United States
                   Environmental Protection
                   Agency
Air and Energy Engineering
Research Laboratory
Research Triangle Park, NC 27711
                   Research and Development
EPA/600/SR-93/044  May 1993
&EPA       Project Summary
                    Characterization  of
                    Emissions  from  the Simulated
                    Open-Burning of Non-Metallic
                    Automobile  Shredder  Residue
                    Jeffrey V. Ryan and Christopher C. Lutes
                     The reclamation process for  recy-
                    clable ferrous and non-ferrous metals
                    from scrap automobiles generates  a
                    non-metallic  waste  product called
                    "fluff," consisting of a combination of
                    plastics, rubber, glass, wood products,
                    and electrical wiring. The waste  prod-
                    uct is often stockpiled or landfilled.  A
                    number of these stockpiles have caught
                    fire,  resulting  in the emission of nu-
                    merous air pollutants. To gain insight
                    into the types and quantities of  these
                    air pollutants, a study was conducted
                    in which the open combustion of fluff
                    was simulated and the resulting  emis-
                    sions collected  and characterized.
                    Samples were collected and analyzed
                    for volatile and semivolatile organics,
                    particulate, and metal aerosols. Typical
                    combustion process gases—carbon di-
                    oxide, carbon monoxide, nitric oxide,
                    oxygen, and unburned hydrocarbons—
                    were monitored continuously. The
                    samples were analyzed using gas chro-
                    matography (GC)/mass  spectroscopy,
                    GC/flame ionization detection, gravimet-
                    ric, and atomic  emission methodolo-
                    gies to identify and quantify the  types
                    of compounds present in the open com-
                    bustion process emissions. The result-
                    ing mass/volume concentrations were
                    related to the measured net mass  of
                    material consumed  through combus-
                    tion  and known dilution air volume  to
                    derive an estimate of overall emissions.
                    Volatile and semivolatile organics char-
                    acterized included mono- and polyaro-
                    matic hydrocarbons,  substituted
                    alkanes and alkenes, aldehydes, nitrites,
                    phenols, chlorinated aromatics, hetero-
cycles, and polychlorinated dibenzodi-
oxins and furans. Of the 11 metal aero-
sols characterized, cadmium, copper,
lead, and zinc were found in significant
quantities. The emission characteriza-
tions performed indicated that substan-
tial quantities of air  pollutants are
emitted. For the organic pollutants
alone, the emission of more than 200
g/kg of fluff combusted was observed.
   This Project Summary was devel-
oped by EPA's Air and Energy Engi-
neering Research Laboratory, Research
Triangle Park, NC, to announce key find-
ings of the research project that is fully
documented in a separate report of the
same title (see Project Report ordering
information at back).

Introduction
  The reclamation process for ferrous and
non-ferrous metals from scrap automo-
biles generates a non-metallic waste prod-
uct called "fluff." For the most part, fluff
consists of a combination of plastics such
as polyethylene, polypropylene, acryloni-
trile-butadiene-styrene, polyurethane foam,
polyvinylchloride, rubber, glass, wood prod-
ucts, cloth, paper, dirt, and electrical wir-
ing. Conservatively, it can  be estimated
that 9.1  x 108 kg (2 x 109 Ib)  of fluff  is
produced annually.
  The automobile fluff is discarded at land-
fills or, more commonly, stockpiled on site.
At several automobile reclamation facili-
ties, these stockpiles have caught fire.
One such stockpile fire, in Montvale, VA,
burned for 38 days emitting unknown quan-
tities of potentially harmful air pollutants. It
was estimated that 13,000-16,000 bales
                                                                    Printed on Recycled Paper

