EPA-450/4-84-007n
                                         May 1987
Locating And Estimating Air Emissions
             From Sources Of
    Polychlorinated Biphenyls (PCB)
             U.S. ENVIRONMENTAL PROTECTION AGENCY
                  Office Of Air And Radiation
             Office Of Air Quality Planning And Standards
             Research Triangle Park, North Carolina 27711

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This report has been reviewed by the Office Of Air Quality Planning And Standards, U.S. Environmental
Protection Agency, and has been approved for publication as received from the contractor. Approval does
not signify that the contents necessarily reflect the views and policies of the Agency, neither does mention
of trade names or commercial products constitute endorsement or recommendation for use.
                                     EPA-450/4-84-007n

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                                    CONTENTS
Figures	      iv
Tables	.....'	       v

    1.   Purpose of Document	       1
    2.   Overview of Document Contents	       3
    3.   Background	       5
              Nature of Pollutant	       5
              Overview of Production and Uses	      11
    4.   PCB Emission Sources	      28
              Disposal/Destruction Methods	      29
              Accidental Releases	      55
    5.   Source Test Procedures	      64

References	      67
                                    iii

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                                    FIGURES
Number

  1

  2


  3

  4

  5
Chemical use tree {or PCBs	,

Domestic sales of Monsanto's polychlorinated biphenyls
     in the United States (by use)	,

Disposal requirements for PCBs and PCB items	

Evaporative loss of ^C-Aroclor 1242....	

Volatilization of PCB isomers from dry Ottawa Sand
     contaminated with Aroclor 1254	

Volatilization of PCB isomers from wetted Ottawa Sand
     contaminated with Aroclor 1254.	

Surface volatilization of Aroclor 1254 from itself as
     a function of time	

Method 5 sampling train modified for the measurement of
     PCBs from incinerators	
Page

 19


 21

 30

 48,


 60


 60.


 61


 65
                                    xv

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                                     TABLES

Number   '                                                                 Page

  1      Composition of Polychlorinated Biphenyls	      6

  2      Melting Points and Solubilities of Some PCB Isomers	      7

  3      Percent Composition of Selected Aroclors	     10

  4      Chemical and Physical Properties of Aroclors
              1016 through 1260	     12

  5      Chemical and Physical Properties of Aroclors
              1262 through 5460	     15

  6      Common Trade Names for PCB Dielectric Fluids	     18

  7-     The Uses of PCBs Prior to 1970.....	     22

  8      PCB Emissions From Annex I Incinerators Burning Liquid
              Wastes	     33

  9      PCB Emission Factors for Sewage Sludge Incinerators	     36

 10      PCB Emission Factors for Municipal Refuse Incinerators	     36

 11      High Efficiency Boilers Permitted to Burn PCB Liquids	     40

 12      PCB High Efficiency Boiler Test Results	     42

 13      PCB Contaminated Materials Acceptable for Land Disposal	     44

 14      PCB Annex II Chemical Waste Landfills	     46 •

 15      PCB Emission Factors for Chemical Dechlorination Methods....     54

 16      Estimated PCB Leakage/Spillage from Utility Industry
              Closed Systems Equipment	     56

 17      Estimated PCB Leakage/Spillage from all Closed Systems
              Equipment (Utility and Nonutility)	     57

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                                   SECTION 1
                              PURPOSE OF DOCUMENT

    EPA, States and local air pollution control agencies are becoming
increasingly aware of the presence of substances in the ambient air that may
be toxic at certain concentrations.  This awareness, in turn, has led to
attempts to identify source/receptor relationships for these substances and to
develop control programs to regulate emissions.  Unfortunately, very little
information is available on the ambient air concentrations of many of these
substances or on the sources that may be discharging them to the atmosphere.
    To assist groups interested in inventorying air emissions of various
potentially toxic substances, EPA is preparing a series of documents such as
this that compiles available information on sources and emissions of these
substances.  This document specifically deals with polychlorinated biphenyls
(PCBs).  Its intended audience includes Federal, State and local air pollution
personnel and others who are interested in locating potential emitters of PCBs
and making preliminary estimates of air emissions therefrom.
    Because of the limited amounts of data available on PCB emissions, and
since the configuration of many sources will not be the same as those
described herein, this document is best used as a primer to inform air
pollution personnel about 1) the types of sources that may emit PCBs,
2) source variations and release points that may be expected within these
sources, and 3) available emissions information indicating the potential for
PCBs to be released into the air from each source.
    The reader is strongly cautioned that using the emissions information
contained in this document will not yield an exact assessment of emissions
from any particular source.  Since insufficient data are available to develop
statistical estimates of the accuracy of these emission factors, no estimate
can be made of the error that would result when these factors are used to
calculate emissions from any given source.  It is possible, in some extreme
cases, that orders-of-magnitude differences could result between actual and
calculated emissions, depending on differences in source configurations,

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control equipment and operating practices.  Thus, in situations where an
accurate assessment of PCB emissions is necessary, source-specific information
should be obtained to confirm the existence of particular emitting operations,
the types and effectiveness of control measures, and the impact of operating
practices.  A source test and/or material balance should be considered as the
best means to determine air emissions directly from an operation.
    This document presents information on rules governing the use and disposal
of PCBs.  The information contained herein represents the regulatory status of
PCBs as of the compilation date of the document (February 1986).  Because of
the dynamics involved in regulating PCBs, rules are frequently revised.
Therefore, the reader should consult references such as the Code of Federal
Regulations to determine the current regulatory status.

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                                   SECTION 2
                         OVERVIEW OF DOCUMENT CONTENTS

    As noted in Section 1, the purpose of this document is to assist Federal,
State and local air pollution agencies and others who are interested in
locating potential air emitters of polychlorinated biphenyls (PCBs) and making
gross estimates of air emissions therefrom.  Because of the limited background
data available} the information summarized in this document does not and
should not be assumed to represent the source configuration or emissions
associated with any particular source.
    This section provides an overview of the contents of this document.  It
briefly outlines the nature, extent and format of the material presented in  •
the remaining sections of this report.
    Section 3 of this document provides a brief summary of the physical and
chemical characteristics of PCBs, their commonly occurring forms and an
historical overview of their production and uses.  With minor exceptions, PCBs
are no longer produced in the United States (domestic production ceased in
1977) and have been used only in closed systems (e.g., transformers,
capacitors) since 1971.  A chemical use tree summarizes the quantities of PCBs
consumed in various end use categories in the United States.  This background
section may be useful to someone who needs to develop a general perspective on
the nature and uses of PCBs.
    Section 4 of this document focuses on major industrial source categories
that may discharge PCB air emissions.  This section discusses disposal methods
and sources of accidental releases of PCBs.  For each major source category
described in Section 4, available emissions information — including emission
factor estimates — is presented that shows the potential for PCBs emissions.
    The final section of this document summarizes available procedures for
source sampling and analysis of PCBs.  Details are not prescribed nor is any
EPA endorsement given to any of these sampling-and analytical procedures.  At
this time, EPA generally has not evaluated these methods.  Consequently, this
document merely provides an overview of applicable source sampling procedures,
citing references for those interested in conducting source tests.

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    This document does not contain any discussion of health or other
environmental effects of PCBs, nor does it include any discussion of ambient
air levels or ambient air monitoring techniques.
    Comments on the contents or usefulness of this document are welcomed, as
is any information on process descriptions, operating practices, control
measures and emissions information that would enable EPA to improve its
contents.  All comments should be sent to:
              Chief, Noncriteria Emissions Section (MD-14)
              Air Management Technology Branch
              U.S. Environmental Protection Agency
              Research Triangle Park, N.C.  27711

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                                   SECTION 3
                                   BACKGROUND

NATURE OF POLLUTANT

    The term "polychlorinated biphenyls (PCBs)" refers to a class of organic
chemicals produced by the chlorination of biphenyl.  Ten classes of PCBs may
be formed (these include monochlorobiphenyl, although it is not technically
polychlorinated), depending on the specific number of chlorine substitutions
on the biphenyl molecule.  These compounds, in increasing order of chlorine
substitution, are monochlorobiphenyl, dichlorobiphenyl, trichlorobiphenyl, and
so on.  Several isomers of each PCB molecule are possible (for a total of
209), but not all are likely to be formed during the manufacturing processes.
The biphenyl structure with possible substitution sites is shown below:1
                              5'   6'        23
                              3'   2'        65

PCB molecules and their molecular weights are presented in Table 1.  Table 2
presents properties of selected isomers.
    In general, higher PCB chlorine content corresponds to greater resistance
to chemical degradation.  PCB isomers, which range from liquids to high
melting crystalline solids, exhibit low solubility in water, low vapor
pressure, low flammability, high heat capacity, moderate heat of vaporization,
and low electrical conductivity.  These properties, as well as favorable
dielectric constants and suitable viscosity-temperature relationships, make
                                              t
them extremely advantageous for use as dielectric and heat transfer  fluids.^

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              TABLE 1.  COMPOSITION OF POLYCHLORINATED BIPHENYLS2
Compound
Monochlorob ipheny 1
Dichlorobiphenyl
Trichlorobiphenyl
Tetrachlorob ipheny 1
Pentachlorobiphenyl
Hexachlorob ipheny 1
Heptachlorobiphenyl
Octochlorob ipheny 1
Nanochlorobiphenyl
Decachlorob ipheny 1
Empirical
form'ula
Ci2H9Cl
C12H8C12
C12H7C13
C12H6C14
C12H5C15
C12H4C16
C12H3C17
C12H2C18
Ci2HCl9
C12cll0
Molecular
weight3
188 ;
222
256
1
290
324
358
392
426
460
494
Weight percent
chlorine3
18.6
31.5
41.0
48.3
54.0
58.7
62.5
65.7
68.5
79.9
Number of
isoisers
3
12
24
42
46
42
24
12
3
1
aBased on Cl35.

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TABLE 2.  MELTING POINTS AND  SOLUBILITIES OF SOME FOB IS011ERS
Compound
Monochlorobiphenyls
2-
3-
4-
Dichlorobiphenyls
2,*-
2,2'-
2,3'-
2,4'-
4i4'-
Trichlorobiphenyls
2,A,4'-
2,2',3-
2,2',5-
2,4',5-
2', 3, 4-
Tetrachlorobiphenyls
2,3,4,4'-
2,2', 3, 3'-
2,2',3,5'-
2,2',4,4'-
2, 2', 4, 5'-
2, 2', 5,5'-
2, 3', 4,4'-
2,3',4',5-
3, 3', 4,4'-
Pentachlorobiphenyls
2, 3,3', 4, 4'-
2, 3,3', 4', 6-
2, 2', 3,4,5'-
2, 2', 3,3', 6-
2,21,3,5I,6-
2,2I,4,5,5I-
2, 2', 4,4', 5-
2J2',3',4,5-
2, 3', 4,4', 5-
CAS
number^

2150-60-7
--
2051-62-9

—
13029-08-8
25569-80-6
34883-43-7
2050-68-2

7012-37-5
38444-78-9
37680-65-2
16606-02-3
38444-86-9

33025-41-1
—
41464-39-5
--
41464-40-8
35693-99-3
32598-10-0
32598-11-1
32598-13-3

--
38380-03-9
—
52663-60-2
38379-99-6
37680-73-2
38380-01-7
41464-51-1
31508-00-6
Melting
point*
(°c)

34
--
77.7

—
60.5
—
44.5-56
149-150

57-58
28.1-28.8
43-44
67
65-66

142
—
49-50
--
66-68.5
87-89
127-127.5
104-105
182-184

117-118.5
—
111.5-113
. '
98.5-100
76.5-77.5
--
81-82
112-113
Solubility
in water^
(mg/1)

5.90
3.50
1.19

1.40
1.50
«_
1.88
0.08

0.085
__
—
—
0.078

--
0.034
0.170
0.068
—
0.046
0.058
0.041
0.175

__
--
0.022
--
—
0.031
--
--
~—
                          (continued)

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                             TABLE 2.  (continued)


Compound
Hexachlorobiphenyls
2, 2', 3, 4,4', 5-
2, 2', 3, 4,4', 5'-
2, 2', 3,3', 4, 6-
2, 2', 3,3', 6, 6-
2, 2', 4,4', 5, 5'-
2,2', 3', 4,5,6'-

