Characterization of Emissions from the Simulated Open
Burning of Scrap Tires
Acurex Corp., Research Triangle Park, NC
Prepared for:
Environmental Protection Agency, Research Triangle Park, NC
/
Oct 89
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EPA-600/2-89-054
October 198S
CHARACTERIZATION OF EMISSIONS
FROM THE SIMULATED OPEN BURNING OF SCRAP TIRES
Prepared by:
Jeffrey V. Ryan
Acurex Corporation
Environmental Systems Division
Eastern Regional Office
P.O. Box 13109
Research Triangle Park, NC 27709
EPA Contract No. 68-02-4701
Task No. 88-41
EPA Project Officer: Paul M. Lemieux
Air and Energy Engineering Research Laboratory
Combustion Research Branch
Research Triangle Park, NC 27711
AIR AND ENERGY ENGINEERING RESEARCH LABORATORY
OFFICE Of RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
RESEARCH TRIANGLE PARK, NC 27711
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PREFACE
The CTC was established by EPA's Office of Research and Development (ORD) and
Office of Air Quality Planning and Standards ( OAQPS) to provide technical assistance to State
and Local air pollution control agencies. Three levels of assistance can be accessed through the
CTC. First, a CTC HOTLINE has been established to provide telephone assistance on matters
relating to air pollution control technology. Second, more in-depth engineering assistance can be
provided when appropriate. Third, the CTC can provide technical guidance through publication of
technical guidance documents, development of personal computer software, and presentation of
workshops on control technology matters.
The technical guidance projects, such as this one, focus on topics of national or regional
interest that are identified through contact with State and Local agencies. In this case, the CTC
became interested in examining pollutants emitted from open air tire burning, and providing
qualitative and semi-quantitative estimates of the emissions. The document discusses a series of
small-scale controlled simulations of open air tire burning that were performed at the
Environmental Research Center in Research Triangle Park, NC.
NOTICE
This document has been reviewed in accordance with
U.S. Environmental Protection Agency policy and
approved for publication. Mention of trade names
or commercial products does not constitute endorse-
ment or recommendation for use.
11
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TABLE OF CONTENTS
Section Page
List of Figures iv
List of Tables v
Acknowledgement vi
1 Introduction .1
2 Experimental Approach 3
2.1 Project Description 3
2.2 Experimental Apparatus 3
2.2.1 Bum Hut 3
2.2.2 Sample Shed 5
2.2.3 HAPML 5
2.3 Experimental Methods and Procedures 8
2.3.1 Simulation of Open Air Combustion 8
232 CEMs 8
2.3.3 Volatile Organics 9
2.3.4 Semi-Volatile Organics 10
2.3.5 Airborne Metals Particulate 12
2.3.6 PMio Particulate Collection 12
3 Data, Results, and Discussion 13
3.1 Bum Rate Results .13
3.2 CEM Data 19
3.3 Volatile Organic Emission Data .19
3.4 Semi-Volatile Organics .39
3.5 Particulate Loading 45
3.6 Airborne Metals 51
4 Summary and Conclusions .55
5 References 57
Appendix A: Quality Control Evaluation Report 59
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LIST OF FIGURES
Hours Pace
2-1 Diagram of bum hut 4
2-2 Locations of required test equipment .6
2-3 Diagram of sampling systems used 7
3-1 Bum rate vs. elapsed time—Day 1 "CHUNK" condition .15
3-2 Bum rate vs. elapsed time—Day 2 "CHUNK" condition 16
3-3 Bum rate vs. elapsed time—Day 1 "SHRED" condition 17
3-4 Bum rate vs. elapsed time—Day 2 "SHRED" condition 18
3-5 CEM concentrations vs. elapsed time—Day 1 "CHUNK* condition 24
3-6 CEM concentrations vs. elapsed time—Day 2 "CHUNK" condition 25
3-7 CEM concentrations vs. elapsed time—Day 1 "SHRED" condition.. 26
3-8 CEM concentrations vs. elapsed time—Day 2 "SHRED" condition.. 27
iv
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LIST OF TABLES
Tabte Page
1-1 Analysis of a Passenger Car Tire 2
3-1 Bum Rate Summary Data 14
3-2 Tire Bum Data: "CHUNK" Conditions Day 1 20
3-3 Tire Bum Data: "CHUNK" Condfifon Day 2 21
3-4 Tire Bum Data: "SHRED" Condition Day 1 22
3-5 Tire Bum Data: "SHRED" Condition Day 2 23
3-6 Compounds Identified By GC/MS From VOST Runs 28
3-7 Quantitation and Emission Summary of Compounds Identified in VOST Samples: Day 1
"CHUNK" Condition , 31
3-8 Quantitation and Emission Summary of Compounds Identified in VOST Samples: Day 2
"CHUNK" Condition 23
3-9 Quantitation and Emission Summary of Compounds Identified in VOST Samples: Day 1
"SHRED" Condition 35
3-10 Quantitation and Emission Summary of Compounds Identified in VOST Samples: Day 2
"SHRED" Condition 37
3-11 Compounds Identified by GC/MS from XAD-2 Extracts .40
3-12 Quantitation and Emission Summary of Compounds Identified in XAD-2 Extracts 42
3-13 Organic Emission Summary 44
3-14 PAH Quantitation and Emission Summary: Day 1 "CHUNK" Condition 46
3-15 PAH Quantitation and Emission Summary: Day 2 "CHUNK" Condition .47
3-16 PAH Quantitation and Emission Summary: Day1 "SHRED" Condition. . . 48
3-17 PAH Quantitation and Emission Summary: Day 2 "SHRED" Condition 49
3-18 Paniculate Collection Summary 50
3-19 Airborne Paniculate Metals Summary 52
3-20 Airborne Paniculate Metals Quantitiation and Emission Summary: "CHUNK" Condition. ... 53
3-21 Airborne Paniculate Metals Quantitiation and Emission Summary: "SHRED" Condition 54
A Data Quality Summary for Accuracy, Precision, and Completeness 60
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ACKNOWLEDGEMENT
This document has been prepared for the U.S. Environmental Protection Agency (EPA) by
Acurex Corporation Environmental Systems Division. The research was conducted by Jeff Ryan, Rick
Rinehart, and Ken Krebs under the direction of EPA Task Officer Paul Lemieux. The autlrors would like
to recognize Sharon Noten of EPA's Control Technology Center for isolating and funding this study.
vl
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SECTION 1
INTRODUCTION
Approximately 240 million vehicle tires are discarded annually. 1 Although viable methods for
reclamation exist, less than 25 percent are re-used or re-processed. The remaining 170 million scrap
tires are discarded in landfills, above-ground stockpiles, or illegal dumps.
Many landfills are refusing to accept tires because they present not only disposal but also
health-related problems. After burial, tires often float to the surface and become partially filled with water.
Cutting the tire in half or in pieces can reduce this tendency. However, it is very costly to cut or shred
tires into a condition suitable for landfill, and in any event, many sites lack the necessary equipment.
