United States
Environmental Protection
Agency
Office of Pesticides
and, Toxic Substances
EPA 560/4-88-004f
March 1988
&EPA Title HI Section 313
Release Reporting
Guidance
Estimating Chemical Releases From
Formulation of Aqueous Solutions
Emergency Planning and
Community Right-to-Know Act of 1986
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Estimating Chemical Releases From
Formulation of Aqueous Solutions
Formulators of aqueous solutions may be
required to report annually any releases to
the environment of certain chemicals regu-
lated under Section 313, Title III, of the
Superfund Amendments and Reauthorization
Act (SARA) of 1986. If your facility is classi-
fied under SIC codes 20 through 39 and has
10 or more full-time employees, for calendar
year 1987 you must report all environmental
releases of any Sectipn 313-listed chemical or
chemical category manufactured or processed
by your facility in an amount exceeding
75,000 pounds per year or otherwise used in
an amount exceeding 10,000 pounds per
year. For calendar years 1988 and 1989 (and
beyond), the threshold reporting quantity for
manufactured or processed chemicals drops
to 50,000 and 25,000 pounds per year,
respectively.
This document has been developed to
assist formulators of aqueous solutions,
emulsions, and slurries in the completion of
Part III (Chemical Specific Information) of the
Toxic Chemiqal Release Inventory Reporting
Form. Included herein is general information
on toxic chemicals used and process wastes
generated, along with several examples to
demonstrate the types of data needed and
various methodologies available for esti-
mating releases. If your facility performs
other operations in addition to formulation of
aqueous solutions, emulsions, and slurries,
you must also include any releases of toxic
chemicals from these operations.
Step One
Determine if your facility processes or
uses any of the chemicals subject to
reporting under Section 313,
A suggested approach for determination
of the chemicals your facility uses that could
be subject to reporting requirements is to
make a detailed review of the chemicals and
materials you have purchased. If you do not
know the specific ingredients of a chemical
formulation, consult your suppliers for this
information. If they will not provide this in-
formation, you must follow the steps outlined
to handle this eventuality in the instructions
provided with the Toxic Chemical Release
.Inventory Reporting Form.
Many chemicals typically used in the,
formulation of aqueous solutions, emulsions,
and slurries are subject to reporting under
Section 313. You should also determine
whether process operations at your facility
actually create any of the listed chemicals.
The list presented here includes many of
the water-soluble Section 313 chemicals that
may be used in aqueous-based formulations.
It does not necessarily include all of the
chemicals your facility uses that are subject
to reporting, and it may include many chemi-
cals that you do not use. You should also
determine whether any of the listed chemicals
are created during processing at your facility.
Acids: Sulfuric acid, hydrochloric acid,
nitric acid, phosphoric acid, hydrofluoric
acid
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Bases: Sodium hydroxide, ammonia,
hydrazine
Co-solvents: Methanol, acetone,
n-butanol, acetonitrile, sec-butyl alcohol,
tert-butyl alcohol, methylene chloride,
ethylene glycol, 2-methoxyethanol,
methylene bromide, methyl ethyl ketone,
methyl isobutyl ketone, glycol ethers,
2-ethoxyethanol
Dyes: C.I. Acid Blue 9 (diammonium
salt), C.I. Acid Blue 9 (disodium salt),
C.I. Acid Green 3, C.I. Basic Green 4,
C.I. Basic Red 1, C.I. Disperse Yellow 3,
C.I. Food Red 5, C.I. Direct Black 38,
C.I. Direct Blue 9, C.I. Direct Brown 95
Textile chemicals: Acetamide, bis (2-
cliloroethyl) ether, 2,4-diamino anisole,
2,4-diaminoanisole sulfate, urethane
(ethyl carbamate), sodium sulfate,
ethyleneimine, 2-phenylphenol,
diepoxybutane, peracetic acid,
phenylenediamine, acetamide
Metal chelating agents, corrosion
inhibitors, metal treatment chemicals:
Cupferron, quinoline, thiourea, hydrogen
cyanide, calcium cyanamide, nitriloacetic
acid, cyanide compounds
Preservatives, disinfectants, biocides:
Chlorothalonil, cresols (mixed isomers),
o-cresol, 2,4-dimethylphenol,
2-phenylphenol, 2,4,5-trichlorophenol,
formaldehyde, phenol, mercury com-
pounds, zinc oxide (zinc compounds)
Fertilizers: Ammonium nitrate,
ammonium sulfate, calcium cyanamide,
metal compounds
Detergent additive: Sodium sulfate
Many non-water-soluble Section 313
chemicals also may be emulsified or dis-
persed into water. These include:
Pesticides, herbicides, fungicides: Too
numerous to list here; consult the Section
313 list.