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of fluff, weighing approximately 1,360 kg
(3,000 Ib) each, were burned in the fire.
During the fire,  several  attempts  were
made both to extinguish it and to acceler-
ate  combustion.  The  Commonwealth of
Virginia's Department of Air Pollution Con-
trol  contacted EPA's Control Technology
Center (CTC) requesting  emissions data
on combustion of this material. Unfortu-
nately, data  pertaining to  the open burn-
ing  of fluff or any similar material  were
extremely limited. As a result, the CTC felt
that a study  characterizing the emissions
resulting from the open combustion of fluff
was warranted. Under contract to EPA's
Air  and  Energy  Engineering  Research
Laboratory (AEERL), Acurex Environmen-
tal performed a study which identified and
quantified organic and inorganic emission
products  produced  during the  simulated
open  combustion  of fluff.  The study was
designed  to  roughly  estimate emission
rates  (within  an order of  magnitude) for
volatile arid semivolatile organics, particu-
late, and selected metal aerosols identi-
fied in combustion emissions.  Emphasis
was placed on gaining a broad overview
of the pollutants produced.

Experimental
  The project consisted of replicate tests
to collect  and qualitatively and quantita-
tively  characterize organic and inorganic
emissions resulting from  the  simulated
open combustion of actual automobile fluff
waste. Small quantities (9-11 kg, 20-25 Ib)
of fluff, obtained from an automobile rec-
lamation facility, were combusted in a test
facility designed for simulation of  open
combustion conditions (see Figure  1). A
representative air sample  from the burn
hut  environment is delivered  to a  sam-
pling facility,  adjacent to the burn hut.
  The sampling facility contains most of
the  associated sampling  equipment: the
volatile organic sampling train (VOST) sys-
tem, the semivolatile organics/particulate
sample collection  systems, and the  par-
ticulate removal system for the continuous
emission monitors (CEMs).
  Fixed combustion gases—carbon  mon-
oxide (CO),  carbon dioxide (CO2),  nitric
oxide (NO),  oxygen (02),  and  unburned
hydrocarbons (THC)—were measured con-
tinuously using on-line process analyzers.
Volatile organics were collected using the
VOST system. Semivolatile organics and
particulate were collected  using a sample
system modified for use in this study. Two
separate  semivolatile organic/particulate
collection systems were operated simulta-
neously during the test period. One sample
system was  used to collect samples for
general semivolatile organic and particu-
                 Sample Duct
                                 Fluff Combustion
                                    Container
       Air Inlet

                                                                  Air Inlet
                                 Weighing Platform
Figure 1.  Diagram of burn hut.
late characterization, while the remaining
system was used to collect samples for
polychlorinated dibenzodioxin (PCDD) and
polychlorinated  dibenzofuran  (PCDF)
analyses. A separate particulate sampling
system was used to collect metal  aero-
sols. A medium volume (4 cfm, 0.00189
m3s) ambient particulate sampler was used
to collect  particulate 10-um in diameter
and less.
  The VOST samples were analyzed by
gas chromatography/mass spectroscopy/
flame ionization detection (GC/MS/FID) on
a purge-and-trap thermal desorption sys-
tem. Compounds were identified  using
multi-component calibration standard com-
parisons, mass spectral library searches,
and investigator  interpretation.  Identified
analytes were quantified using a combi-
nation of GC/MS and GC/FID system re-
sponses based on the characteristics  of
the identified compound.
  The semivolatile organics from the gen-
eral organics samples were retrieved from
the collection media by soxhlet extraction
using dichloromethane.  The XAD-2 was
extracted separately from the particulate
fraction. Both the particulate extracts and
the XAD-2 extracts were analyzed indi-
vidually for total chromatographable or-
ganics (TCO)—(organic compounds with
boiling points of 100-300 °C)—and  total
gravimetric organics  (GRAV)—(organic
compounds with boiling points > 300 °C).
  Individual semivolatile organic  com-
pounds were identified and quantified us-
ing  an approach similar  to that used for
the  volatile organics. The XAD-2 and par-
ticulate extracts were analyzed separately
by GC/MS to obtain mass spectral infor-
mation. The mass spectra of acquired data
were compared to mass spectra of multi-
component standard mixes as well as the
mass spectral database to  assign com-
pound identification. Identified  analytes
were  quantified using a combination of
GC/MS and GC/FID system responses
based on  the characteristics of the com-
pound identified.
  The PCDD/PCDF samples were  ana-
lyzed by low  resolution GC/MS. Isotopi-
cally labeled homologues for all congeners
were used for qualitative and quantitative
purposes.
  Metals potentially present  in fluff were
chosen for characterization. The samples
were analyzed by inductively coupled ar-
gon  plasma-atomic  emission (ICAP) for
aluminum  (Al), arsenic (As), barium (Ba),