Steel-belted radiate which comprise the majority of the nation's discarded tires, are particularly difficult to
cut and/or shred. Often, they are simply stockpiled or illegally dumped. These stockpiles and dumps can
become a breeding ground for many insects, especially mosquitos, where water collects in the tires and
creates an ideal breeding habitat. The introduction and spread of several mosquito species has been
directly attrtouted to the presence of refuse tires.2
The growing incidence of tire fires creates another potential health hazard. More tire stockpiles
and Btegal dumps are coming into existence, and with them the occurrence of tire fires. These fires, often
started by arson, generate a huge amount of heat, making them extremely difficult to extinguish. Some of
these tire fires have continued for months. For example, the Rhinehart tire fire in Winchester, Virginia,
burned for nearly 9 months.3 potentially exuding large quantities of harmful compounds.
Very little information is available in regard to the open burning of scrap tires. Information is
available as to the composition of tires. Table 1-1 lists the proximate and ultimate analyses of a typical
tire.
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TABLE 1-1. ANALYSIS OF A PASSENGER CAR TIRE4
Proximate, percent:
Moisture
Volatile Matter
Fixed Carbon
Ash
Ultimate. Percent
Hydrogen
Carbon
Nitrogen
Oxygen
Sulfur
Ash
0.5
62.3
31.5
5.7
7.1
83.2
0.3
2.5
1.2
5.7
The EPA's Control Technology Center (CTC) received numerous requests from state and local
agencies nationwide for information pertaining to tire fires and their effects. Because very little
information was available, the steering committee felt a study investigating this potential problem was
warranted. Through lite guidance of the Combustion Research Branch (CRB) of EPA's Air and Energy
Engineering Research Laboratory (AEERL), Acurex conducted a study which identified and quantified
organic and inorganic emission products produced during the simulated open combustion of scrap tires.
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SECTION 2
EXPERIMENTAL APPROACH
2.1 PROJECT DESCRIPTION
The project consisted of a parametric study to collect organic and inorganic emissions from the
simulated open combustion of scrap tires. Small quantities (10-20 Ib, 4.5-9.0 kg) of scrap-tire material
were burned under two Different controlled conditions determined by the size of the material (see
Section 2.3.1). The conditions were evaluated in duplicate on successive days. An existing bum hut
used for similar projects was modified to accommodate this task. A separate outbuilding housed the
required organic and paniculate sampling equipment. CRB's Hazardous Air Pollutants Mobile Laboratory
(HAPML) was used to monitor fixed combustion gases. Organics were collected using the Volatile
Organic Sampling Train (VOST) and a semi-volatile collection system using XAD-2 and paniculate filters.
Paniculate was also collected to assess airborne metals. The organic constituents were analyzed both
qualitatively and quantitatively by GC/MS, GC/FID, HPLC, and gravimetric methodologies.
2.2 EXPERIMENTAL APPARATUS
2.2.1 Bum Hut
The burn hut was an 8-ft x 8-ft x 8-ft (2.4-m x 2.4-m x 2.4-m) outbuilding modified for smaB-scale
combustion experiments (see Figure 2-1). The building had been fined with a cooled, dilution air handling
system capable of delivering nominally 1,200 ft3/min (34.0 m3/min). A 16-in x 16-in x 16-in
(.4-m x .4-m x .4-m) stainless-steel bum pit insulated with fire brick was mounted on a weigh scale to
continuously monitor weight differential. A PM-io ambient sampler was located in the hut to collect
particulate matter 10 urn in diameter or less. A deflector shield was located 4 ft (1.2 m) over the pa to
deflect flames, protect the ceifing, and enhance ambient mixing. The gaseous sample duct opening was
located directly over the deflector shield. This duct transported a representative portion of gaseous
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Sample Duct
\
Air Inlet
Burn Pit
Weighing Platform
Air Inlet'
Figure 2-1. Diagram of burn hut.
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sample to the sample shed immediately adjacent to the bum hut (see Figure 2-2). The duct was
insulated outside the hut to minimize heat loss and condensation of organics.
2.22 Samoteotvad
The sample shed contained the majority of the sampling equipment: the VOST system, the
semt-votatOo organic collection system, the airborne metals paniculate collection system, the continuous
emission monitor (OEM), the paniculate removal system, and the digital readout for the weigh scale. All
gaseous samples were extracted from a sampling manifold within the duct. The manifold consisted of
3/8-in O.D. (9.5 mm) stainless-steel tube probes positioned so that the opening was directed Wo the flow
of the sample stream. The sample stream was pulled into the sample shed by vacuum, using an induced
draft (ID) fan located downstream of the sample manifold. Figure 2-3 diagrams the individual sampling
systems and illustrates how each obtained a representative sample from the duct.
Volatile organics were collected on Tenax-GC using the VOST system, which is fully descrtoed in
Method 0030 found in SW-846.4 Semi-volatile organics were collected using a sample system modified
for use in this study. A 3/8-in O.D. (9.5 mm) stainless-steel tube was connected to a filter housing.
Paniculate was collected on a 142 mm, teflon-coated, glass-ffoer finer located in the fitter housing.
Downstream of the filter, a water-cooled condenser normally used for glass-SASS applications was
located upstream of the XAD-2 canister. This canister contained roughly 150 g of the organic sorbent
material. The XAD-2 module was connected to the pump and metering system, which was run under
vacuum. A similar system without the condenser and XAD-2 module was used for the airborne metals
paniculate capture. In this case, a quartz-fber filter was used. Paniculate removal of the CEM gaseous
sample was accomplished by a high-surface area/low-pressure drop spun-glass filter housed in a heated
box that was directly affixed to the sample manifold.
2.23 HAPML
A healed sample line was connected from the paniculate conditioning fitter to the sample
manffold in the HAPML A portion of the heated sample was routed to the SOa analyzer as well as to the
Total Hydrocarbon (THC) analyzer. The remaining portion of the sampte stream was further conditioned
for moisture removal by a refrigeration condenser and silica gel before being routed to the 02, CO2, and
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O>
Hazardous Air
Pollutants Mobile
Laboratory
o
c
CEMs -O2
-CO2
-CO
-THC
-SO2
Heated
Sample
Line i
O
EPA
Sample Shed
Sampling Control Center
Particulate Sampling
Volatile and Semi-Volatile
Organic Sampling
Airborne Metals Sampling
Insulated
Sample
Duct
Burn Hut
Figure 2-2. Locations of required lest equipment.
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Duct Cross Section
FROM BURN HUT
142 mm
quartz
filter
h Heated
Spun Glass
Filter
VOST System
Condensers,
meters,
pumps
cooled
condenser
.
coated
filter
Dry Gas
Meter
XAD-2
Canister
Vacuum
Pump
Vacuum
Pump
Figure 2-3. Diagram of sampling systems used.
Note: 1"
= 2.54 cm
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CO analyzers. The analog output of the Individual analyzers was recorded by a computerized oata
acquisition system using 5 min averages. Data were stored continuously.
2.3 EXPERIMENTAL METHODS AND PROCEDURES
2.3.1 Simulation of Open Air Combustion
Representative tire material was obtained from tocal tire dealers. Owing to the difficulty in cutting
steel-belted radials, bias ply tires were used in this study. Both truck and passenger car tires were
sampled. The tires were cut into two distinct sizes to vary initial surface area and combustion rate. One
size was -1/4-1/6 of an entire tire and will be referred to as the "CHUNK" condition. The other size
consisted of 2-in by 2-in pieces of tire and will be referred to as the "SHRED" condition.