Metal-containing pigments: Titanium
dioxide and compounds containing zinc,
lead, chromium, barium, cadmium,
nickel, molybdenum, antimony, and
copper
Metal-containing paint driers: See the
metal compound categories in the Section
313 list.
Step Two
Determine if your facility surpassed the
threshold quantities established for
reporting of listed chemicals last year.
You must submit a separate Toxic Chemi-
cal Release Inventory Reporting Form for
each listed chemical that is "manufactured,"
"processed," or "otherwise used" at your
facility in excess of the threshold quantities
presented earlier. Manufacture includes
materials produced as products, byproducts,
and impurities. Toxic compounds that are
incorporated into your products would be
considered "processed" because they become
part of the marketed finished product. De-
greasing solvents, cleaning agents, and other
chemicals that are used in processing but do
not become part of the finished product
would be considered "otherwise used."
The amount of a chemical processed or
otherwise used at your facility represents the
amount purchased during the year, adjusted
for beginning and ending inventories. To
ascertain the amount of chemical in a mixed
formulation, multiply the amount of the
mixture (in pounds) by the concentration of
the chemical (weight percent) to obtain the
amount of chemical processed.
A listed chemical may be a component of
several formulations you purchase, so you
may need to ask your supplier for informa-
tion on the concentration (percentage) of the
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chemical in each. For chemical categories,
your reporting obligations are determined by
the total amounts of all chemicals in the
category.
Example: Calculating annual pro-
cessing of sodium hydroxide.
In 1987, a plant processed from
inventory 75,000 pounds of a solution
containing sodium hydroxide (NaOH) at 50
percent by weight. It also purchased
50,000 pounds of solid sodium hydroxide
at 100 percent by weight, which was
processed into aqueous solutions at the
facility.
Amount of NaOH processed =
(75,000 Ib x 0.50) (used from
inventory) +
(50,000 Ibx 1.00) (purchased)
= 87,500 Ib
You must complete a report for each
chemical for which a threshold is exceeded.
The thresholds apply .separately; therefore, if
you both process and use a chemical and
either threshold is exceeded, you must report
for both activities. If neither threshold is
exceeded, no report is needed.
Step Three
Identify points of release for the
chemical(s) subject to reporting.
An effective means of evaluating points of
release for listed toxic chemicals is to draw a
process flow diagram identifying the opera-
tions performed at your facility. The figure
below is an example flow diagram for formu-
lation of aqueous solutions. Because each
facility is unique, you are strongly urged to
develop a flow diagram for your particular
operations that details the input of materials
and chemicals and the waste sources resul-
ting from the operation of each unit.
Releases of the chemicals processed in
your industry may emanate from the follow-
ing sources: equipment cleaning, filter solids,
volatilization, discarded containers and sam-
ples, or airborne particulates. Releases also
may result from wastewater treatment or
occur from other wastes containing the
chemical. Your reporting must account for
all releases.