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cadmium (Cd), total chromium (Cr), cop-
per (Cu), lead (Pb), magnesium (Mg), se-
lenium (Se), and zinc (Zn).

Results and  Discussion
  Nominally,  11 kg (25 Ib) of fluff was
evaluated for each test.  Not all of the
material tested  was actually combusted
during the testing. Only about 45% of the
mass of fluff placed in the  combustion
apparatus was actually combusted during
the 200 min test. The remaining ash and
incombustible material was not character-
ized.
  Maximum burn  rates were  observed
within 20 min of  material  ignition.  After
this time, burn rates gradually decreased
throughout  the burn. Peak temperatures,
observed by  a  thermocouple placed  di-
rectly over the combustion apparatus, cor-
relate well with peak burn rates. Similarly,
peak concentrations for CO, CO2, and NO
emissions,  correlate reasonably  well with
peak  burn  rates.  During the burns,  O2
concentrations remained greater than 19%.
  GC/MS analysis of the collected VOST
samples identified more  than  50  com-
pounds. However, for the range of volatile
compounds characterized, more than 100
peaks were evident in the GC/FID  chro-
matograms. Most of the compounds iden-
tified were alkanes, alkenes, cycloalkanes,
and alkyl substituted aromatics. However,
aldehydes,  ketones, alcohols, nitriles, and
chlorinated  aromatics were also identified.
The types of volatile compounds identified
are consistent with compounds identified
during thermal  decomposition studies  of
individual plastics.
  Figure 2 depicts estimated emissions
for  volatile organic compounds  (VOCs)
common to Title III of the Clean Air Act
Amendments' (CAAA) Hazardous Air Pol-
lutants (HAP) list. Benzene represents the
largest  single VOC emitted, generating
nearly 10 g for every kg of fluff consumed
in combustion.
  The compounds identified in the XAD-2
and particulate fractions are similar to the
types of compounds identified in the VOST
samples. In addition, phenols,  polycyclic
aromatic hydrocarbons (PAHs), phthalates,
and heterocycles  were identified. Again,
the types of  compounds identified  were
consistent with the types of organics iden-
tified  in  various studies  of the thermal
decomposition  of plastics.  Many of the
compounds identified common to the HAP
list were PAHs.
  Table  1  presents estimated emissions
data  for selected  individual compounds
present in the XAD-2 and particulate frac-
tions. Because  of the complexity of the
sample and its components, identifying  all
   Uj
40


35


30


25


20
    S 15
   .^
   "w
   Uj
      10
                 Benzene

                 Toluene

                 Chlorobenzene

            T77\ Ethyl Benzene

            I	1 M/PXylene
                 1                   '         I         '          I
           Test 1, Sample 1   '    Test 2, Sample 1  '    Test 3, Sample 2  '
                    Test 1, Sample 3      Test 2, Sample 2       Test 3, Sample 3
Figure 2.  Estimated emissions for volatile HAPs.