Sufficient material was placed into the bum pit such that total weight approximated two tires
(~30 b. 13.6 kg), as indicated on the scale. Prior to tire material ignition, the CEMs were run for 15 min to
obtain a background reading. During this time, the dilution air system was operating and continued to
operate throughout the duration of test period. The dilution air system continuously added 1,200 ft3/min
(34.0 m3/min) to the bum hut. After the baseline period had been established, the tire material was
ignited with a propane torch. When combustion became self-sustaining (-5 min), the torch was removed
and the nut door was closed.
With the exception of the first day of testing, 30 min elapsed prior to the initiation of the sampling
equipment. On Day 1, sampling systems were activated after 15 min. At the start and end of each
sample condition as well as roughly every 20 min, the time and tire material weight were recorded.
Temperatures inside the bum hut and in the sample duct were also recorded at this time.
2.3.2 CEMs
Fixed combustion gases were measured continuously using on-line analyzers. Prior to sampling,
a 3-point caH>ration was performed on each instrument Once suitable linearity was verified, a span
check before and after each sample period was conducted. This span check was used to verify
instrument performance and integrity and to validate collected data.
The analog output of each analyzer was converted digitally and then acquired on a computer
using 5 min averages. The data were continuously stored, and hardcopy was also produced.
8
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2.3.3 VolatBe Organfcs
Volatile organics were collected using an unmodified VOST system operated according to
Method 0030 found in SW-846.5 During this study, no stack probe was used. An insulated section of
1/4-in Teflon tubing affixed to the sampling manifold, was used to transport the gaseous sample from the
sample duct to the VOST system. The sampte was drawn through the Tenax and Tenax/charcoal tubes
at a nominal flow rate of 0.5 L/min for 40 min, for a total sample of 20 L The sample tube sets were
submitted to quality control contamination checks (QC'd) prior to use and were stored refrigerated at 1 °C
in Teflon bags both prior to and after use. Daily field blanks were performed, and all samples were
analyzed within 30 days.
The VOST samples were analyzed by GC/MS on a purge and trap system devoted to VOST
sample analyses. Method 5040 of SW-846 best represents the procedure used for sample analyses.6
The identification of unknowns was accomplished using mass spectral Itorary searches as well as
investigator interpretation. Quantification of the identified unknowns was based upon the toluene
response factor obtained during initial caltoratfon.
Prior to calibration or the analysis of samples, the MS was tuned with pert tourotrtoutylamine
(PFTBA) to linearize the working range of mass units (45-420 amu). Following initial linearization, a
multipoint calibration using toluene was performed. This caltoration was used to quantify the QC samptes
analyzed at the beginning and end of each sample period as well as after every third sample. The QC
sample contained known concentrations of toluene and bromoftourobenzene (BFB). The BFB was used
to confirm ion abundance criteria, thereby verifying mass linearity of the instrument.
As stated earfier, the tenax tube samples were analyzed on a dedicated purge and trap GC/MS
system. The samples were desorbed in a clamshell heater maintained at 190 °C using a helium carrier at
a nominal flow rate of 25 mL/min onto a Tenax trap at room temperature for 10 min. At this point, the trap
was heated rapidly to 225 °C, and the carrier was directed onto a 30 m DB-624 megabore column. The
carrier flow at this condition was nominally 5.6 mL/min. The oven temperature was maintained at 30 °C
for 5 min; then a temperature ramp was invoked at 5 °C/mtn until reaching 160 °C, where the temperature
was held for 15 more minutes. As the sample constituents edited from the column, they passed through
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a jet separator before being introduced into the MS. A spectral sweep from 45-420 amu was performed
each second. Data were acquired and stored by computer. Integration of peak areas was performed by
manually establishing baseline and integration limits. Identification of unknowns was accomplished using
the system mass spectral Iforary, employing both the forward and reverse searching capabilities.
Compound boiling point was also used to help identify the unknown.
2.3.4 Semi-Volatite Organics
Semi-volatile organics were collected on both the paniculate filters as weB as the XAO-2 organic
sorbert. The system used for this was a major modification of that used for glass SASS. The
teflon-coated ftoer fitter used for paniculate collection was desiccated, tared, and placed in aluminum foil
and a zip-lock bag prior to use. After sample collection, the samples were stored refrigerated at 1 °0 until
being desiccated, weighed, and extracted. The filter housing system was located immediately upstream
of the XAD-2 canister. Cleaned and QC'd XAD-2 resin was placed in the canisters, sealed in teflon bags,
and stored refrigerated prior to use. After sampling, the canisters were reseated in the teflon bags and
stored refrigerated until being extracted less than 14 days later. The gaseous sample was collected at an
average flow rate of 2-2.5 dm for -3 h. During the 'CHUNK" condition, the paniculate filters became
loaded to the point that replacements were required.
Organics were retrieved from the collection media by soxhlet extraction using dichloromethane.
The XAD-2 was extracted separately from the paniculate fraction. Following the 24-h extraction, the
samples were concentrated to 10 ml using a 3-ball Snyder column system. All organic concentrates
were stored refrigerated unti needed.
Both the paniculate extracts and the XAD-2 extracts were analyzed for total chromatographabte
organics (TCO)—(organic compounds with boiling points between 100-300 °C) and GRAV—(organic
compounds with boiling poiftts greater than 300 °C). The TCO analysis was done by GC/FID.7 A
multipoint caB>ratk>n was conducted using an alkane mix standard. The C7, C10, C12, C14, C17 mix
was used to quantify and identify the temperature window. All peaks with retention times falling between
but not including the C7 and C17 retention times were quantified. The response factor of the sum of C10,
C12. and C14 areas was used for quantification. The analysts was performed using a 30 m DB-5
10
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megabore column with a flow rate of 8 mL/rm'n. The 2-5 ui. injection was made with the oven temperature - \
|
hekJ at 40 °C for 3 min and then ramped to 250 °C at 20 0C/minand held for 15 min after reaching final jj
->
temperature. ?
The GRAV analysis was done gravimetricalty. Aluminum weigh boats were desiccated, tared,
and then filled with 0.5 ml of the organic extract and allowed to evaporate. After evaporation, the boats
were again desiccated and weighed. Organic compounds with boiling points greater than 300 °C
represent the net gain. The analysis was performed in duplicate and included an audit sample.
Identification of unknown organfcs was again accomplished using a GC/MS system. For Equid
work, a Hewlett Packard GC/MSO system configured for capillary columns was used. Split injections of
1-2 uL at a ratio of 100:1 were introduced onto a 30 m SPB-5 capillary column. An initial oven
temperature of 40 °C was maintained for 5 min before ramping the temperature to 250 °C at 5 °C/min.
The final temperature was held for 15 min. Compounds were identified using library spectral matching.
The Wiley LJbrary was used during spectral searching and matching. Again, boiling points were used 'm
assisting investigator interpretation in determining compound identity. In several cases, known standards
were used to confirm identifications.
Quantification of unknowns was accomplished through comparison of the GC/MSD runs with
Injections run under similar conditions using a GC/FID system. The SPB-5 column is virtually identical to
the DB-5 column used, the only real differences being in the manufacturer, stationary phase thickness,
and column ID. The injections were made on the same system as was used for the TOO analyses. The
only change made was to alter the temperature ramp to match that of the GC/MSD runs. Several
standard mixes containing compounds identified by GC/MS were prepared and run on the GC/FID
system. The retention times of these standards were used as markers to relate the MS runs with the FID
runs. The elution order of the MS runs was assumed to be identical to that of the FID runs. A linear
relationship between the retention times of the runs was determined, and, along with comparison'of peak
magnitude, compound identifications were assigned to the FID runs. Quantification of individual peaks
was performed with the same response factor used for TCO quantifications.