CAS
number-^

35694-06-5
35065-28-2
38380-05-1
38411-22-2
35065-27-1
38380-04-0
Melting
point^
(°C)

77-78
114-114.5
•
--
103-104
—
Solubility
in water-*
(mg/1)

—
--
--
—
0.088
—
Heptachlorobiphenyls

     2,2',3,4',5,5'-
     2,2',3,3'4,5,6'-
     2,2',3,3',4,4',5-

Octochlorobiphenyl

     2,2',3,3',4,4')5S5I-

Decachlorobiphenyl
35065-29-3
38441-25-5
35065-30-6
  109-110
130.5-130.7
134.5-135.5
                                       0.007

                                       0.015

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     Individual PCB  isomers have been prepared  in  the  laboratory by various
synthetic routes.?  However,  for  commercial  purposes,  PCBs  are  used and  sold
as a mixture of  isomers.  Large-scale U.S. production  of  PCBs was  stopped
voluntarily in October  1977.because of  the tendency of PCBs to  accumulate and
persist  in the environment and because  of their toxic  effects.7 The principal
U.S. producer of  PCBs was Monsanto Industrial  Chemicals Company which made  the
products under the  registered trademark of Aroclor.  As presented  in Table  3,
several Aroclor products were marketed  prior to 1977 with various
compositions.  After 1977, manufacture  of PCBs in  the  U.S.  was  restricted to
situations requiring special authorization or  exemptions  by EPA, '  Manufacture
of PCBs currently consists of low level incidental generation associated with
the  production of other compounds and the manufacture  of  small  quantities of
pure PCBs for research and development.^2
     All Aroclor products are designated by a four digit number,  usually
beginning with the  prefix 12 to represent the biphenyl  starting material, and
a second set of digits to represent the approximate chlorine percentage.  For
example, Aroclor  1242 is a chlorinated biphenyl containing,  approximately 42-
percent chlorine.  Aroclors beginning with the prefixes 25  and  44  are blends
of PCBs and chlorinated terphenyls while the prefix 54  represents  a
chlorinated terphenyl mixture with no biphenyl.  Aroclor  1016 contains
41 percent chlorine by weight but the penta-, hexa-, and heptachlorobiphenyl
content has been significantly reduced.8
    Commercial mixtures of PCBs have been produced by companies  in countries
other than the U.S. and have been sold under various tradenames with various
systems for product identification.  These companies'  tradenames are discussed
in the subsection titled "Overview of Production and Uses."
    The commercial mixtures of PCBs have properties quite different from the
individual isomers, particularly in crystallinity and liquid range.  PCBs are
generally chemically inert and react with other materials only under high
temperatures or extreme conditions.  They are insoluble in water, glycerol,
and glycols but are soluble in most of the common organic solvents.  PCBs are
highly resistant to oxidation.  They are permanently thermoplastic in the
higher chlorination levels and are considered extremely useful in energy

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transfer applications.  However, under elevated temperatures, the chlorine can
react with metal to cause corrosion.?  Chemical and physical properties of
selected Aroclors are presented in Tables 4 and 5.
    PGBs are not reactive chemically under normal environmental conditions.
However, their use in quenching of heated metals, as heat-transfer media, and
in transformer oil, may lead to the formation of degradation products such as
dibenzofurans, polychloroquaterphenyls, polychloroquaterphenyl ethers,
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no chlorodibenzofurans being detected.  Because of the mixed results, no
assessment of the accumulation of chlorodibenzofurans due to photodegradation
of PCBs can be made.10
    Biodegradation of PCBs has been reported to depend on the degree of
chlorination.  Although lower chlorinated biphenyls are readily transformed by
bacteria, biodegradation of the pentachlorophenyls may be extremely slow, and
that of hexa- and higher chlorinated biphenyls is practically negligible.11
    PCBs are remarkable among organic industrial chemicals for their low
solubility in water, their high octanol/water partition coefficients,
accumulation coefficients, and their resistance to in-vivo degradation.  As a
result, they exhibit extraordinarily high values for bioaccumulation in animal
tissues, especially in fish and other aquatic organisms.  Bioaccumulation in
fish may take place either through ingestion of contaminated food organisms or
by direct absorption through the skin.1^
                                              i
OVERVIEW OF PRODUCTION AND USES

    PCBs were first formulated in 1881 and were manufactured on a commercial
scale in the United States as early as 1929.1^  Monsanto was the principal
manufacturer in the United States until 1977 when they voluntarily ended

                                   11

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production because of widespread environmental concerns about PCBs.  Monsanto
marketed PCBs under the tradenames "Askarel" and "Aroclor."8'13  Dielectric
fluids containing PCBs have been marketed by several companies under a variety
of tradenames which are listed in Table 6.
    Before 1977, PCBs were produced by the chlorination of -biphenyl with
anhydrous chlorine, using iron filings or ferric chloride as catalysts.  The
crude product was purified to remove traces of hydrogen chloride and
catalyst.8  Commercially produced PCBs contained no major components other
than chlorobiphenyls.  Small amounts of chlorodibenzofurans have been detected
in PCB mixtures, possibly as a result of aqueous alkaline washing and steam
distillation in the production process.  PCB mixtures were sold in two
grades:  a purified grade and a darker, less pure, technical grade.^
    Uses of PCBs are presented in Figure 1.  Prior to 1957, virtually all PCBs
were used in the manufacture of electrical transformers and capacitors.  As
discussed earlier, PCBs exhibit low flammability, high heat capacity, and low
electrical conductivity and are virtually free of fire and explosion hazards.
Consequently, PCBs can be used where failures of oil insulated transformers
would present a potential danger to life and property.  PCBs were therefore
used wherever fire protection was particularly important -- for about
5 percent of all transformers.^
    The PCB containing fluids used in transformers are called "askarels."^
These fluids typically contain from 60 to 70 percent PCBs by weight, and from
30 to 40 percent chlorobenzene.^  The amount of askarel contained in a
transformer varies with transformer size.  The literature reports that the
quantity ranges from 150 to 1,890"liters (40 to 500 gal) which weighs 235 to
2,932 kg (516 to 6,450 lb).20
    PCBs have been used in electrical capacitors for many of the same
reasons.  They are needed for safety, reliability and long life and to achieve
sizes compatible with equipment and installation requirements.  PCBs were used
principally in high voltage power capacitors for'power factor correction in
the distribution of electric power; in low voltage power capacitors installed
in industrial plants (typically in large motors); in ballast capacitors to
improve the efficiency of lighting systems; and in small industrial capacitors
                                    17

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-------
for power factor improvement in  such equipment as  air  conditioning units,
pumps, fans, etc.21  The large high voltage capacitors typically weigh  54 kg
(120 Ib) of which 11 kg  (25 Ib)  are PCBss while  the  small ballast capacitors
weigh 1.6 kg (3.5 Ib) of which 0.05 kg  (0.1 Ib)  are  PCBs,,22
    Transformers and capacitors  continued to be  the  main products using PCBs
after 1957, however, additional  industrial applications began  to absorb a
share of PCB production at this  time.   The relative  product use of PCBs for
industrial application between 1957 and 1971, when Monsanto restricted  sales
to closed systems (capacitor and transformer applications), is shown  in
Figure 2.  Additional PCB applications  included  uses in hydraulic fluids and
lubricants, plasticizers, heat transfer fluids,  investment castings,  and in
miscellaneous industrial applications.   These applications are considered
either "nominally closed" or "open systems" due  to the ease with which  the
PCBs may enter the atmosphere during use (when compared to
transformer/capacitor use).  The grade  of Aroclor  used in each of the
aforementioned applications is shown in Table 7.   PCBs were employed  in
industrial hydraulic and lubricant applications  because they exhibited  good
heat and fire resistance and they were  relatively  inexpensive additives that
depressed fluid pour points.  These qualities are  essential when hydraulic
fluids are used in or near a hot operating environment.  For example,
hydraulic dye casting machinery and aircraft engines are two applications
where moderately high operating temperatures combined  with a high probability
for accidents often lead to hydraulic system leaks and the possibility  of
fire.  PCBs were used as lubricants due  to the previously mentioned qualities,
and also because of their oxidation and  foam resistance characteristics and
their low vapor pressure.25
    PCBs gained widespread use in plasticizers because PCBs are permanently
thermoplastic, chemically stable, non-oxidizing, non-corrosive, fire
resistant, and are excellent solvents.   In addition, they are not normally
attacked by acids, alkalines or water and are insoluble in water, glycerol and
glycols.  These compatibility properties are especially useful in
plasticizers.  A plasticizer is a material incorporated in a plastic to
increase its workability and flexibility.  A plasticizer typically is added to
                                    20

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      35,000
     30,000
_   25,000
 en
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en
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en

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15,000
10,000
      5,000
                      1   I   '   I   '  I  '  i   '   I   '  i
                                      HEAT
                                      TRANSFER
                            MISC.

                            INDUSTRIAL
                     PLASTICIZER .
                     APPLICATIONS
           HYDRAULICS

           LUBRICANTS
                        CAPACITOR
            I  I   I   I   I   I   I   I   I   I   I  I  I
                                                        i
           1957
                 1961
 IS65

YEAR
1969
'71
I   I
EST.
Figure 2.  Domestic sales of Monsanto1s Polychlorinated Biphenyls

          in the U.S.  (by use).
                           21

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               TABLE 7.  THE USE OF PCBs PRIOR TO 197024
           Use
 Grade(s)  of Aroclor
Electrical capacitors

Electrical transformers

Vacuum pumps

Hydraulic fluids
Plasticizer in synthetic
     resins

Adhesives
Wax extenders

Pesticide extenders

Inks

Lubricants

Cutting oils

Carbonless copying paper

Heat transfer systems
 1221,  1242,  1254

 1242,  1254,  1260

 1248,  1254

 1232,  1242,  1248,
 1254,  1260

 1248,  1254,  1260,  1262
 1268

 1221,  1232,  1242,  1248,
 1254

 1242,  1254,  1268
>1254
 1242
                                    22

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change the viscosity, make the plastic softer (lower its elastic modulus) or
impact some other specific property.  PCBs added several of these properties
at a relatively low cost.26
    Heat transfer fluids are used to absorb thermal energy from a source and,
by cooling or phase change, deliver heat to a place'of utilization.  PCBs have
been used for these fluids due to their fire resistance, their low power and
viscosities, their good thermal stability and their high heat capacity.2?  In
addition, they are inert and are relatively inexpensive.  However, the
principle reason for use of PCBs as heat transfer fluids is their
fire-resistance.  This is a critical factor in cases where the possibility
exists that fire from high temperature leaks could endanger life and property.
    PCBs were als'o used by the investment casting industry in the production
and subsequent use of PCB-filled pattern waxes.  The investment casting
process is a lost wax casting process.  A pattern is molded by the injection
of the molten casting wax into a metallic die where the wax cools and
solidifies to form the desired shape.  The wax pattern is then surrounded by a
slurry containing a refractory ceramic (known as the investment) to form the
final mold.  After the model dries to an appropriate strength, the wax pattern
is smelted in an autoclave and the wax is recovered for possible future use or
disposal.  Residues of wax remaining in the pores of the ceramics mold are
burned out in a furnace at 1000°C to 1100°C.  Molten metal may then be poured
into the cavity of the ceramic mold to form a casting.  Addition of fillers
such as PCBs or polychlorinated triphenyls (PCTs) to investment casting waxes
was a development of the 1960's.  By reducing the wax content through addition
of low shrinkage fillers, volumetric shrinkage of the ceramic mold may be
controlled.  Between 300,000 and 500,000 kg of PCBs were imported from Italy
for this application in 1972.28
    PCBs are also found used in a host of minor industrial uses.  They were
used in laminating adhesive formulations involving polyurethanes and
polycarbonates to prepare safety and acoustical glasses.  The laminates
improved strength and resistance to delamination over a broad temperature
range, and improved sound absorption and energy dissipation properties.  PCBs
were also used in adhesive formulas to improve toughness and resistance to
oxidative and thermal degradation when laminating ceramics and metals.2^
                                    23

