United States
           Environmental Protection
           Agency
Office of Pesticides
and Toxic Substances
&EPA     Title III Section 313
           Release Reporting
           Guidance
EPA 560/4-88-0043
January 1988
          Estimating Chemical Releases From
          Monojilament Fiber Manufacturing

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             Estimating Chemical Releases From
                                          i
             Monofilament Filler Manufacturing
    Manufacturers of monofilament fibers
 may be required to report annually any re-
 leases to the environment of certain chemi-
 cals regulated under Section 313, Title III, of
 the Superfund Amendments and Reautho-
 rization Act (SARA) of 1986. If your facility is
 classified under SIC codes 20 through 39
 (monofilament fiber manufacturers generally
 fall under SIC codes 2823 and 2824) and has
 10 or more full-time employees, for calendar
 year 1987 you must report all environmental
 releases of any Section 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, re-
 spectively.

    This document has been developed to
 assist monofilament fiber manufacturers in
 the completion of Part III (Chemical Specific
 Information) of the Toxic Chemical 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 avail-
 able for estimating releases.  If your facility
 performs other operations in addition to
 monofilament  fiber manufacturing, 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.
   The list presented here includes chemi-
 cals typically used in monofilament fiber
 manufacture that are subject to reporting
 under Section 313. This list does not neces-
 sarily include all of the chemicals your facility
 uses that are subject to reporting, and it may
 include many chemicals that you do not use.
You should also determine whether any of the
 listed chemicals are created during process-
ing at your facility.
   Polymer constituents: Propylene,
   ethylene glycol, terephthalic acid, acrylo-
   nitrile, carbon disulfide, methyl acrylate,
   p-phenyldiamine, ethylene, vinyl chloride,
   vinyl acetate

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   Solvents/precipitants: Acetone, tolu-
   ene, sodium hydroxide, sulfuric acid,
   methyl ethyl ketone, aqueous ZnCl2
   Flame retardants: Decabromodiphenyl
   oxide, vinyl bromide, hexachloropenta-
   diene
   Promoters/activators: Hydrazine,
   hydroquinone
   Pigments:  Titanium dioxide
   Lubricants: Ammonium salts
            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 byproducts or impu-
rities. Toxic compounds that are incorpo-
rated into your products (for example, a flame
retardant applied to a fiber) would be con-
sidered "processed" because they become
part of the marketed finished product.  De-
greasing solvents, cleaning agents, and other
chemicals that 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.
    Example:  Calculating annual use of
    sulfuric acid through purchases and
    inventory changes.
       During 1987, a plant purchased and
    used 20,000 pounds of sulfuric acid at 40
    percent by weight. From inventory it used
    10,000 pounds of sulfuric acid at 40 per-
    cent by weight. The site also used 4,000
    pounds of a formulation containing 15 per-
    cent sulfuric acid by weight.
    Amount of sulfuric acid used -
       (20,000 Ib sulfuric acid x 0.40) +
       (10,000 Ib suLfuric acid x 0.40) +
       (4,000 Ib suljuric acid xO.15)
       = 12,600 Ib
    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
 chemical in each. For chemical categories,
 your reporting obligations are determined by
 the total amounts of all chemicals in the
 category.
    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.

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            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
 on the right is a generalized flow diagram for
 monofilament fiber manufacturing.  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 re-
 sulting from the operation of each unit.
    Air emissions of volatile chemicals will
 occur  during fiber spinning and processing.
 Solvent recovery systems, vessel washings,
 and condensate may produce water releases.
 Potential sources of solid wastes include filter
 cakes, distillation fractions, spent catalysts,
 and vessel and tank residues.  If a water
 treatment plant is located on site, releases
 also may occur from disposal of the sludge.
 Your reporting must account for all releases.
            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 facil-
ities be reported for each toxic chemical
meeting the threshold reporting values.  The
usual approach entails first estimating
                                                                             VOCAIR
                                                                            EMISSIONS
   AIR EMISSIONS
   AIR EMISSIONS,
    FILTER CAKE
 SPINNING WASTE,
  AIR EMISSIONS,
 SPINNERET WASH
 WATER, COOLING
 TOWER SLOWDOWN
SPENT LUBRICANT,
CLEANING WASTES,
SOLVENT VAPORS
   AIR EMISSIONS
 Example Flow Diagram of Monofilament
           Fiber Manufacturing

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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 Re-
covery 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
   If you have not measured air emissions
from your process, you can use one of the
following approaches to estimate releases to
air.