11
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A portion of the liquid concentrates was also analyzed for pclycyclic aromatic hydrocarbons
(PAHs). This analysis was subcontracted and used EPA Method 610 as the referenced procedure.8
Unfortunately, the reported concentrations were reported as ug/total sample. A problem arises in
that the volume of sample sent for analysis was not originally known since it is normally not required, it is
common practice however, to mark the level of liquid in each sample vial. After retrieving the sample
vials, these marks were used to determine the initial volume of each sample sent. From this, total sample
concentrations were determined.
2.3.5 Airborne Metals Paniculate
Paniculate matter was collected using a separate sampling system in order to characterize
airborne metals emissions. A gaseous sample was drawn across a 142 mm quartz-fiber filter under
vacuum at an average flow rate of 2-2.5 dm for -3 h. During the "CHUNK" condition, two paniculate
reters were required. The quartz filters used were desiccated and tared, then placed in aluminum foil and
a zip-lock bag prior to use. Following sample collection, the samples were refrigerated until they were
again desiccated and reweighed. Ultimately, the samples were delivered to an outside analytical
laboratory for metals quantification. Specific metals common in tire-ash residue were chosen for
quantification.9 The samples were analyzed using inductively coupled argon plasma (ICAP)
methodology.1!0
2.3.6 PMifl Paniculate Collection
An Andersen medium volume ambient paniculate sampler was used to collect paniculate of
10 um in diameter or less. The sampler is designed so than when a flow of 4 cfm is maintained on the
system, paniculate of 10 um in diameter or less only is collected on the filter. The 110 mm fiber filters
were desiccated and tared, then placed in aluminum foil and a zip-lock bag prior to use. Following
sampling, the fitters were desiccated and weighed to determine total amount collected.
12
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SECTION 3
DATA. RESULTS, AND DISCUSSION
3.1 BURN RATE RESULTS
As stated earlier, the size of tire material was varied to alter the combustion conditions and to
gain insight into the mechanisms governing bum rate. Table 3-1 contains summary data of the observed
bum rates for the two conditions. Rates were calculated by dividing the amount of tire material burned by
the length of the bum and then normalizing to a mass per hour basts. The data show that the "CHUNK"
condition produced a higher bum rate than the "SHRED" condition. Almost double the amount of material
was combusted during similar periods.
Although several trial bums were conducted prior to actual testing, the first day of testing under
•CHUNK" condition resulted in modifying the amount of tire material ignited in the bum pit. Approximately
33 b (15.0 kg) were used initially. The result was vigorous combustion; the potential for the fire to
become uncontrollable was a concern. Temperatures in the bum hut and in the sample duct became
dangerously high; therefore, investigators decided to reduce the weight of tire material for the three
remaining tests to -27 fc (12.3 kg). By doing so, no other major problems were observed relating to the
actual burning of tire material.
Figures 3-1 through 3-4 are plots of the bum rate vs. the elapsed time of the test run. M plots
show a high initial bum rate, but as time elapsed, it diminished. In both of the "SHRED" runs, after more
than midway through the test period, the bum pft had to be agitated to sustain combustion. This agitation
would account for the visWe increase in bum rates occurring at that point.
Under both conditions, an initial high bum rate was observed to gradualy level off unffl a steady
rate was achieved. Examination of the tire material suggested a posstote explanation. Along the tread
portion, of the tires, a much thicker layer of rubber was found in relation to the sidewall. In adoption, the
rubber of the sidewaH portion seemed impregnated into the belt material, yet the rubber in the tread
13
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TABLE 3-1. BURN RATE SUMMARY DATA
DAY 1 CHUNK CONDITION
TOTAL WEIGHT BURNED - 20.0 to
AVG BURN RATE
ELAPSED
TIME
(min)
0
14
23 '
35
50
65
74
88
128
162
194
- 6.2 Ib/h
BURN
RATE
(Ib/h)
0
. 3.4
25.3
19.0
7.2
6.4
6.7
6.0
4.2
3.2
2.3
DAY 2 CHUNK CONDITION
TOTAL WEIGHT BURNED - 16.4 Ib
AVG BURN RATE
ELAPSED
TIME
(min)
0
11
20
31
51
74
87
102
122
142
152
196
.5.0 Ib/h
BURN
RATE
(Ib/h)
0
2.2
16.0
18.0
8.4
6.8
4.6
6.4
1.8
1.8
2.4
1.1
DAY 1 SHRED CONDITION
TOTAL WtlGHT BURNED > 10.6 Ib
AVG BURN RATE
ELAPSED
TIME
(min)
0
10
30
52
73
98
117
138
152
176
193
214
« 3.0 Ib/h
BURN
RATE
(Ib/h)
0
9.6
6.0
3.3
2.3
2.4
2.5
3.4
2.6
1.5
2.1
2.3
DAY 2 SHRED CONDITION
TOTAL WEIGHT BURNED - 1 1.8 Ib
AVG BURN
ELAPSED
TIME
(min)
0
20
30
60
96
107
120
137
147
187
203
RATE - 3.5 Ib/h
BURN
RATE
(Ib/h)
0
9.0
3.6
3.2
2.0
4.4
6.5
4.2
3.1
2.1
1.5
Note: 11b/h » 0.45 kg/h
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DAY 1 CHUNK CONDITION
g
CC
ID
CO
UJ
CC
40
60 80 100 120
ELAPSED TIME (WIN)
Figure 3-1. Bum rate vs. elapsed time—Day 1 "CHUNK" condition.
i i r
140 160 180 200
Note: 11b/h - 0.45 kg/h
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DAY 2 CHUNK CONDITION
cc
I
CD
UJ
CC
40
60 80 100 120
ELAPSED TIME (MIN)
Figure 3-2. Bum rate vs. elapsed time—Day 2 "CHUNK" condition.
140 160 180
Note: 11b/h - 0.45 ko/h
200
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DAY 1 SHRED CONDITION
E*
§
ui
DC
z
IT
ID
CO
UJ
CC
ou -
28 -
26 -
24 -
22 -
20 -
18 -
16 -
14 -
12 -
10 -
8 -
6 -
4 -
2 -
0 -«
(
Pv
/\
/ ^^
/ ^B-^ D n-— -°-^
i
r i . i i i i i i i i i
) 40 80 120 160 200
ELAPSED TIME (MIN) Note: 1 to/h - 0.45 kg/h
Figure 3-3. Bum rate vs. elapsed time—Day 1 "SHRED" condition.
-------
DAY 2 SHRED CONDITION
30
I
cc
CO
LLJ
CC
28 -
26 -
24 -
22 -
20 -
18 -
16 -
14 -
12 -
10 -
8 -
6 -
4 -
2 -
0
40
60 80
ELAPSED TIME (MIN)
Figure 3-4. Bum rate vs. elcpsed time—Day 2 "SHRED" condition.
IOO 120 140 160 180 200
Note: 1 to/h - 0.45 kg/h
-------
surface contained no belt material. It may be that the tread material is consumed first while the belt
containing rubber may be more difficult to bum and more uniform in its combustion.