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    PCBs were employed with textile coating mixtures for ironing board covers,
as coatings for polypropylene films and yarns and in sealing  formulations to
waterproof canvas.  These applications took advantage of PCBs1 ability to
resist photochemical degradation, oxidation and  fire.30
    PCBs were used in paints and varnishes to impart weatherability, luster
and adhesion.  In combination with other plasticizers, they were employed to
prepare film casting solutions for electrical coatings, insulating  tapes and
protective lacquer.  PCBs are compatible with epoxy resins and give good final
hardness and impact resistance to resin.  These  PCB resins were then used as
protective coatings for metals.  In addition, PCBs were used  in sealing and
caulking compositions to seal joints against water, dust, gas, heat and
certain chemicals.  Here, again, the good chemical and physical resistance
properties of PCBs, their elasticity, weatherability and relative low cost
made PCBs a valuable additive.31
    Chlorinated biphenyls were employed as part  of the formulations used to
prepare pressure sensitive record and colored copying papers, including
graphic duplicating processes, xerographic transfer processes and solvent free
printing.  PCBs used in this application later found their way into many paper
products, when the carbonless copy paper was recycled into a host of other
paper goods, including food packaging.32
    Finally, PCBs were employed for an assortment of miscellaneous uses such
as a soil erosion retardant, in combined insecticide and bactericide
formulations, in plastic decorative articles, as a metal quencher and as an
aid in fusion cutting of stacked metal plates.33
    By 1970, 60 percent of PCBs sales were for closed system electrical and
heat transfer uses, 25 percent for plasticizer applications, 10 percent for
hydraulic fluids and lubricants, and less than 5 percent for miscellaneous
applications such as surface coatings, adhesives, printing inks, and pesticide
extenders.  In late 1970 Monsanto confined PCB sales to closed systems.  By
1971, 90 percent of all PCBs were used in this 'manner, and by 1972,
100 percent.24  Monsanto ceased manufacture of PCBs completely in 1977 due to
increased environmental concerns and the availability of replacement products
to the electrical industry.?
                                    24

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    On February 17, 1978, EPA issued a rule governing the marking and disposal
of PCBs.15  The rule applied to any substance, mixture, or item with 500 ppm
or greater PCB concentrations.  In 1979, EPA issued the PCS Ban Rule which
superceded the previous labeling and disposal regulation and lowered the
cut-off point from 500 ppm to 50 ppm.  The final rule was published in the
Federal Register on May 31, 1979, and specifically does the following:

    (1)  classifies the use of PCBs in transformers, capacitors, and
         electromagnets as "totally enclosed;"
    (2)  prohibits, unless authorized or exempted by EPA, the manufacturing,
         processing, distribution in commerce, and the use of PCBs except in a
         totally enclosed manner;
    (3)  provides authorizations for certain processing, distribution in
         commerce, and use of PCBs in a non-totally enclosed manner.
    (4)  prohibits waste oil containing any detectable concentrations of PCBs
         from being used as a sealant, coating, or dust control agent.

Also, the February 17, 1978 PCB Disposal and Marking Rule requirements were
integrated into the PCB Ban Rule.15
    Because the Toxic Substances Control Act (TSCA) considers the term
"import" to be.synonomous with "manufacture", no PCBs (except waste) could be
imported or exported after July 2, 1979 under the Ban Rule unless an exemption
was obtained.  Anyone wanting an exemption from the PCB
manufacturing/importation ban or the PCB processing/distribution ban must
petition EPA for if.  In some instances, individuals may not have to seek
separate exemptions when the Agency grants "class" exemptions from certain
processing and commercial distribution bans.  EPA also could grant exceptions,
known as authorizations, without a specific request from those who would
benefit from the authorization to enable the continued processing,
distribution, or use of PCBs in a non-totally enclosed manner after
July 2, 1979.  Exemptions are only valid for a maximum of one year, while
authorizations may be granted for longer periods of time.  Examples of
non-totally enclosed PCB activities and uses which have been authorized by EPA
are as follows s^
                                    25

-------
    •    Servicing PCB Transformers and PCB-Contaminated Transformers;
    •    Use in and Servicing of Railroad Transformers;
    •    Use in and Servicing of Mining Equipment;
    •    Use in Heat Transfer Systems;
    •    Use in Hydraulic Systems;
    •    Use in Carbonless Copy Paper;
    •    Pigments;
    •    Servicing Electromagnets;
    •    Use in Natural Gas Pipeline Compressors;
    •    Small Quantities for Research & Development;
    •    Miscroscopy Mounting Medium.

    On October 30, 1980, in response to a petition from the Environmental
Defense Fund, the U.S. Court of Appeals for the District of Columbia Circuit
set aside portions of the May 31, 1979 Ban Rule.  The court remanded the set
aside portions to EPA for further action.  Responding to the court order, EPA,
on August 25, 1982, amended the May 31, 1979 rule by authorizing the totally
enclosed use of PCBs in certain electrical equipment.33  Among other things,
this amendment authorizes the continued use of PCB small capacitors, the use
of PCB large capacitors until 1988 or longer if certain conditions are met,
and the use of PCB transformers and PCB-contaminated transformers, if certain
conditions are met.  The 1979 rule was further amended on October 21, 1982
when EPA issued a rule excluding from regulation the manufacture, processing,
distribution in commerce, and use of PCBs created in closed manufacturing
processes and controlled waste manufacturing processes.-*3  EPA considers these
PCBs to present very low risks.  This rule permits the manufacture,
                                               t
processing, and distribution in commerce of PCBs without an exemption,
provided that (1) the PCBs are released only in concentrations below the
practical limits of quantitation for PCBs in air emission, water effluents,
                                   26

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products, and process wastes and (2) the wastes from these manufacturing
processes are controlled and disposed of in accordance with the methods for
disposal specified in the rule.33
    On July 10j 1984, a third amendment to the 1979 rule was issued by EPA
that excludes from the TSCA ban on PCBs certain processes that inadvertently
generate PCBs in low level concentrations.  Other rules were issued by EPA en
the same date which dealt with over 100 pending exemption petitions to
manufacture, process and distribute PCBs in commerce and which authorized the
use of PCBs in certain kinds of microscopy, and research and development
situations.  EPA believes that the PCBs permitted by these activities would
not present an unreasonable risk to human health or the environment.33
    Results from a study of the current distribution of PCBs in the United
States are as follows:

         Category                    Amount                      Percent
    Presently in use              3.40 x 108 kg                    60%
    In landfills and dumps        1.32 x 108 kg                    23%
    Released to environment       0.68 x 10** kg                    127»
    Destroyed                     0.25 x 108 Kg                     5%
                   TOTAL          5.65 x 108 Mg                   100%

The results indicate that of the 5.65 x 108 kilograms (1.25 x 109 Ibs) sold
between 1930 and 1977, 95 percent remains in service, in landfills, or at
large in the environment.^3
                                   27

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                                   SECTION 4
                              PCB- EMISSION SOURCES

    The development of emission factors for PCBs presents unique problems not
encountered with standard emission factor development.  These problems can be
summarized as follows:

    •    PCBs have not been produced (except for limited cases) in the U.S.
         since 1977;
    •    PCBs have not been used in "open systems" (those with maximum
         atmospheric release potential) since 1971;
    •    Atmospheric evaporation, transformation and degradation of PCBs 'are
         complex phenomena dependent upon many variables; and
    •    Little research has been conducted to quantify PCB emission rates
         from product use and/or disposal.

    Due to the ban on PCB production and open system use, PCB emissions from
these sources have effectively been halted.  Release to the environment as a
consequence of all PCB use occurred prior to 1970 and was, for the most part,
unintentional.  The major mechanisms by which PCBs are lost to the environment
include aerosolization (during leaks and spills), adsorption onto particulates
(during combustion), and volatilization.  Prior to 1970, the major pathways by
which PCBs were released during use included spillage and vaporization of FCB
containing paints, coatings and plastics; migration and leaching froiu surface
coatings and packaging; leakage from faulty heat exchange systems and
partially sealed hydraulic systems; and burnout of PCB containing ballasts in
fluorescent light fixtures.34-  As the PCB-containing products have been
discarded, the major source of PCB emissions into the environment has shifted
to disposal/destruction methods (e.g., incineration, landfilling).  Incomplete
combustion in an incinerator or boiler may result in the release of PCBs or
PCB byproducts.  Another source of PCB emissions is accidental release due to
failure of an existing piece of PCB equipment (resulting in spills or leaks)
                                   28

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or an accident (e.g., fire) to a piece of PCS equipment in service.  This
section discusses these activities and presents information on the potential
for PCB releases from each.

DISPOSAL/DESTRUCTION METHODS

    EPA's PCB regulations  (40 CFR 761) set specific disposal requirements for
PCBs and PCB items currently in service.35  The requirements are summarized in
Figure 3.  The regulations make distinctions between PCBs, PCB articles (items
that contain PCBs and whose surface(s) have been in direct contact with PCBs),
and PCB containers (barrels, drums, containers, etc. that contain PCBs and
whose surface(s) have been in direct contact with PCBs).  Within these
categories, the regulations make a further distinction based on the PCB
concentration of the waste.  Acceptable PCB disposal technologies are then
based on this PCB concentration.  There are a limited number of disposal
options, summarized as follows:

    •    "Annex I" Incinerators;
    •    High Efficiency Boilers;
    •    "Annex II" Chemical Waste Landfills; and
    •    Other Approved Disposal Methods.

A brief review of these disposal techniques will serve to highlight the
principal characteristics of each.

Annex I Incinerators

Technology Descriptions—

    These incinerators take their designation from the technical standards and
other criteria that they are required to meet when destroying liquid PCB
wastes.  These standards and criteria are found in Annex I of EPA's PCB
                                    29

-------
                                                          WASTE CHARACTERIZATION
                                                                                                                     DISPOSAL REQUIREMENTS
                                      t— Mineral Oil Dielectric fluid*
                                             Frena PCS Tranaformera
                                       — Mineral Oil Dielectric Fluid*
                                             From FOB Contaminated
                                             Transformer*
                                          PCS Liquid Haite* Other Than   	
                                             Mineral Oil  Dielectric fluid
                                                                               Thoae Analyzing > 500 PPM FOB
                                                                               Thoae Analyzing 50 - 500 PPM PCB —
                                                                               Thoae Analyzing > 500 PPM PCB
                                                                           	 Thoae Analyzing 50 - 500 PPM PCB —
                                      1— Bon-Liquid PCB Waate* —
                                             (e.g.  Contaainated
                                             Material*  from Spill*)
                                      — Dredged Material! and -
                                             Municipal  Sewage
                                             Treatment  Sludge*
                                             Containing FGBa
                      PCB Article*
                                          Iran*former•
    CFCB Tran*former* —••—•—'-—•—•-—



    PCB Contaminated tran*former*
                                      —— PCB Capacitor*
                                          PCB Hydraulic Machine*
C
                                      -— Other PCB Articles
r—


*—*
                      PCB Container* —
                                         • fho«* U*ed  to Contain Only PCB*  •
                                             At a Concentration < 500 PPM
                                          Other PCB Container*
    Thoae Containing > 1000 PPM PCB


    Tboae Containing < 1000 PPM PCB


    Those Containing PCB Fluid* 	
                                                                              Those Hoc Containing PCS Fluid*
                                           Annex I Incinerator'"

                                           Annex X Incinerator

                                           Bigh Efficiency  Boiler 140 CFR 761.10

                                           Annex I Incinerator

                                           Annex I Incinerator

                                      	 High Efficiency  Boiler [40 CFR 761.10U)(3)(111) I

                                           Other Approved Incinerator

                                           Annex II Chemical Ua*te Landfill

                                           Annex I Incincerator

                                           Annex II Chemical Waate Landfill

                                           Annex I Incinerator

                                                                  Landfill
•C
E      Annex I Incinerator

      Annex II Chemical  Wa*te Land

      Other Approved Dicpoial Method
       (40 CFR 761.10(*)(5KUi]

C      Annex I Incinerator

      Drained and Rlnaed tranaforcer*
                                     May be Disposed
       of In Annex II  Chemical Waste Landfill

    - Disposal of Drained Transformers
       1* Not Regulated

    * Annex I Incinerator*^'

    * Drained and Rinsed Machine* Hay be Disposed of
       A* Municipal Solid Hast* or Salvaged

    • Drained Machine* May be Disposed of as
       Municipal  Solid Waste or Salvaged

    * Drained Machine* May be Disposed of Per
       Annex I or Annex II

    1  Annex I Incinerator or Annex II Chemical
       Wa*t* Landfill

    '  A*  Municipal Solid Waste Provided  any  Liquid
       PC&a are Drained Prior to  Disposal

    - Annex I Incinerator
E                                          Annex I Incinerator

                                          Annex II,  Provided Any Liquid PCB* Are
                                           Drained Prior to Disposal

                                          Decontaminate Per Annex IV
                      (1)   Annex I Incinerator defined in 40 CFR 761.40.
                      (2)   Requirement* for other  approved incinerator* are defined in 40 CFR 761.10(c).
                      (3)   Annex II chemical v**t« landfill* are described In 40 CFR 761.41.   Annex II diapoaal la permitted If the PCB vaate
                           analyze* It** than 500  pom PCB and 1* not  Ignltabl* a* per 40 CFR  Fart 761.Al(b)(8)(iii).
                      (4)   Dl*po**l of containerized capacitor* in Annex  II landfill* 1* permitted until Kerch 1(  1981.  Thereafter, only Annex I
                           Incineration la permitted.
                                        Figure  3.    Disposal  requirements  for  PCBs  and  PCB  items.
                                                                                                                                            36
                                                                                 30

-------
regulations.35  The minimum operating requirements for disposal of liquid
wastes presented in Annex I include:

    •    2 second dwell time at 1200°C (2190°F) and 3 percent excess oxygen; or
    •    1.5 second dwell time at 1600°C (2910°F) and 2 percent excess oxygen.