compounds present in  the  organic frac-
tions was not within the scope of this
study.
  Separate samples were also collected
for characterization of PCDD/PCDF emis-
sions. Separate analyses were performed
on  the XAD-2  and  particulate  filter
samples. The total PCDD/PCDF emission
results are summarized in Figure 3,
  Overall, the resulting emissions favored
the formation  of the less-substituted chlo-
rinated dibenzofurans. The tetrachloro and
pentachloro dibenzofurans (TCDF/PeCDF)
were roughly an order of magnitude greater
in  concentration  than  the dioxin homo-
logues. These profiles are similar to those
observed from soil samples collected from
scrap automobile incineration sites in the
Netherlands.
  Of the 11 metals targeted, only Cd, Cu,
Pb, and Zn were detected in the samples
collected. Figure  4 presents the emission
rates for these metals. It is interesting that
Cu  is present  in relatively large concentra-
tions; Cu compounds have  been investi-
gated  as  catalysts  in  the  formation of
PCDDs/PCDFs in municipal waste incin-
eration processes.
  Particulate matter was collected by sev-
eral different sampling systems: the semi-
volatile organics systems,  the  metal
aerosol system,  and the PM10 (airborne
particles with diameters < 10 urn) ambient
sampler. A comparison of  the  PM10 to
total particulate, based  on total averaged
values, indicates that  PMin consists of
                                   about 40% of the total particulate matter
                                   collected.
                                     To assess the overall organic emissions,
                                   the volatile and semivolatile organics emis-
                                   sion data were summarized. The total or-
                                   ganics  emitted  (volatile, vapor-phase
                                   semivolatile, and particulate-bound semi-
                                   volatile) averaged more than 200 g/kg fluff
                                   combusted. The actual mass contribution
                                   from each fraction is summarized in Table
                                   2.
                                     As  a measure of the  quality of esti-
                                   mated mass emissions, a total mass bal-
                                   ance was performed. The diversity of the
                                   measurements performed during testing
                                   enabled the determination of total mass
                                   emissions: they included most classes of
                                   observed products of incomplete combus-
                                   tion as well as several common gaseous
                                   products of complete combustion. The ac-
                                   tual mass balances, based  on  individual
                                   and overall  test average emission  rate
                                   values, are presented in Table 3.

                                   Summary and Conclusions
                                     The primary objective of this study was
                                   to characterize, as completely as possible,
                                   the emissions resulting from the simulated
                                   open  combustion of fluff. This necessi-
                                   tated an approach where qualitative infor-
                                   mation was given greater emphasis than
                                   quantitative information. This approach pro-
                                   vided  the data and insight to direct subse-
                                   quent, specialized, and more quantitatively
                                   detailed investigations. An  attempt  was
                                   made to characterize the diversity of the
                                   emissions as efficiently as possible.

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Table 1.   Estimated Emissions for Selected Pollutants (g/kg)
Compound
Ethyl Benzene
m- or p-Xylene
Ethynyl Benzene
Styrene
Benzaldehyde
Phenol
1,2 Dichlorobenzene
Naphthalene
Methylethylphenol
Biphenol
Acenaphthylene
Caprolactam
Phenanthrene
Fluoranthrene
Pyrene
Terphenyl
Bis(-2Ethylhexyl)-
phthalate
XAD
Test 1
2.26
1.03
0.38
6.27
1.20
1.39
ND
0.90
0.49
0.29
0.20
ND
0.211
ND
ND
ND
ND

XAD
Test 2
2.05
1.11
0.39
6.49
1.53
1.59
0.17
0.95
ND
0.30
0.18
ND
0.177
ND
ND
ND
ND

XAD
Average
2.16
1.07
0.38
6.38
1.36
1.49
0.09
0.92
0.24
0.29
0.19
0.000
0.194
0.000
0.000
0.000
0.000

Particulate Particulate
Test 1 Test 2
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.068
ND
0.110
0.050
0.761

ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.380
0.129
0.109
0.118
0.070
1.995

Particulate
Average
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.190
0.099
0.055
0.114
0.060
1.378