32 CEM DATA
Combustion gas products were monitored continuously throughout the test period. Tables 3-2
through 3-5 contain the 5 min averages from the Oa, CO2. SO2. CO, and THC analyzers. On Day 1 of
the "CHUNK" condition, the CO2 analyzer was inoperable; therefore no data were acquired for this test
point It should also be noted that considerable problems were encountered with the SO2 analyzer and
that not an SOa data can be considered reliable. On Day 2 of the "CHUNK" condetion, the instrument
suddenly went negative midway through the run. The analyzer was rezeroed and the span was checked.
The process was completed within 5 min and accounts for the absence of data at the 75 min mark. This
problem was also encountered on Day 2 of the "SHRED" condition, with a 10 min lapse in data occurring
at the 55 min mark. Instrument problems were encountered during the post-run span checks on both
days of the "SHRED" condition. Although the predetermined accuracy limits of ±15 percent were
exceeded, the SO2 values are within the same order of magnitude and still provide insight into the
combustion condition. They are therefore included.
Figures 3-5 through 3-8 are plots of CEM values over the elapsed time of the test. Comparing
these plots with the respective plots pertaining to bum rate shows a relationship between high emissions
of CO, SO2. and THC at high bum rates.
3.3 VOLATILE ORGANIC EMISSION DATA
kJenffication of unknown organics using the MS proved to be highly successful. Table 3-6 fists
the more than 50 compounds identified from the VOST sampJes collected during testing. The majority
are aBphaticafiy. oteftnicaJly. or acetytenically substituted aromatics. The predominant formation of
aromatic hydrocarbons is Bcety due to the high thermodynamic stability of aromatic structures. A
representative of each compound class is found in mono- through poly-substituted aromatic
hydrocarbons. CycEc akanes, akenes, and dienes were also present. It is not surprising to identify
butadiene in the samples because it is a major constituent of the tire fabrication process. A halogenated
19
-------
TABLE 3-2. TIRE BURN DATA: CHUNK CONDITION DAY 11
Start Time: 13:03:23.14; Run Date: 1-31-1989
Time
(min)
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
105
110
115
120
125
130
135
140
145
150
155
160
165
170
175
180
185
190
195
200
205
02
(%[dry))
21.4
21.2
21.2
21.2
21.1
21.0
20.5
19.3
19.5
20.0
20.4
20.5
20.6
20.7
20.8
20.9
21.0
21.0
21.0
21.0
21.1
21.1
21.1
21.1
21.1
21.1
21.1
21.1
21.1
21.1
21.1
21.1
21.1
21.1
21.1
21.1
21.1
21.2
21.3
21.2
21.3
21.3
CO
(ppm [dry])
0
0
0
0
0
6
160
425
310
226
151
130
123
117
97
84
78
73
69
64
62
53
51
49
48
46
49
67
67
69
75
77
75
72
75
76
76
74
73
73
73
70
SO2
(ppm (wet])
0
2
1
0
1
5
40
103
92
69
53
49
42
38
33
28
28
25
23
23
22
20
20
20
20
21
23
23
23
26
27
27
29
28
30
29
28
28
27
26
27
24
•THC
(ppm (wet))
1
1
1
1
4
5
35
68
45
38
29
26
24
19
15
12
11
10
9
9
8
7
7
7
7
7
8
9
10
11
12
13
13
13
14
14
14
13
13
12
13
14
•As propane
1 No CO2 data collected on this test point—instrument inoperable.
20
-------
TABLE 3-3. TIRE BURN DATA: CHUNK CONDITION DAY 2
Start Time:14:20:57.53; Run Date: 2-01-1989
Time
(min)
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
105
110
115
120
125
130
135
140
145
150
155
160
165
170
175
180
185
190
195
200
205
210
Oa
(%[dryj)
21.4
21.5
21.5
21.5
21.5
21.4
20.9
20.5
20.4
20.5
20.7
20.8
20.9
21.1
21.1
21.1
21.2
21.4
21.4
21.6
21.6
21.6
21.6
21.6
21.6
21.7
21.7
21.7
21.8
21.8
21.9
21.9
22.0
21.9
22.0
22.0
22.0
22.0
22.0
22.0
22.0
22.0
22.0
C02
(%[dry])
0
0
0
0
0
0
0.1
0.3
0.5
0.6
0.5
0.4
0.4
0.3
0.3
0.3
0.2
0.2
0.2
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
CO
(ppm [dry])
1
1
1
1
2
13
140
142
196
195
160
150
138
109
110
121
100
79
59
46
39
40
58
75
84
82
76
75
76
63
64
75
74
79
69
67
68
69
69
69
67
59
70
SO2
(ppm [wet])
11
6
0
-3
-5
-1
39
47
67
68
61
60
55
45
41
38
-40
-49
28
24
26
22
23
28
29
24
18
20
18
12
14
19
21
22
23
21
21
20
21
23
25
22
19
THC
(ppm {wet])
4
4
4
4
7
8
32
22
40
41
36 .
35
31
24
23
23
18
11
6
9
8
7
9
13
14
15
13
13
11
11
10
19
19
22
22
20
17
17
17
19
17
18
16
•As propane
21
-------
TABLE 3-4. TIRE BURN DATA: SHRED CONDITION DAY 1
Start Time: 13:02:13.99; Run Date: 2-02-1989
Time
(min)
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
105
110
115
120
125
130
135
140
145
150
155
160
165
170
175
180
185
190
195
200
205
210
215
220
225
Oa
(%[dry])
20.4
20.4
20.4
20.5
20.4
19.6
19.8
20.0
20.1
20.0
20.2
20.2
20.3
20.3
20.3
20.3
20.4
20.4
20.4
20.3
20.3
20.4
20.4
20.4
20.4
20.4
20.4
20.1
20.2
20.3
20.3
20.4
20.4
20.4
20.4
20.4
20.5
20.5
20.5
20.5
20.5
20.5
20.5
20.6
20.7
20.7
COa
(%[dry])
0
0
0.1
0
0.1
0.2
0.5
0.4
0.2
0.2
0.2
0.2
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.2
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0
0
0
0
0
0
0
CO
(ppm [dry])
2
2
1
1
2
149
141
85
77
103
97
85
75
71
64
58
53
52
48
46
43
39
37
33
30
29
29
160
135
107
89
79
67
56
52
42
39
35
34
30
29
25
24
22
22
22
SO2
(ppm [wet])
4
4
9
3
13
54
51
39
33
38
33
28
24
24
22
16
14
14
15
16
16
15
12
15
16
14
20
41
28
20
20
18
15
15
16
15
15
14
13
13
15
13
9
6
5
-7
•THC
(ppm [wet])
2
2
2
2
10
40
30
15
16
19
18
16
15
16
15
15
15
15
14
14
13
13
13
14
13
13
17
25.
16
14
14
14
13
13
16
17
17
14
15
14
17
16
14
13
13
12
•Aspropana
22
-------
TABLE 3-5. TIRE BURN DATA: SHRED CONDITION DAY 2
Start Time: 10:40:13.18; Run Date: 2-03-1989
Time
(min)
0
5
10
15
20
25
30
35
40
45
50
55
70
75
80
85
90
95
100
105
110
115
120
125
130
135
140
145
150
155
160
165
170
175
180
185
190
195
200
205
210
215
220
02
(%[dryl)
22.0
21.8
21.9
21.9
21.9
21.7
20.9
21.2
21.5
21.6
21.7
21.7
21.8
21.8
21.9
21.9
21.9
21.9
22.0
22.0
22.0
22.0
22.0
22.0
21.7
21.5
21.7
21.8
21.9
21.9
21.9
21.9
22.0
22.0
22.0
22.0
22.1
22.1
22.1
22.1
22.1
22.1
22.1
CO2
(%[dryD
0
0
0
0
' 0
0
0.3
0.4
0.3
0.1
0.1
0.1
0.1
0.1
0
0
0
0
0
0
0
0
0
0
0
0.2
0.2
0.1
0.1
0.1
0.1
0
0
0
0
0
0
0 .
