg/l
NR
45 mg/l
69 mg/l
NR
NR
38 mg/l
NR
NR
16,300 mg/l
NR
NR
NR
931 mg/l
216 g/cu m
850 g/cu K
51 g/ cu m
51 g/ cu m
213 g/cu m
931 mg/l
140 kg/day
16,300 mg/l
213 g/cu R
216 g/cu m
38 mg/l
Hydraulic
Res. Time
7hr
3 days
7hr
7
30 nin
7days
NR
7hr
7 hr
7 hr
NR
5 days
NR
5 days
NR
7 days
7 hr
NR
NR
42 days
28 days
NR
12.0 hr
30 min
7
8 hrs
NR
NR
NR
NR
NR
NR
NR
NR
NR
30 min
7
NR
NR
NR
Acclimation
HR
HR
HR
HR
HR
HR
HR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
?
NR
HR
None
None
NR
NR
NR
NR
NR
NR
NR
1
NR
NR
NR
NR
Reference
Hahmud and Thanh, no date
Hahmud and Thanh, no date
Hahmud and Thanh, no date
Cormack and Hsu, 1983
SCS Engineering, 1979
Mahmud and Thanh, no date
Keinath, 1984
Hahmud and Thanh, no date
Hahmud and Thanh, no date
Hahmud and Thanh, no date
SCS Engineering, 1979
Mahmud and Thanh, no date
Jank and Foulie, no date
Hahmud and Thanh, no date
Jank and Foulie, no date
Hahmud and Thanh, no date
Hahmud and Thanh, no date
Osantouski and Hendriks, no date
Jank and Foulie, no date
Gericke and Fischer, 1981
Gericke and Fischer, 1981
Snider and Manning, 1982
Leuenberger et al. 1985.
SCS Engineering, 1979
Cormack and Hsu, 1983
Kincannon et al, no date
HcCarty and Reinhard, 1980
HcCarty and Reinhard, 1980
Feiler, 1979
Keinath, 1984
Keinath, 1984
Keinath, 1984
Keinath, 1984
Keinath, 1984
Feiler, 1979
SCS Engineering, 1979
Cormack and Hsu, 1983
Keinath, 1984
Keinath, 1984
Snider and Manning, 1982
(continued)
-------
TABLE A-l (continued)
Chemical
Toluene
Toluene
Toluene
Toxaphene
Trichlorethylene
Trichlorobenzene (1,2,4-)
Trichlorobenzene (1,2,4-)
Trichlorobenzene (1,2,4-)
Trichlorobenzene (1,2,4-)
Trichlorobenzene (1,2,4-)
Trichloroethane
Trichloroethane (1, ,1-)
Trichloroethane (1, ,1-)
Trichloroethane (1, ,1-)
Trichloroethane (1, ,1-)
>>*• Trichloroethane (1, ,1-)
VJ3 Trichloroethane (1, ,1-)
Trichloroethane (1, ,1-)
Trichloroethane (1, ,2-)
Trichloroethane (1, ,2-)
Trichloroethane (1, ,2-)
Trichloroethane (1, ,2-)
Trichloroethylene
Trichloroethylene
Trichloroethylene
Trichloroethylene
Trichloroethylene
Trichloroethylene
Trichloroethylene (2)
Trichlorophenol (2,4,6-)
Trimethyl Benzene (1,2,4)
Xylene (p and m)
Xylene, ra
Xylene, m
Xylene, m
Xylene, o
Xylene, o
Xylene, o
Xylene, p
Percent
Removal
>99
97.10
98.00
98.0
15.0
97.80
99.90
84.30
>89.00
99.90
23.0
17.0
59-100
99.40
>96.30
98.50
95.00
>99
80.00
65.60
99.90
100.00
97.80
23.0
65-100
>95.7
97.00
>99
99.90
28.0
>90
>90
41.00
33.0
52.0
29.00
9.00
>90
38.00
===KS«»==c==:sa===s==s=s====s
Waste Stream
Raw Uastewater
Coke Plant Effluent
Municipal Sewage
Trickling Filter Effl
Ind/domestic wasteuater
Dyestuff Manufact Waste
Domestic/Ind. Wastewater
Paper/Petrochemical Wastes
Pulp waste
Pulp waste
Industrial Wastewaters
NR
Domestic Uastewater
Trickling Filter Effl
Domestic/Ind. Wastewater
Raw Wastewater
Raw Wastewater
NR
Ind/domestic uastewater
Industrial Wastewaters
Trickling Filter Effl
Acid waste
Industrial Wastewaters
Domestic Wastewater
NR
Raw Wastewater
Ind/domestic Wastewater
Pulp waste
Petroleum refinery wastes
Petroleun refinery wastes
Domestic/Ind. Wastewater
Acid waste
Acid waste
Petroleum refinery wastes
Domestic/Ind. Wastewater
Initial
Chem Cone
255 ug/l
5ug/l
607 ug/l
150 ug/l
NR
2.2 mg/l
0.23 ug/l
NR
28 ug/l
NR
NR
17-20 ug/l
50-200 ug/l
27 ug/l
NR
NR
132 ug/l
133 ug/l
50-200 ug/l
2.2 mg/l
49-50 ug/l
NR
NR
24-29 ug/l
23 ug/l
50-200 ug/l
107 ug/l
2.2 mg/l
NR
NR
NR
NR
NR
NR
Treatment
Activated Sludge
Activated sludge
Activated Sludge
Plug Flow A.S.
Activated Sludge
Secondary Treatment
Deep Shaft-Biological
Activated Sludge
Secondary Treatment
Activated Sludge
Two stage bio.
Two stage bio.
Activated Sludge
Activated Sludge
Bio/Act Carbon
Secondary Treatment
Secondary Treatment
Aeration Basin
Aeration Basin
Activated Sludge
Deep Shaft-Biological
Activated Sludge
Secondary Treatment
Activated sludge
Activated Sludge
Bio/Act Carbon
Activated Sludge
Aeration Basin
Deep Shaft-Biological
Two stage bio.
Activated sludge/AC
Activated sludge/AC
Secondary Treatment
Activated Sludge
Activated sludge
Activated Sludge
Activated Sludge
Activated sludge/AC
Secondary Treatment
Scale
Pilot
Pilot
Pilot
Pilot
Pilot
Full
Pilot
Full
Full
Full
Full
Full
Full
Pilot
Pilot
Full
Full
Pilot
Pilot
Pilot
Pilot
Full
Full
Pilot
Full
Pilot
Pilot
Pilot
Pilot
Full
Full
Full
Full
Pilot
Pilot
Pilot
Pilot
Full
Full
Temp
C
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
Susp Solids
Cone
2900 mg/l
NR
45 mg/l
430 mg/l
NR
NR
NR
213 g/cu m
NR
NR
NR
NR
931 mg/l
NR
16,300 mg/l
NR
NR
2900 mg/l
2900 mg/l
NR
NR
931 mg/l
NR
NR
931 mg/l
16,300 mg/l
NR
2900 mg/l
NR
NR
38 mg/l
38mg/l
NR
NR
NR
NR
NR
38 rag/I
NR
Hydraulic
Res. Time
7.5 hr
SRT=5 days
NR
7 days
8 hrs
NR
30 min
NR
NR
NR
12.0 hr
12.0 hr
NR
NR
1
NR
NR
7.5 hr
7.5 hr
NR
30 min
NR
NR
8.0 hr
NR
?
NR
7.5 hr
30 min
12.0 hr
NR
NR
NR
8 hrs
8.0 hr
8 hrs
8.0 hr
NR
NR
Acclimation
NR
NR
NR
NR
NR
None
?
NR
None
?
NR
NR
NR
NR
NR
None
None
NR
NR
NR
7
NR
None
NR
NR
NR
NR
NR
?
NR
NR
NR
None
NR
NR
NR
NR
NR
None
Reference
Petrasek et al.,1983b
Bishop, 1982
Osantowski and Hendriks, no date
Petrasek et al, 1983
Kincannon et al, no date
Mccarty and Reinhard, 1980
SCS Engineering, 1979
Keinath, 1984
Mccarty and Reinhard, 1980
SCS Engineering, 1979
Leuenberger et al. 1985.
Leuenberger et al. 1985.
Feiler, 1979
Bishop, 1982
Cormack and Hsu, 1983
Mccarty and Reinhard, 1980
Mccarty and Reinhard, 1980
Petrasek et al.,1983b
Petrasek et al.,1983b
Bishop, 1982
SCS Engineering, 1979
Feiler, 1979
McCarty and Reinhard, 1980
Kincannon et al., no date
Feiler, 1979
Cormack and Hsu, 1983
Bishop, 1982
Petrasek et al.,1983b
SCS Engineering, 1979
Leuenberger et al. 1985.
Snider and Manning, 1982
Snider and Manning, 1982
McCarty and Reinhard, 1980
Kincannon et al, no date
Kincannon et al., no date
Kincannon et al., no date
Kincannon et al., no date
Snider and Manning, 1982
Mccarty and Reinhard, 1980
(1) Name reported in Versar report as bis (2-ethylhexyl) phthalate
(2) Name reported in Versar report as trichloroethylene
(3) Name reported in Versar report as carbon tetrachloride
(4) Name reported in Versar report as dichloropropene (trans 1,3)
(5) Name reported in Versar report as bromodichloromethane
(6) Name reported in Versar report as methylene chloride
Extracted from Estimation of Removal of Organic Chemicals During
Versar, Inc. Prepared for US EPA, OTS, Contract No. 68-02-3968.
Wastewater Treatment, Draft Final Report,
-------
REFERENCES FOR TABLE A-l
Cormack, J. W., D. Y. Hsu, and R. 6. Simms. 1983. A Pilot Study for the
Removal of Priority Pollutants by the PACT Process. Proc. 38th Indust. Waste
Conf. Purdue University, Lafayette, Indiana. Ann Arbor, Mich: Ann Arbor
Science, pp. 403-415.
Feiler, H. 1979. Fate of Priority Pollutants in Publicly Owned Treatment
Works. EPA-440/1-79-300.
Gerike, P., and W. F. Fischer. 1981. A Correlation Study of Biodegradability
Determinations with Various Chemicals in Various Tests. II. Additional
Results and Conclusions. Ecotoxicol Environ. Safety 4:45-55.
Herzbrun, P. A., R. L. Irvine and Malinowski. 1985. Biological Treatment of
Hazardous Waste in Sequencing Batch Reactors. J. Water Poll. Control Fed.
57(12):1163-1167.
Jank, B. E., and P. J. A. Fowlie. 1980. Treatment of a Wood Preserving
Effluent Containing Pentachlorophenol by Activated Sludge and Carbon Adsorption,
Proc. 35th Ind. Waste Conf. Ann Arbor, Michigan: Ann Arbor Sci. pp. 63-79.
Keinath, T. M. 1984. Technology Evaluation for Priority Pollutant Removal
from Dyestuff Manufacture Wastewaters. EPA-600/2-84-055.
Kincannon, D. F., A. Esfandi, and T. S. Manickam. 1982. Compatibility of
Semiconductor Industry Wastewater with Municipal Activated Sludge Systems
Proc. 37th Ind. Waste Conf. pp. 533-539.
Kincannon, D. F., and E. L. Stover. 1983. Determination of Activated Sludge
Biokinetic Constants for Chemical and Plastic Industrial Wastewaters. EPA-
600/2-83-0783a.
Kincannon, D. F., A. Weinert, R. Padorr, and E. L. Stover. 1982. Predicting
Treatability of Multiple Organic Priority Pollutant Wastewaters from Single-
Pollutant Treatability Studies. Proc. 37th Ind. Waste Conf. Ann Arbor,
Michigan: Ann Arbor Sci. pp. 34-42.
Leuenberger, C., W. Giger, R. Coney, J. W. Graydon, and E. Molnar-Kubica.
1985. Persistent Chemicals in Pulp Mill Effluents. Occurrence and Behaviour
in an Activated Sludge Treatment Plant. Water Res. 19(7)-.885-894.
Mahmud Z., and N. C. Thanh. Biological Treatment of Refinery Wastes. Purdue,
Ind. Waste Treatment Conf. pp. 515-525.
McCarty, P. L., and M. Reinhard. 1980. Trace Organics Removal by Advanced
Wastewater Treatment. J. Water Poll. Control Fed. 52(7):1907-1922.
Osantowski, R., and R. V. Hendriks. Physical/Chemical and Biological Treatment
of Coke-Plant Wastewater. Proc. 37th Ind. Waste Conf. pp. 168-176.
A-10
-------
Petrasek, A. C., I. J. Kugelman, B. M. Austern, T. A. Pressley, L. A. Winslow,
and R. H. Wise. 1983a. Fate of Toxic Organic Compounds in Wastewater Treat-
ment Plants. J. Water Poll. Control Fed. 55(10):1286-1296.
Petrasek, A. C., B. M. Austern, and T. W. Neiheisel. 1983b. Removal and
Partitioning of Volatile Organic Priority Pollutants in Wastewater Treatment.
9th U.S.-Japan Conference on Sewage Treatment Technology. Tokyo, Japan.
SCS Engineering. 1979. Selected Biodegradation Techniques for Treatment
and/or Ultimate Disposal of Organic Materials. U.S. Environmental Protection
Agency 600/2-79-006.
Snider, E. H., and F. S. Manning. 1982. A Survey of Pollutant Emission
Levels in Wastewaters and Residuals From the Petroleum Refining Industry.
Environ. International 7:237-258.
Walters, W. J., N. H. Corfis, and B. E. Jones. 1983. Removal of Priority
Pollutants in Integrated Activated Sludge-Activated Carbon Treatment Systems.
J. Water Poll. Control Fed. 55(4):369-376.
Vela, G. R., and J. R. Ralson. 1978. The Effect of Temperature on Phenol
Degradation in Wastewater. Can. J. Microbiol. 24:1366-1370.
A-ll
-------
The data for Table A-2 were extracted from "Report to Congress on the
Discharge of Hazardous Waste to Publicly Owned Treatment Works", U.S. Envi-
ronmental Protection Agency, EPA/530-SW-86-004, 1986. The following notes
apply to this table:
0 The data from this table apply only to secondary biological waste-
water treatment plants receiving low concentrations (= 500 ppb) of
the compounds listed. A number of design and operational factors
will affect the fate of these compounds in any given treatment
plant. These numbers are useful only as rough approximations of
pollutant fate.
0 All percentages are based on influent loading. The original ref-
erence provided removals for volatilization and sludge partitioning
as a percentage of overall removal. This data was translated to
removals based on influent loading by assuming that all material
not volatilized, transferred to sludge, or passed through untreated
was biodegraded.
0 (Percent volatilized to air) + (percent partitioned to sludge) +
(percent biodegraded) + (100 - overall percent removal) = 100.
0 Percent biodegraded was determined by difference in the preceding
equation.
0 The percentage which is discharged to receiving waters equals 100
minus the "overall percent removal" (percent discharged to
receiving wastes = 100 - overall percent removal).
0 (Percent volatilized to air) + (percent partitioned to sludge) +
(percent biodegrded) + (percent discharged to receiving waters) =
100.
0 "Acclimated" represents those processes which receive a relatively
steady amount of the pollutant in question, such that biodegradtion
rates stabilize. "Unacclimated, Median and Low" refer to processes
which receive unsteady or "slug" loadings of the pollutant in
question.
A-12
-------
TABLE A-2. FATE OF HAZARDOUS AND/OR TOXIC POLLUTANTS AT LOW CONCENTRATIONS IN
SECONDARY, BIOLOGICAL WASTEWATER TREATMENT PLANTS
POLLUTANT
2,4-D
ACENAPHTHYLENE
ACETALDEHYDE
ACETONE
ACROLEIN
ACRYLAMIDE
ACRYLIC ACID
ACRYLONITRILE
ALDRIN
ANILINE
ANTHRACENE
ANTIMONY
ARSENIC
BARIUM
BENZAL CHLORIDE
BENZENE
BENZOTRICHLORIDE
BENZYL CHLORIDE
BIS-2-CHLOROETHYL ETHER
BIS-2-ETHYLHEXYL PHTHALATE
BROMOMETHANE
BUTYL BENZYL PHTHALATE
CADMIUM
CAPTAN
CARBON DISULFIDE
CARBON TETRACHLORIDE
CHLORDANE
CHLOROBENZENE
CHLOROBENZILATE
CHLOROETHANE
CHLOROFORM
CHLOROMETHANE
ACCLIMATED
%
90
95
95
95
95
90
90
90
90
95
95
60
50
90
90
95
90
90
90
90
95
95
27
90
95
90
90
90
90
95
90
95
3VERAL
'ERCEN
3EMOVA
UNACC
MEDIAN
%
60
90
95
50
95
62
85
75
90
85
90
60
50
90
55
90
45
90
50
90
95
90
27
50
85
85
90
90
60
90
80
90
JMATED
LOW
%
50
90
95
30
95
50
80
70
90
80
90
60
50
90
50
90
40
90
30
90
95
90
27
30
80
80
90
90
50
90
80
90
IPERCEN
VOLATILE
ACCLIMATED
%
0
19
0
0
0
0
0
0
0
0
0
0
0
0
0
24
18
23
0
0
86
0
0
0
76
72
9
27
9
76
63
86
TO AIR
UNACCL
MEDIAN
%
0
54
5
3
5
0
0
4
0
0
0
0
0
0
17
72
14
45
3
0
90
0
0
0
77
77
9
45
6
81
72
86
F
;D
IMATED
LOW
%
0
54
5
2
5
0
0
4
0
0
0
0
0
0
15
72
12
45
2
0
90
0
0
0
72
72
9
45
5
81
72
86
PERCENT
PARTmONED
TO SLUDGE
ACCLIMATED
%
7
9
10
10
10
9
9
9
33
10
52
60
50
90
7
2
7
7
9
66
0
43
27
7
1
12
33
14
7
1
2
1
UNACCLIMATED
MEDIAN
%
5
8
10
5
10
6
9
8
33
9
50
60
50
90
4
2
4
7
5
66
0
41
27
4
1
9
33
14
5
1
2
1
LOW
%
4
8
10
3
10
5
8
7
33
8
50
60
50
90
4
2
3
7
3
66
0
41
27
2
1
8
33
14
4
1
2
1
I
BK
ACCLIMATED
%
83
67
85
85
85
81
81
81
57
86
43
0
0
0
83
69
65
60
81.