ND = Not Detected
  The diversity of data produced from this
study is sufficiently comprehensive to pro-
vide a semiquantitative characterization of
the emissions resulting from the simulated
open  combustion of automobile recycling
fluff. While  the  data may be adequate
from a physical  and chemical character-
ization standpoint, data are lacking as to
the toxic  effects from these  emissions.
The relationship of this experiment to ac-
tual uncontrolled fluff combustion has not
been established.
    0.0032

     0.003

    0.0028

    0.0026

oi  0.0024

S  0.0022

     0.002

    0.0018

    0.0016

    0.0014

    0.0012

     0.001

    0.0008

    0.0006

    0.0004

    0.0002

         0
                                                           TCDDs
                           PeCDDs
                                                                                                   ^H  First Fluff Test

                                                                                                   ES8SSI  Second Fluff Test

                                                                                                         Third Fluff Test

                                                                                                   I    I  Average
HxCDDs
                                                                  TCDFs
                                 PeCDFs
HpCdds
OCDDs
      HxCDFs     HpCDFs
                                                                                                                  OCDFs
                                           Figure 3.   Total estimated PCDD/PCDF emissions.

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                                   Only Detected Metals Shown
  g
  o
  w
  .w
  1
  1
  CO

  .w
  LU
                  First Fluff Test

                  Second Fluff Test

                  Third Fluff Test

            I    I  Average
               Cadmium             Copper


Figure 4.  Estimated emissions for selected metals.
                     Zinc
Table 2.    Estimated Emissions for Classes of Pollutants (g/kg)
                                  Day 1
Day 2
 Table 3.    Mass Balance for Combustion Emissions (g/kg)
                                  Day 1
Day 2
Day 3
Day 3
Average
Volatiles:
         Early in test               5.93           43.06           25.73        24.91
         Mid-test                 17.28           69.16           70.87        52.44
         Late in test               62.54            NA             58.44        60.49
Semivolatiles:
         XAD-2 TCO              56.99           50.05           90.72        65.92
         XAD-2GRAV             6.68           10.12           23.58         13.46
         Paniculate TCO            0.61             1.27            0.85          0.91
         Particulate GRAV         53.78           69.11          113.71        78.87
Particulates:
         General Organic Train     91.25          116.17          183.44        130.29
         Dioxin Train              85.82          115.68          188.63        130.04
         Metals Train              81.55           89.93          174.49        115.32
         Average (3 trains)         86.20          107.26          182.19        125.22

PM                               66.03          NA              41.11        53.57
Average
 Volatiles                          28.58          56.11           51.68         45.46
 Vapor-phase Semivolatiles          63.67          60.17          114.30         79.38
 Particulate                        86.20          107.26          182.19        125.22
  (Average 3 trains)
 COasC                          67.93          71.54           72.09         70.52
 CO asC                        915.71          746.30          771.93        811.31
 NO2asN                           NA              2.54            2.43          2.49

 Sum                            1162.10        1043.92         1194.62       1134.37

 NA = Not Available
 •U.S. Government Printing Office: 1993 — 750-071/60246

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 J.V. Ryan and C.C. Lutes are with Acurex Environmental Corporation, Research
  ' Triangle Park, NC 27709.
 Paul M. Lemieux is the EPA Project Officer (see below).
 The complete report, entitled "Characterization of Emissions from the Simulated
   Open-Burning of Non-Metallic Automobile Shredder Residue," (Order No. PB93-
   172914; Cost: $19.50), will be available only from:
         National Technical Information Service
         5285 Port Royal Road
         Springfield, VA 22161
         Telephone: 703-487-4650
 The EPA Project Officer can be contacted at:
         Air and Energy Engineering Research Laboratory
         U.S. Environmental Protection Agency
         Research Triangle Park, NC27711
United States
Environmental Protection Agency
Center for Environmental Research Information
Cincinnati, OH 45268

Official Business
Penalty for Private Use
$300
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POSTAGE & FEES PAID
         EPA
   PERMIT No. G-35
EPA/600/SR-93/044

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