    The dwell time refers to the residence time of the PCBs in the combustion
chamber, while the oxygen content is measured in the stack gas.  Additional
criteria, including monitoring requirements, approval conditions, and trial
burn requirements, are also included in the Annex I citation.  These
requirements should be referenced directly to resolve any questions.
    While the .Annex I incinerators were established for liquid PCS wastes,
they may also be employed for solid PCB disposal, provided a destruction and
removal efficiency of 99.9999 percent is met.  Eeference 36 provides a
complete description of operating principles, advantages and disadvantages and
test data for each incinerator design.
    Commercial or industrial incinerators that are intended to destroy liquid
PCB wastes must demonstrate compliance with the Annex I requirements through a
comprehensive trial burn program.  As of 1986, four stationary commercial
incinerators, eight industrial incinerators and two mobile incinerators were
approved as Annex I incinerators under these requirements.37-40  However,
these numbers are subject to change as new approvals are granted, operations
are terminated, and so on.  The commercial units include those operated by
Rollins Environmental Services in Deer Park, Texas; Energy Systems Company
(ENSCO) in El Dorado, Arkansas; General Electric Company in Pittsfield,
Massachusetts; and SCA in Chicago, Illinois.  In addition to approval under  .
the Annex I requirements, Rollins and ENSCO have been approved for solid PCB
disposal under the 99.9999 percent destruction requirement.
                                              i '
    The industrial PCB incinerators approved under Annex I are operated by the
General Electric Company in Waterford, New York; by Dow Chemical in Freeport,
Texas; Oster Creek, Texas; and Plaquemine, Louisiana; by Vulcan Materials in
Geismar, Louisiana; by PPG in Lake Charles, Louisiana; by LaPort Chemical
Corporation in Pasadena, Texas; and by Los Alamos Scientific in Los Alamos,
                                   31

-------
New Mexico.  The Annex I mobile incineration systems are operated by EPA,
Edison, New Jersey; and by Pyrotech, Tullahoma, Tennessee.  The Annex  I mobile
systems have been tested and approved to operate in all ten U.S. EPA regions.^
    Finally, it must be mentioned that municipal sewage sludge incinerators
are used to incinerate PCB-containing sludges at certain locations throughout
the country.  This condition has resulted from the inadvertent PCB
contamination of municipal sewer systems resulting from historical PCB
disposal.  As sludge incinerators are not designed to operate in the
temperature ranges specified for the Annex I requirements, they do not insure
sufficient destruction of the PCBs.  In addition, municipal waste incinerators
have been identified as potential PCB emission sources due to their processing
of PCB-containing wastes.  Sewage sludge and municipal incinerators are
discussed later in this section.

Emissions—

    ApprovedIncineration of Liquid PCB Wastes-Published PCB destruction
efficiency test data for 11 of the EPA approved Annex I liquid waste
incinerators are presented in Table 8.  The location and type of incinerator
associated with each facility is also presented along with the PCB emission
factor that results from applying the stated destruction efficiency on inlet
PCB level for each unit.  The units for the emission factors are grams of PCB
emitted per kilogram of PCB charged (g/kg).  As can be seen from the table,
these emission factors vary as much as four orders of magnitude.  However,
this is not reflective of optimum Annex I incinerator performance.  Several of
these tests were not compliance determinations, but rather research and
development efforts, and were not necessarily conducted under optimum
conditions.  Furthermore, several of the destruction efficiency values were
reported to only two significant figures, making it impossible to calculate an
emission factor less than 0.1 g/kg.  For those'test results that were reported
to five or six significant figures, the corresponding emission factor is, in
most instances, less than 0.001 g/kg.  This level is indicative of optimum
Annex I performance.  The average PCB destruction efficiency for all
stationary incinerator test data presented in the table is 99.997.  This
corresponds to an emission factor of 0.03 g/kg.

                                   32

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    Approved Incineration of Non-Liquid PCB Wastes-Approved incinerators
burning non-liquid PCB articles (such as PCB capacitors) have a mass PCB
emission limitation of 0.001 g PCB/kg of PCB introduced into the incinerator.
This is equivalent to a PCB destruction efficiency of 99.9999 percent and an
emission factor of 0.001 g/kg.

    Sewage Sludge and Municipal Waste Incineration-While neither approved nor
recommended for PCB waste destruction, sewage sludge and municipal waste
                                                                    43-46
incinerators have been identified as potential PCB emission sources.
This can happen when sludge has been contaminated by past industrial
discharges of PCBs or when municipal refuse contains miscellaneous PCB-laden
trash such as fluorescent light ballast capacitors and carbonless copy paper.
While these PCB-containing products are no longer being manufactured, they
will continue to appear in waste streams until their economic life has been
completed.  With time, the quantities of PCB-contaminated sludge and
PCB-containing wastes incinerated in municipal incineration facilities should
slowly decrease.  In addition, the presence of PCE'S in these waste streams,
especially sewage sludge, is highly site specific, dependent upon local
manufacturing and waste discharge characteristics.  Therefore, the PCB
emission factors presented for these incineration facilities will not
necessarily apply to a particular site.
    Emission data for sewage sludge incinerators and municipal solid waste
refuse incinerators are presented in Tables 9 and 10, respectively.  As is
clear from these tables, there is very little data on PCB emissions from
either of these incinerator types.  The New Bedford, Massachusetts and Palo
Alto, California sewage sludge incinerator tests were conducted specifically
to ascertain the PCB destruction efficiency of these units.  Consequently, the
PCB destruction efficiency of these units was reported and an emission factor,
                                     35

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in terms of grams PCBs emitted per kilogram PCB charged, can be calculated.
These factors are presented in Table 9 and show the poor PCB destruction
efficiency that results from use of a sludge incinerator for PCB disposal.  As
the New Bedford, Massachusetts sludge routinely contains PCBs, it was also
possible to calculate a PCB emission factor in terms of grams of PCBs per kg
of sludge feed, and this value is presented in the table.  For the Palo Alto,
California test, PCBs were deliberately added to the sludge, so this sludge
feed emission factor does not apply.  Three other sewage sludge incinerator
test results reported PCB emissions in the stack gas.  These tests did net
investigate the source of the PCBs, the sludge feed PCB concentration, or the
PCB destruction efficiency of the incinerator.  They addressed only PCB stack
gas emissions and reported these emissions in terms of unit mass of PCBs per
unit mass of sludge feed.  These emission factors are also reported in Table 9
(shown as micrograms of PCBs per kilogram sludge in the table).  Note the
order of magnitude discrepancy that exists between the two highest and
two lowest emission factors.  For those sludge incinerators such as New
Bedford and Detroit that are known to be processing PCB contaminated sludge,
the emission factor is 43 micrograms per kilogram sludge (ug/kg).  However,
for the Wyandotte and Akron incinerators, where the source of PCBs is not
known, the emission factor is 4.5 ug/kg sludge.  Based on this limited data
base, it is recommended that the larger emission factor be used when the
sludge is known to contain PCBs, while the smaller value should be employed
when the presence of PCBs is not known or unclear.
    A similar lack of data on PCB emissions exists for municipal refuse
incinerators.*  Data for three incinerators are presented in Table 10.
Averaging test results for the three incinerators gives an overall emission
factor of 18 ug PCBs/kg refuse.  Stack gas emissions of PCBs from the three
incinerators were quantified without determining the incinerator's PCB
destruction efficiency.  While not stated, it is assumed that the PCBs were
(*)Data concerning PCBs from municipal refuse incinerators are currently being
developed by the Office of Solid Waste under the Agency's comprehensive study
of municipal waste combustion.
                                    37

-------
contained in certain segments of the trash.  This is confirmed by published
research findings.  The municipal refuse incinerator studied in Chicago in
1976 consisted of four identical furnaces of the water wall type with a
reciprocating grate stoker and capacity of 400 tons refuse per incinerator per
day.^°  No information was available on design or operation of the other
incinerators tested.
    As part of a recent study on the PCB emissions from burning of coal/refuse
mixtures, the PCB content of various consumer paper products was analyzed.^
This study indicates that such paper products as magazine covers and paper
towels contained up to 139 micrograms of PCB per kilogram of paper (ug/kg).
These levels, which were reported in 1981, were attributed to the repeated
recycle of waste paper containing PCBs.  For example, carbonless copy paper
manufactured prior to 1971 contained PCB levels as high as 7 percent.  This
copy paper then became a component of waste paper which was recycled.  The
PCBs inevitably were introduced into other paper products, resulting in
continued measurable levels in municipal refuse some 4 years after the PCB
manufacturing ban was imposed.  Refuse derived fuel (RDF) manufactured from
these paper products had PCB levels of 8,500 ug/kg, indicating that this fuel
is also a source of atmospheric PCBs.  Therefore, it must be assumed that
municipal refuse does contain detectable levels of PCBs, and that some of
these PCBs will enter the atmosphere when the refuse is incinerated.
    The average emission factor for these two municipal incinerator sets was
3.3 ug of PCBs emitted per kilogram of refuse.   This is approximately equal to
the emission .factor for sewage sludge incinerators which have no obvious
source of PCB contamination.  As with sewage sludge incinerator discharges,
PCB emissions from municipal incinerators are expected to gradually decrease
as the consumer waste products containing PCBs  outlive their useful life and
are discarded, and as recycled PCB articles constitute an increasingly smaller
portion of the incinerator's waste stream.
                                   38

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High Efficiency Boilers


    Conventional industrial and utility boilers can be used to destroy PCBs if

proper combustion conditions are maintained.  These conditions are defined in

the regulations, and include:^5


    1.   The boiler must be rated at a minimum of 50 million Btu/hour.

    2.   The concentration of PCBs in PCB-contaminated fluid shall not exceed
         500 ppm and the rate of PCB-contaminated fluid flow to the boiler
         shall not exceed 10 percent of the total fuel feed rate.

    3.   The waste feed rate to the boiler, the coal and/or oil feed rate and
         the total of both shall be recorded in regular intervals no greater
         than 15 minutes apart.

    4.   The PCB-contaminated fluids shall not be fed to the boiler until it
         is operating at normal operating temperature.

    5.   The carbon monoxide (CO) concentration in the stack gas shall not
         exceed 100 ppm for coal fed units, or 50 ppm for oil or natural gas.
         fired units.

    6.   The excess oxygen (02) in the stack gas shall not be less than 3
         pe'rcent.

    7.   CO and D£ will be monitored in the stack gas-continuously when the
         unit is burning contaminated fluid and will be checked at least once
         every hour.