24
10
52
0
83
18
6
48
50
74
18
25
9
'ERCENT
IDEGRADED
JNACCLIMATED
MEDIAN
%
55
28
81
43
81
56
77
64
57
77
41
0
0
0
34
16
28
38
43
24
5
50
0
46
8
0
48
32
49
8
6
4
LOW
%
46
28
81
26
81
45
72
60
57
72
41
0
0
0
31
16
25
38
26
24
5
50
0
28
7
0
48
32
41
8
6
4
1
1—>
GO
(continued)
-------
TABLE A-2 (continued)
POLLUTANT
2-CHLOROPHENOL
CHROMIUM
CRESOLS
CUMENE
CYANIDE
CYaOHEXANE
DI-N-BUTYL PHTHALATE
DI-N-OCTYL PHTHALATE
DIBROMOMETHANE
1,2-DICHLOROBENZENE
1, 3-DICHLOROBENZENE
1,4-DICHLOROBENZENE
1,2-DICHLOROETHANE
1.1 -DICHLOROETHYLENE
2,4-DICHLOROPHENOL
1 ,2-DICHLOROPROPANE
DICHLORVOS
DCOFOL
DIETHYL PHTHALATE
3,3-DIMETHOXY BENZIDINE
2,4-DIMETHYL PHENOL
DIMETHYL PHTHALATE
2,4-DINITROPHENOL
1,4-DIOXANE
EPICHLOROHYDRIN
ETHYL BENZENE
ETHYLENE OXIDE
ETHYLENETHIOUREA
FORMALDEHYDE
HEXACHLORO-1 ,3-BUTADIENE
HEXACHLOROETHANE
HYDRAZINE
ACCLIMATED
%
95
70
95
95
60
95
90
90
85
90
90
90
90
95
95
90
90
90
90
80
95
95
90
90
87
95
90
85
85
95
95
95
OVERALL
PERCEN
REMOVA
UNACCl
MEDIAN
%
65
70
50
95
60
95
90
90
80
87
87
87
50
90
55
70
50
90
75
30
85
65
75
50
59
90
50
67
85
90
90
85
IMATED
LOW
%
60
70
40
95
60
95
90
90
80
85
85
85
30
90
50
70
30
90
70
20
80
60
70
40
25
90
40
60
80
90
90
80
iPERCENJr
VOLATILIZED
ACCLIMATED
%
0
0
0
38
0
10
0
0
43
45
45
45
45
76
0
45
0
45
0
0
0
0
0
0
0
24
0
0
0
0
0
0
TO AIR
LJNACCL
MEDIAN
%
0
0
0
57
3
86
0
0
64
78
78
78
45
81
0
63
0
45
0
0
0
0
0
0
0
72
3
0
4
5
5
4
MATED
LOW
%
0
0
0
57
3
86
0
0
64
77
77
77
27
81
0
63
0
45
0
0
0
0
0
0
0
72
2
0
4
5
5
4
PERCENT
PARTITIONED
TO SLUDGE
ACCLIMATED
%
8
70
8
4
57
4
20
7
13
32
3
23
5
0
8
0
9
8
1
8
8
0
9
9
9
6
9
9
9
9
9
10
UNACCLIMATED
MEDIAN
%
5
70
4
4
57
4
20
7
12
9
3
9
3
0
4
0
5
8
1
3
7
0
8
5
6
5
5
7
9
8
8
9
LOW
%
5
70
3
4
57
4
20
7
12
9
3
9
2
0
4
0
3
8
1
2
6
0
7
4
3
5
4
6
8
8
8
8
I
BK
ACCLIMATED
%
87
0
87
53
3
82
70
83
30
14
42
23
41
19
87
45
81
37
89
72
87
95
81
81
78
66
81
77
76
86
86
85
ERCENT
DEGRADED
UNACCLIMATED
MEDIAN
%
60
0
46
34
0
6
70
83
4
0
6
0
3
9
51
7
45
37
74
27
78
65
68
45
53
13
43
60
72
77
77
72
LOW
%
55
0
37
34
0
6
70
83
4
0
6
0
2
9
46
7
27
37
69
18
74
60
63
36
23
13
34
54
68
77
77
68
I
l-»
.p»
(continued)
-------
TABLE A-2 (continued)
POLLUTANT
LEAD
MALEIC HYDRAZIDE
MERCURY
METHANOL -
METHOXYCHLOR
METHYL ETHYL KETONE
METHYL ISOBUTYL KETONE
METHYLENE CHLORIDE
N-BUTYL ALCOHOL
N-NITROSODIMETHYLAMINE
NAPHTHALENE
NICKEL
NITROBENZENE
2-NITROPROPANE
P-BENZOQUINONE
PARATHION
PCB
PENTACHLOROPHENOL
PHENOL
PHENYLENE DIAMINE
PHOSGENE
PHTHALIC ANHYDRIDE
PYRIDINE
SELENIUM
SILVER
STYRENE
1 ,1 ,2,2-TETRACHLOROETHANE
TETRACHLOROETHYLENE
THIOUREA
TOLUENE
TOLUENE DIAMINE
TOXAPHENE
ACCLIMATED
%
70
90
50
100
90
95
90
95
95
90
95
35
90
95
95
0
92
95
95
90
100
90
15
50
90
90
90
90
90
90
90
95
DVERALll
^ERCEN"
1EMOVA
UNACCI
MEDIAN
%
70
75
50
95
90
50
50
87
90
75
75
35
25
95
50
55
92
25
85
75
100
90
15
50
90
90
25
85
75
90
75
90
IMATED
LOW
%
70
70
50
95
90
30
30
85
90
70
70
35
20
95
40
40
92
20
80
70
100
90
10
50
90
90
20
80
70
90
70
90
IPERCEN
VOLATILIZE
ACCLIMATED
%
0
0
0
1
54
0
0
38
0
"0
0
0
0
86
0
0
9
0
0
0
1
0
0
0
0
23
36
45
0
23
0
57
TO AIR
UNACCL
MEDIAN
%
0
0
3
5
54
3
0
52
0
0
4
0
0
90
0
0
9
0
0
0
5
0
1
0
0
72
15
68
0
72
0
72
r
P
IMATED
LOW
%
0
0
3
5
54
2
0
51
0
0
4
0
0
90
0
0
9
0
0
0
5
0
1
0
0
72
12
64
0
72
0
72
PERCENT
PARTITIONED
TO SLUDGE
ACCLIMATED
%
70
9
48
10
8
10
9
13
10
9
27
35
9
1
8
0
22
17
14
9
10
9
2
50
90
14
4
3
9
25
9
4
UNACCLIMATED
MEDIAN
%
70
8
48
10
8
5
5
12
9
8
21
35
3
1
4
4
22
5
13
8
10
9
2
50
90
14
- 1
3
8
18
8
4
LOW
%
70
7
48
10
8
3
3
12
9
7
20
35
2
1
3
3
22
4
12
7
10
9
1
50
90
14
1
•2
7
18
7
4
I
PERCENT
BIODEGRADED
ACCLIMATED
%
0
81
2
90
28
85
81
44
86
81
68
0
81
9
87
0
61
78
81
81
90
81
13
0
0
54
50
42
81
42
81
34
JNACCLIMATED
MEDIAE
%
0
68
0
81
28
43
45 •
23
81
68
50
0
23
4
46
51
61
21
72
68
85
81
13
0
0
5
9
14
68
0
68
14
LOW
%
0
63
o :
81
28
26
27
22
81
63
47
0
18
4
37
37
61
16
68
63
85
81
9
0
0
5
7
14
63
0
63
14
l-»
CJ1
(continued)
-------
TABLE A-2 (continued)
POLLUTANT
TRANS-1 ,2-DICHLOROETHYLENE
TRIBROMOMETHANE
1 ,2.4-TRICHLOROBENZENE
1 ,1 ,1 -TRICHLOROETHANE
1,1,2-TRICHLOROETHANE
TRICHLOROETHYLENE
2.4,6-TRICHLOROPHENOL
1,1,2-TC 1,2,2-TF ETHANE
TRIFLURALIN
VINYL CHLORIDE
XYLENES
ACCLIMATED
%
90
65
85
95
80
95
95
90
90
95
95
OVERALL
PERCEN
lEMOVAl
UNACCI
MEDIAN
%
80
35
85
90
25
87
55
85
90
95
87
IMATED
LOW
%
80
30
85
85
20
85
50
80
90
95
85
IPERCENJT
VOLATILIZED
ACCLIMATED
%
63
36
43
76
40
67
0
63
0
86
24
TO AIR
UNACCL
MEDIAN
%
72
21
51
81
20
70
0
68
0
90
70
MATED
LOW
%
72
18
51
77
16
68
0
64
0
90
68
PERCENT
PARTmONED
TO SLUDGE
ACCLIMATED
%
27
5
8
1
0
6
8
4
33
2
14
UNACCLIMATED
MEDIAN
%
8
3
8
1
0
5
4
3
33
2
13
LOW
%
8
2
8
1
0
5
4
3
33
2
13
j |
PERCENT
BIODEGRADED
ACCLIMATED
%
0
24
35
18
40
23
87
23
57
8
57
UNACCLIMATED
MEDIAN
%
0
11
26
8
5
12
51
14
57
3
4
LOW
%
0
10
26
8
4
12
46
13
57
3
4
CTl
-------
APPENDIX B
CHEMICAL AND PHYSICAL DATA FOR
THE LISTED CHEMICALS
\
i
B-l
-------
APPENDIX B
The chemical/physical property data in Appendix B was
obtained primarily from chemical databases previously compiled by
EPA, from computer searches, and from various handbooks. Data
was compiled only for those chemicals listed individually by CAS
number and not for chemicals reportable by chemical category
name. Each property has been referenced, but these references do
not appear in the Appendix due to space considerations.
Interested persons may obtain a copy of this Appendix with the
appropriate reference numbers and a listing of the references
from:
Kathleen Franklin
USEPA TS-779
401 M St. SW
Washington, DC 20460
Data sources used to compile this database and to obtain
induvidual references are listed below.
Hansen, S.A.
Czarnecki,
nten-
Ohio:
R.J., Osantowski, R.A. Sept 1987.
Treatability
Radian Corporation. Contents of the USEPA (WERL) -rreaizaDi nr
Database. Cincinnati, Ohio: US Environmental Protection Agency,
Office of Research and Development, wai-^r KnrH n^P>r i no R^s^avr-
Laboratory. Contract No. 68-03-3371.
Water Engineering Research
USEPA. Feb 1985. US Environmental Protection Agency.
Physical/Chemical Properties and Categorization of RCRA Wastes
According to Volatility. Research Triangle Park, NC: USEPA,
Office of Air Quality Planning and Standards. EPA 450/3-85-007.
USEPA. Dec
Emergency
Profiles.
Agency.
1985. US Environmental Protection
Preparedness Program- Interim Guidance:
Washington, DC: USEPA, Office of Toxic Substances,
•» m . . 1_ __ _ 1 _ _
Chemical
Chemical
Profiles. Washington, DC: USEPA
Economics and Technology Division.
USEPA. Oct 1986. US Environmental Protection Agency. Superfund
Public Health Evaluation Manual. Washington, DC: USEPA, Office
of Emergency and Remedial Response. EPA 540/1-86-060. (OSWER
Directive 9285.4-1)
USEPA. 1987. US Environmental Protection Agency. Computer
printout of referenced chemical/physical properties of a dataset
of chemicals extracted from the Graphical Exposure Modeling
System (GEMS). Washington, DC: USEPA, Office of Toxic
Substances, Economics and Technology Division.
Verschueren, K. 1977. Handbook of Environmental Data on Organic
Chemicals. New York, NY: Van Nostrand Reinhold Company.
Weast, R.C. (ed.) 1981. CRC Handbook of Chemistry and Physics.
62nd edition. Boca Raton, FL: CRC Press, Inc.
B-2
-------
Windholz, M. (ed.) 1983. The Merck Index
Rahway, NJ: Merck and Co., Inc.
Tenth edition
Yalkowsky,
edition.
Pharmacy.
S. 1987. Arizona Database of Aqueous Solubility. 2nd
Tucson, AZ: University of Arizona, College of
Chemical specific data was also obtained through computer
searches of the following databases:
Merck Index
ISHOW
Hazardous Substances Data Base (HSDB)/ Toxnet
Heilbron/ DIALOG
OHMTADS/ Chemical Information System (CIS)
Chemical Hazard Response Information System (CHRIS)/ CIS
CHEMFATE/ Syracuse Research Corporation
Discrepancies between values obtained from different sources were
reconciled where possible by consulting additional data sources.
However, the values in this Appendix have not been subject to
rigorous review and the reader should exercise good judgement
concerning their use.
AMB STATE- physical state of the pure chemical at ambient
conditions: room temperature and atmospheric pressure. For
chemicals with melting or boiling points close to room
temperature (20-30 C), two states are listed with the relevant
melting or boiling temperature. For chemicals reportable only as
solutions, the ambient state is listed for the liquid solution
with the pure chemical state noted. References for ambient state
were not compiled.
MOL WT- molecular weight of the pure chemical in g/g-mole or
Ib/lb-mole. References for molecular weight were not compliled.
SPEC GRAV- Specific gravity is the ratio of the density of the
pure chemical in its ambient state (except as noted) at the
listed temperature to the density of water at a temperature from
4-25 C. If no temperature is listed, then the chemical density
is assumed to be measured at ambient temperature (20-30 C) . To
obtain the density of the chemical, multiply the specific gravity
listed times the density of water (8.33 Ib/gallon or 62.4
lb/ft3).
For chemicals which are gases at ambient conditions, the
vapor density is listed instead of specific gravity. Vapor
density values are noted with an *. Vapor density is the density
of the gas as compared to air (Air = 1) . To obtain the density
of the gas at a specified temperature and pressure, multiply the
vapor density value times the density of air at the same
temperature and pressure. Density of air at 32 F and 760 mm Hg =
0.0808 lb/ft3.
B-3
-------
VAPOR PRESSURE- vapor pressure of the pure chemical at the
listed temperature. Some of the vapor pressure values in this
Appendix, especially those less than 1 mm Hg, are estimated
rather than measured values. Since vapor pressure is a function
of temperature, the vapor pressures listed should only be used if
the chemical is handled at the listed temperature. To estimate
the vapor pressure of a chemical at a temperature different than
listed, the Claussius-Clapeyron equation can be used.
In £2 = AHV (T? - TI)
P! R T! T2
where: P2 = unknown vapor pressure in mm Hg at temperature T2
Pi = known vapor pressure in mm Hg at temperature TI
TI, T2 = temperature in °K = °C + 273
AHV = heat of vaporization of the chemical (obtained
from literature or handbooks) in calorie/g-mole
grams x molecular weight = g-mole
Ibs. x molecular weight x 454 = g-mole
R = 1.987 calorie
K g-mole
WATER SOLUBILITY- water solublity is the maximum concentration
in milligrams (MG) of chemical that will dissolve in one liter
(L) of pure water at neutral pH and a specified temperature. If
no temperature is given, assume ambient temperature (20-30 C) .
Water solubility is also a function of temperature and for most
chemicals increases with the temperature of water. Acid or basic
water conditions will also affect the solubility of many
chemicals. Some chemicals may react or hydrolyze in water,
causing them to decompose. For some chemicals, the only
information on water solubility was qualitative. Miscible means
that the chemical is completely soluble in water and that a
minimum value of 1 x 10 6 MG/L can be assumed as the water
solubility if a numerical value is needed.
1 MG/L = 1 PPM = 0.0001%
B-4
-------
TABLE B-l Chemical/Physical Properties
NAME
Formaldehyde ( monomer ic gas)
Formaldehyde (37% aqueous solution)
2,4-Dinitrophenol
Nitrogen Mustard
Urethane (ethyl carbamate)
Trichlorofon
2-Acety 1 ami nof I uorene
N-Nitrosodiethylamine
Benzamide
Nitroglycerine
Carbon tetrachloride
Parathion
1, 1-Dimethylhydrazine
Propiolactone, beta-
Chlordane
-Lindane
N-Nitrosomorpholine
4-Aminoazobenzene
4-Dimethylaminoazobenzene
Methyl hydrazine
Acet amide
Aniline
Thioacetamide
Thiourea
Dichlorvos
N-Mitrosodimethylamine
Carbaryl
Diethyl sulfate
Methanol
Isopropyl alcohol (mfg. -strong acid processes)
Acetone
Chloroform
Hexachloroethane
Triaziquone
n-butyl alcohol
Benzene
1,1,1-Trichloroethane (Methyl chloroform)
Methoxychlor
Bromoethane (Methyl bromide)
Ethylene
CAS NO.