CO-SOLVENTS
AIR EMISSIONS •
SOLIDS
(PIGMENTS,
ADDITIVES)
i
WATER-
GRINDING/
BLENDING
fc-
FABRIC
FILTER
• AIR EMISSIONS
- SOLID WASTE
• AQUEOUS WASTE
• SOLID WASTE
• AIR EMISSIONS
Example Flow Diagram for Formulation of Aqueous Solutions
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Step Four
Estimate releases of toxic chemicals.
After all of the toxic chemicals and waste
sources have been identified, you can esti-
mate the releases of the individual chemicals.
Section 313 requires that releases to air,
water, and land and transfers to offsite facili-
ties be reported for each toxic chemical
meeting the threshold reporting values. The
usual approach entails first estimating
releases from waste sources at your facility
(that is, wastewater, air release points, and
solid waste) and then, based on the disposal
method used, determining whether releases
from a particular waste source are to air,
water, land, or an offsite disposal facility.
In general, there are four types of release
estimation techniques:
• Direct measurement
• Mass balance
• Engineering calculations
• Emission factors .
Descriptions of these techniques are provided
in the EPA general Section 313 guidance
document, Estimating Releases and Waste-
Treatment Efficiencies for the Toxic Chemical
Release Inventory Form.
Provisions of the Clean Air Act, Clean
Water Act, Resource Conservation and
Recovery Act, and other regulations require
monitoring of certain waste streams. If
available, data gathered for these purposes
can be used to estimate releases. When only
a small amount of direct measurement data
is available, you must decide if another esti-
mation technique would give a more accurate
estimate. Mass balance techniques and
engineering assumptions and calculations
can be used in a variety of situations to
estimate toxic releases. These methods of
estimation rely heavily on process operating
parameters; thus, the techniques developed
are very site-specific. Emission factors are
available for some industries in publications
referenced in the general Section 313 guid-
ance document. Also, emission factors for
your particular facility can be developed in-
house by performing detailed measurements
of wastes at different production levels.
Toxic Releases to Air
As a formulator of aqueous solutions,
your primary solvent will be water. Many
volatile organic compounds are also used as
co-solvents in significant quantities, however,
and VOC emissions to air will result from the
processing and storage of these compounds.
Particulate emissions of reportable solid
chemicals (for example metal-containing
pigments) also may occur. Processing emis-
sions can be estimated by one or more of the
following methods.
1) Use of mass balance
Release of parttculates to the air from
grinding/blending operations may best be
estimated by using a mass balance of the
processing operation.
Amount of particulate chemical released
to air = .•.•'.;..'/ • . :
Amount of solid chemical processed
per year- •
Amount of solids dissolved or
suspended in final product -
Amount of solids in filter cake -
Amount of solids in wastewater sludge
For metal compounds, the amounts reported
as releases should represent the amount of
parent metal, not the amount of metal com-
pound.
If you use fabric filter systems in the
weighing/blending/mixing areas, you can
estimate the particulate emissions based on
the weight of the filtered particulates and an
assumed efficiency of 98 to 99 percent. In
the absence of measured efficiency data, you
could use design efficiencies from the fabric
filter manufacturer, if available.
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Amount ofparticulate air emissions =
Amount of particulates in filter x
((1 -filter efficiency) 4- fitter efficiency]
Example: Estimating releases of a
particulate through a filter.
A facility grinds and blends chromium
(III) oxide (Cr2Cy/or use as a pigment in a
water-based paint. The air around the
grinding operation is exhausted to a filter
with a particulate collection efficiency of 99
percent. According to facility measure-
ments, the annual amount of chromium (III)
oxide solids collected, from the filter is
2,000 pounds.