    8.   The fuel flow, CO and Q£ data recorded shall be retained in file for
         5 years at the boiler address.

    9.   Records of the quantity of contaminated fluid burned in the boiler
         shall be kept on a monthly basis and kept in files at the boiler
         address for at least 5 years.


    EPA has approved 18 high efficiency boilers for PCB disposal based on the

criteria listed above.38  xhe facilities that operate these boilers are listed

in Table 11.  It is uncertain, however, how many of these boilers have

actually burned PCBs, and the total quantity of the PCB fluids destroyed.

This list is subject to change as new approvals are granted, operations are

terminated, and so on.
                                   39

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    TABLES 11.  HIGH EFFICIENCY BOILERS PERMITTED TO BURN PCB LIQUIDS*39'41
          Company
        Location
Public Service Company of
  New Hampshire

New England Power Company

Northeast Utilities

Baltimore Gas & Electric

Potomac Electric & Power

Carolina Power & Light

Duke Power Company

Louisville Gas & Electric

Tennessee Eastman Co.

TVA - Widow's Creek

General Motors Corp.

Hoosier Energy, Inc.

Illinois Power Co.

Northern States Power Company

Otter Tail Power Company

Otter Tail Power Company

Union Electric Company

Washington Water & Power Company
Kerrimac Station, NH


Salem Harbor Station, MA

Middletown, CT

Chase, MD

Korgantown Station, MD

Moncure, NC

Riverbend Station, NC

Louisville, KY

Kingsport, TN

Bridgeport, AL

Bay City, MI

Bloomington, IN

Baldwin, IL

Minneapolis, MN

Fergus Falls, MN

Big Stone, SD

St. Louis, MO

Spokane, WA
*This list is subject to change as new approvals are granted, operations are
 terminated, and so on.  Also, it is uncertain how many of these boilers have
 actually burned PCBs.
                                    40

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Emissions--

    Of the boilers permitted to burn PCB liquids, six are known to have
conducted a PCB destruction efficiency test, even though these tests are not
required by EPA's PCB regulations.38  These six test series results are
presented in Table 12.  In addition, two PCB destruction efficiency tests are
also presented that were conducted on a Florida Power and Light boiler in 1974
and a Continental Can Company boiler in 1976.  However, as of 1986, these
units were not authorized to destroy PCBs.
    Table 12 presents the year of the stack test, the type of primary fuel
fired in the boiler, and the reported destruction efficiency.  As with the
Annex I incinerator test data, the boiler test results have been converted to,
an equivalent emission factor for this study.  The units of this factor are
also grams of PCB emitted per kilogram of PCB burned (g/kg).
    Testing the PCB destruction efficiency of an industrial or utility boiler
presents unique problems because EPA's PCB regulations require that
PCB-contaminated fluids to be incinerated contain no more than 500 ppm of
PCBs.35  Furthermore, these contaminated fluids cannot represent more than 10
percent of the total fuel feed to the boiler.35  Consequently, the total fuel
burned by a high efficiency boiler cannot contain more than 50 parts per
million (ppm) of PCBs.  This ceiling on the PCB concentration fired by a
boiler presents a challenge in determining PCB destruction efficiency.  In
order to ascertain if the boiler is achieving a predetermined destruction
efficiency (e.g., 99.9 percent), a set amount of PCB must be captured from the
stack gas.  However, given current analytical PCB detection limits, and the
rate at which stack gas samples can be collected, sampling times in excess of
4 tp 6 hours per run are often needed to collect a sufficient sample.  For all
tests reported in Table 12, with the exception of the Continental Can test
series, no PCBs were detected in the stack gas sample.  Thus, for the purpose
of determining a PCB destruction efficiency, thp testing company assumed that
PCBs were being emitted at a level identical to the minimum detection limits
of the analytical methodology.  Comparing this asisumed maximum outlet PCB
level with the known inlet PCB level in the fuel permits the calculation of an
                                    41

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estimated minimum PCB destruction efficiency.  These destruction efficiencies,
as can be seen in the table} are generally limited to 99.99 percent.  The
existing PCB sampling and analysis methodologies prohibit the determination of
higher PCB destruction efficiencies unless either the inlet PCB concentration
is increased or the outlet (flue gas) PCB detection sensitivity is increased.
These factors account for the destruction efficiency values in excess of 99.99
percent reported in Table 12.  The PCB regulations currently limit the waste
feed PCB concentration to 500 ppm, effectively capping this option.  The PCB
sensivitity of flue gas sampling can be increased by utilizing a high volume
stack sampling train such as the Source Assessment Sampling System (SASS).
This approach was successfully employed for the Northeast Utilities Test
Program.
    The PCB regulations do not specify a minimum PCB destruction efficiency
for high efficiency boilers.  Six of the approved boilers cited in Table 12
achieved efficiencies in excess of 99.9 percent.  Testing at two of the
boilers resulted in ranges of destruction efficiencies with a minimum value
below 99.9 percent and a maximum value of 99.9 percent or higher.  The
emission factor corresponding to a 99.9 percent destruction efficiency (DE) is
1.0 gram per kilogram while a 99.99 percent DE is equivalent to an emission
factor of 0.1 grams per kilogram.  Averaging the emission factors in Table 12
results in values of 2.0 g PCB/kg PCB burned for oil-fired boilers and 1.0 g
PCB/kg PCB burned for coal-fired boilers.

Annex II Landfills

    Annex II chemical waste landfills can be used for some, but not all, PCB
wastes.  Table 13 lists those PCB wastes that can be disposed in this type of
treatment facility.  The technical requirements for a PCB landfill are set
forth in Annex II of the PCB regulations.35  These requirements address such
factors as thickness and permeability of the soil,, hydrology, flood
protection, topography, ground water monitoring system, leachate collection,
landfill operating and supporting facility standards.  The reader should refer
to Annex II landfill standards to resolve specific questions regarding these
                                    43

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              TABLE 13.  PCS CONTAMINATED MATERIALS ACCEPTABLE FOR
                         LAND DISPOSAL49
                                         Eligible for land disposal
        Description of PCB type            after January ls 1980
PCS Mixture Type

  •  Nonliquid PCB mixtures in the                   No
     form of contaminated soil, rags
     or other solid debris

  *  Soil and solid debris contaminated             Yes
     with PCBs due to a spill or as a
     result of PCB placement in a
     disposal site prior to promulgation
     of final EPA regulations for PCB
     disposal (April 18, 1978)

  •  Dredged materials and municipal                Yes
     sewage sludge that contain PCBs

PCB. Articles

  •  Those articles technically                     Yes
     infeasible for incineration, such
     as drained and flushed transformers3

  •  Sealed capacitors                              No

PCB Containers

  •  Drained containers                             Yes
aWritten application to EPA is required for landfilling articles other than
 transformers.
                                   44

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requirements.  There are currently ten sites that are approved as Annex II
chemical waste landfills.  These sites are listed in Table 14.  However, this
list is subject to change as new approvals are granted, operations are
terminated, and so on.
    In addition to the currently operating sites, there are several sites
throughout the country that have been given permission by the EPA Regional
Offices to conduct a one-time disposal of PCB dredge spoils, contaminated
debris, etc.  It must be recognized that the operating and one-time landfills
are known disposal sites of PCBs that have been reviewed and approved by EPA
since promulgation of its PCB regulations in 1979.  There are, however, many
other conventional sanitary landfills., dumps and other unauthorized and as yet
unidentified disposal sites where PCBs were disposed prior to enactment of the
PCB rules.  It is the PCB emissions from these unknown, unauthorized sites
that cause a problem in estimating total PCB emissions from landfills and
other disposal facilities.  This aspect of the PCB emissions estimation
procedure will be subsequently discussed.

Emissions—

    Estimation of PCB emissions from land disposal facilities, including Annex
II landfills, conventional sanitary landfills, and/or abandoned dump sites, is
difficult.  While data exist on ambient PCB levels in and around landfills,5°
little emission testing has been conducted to quantify mass emission rates of
PCBs.  Furthermore, to calculate PCB emissions from these sources, several
site specific characteristics must be known.  These factors include the
amount, PCB concentration and location of the contaminated waste, the
porosity, organic content and depth of the soil cover employed, and local
temperature, wind speed, and precipitation data.  If these data are available,
then published diffusion equations can be used to calculate landfill
emissions.51  Generally, this information is known for only the newest, most
regulated landfill sites - Annex II landfills.  However, PCBs disposed of in
these landfills are often placed in sealed containers, and PCB emissions from
these sources should not be significant, regardless of site specific
                                    45

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         TABLE 14. 'PCB ANNEX II CHEMICAL WASTE LANDFILLS3'40
                Company
     Location
          CECOS International

          SCA Chemical Waste Services

          Chemical Waste Management

          Chemical Security Systems

          Envirosafe Services of Idaho

          U.S. Ecology

          Chemical Waste Management

          Casmalia Resources

          CECOS International

          U.S. Pollution Control
Niagara Falls, New York

Model City, New York.

Emelle, Alabama

Arlington, Oregon

lit. Home, Idaho

Beatty, Nevada

Kettleman City, California

Casmalia, California

Williamsburg, Ohio

Oklahoma City, Oklahoma
aThis list is subject to change as new approvals are granted,
 operations are terminated, and so on.
                                    46

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conditions.  If sufficient data are available to calculate or estimate PCB
emissions from individual disposal sitesa then a point source emission
estimate can be made.
    Estimating PCB emissions from landfills is further complicated by the
uncertainty regarding the amount and location of PCBs discharged to land
disposal facilities prior to 1970.  These data a:re available, in part, for PCB
manufacturing facilities, but not for the disposal of PCE-containing
products.  Given the widespread use of such PCB-containing consumer items as
paper containers and fluorescent light ballasts, it must be assumed that every
public and commercial landfill site contains PCB products.
    Certain aspects of land disposal of PCBs are known.  If exposed directly
to the atmosphere, a certain portion of-the PCBs will be emitted to the
atmosphere through volatilization, evaporation, and co-distillation.52  in
addition, PCBs may become adsorbed on fine dust in the soil.  This dust may be
entrained by wind, or PCB oil itself may form an aerosol in high wind.  The
Specific amount released is dependent upon the PCB isomer, the type of soil in
contact with the PCB mixture, and the ambient temperature and windspeed.5->
Published data indicate that the less chlorinated (those with four or fewer
chlorine atoms) PCB isomers volatilize faster.53  These less chlorinated
isomers have higher vapor pressures and greater water solubilities and thus
demonstrate increased vaporization and are more mobile in the
environment.54,55  Consequently, PCB wastes with a greater proportion of the
lower isomers will demonstrate a greater loss to the atmosphere.  The type of
soil in contact with the PCB waste affects emissions as soils with greater
organic content tend to bind the PCBs more stromgly, while soils with little
or no organic content (e.g., sand) lose PCBs through evaporation rapidly.5°
This is demonstrated graphically in Figure 4 with the amount of PCB
evaporating varying greatly, depending on the type of soil.  Virtually all of
the PCBs are evaporated from sand, while less than 10 percent was evaporated
from topsoil rich in organic matter.           •
                                   47

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                          after 50 ppb dose
  100
    80
g   60
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                                   Coarse sand
                  200
400       600
   TIME, hours
800
1000
            Figure 4.  Evaporative loss of  C-Aroclor 1242.
                                                    63
                                 48