50-00-0
50-00-0
51-28-5
51-75-2
51-79-6
52-68-6
53-96-3
55-18-5
55 - 21 - 0
55-63-0
56-23-5
56-38-2
57-14-7
57-57-8
57-74-9
58-89-9
59-89-2
60-09-3
60-11-7
60-34-4
60-35-5
62-53-3
62-55-5
62-56-6
62-73-7
62-75-9
63-25-2
64-67-5
67 - 56 - 1
67-63-0
67-64-1
67-66-3
67-72-1
68-76-8
71 - 36 - 3
71-43-2
71-55-6
72 - 43 - 5
74-83-9
74-85-1
AMBSTATE
GAS
LIQUID
SOLID
LIQUID
SOLID
SOLID
SOLID
LIQUID
SOLID
LIQUID
LIQUID
LIQUID
LIQUID
LIQUID
LIQUID
SOLID
SOLID
SOLID
SOLID
LIQUID
SOLID
LIQUID
SOLID
SOLID
LIQUID
LIQUID
SOLID
LIQUID
LIQUID
LIQUID
LIQUID
LIQUID
SOLID
SOLID
LIQUID
LIQUID
LIQUID
SOLID
GAS
GAS
MOL WT
30.03
52
184.11
156.07
89.09
257.45
223
102.14
121.13
227.09
153.84
291.27
60.10
72.1
409.80
290.85
116.11
197.23
225.30
46.07
59.07
93.12
75.13
76.12
220.98
74.08
201.22
154.19
32.04
60.10
58.08
119.39
236.74
231.25
74.12
78.11
133.41
345.66
94.95
28.05
SPECGRAV
.067*
.113
.683
.118
.1
.73
.942
.341
.6
.59
.26
0.7914
1.14
1.60
1.85
0.874
1.159
1.022
1.405
1.415
1.005
1.232
1.1774
0.796
0.785
0.791
1 .4832
2.091
0.810
0.8786
1.35
1.41
3.27*
0.978*
TEMP.(C)
18
24
25
20
20
4
20
25
22
20
25
20
25
20
20
20
25
18
20
23
15
20
20
20
20
20
20
20
25
VAPOR PRESSURE
(mm Hg)
664
1.025
1.49 E-5
decomp. upon stanc
0.315
7.8 E-6
2.1 E+7
1.73
2.5 E-4
113
9.7 E-6
157
1 E-5
3 E-2
3.3 E-7
49.6
1
0.67
0.01
8.1
4 E-5
1
100.00
32.0
185.95
159
0.58
6.5
100
126
1420
>30,400
TEMP.(C)
-22.3
20
20-30
25
20
25
25
20
25
20
25
25
20
20-30
25
65
25
30
20-30
20
47
21.2
20
20
20
25
25
26.1
25
20
20
HATER SOLUBILITY
(mg/l)
50 E+4
37 E+4
5600
very soluble
2.0 E+6
154,000
6.5
408,320
14000
1800
770
11.9
1.193 E+6
1.9
6.8
MISCIBLE
SLIGHTLY SOLUBLE
160
MISCIBLE
410,000
37,000
163,000
1.72 E+6
10,000
1 E+6
40
PRAC.INSOL. DECOMP.
MISCIBLE
MISCIBLE
1 E+6
7,800
50
SPAR. SOLUBLE C.W.
79,000
1780
950
0.1
18,000
1.200
TEMP.(C)
37
37
20
25
25
20-30
25
20
20
20
20
25
25
20
25
20
25
20-30 |
20-30
20
20-30
20
20
20
20
25
25
20
20
Ul
-------
TABLE B-l Chemical/Physical Properties
HAKE
Chloromethane (Methyl chloride)
Kethyl iodide
Hydrogen cyanide (boiling point = 25.6 C)
Hethylene bromide
Chloroethane (Ethyl chloride)
Vinyl chloride
Acetonitrile
Ace t aldehyde
Dichloromethane (Hethylene chloride)
Carbon disulfide
Ethylene oxide (boiling point = 11 C)
Bromoform (Tribromoethane)
D i ch lorobronxxnethane
Vinyl idene chloride (boiling point = 31.9 C)
Phosgene (boiling point = 8.1 C)
Propyleneimine
Propylene oxide
tert-Butyl alcohol (melting point = 25.6 C)
Freon 113
Heptachlor
Hexachlorocyclopentadiene
Dimethyl sulfate
I sobutyra Idehyde
1,2-Dichloropropane
sec-Butyl alcohol
Methyl ethyl ketone
1,1,2-Trichloroethane
Trichloroethylene
Aery I amide
Acrylic acid (melting point 13 C)
Chloroacetic acid
Peracetic acid
1 , 1 ,2,2-Tetrach lorethane
Dimethyl carbamyl chloride (boiling point = 167 C)
2-Nitropropane
4,4l-Isopropylidenediphenol (Bisphenol A)
Cumene- hydroperox i de
Methyl methacrylate
Saccharin
C.I. Food Red 15
CAS HO.
74-87-3
74-88-4
74-90-8
74-95-3
75-00-3
75-01-4
75-05-8
75-07-0
75-09-2
75-15-0
75-21-8
75-25-2
75-27-4
75-35-4
75-44-5
75-55-8
75-56-9
75-65-0
76-13-1
76-44-8
77-47-4
77-78-1
78-84-2
78-87-5
78-92-2
78-93-3
79-00-5
79-01-6
79-06-1
79-10-7
79-11-8
79-21-0
79-34-5
79-44-7
79-46-9
80-05-7
80 - 15-9
80-62-6
81-07-2
81-88-9
AMBSTATE
GAS
LIQUID
GAS/LIQ
LIQUID
GAS
GAS
LIQUID
GAS/LIQ
LIQUID
LIQUID
GAS/LIQ
LIQUID
LIQUID
GAS/LIQ
GAS/LIQ
LIQUID
LIQUID
SOL/LIQ
LIQUID
SOLID
LIQUID
LIQUID
LIQUID
LIQUID
LIQUID
LIQUID
LIQUID
LIQUID
SOLID
SOL/LIQ
SOLID
LIQUID
LIQUID
LIQUID
LIQUID
SOLID
LIQUID
LIQUID
SOLID
SOLID
HOI WT
51
141.95
27.03
173.86
64.52
62.5
41.05
44.1
84.94
76.13
44.06
252.75
163.8
96.94
98.92
57.11
58.08
74.1
187.38
373.35
272.77
126.14
72.10
113
74.12
72.1
133.42
131.4
71.08
72
94.50
76.05
168.86
108
89109
228.28
152
100.11
183.18
479.0
SPECGRAV
1.8*
2.279
0.699LIQ
2.495
2.23*
2.15*
0.79
1.52*
1.3255
1.2632
1.582*
2.89
1.971
1.218
3.42*
0.80
0.859
0.788
1.56
1.58
1.7019
1.3283
0.7938
1.16
0.808
0.805
1.44
1.46
1.122
1.0511
1.58
1.226
1.6
0.992
1.195
1.05
0.936
0.828
TEHP.(C)
20
20
20
20
20
25
20
25
0
20 (solid)
25
9
25
20
20
20
20
20
20
30
20 (liq)
20
15
20
20
25
20
VAPOR PRESSURE
(nro Hg)
4310
400
730
45.8
1180
2660
100
740
438.0
360
1095
5.6
500
1215
112
445
42
270
3.0 E-4
8.0 E-2
0.5
170
50
10.0
77.5
24
75
0.007
4
6.5 E-2
4.2
2.49
17.5
0.20
0.24
40.0
2.69 E-3
TEHP.(C)
25
25
25
25
20
25
25
20
25
25
20
25
20
20
20
20
25
20-30
25
25
20
20
25
21.7
20
25
25
20
20-30
25
25
25
25
170
20
25.5
25
WATER SOLUBILITY
(mg/l)
4000
14,000
5.6 E+7
11,700
5,740
9,150
2.2 E+6
INFINITELY SOLUBLE
20,000
2,940
2.1 E+6
1,250
2,250
SLIGHTLY SOLUBLE
3.1 E+6
405,000
SOLUBLE
10
0.18
6.4
28,000
110,000
2,700
200,000
270,000
4500
1,100
2.155 E+6
1 E+6
VERY SOLUBLE
VERY SOLUBLE
2,857
1.44 E+7
17
3,400
10,000
15,000
448
15,000
TEHP.(C)
25
20
25
15
20
20.5
25
20
20
25
25
25
25
20
20-30
25
25
18
20-30
20
20
20
20
30
20-30
25
20-30
25
83
25
25
25
22
W
-------
TABLE B-l Chemical/Physical Properties
NAME
1 -Amino-2-methylanthraquinone
Qui ntozene (Pentach loroni trobenzene)
Oi ethyl phthalate
Dibutyl phthalate
Phthalic anhydride
Butyl benzyl phthalate
N-Nitrosodiphenylamine
2,6-Xylidine (2,6-Dimethyaniline)
Hexachloro-1,3-butadiene
Pentachlorophenol (PCP)
2,4,6-trichlorophenol
2-Nitrophenol
Picric acid
o-Anisidine
2-Phenylphenol
Michler's ketone
Toluene 2,6-diisocyanate
Naphthalene
Quinoline
beta Naphthylamine
3,3'-Dichlorobenzidene
Biphenyl
4-Aminobiphenyl
Benzidine
4-Nitrobiphenyl
Benzoyl peroxide
Safrole
2,4-D [Acetic acid,(2,4-dichlorophenoxy)-]
o-Xylene
o-Cresol (melting point = 31.1 C)
1 ,2-Dichlorobenzene
o-Toluidine
1 ,2,4-Trimethylbenzene
2,4-Diaminotoluene
2,4,5-Trichlorophenol
Styrene oxide
1,2-Dibromo-3-chloropropane (DBCP)
Methyl acrylate
Ethylene thiourea
C.I. Solvent Yellow 3
CAS NO.
82 - 28 - 0
82-68-8
84-66-2
84-74-2
85-44-9
85-68-7
86-30-6
87-62-7
87-68-3
87-86-5
88-06-2
88-75-5
88-89-1
90-04-0
90-43-7
90-94-8
91-08-7
91-20-3
91-22-5
91-59-8
91-94-1
92-52-4
92-67-1
92-87-5
92-93-3
94-36-0
94-59-7
94-75-7
95-47-6
95-48-7
95-50-1
95-53-4
95-63-6
95-80-7
95-95-4
96-09-3
96-12-8
96-33-3
96-45-7
97-56-3
AMBSTATE
SOLID
SOLID
LIQUID
LIQUID
SOLID
LIQUID
SOLID
LIQUID
LIQUID
SOLID
SOLID
SOLID
SOLID
LIQUID
SOLID
SOLID
SOL/LIQ
SOLID
LIQUID
SOLID
SOLID
SOLID
SOLID
SOLID
SOLID
SOLID
LIQUID
SOLID
LIQUID
SOLID
LIQUID
LIQUID
LIQUID
SOLID
SOLID
LIQUID
LIQUID
LIQUID
SOLID
SOLID
MOL WT
237.26
295.34
222.2
278.34
148.11
312.36
198.23
121.18
261
266.35
197.46
139.11
229.11
125.15
170.2
268.35
174.2
128.16
129.15
143.18
253.13
154.2
169.22
184.23
199.2
242.23
162
221
106.17
108.15
174.0
107.15
120.2
122.17
197.46
120.2
236.36
86.09
102
225.28
SPECGRAV
1.718
1.120
1.0484
1.527
1.23
0.9842
.675
.978
.490
.657
.763
.0923
.213
1.152
1.095
1.061
0.8660
1.160
1.250
1.328
1.334
1.1
0.88
1.047
1.305
1.004
0.876
1.05
2.093
0.958
TEMP.(C)
25
25
20
4
20
15.5
22
75
20
20
25
20
98
20
20
20
20
25
15
20
20
20
20
14
20
VAPOR PRESSURE
(mm Hg)
2.38 E-3
8.1 E-3
1.4 E-5
0.0002
0.3
1
2
0.0002
0.12
0.19
1.0
0.10
1.0
0.232
9.1 E-3
0.0559
1.2 E-7
1
6 E-5
1 E-5
0.0709
1.59 E-4
10
2.4 E-1
1.440
0.1
2.030
3.8 E-5
0.0496
0.3
0.513
70
TEMP.(C)
25
25
20
20
100
44
20-30
20
20-30
25
195
30
100
25
25
25
25
70.6
20-30
25
25
25
32.1
25
25
20
25
20-30
25
20
25
20
WATER SOLUBILITY
(mg/l)
INSOLUBLE
0.032
900
13
6,200
3
SLIGHTLY SOLUBLE
INSOLUBLE
0.15
900
1,600
23,000
SLIGHTLY INSOLUBLE
PRAC. INSOLUBLE
PRAC. INSOLUBLE
REACTS
34.4
60 000
1,700
12.3
7 c
§ • j
842
280
LUU
INSOLUBLE
SPAR. SOLUBLE
1,500
900
213
25 115
_ J f t I J
145
16 900
IUf 7UU
57
47,700
<2,000
? nnn
., ouu
1,000
52,000
0,418
PRAC. INSOLUBLE
TEMP. CO
75
CmJ
?fi
£U
>•»
C.J
26.7
P5
C*J
pfi-^n
CU JU
on
£U
20
C.w
20
C,\J
20
Cm\J
25
on
cu
PR
C.J
25
oc
CJ
20-30
on
C\J
pn.-xn
£>U JU
20
?5
t-j
Oft
CU
PR
C.J
on
c.v
?n
C\i
20-30
P5
C.J
on
C\J
P1?
C.J
pn
1U
PR
-J
-------
TABLE B-l Chemical/Physical Properties
HAKE
Benzoic trichloride (Benzotrichloride)
Cunene
Benzal chloride
Benzoyl chloride
Nitrobenzene (melting point = 5.5 C)
5-Nitro-o-anisidine
4-Nitrophenol
Terephthalic acid
Ethylbenzene
Benzyl chloride
N-Nitrosopiperidine
4,4'-Methylenebis(2-chloroani line) (MBOCA)
4,4'-Methylene bis(N,N-dimethyl) benzenamine
Methylene bis(phenylisocyanate) (MBI) (melt.pt. = 37C)
4,4'-Methylene dianiline
4,4'-Diaminodiphenyl ether
Bis(2-ethylhexyl) adipate
p-Anisidine (melting point = 57.2 C)
2,4-Dimethylphenol (melting point = 25.4 C)
p-Xylene
p-Cresol (melting point = 34.8 C)
1,4-Dichlorobenzene (melting point = 53.1 C)
p-Phenylenedi ami ne
Quinone
1,2-Butylene oxide
Epichlorohydrin
1,2-Dibromoethane (Ethylene dibromide)
1,3-Butadiene
Acrolein
Allyl chloride
1,2-Dichloroethane (Ethylene dichloride)
Acrylonitrile
Ethylene glycol
Chloromethyl methyl ether
Vinyl acetate
Methyl isobutyl ketone
Maleic anhydride
m-Xylene
m-Cresol
CAS NO.
98-07-7
98-82-8
98-87-3
98-88-4
98-95-3
99-59-2
100 - 02 - 7
100 - 21 - 0
100 - 41 - 4
100 - 42 - 5
100 - 44 - 7
100 - 75 - 4
101 - 14 - 4
101 - 61 - 1
101-68-8
101-77-9
101 - 80 - 4
103 - 23 - 1
104 - 94 - 9
105 - 67 - 9
106 - 42 - 3
106 - 44 - 5
106 - 46 - 7
106 - 50 - 3
106-51-4
106-88-7
106 - 89 - 8
106 - 93 - 4
106-99-0
107 - 02 - 8
107 - 05 - 1
107-06-2
107 - 13 - 1
107 - 21 - 1
107 - 30 - 2
108 - 05 - 4
108 - 10 - 1
108-31-6
108 - 38 - 3
108-39-4
fWBSTATE
I QUID
I QUID
I QUID
LIQUID
SOL/LIQ
SOLID
SOLID
SOLID
LIQUID
LIQUID
LIQUID
LIQUID
SOLID
SOLID
SOLID
SOLID
SOLID
LIQUID
SOLID
SOL/LIQ
LIQUID
SOLID
SOLID
SOLID
SOLID
LIQUID
LIQUID
LIQUID
GAS
LIQUID
LIQUID
LIQUID
LIQUID
LIQUID
LIQUID
LIQUID
LIQUID
SOLID
LIQUID
LIQUID
HOL WT
95.48
20.19
61.03
40.57
23.11
68.16
39.11
166.13
106.17
104.14
126.58
114.15
267
254.36
250.26
198.26
200.2
370
123.15
122.17
106.17
108.13
147.00
108.14
108.09
72.1
92.53
187.88
54.09
56.06
76.53
99
53.60
62.1
80.52
86.09
100.2
98.06
106.16
108.13
SPECGRAV
1.3756
0.8620
1.26
1.22
1.2037
1.2068
1.479
1.510
0.867
0.9045
1.100
1 .0631
1.44
1.19
0.925
1.071
1.036
0.86
1.0347
1.2475
1.318
0.83
1.801
2.701
1.87*
0.8389
0.94
1.25
0.8004
1.113
1.0605
0.932
0.8017
0.934
0.864
1.038
TEHP.(C)
20
20
4
5
20 (liq)
20
20
25
20
18.5
50 (liq)
20
57
20 (solid)
20
20
20
20
20
25
20
20
20
25
20
20
20
20
20
20
20
VAPOR PRESSURE
(mm Hg)
0.157
3.2
0.30
0.4
0.407
0.75
9.50
I
0.244
6 E-6
0.1
1 E-5
2.60
0.051
10
0.108
0.680
1.00
0.140
18.8
1117
910
269.0
340
61
100.0
0.120
214
83.0
7.1
0.00005
10
0.153
TEHP.(C)
25
20
20
20
25
20
25
20
22
25
25
148.9
25
20
20
27.3
25
25
98.8
24.6
25
25
20
25
20
20
22.8
20
25
20
25
20
28.3
25
WATER SOLUBILITY
(ng/O
60
0
410
DECOMPOSES
,800
SLIGHTLY SOLUBLE
1,600
19
177
300
1,619
284,318
15
INSOLUBLE
2,000 (REACTS)
SLIGHTLY SOLUBLE
INSOLUBLE
90
SPAR. SOLUBLE
7,900
198
19,000
69
38,000
1,500
82,400
65,800
4,300
740
265,822
100
8,300
74,000
117,000
DECOMPOSES
20,000
19,000
163,000
175
23,500
TEHP.(C)
25
if*
id
25
25
25
25
25
25
25
25
25
20
20
20
20
20
20
24
25
25
20
25
on
ZU
20
20
*3rt
20
20
20
25
25
20
00
-------
TABLE B-l Chemical/Physical Properties
NAME
Bis(2-chloro-1-methytethyl) ether
Melamine
Toluene
Chlorobenzene
Phenol
2-Methoxyethanol (methyl cellosolve)
2-Ethoxyethanol
Cyclohexane
Pyridine
Oiethanolamine (melting point = 28 C)
bis (2-chloroethyl) ether
Propoxur
Propylene (Propane)
Dicofol
w 2-Aminoanthraquinorte
1 Di(2-ethylhexyl)phthalate (DEHP)
n-Dioctyl phthalate
Hexach lorbenzene
3,3'Dimethoxybenzidene
3,3'-Diniethylbenzidene (o-Tolidine)
Anthracene
p-Cresidine
Catechol
1,2,4-Trichlorobenzene (melting point 17 C)
2,4-Dichlorophenol
2,4-Dinitrotoluene
N,N-Dimethylaniline
1 ,2-Diphenylhydraz'ine (Hydrazobenzene)
Hydroquinone
Propionaldehyde
Butyraldehyde
1,4-Dioxane
Tris-(2,3-dibromopropyl)phosphate
Chloroprene
Tetrachloroethylene (Perchloroethylene)
C.I. Vat Yellow 4
Dimethyl phthalate
Dibenzofuran
Captan
Chloramben
CAS NO.