0
0
0
0
0
CO
(ppmfdry])
0
0
0
0
1
48
217
132
74
62
76
89
75
68
59
52
49
44
40
38
35
33
33
33
106
149
110
99
88
79
68
65
59
57
49
45
42
40
35
30
28
26
25
SOa
(ppm[wetD
5
5
2
-1
-2
15
62
48
23
11
7
13
17
23
28
31
31.
. 26
22
21
21
24
30
29
... 49
76
64
55
50
45
41
40
36
25
22
26
24
30
24
17
15
15
20
THC
(ppm [wet])
3
3
3
3
3
19
49
30
17
14
14
18
8
17
16
15
15
14
13
13
13
12
12
12
30
24
16
14
12
11
10
11
11
11
10
14
17
14
13
14
13
12
11
'As propane
23
-------
GL
Q.
i
LU
O
8
500
400 H
300 H
200
100
DAY 1 CHUNK CONDITION
CEM VALUES
i i i •»• i i i i i i
100
120
140
160
180
200
ELAPSED TIME OF BURN (MIN)
+ SO2PPM o
CO PPM + SO2PPM o THC PPM as propane
Figure 3-5. CEM concentrations vs. elapsed time—Day 1 "CHUNK* condition.
-------
a.
a.
LU
o
O
o
500
400 -
300 -
200 -
100 -
DAY 2 CHUNK CONDITION
CEM VALUES
60
80
100
120
140
160
180
200
ELAPSED TIME OF BURN (MIN)
+ SO2PPM ° THC PPM as propane
CO PPM
Figure 3-6. CEM concentrations vs. elapsed time—Day 2 "CHUNK" condRton.
-------
O
I
UJ
o
500
400 -
300 -
200 -
DAY 1 SHRED CONDITION
OEM VALUES
20 40 60 80 100 120 140 160 180 200
0
CO PPM
ELAPSED TIME OF BURN (MIN)
+ SO2PPM o THC PPM as propane
Figure 3-7. CEM concflntrattons vs. elapsed tlm«-rDay 1 "SHRED" condition.
-------
500
DAY 2 SHRED CONDITION
GEM VALUES
400 -
a.
a.
§
H'
LJU
O
o
O
300 -
200 -
100 -
40
60 80 100 120 140
ELAPSED TIME OF BURN (MIN)
160
180
200
a CO PPM + SO2PPM ° THC PPM as propane
Figure 3-8. OEM concentrations vs. elapsed time—Day 2 "SHRED" condition.
-------
TABLE 3-6. COMPOUNDS IDENTIFIED BY GC/MS FROM VOST RUNS
Compound Identified Formula
BUTADIENE C4H6
TRICHLOROFLOUROMETHANE CCfcF
PENTADIENE
CYCLOPENTADIENE
BENZENE
THIOPHENE C4H4S
ALIPHATIC ALKANE C?Hi6
ALIPHATIC ALKENE
DIENE
METHYL CYCLOHEXENE
METHYL HEXADIENE C?H12
HEPTADIENE C?Hi2
METHYL BENZENE
METHYL THIOPHENE
ALIPHATIC ALKANE C8H18
ALIPHATIC ALKENE
DIMETHYL HEXADIENE
ETHENYL CYCLOHEXENE
ETHYL BENZENE
DIMETHYL BENZENE
ETHYNYL BENZENE
ETHENYL BENZENE
METHYLETHYL BENZENE
CYCLIC ALKENE
ETHENYLDIMETHYLCYCLOHEZENE
PROPYL BENZENE CgHi2
ETHYL.METHYL BENZENE CsHi2
TRIMETHYL BENZENE CgHi2
METHYL.ETHENYL BENZENE
BENZALDEHYDE
TRIMETHYL BENZENE
ETHENYLMETHYL BENZENE
ETHENYL.METHYL BENZENE
BENZOFURAN
METHYL,METHYLETHYL C.H.
LIMOMENE C10H16
METHYL,METHYLETHYL BENZENE
ISOCYANO BENZENE
DIHYDROINDENE
METHYL.PROPYL BENZENE
TETRAMETHYL BENZENE
ETHYNYL.METHYL BENZENE CgHs
PHENOL CeHeO
ALIPHATIC AROMATIC C1QH12
METHYL.METHYLETHEN'i'L BENZENE
ETHENYL.DIMETHYL BENZENE
(continued)
28
-------
TABLE 3-6. COMPOUNDS IDENTIFIED BY GC/MS FROM VOST RUNS (concluded)
Compound Identified Formula
TETRAMETHYLBENZENE C10H14
METHYL INDENE
METHYLENEINDENE
DIMETHYLDIHYDRO INDENE
DIMETHYL.METHYLPROPYL BENZENE
NAPHTHALENE C-|()H8
BENZOTHIOPHENE
BENZODIAZINE
METHYL NAPHTHALENE
29
-------
compound, trichloroftouromethane, was also identified in several of the collected samples. This
chtoroftourocarbon (CFC), also known as FREON-11, was probably emitted by the air conditioners used
to dilute the air in the bum hut. Several sulfonated compounds were identified in the samples. Thfophene
and substituted thfophenes were delated. Nitrogenated hydrocarbons were found. Isocyano benzene
and benzodiazine were isolated in multiple samples.
The average gaseous concentration and estimated emissions of identified volatile organics at
various bum rates are presented in Tables 3-7 through 3-10. These values are estimates and are
calculated using the MS response to toluene.
The data do not reveal consistent trends in either the types or amounts of emissions under varied
bum rates. Benzene is emitted in large quantities under both conditions. Average gaseous concentration
concentrations increase with increased bum rate, but this is true with the majority of the compounds
presented. It is interesting to note, however, that as the bum rate decreased, the amount of specific
compounds emitted tended to increase with respect to the amount of tire material combusted. It may be
that during the latter portion of the bum period, the remaining rubber in the tire material was bound with
the cord material and became difficult to bum. In this lower temperature regime, the rubber continued to
be pyrolyzed, but less was combusted while the volatiles reacted to form the types of compounds
identified.