Amount ofCr2O3 released to air =
2.000 pounds x
[(1 - 0.99) + 0.99]
= 20lb
To report as a release of parent metal (Cr),
adjust as follows:
Amount of metal released =
Amount of metal compound released x
Molecular weight of parent metal
portion -s-
Molecular weight of metal compound
Molecular weight ofCr = 52
Molecular weight ofCr2O3 = 152
Amount ofCr released to air =
20 Ib Cr203 x
(52x2)+152
= 14 Ib
2) Use of empirical equations for volatile
emissions
a) Emissions from storage
Breathing and working loss emissions for
volatile compounds such as co-solvents can
be estimated for different storage tanks
(fixed-roof, internal and external floating-roof)
by using equations from EPAs Compilation of
Air Pollutant Emission Factors (AP-42). The
molecular weight and vapor pressure of the
chemical, tank design parameters, and opera-
ting conditions are used in these empirical
equations. The equations and how to use
them can be found in Chapter 3 and Appen-
dix C of the general Section 313 guidance
document. Storage tank emissions should be
reported as stack emissions on the reporting
form.
b) Emissions from loading
Losses due to vapors generated from load-
ing of products, from evaporation of products,
and from evaporation of residual product in
returned cargo carriers can be estimated by
the following equation:
L= 12.46x SxPxM* T
where L = vapor loss, Ib/1,000 gal of
liquids loaded
P = liquid vapor pressure, psia
M = molecular weight
T = liquid temperature, °R (°F+ 460)
S = saturation factor (see below)
Mode of operation
Sfactor
Submerged loading:
Clean cargo vessel 0.50
Normal dedicated service 0.60
Dedicated vapor balance service 1.00
Splash loading:
Clean cargo vessel 1,45
Normal dedicated service 1.45
Dedicated vapor balance service 1.00
Uncontrolled/unrecovered loading emis-
sions should be reported as fugitive emis-
sions on the form. The cargo carriers may be
drums, bins, trucks, or railcars.
If your facility recovers these vapor losses,
the losses should be adjusted by the vapor
recovery efficiency to yield release amounts:
Release =
Lossesx
(1 - vapor recovery efficiency)
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3) Use of emission factors
You can use emission factors to estimate
emissions from equipment leaks (valves,
pumps, flanges). Such factors may be devel-
oped by your facility (from measurements) or
by your industry (obtainable from published
studies). If factors are not available from
either of these sources, you can use the EPA
SOCMI factors, which represent average fu-
gitive equipment emissions of volatile organic
compounds in the synthetic organic chemical
manufacturing industry. These factors are
available in Appendix D of the Section 313
general guidance document.
Example: Using fugitive emission
factors to estimate equipment leak
emissions.
A latex paint formulator uses three
different volatile organic co-solvents. Each
solvent is pumpedfrom storage into a mix
tank. For each solvent, the following
equipment components must be considered
for fugitive emission leaks: 12Jlanges, 3
valves, 1 sample connection, and 1 pump
seal For light liquids with vapor pressure
greater than 1 psia (5 mm Hg) at 100 °F,
the following factors can be used to
estimate fugitive emissions:
Number of
equipment
components
12Jlanges
3 valves
1 sample
connection
1 pump seal
Total
Emission
factor,
Ib/h
x 0.0018 =
x 0.016
x 0.033
x 0.11
Emissions,
Ib/h
0.0216
0.048
0.033
0.11
0.2126
Annualfugitive emissions =
0.2126 Ib/hx8760 h/yr
= l,862lb
Fugitive equipment releases for each of the
three chemicals is therefore approximately
1,900 pounds per year.
Toxic Releases Via Wastewater
If you have monitored your wastewater
discharge for any of the listed chemicals, you
can easily calculate the releases of such
chemicals to water. If you have not moni-
tored your waste streams, you must consider
how much each individual source at your
facility contributes to wastewater loading.
Potential sources of water release are
equipment-cleaning water, drum-cleaning
waste, and off-specification product or sam-
ples. If you do not have monitoring data for
your wastewater and you wash out mixing
vessels or empty drums with water, assume
that up to 1 percent of the vessel content may
be lost during each cleaning occurrence. You
should base your estimates of the releases of
off-specification product and samples on the
method by which you dispose of them and on
your knowledge of the process (for example, if
0.1 percent of the batches last year were off-
spec but were not reworked; therefore, they
were released to water).