1) Volatile organic compounds
   Releases of solvents and other volatile
organic compounds used in your process will
be primarily to air. Releases to air can be
estimated as follows:
   Amount of solvents released to air =
       amount used -
       amount accounted/or by other wastes
       destroyed in treatment
In other words, rather than directly esti-
mating air releases, you should estimate
other releases first and then subtract them
from the quantity known to be used.

   Example: Estimating release of
   carbon disulfide used as a fiber
   constituent in fiber spinning.
   Amount of carbon disulfide released
    to air =
       100,000 Ib used in 1987 -
       10,000 Ib accounted/or in. sludges
       incinerated on site -
       1,000 Ib discharged in wastewater -
       5,000 Ib in sludge shipped offsite -
       50,000 Ib accounted for in fiber
       product
       = 34,000 Ib

    If you use acetone, dimethylformamide
 (DMF), or dimethylacetamide (DMAc) as the
 solvent in dry or wet spinning processes, you
 may be able to use the emission factors given
 in the table at the top of the following page.

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                   Solvent Usage and Emission Factors for Several Types
                      of Monofilament Fiber Manufacturing Processes
     Plant
   Emission factors, kg/1000 kg of fiber produced
                       Solvent    Solvent
           Makeup   residual     losses
Solvent     solvent     in fiber    to water   Emissions
Wet spin*
Dry spin*
Dry spin
Filter-tow dry spin
Filament yam dry spin
DMAc
DMF
Acetone
Acetone
Acetone
70
70
155
130
175
5
5
5
Negligible
10
25
20
10
10
20
40
45
140
120
145
     *These plants have a filament washing stage that extracts residual solvent and monomer
      from the fiber.
In the following example, these factors are
used to calculate air releases.

   Example:  Using emission factors to
   estimate VOC releases

       A plant produced 120,000 kilograms of
   modacrylic in 1987.  Acetone was used as
   the solvent Based on the VOC estimate
  for acetone from the preceding table,
   Amount of acetone released to air =
       120,000 kg ffoerx
       140 kg acetone/1,000 kg fiber x
      2.2 lb/1 kg

      = 36,960 Ib
                   Using this approach, the plant in this
                   example could report air emissions of
                   37,000 pounds of acetone.
                2) Particulates

                   Two methods can be used to estimate the
                particulates released to air. The first entails
                the use of available emission factors for gen-
                eral monofilament, polypropylenes, or poly-
                vinyl chloride manufacturing. The table
                shown at the bottom of this page presents
                selected air emission factors. In the following
                example, these factors are used to estimate
                the release of particulates to air during the
               manufacture of polypropylene.
                     Air Emission Factors for General Monofilament,
                  Polyvinyl Chloride, and Polypropylene Manufacturing
Particulate
Type
General
Polyvinyl chloride
Polypropylene
Ib/ton
Pigment
5-10
35
3
kg/MT
Pigment
2.5-5
17.5
1.5
Gases
Ib/ton
Product
17
0.7
kg/MT
Product
8.5
0.35

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   Example: Using emission factors to
   estimate particulate emissions to air.
      A plant produced 500,000 pounds of
   polypropylene in 1987.  The pigment con-
   tent of this fiber was 8 percent. Based on
   the emission factors provided in the pre-
   ceding table, the particulate releases can
   be calculated as follows:
   Amount of pigment released =
      500,000 Ib fiber x
      0.08 Ib pigment/1 Ib fiber x
      1 ton/2,000 Ib x
      3 Ib particulate/1 ton pigment
      = 60Zb
   The  second method entails back-
calculating the particulate emissions from the
weight of the particulate collected in the
baghouse with design efficiencies provided by
the baghouse manufacturer. If reported
values are not available, an efficiency of 98 to
99 percent should be assumed.
   Most of the particulate matter released to
air will become airborne during the dope
preparation or blending operation. Based on
the weight percent of the chemical of interest
that enters the blender, the amount of spe-
cific chemical released to air in the form of
particulates can be estimated as follows:
   Amount of chemical released to air =
        amount of particulate released to air x
        weight percent of chemical entering the
        blender
    Example: Using baghouse efficiency
    to estimate particulate emissions to
    air.
        A polyester textile fiber manufacturing
    plant collected 250,000 pounds of
    parttculates  in the baghouse filters from
    the blending operations in 1987. The
    baghouse manufacturer claims a 99.3
    percent efficiency for these filters. If the
    weight percent of titanium dioxide (TiOJ in
   the fiber is 8 percent, the amount of this
   chemical released to the air can be calcu-
   lated as follows:
   Amount ofTiO2 released =
       250,000 Ib particulate collected x
       (0.007/0.993) x
       0.08 Ib TiO2/l Ib particulate
       = 140 Ib