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    Since the vapor pressure of all PCB mixtures (Aroclors) increases with
temperature,57 the rate of PCB volatilization also increases with
temperature.  In addition, studies have shown that the volatilization will
increase with wind speed.58'  One published PCB emission study attempted to
quantify the effect of temperature and wind speed.  This study was undertaken
in conjunction with the dredging and subsequent land disposal of PCB sediments
from the Hudson River in New York.53  PCB emissions from landfills without
covers and dump sites at this disposal operation were estimated to be 3,000
Ib/yr for a total quantity of 700,000 Ibs of PCBs landfilled.  This translates
to an emission factor of 4.286 g/kg of PCB landfilled.  While this was an
annual estimate, it is assumed that it is valid for only the first year after
PCBs are placed on the land.  Within this year, the relatively rapid
volatilization of the lower PCB isomers would occur, the soil effects would be
exhibited, and the seasonal variations in PCB emissions due to weather effects
would be demonstrated.  No estimate was given for the decrease of these
emissions in the second or subsequent years after disposal of the contaminated
dredge spoils, although a significant decrease would be expected.
    PCBs covered by soil in a managed landfill setting are affected by
additional factors.  Soils slow diffusion of the PCBs to the atmosphere.  This
is especially true for finely divided soils and those with a higher moisture
content.  In addition, cover material with a higher organic content or with a
lower porosity will also limit emissions.  PCBs buried in the ground may also
be affected by other factors which would affect their volatility and emission
potential.  Research studies indicate that microbial action and chemical
decomposition may act on soil-based PCBs and reduce them to less chlorinated
compounds.5^  These by-product compounds may subsequently migrate through the
soil and be released to the atmosphere.  One published estimate states "we
conclude that most PCB isomers with four or fewer chlorine atoms have been
degraded in the environments possibly by microbial action."60  Several other
literature  sources cite a PCB half-life in the'soil (the time required to
reduce the PCB concentration to one-half of its initial value) to be from 5 to
6 years.61,62  Tfce pcs reduction is attributed to volatilization, microbial
action and/or chemical decomposition.  These estimates remain to be proven in
the field and are possibly contradicted by other published data.  Two recent
                                    49

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studies conducted following spills of PCB liquids noted no change in soil
based PCB levels, even 2 years after the initial spill.63'6*  It is not known
if the same PCBs were encountered in all these studies.  This PCB reduction
mechanism requires additional research.
    Only one published reference estimated PCB mass emissions from
landfills."  This study reported the results of sampling at seven different
municipal landfills.  Six of these samples were obtained in 1981 and they
indicated an average PCB emission of 190 nanograms (190 x 10~9 g) of PCB per
cubic meter of methane gas generated.  The study stated that "based on an
estimate that municipal landfills generate 2 x 1012 ft3/yr of methane
nationwide, the results found in this project indicate that such landfills
contribute about 18 kg/yr of PCBs to the atmosphere."6^
    The many site specific and unknown factors involved with calculating PCB
emission rates from landfills make determination of a,generally applicable PCB
emission factor for this source category difficult.*

Other Approved Disposal Methods

Thermal Method—

    In addition to incinerators and boilers, the EPA Regional Administrators
are given authorization by the PCB regulations to approve other thermal
destruction techniques if these processes can effect destruction of PCBs
equivalent to that of incinerators or boilers.  The only technology to gain
such an approval to date is the pyrolysis process operated by the Huber
Corporation in Borger, Texas.  This system will treat contaminated soils.
(*)lnformation related to emissions of toxic compounds from landfills is
currently under development by the Emission Standards and Engineering Division
of the Office of Air Quality Planning and Standards under the Agency's
comprehensive study of hazardous waste treatment, storage, and disposal
facilities.
                                    50

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Several thermal technologies, however, have received short duration (6 month)
approval to conduct research and .development projects.  These include such
diverse projects as use of a -fluid wall reactor, a cement kiln, a diesel
engine, a steam stripping operation, an aluminum melting furnace and a molten
salt process.^

Chemical Dechlorination and Other Konthermal Methods--

    The PCB regulations also give the EPA Regional Administrators the
authority to approve nonthermal PCB disposal methods if they achieve a PCB
disposal/destruction equivalent to that of an Annex I incinerator.  This
mechanism has been used by 11 companies nationwide to gain commercial scale
approval of their chemical dechlorination disposal processes.
    Chemical dechlorination processes use chemical reagents to break apart the
extremely stable PCB molecule, rearranging it to form other chemical compounds
that are considered harmless and environmentally safe.  These processes
destroy the PCB molecule but do not break down the biphenyl structure of the
molecule.  Only the chlorine atoms which give the PCB molecule chemical and
biological stability are removed.
    Most chemical dechlorination processes use a sodium reagent to strip away
the chlorine atoms from the PCB molecule.  The wastes generated from the
process are sodium chloride and nonhalogenated polyphenyls.  The exact
constituents of the polyphenyls are often not known, but indications show that
the sodium chloride and polyphenyls can be disposed of safely.6°
    Most applications involve destruction of PCBs that contaminate otherwise
valuable oil.  The sodium dechlorination processes can be run at ambient or
moderate temperature and, although they chemically destroy the PCBs contained
in oil, they do not destroy the oil itself.  Therefore, the oil can be
recycled for reuse.  Sodium dechlorination is limited in that it is only
capable of economically dechlorinating PCBs in'otherwise valuable oil.
                                   51

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    Dechlorination of PCBs by sodium reagents must be conducted in nitrogen or
similarly inert atmospheres to prevent excessive reagent consumption and fire
hazard due to the hydrogen generation on contact with any water or moisture
present in the oil.""  These dechlorination processes are significant because
they are widely used commercial scale technologies that offer the additional -
benefit of being mobile.  They are currently employed for the decontamination
of mineral oil dielectric fluids from transformers, although additional
research is being conducted on other PCB wastes as well.
    Other nonthermal PCB treatment technologies that have been investigated or
actually approved for commercial scale PCB disposal include physical/chemical
extraction techniques and biological reduction methods.  The physical/chemical
techniques extract the PCBs from transformers or capacitors and concentrate
them for disposal.  They do not destroy the PCBs.  Four companies are
currently permitted by EPA to extract the contained PCBs using these
physical/chemical methods.  These companies are Quadrex HPS, Inc. in
Gainesville, Florida; Environmental International Electrical Services, Inc. in
Kansas City, Kansas; Rose Chemical in Kansas City, Missouri; and PCB
Treatment, Inc. in Kansas City, Missouri.^  Quadrex has been approved for
operation in all ten U.S. EPA regions.^0
    Many bench scale studies have investigated the biodegradability of FCBs.
The PCB concentrations used in these tests have ranged from a few ppb to 1,000
ppm.  In general, these studies have shown that biodegradation can occur, but
the residence times are long and the actual rate of degradation is dependent
on the specific PCB isomer and its chlorine content. *>7  while not a principal
commercial disposal technique or emission source at this time,
biodegradability of PCBs may possibly be used to a greater extent in the
future, especially with regard to spills cleanup.  A commercial scale
biodegradation approval has been issued by EPA Region VI to Detox, Inc. of
Houston, Texas for the treatment of PCB contaminated soils and sludges
although the process is not yet operational.40»68
                                   52

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    Emissions—The 13 companies that are currently approved for chemical
dechlorination of PCS fluids are presented in Table 15.  The PCB concentration
of the waste stream treated by each dechlorination technology is presented in
the table.  Because each technology was required to treat the contaminated
fluids until an outlet PCB concentration of less than 2 ppm was achieved, the
PCB destruction efficiency of each system can be calculated usirg the known
input concentration and the 2 ppm value as a maximum outlet value.  These
destruction efficiency values are also shown on the table, together with an
emission factor which is based on this destruction efficiency.  The emission
factor is in units of micrograms of PCBs released per kilogram of PCB treated.
    Until April 1983, approval of these dechlorination methods was issued by
EPA Regional Offices using a phased approval.  A company typically applied for
approval to dechlorinate PCBs at a specified level, e.g.s 1,000 ppm.  It was
then tested to demonstrate destruction of PCBs to below 2 ppm (the generally
accepted PCB detection limits for this technology).  Certain dechlorination
technologies require that the contaminated PCB fluids be recycled several
times through the process in order to meet this 2 ppm outlet level.  Upon
successful demonstration of PCB removal, the technology was approved with such
items as the maximum processing rate, the maximum inlet PCB concentration and
the recycling rate specified in the approval.  If the company subsequently .
requested approval to decontaminate fluids at a higher PCB level, it was
required to conduct another PCB destruction efficiency test in the region
handling the application.  This test series was conducted in one EPA region
and the resulting test data were usually accepted by all other regions.
    Subsequent to April 29, 1983, all PCB disposal technologies (nonthermal
and thermal alike) that are to be used in more than one EPA Region have to be
approved by EPA Headquarters.  Their approval procedure is expected to be
similar to that previously outlined.
                                    53

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    Since all chemical dechlorination techniques require that the outlet PCB
level be less than 2 ppm, the calculated PCB destruction efficiency is
dependent upon the inlet PCB level.  As shown in Table 15, these inlet PCB
levels vary from 500 to 10,000 ppm, depending on the technology used.
Consequently, the reported PCB destruction efficiencies range from 99.60 to
99.97.  The PCB emission factors corresponding to these destruction
efficiencies range from 4.0 to 0.3 g of PCBs emitted per kilogram of PCB
processed.

ACCIDENTAL RELEASES

Description

    In addition to the principal point and area sources previously discussed,
incidental emissions of PCBs may result from intermittent, accidental releases
such as spills, leaks, fires, etc.  These accidental PCB discharges may enter
the atmosphere through failure and subsequent rupture of an existing piece of
PCB equipment or through an accident (e.g., fire) to a piece of PCB equipment
in service.  Both of these sources of PCB releases can be estimated on a
national basis.
    The PCBs that remain in active service at this time are those contained in
"closed systems", i.e., those pieces of electrical equipment that completely
enclose the PCBs and do not provide direct atmospheric access of the PCBs
during normal use.  This equipment includes PCB transformers, capacitors,
voltage regulators, circuit breakers, and reclosures.  The number of each of
these items, the pounds of PCBs they contain, and the estimate of annual
pounds of PCBs leaked and/or spilled was investigated by the Edison Electric
Institute and by the Utility Solid Wastes Activity Group (EEI/USWAG) for
EPA. 69  These data were subsequently reported in the April 22, 1982 Federal
Register relative to a proposed modification t6 the PCB regulations.^^  These
Federal Register data are presented in Tables 16 and 17.  An additional column
was added to Table 17 to update utility PCB spills/leaks to cover the entire
population of electrical equipment including that owned by industrial firms.
These tables indicate that over 99 percent of the total quantity of PCBs
                                    55

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 TABLE  17.   ESTIMATED PCS LEAKAGE/SPILLAGE FROM ALL CLOSED SYSTEMS
               EQUIPMENT  (UTILITY AND  NONUTILITY)  ?0


PCB transformers
(Aafcarel)
Large FCB capacitors
Mineral oil
transformers

Percentage
of equipment
owned by
utility industry
30*
85b
80"


Percentage
of equipment
owned by non-
utility Industry
70
15
20


Estimated
total number
of units
132,133
3, 294 „ 846
25,284,285

Upper bound
estimate of annual
pounds of PCBs
leaked/spilled
based on total
equipment
population
68,160
434,413
1,033

Large FCB capacitors
Mineral oil
transformers
Mineral voltage
regulators
Mineral oil
circuit breakers
Mineral oil reclosers
Mineral oil cable
' FCB electromagnets
Mineral oil
electromagnets
Small FCB capacitors
85b
80"
85°
85C
85«
85C
1
1-
e
15
20
15
15
15
15
99
99d
e
3, 294 „ 846
25,284,285
170,775
212,869
200,186
7,700 miles
200
7,600
500,000,000£
434,413
1,033
6
60
8
—
—
--
~
•Sourcet  Microeconomic Impacts of the Proposed "FOB B«n Regulations",
 Versar,  Inc., 1978.

bA» reported by the National Electrical Manufacturers Association and referenced
 in the EEI/USHAG study.

cAs*umes  *  distribution equal to that for large PCB capacitors.

^Assumes  that electric utility industry rarely use* electromagnets.

"Small capacitors are used by industry and by consumern.  EPA has no information
 indicating that distribution.
                                                 *
^Assumes  870 million existed in  1977 and 10 percent ar<» removed from service
 annually,  due to equipment or appliance obsolescence und capacitor failure.