108-60-1
108 - 78 - 1
108-88-3
108 - 90 - 7
108 - 95 - 2
109-86-4
110 - 80 - 5
110 - 82 - 7
110-86-1
111 - 42 - 2
111 - 44 - 4
114 - 26 - 1
115 - 07 - 1
115 - 32 - 2
117 - 79 - 3
117 - 81 - 7
117-84-0
118 - 74 - 1
119 - 90 - 4
119 - 93 - 7
120 - 12 - 7
120 - 71 - 8
120 - 80 - 9
120 - 82 - 1
120 - 83 - 2
121 - 14 - 2
121 -69-7
122-66-7
123 - 31 - 9
123-38-6
123 - 72 - 8
123 - 91 - 1
126 -72-7
126-99-8
127 - 18 - 4
128-66-5
131 - 11 - 3
132 - 64 - 9
133 - 06 - 2
133 - 90 - 4
AHBSTATE
LIQUID
SOLID
LIQUID
LIQUID
SOLID
LIQUID
LIQUID
LIQUID
LIQUID
SOL/LIQ
LIQUID
SOLID
GAS
SOLID
SOLID
LIQUID
LIQUID
SOLID
SOLID
SOLID
SOLID
SOLID
SOLID
LIQUID
SOLID
SOLID
LIQUID
SOLID
SOLID
LIQUID
LIQUID
LIQUID
LIQUID
LIQUID
LIQUID
SOLID
LIQUID
SOLID
SOLID
SOLID
HOL UT
171.07
126.13
92.14
112.56
94.11
76.1
90.1
84.16
79.1
105.14
143.02
209.24
42.08
370.47
223.23
390.62
390.62
284.20
244
212.30
178.22
127.07
110.11
181.45
163.0
182.14
121.18
184.23
110.11
58.1
72.1
88.20
697.93
88.5
165.83
332.36
194.19
168.11
300.59
206.03
SPECGRAV
1.11
1.573
0.867
1.1066
1.0722
0.97
0.93
0.779
0.982
1.092
1.22
1.49*
0.99
0.9861
2.044
1.24
1.371
1.574
1.383
1.521
0.956
1.158
1.332
0.807
0.817
1.033
0.958
1.626
1.196
1.0886
1.74
TEHP.(C)
16
20
20
20
20
20
20
30
20
20
23
27
15
10
60
15
20
16
15
20
20
20
20
20
15;6
99
20
VAPOR PRESSURE
(mm Hg)
0.85
50
28.10
10.0
0.20
6.2
5.5
100.0
20
0.010
0.7
0.010
1.0
SUBLIMES
0.10
6.8 E-8
1.09 E-5
1.9 E-7
2.9 E-7
1.95 E-4
5.0
0.46
0.13
5.1 E-3
1.10
2.6 E-5
1.0
235
71
40.0
4.80 E-3
200
19
<0.01
0.10 E-4
7 E-3
TEMP.(C)
20
315
25
22.2
20
20
25
25.5
25
20
20
120
-131.9
20
25
20-30
25
25
20-30
104
25
25
20-30
30
20-30
132.4
20
20
25.2
65
20
25
20
20
100
WATER SOLUBILITY
(mg/l)
1,700.
2,700
570
500
82,000
MISCIBLE
MISCIBLE
49
3 E+8
950,000
10,200
2,000
410
8 E-4
INSOLUBLE
1.3
0.4
4.95 E-3
1,800
46
4.5 E-2
SPAR. SOLUBLE H.U.
311,000
30
4,500
300
INSOLUBLE
1,840
260,000
200,000
37,000
6 E+6
10,000
145
4,300
10
0.50
700
TEMP.(C)
20-30
20
25
20
20
20
25
-1
25
20
20
20
25
25
25
25
20-30
20
20
20
22
20-30
20
20
25
20
25
25
25
20 |
25 |
-------
TABLE B-l Chemical/Physical Properties
HAHE
o-Anisidine hydrochloride
alpha-Naphthylamine
Cupferron
Nitrilotriacetic acid
4,4'-Thi
6.5 E-5
39.20
4
160
14.4
6.0 E-6
0.090
1.2 E-6
0.004
1.05 E-6
200
2.1
25
30
0.01
1058.3
1.8 E-2
0.4
348
1.19 E-3
0.07
33.5
16.3
4.11
4.2 E-8
6.37 E-4
TEHP.(C)
20-30
20
20
20
25
25
30
20-30
20
25
25
25
20
22
20
25
20-30
20-30
20
25
30
25
25
25
20
25
WATER SOLUBILITY
<»g/l>
SOLUBLE
1,700
FREELY SOLUBLE
1,280
SL. SOLUBLE H.U.
20,000
1,600
2.66 E+6
SLIGHTLY SOLUBLE
INSOLUBLE, REACTS
3.41 E+8
2.7 E-2
DECOMPOSES
1,000
2.1
680
21.9
PRAC. INSOLUBLE
290
6,300
DECOMPOSES (INSOL)
110
2,700
DECOMPOSES(22,000)
VERY SOLUBLE
REACTS
1,320
9,900
REACTS
1.5 E+4
MISCIBLE
6.89 E+8
3.31 E+8
INSOLUBLE
1,100
11
SOLUBLE.
2.3 E+6
TEHP.(C)
20
22.5
20
20
20-30
20-30
25
25
20-30
20-30
25
20
25
25
20-30
20-30
20-30
20-30
20-30
25
22
25
bd
-------
TABLE B-l Chemical/Physical Properties
NAME
Decabromodiphenyl oxide
Sodiuni hydroxide (solution) pure = solid
Molybdenum trioxide
Thorium dioxide
Cresol (mixed isomers)
Xylene (mixed isomers)
Asbestos (friable)
Hexachloronaphthalene
Polychlorinated biphenyls (PCBs)
Aluminum oxide
Diepoxybutane
Trifluralin
Methyl tert-butyl ether
Nitrofen
Chlorothalonil
C.I. Direct Black 38
Fluometuron
Octach I oronaph tha I ene
Dial late
C. . Direct Blue 6
C. . Acid Blue 9, diammonium salt
C. . Disperse Yellow 3
C. . Solvent Orange 7
C. . Food Red 5
C. . Acid Blue 9, disodium salt
N-Nitroso methyl vinyl amine
C.I. Acid Green 3
Ammonium nitrate (solution) pure = solid
Aluminum (fume or dust)
Lead
Manganese
Mercury
Nickel
Si Iver
Thallium
Antimony
Arsenic
Barium
Beryllium
Cadmium
CAS NO.
1163 - 19 - 5
1310 - 73 - 2
1313 -27-5
1314 - 20 - 1
1319 - 77 - 3
1330 - 20 - 7
1332 - 21 - 4
1335 - 87 - 1
1336 - 36 - 3
1344 - 28 - 1
1464 - 53 - 5
1582 - 09 - 8
1634 - 04 - 4
1836 - 75 - 5
1897 - 45 - 6
1937 -37-7
2164 - 17 - 2
2234 - 13 - 1
2303 - 16 - 4
2602 - 46 - 2
2650 - 18 - 2
2832 - 40 - 8
3118 -97-6
3761 - 53 - 3
3844 - 45 - 9
4549 - 40 - 0
4680 - 78 - 8
6484 - 52 - 2
7429 - 90 - 5
7439 - 92 - 1
7439 - 96 - 5
7439 - 97 - 6
7440 - 02 - 0
7440 - 22 - 4
7440 - 28 - 0
7440 - 36 - 0
7440 - 38 - 2
7440 - 39 - 3
7440 - 41 - 7
7440 - 43 - 9
AMBSTATE
SOLID
LIQUID
SOLID
SOLID
LIQUID
LIQUID
SOLID
SOLID
LIQUID
SOLID
LIQUID
SOLID
LIQUID
SOLID
SOLID
SOLID
SOLID
SOLID
LIQUID
SOLID
SOLID
SOLID
SOLID
SOLID
SOLID
SOLID
LIQUID
SOLID
SOLID
SOLID
LIQUID
LIQUID
SOLID
SOLID
SOLID
SOLID
SOLID
SOLID
SOLID
MOL WT
959.12
40.01
43.95
264.05
108.13
106.16
554.2
334.85
328
101.94
86.10
335.29
88.15
284.10
265.89
783.0
232.21
403.74
270.24
936.82
783.01
269.33
276.17
482.4
792.85
86.02
690.80
80.05
204.12
207.19
54.94
200.59
58.71
107.87
204.37
121.75
74.92
137.24
9.01
112.41
SPECGRAV
1.53
4.696
10.0
1.03
0.86
2.5
1.38-1.6
4
1.113
1.294
0.7404
1.33
1.70
2.00
0.65
1.725
2.702
11.29
7.2
13.594
8.90
10.5
11.85
6.684
5.727
3.51
1.85
8.642
TEMP.(C)
(50% soln)
26
25
25
20
18
25
20
90
25
25 (solid)
20
20
20
25
14
20
20
VAPOR PRESSURE
(mm Hg)
1
0.24
10
7.7 E-5
1
1.52
1.99 E-4
245
8 E-6
0.01
5 E-5
<1
<1
6.74 E-3
1 E-7 (est)
1 E-7 (est)
12.3
11
1
1 E-5
1
1.3 E-3
1
1
1
1
10
1 E-5
TEMP.(C)
734
20-30
27-32
20-30
2148
25
30
25
40
40
20
20-30
25
25
20-30
210
1284
483
1292
25
1810
1357
825
886
372
1049
148
WATER SOLUBILITY
(mg/l)
MISCIBLE
490
INSOLUBLE
31,000
175
0.031
PRAC. INSOLUBLE
8.3 E+7
24
48,000
1
0.6
GOOD
80
INSOLUBLE
14
GOOD
200,000
3.8
20,000
SOLUBLE
7.6 E+5
SOLUBLE
2 E6
INSOLUBLE
INSOLUBLE
DECOMPOSES
0.03
INSOLUBLE
INSOLUBLE
INSOLUBLE
INSOLUBLE
INSOLUBLE
REACTS SLOWLY
SL.SOL.H.W..DECOHP
INSOLUBLE
TEHP.(C)
28
20-30
25
20-30
25
22
22
25
20-30
20
60
22
20-30
25
-------
TABLE B-l Chemical/Physical Properties
NAME
Chromium
Cobalt
Copper
Vanadium (fume or dust)
Zinc (furoe or dust)
Titanium tetrachloride
Hydrochloric acid
Phosphoric acid (melting point = 42.4 C)
Hydrogen fluoride (boiling point = 49.2 C)
Ammonia
Ammonia water (28% in water)
Sulfuric acid
Nitric acid
Phosphorus (yellow or white)
Sodium sulfate (solution) pure = solid
w Selenium (amorphous form)
i-' Selenium (crystalline or red form)
10 Selenium (gray or metallic form)
Chlorine
Ammonium sulfate (solution) pure = solid
Toxaphene
Hydrazine sulfate
Chlorine dioxide (boiling point = 11 C)
Zineb
Haneb
Titanium dioxide (rutile form)
Titanium dioxide (anatase form)
Titanium dioxide ( brook ite form)
C.I. Direct Brown 95
N - N i t rosonorn i cot i ne
Osmium tetroxide
Dichlorobenzene (mixed isomers)
Diaminotoluene (mixed isomers)
2,4-Diaminoanisole sulfate
CAS NO.
7440 - 47 - 3
7440 - 48 - 4
7440 - 50 - 8
7440 - 62 - 2
7440 -66-6
7550 - 45 - 0
7647 - 01 - 0
7664 - 38 - 2
7664 - 39 - 3
7664 - 41 - 7
7664 - 41 - 7
7664 - 93 - 9
7697 - 37 - 2
7723-14-0
7757 - 82 - 6
7782 - 49 - 2
7782 - 49 - 2
7782 - 49 - 2
7782 - 50 - 5
7783 - 20 - 2
8001 - 35 - 2
10034 - 93 - 2
10049 - 04 - 4
12122 -67-7
12427 - 38 - 2
13463 -67-7
13463 -67-7
13463 -67-7
16071 - 86 - 6
16543 - 55 - 8
20816 - 12 - 0
25321 - 22 - 6
25376 - 45 - 8
39156 - 41 - 7
AHBSTATE
SOLID
SOLID
SOLID
SOLID
SOLID
LIQUID
GAS
SOL/LIQ.
GAS/LIQ
LIQUID
LIQUID
LIQUID
LIQUID
SOLID
LIQUID
SOLID
SOLID
SOLID
GAS
LIQUID
SOLID
SOLID
GAS
SOLID
SOLID
SOLID
SOLID
SOLID
SOLID
LIQUID
SOLID
LIQUID
SOLID
SOLID
HOL UT
52
58.93
63.55
50.94
65.38
189.73
36.46
98.00
20.01
17.03
17.03
98.08
63.01
30.97
142.06
78.96
78.96
78.96
70.91
132.14
414
130.12
67.46
275.75
265.29
79.90
79.90
79.90
762.15
177.08
254.20
174.0
122.17
236.08
SPECGRAV
7.20
8.9
8.92
5.96
7.14
1.726
1.268*
1.8741
0.991
0.6*
0.90
1.841
1.5027
1.8
2.7
4.28
4.26 RED
4.81
2.5*
1.65
2.016
1.642
1.92
4.23
3.90
4.13
4.906
1.2884
TEHP.(C)
28
25 (liq)
19.5 (liq)
25
20
solid
20
-34.6
25
7
0
22
20
VAPOR PRESSURE
(mm Kg)
1 E-5
1
1
10
30400
800
7600
10
47.8
0.026
1
1
1
7600
0.4
760
NEGLIGIBLE
7.5 E-8
11
0.68-2.1
TEHP.(C)
907
1628
487
21.3
17.8
25
25.7
31
20
20
356
356
356
30
25
11.1
20
27
25
WATER SOLUBILITY
(»g/l)
INSOLUBLE
INSOLUBLE
INSOLUBLE
INSOLUBLE
INSOLUBLE
SOLUBLE
673,000
1 E+6
200,000
440,000
SOLUBLE
SOLUBLE
0.33
330,000
INSOLUBLE
INSOLUBLE
INSOLUBLE
5,700
434,700
3
29,000
<1
40
INSOLUBLE
INSOLUBLE
INSOLUBLE
GOOD
62,300
140
SOLUBLE
SOLUBLE
TEHP.(C)
30
25
28
33
199
199
137
30
25
22
25
25
25
-------
APPENDIX C
ESTIMATING ATMOSPHERIC RELEASES
FROM STORAGE OF ORGANIC LIQUIDS
(From "Compilation of Air Pollutant
Emission Factors" Volume 1,
EPA Publication AP-42 4th Edition
September 1985)
C-l
-------
4.3 STORAGE OF ORGANIC LIQUIDS
A.3.1 Process Description
Storage vessels containing organic liquids can be found in many
industries, including (1) petroleum producing and refining, (2) petro-
chemical and chemical manufacturing, (3) bulk storage and transfer
operations, and (4) other industries consuming or producing organic liquids.