The estimated emissions presented are estimations based on several variables. They were
obtained by assuming that the dilution air added to the bum hut was at a constant volume and that the
amount of air added equaled the amount exiting the hut. It was also assumed that the gas mixture
collected in the sample duct was well mixed and representative of the gas mixture found throughout the
bum hut. The average gaseous concentration or average concentration of the sample over a given
period was determined oy dividing the total collected amount (obtained by GC/MS analysis) by the
volume of sample collected. This value was then multiplied by the amount of air added to the bum hut in
1 h. This value is the amount of a specific compound emitted on an hourly basis, and it was then divided
by the turn rate determined for that period. The bum rate, as outlined earlier, was determined by dividing
30
-------
TABLE 3-7. QUANTITATION AND EMISSION SUMMARY OF COMPOUNDS IDENTIFIED IN VOST SAMPLES: DAY 1 CHUNK CONDITION1-2
SET1
BURN RATE- 6.63 kfl/h
VOL SAMP -0.01 673 m3
COMPOUND IDENTIFIED
BUTADIENE
TRICHLOROFLOUROMETHANE
PENTADIENE
CYCLOPENTADIENE
BENZENE
METHYL BEN2ENE
ETHYL BENZENE
DIMETHYL BENZENE
ETHYNYL BENZENE
ETHENYL BENZENE
METHYLETHYL BENZENE
PROPYL BENZENE
ETHYUMETHYL BENZENE
TRIMETHYL BENZENE
ETHYUMETHYL BENZENE
METHYL.ETHENYL BENZENE
BENZALDEHYDE
ETHENYLMETHYL BENZENE
ETHENYL.METHYL BENZENE
BENZOFURAN
UMONENE
METHYL.METHYLETHYL BENZENE
ISOCYANO BENZENE
DIHYDRCMNDENE
ETHYNYL.METHYL BENZENE
AVERAGE
GASEOUS
CONCENTRATION
(mfl/m3)
0.136
1.003
0.000
0.273
3.872
1.219
0.090
0.481
0.974
1.205
0.000
0.010
0.029
0.012
0.000
0.025
0.566
0.315
0.000
0.169
0.000
0.000
1.330
0.000
1.347
ESTIMATED
EMISSIONS
(mg/kg TIRE)
41.7
308.5
0.0
84.0
1190.9
375.0
30.4
147.9
299.5
370.6
0.0
3.1
9.0
3.7
0.0
7.5
174.0
96.7
0.0
51.9
0.0
0.0
409.1
0.0
414.4
SET 2
BURN RATE- 2.27 kg/h
VOL SAMP - 0.02024 m3
AVERAGE
GASEOUS
CONCENTRATION
(mg/m3)
0.066
0.000
0.038
0.011
1.159
0.332
0.052
0.124
0.092
0.210
0.008
0.006
0.020
0.008
0.000
0.009
0.075
0.020
0.015
0.016
0.000
0.000
0.063
0.000
0.172
ESTIMATED
EMISSIONS
(mo/kg TIRE)
59.1
0.0
34.5
10.1
1041.2
298.6
46.8
111.8
83.0
188.6
7.4
5.3
18.1
6.7
0.0
8.4
67.6
17.9
13.5
14.4
0.0
0.0
56.2
0.0
154.2
SET3
BURN RATE - 1. 27 kg/h
VOL SAMP . 0.02022 m3
AVERAGE
GASEOUS
CONCENTRATION
(mg/fn3)
0.115
0.015
0.092
0.043
1.316
0.535
0.066
0.238
0.105
0.489
0.035
0.020
0.076
0.019
0.012
0.024
0.129
0.047
0.024
0.014
0.010
0.014
0.108
0.010
0.249
ESTIMATED
EMISSIONS
(mg/kg TIRE)
165.0
23.4
147.7
68.3
2113.4
859.3
106.2
382.4
168.2
784.6
56.7
32.4
122.6
30.6
18.5
38.4
207.3
75.6
37.8
22.1
16.5
21.9
172.9
16.7
399.0
(continued)
-------
TABLE 3-7. QUANTITATION AND EMISSION SUMMARY OF COMPOUNDS IDENTIFIED IN VOST SAMPLES: DAY 1 CHUNK CONDITION
(concluded)1,2
SET1
COMPOUND IDENTIFIED
METHYL.METHYLETHYL BENZENE
PHENOL
METHYL.METHYLETHENYL BENZENE
ETHENYL.DIMETHYL BENZENE
METHYL INDENE
METHYL INDENE
METHYLENE INDENE
NAPTHALENE
BENZOTHIOPHENE
BENZODIAZINE
METHYL NAPTHALENE
METHYL NAPTHALENE
TOTALS
BURN RATE
VOL SAMP.
AVERAGE
GASEOUS
CONCENTRATION
(mg/m3)
0.000
0.011
0.066
0.023
0.082
0.056
0.074
2.963
0.000
0.033
0.342
0.212
16.016
-6.63kg/h
0.01 673 m3
ESTIMATED
EMISSIONS
(mo/kg TIRE)
0.0
3.5
20.2
7.0
25.2
17.3
22.9
908.1
0.0
10.0
105.1
65.1
6202.2
SET 2
BURN RATE
VOL SAMP -
AVERAGE
GASEOUS
CONCENTRATION
(mg/m3)
0.000
0.000
0.000
0.000
0.014
0.014
0.011
0.668
0.018
0.016
0.077
0.052
3.369
-2.27 koto
0.02024 m3
ESTIMATED
EMISSIONS
(mo/kg TIRE)
0.0
0.0
0.0
0.0
12.9
12.9
9.6
600.2
16.4
14.3
69.6
47.1
3026.2
SETS
BURN RATE
VOL SAMP -
AVERAGE
GASEOUS
CONCENTRATION
(mo/m3)
0.018
0.000
0.036
0.000
0.035
0.037
0.021
0.749
0.011
0.013
0.101
0.068
4.904
-1.27k01)
0.02022 m3
ESTIMATED
EMISSIONS
(mg/kg TIRE)
29.2
0.0
58.2
0.0
55.9
59.7
32.9
1201.9
18.5
21.1
162.0
110.0
7873.1
1 Concentrations determined using system response to toluene.
2 Average gaseous concentrations and estimated emissions are based on controlled dilution of pit emissions. It Is unknown how well this dilution
represents ambient air exchange under actual conditions.