Hotei Dashes indicate no data available.
                                   57

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currently contained in electrical equipment are found in PCB transformers
(those containing > 500 ppm of PCBs) and large PCB capacitors  (those
containing > 3 Ibs of PCBs).  The following discussion wills therefore,
concentrate on these items,.although it is applicable to all PCB equipment.
    PCB transformers have an estimated operating life of 40 years,19 while  the
life span of PCB capacitors is estimated at 20 years.22  Until this equipment
lives out its useful operating life and is eventually retired and replaced
with a non-PCB substitute, it will pose a potential threat of PCB emissions
from leaks and/or spills.  Leaks/spills typically occur in transformers when
the gasket joining the top to the body corrodes, tears, or physically fails.
PCBs can then leak past this failed section and potentially spill onto the
surrounding ground.  PCB capacitors typically fail by rupturing, exposing the
contained PCBs to the environment.  This is due to environmental and
weathering effects (e.g., lightning) or material failures (e.g.., metal
fatigue).
    One additional intermittent source of PCBs that was investigated concerned
fires involving PCB equipment.  Transformer and capacitor fires are
infrequent, but when they occur, they can release PCBs as well as toxic
incomplete combustion byproducts such as dioxins and dibenzofurans.71,72
Transformer fires have especially gained widespread attention recently due  to
the elevated PCB contamination levels that resulted from fires in the interior
of buildings in Binghampton, New York and San Francisco, California.

Emissions--

    The EE1/DSWAG report estimated that the average quantity of PCBs spilled
when a PCB transformer leaks or spills varies from 0.56 to 64.5 pounds per
incident, while the spill/leak rate for capacitors is 2.0 to 17.1 pounds per
incident.73  These data translate into the annual leak/spill quantities cited
in Table 17.  When these data are proportioned'to account for non-utility
(industrial) equipment as well, the total amount of PCBs spilled/leaked is
estimated at 503,680 pounds, as indicated in Table 17.  This is an upper-bound
                                   58

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estimate of the potential PCBs released and, as such, does not take into
account spill cleanup procedures which are designed to remove, contain, and
dispose of fluid that has leaked or spilled.
    The proportion of spilled PCB that enters the atmosphere will depend on
the surface onto which the PCBs are spilled (concrete, soil), the PCB isoiaers
that are spilled, the ambient temperature and windspeed, and the cleanup
schedule.  As discussed for landfills, PCBs will evaporate and volatilize more
rapidly from a nonporous surface such as cement or sandy soil, than they will
from an organic rich topsoil.  Also, in dry conditions or high winds, PCBs may
become entrained either as an aerosol or by being adsorbed on fine soil
particles that are subject to entrainment.
    Due to their nonflammability characteristics, PCB transformers are
typically installed as safety precaution in urban settings where the
consequences of a transformer fire would be most severe.  These installations
include schoolss hospitals and office buildings.  Consequently, it can be
assumed that the average PCB unit is mounted on a solid base.  This would
enhance vaporization potential in the event of a leak or spill.  In addition,
PCB transformers and capacitors have historically used Aroclors 1242, 1254,
and 1016.8  -j^g 1242 and 1016 mixtures contain up to 90 percent by weight of
the lower isomer PCBs (less than four chlorine atoms), while Aroclor 1254
contains only 20 percent by weight of the lower isomer PCBs.74  These lower
isomers are more likely to be evaporated from an impervious surface.  This is
shown graphically in Figures 5 and 6.  For both wet and dry sand, up to 80
percent of the PCBs are lost to the atmosphere within 4 weeks of the spill.
These results indicate that for Aroclors 1016 and 1242, a majority of the
spilled PCBs may be volatilized if the contaminated surface beneath the
transformer or capacitor is sand or concrete and cleanup is not prompt.
However, volatilization in actual field conditions may be less because of
removal by other mechanisms such as run-off, percolation, and so on.
    Temperature also plays an important role in the amount of PCB evaporated
from a spill because of the increase in vapor pressure that occurs with
increasing temperature.^5  Figure 7 shows the variation in volatilization
rates for temperatures of 26°C (79°F) and 60°C (140°F).
                                    59

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Z LOST
          20


          40


          60


          80
                 PCS 1254 Vapor Loss <§ 26*C from Dry Sand
                                               7C1
                                2         3
                                TIME  (weeks)
    Z LOST
       20

       [
       40


       60


       80
             _  PCS 1254 Vapor Loss @  26*C from Wetted Sand
                                                  7C1
                                2         3

                               TIME (weeks)
Figures 5 and 6.  Volatilization of PCB isomers from Ottawa Sand
                  contaminated with Aroclor 1254.
                              60

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    Finally, the rapidity with which spills are cleaned up will affect the
amount discharged to the atmosphere.  Final EPA regulations affecting PCB
electrical equipment require quarterly inspections of PCB transformers, but no
mandatory inspections for PCB capacitors.?^  The purpose of the inspections is
to minimize environmental releases that result from spills and leaks.
However, the utility industry has stated?? that a large failure of a PCB
transformer or capacitor would cause a service interruption and this would be
addressed immediately, so the quarterly inspection is not necessarily an
accurate indicator of the response time required for cleanup of a spill or
leak.  No estimate of the average response time for a PCB leak was found in
the literature.
    The number and diversity of factors affecting PCB emissions from spills
and leaks makes estimation of an emission factor difficult.  Immediate cleanup
of a transformer spill that occurs in New England in mid-winter may result ir,
a negligible release of PCBs, while a continuous leak that occurs in the
middle of the summer in the southwest may lead to a substantial PCB release.
Each case should be treated individually. Emissions from spilled PCBs are
somewhat analagous to those from uncovered dredge spoils.  Although the
emission factor for dredge spoils is only a very rough approximation, it can
be applied to PCB spills in lieu of additional data.  An estimated PCB
emission rate of 4.286 g/1 of landfilled PCBs was reported for the dredge
spoils cleanup project in New York (see Emissions from Annex II Landfills).
    For fires involving PCB transformers or capacitors, the amount of PCBs
released is dependent upon the extensiveness of the fire and the speed at
which it is extinguished.  A number of these fires have been documented.  A
New York fire involving 200 gallons of transformer fluid containing some 65
percent by weight PCEs resulted in a release of up to 1,300 pounds of PCBs.78
A capacitor fire which burned uncontrolled for two hours in Sweden resulted in
the destruction of 12 large utility capacitors containing an estimated 25
pounds of PCBs each, for a total potential release of 300 pounds.  However,
data are incomplete on the exact amount of PCBs released as a result of these
two fires.
                                   62

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    An ongoing EPA investigation into the annual number of FOB transformer
fires sets this figure at approximately 20 per year.75  The number of PCB
capacitor fires is unknown.  As these PCB items reach the ends of their
economic lives or are retired due to premature failure, their susceptibility
to fires will be eliminated and the overall number of FOB transformer and
capacitor fires will be reduced.
                                    63

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                                   SECTION 5
                             SOURCE TEST PROCEDURES

    PCS emissions from industrial, sewage sludge, and municipal refuse
incinerators can be measured using a modification of EPA Reference
Method 5.80  This method begins with a sample of gaseous and particulste PCBs
being withdrawn ispkinetically from the source through a series of four
impingers with a Florisil absorbent tube between the third and fourth
impinger, as shown in Figure 8.
    The first and second impingers are of the Greenburg-Smith design.  The
final two impingers are of the Greenburg-Smith design modified by replacing
the tip with a 1.3 cm (1/2 inch) ID glass tube extending to 1.3 cm from the
bottom of the flask.  The absorbent tube has a 2.2 cm inner diameter, is at
least 10 cm long, and has four deep indentions on the inlet end to aid in
retaining the absorbent.  Ground glass caps are used to seal the
absorbent-filled tube prior to and following sampling.  The Flcrisil is
activated by heating to 650°C for 2 hours in a muffle furnace.  After allowing
to cool to near 110°C, the clean, active Florisil should be transferred to a
clean, hexane-washed glass jar, sealed with a TFE®-lined lid, and stored at
110°C, until taken to the field for use.  If the Florisil is stored more than
1 month it must be reactivated before use.80
    In assembling the sampling train, sealant greases should not be used.
Place 200 ml of water in each of the first two impingers and leave the third
empty..  If the preliminary moisture determination shows that the stack gases
are saturated or supersaturated, one or two additional empty impingers should
be added to the train between the third impinger and the Florisil tube.  Place
200 to 300 grams or more of silica gel in the last impinger.  Weigh each
impinger and record the weights.  Crushed ice is placed around the impingers
after the sample train is assembled.80
    The sample is collected by pumping air through the sampling train.  At the
end of the sampling run, the probe is removed from the stack and proper
cleanup procedures are followed.  The first three impingers are removed, the
outsides are wiped off, and the weights are recorded.80
                                    64

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                             65

-------
    The sample is extracted from the impingers and absorbent tube.  The
extract is dried and cleaned and is then perchlorinated with antimony
pentachloride.  Hexane is added to the reaction mixture to remove the residual
antimony pentachloride.  The solution is allowed to separate into layers and
the upper layer is filtered through a column of anhydrous sodium sulfate.^O
    The filtered sample is then assayed for decachlorobiphenyl  (DCB) by gas
chromatography (GC).  The recommended GC column is 2 mm ID by 1.8 m glass
packed with 3 percent OV-210 on 100/120 mesh inert support such as
supercoportf  The GC should be fitted with an electron capture detector
capable of operation at 300°G.  Column temperature and carrier gas flow
parameters of 240°C and 30 ml/minute are typically appropriate.80
    The peak area corresponding to the retention time of DCS is measured and
compared to peak areas for a set of standard DCB solutions to determine the
DCB concentration.  The concentrations of the standard solutions should allow
fairly close comparison with DCB in the sample extracts.  Standard
concentrations of 25 to 50 piccgrams/microliter may be appropriate.^^
                                   66

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                                   REFERENCES


 1. Polychlorinated Biphenyls.  National Research Council, National  Academy  of
    Sciences, Washington, B.C., 1979.  pp.  1-2.

 2. Durfee, R.L., et al.  PCBs in the United States  -  Industrial Use and
    Environmental Distributions.  U.S. Environmental Protection Agency,
    Washington, B.C.  Publication No. EPA 560/6-76-005, February 1976.
    pp. 35-36.

 3. Reference 1, pp. 144-145.

 4. Reference 1, p. 153.

 5. Reference 2, p. 47.

 6. Reference 2, p. 1.

 7. Encyclopedia of Chemical Technology, 3rd Edition, Volume 5.  Wiley
    Interscience Publication, New York, NY, 1979.  pp. 844-846.

 8. Hutzinger, 0., Safe, S., and V. Zitko.  The Chemistry of PCBs.   CRC Press,
    Cleveland, Ohio, 1974.  pp. 7-12.

 9. Letter from Alice Mayer, Chemical Manufacturers Association to
    David Misenheimer, GCA/Technology Division providing data on physical
    properties of Aroclors.  January 23, 1986.

10. Reference 1, pp. 150-151.

11. Reference 1, p. 154.

12. Reference 1, pp. 159-160.

13. NRECA PCB Equipment Operations and Management Manual.   National Rural
    Electric Cooperative Association, Washington, D.C., March 1983.  p. 6.

14. EPA's Final PCB Ban Rule:  Over 100 Questions and Answers to Help You Meet
    These Requirements.  U.S. Environmental Protection Agency,  Office of Toxic
    Substances, Washington, D.C.,  June 1979.  pp. 2-8.

15. Reference 1, p. 147.

16. Reference 1, p. 14.

17. PCBs and the Environment, COM-72-10419,  Interdepartmental Task Force on
    PCBs,  Department of Agriculture,  March 1972, p.  52.
                                    67

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18. Fullers B., Gordon, J., and M. Kornreich.  Environmental Assessment of
    PCBs in the Atmosphere.  EPA 450/3-77-045, U.S. Environmental Protection
    Agency, Office of Air Quality Planning and Standards, Research Triangle
    Park, North Carolina, November 1977, p. 4-20,.

19. Disposal of Polychlorinated Biphenyls (PCBs) and PCB Contaminated
    Materials, Volume 1.  EPK.I FP-1207, Electric Power Research Institute,
    Palo Alto, California, October 1979, p. 3-3.

20. Reference 18, p. 4-21.

21. Cantos, G., Durfee, R.L., Hackman III, E.E., and K. Price.  Assessment of
    Wastewater Management, Treatment Technology and Associated Costs for
    Abatement of PCBs Concentrations in Industrial Effluents.
    EPA 560/6-76-006, U.S. Environmental Protection Agency, Office of Toxic
    Substances, Washington, D.C., January 30, 1976, pp. 32-34.