Organic liquids in the petroleum industry, usually called petroleum liquids,
generally are mixtures of hydrocarbons having dissimilar true vapor pressures
(for example, gasoline and crude oil). Organic liquids in the chemical
industry, usually called volatile organic liquids, are composed of pure
chemicals or mixtures of chemicals with similar true vapor pressures (for
example, benzene or a mixture of isopropyl and butyl alcohols).
Five basic tank designs are used for organic liquid storage vessels,
fixed roof, external floating roof, internal floating roof, variable vapor
space, and pressure (low and high).
Fixed Roof Tanks - A typical fixed roof tank is shown in Figure 4.3-1.
This type of tank consists of a cylindrical steel shell with a permanently
affixed roof, which may vary in design from cone or dome shaped to flat.
Fixed roof tanks are commonly equipped with a pressure/vacuum vent
that allows them to operate at a slight internal pressure or vacuum to
prevent the release of vapors during very small changes in temperature,
pressure or liquid level. Of current tank designs, the fixed roof tank is
the least expensive to construct and is generally considered the minimum
acceptable equipment for storage of organic liquids.
Gauge Batch
Mantel*
Hanholo
Nozzle (For
•ubMrged fill
or drainage)
9/85
Figure 4.3-1. Typical fixed roof tank.1
Evaporation Loss Sources
C-2
4.3-1
-------
External Floating Roof Tanks - A typical external floating roof tank is
shown in Figure 4.3-2. This type of tank consists of a cylindrical steel
shell equipped with a roof which floats on the surface of the stored liquid,
rising and falling with the liquid level. The liquid surface is completely
covered by the floating roof, except at the small annular space between the
roof and the tank wall. A seal (or seal system) attached to the roof
contacts the tank wall (with small gaps, in some cases) and covers the
annular space. The seal slides against the tank wall as the roof is raised
or lowered. The purpose of the floating roof and the seal (or seal system)
is to reduce the evaporation loss of the stored liquid.
Internal Floating Roof Tanks - An internal floating roof tank has both a
permanent fixed roof and a deck inside. The deck rises and falls with the
liquid level and either floats directly on the liquid surface (contact
deck) or rests on pontoons several inches above the liquid surface (non-
contact deck). The terms "deck" and "floating roof" can be used
interchangeably in reference to the structure floating on the liquid inside
the tank. There are two basic types of internal floating roof tanks, tanks
in which the fixed roof is supported by vertical columns within the tank,
and tanks with a self-supporting fixed roof and no internal support columns.
Fixed roof tanks that have been retrofitted to employ a floating deck are
typically of the first type, while external floating roof tanks typically
have a self-supporting roof when converted to an internal floating roof
tank. Tanks initially constructed with both a fixed roof and a floating
deck may be of either type.
The deck serves to restrict evaporation of the organic liquid stock.
Evaporation losses from decks may come from deck fittings, nonwelded deck
seams., and the annular space between the deck and tank wall. Typical
contact deck and noncontact deck internal floating roof tanks are shown in
4.3-2
Figure 4.3-»2. External floating roof tank.1
EMISSION FACTORS
C-3
9/85
-------
Figure 4.3-3. Contact decks can be aluminum sandwich panels with a honey-
comb aluminum core floating in contact with the liquid, or pan steel decks
floating in contact with the liquid, with or without pontoons. Typical
noncontact decks have an aluminum deck or an aluminum grid framework
supported above the liquid surface by tubular aluminum pontoons or other
bouyant structures. Both types of deck incorporate rim seals, which slide
against the tank wall as the deck moves up and down. In addition, these
tanks are freely vented by circulation vents at the top of the fixed roof.
The vents minimize the possibility of organic vapor accumulation in con-
centrations approaching the flammable range. An internal floating roof
tank not freely vented is considered a pressure tank.
Pressure Tanks - There are two classes of pressure tanks in general use,
low pressure (2.5 to 15 psig) and high pressure (higher than 15 psig).
Pressure tanks generally are used for storage of organic liquids and gases
with high vapor pressures and are found in many sizes and shapes, depending
on the operating pressure of the tank. Pressure tanks are equipped with a
pressure/vacuum vent that is set to prevent venting loss from boiling and
breathing loss from daily temperature or barometric pressure changes. High
pressure storage tanks can be operated so that virtually no evaporative or
working losses occur. In low pressure tanks, working losses can occur with
atmospheric venting of the tank during filling operations.
Variable Vapor Space Tanks - Variable vapor space tanks are equipped with
expandable vapor reservoirs to accomodate vapor volume fluctuations attribut-
able to temperature and barometric pressure changes. Although variable
vapor space tanks are sometimes used independently, they are normally
connected to the vapor spaces of one or more fixed roof tanks. The two
most common types of variable vapor space tanks are lifter roof tanks and
flexible diaphragm tanks.
Lifter roof tanks have a telescoping roof that fits loosely around the
outside of the main tank wall. The space between the roof and the wall is
closed by either a wet seal, which is a trough filled with liquid, or a dry
seal, which uses a flexible coated fabric.
Flexible diaphragm tanks use flexible membranes to provide expandable
volume. They may be either separate gasholder units or integral units
mounted atop fixed roof tanks.
4.3.2 Emissions And Controls
Emission sources from organic liquids in storage depend upon the tank
type. Fixed roof tank emission sources are breathing loss and working
loss. External or internal floating roof tank emission sources are standing
storage loss and withdrawal loss. Standing storage loss includes rim seal
loss, deck fitting loss and deck seam loss. Pressure tanks and variable
vapor space tanks are also emission sources.
Fixed Roof Tanks - Two significant types of emissions from fixed roof tanks
are breathing loss and working loss. Breathing loss is the expulsion of
vapor from a tank through vapor expansion and contraction, which are the
results of changes in temperature and barometric pressure. This loss
occurs without any liquic level change in the tank.
9/85
Evaporation Loss Sources
4.3-3
C-4
-------
C«at«r Teat
Tent
Maahol*
V«nt
Tank Support Celuao
with Column W«U
Contact Deck Type
&tat*r Vent
lla
Pontoon*
Support Cal .
with Colum Veil
Vapor Spae*
Noncontact Deck Type
4.3-4
Figure 4.3-3. Internal floating roof tanks.1
EMISSION FACTORS
C-5
9/85
-------
The combined loss from filling and emptying is called working loss.
Filling loss comes with an increase of the liquid level in the tank, when
the pressure inside the tank exceeds the relief pressure and vapors are
expelled from the tank. Emptying loss occurs when air drawn into the tank
during liquid removal becomes saturated with organic vapor and -expands,
thus exceeding the capacity of the vapor space.
The following equations, provided to estimate emissions, ere applicable
to tanks with vertical cylindrical shells and fixed roofs. These tanks
•ust be substantially liquid and vapor tight and must operate approximately
at atmospheric pressure. Fixed roof tank breathing losses can be estimated
from2:
. 0.68
/ P \
= ? ?f> v 10-2M I I D1 ."3u0.5lAT°«
- J..& x iu riyi p^_ p i i) n ai
(1)
where:
LD = fixed roof breathing loss (Ib/yr)
a
My = molecular weight of vapor in storage tank (Ib/lb mole), see
Note 1
P. = average atmospheric pressure at tank location (psia)
P = true vapor pressure at bulk liquid conditions (psia), see Note 2
D = tank diameter (ft)
H = average vapor space height, including roof volume correction
(ft), see Note 3
AT = average ambient diurnal temperature change (°F)
Fp = paint factor (dimensionless), see Table 4.3-1
C = adjustment factor for small diameter tanks (dimensionless), see
Figure 4.3-4
Kp = product factor (dimensionless), see Note 4
Notes: (1) The molecular weight of the vapor, My, can be determined by
Table 4.3-2 for selected petroleum liquids and volatile
organic liquids or by analysis of vapor samples. Where
mixtures of organic liquids are stored in a tank, M» can be
estimated from the liquid composition. As an example of the
latter calculation, consider a liquid known to be composed
of components A and B with mole fractions in the liquid X
and X., respectively. Given the vapor pressures of the pure
9/85
Evaporation Loss Sources
4.3-5
C-6
-------
TABLE A.3-1. PAINT FACTORS FOR FIXED ROOF TANKS3
Tank color
Roof
Shell
Paint factors (Fp)
Paint condition
Good Poor
White
Aluminum (specular)
White
Aluminum (specular)
White
Aluminum (diffuse)
White
Light gray
Medium gray
White
White
Aluminum (specular)
Aluminum (specular)
Aluminum (diffuse)
Aluminum (diffuse)
Gray
Light gray
Medium gray
1.00
l.OA
1.16
1.20
1.30
1.39
1.30
1.33
l.AO
1.15
1.18
1.2A
1.29
1.38
1.A6
1.38
1.441
1.581
Reference 2.
Estimated from the ratios of the seven preceding paint factors,
1.0
0.8
0.6
0.4
0.2
10 20
TANK DIAMETER, ft
30
Figure A.3-4. Adjustment factor (C) for small diameter tanks.2
4-3-6 EMISSION FACTORS 9/85
C-7
-------
VO
00
tn
TABLE 4.3-2. PHYSICAL PROPERTIES OF TYPICAL ORGANIC LIQUIDS*
o
i
00
w
CO
•a
o
1-1
to
O
o
o
VI
v>
co
o
c
<-f
o
n
o>
Organic liquid
Petroleum Liquids0
Gasoline RVP 13
Gasoline RVP 10
Gasoline RVP 7
Crude oil RVP 5
Jet naphtha (JP-4)
Jet kerosene
Distillate fuel no. 2
Residual oil no. 6
Volatile Organic Liquids
Acetone
Acrylonitrile
Benzene
Carbon disulfide
Carbon tetrachloride
Chlorofona
Cyclohexane
1,2-Dichloroethane
Ethylacetate
Ethyl alcohol
Isopropyl alcohol
Methyl alcohol
Methylene chloride
Methylethyl ketone
Methylnethacrylate
1 , 1 , 1-Trichloroethane
Trichloroethylene
Toluene
Vinylacetate
Vapor
molecular
weight
g 60°F
62
66
68
50
80
130
130
190
58
53
78
76
154
119
84
99
88
46
60
32
85
72
100
133
131
92
86
Product
density (d),
Ib/gal
g 60°F
5.6
5.6
5.6
7.1
6.4
7.0
7.1
7.9
6.6
6.8
7.4
10.6
13.4
12.5
6.5
10.5
7.6
6.6
6.6
6.6
11.1
6.7
7.9
11.2
12.3
7.3
7.8
Condensed
vapor
density (w),
Ib/gal
@ 60°F
4.9
5.1
5.2
4.5
5.4
6.1
6.1
6.4
6.6
6.8
7.4
10.6
13.4
12.5
6.5
10.5
7.6
6.6
6.6
6.6
11.1
6.7
7.9
11.2
12.3
7.3
7.8
r
40°F
4.7
3.4
2.3
1.8
0.8
0.0041
0.0031
0.00002
1.7
0.8
0.6
3.0
0.8
1.5
0.7
0.6
0.6
0.2
0.2
0.7
3.1
0.7
0.1
0.9
0.5
0.2
0.7
1
50°F
5.7
4.2
2.9
2.3
1.0
0.0060
0.0045
0.00003
2.2
1.0
0.9
3.9
1.1
1.9
0.9
0.8
0.8
0.4
0.3
1.0
4.3
0.9
0.2
1.2
0.7
0.2
1.0
frue vapor
60°F
6.9
5.2
3.5
2.8
1.3
0.0085
0.0074
0.00004
2.9
1.4
1.2
4.8
1.4
2.5
1.2
1.0
1.1
0.6
0.6
1.4
5.4
1.2
0.3
1.6
0.9
0.3
1.3
pressure i
70°F
8.3
6.2
4.3
3.4
1.6
0.011
0.0090
0.00006
3.7
1.8
1.5
6.0
1.8
3.2
1.6
1.4
1.5
0.9
0.7
2.0
6.8
1.5
0.6
2.0
1.2
0.4
1.7
in psia at:
80°F
9.9
7.4
5.2
4.0
1.9
0.015
0.012
0.00009
4.7
2.4
2.0
7.4
2.3
4.1
2.1
1.7
1.9
1.2
0.9
2.6
8.7
2.1
0.8
2.6
1.5
0.6
2.3
90°F
11.7
8.8
6.2
4.8
2.4
0.021
0.016
0.00013
5.9
3.1
2.6
9.2
3.0
5.2
2.6
2.2
2.5
1.7
1.3
3.5
10.3
2.7
1.1
3.3
2.0
O.S
3.1
100°F
13.8
10.5
7.4
5.7
2.7
0.029
0.022
0.00019
7.3
4.0
3.3
11.2
3.8
6.3
3.2
2.8
3.2
2.3
1.8
4.5
13.3
3.3
1.4
4.2
2.0
1.0
4.0
«*
I
{"References 3-4.
For » more comprehensive listing of volatile organic liquids, see Reference 3.
CRVP = Reid vapor pressure in psia.
-------
components, P and P, , and the molecular weights of the pure
components, Ma and M^ My is calculated:
+M
where: P , by Raoult's law, is:
P — P Y •*• P Y
t ~ a a VT>
(2) True vapor pressures for organic liquids can be determined
from Figures 4.3-5 or 4.3-6, or Table 4.3-2. In order to
use Figures 4.3-5 or 4.3-6, the stored liquid temperature, T_,
must be determined in degrees Fahrenheit. T_ is deter-
mined from Table 4.3-3, given the average annual ambient
temperature, TA> in degrees Fahrenheit. True vapor pressure
is the equilibrium partial pressure exerted by a volatile
organic liquid, as defined by ASTM-D-2879 or as obtained
from standard reference texts. Reid vapor pressure is the
absolute vapor pressure of volatile crude oil and volatile
nonviscous petroleum liquids, except liquified petroleum
gases, as determined by ASTM-D-323.
(3) The vapor space in a cone roof is equal in volume to a
cylinder, which has the same base diameter as the cone and is
one third the height of the cone. If information is not
available, assume H equals one half tank height.
(4) For (.rude oil, Kr = 0.65. For all other organic liquids,
KC = i.o. L
Fixed roof tank working losses can be estimated from2:
= 2.40 x io-5 MVPVNKNKC
(2)
where:
Ly = fixed roof working loss (Ib/year)
My = molecular weight of vapor in storage tank (Ib/lb mole), see Note 1
to Equation 1
P = true vapor pressure at bulk liquid temperature (psia), see Note 2
to Equation 1
V = tank capacity (gal)
K = number of turnovers per year (dimensionless)
,,. _ Total throughput per year fgal)
Tank capacity, V fgal)
EMISSION FACTORS
C-9
9/85
-------
i
• •
• 7
• t
•10
•11
•12
• 13
• 14
• II
•20
j— 2
— 3
_4
— S
9
a
-10
1—16
140
130
120 *-=
110 —=
.3
a
100 —3
_3
a
90 -
•0 —=
Ul
§
c
"* V
70-1 g
•Ji
«o —s a
11
50 —= "
30 —=
20 —-
10 —E
0 —=1
Figure A.3-5. True vapor pressure (P) of crude oils (2-15 psi RVP).(
9/85
Evaporation Loss Sources
A. 3-9
C-10
-------
••— 0.20
— 0.30
fc»
1— 0.40
V-
1— 0.50
0.80
0.70
£— 0.80
£- 0.90
!— 1.00
r
IF
ft. i-
1.50
2.00
2.50
P- ISO
[=- 4.00
1
I
I
=- 6.00
— 7.00
— 8.00
• 9.00
•10.0
— 11.0
-12.0
•13.0
•14.0
•15.0
• 16.0
•17.0
-18.0
-19.6
-20.0
-21.0
-22.0
-23.0
-24.0
120 —
110
100 —
90-
80-
-. 5
to 1
r ui
- i-
~ a
SO-! §
- a
— \u
-41
30—
20-=
S - SLOPE Of THE ASTM DISTILLATION
CURVE AT 10 PERCENT EVAPORATED
= PEG F AT 18 PERCENT MINUS PEG F AT S PERCENT
10
IN THE ABSENCE OF DISTILLATION DATA
THE FOLLOWING AVERAGE VALUE OF 5 MAY BE USED:
MOTOR GASOLINE 3
AVIATION GASOLINE 2
LIGHT NAPHTHA 19-14 IB RVPI 3.5
NAPHTHA (2-8 LB RVPI 2.5
Nun DathvJ line illu«trjle» sample pfohtem for RVP - III poumh per square inch.
SOL'Ri'E: NomoyMph drawn frtxn the Jala of the Njtmnal Burvau of SlanUartb.
- .M. ami T. = f<: 5 F
Figure 4.3-6. True vapor presure (P) of refined petroleum liquids
like gasoline and napththas (1-20 psi RVP).6
4.3-10
EMISSION FACTORS
C-ll
9/85
-------
K.J = turnover factor (dimensionless) , see Figure 4.3-7
v = product factor (dimensionless), see Note 1
C
Note: (1) For crude oil, K,, = 0.84. For all other organic liquids,
Kc = 1.0.
TABLE 4.3-3. AVERAGE STORAGE TEMPERATURE (Tg)
AS A FUNCTION OF TANK PAINT COLOR
Tank color
Average storage temperature,
TS
White
Aluminum
Gray
Black
2.5
3.5
5.0
fReference 5.
T. is the average annual ambient temperature in
degrees Fahrenheit.
1.0
0.8
0.6
0.4
0.2
100 200
300
400
ANNUAL THROUGHPUT
CAPACITY
TURNOVERS PER TEAR -
Bote: For 36 turnovers per year or lees, KN - 1.0
9/85
Figure 4.3-7. Turnover factor (Kj^) for fixed roof tanks.