If your facility treats wastewater on site,
you should adjust the totals lost to water to
yield the "release" values. If available, use
actual plant operating data on removal effi-
ciency. Primary treatment may filter out
chemicals with low water solubility and allow
water-soluble chemicals to pass through.
You could estimate the amount released from
primary filtering operations based on-the
water solubility of the chemical if the waste-
water flow rate is known:
Amount of chemical passing throughfilter
(Ib/day) =
Water solubility (mg/liter) x
Wastewater flow rate (gal/day) +
453,600 mg/lbx
3.78 liter/gal
If secondary biological treatment is used,
however, water-soluble chemicals may be
biodegraded. Published treatment efficiency
data may be used if such data exist for the
biological wastewater treatment method used
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for the chemical at your site. The adjusted
releases to water may be estimated as
follows:
Amount of chemical released after
treatment =
amount lost in process water x
(1 - removal efficiency)
If no data are available, assume treatment
does not remove the chemical.
Other Toxic Releases
Other wastes in the formulation of aque-
ous solutions, emulsions, and slurries from
which toxic chemicals may be released
include:
• Residues from pollution control
devices
• Spent filters
• Product rejects
• Treatment sludges
• Empty chemical containers
Releases from these sources may already
have been accounted for, depending on the
release estimation methods used. These
items (and any other of a similar nature)
should be included in your development of a
process flow diagram.
You can estimate the amounts of solids
lost from the process by using data from
waste generation/shipping records. Alterna-
tively, if no data are available and if you
discard (to landfill) "empty" drums that have
not been cleaned, you can estimate the re-
lease as 1 percent of normal drum content.
For mixtures, adjust the release for the con-
centrations of the chemical.
Step Five
Complete the Toxic Chemical Release
Inventory Reporting Form.
After estimating the quantity of each
chemical released via wastewater, solid
waste, and air emissions, you must deter-
mine the amount of each chemical released to
water, land, or air or transferred to an offsite
disposal facility. This determination will be
based on the disposal method you use for
each of your waste streams. Enter the re-
lease estimates for each chemical or chemical
category in Part III of the Toxic Chemical
Release Inventory Reporting Form. Also enter
the code for each treatment method used, the
weight percent by which the treatment re-
duces the chemical in the treated waste
stream, and the concentration of the chemi-
cal influent to treatment (see instructions).
Report treatment methods that do not affect
the chemical by entering "0" for removal effi-
ciency.
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For More Information
Emergency Planning
and Community
Right-to-Know
Hotline
Small Business
Ombudsman
Hotline
(800) 535-0202
or
(202) 479-2449
(in Washington, D.C.
and Alaska)
(800)368-5888
or
(703) 557-1938
(in Washington, D.C.
and Virginia)
The EPA brochure, Emergency Planning
and Community Right-to-Know Act, Section
313 Release Reporting Requirements (EPA
560/4-88-001) presents an overview of the
new law. It identifies the types of facilities
that come under the provisions of Section
313, the threshold chemical volumes that
trigger reporting requirements, and what
must be reported. It also contains a complete
listing of the chemicals and chemical
categories subject to Section 313 reporting.
The EPA publication, Estimating Releases
and Waste-Treatment Efficiencies for the
Toxic Chemical Release Inventory Form (EPA
560/4-88-002), presents more detailed infor-
mation on general release estimation tech-
niques than is included in this document.
Additional Sources of Information
on Releases From. Formulation of
Aqueous Solutions
U.S. Environmental Protection Agency. Com-
pilation of Air Pollutant Emission Factors,
AP-42, Fourth Edition. Research Triangle
Park, North Carolina. September 1985.
U.S. Environmental Protection Agency.
Emission Factors for Equipment Leaks of
VOCandHAP. EPA 450/3-86-002. PB 86-
171527. Research Triangle Park, North
Carolina. January 1986.
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*U.S. Governaent Printing Offite : 1988 - 516-002/80168
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