22. Reference 19, p. 3-6.

23. Reference 8, p. 9.

24. Reference 18, pp. 4-12 to 4-13.

25. Reference 17, p. 54.

26. Reference 17, p. 59.

27. Reference 17, p. 58.

28. Reference 18, pp. 4-9, 4-18.

29. Reference 17, p. 62.

30. Reference 17, p. 64.

31. Reference 17, p. 65.

32. Reference 18, p. 4-34.

33. TSCA Chemical-In-Progress Bulletin, U.S. Environmental Protection Agency,
    Office of Pesticide and Toxic Substances, Washington, B.C.  Vol. 5, No. 4,
    September 1984.

34. Reference 18, p. 1-8.

35. Polychlorinated Biphenyls (PCBs), Manufacturing, Processing, Distribution
    in Commerce and Use Prohibitions, 40 CFR Part 761, Federal Register,
    Volume 44, No. 106, May 31, 1979, pp. 31514-31568.
                                    68

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 36. Ackerman, D.G.,  et  al.   Guidelines  for  the Disposal of PCBs and PGB Items
    by  Thermal Destruction.   EPA 600/2-81-022,  U.S.  Environmental Protection
    Agency,  Industrial  Environmental  Research Laboratory,  Research Triangle
    Park, North  Carolina, February  1981,  p.  7.

 37. Letter  from  Ed Cohen, EPA Region  III  Hazardous Waste Management Division
    to  Tom  Lahre, Office of  Air  Quality Planning  and Standards,  U.S.
    Environmental Protection Agency.  February 7,  1985

 38. Mclnnes, R.G., and  R.C.  Adams.  Provision of  Technical Assistance to
    Support  Implementation of the PCS Regulations  (January -  December 1983),
    U.S. Environmental  Protection Agency, Office  of  Research  and Development,
    Washington,  D.C., May 1984.

 39. Telephone conversation between  Joan Juzitis, EPA Region I Air and
    Hazardous Materials Division and  David Misenheimer,  GCA/Technology
    Division, February  4, 1986.

 40. Information  on PCS  disposal  companies sent  by John  Smith,  Office  of Toxic
    Substances,  U.S. Environmental  Protection Agency to  David Misenheimer,
    GCA/Technology Division,  January  31,  1986.

 41. Reference 38, Appendices  C and  D,

 42. Reference 36, p. 55.

 43. Piispanen, W., Cass, R.W., Bradway, R.M., and A.S. Werner.   PCB Compounds
    Emanating from the New Bedford  Municipal  Sewage  Sludge Incinerator,  Final
    Report Prepared by GCA/Technology Division, Bedford, Massachusetts.  EPA
    Contract No. 68-01-3154,  Task Order No.  24, September  1977.

 44. Whitmore, F.C.  Destruction  of  Polychlorinated Biphenyls  in  Sewage  Sludge
    During Incineration, Final Report Prepared by Versar,  Inc.,  Springfield,
    Virginia for U.S. Environmental Protection Agency, Washington,  D.C.  EPA
    Contract No. 68-01-1587.

 45. Murphy, T.J., et al.  PCB Emissions to the Atmosphere  from Municipal
    Landfills and Incinerators,  Paper presented before The American Chemical
    Society, Division of Environmental Chemistry,- Kansas City, Missouri,
    September 1980.

 46. Petkus, E.J., G.S. Kimura, and W.T.  Throp.  Polychlorinated Biphenyl
    Emissions from a Municipal Incinerator.  Paper presented at 70th Meeting
    of the Air Pollution Control Association, Toronto, Canada, June 1977.

47. Richard, J.J., and G.A.  Junk.  Polychlorinated Biphenyls in Effluents from
    Combustion of Coal/Refuse, Environmental Science and Technology, Vol. 15,
    No.  9,  September 1981.   pp.  1095-1100.
                                    69

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48. Hunt, G.T., Wolf, P., and P.F. Fennelly.  Incineration of Polychlorinated
    Biphenyls in High Efficiency Boilers:  A Viable Disposal Option,
    Environmental Science and Technology, Vol. 18, No. 3, 1984.  pp. 171-179.

49. Reference 19, p. 7-6.

50. MacLeod, K.E.  Sources of Emissions of Polchlorinated Biphenyls into the
    Ambient Atmosphere and Indoor Air.  EPA 600/4-79-022, U.S. Environmental
    Protection Agency, Health Effects Research Laboratory, Research Triangle
    Park, North Carolina, March 1979.  p. 38.

51. Shen, Dr. T.T.  Estimating Hazardous Air Emissions from Disposal Sites,
    Pollution Engineering, Vol. 13, No. 8, August  1981.  pp. 31-34.

52. Reference 18, pp. 4-35.

53. Tofflemire, T.J., Eng, D.,'and T.S. Shen.  Volatilization of PCB from
    Sediment and Water:  Experimental and Field Data Proceedings of the
    Mid-Atlantic Industrial-Waste Conference, Pennsylvania State University,
    July 15-17, 1979.  pp. 100-109.

54. Nisbet, I.C., and A.F. Sarofim.  Rates and Routes of Transport of PCBs  in
    the Environment, Environmental Health Perspectives, Volume 1, April 1972,
    pp. 25-27.

55. Reference 8, pp. 10-17.

56. Reference 53, p. 9.

57. Reference 53, p. 27.

58. Reference 53, p. 30.

59. Destruction Technologies  for Polychlorinated Biphenyls, Environment
    Canada, Waste Management  Branch, Toronto, Canada, 1982.  p. 76.

60. Reference 54, p. 29.

61. Reference 18, pp.  1-16.

62. McClure, V.E.  Transport  of Heavy Chlorinated  Hydrocarbons in the
    Atmosphere, Environmental Science and Technology, Vol. 10, No.  13,
    December 1976.   pp.  1223-1229.

63. Follow-up Study  of the Distribution and Fate of Polychlorinated Biphenyls
    and  Benzenes in  Soil and  Ground Water Samples  After an Accidental Spill of
    Transformer Fluid.   EPA 904/9-76-014, U.S. Environmental Protection
    Agency, Atlanta, Georgia,  January 1976.   p. 1.

64. Reference  19, p. 7-1.
                                     70

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65. Reference 45, p.  208.

66. Reference 56, p.  48.

67. Mclnnes, R.G., and R.J. Johnson.  Provision  of  Technical  Assistance  to
    Support Implementation off  the PCB Regulations  (January  -  December  1982),
    U.S. Environmental Protection Agency, Office of Research  and  Development,
    Washington, B.C., May 1983, Appendix G.

68. Letter from Judy  Gordon, Office of Solid Waste,  U.S. Environmental
    Protection Agency to Tom Lahre, Office of Air Quality Planning  and
    Standards, U.S. Environmental Protection Agency.  February 4, 1985.

69. Comments.and Studies on the Use of Polychlorinated Biphenyls  in Response
    to an Order of the U.S. Court of Appeals for the District of  Columbia
    Circuit, Submitted by the Utility Solids Waste  Activities Group, the
    Edison Electric Institute, and the National  Rural Electric Cooperative
    Association, February 12,  1982.

70. Polychlorinated Biphenyls  (PCBs); Use in Electrical Equipment:  Proposed
    Rules, 40 CFR Part 761, Federal Register, Vol.  47, No.  78,
    April 22, 1982.  pp. 17426-17446.

71. Jansson, B., and G. Sundstrom.  Formation of Polychlorinated Dibenzofurans
    (PCDF) During a Fire Accident in Capacitors  Containing  Polychlorinated
    Biphenyls (PCBs).

72. Rappe, C., et al.  Polychlorinated Dioxins (PCDDs), Dibenzofurans (PCDFs),
    and other Polynuclear Aromatics (PCPNAs) Formed During  Fires, Chemical
    Scripta, Vol. 20, 1982.  pp. 56-61.

73. Reference 69, p.  13.

74. Reference 8, p. 23.

75. Haque, R., Schmedding,  D.W., and V.H.  Freid.   Aqueous Solubility,
    Adsorption and Vapor Behavior of Polychlorinated Biphenyl Aloclor 1254,
    Environmental Science and Technology,  Vol.  8, No. 2,  February 1974.
    pp. 139-142.

76. Polychlorinated Biphenyls (PCBs) Used in Electrical Equipment, Final Rule,
    40 CFR Part 761,  Federal Register,  Vol.  47,  No.  165,  August 25,  1982.
    pp. 37342-37360.

77. Bosy,  B., et al.   Analysis of Public Comments on a Proposed PCB Rule,
    Prepared by GCA/Technology Division  for U.S.  Environmental Protection
    Agency,  Office of Pesticides and Toxic Substances.   Contract 68-01-5960,
    Technical Directive No.  16, Washington,  D.C., August  1982.  pp.  68-73.
                                    71

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78. Schecterj A.  Contamination of an Office Building in Binghampton, New York
    by PCBs, Dixons, Furans, and Biphenylenes After an Electrical Panel and
    Electrical Transformer Incident, Chemosphere,, Vol. 12, No. 415, 1983.
    pp. 669-680.

79. Telephone conversation between Suzanne Ruzinski, EPA Office of Toxic
    Substances and Robert McTnnes, GCA/Technology Division, June 26, 1984.

80. Haile, C.L., and E. Baladi.  Methods for Determining the Polychlorinated
    Biphenyl Emissions from Incineration and Transformer Filling Plants.
    EPA-600/4-77-078, U.S. Environmental Protection Agency, Research Triangle
    Park, NC.  November 1977.  pp. 52-73.

81. Reference 80, p. 54.

82. Telephone conversation between Jane Kim, EPA Office of Toxic Substances
    and David Misenheimer, Alliance Technologies Corporation  (formerly GCA
    Technology Division), November 18, 1986.
                                    72

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                                    TECHNICAL REPORT DATA
                             (Please read Instructions on tin; reverse before c
 1. REPORT NO.
  EPA-450/4-84-007n
                                                            3. RECIPIENT'S ACCESSION NO.
                         AIR EMISSIONS  FROM
SOURCES OF POLYCHLORINATED BIPHENYLS  (PCB)
                                                            5. REPORT DATE
                                                              May  1987
                                                            6. PERFORMING ORGANIZATION CODE
 '. AUTHORlS)
           Alliance Technologies
           Chapel  Hill, NC  27514
                                                            8. PERFORMING ORGANIZATION REPORT -,C
 9. PERFORM
          •IG ORGANIZATION NAME AND ADDRESS
                                                             10. PROGRAM ELEMENT NO.
                                                            11. CONTRACT.GRANT NO.
 12. SPONSORING AGENCY NAME AND ADDRESS
   U.S. Environmental  Protection Agency
   Office Of Air  Quality Planning And Standards
   Air Management Technology Branch   (MD-14)
   Research'Triangle Park,  NC  27711
                                                          13. TYPE OF REPORT AND PERIOD COVERED
                                                          14. SPONSORING AGENCY CODE
 15. SUPPLEMENTARY NOTES
   EPA Project  Officer:   David C. Misenheimer
   To assist groups  interested in inventorying air emissions of various  potentially
   toxic substances,  EPA is preparing a  series of documents such as  this to compile
   available information on sources and  emissions of these substances.   This document
   deals specifically with Polychlorin-ated  Biphenyls.  Its intended  audience includes
   Federal, State  and local air pollution personnel  and others interested in locating
   potential emitters of Polychlorinated Biphenyls and in making gross estimates of
   air emissions therefrom.

   This document presents information on 1)  the types of sources that may emit
   Polychlorinated Biphenyls, 2) process variations  and release points that may be
   expected within these sources, and 3) available emissions information indicating
   the potential for  Polychlorinated Biphenyls release into the air  from each
   ooeration.
                                KEY WORDS AND DOCUMENT ANALYSIS
                  DESCRIPTORS
                                              b.IDENTIFIERS/OPEN ENDED TERMS
                                                                            COSAT1 I-'ield/Crc
   Polychlorinated  Biphenyls
   Sources
   Locating Emissions  Sources
   Toxic Substances
                                              19. SECURITY CLASS (This Report 1
                                              20. SfcCURITY CLASS (This page)
                                                                          21. NO. OF PAGES
                                                                             80
                                                                         22. PRICE
EPA Form 2220-1 (Rev. 4-77)   PREVIOUS EDITION is OBSOLETE

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