Evaporation Loss Sources 4.3-11
C-12
-------
Several methods are used to control emissions from fixed roof tanks.
Emissions from fixed roof tanks can be controlled by the installation of an
internal floating roof and seals to minimize evaporation of the product
being stored. The control efficiency of this method ranges from 60 to
99 percent, depending on the type of roof and seals installed and on the
type of organic liquid stored.
The vapor recovery system collects emissions from storage vessels and
converts them to liquid product. Several vapor recovery procedures may be
used, including vapor/liquid absorption, vapor compression, vapor cooling,
vapor/solid adsorption, or a combination of these. The overall control
efficiencies of vapor recovery systems are as high as 90 to 98 percent,
depending on the method used, the design of the unit, the composition of
vapors recovered, and the mechanical condition of the system.
Another method of emission control on fixed roof tanks is thermal
oxidation. In a typical thermal oxidation system, the air/vapor mixture is
injected through a burner manifold into the combustion area of an incin-
erator. Control efficiencies for this system can range from 96 to
99 percent.
External And Internal Floating Roof Tanks - Total emissions from floating
roof tanks are the sum of standing storage losses and withdrawal losses.
Standing storage loss from internal floating roof tanks includes rim seal,
deck fitting, and deck seam losses. Standing storage loss from external
floating roof tanks, as discussed here, includes only rim seal loss, since
deck fitting loss equations have not been developed. There is no deck seam
loss, because the decks have welded sections.
Standing storage loss from external floating roof tanks, the major
element of evaporative loss, results from wind induced mechanisms as air
flows across the top of an external floating roof tank. These mechanisms
may vary, depending upon the type of seals used to close the annular vapor
space between the floating roof and the tank wall. Standing storage emis-
sions from external floating roof tanks are controlled by one or two separate
seals. The first seal is called the primary seal, and the other, mounted
above the primary seal, is called the secondary seal. There are three basic
types of primary seals used on external floating roofs, mechanical (metallic
shoe), resilient (nonmetallic), and flexible wiper. The resilient seal can
be mounted to eliminate the vapor space between the seal and liquid surface
(liquid mounted), or to allow a vapor space between the seal and liquid
surface (vapor mounted). A primary seal serves as a vapor conservation
device by closing the annular space between the edge of the floating roof
and the tank wall. Some primary seals are protected by a metallic weather
shield. Additional evaporative loss may be controlled by a secondary seal.
Secondary seals can be either flexible wiper seals or resilient filled
seals. Two configurations of secondary seal are currently available, shoe
mounted and rim mounted. Although there are other seal system designs, the
systems described here compose the majority in use today. See Figure 4.3-8
for examples of primary and secondary seal configurations.
Typical internal floating roofs generally incorporate two types of
primary seals, resilient foam filled seals and wipers. Similar In design
4.3-12
EMISSION FACTORS
C-13
9/85
-------
HETALLIC WEATHER
SHIELD
ELASTOttERIC WIPER SEAL
NONCOHTACT IKTERNAL
FLOATIHC ROOF
PONTOOH
N* METAL SEAL RING
TANK WALL
POHTOON'
a. Liquid mounted seal with
weather shield.
RIH-HOUHTED
SECONDARY SEAL
c. Vapor mounted seal with
rim mounted secondary seal.
b. Elastomeric wiper seal.
d. Metallic shoe seal with shoe
mounted secondary seal.
Figure A.3-8. Primary and secondary seal configurations.1
9/85 Evaporation Loss Sources 4.3-13
C-14
-------
to those in external floating roof tanks, these seals close the annular
vapor space between the edge of the floating roof and the tank wall.
Secondary seals are not commonly used with internal floating roof tanks.
Deck fitting loss emissions from internal floating roof tanks result
from penetrations in the roof hy deck fittings, fixed roof column supports
or other openings. There are no procedures for estimating emissions fro*
external roof tank deck fittings. The most common fittings with relevance
to controllable vapor losses are described as follows:1
1. Access Hatch. An access hatch is an opening in the deck with a
peripheral vertical well that is large enough to provide passage of workers
and materials through the deck for construction or servicing. Attached to
the opening is a removable cover which may be bolted and/or gasketed to
reduce evaporative loss. On noncontact decks, the well should extend down
into the liquid to seal off the vapor space below the deck.
2. Automatic Gauge Float Well. A gauge float is used to indicate the
level of liquid within the tank. The float rests on the liquid surface,
inside a well that is closed by a cover. The cover may be bolted and/or
gasketed to reduce evaporation loss. As with other similar deck penetra-
tions, the well extends fixed into the liquid on noncontact decks.
3. Column Well. For fixed roofs that are column-supported, the
columns pass through deck openings with peripheral vertical wells. On
noncontact decks, the well should extend down into the liquid. The wells
are equipped with closure devices to reduce evaporative loss and may be
gasketed or ungasketed to further reduce the loss. Closure devices are
typically sliding covers or flexible fabric sleeve seals.
4. Ladder Well. Some tanks are equipped with internal ladders that
extend from a manhole in the fixed roof to the tank bottom. The deck
opening through which the ladder passes has a peripheral vertical well. On
noncontact decks, the well should extend down into the liquid. The wells
are typically covered with a gasketed or ungasketed sliding cover.
5. Roof Leg or Hanger Well. To prevent damage to fittings underneath
the deck and to allow for tank cleaning or repair, supports are provided to
hold the deck a predetermined distance off the tank bottom. These supports
consist of adjustable or fixed legs attached to the floating deck or hangers
suspended from the fixed roof. For adjustable legs or hangers, the load-
carrying element passes through a well or sleeve into the deck. With
noncontact decks, the well should extend into the liquid.
6. Sample Pipe or Well. A funnel-shaped sample well may be provided
to allow for sampling of the liquid with a sample thief. A closure is
typically located at the lower end of the funnel and frequently consists of
a horizontal piece of fabric slit radially to allow thief entry. The well
should extend into the liquid on noncontact decks. Alternatively, a sample
well may consist of a slottled pipe extending into the liquid, equipped
with a gasketed or ungasketed sliding cover.
4.3-14
EMISSION FACTORS
C-15
9/85
-------
7. Vacuum Breaker. A vacuum breaker equalizes the pressure of the
vapor space across the deck as the deck is either being landed on or floated
off its legs. The vacuum breaker consists of a well with a cover. Attached
to the underside of the cover is a guided leg of such length that it contacts
the tank bottom as the internal floating deck approaches. When in contact
with the tank bottom, the guided leg mechanically opens the breaker by
lifting the cover off the well; otherwise, the cover closes the well. The
closure may be gasketed or ungasketed. Because the purpose of the vacuum
breaker is to allow the free exchange of air and/or vapor, the well does
not extend appreciably below the deck.
The decks of internal floating roofs typically are made by joining
several sections of deck material, resulting in seams in the deck. To the
extent that these seams are not completely vapor tight, they become a
source of emissions. It should be noted that external floating roof tanks
and welded internal floating roofs do not have deck seam losses.
Withdrawal loss is another source of emissions from floating roof
tanks. This loss is the vaporization of liquid that clings to the tank
wall and is exposed to the atmosphere when a floating roof is lowered by
withdrawal of liquid. There is also clingage of liquid to columns in
internal floating roof tanks which have a column supported fixed roof.
Total Losses From Floating Roof Tanks - Total floating roof tank emissions
are the sura of rim seal, withdrawal, deck fitting, and deck seam losses.
It should be noted that external floating roof tanks and welded internal
floating roofs do not have deck seam losses. Also, there are no procedures
for estimating emissions from external floating roof tank deck fittings.
The equations provided in this Section are applicable only to freely vented
internal floating roof tanks or external floating roof tanks. The equations
are not intended to be used in the following applications: to estimate
losses from closed internal floating roof tanks (tanks vented only through
a pressure-vacuum vent); to estimate losses from unstabilized or boiling
stocks or from mixtures of hydrocarbons or petrochemicals for which the
vapor pressure is not known or cannot be readily predicted; or to estimate
losses from tanks in which the materials used in the seal system and/or
deck construction are either deteriorated or significantly permeated by the
stored liquid.6 Total losses may be written as:
L =
(3)
where:
L_ = total loss (Ib/yr)
L_ = rim seal loss (see Equation 4)
I*. & withdrawal loss (see Equation 5)
L_ = deck fitting loss (see Equation 6)
L_. = deck seam loss (see Equation 7)
9/85
Evaporation Loss Sources
C-16
4.3-15
-------
Rim Seal Loss - Rim seal loss from floating roof tanks can be estimated
by the following equation5-6:
= K
(4)
where:
LH = rim seal loss (Ib/yr)
Kg = seal factor (lb-mole/(ft (mi/hr)n yr)), see Table 4.3-4
V = average wind speed at tank site (mi/hr), see Note 1
n = seal related wind speed exponent (dimensionless), see Table 4.3-4
P* = vapor pressure function (dimensionless), see Note 2
P
P* = P~
where:
P = true vapor pressure at average actual liquid storage
temperature (psia), see Note 2 to Equation 1
PA = average atmospheric pressure at tank location (psia)
D = tank diameter (ft)
My - average vapor molecular weight (Ib/lb-mole), see Note 1 to
Equation 1
KC = Product factor (dimensionless), see Note 3
Notes: (1) If the wind speed at the tank site is not available, wind
speed data from the nearest local weather station may be
used as an approximation.
(2) P* can be calculated or read directly from Figure 4.3-9.
(3) For all organic liquids except crude oil, K,, = 1.0. For
crude oil, Kc = 0.4. c
Withdrawal Loss - The withdrawal loss from floating roof storage tanks
can be estimated using Equation 5.5-6
tw =
(0.943)QCW.
(5)
4.3-16
EMISSION FACTORS
C-17
9/85
-------
TABLE A.3-4. SEAL RELATED FACTORS FOR FLOATING ROOF TANKS'
Tank and seal type
Welded Tank
Riveted Tank
n
External floating roof tanks
Metallic shoe seal
Primary seal only
With shoe mounted secondary seal
With rim mounted secondary seal
Liquid mounted resilient seal
Primary seal only
With weather shield
With rim mounted secondary seal
Vapor mounted resilient seal
Primary seal only
With weather shield
With rim mounted secondary seal
Internal floating roof tanks
Liquid mounted resilient seal
Primary seal only e
With rim mounted secondary seal
Vapor mounted resilient seal
Primary seal only e
With rim mounted secondary seal
1.2
0.8
0.2
1.1
0.8
0.7
1.2
0.9
0.2
3.0
1.6
6.7
2.5
1.5
1.2
1.0
1.0
0.9
0.4
2.3
2.2
2.6
0
0
0
0
1.3
1.4
0.2
NA
NA
NA
NA
NA
NA
NA
NA
NA
1.5
1.2
1.6
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
aBased on emissions from tank seal systems in reasonably good working
condition, no visible holes, tears, or unusually large gaps between
the seals and the tank wall. The applicability of K decreases in
cases where the actual gaps exceed the gaps assumed Suring develop-
,ment of the correlation.
Reference 5.
jNA = Not Applicable.
Q _ f
elf tank specific information is not available about the secondary
seal on an internal floating roof tank, then assume only a primary
seal is present.
9/85
Evaporation Loss Sources
C-18
4.3-17
-------
1.0
.9
.8
.7
.6
.5
.3
u
1
2 0.1
M
09
.Oi
.07
.06
.06
.04
.03
.02
0.01
M-
X
/
X
X
£
Atmospheric pressure - 14.7 pounds per square inch absolute. —
1
1.0
9
8
7
6
5
01
09
08
07
.06
.05
.04
03
.02
1 2 3
nni
« 78 9 10 11
TRUE VAPOR PRESSURE. P (p*.l
12 13 14
NOT*: Ouhcd line illiotrato temple problem for P - 5.4 pounds per square inch absolute.
4.3-18
Figure 4.3-9. Vapor pressure function (P*).5
EMISSION FACTORS
C-19
9/85
-------
where:
= withdrawal loss (Ib/yr)
Q = throughput (bbl/year) (tank capacity [bbl] times annual turnover
rate)
C = shell clingage factor (bbl/1,000 ft2), see Table 4.3-5
WT = average organic liquid density (Ib/gal), see Note 1
L
D = tank diameter (ft)
N = number of columns (dimensionless), see Note 3
C
F = effective column diameter (ft) [column perimeter (ft)/n], see
C Note 4
Notes: (1) If W. is not known, an average value of 5.6 Ib/gallon can be
assumed for gasoline. An average value cannot be assumed
for crude oil, since densities are highly variable.
(2) The constant, 0.943, has dimensions of (1,000 ft3 x gal/bbl2)
(3) For self-supporting fixed roof or an external floating roof
tank:
For column supported fixed roof:
Nr = use tank specific information, or see Table 4.3-6.
u
(4) Use tank specific effective column diameter; or
Fc = 1.1 for 9 inch by 7 inch builtup columns,
0.7 for 8 inch diameter pipe columns, and
1.0 if column construction details are not
known.
Deck Fitting Loss - Deck fitting loss estimation procedures for external
floating roof tanks are not available. Therefore, the following procedure
applies only to internal floating roof tanks.
Fitting losses from internal floating roof tanks can be estimated by
the following equation6:
Lj, = FF P*MVKC (6)
9/85
Evaporation Loss Sources
C-20
4.3-19
-------
TABLE 4.3-5. AVERAGE CLINGAGE FACTORS (C) (bbl/1,000 ft2)*
Liquid
Gasoline
Single component
stocks
Crude oil
Light rust
0.0015
0.0015
0.0060
Shell condition
Dense rust
0.0075
0.0075
o.n^n
Gunite lined
0.15
0.15
n fin
^Reference 5.
If no specific information is available, these values can be assumed
to represent the most common condition of tanks currently in use.
TABLE 4.3-6. TYPICAL NUMBER OF COLUMNS AS A
FUNCTION OF TANK DIAMETER FOR INTERNAL FLOATING
ROOF TANKS WITH COLUMN SUPPORTED FIXED ROOFS3
Tank diameter range
D (ft)
Typical number
of columns, NC
0 < D S
85 < D 5
100 < D S
120 < D £
135 < D S
150 < D S
170 < D S
190 < D £
220 < D S
235 < D 3
270 < D S
275 < D S
290 < D £
330 < D £
360 < D £
85
100
120
135
150
170
190
220
235
270
275
290
330
360
400
1
6
7
8
9
16
19
22
31
37
43
49
61
71
81
4.3-20
Reference 1. This table was derived from a survey
of users and manufacturers. The actual number of
columns in a particular tank may vary greatly with
age, fixed roof style, loading specifications,
and manufacturing perogatives. Data in this table
should not supersede information on actual tanks.
EMISSION FACTORS
C-21
9/85
-------
where:
** =
F^. =
the fitting loss in pounds per year
total deck fitting loss factor (Ib-mole/yr)
where :
X = number of deck fittings of a particular type
i (i = 0,l,2,...,n) (dimensionsless)
K., = deck fitting loss factor for a particular type fitting
Ti (i = 0,1,2,..., n) (Ib-mole/yr)
n = total number of different types of fittings
(dimensionless)
P*, M.., K_ = as defined for Equation 4
The value of F., may be calculated by using actual tank specific data
for the number of each fitting type (N- ) and then Multiplying by the
fitting loss factor for each fitting (1C ).* Values of fitting loss factors
and typical number of fittings are presented in Table 4.3-7. Where tank
specific data for the number and kind of deck fittings are unavailable,
then F,, can be approximated according to tank diameter. Figures 4.3-10 and
4.3-11 present F_ plotted against tank diameter for column supportec fixed
roofs and self-supporting fixed roofs, respectively.
Deck Seam Loss - Deck seam loss applies only to internal floating roof
tanks with bolted decks. External floating roofs have welded decks and,
therefore, no deck seam loss. Deck seam loss can be estimated by the
following equation:6
(7)
where
L_ = deck seam losses (Ib/yr)
}L^ = deck seam loss per unit seam length factor (Ib-mole/ft yr)
= 0.0 for welded deck and external floating roof tanks,
0.34 for bolted deck
SD = deck seam length factor (ft/ft2)
seam
Sleek
9/85
Evaporation Loss Sources
4.3-21
C-22
-------
TABLE 4.3-7. SUMMARY OF INTERNAL FLOATING DECK FITTING LOSS
FACTORS (Kp) AND TYPICAL NUMBER OF FITTINGS (Nf)a
Deck fitting type
Deck
fitting loss
factor, K_.
(Ib-mole/yr)
Typical number
of fittings,
N,,
Access hatch
Bolted cover, gasketed
Unbolted cover, gasketed
Unbolted cover, ungasketed
Automatic gauge float well
Bolted cover, gasketed
Unbolted cover, gasketed
Unbolted cover, ungasketed
Column well
Builtup column-sliding cover, gasketed
Builtup column-sliding cover, ungasketed
Pipe column-flexible fabric sleeve seal
Pipe column-sliding cover, gasketed
Pipe column-sliding cover, ungasketed
Ladder well
Sliding cover, gasketed
Sliding cover, ungasketed
Roof leg or hanger well
Adjustable
Fixed
Sample pipe or well
Slotted pipe-sliding cover, gasketed
Slotted pipe-sliding cover, ungasketed
Sample well-slit fabric seal,
10% open area
1.6
25b
5.1
15,
28b
33.