Toxic Releases Via Wastewater
   The solvent recovery system, equipment
cleaning effluent, condensate, and washing
stage effluent are all potential sources for
water release.  If plant monitoring data for
the water releases are available for the chemi-
cals of interest, the water releases can be
calculated directly.
   Data on solvent emissions to water are
available for some dry and wet spinning
processes, as shown in the table of solvent
usage and emission factors on page 5. The
estimates in the table giving losses to water
include losses from the solvent recovery
system, any washing stage, and equipment
cleaning. The following example shows the
use of these factors to estimate water re-
leases.
    Example:  Using emission factors to
    estimate water releases.
       A plant produced 120,000 kilograms of
    modacrylic in 1987 by dry spinning.
    Acetone was used as the solvent. Emis-
    sion factors can be used to calculate
    acetone losses asfoUows:
    Amount of acetone released to water =
        120,000 kg fiber x
        10kg acetone/1,000 kg fiber x
        2.2 lb/1 kg
        = 2,640 Ib
     Using this approach, the plant in this
     example could report water releases of
     2,600 pounds of acetone.

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v   If your facility uses a listed mineral acid
or base but this acid or base is effectively
neutralized in use or during wastewater
treatment (to pH 6 to 9, as required by most
effluent standards), no release quantities
should be reported for these substances.
   If wastewater treatment occurs on site,
you should adjust the total losses to yield the
release. If available, use plant operating data
on removal efficiency for this purpose. Pub-
lished data also may be used, if such data are
available for the specific chemical treated by
the method used at your plant (for example,
biological wastewater treatment). The amount
of chemical released to water after waste-
water treatment can thus be calculated as:
   Amount of chemical released  to water =
       amount lost in process water x
       (1 - removal efficiency)
If no data are available, assume treatment
does not remove the chemical.

Toxic Releases Via Solid Waste
   The possible sources of nonaqueous
waste to be landfilled or otherwise disposed of
include filter cakes, distillation fractions,
spent catalyst, vessel and tank residues, and
drums. Assuming that the monomer weight
percent in the dope is known, the loss in the
filter cake will be:
    Amount of monomer in filter cake =
       amount offUter cake x
       weight percent of monomer

    When a wastewater treatment plant is
located on site, some chemicals will also be
transferred from thej^uid to sludge and
 some will be chemicfly or biologically
destroyed or neutralized.  Loss to the sludge
will be:
   Amount of chemical in sludge =
       amount lost from process -
       amount lost in water
Alternatively, you may have data on the con-
centration of chemicals in the sludge.

   For organic chemicals in general, some
degradation may occur during treatment so
that all of the chemical is not transferred to
the sludge. The amount of organic com-
pounds in the sludge may be estimated by
using measured data or by subtracting the
amount biodegraded from the total amount
removed in treatment.  Removal may be
determined from operating data, and the
extent of biodegradation may be obtained
from published studies. If the biodegrad-
ability of the chemical cannot be measured or
is not known, you should assume that all
removal is due to adsorption of sludge.

Other Toxic Releases
   Monofilament fiber manufacturing pro-
duces other wastes from which toxic chemi-
cals may be released. These include:
   •   Residues from pollution control
       devices
   •   Wash water from equipment
       cleaning
   •   Product rejects
   •   Used equipment
   •   Empty chemical containers

   Releases from these sources may already
have been accounted for, depending on the
release estimation methods used.  These


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items (and any other of a similar nature)
should be included in your development of a
process flow diagram.
   The contribution of sources of wastes
such as cleaning out vessels or discarding
containers should be small compared with
process losses.  If you do not have data on
such sources (or any monitoring data on
overall water releases), assume up to 1 per-
cent of vessel content may be lost during
each cleaning occurrence. For example, if
you discard (to landfill) "empty" drums that
have not been cleaned, calculate the release
as 1 percent of normal drum content.  If the
drums are washed before disposal, this may
contribute 1 percent of the content to your
wastewater loading.
            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 Re-
lease 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 in the influent to treatment (see instruc-
tions). Report treatment methods that do not
affect the chemical by entering "0" for re-
moval efficiency.
                                           8

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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, Title III Section 313
Release Reporting Requirements (EPA 560/4-
87-001) 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 re-
porting 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 information on gen-
eral release estimation techniques than is
included in this document.
                                         9

                         *U.S. Government Printing Office : 1988 - 516-002/80167

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United States
Environmental Protection
Agency


Office of Pesticides and
Toxic Substances, WH-562A
Washington, D.C. 20460
Official Business
Penalty for Private Use
$300

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