47b
10
19
32
56h
76b
7.91
0
44
57
12*
(see Table 4.3-6)
(5 + -K
10
—]
600
Stub drain, 1 inch diameter 1.2 (-^-)
125
Vacuum breaker 1
Weighted mechanical actuation, gasketed 0.7
Weighted mechanical actuation, ungasketed 0.9
.Reference 1.
If no specific information is available, this value can be assumed to
Represent the most common/typical deck fittings currently used.
,D = tank diameter (ft).
Not used on welded contact internal floating decks.
4.3-22
EMISSION FACTORS
C-23
9/85
-------
MOO
WOO
7000
MOO
WOO
§600
WOO
4800
4000
awo
woo
awo
2000
1100
woo
800
•
•
•
•
L— -**
^
5^
MOEODECK(S«wNola)
A
f
1 1 1 1
/
//
/
//
/
[/
/
/
/
/ /
/
/
f / ^ WELDED DECK
/ F, - (0.0385) D* * (1 J92) I
/
/
/
' /
/
) + 134.2
10 WO 150 200 260
TANK DIAMETER. 0(W
360
BASIS- Finings include: (1) access hatch, with ungaskftrd. unbolted cover. (2) built-up column wells, with
Mgasketed. sliding cover. (3) adjustable deck legs; (4) gauge float well, with ungasketed. unbolted cover. (S)
ladder well, with ungasketcd sliding cover. (6) sample well, with slit fabric seal (10 percent open area); a) 1-
tacfa dUmettr stub drains (only on bohed deck); and (S) vacuum breaker, with gasketed weighted mechanical
actuation. This basis was derived from a survey of users and manufacturers. Other fittings may be typically used
within particular companies or organizations to reflect standards and/or specifications of that group. This figure
should mot supenede informatioo based on actual tank data.
NOTE: If no specific informition is available, assume bohed decks are the most common/typical type currently in
ase in tanks with column-supported fued roofs.
Figure A.3-10. Approximated total deck fitting loss factors (Ff) for
typical fittings in tanks with column supported fixed roofs and either a
bolted deck or a welded deck.6 This figure is to be used only when tank
specific data on the number an<\ kind of deck fittings are unavailable.
9/85
Evaporation Loss Sources
4.3-23
C-24
-------
4900
4000
3300
3000
2300
2000
1900
1000
900
' • • '
BOLTED DECK
f, - (0.0228) O* + (0.79) 0 + 109.2
•'••
\
7
•'''••••
V
\
WEIDEO DECK (SM Not*)
F, - (0.0132) Of + (0.79) 0 + 109.2
100
190
300
390
400
200 290
TANK DIAMETER. 0 (ft)
BASIS: Fittings include: (1) access hatch, with ungasketed, unbolted cover (2) adjustable deck legs- (3) gauge
float well, with ungasketed, unbofeed cover. (4) sample well, with slit fabric seal (10 percent open area): (5) I-
wch diameter stub drains (only on bolted deck): and (6) vacuum breaker, with gasketed weighted mechanical
actuation. This basil was derived from a survey of users and manufacturers. Other fittings may be typically used
within particular companies or organizations to reflect standards and/or specifications of that group. This figure
should not supersede information based on actual tank data.
NOTES: If no specific informatioa is available, assume welded decks are the most common/typical type currently
in use in tanks with self-supporting fixed roofs.
Figure 4.3-11. Approximated total deck fitting loss factors (F ) for
typical deck fittings in tanks with self-supporting fixed roofsfand
either a bolted deck or a welded deck.6 This figure is to be used only
when tank specific data on the number and kind of deck fittings are
unavailable.
4.3-24
EMISSION FACTORS
C-25
9/85
-------
where:
L = total length of deck seams (ft)
seam
A. . = area of deck (ft2) = n D2/4
deck
D, P*, My, KC = as defined for Equation 4
If the total length of the deck seam is not known, Table 4.3-8 can be
used to determine Sn. Where tank specific data concerning width of deck
sheets or size of deck panels are unavailable, a default value for S^ can
be assigned. A value of 0.20 (ft/ft2) can be assumed to represent tfie most
common bolted decks currently in use.
TABLE 4.3-8. DECK SEAM LENGTH FACTORS
FOR TYPICAL
DECK CONSTRUCTIONS FOR INTERNAL FLOATING ROOF TANKS
Deck construction
Typical deck seam
length factor,
SD (ft/ft2)
Continuous sheet construction
5 ft wide
6 ft wide
7 ft wide
Panel construction
5 x 7.5 ft rectangular
5 x 12 ft rectangular
0.20^
0.17
0.14
0.33
0.28
Reference 6. Deck seam loss applies to bolted decks only.
b ,
Sn = -t where W = sheet width (ft)
» W
clf no specific information is available, these
factors can be assumed to represent the most common bolted
decks currently in use.
D
gH. where W = panel width (ft) and L = panel
LW length (ft)
Pressure Tanks - Losses occur during withdrawal and filling operations in
low pressure (2.5 to 15 psig) tanks when atmospheric venting occurs. High
pressure tanks are considered closed systems, with virtually no emissions.
Vapor recovery systems are often found on low pressure tanks. Fugitive
losses are also associated with pressure tanks and their equipment, but
9/85
Evaporation Loss Sources
C-26
4.3-25
-------
with proper system maintenance, these losses are considered insignificant
No appropriate correlations are available to estimate vapor losses from
pressure tanks. *
Variable Vapor Space Tanks - Variable vapor space filling losses result
when vapor is displaced by liquid during filling operations. Since the
variable vapor space tank has an expandable vapor storage capacity, this
loss is not as large as the filling loss associated with fixed roof tanks.
Loss of vapor occurs only when the tank's vapor storage capacity is
6XC
Variable vapor space system filling losses can be estimated from:3-7
= (2.40 x 10-2) _.
(8)
where:
Ly = variable vapor space filling loss (lb/103 gal throughput)
My = molecular weight of vapor in storage tank (Ib/lb-mole), see Note 1
to Equation 1
P = true vapor pressure at bulk liquid conditions (psia), see Note 2
to Equation 1
Vj = volume of liquid pumped into system, throughput (bbl)
V2 = volume expansion capacity of system (bbl), see Note 1
N2 = number of transfers into system (dimensionless), see Note 2
Notes: (1) V2 is the volume expansion capacity of the variable vapor
space achieved by roof lifting or diaphragm flexing.
(2) Nj; is the number of transfers into the system during the
time period that corresponds to a throughput of Vj.
The accuracy of Equation 8 is not documented. Special tank operating
conditions may result in actual losses significantly different from the
estimates provided by Equation 8. It should also be noted that, although
not developed for use with heavier petroleum liquids such as kerosenes and
fuel oils, the equation is recommended for use with heavier petroleum
liquids in the absence of better data.
4.3.3 Sample Calculations
Three sample calculations to estimate emission losses are provided,
fixed roof tank, external floating roof tank, and internal floating roof
4.3-26
EMISSION FACTORS
C-27
9/85
-------
tank. Note that the same tank size, tank painting, stored product, and
ambient conditions are employed in each sample calculation. Only the type
of roof varies.
Problem I - Estimate the total loss from a fixed roof tank for 3 months
based on data observed during the months of March, April and May and given
the following information:
Tank description:
Stored product:
Ambient conditions:
Calculation:
Fixed roof tank; 100 ft diameter; 40 ft height;
tank shell and roof painted specular aluminum
color.
Motor gasoline (petroleum liquid); Reid vapor
pressure (RVP), 10 psia; 6.1 Ib/gal liquid
density; no vapor or liquid composition given;
375,000 bbl throughput for the 3 months.
60°F average ambient temperature for the 3 months;
10 mi/hr average wind speed at the tank site for
the 3 months; assume 14.7 psia atmospheric pres-
sure; average maximum daily temperature, 68°F;
average minimum daily temperature, 47°F.
Total loss = breathing loss + working loss.
(a) Breathing Loss - Calculate using Equation 1.
iP.68
where:
T. =
= 2.26 x 10-*
= breathing loss (Ib/yr)
= 66 Ib/lb-mole (from Table 4.3-2 and RVP 10 gasoline)
60°F (given)
(1)
T = 62.5°F (from Table 4.3-3, for an aluminum color tank in good
S °
condition and TA = 60°F)
RVP = 10 psia (given)
14.7 psia (assumed)
P =
t\
P
= 5.4 psia (from Figure 4.3-6, for 10 psia Reid vapor pressure
gasoline and Tg = 62.5°F)
= 100 ft (given)
= 20 ft (assumed H = % tank height)
9/85
Evaporation Loss Sources
C-28
4.3-27
-------
AT = 21°F (average daily maximum, 68°F, minus average daily
minimum, 47°F)
Fp = 1.20 (from Table 4.3-1 and given specular aluminum tank color)
C =1.0 (tank diameter is larger than 30 ft)
KC = 1.0 (value appropriate for all organic liquids except crude oil)
LB (Ib/yr) =
/ 5 4 \ °*68
(2.26 X 10-2)(66)|., _'_ . I finnll.73/'?ni0.5I/'oi\0.50/, **\,, «N/-^ QN _
75,323 Ib/yr
For the 3 months, Lfi = 75^323 = 18,831 Ib
Working Loss - Calculate using Equation 2.
Ly = 2.40 x 10-5 MVPVNKNKC (2)
where:
Ly = working loss (Ib/yr)
^ = 66 Ib/lb-mole (from Table 4.3-1 and RVP 10 gasoline)
P = 5.4 psia (calculated for breathing loss above)
V = 2,350,000 gal
where: V (cubic feet) = n D* h
n = 3.141
D = 100 ft
h = 40 ft
v _ 3.141(100)2(40^
4
= 314,100 cubic ft
V (gal) = (7.48 gal/ft3) V (ft3)
V (gal) = 7.48 (314,100) = 2,349,468 gal, round to 2,350,000 gal
jj _ throughput/year
tank volume
- (375.000 bbl)(4)(42 gal/bbl) ^ o
2,350,000 gal = 26'8
4'3"28 EMISSION FACTORS 9/85
C-29
-------
K., = 1.0 (from Figure 4.3-7 and N = 26.8)
K = 1.0 (value appropriate for all organic liquids except crude oil)
C
Ly (Ib/yr) =
2.40 x 10-5 (66)(5.4)(2.35xl06)(26.8)(1.0)(1.0) = 538,705 Ib/yr
For the 3 months, L. = 538>705 = 134,676 Ib
* 4
(c) Total Loss for the 3 months -
= 18,831 + 134,676
= 153,507 Ib
Problem II - Estimate the total loss from an external floating roof tank
for 3 Months, based on data observed during the months of March, April and
May and given the following information:
Tank description:
Stored product:
External floating roof tank with a mechanical
(metallic) shoe primary seal in good condition;
100 ft diameter; welded tank; shell and roof
painted aluminum color.
Motor gasoline (petroleum liquid); Reid vapor
pressure, 10 psia; 6.1 Ib/gal liquid density; no
vapor or liquid composition given; 375,000 bbl
throughput for the 3 months.
Ambient conditions: 60°F average ambient temperature for the 3 months;
10 mi/hr average wind speed at tank site for the
3 months; assume 14.7 psia atmospheric pressure.
Calculation:
Total loss = rim seal loss + withdrawal loss
deck fitting loss + deck seam loss.
(a) Rim Seal Loss - Calculate the yearly rim seal loss from Equation 4.
(4)
where:
= rim seal loss (Ib/yr)
K =1.2 (from Table 4.3-4, for a welded tank with a mechanical shoe
S primary seal; note that external floating roofs have welded decks
only)
9/85
Evaporation Loss Sources
4.3-29
C-30
-------
n =
1.5 (from Table 4.3-4, for a welded tank with a mechanical shoe
primary seal)
V = 10 mi/hr (given)
TA = 60°F (given)
Tg = 62.5°F (from Table 4.3-3, for an aluminum color tank in good
condition and TA = 60°F)
A
RVP = 10 psia (given)
P
P ^
A
P* =
5.4 psia (from Figure 4.3-6, for 10 psia Reid vapor pressure
gasoline and T_ = 62.5°F)
O
14.7 psia (assumed)
£33) .0-1M
(can also be determined from Figure 4.3-9 for P = 5.4 psia)
D = 100 ft (given)
My = 66 Ib/lb-mole (from Table 4.3-2 and RVP 10 gasoline)
KC = 1.0 (value appropriate for all organic liquids except crude oil)
To calculate yearly rim seal loss based on the 3 month data, multiply
the Kg, KC, P*, D, My, and V^ values, as in Equation 4.
1^ = (1.2)(10)1-5(0.114)(100)(66)(1.0)
= 28,551 Ib/yr
For the 3 months, L = (2*}'551) = 7,133 lb
(b) Withdrawal Loss - Calculate the withdrawal loss from Equation 5.
= (0.943)
(5)
where:
-3-30
= withdrawal loss (Ib/yr)
EMISSION FACTORS
C-31
9/85
-------
Q = 3.75 x 10s bbl for 3 months = 1.5 x 106 bbl/yr (given)
C = 0.0015 bbl/1,000 ft2 (from Table 4.3-5, for gasoline in a steel
tank with light rust assumed for tank in good condition as given)
WT =6.1 Ib/gal (given)
it
D = 100 ft (given)
N = 0 (value for external floating roof tanks)
C
F_ = 1.0 (default value when column diameter is unknown; however,
there are no columns in this tank, and an FC value is used only
for calculation purposes)
To calculate yearly withdrawal loss, use Equation 5.
T „,., N (0.943)(1.5 x 106)(0.0015)(6.1) (0.0)0-0)
L (Ib/yr) = * j^ 1 + 100
= 129 Ib/yr
To calculate withdrawal loss for 3 months, divide by 4.
For the 3 months, L^ = 129/4 = 32 Ib
(c) Deck Fitting Loss - As stated, deck fitting loss estimation procedures
for external floating roof tanks are not available. The deck fittirg
loss for the 3-month period is unknown and will be assumed to 0.
(d) Deck Seam Loss - External floating roof tanks have welded decks;
therefore, there are no deck seam losses.
(e) Total Loss for the 3 months - Calculate the total loss using Equation 3.
LT = LR + *V + LF * LD
where:
L_ = total loss (lb/3 mo)
L_ = 7,138 lb/3 mo
Ly = 32 lb/3 mo
L_. = 0 (assumed)
LT = 7,138 + 32 + 0 + 0
= 7,170 lb/3 mo
9/85
Evaporation Loss Sources
C-32
4.3-31
-------
Problem III - Estimate the total loss for 3 months from an internal
floating roof tank based on data observed during the months of March, April
and May and given the following information:
Tank description:
Stored product:
Freely vented internal floating roof tank;
contact deck made of welded 5 ft wide continuous
sheets, with vapor mounted resilient seal; the
fixed roof is supported by 6 pipe columns; tank
shell and roof painted aluminum; 100 ft diameter.
Motor gasoline (petroleum liquid); Reid vapor
pressure of 10 psia; 6.1 Ib/gal liquid density;
no vapor or liquid composition given; 375,000 bbl
throughput for the 3 months.
Ambient conditions: 60°F average ambient temperature for the 3 months;
10 mi/hr average wind speed at the tank site for
the 3 months; assume 14.7 psia atmospheric
pressure.
Calculation:
Total loss = rim seal loss + withdrawal loss +
deck fitting loss + deck seam loss.
(a) Rim Seal Loss - Calculate yearly rim seal loss using Equation 4.
= KSV"P*DMVKC
(A)
where:
L., = rim seal loss (Ib/yr)
Kg = 6.7 (from Table 4.3-4; for a welded tank with a vapor mounted
resilient seal and no secondary seal)
V = 10 mi/hr (given)
n = 0 (from Table 4.3-4 for a welded tank with a vapor mounted
resilient seal and no secondary seal)
P* = 0.114 (calculated in Problem II)
D = 100 ft (given)
My = 66 Ib/lb-mole (from Table 4.3-2 and RVP 10 gasoline)
KC = 1.0 (value appropriate for all organic liquids except crude oil)
For the 3 months,
= 6.7(10)°(0.114)(100)(66)(1.0)
= 5,041 Ib/yr
= 5>°41 = 1,260 Ib
4.3-32
EMISSION FACTORS
9/85
C-33
-------
(b) Withdrawal Loss - Calculate using Equation 5.
= (0.943)
QCW.
(5)
where:
I., = withdrawal loss (Ib/yr)
Q = 1.5 x 106 bbl/yr (calculated in Problem II)
C = 0.0015 bbl/1,000 ft2 (from Table 4.3-5, light rust)
W, = 6.1 Ib/gal (given)
jj
D = 100 ft (given)
Nc = 6 (given)
Fp = 1.0 (default value since column construction details are unknown)
(0.943)(1.5xl06)(0.0015)(6.1)
100
100
= 137 Ib/yr
For the 3 months, Ly = ^- = 34 Ib
(c) Deck Fitting Loss - Calculate using Equation 6.
(6)
where:
= deck fitting loss (Ib/yr)
Fv = 700 Ib-mole/yr (interpreted from Figure 4.3-10, given tank diameter
F of 100 ft)
P* = 0.114 (calculated in Problem II)
M.. = 66 Ib/lb-mole (from Table 4.3-2 and RVP 10 gasoline)
Kr = 1.0 (value appropriate for all liquid organics except crude oil)
v»
Ij. = 700(0. 114)(66)(1.0)
= 5,267 Ib/yr
For the 3 months,
= 1,317 Ib
9/85
Evaporation Loss Sources
4.3-33
C-34
-------
(d) Deck Seam Loss - Calculate using Equation 7.
(7)
where:
= deck seam loss (Ib/yr)
= 0 for welded seam deck, therefore
Total Loss for 3 months - Calculate from Equation 3.
LT
(3)
where:
Lj. = total loss (Ib/yr)
LR =1,260 lb/3 mo
Ly = 34 lb/3 mo
LF = 1,317 lb/3 mo
LD=0
LT = 1,260 + 34 + 1,317 + 0
For the 3 months, LT = 2,611 Ib
References for Section 4.3 -
!• VOC Emissions From Volatile Organic Liquid Storage Tanks -
Background
2.
3.
4.
5.
Information for Proposed Standards. EPA-450/3-81-QQ3a> II. S
mental Protection Agency, Research Triangle Park, NC, July 1984.
Background Documentation for Storage of Organic Liquids. EPA Contract
No. 68-02-3174, TRW Environmental, Inc., Research Triangle Park. NC
May 1981.
Petrochemical Evaporation Loss From Storage Tanks. Bulletin No. 2523,
American Petroleum Institute, New York, NY, 1969.
Henry C. Barnett, et al., Properties of Aircraft Fuels. NACA-TN 3276,
Lewis Flight Propulsion Laboratory, Cleveland, OH, August 1956.
Evaporation Loss From External Floating Roof Tanks. Second Edition,
Bulletin No. 2517, American Petroleum Institute, Washington, D. C.,
1980.
4.3-34
EMISSION FACTORS
9/85
C-35
-------
6. Evaporation Loss From Internal Floating Roof Tanks, Third Edition,
Bulletin No. 2519, American Petroleum Institute, Washington, D. C.,
1983.
7. Use of Variable Vapor Space Systems To Reduce Evaporation Loss,
Bulletin No. 2520, American Petroleum Institute, New York, NY, 1964.
9/85
Evaporation Loss Sources
C-36
4.3-35
-------
APPENDIX D
TABLE OF UNCONTROLLED FUGITIVE EMISSION
FACTORS FOR THE SYNTHETIC ORGANIC
CHEMICALS MANUFACTURING INDUSTRY
D-l
-------
TABLE D-l. AVERAGE FUGITIVE EMISSION FACTORS FOR THE
SYNTHETIC ORGANIC CHEMICALS MANUFACTURING INDUSTRY (SOCMI)0
Fugitive-emission source
Emission factor (Ib/h)
Pump seals
Light liquids
Heavy liquids
Valves (in-line)
Gas
Light liquid
Heavy liquid
Gas safety-relief valves
Open-ended lines
Flanges
Sampling connections
Compressor seals
0.11
0.047
0.012
0.016
0.00051
0.23
0.0037
0.0018
0.033
0.50
Emission Factors for Equipment Leaks of VOC and HAP,
EPA-450/3-86-002, January 1986, Table 3-4. These factors
take into account a leak frequency determined from field
studies in the synthetic organic chemicals manufacturing
industry. Light liquids have a vapor pressure greater
than 0.1 psia at 100°F.
D-2
-------
TABLE D-2. LEAKING AND NONLEAKING AVERAGE FUGITIVE EMISSION FACTORS FOR THE
SYNTHETIC ORGANIC CHEMICALS MANUFACTURING INDUSTRY (SOCMI)3
Fugitive-
emission source
Leaking (>10,000 ppm)
emission factor (lb/h)
Nonleaking (<10,000 ppm)
emission factor (Ib/h)
Pump seals
light liquids
Heavy liquids
Valves (in-line)
Gas
Light liquid
Heavy liquid
Gas safety-relief
valves
Open-ended lines
Flanges
Sampling connec-
tions
Compressor seals
0.96
0.85
0.099
0.19
0.00051
3.72
0.0263
0.083
3.54
0.026
0.030
0.0011
0.0038
0.00051
0.098
0.0033
0.00013
0.20
Emission Factors for Equipment Leaks of VOC and HAP, EPA-450/3-86-002,
January 1986, Table 3-3. These factors take into account a leak frequency
determined from field studies in the synthetic organic chemicals manufac-
turing industry. Light liquids have a vapor pressure greater than
0.1 psia at 100°F.
D-3
-------
-------
APPENDIX E
Table of Contents of EPA Publication
AP-42, Volume I
"Compilation of Air Pollutant Emission Factors"
E-l
-------
CONTENTS
INTRODUCTION
1 .
2.
3.
4.
5.
EXTERNAL COMBUSTION SOURCES
1 .7 Lignite Combustion •
1.11 Waste Oil Disposal
SOLID WASTE DISPOSAL
2.1 Refuse Incineration •
2.2 Automobile Body Incineration
2 .3 Conical Burners
INTERNAL COMBUSTION ENGINE SOURCES
Glossary Of Terms
3.1 Highway Vehicles
3.2 Off Highway Mobile Sources
3 .3 Off Highway Stationary Sources
EVAPORATION LOSS SOURCES °"
4 .3 Storage Of Organic Liquids
4.4 Transportation And Marketing Of Petroleum Liquids .....
4.5 Cutback Asphalt, Emulsified Asphalt And Asphalt Cement
4.6 Solvent Degreasing
4 .7 Waste Solvent Reclamation
4.9 Graphic Arts '
4 .11 Textile Fabric Printing
CHEMICAL PROCESS INDUSTRY
5.1 Adipic Acid •
5.2 Synthetic Ammonia
5 .3 Carbon Black
5.5 Chlor-Alkali
5.8 Hydrofluoric Acid
5.9 Nitric Acid "
Page
,1
. . 1.1-1
. . 1.1-1
. . 1.2-1
. . 1.3-1
. . 1.4-1
. . 1.5-1
.. 1.7-1
In i
. . 1.11-1
.. 2.0-1
.. 2.2-1
.. 2.4-1
3-1
\fr\ 1 T T
.. 4.1-1
. . 4.4-1
.. 4.5-1
. .. 4.9-1
... 4.10-1
. .. 5.1-1
. .. 5.1-1
50 i
. .. 5.4-1
. .. 5.5-1
. .. 5.6-1
57 n
5Q -I
S 9-1
E-2
-------
Page
5,
5,
10
11
5.12
5
5
5
5
5
5,
5,
5,
5,
5,
5,
13
14
15
16
17
18
19
20
21
22
23
5.24
FOOD
6.1
6.2
6.3
6.4
6.5
6.6
6.7
6.8
6.9
6.10
6.11
6.12
6.13
6.14
6.15
6.16
6.17
6.18
Paint Ard Varnish 5.10-1
Phosphoric Acid 5.11-1
Phthalic Anhydride 5.12-1
Plastics 5.13-1
Printing Ink 5.14-1
Soap And Detergents 5.15-1
Sodium Carbonate 5.16-1
Sulfuric Acid 5.17-1
Sulfur Recovery 5.18-1
Synthetic Fibers 5.19-1
Synthetic Rubber 5.20-1
Terephthalic Acid 5.21-1
Lead Alkyl 5.22-1
Pharmaceuticals Production 5.23-1
Maleic Anhydride 5.24-1
AND AGRICULTURAL INDUSTRY
Alfalfa Dehydrating
Coffee Roasting
Cotton Ginning
Feed And Grain Mills And Elevators
Fermentation
Fish Processing
Meat Smokehouses
Ammonium Nitrate Fertilizers
Orchard Heaters
Phosphate Fertilizers 6
Starch Manufacturing 6
Sugar Cane Processing 6
Bread Baking 6
Urea 6
Beef Cattle Feedlots 6
Defoliation And Harvesting Of Cotton 6
Harvesting Of Grain 6
Ammonium Sulfate 6
METALLURGICAL INDUSTRY
7.1 Primary Aluminum Production
7.2 Coke Production
7.3 Primary Copper Smelting
7 .4 Ferroalloy Production ...
7 .5 Iron And Steel Production
7.6 Primary Lead Smelting
7.7 Zinc Smelting
7.8 Secondary Aluminum Operations
7.9 Secondary Copper Smelting And Alloying
7.10 Gray Iron Foundries 7
7.11 Secondary Lead Smelting 7
7.12 Secondary Magnesium Smelting 7
7.13 Steel Foundries 7
7.14 Secondary Zinc Processing 7
7.15 Storage Battery Production 7
6.1-1
6.1-1
6.2-1
6.3-1
6.4-1
6.5-1
6.6-1
6.7-1
6.8-1
6.9--1
.10-1
.11-1
.12-1
.13-1
.14-1
.15-1
.16-1
.17-1
.18-1
7.1-1
7.1-1
7.2-1
7.3-1
7.4-1
7.5-1
7.6-1
7.7-1
7.8-1
7.9-1
.10-1
.11-1
.12-1
.13-1
.14-1
.15-1
E-3
-------
Page
7.16 Lead Oxide And Pigment Production 7.16-1
7.17 Miscellaneous Lead Products 7.17-1
7.18 Leadbearing Ore Crushing And Grinding ».. 7.18-1
8. MINERAL PRODUCTS INDUSTRY 8.1-1
8.1 Asphaltic Concrete Plants 8.1-1
8.2 Asphalt Roofing 8.2-1
8.3 Bricks And Related Clay Products 8.3-1
8.4 Calcium Carbide Manufacturing 8.4-1
8.5 Castable Refractories 8.5-1
8.6 Portland Cement Manufacturing 8.6-1
8.7 Ceramic Clay Manufacturing 8.7-1
8.8 Clay And Fly Ash Sintering 8.8-1
8.9 Coal Cleaning 8.9-1
8.10 Concrete Batching 8.10-1
8.11 Glass Fiber Manufacturing 8.11-1
8.12 Frit Manufacturing 8.12-1
8.13 Glass Manufacturing 8.13-1
8.14 Gypsum Manufacturing 8.14-1
8.15 Lime Manufacturing . 8.15-1
8.16 Mineral Wool Manufacturing 8.16-1
8.17 Perlite Manufacturing 8.17-1
8.18 Phosphate Rock Processing 8.18-1
8.19 Construction Aggregate Processing 8.19-1
8.20 [Reserved] 8.20-1
8.21 Coal Conversion 8.21-1
8.22 Taconite Ore Processing 8.22-1
8.23 Metallic Minerals Processing 8.23-1
8.24 Western Surface Coal Mining 8.24-1
9. PETROLEUM INDUSTRY 9.1-1
9.1 Petroleum Refining 9.1-1
9.2 Natural Gas Processing 9.2-1
10. WOOD PRODUCTS INDUSTRY 10.1-1
10.1 Chemical Wood Pulping 10.1-1
10.2 Pulpboard 10.2-1
10.3 Plywood Veneer And Layout Operations 10.3-1
10.4 Woodworking Waste Collection Operations 10.4-1
11. MISCELLANEOUS SOURCES 11.1-1
11.1 Forest Wildfires 11.1-1
11.2 Fugitive Dust Sources 11.2-1
11.3 Explosives Detonation 11.3-1
APPENDIX A Miscellaneous Data And Conversion Factors A-l
E-4
-------
APPENDIX F
UNIT CONVERSION FACTORS
(FROM U.S. COAST GUARD COMMANDANT INSTRUCTION
M.I 6465.12A
F-l
-------
CONVERSION FACTORS
To Convert
L*ngth
inches
inches
feet
feet
feet
feet
yards
yards
miles (U.S. statute)
miles (U.S. statute)
miles (U.S. statute)
miles (U.S. statute)
meters
meters
meters
nautical miles
ATM
square inches
square inches
square feet
square feet
square meters
square mites
square yards
Volom*
cubic inches
cubic inches
cubic feet
cubic feet
cubic feet
cubic meters
liters
quarts (U.S. liquid)
U.S. gallons
U.S. gallons
U.S. gallons
barrels (petroleum)
Imperial gallons
milliliters
Tim*
seconds
seconds
seconds
minutes
minutes
minutes
hours
hours
hours
To
Multiply by
millimeters
feet
inches
meters
yards
miles (U.S. statute)
feet
miles (U.S. statute)
feet
yards
meters
nautical miles
feet
yards
miles (U.S. statute)
miles (U.S. statute)
square centimeters
square feet
square inches
square meters
square feet
square yards
square feet
cubic centimeters
cubic feet
cubic inches
cubic meters
U.S. gallons
cubic feet
quarts (U.S. liquid)
liters
barrels (petroleum)
cubic feet
Imperial gallons
U.S. gallons
U.S. gallons
cubic centimeters
minutes
hours
days
seconds
hours
days
seconds
minutes
days
25.4*
O.OB33
12*
0.3048*
0.3333
0.0001894
3*
0.0005682
5280*
1760*
1609
0.868
3.281
1.094
0.0006214
1.152
6.452
0.006944
144*
0.09290
10.76
3.097.600*
9*
16.39
0.0005787
1728*
0.02832
7.481
35.31
1.057
0.9463
0.02381
0.1337
0.8327
42*
1.201
1*
0.01667
0.0002778
0.00001157
60*
0.01667
0.0006944
3600*
60*
0.04167
•Exact value
F-2
-------
(Continued)
To Convert
Mass or Weight
pounds
pounds
pounds
pounds
tons (short)
tons (metic)
tons (long)
kilograms
tonnes (metic tons)
Energy
calories
calories
Btu (British thermal units)
Btu
joules
joules
Velocity
feet per second
feet per second
feet per second
meters per second
meters per second
miles per hour
miles per hour
knots
knots
knots
pounds per cubic foot
grams per cubic centimeter
grams per cubic centimeter
kilograms per cubic meter
Pressure
pounds per square inch (absolute)
(psia)
psia
psia
psia
pounds per square inch (gauge)
(psig)
millimeters of mercury (torr)
millimeters of mercury (torr)
inches of water
kilograms per square centimeter
inches of water
kilograms per square centimeter
atmospheres
kilograms per square centimeter
atmospheres
bars
kilonewtons per square meter (kN/
m2)
bars
kilonewtons per square meter (kN/
m2)
bars
Viscosity
centipoises
pounds per foot per second
'Exact value
To
Multiply by
kilograms
short tons
long tons
metric tons
pounds
pounds
pounds
pounds
kilograms
Btu
joules
calories
joules
calories
Btu
meters per second
miles per hour
knots
feet per second
miles per hour
meters per second
feet per second
meters per second
miles per hour
feet per second
ensity
grams per cubic centimerter
pounds per cubic foot
kilograms per cubic meter
grams per cubic centimeter
atmospheres
inches of water
millimeters of mercury (torr)
psia
psia
kN/m2
psia
millimeters of mercury (torr)
kN/m2
atmospheres
kN/m2
psia
psia
kN/m2
psia
atmospheres
atmospheres
kilograms per square centimeter
pounds per foot per second
centipoises
F-3
0.4536
0.0005*
0.0004464
0.0004536
2000*
2205
2240*
2.205
1000*
0.003968
4.187
252.0
1055
0.2388
0.0009479
0.3048
0.6818
0.5921
3.281
2.237
0.4470
1.467
0.5148
1.151
1.689
0.01602
62.42
1000*
0.001
kilonewtons per square meter (kN/m2) 6.895
0.0680
27.67
51.72
add 14.70
0.01934
0.1333
0.03614
735.6
0.2491
0.9678
101.3
14.22
14.70
100*
0.1450
0.9869
0.009869
1.020
0.0006720
1488
-------
(Contlnutd)
To Convert
centipoises
centipoises
poises
grams per centimeter per second
newton seconds per square meter
Thermal Conductivity
Btu per hour per foot per 'F
Btu per hour per foot per 'F
watts per meter-kelvin
kilocalories per hour per meter per
•c
kilocalories pef hour per meter per
•C
Heat Capacity
Btu per pound per *F
Btu per pound per "F
Joules per kilogram-Kelvin
calories per gram per 'C
Concentration (In watar solution)
parts per milton (ppm)
milligrams per liter
milligrams per cubic meter
grams per cubic centimeter
grams per cubic centimeter
pounds per cubic foot
Temperature
degrees Kelvin CK)
degrees Rankine ('R)
degrees centigrade ('C)
degrees Fahrenheit (*F)
To
poises
newton seconds per square meter
grams per centimeter per second
poises
centipoises
watts per meter-kelvin
kilocalories per hour per meter per *C
Btu per hour per foot per 'F
watts per meter-kelvin
Btu per hour per foot per *F
calories per gram per °C
joules per kilogram-Kelvin
Btu per pound per *F
Btu per pound per *F
milligrams per liter
ppm
grams per cubic centimeter
milligrams per cubic meter
pounds pef cubic foot
grams per cubic centimeter
degrees Rankine (*R)
degrees Kelvin ('«)
degrees Fahrenheit (*F)
degrees centigrade (*C)
Multiply by
degrees centigrade (*C)
degrees Fahrenheit (4F)
Flow
cubic feet per second
U.S. gallons per minute
Universal Gaa Constant (R)
8.314 joules per gram mole-
ketvin
1.987 calories per gram mole-
kervin
1.987 Btu per pound mole per
•F
10.73 psia-cubic feet per
pound mole per *F
82.057 atm-cubic centimeters
per gram mole-kelvin
62.361 millimeters mercury liter
per gram mole-kelvin
degrees Kelvin CK)
degrees Rankine (*R)
U.S. gallons per minute
cubic feet per second
O.OT
0.001'
r
r
1000*
1.731
1.488
0.5778
1.163
0.6720
r
4187
0.0002388
r
1*
r
1X10*
62.42
0.01602
1.8*
0.5556
first multiply by 1.8.
then add 32
first subtract 32,
then multiply by
0.5556
add 273.2
add 459.7
448.9
0.002228
* Exact value *° "
•£U. S.GOVERNMENT PRINTING OFF ICEI I 989-617-O03/84335
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