-------
TABLE 3-8. QUANTITATION AND EMISSION SUMMARY OF COMPOUNDS IDENTIFIED IN VOST SAMPLES: DAY 2 CHUNK CONDITION1-2
SET1
BURN RATE- 3.5 kg/h
VOL SAMP • 0.0186 m3
COMPOUND IDENTIFIED
BUTADIENE
TRICHLOROFLOUROMETHANE
PENTADIENE
CYCLOPENTADIENE
BENZENE
THIOPHENE
METHYL CYCLOHEXENE
METHYL HEXADIENE
HEPTADIENE
METHYL BENZENE
METHYL THIOPHENE
DIMETHYL HEXADIENE
ETHENYL CYCLOHEXENE
ETHYL BENZENE
DIMETHYL BENZENE
ETHYNYL BENZENE
ETHENYL BENZENE
METHYLETHYL BENZENE
PROPYL BENZENE
ETHYUMETHYL BENZENE
TRIMETHYL BENZENE
ETHYL.METHYL BENZENE
METHYL.ETHENYL BENZENE
BENZALDEHYDE
ETHENYLMETHYL BENZENE
AVERAGE
GASEOUS
CONCENTRATION
(mgAnS)
0.135
0.057
0.037
0.164
2.970
0.042
0.000
0.000
0.000
1.556
0.014
0.000
0.000
0.088
0.506
0.804
1.054
0.000
0.000
0.032
0.017
0.000
0.030
0.407
0.083
ESTIMATED
EMISSIONS
(mg/kg TIRE)
78.6
33.3
21.8
95.3
1730.3
24.6
0.0
0.0
0.0
906.7
8.0
0.0
0.0
51.2
295.0
468.6
614.2
0.0
0.0
18.6
9.9
0.0
17.6
289.8
48.6
SET 2
BURN RATE- 1.7 kg/h
VOL SAMP. 0.02053 m3
AVERAGE
GASEOUS
CONCENTRATION
(mg/m3)
0.147
0.000
0.134
0.034
1.272
0.030
0.000
0.026
0.019
0.855
0.020
0.011
0.000
0.239
0.379
0.095
0.495
0.059
0.029
0.121
0.026
0.020
0.019
0.154
0.106
ESTIMATED
EMISSIONS
(mg/kg TIRE)
175.8
0.0
161.2
40.9
1625.6
35.8
0.0
31.7
22.6
1025.7
24.5
13.0
0.0
287.2
454.7
113.6
593.2
70.3
35.2
145.5
30.9
23.9
23.2
184.7
126.6
SET 3
BURN RATE - .5 kg/h
VOL SAMP -0.0201 5 m3
AVERAGE
GASEOUS
CONCENTRATION
(mg/m3)
0.314
0.000
0.146
0.000
1.290
0.064
0.030
0.095
0.031
1.486
0.000
0.038
0.038
0.537
0.789
0.010
0.748
0.161
0.066
0.338
0.048
0.057
0.057
0.213
0.232
ESTIMATED
EMISSIONS
(mo/kg TIRE)
1279.0
0.0
597.0
0.0
5262.5
261.8
124.2
387.0
126.2
6060.3
0.0
153.3
153.9
2189.6
3219.4
40.6
3051.1
667.9
349.7
1378.9
194.2
231.9
234.1
868.1
947.2
(continued)
-------
TABLE 3-8. QUANTITATION AND EMISSION SUMMARY OF COMPOUNDS IDENTIFIED IN VOST SAMPLES: DAY 2 CHUNK CONDITION
(concluded) 1,2
SET1
BURN RATE -
VOL SAMP-0.0186 m3
COMPOUND IDENTIFIED
AVERAGE .
GASEOUS
CONCENTRATION
(mg/m3)
ESTIMATED
EMISSIONS
(mg/kg TIRE)
8ET2
BURNRATE.1.7kg/h
VOL SAMP-0.02053 m3
AVERAGE
GASEOUS ESTIMATED
CONCENTRATION EMISSIONS
(mg/m3) (mo/kg TIRE)
SETS
BURN RATE - .5 kg/h
VOL SAMP- 0.02015 m3
AVERAGE
GASEOUS
CONCENTRATION
(mg/m3)
ESTIMATED
EMISSIONS
ETHENYL.METHYL BENZENE
BENZOFURAN
LIMONENE ,
METHYUMEW
ISOCYANO BEh
DIHYDROINDE^
METHYUPROP
ETHYNYL,MET>
METHYUMETH
METHYL.METH'
ETHENYL.DIME
METHYL INDEN
METHYL INDEN
METHYLENE IN
DIMETHYLDIHV
NAPTHALENE
BENZOTHIOPH
BENZOOIAZINE
METHYL NAPTI
METHYL NAPTI
TOTALS
1 Concentrat
2 Average ga
represents ai
LETHYL BENZENE
ZENE
E
LBENZENZE
YL BENZENE
LETHYL BENZENE
LETHENYL BENZENE
HYL BENZENE
;
)ENE
)ROINDENE
NE
ALENE
ALENE
0.059
0.118
0.000
0.000
0.308
0.000
0.000
1.268
0.000
0.012
0.067
0.085
0.062
0.074
0.000
2.602
0.000
0.020
0.372
0.212
13.366
34.1
68.5
0.0
0.0
179.5
0.0
0.0
750.4
0.0
7.2
38.9
49.5
36.2
42.B
0.0
1515.8
0.0
11.7
216.6
123.3
7786.7
0.000
0.000
0.024
0.058
0.126
0.016
0.000
0.219
0.026
0.069
0.000
0.037
0.060
0.018
0.010
0.707
0.030
0.020
0.104
0.067
6.864
0.0 0.000
0.0 0.000
28.6 0.028
70.0 6.053
151.6 0.274
19.7 iO.050
0.0 0.000
263.0
31.8
71.3
0.0
44.8
59.6
21.7
12.4
848.2
36.3
24.5
124.9
79.8
7033.8
>ns determined using system response to toluene.
teous concentrations and estimated emissions are based on controlled dilution of pit emissions. It is unkrx
btent air exchange under actual conditions.
0.300
0.070
0.103
0.000
0.136
0.231
0.039
0.029
0.425
0.020
0.000
0.131
0.056
8.753
wn how well
0.0
0.0
116.1
215.7
1116.1
202.3
0.0
1223.0
285.2
420.4
0.0
554.6
940.1
159.9
117.1
1733.6
82.3
0.0
533.9
228.K
35696.7
this dilution
-------
TABLE 3-9i QUANTITATION AND EMISSION SUMMARY OF COMPOUNDS IDENTIFIED IN VOST SAMPLES: DA>
1 SHRED CONDITION1-2
1
1
SET
BURN RATE
1
• 1.3k0/h
1 VOL SAMP « 0.02225 m3
1
1
I
COMPOUND IDENTIRED
BUTADIENE ]
PENTADIENE \
BENZENE |
THIOPHENE \
METHYL CYCLQHEXENE
METHYL HEXACJ1ENE
HEPTADIENE I
METHYL BENZEME
METHYL THIOPHENE
DIMETHYL HEXMOIENE
ETHENYL CYCLOHEXENE
ETHYL BENZENB
DIMETHYL BENZENE
ETHYNYL BENZENE
ETHENYL BENZENE
METHYLETHYL BENZENE
ETHENYLDIMEWLCYCLOHEXENE
PROPYL BENZENE
ETHYL.METHYL BENZENE
TR1METHYL BENZENE
ETHYL.METHYL BENZENE
METHYL.ETHENYU BENZENE
BENZALDEHYDE
ETHENYLMETHYL BENZENE
AVERAGE
GASEOUS
CONCENTRATION
(mg/m3)
0.134
0.784
1.271
0.037
0.025
0.054
0.000
0.637
0.020
0.061
0.063
0.130
0.679
0.087
0.345
0.095
0.243
0.037
0.223
0.041
0.038
0.040
0.201
0.037
ESTIMATED
EMISSIONS
(mo/kg TIRE)
210.7
1229.8
1992.9
58.0
39.6
84.2
0.0
998.8
31.9
95.0
98.6
204.4
1065.1
136.4
540.5
148.2
380.8
68.3
350.3
63.9
59.8
63.2
314.7
58.0
SET 2
BURN RATE -
1.4kg/h
VOL SAMP. 0.02043 m3
AVERAGE
GASEOUS
CONCENTRATION
(mg/m3)
0.141
0.697
1.616
0.025
0.018
0.043
0.021
0.650
0.000
0.020
0.000
0.066
0.713
0.174
0.435
0.073
0.195
0.051
0.227
0.034
0.036
0.043
0.195
0.024
SETS
BURN RATE.. 8 MI
VOL. SAMP. 0.01896 m3
i
AVERAGE
ESTIMATED GASEOUS ESTIMATED
EMISSIONS CONCENTRATION EMISSIONS
(mg/kg TIRE) (mgMi3) (mo/kg TIRE)
204.6
1015.1
2353.4
36.1
26.6
63.2
30.0
946.5
0.0
29.2
0.0
95.7
1038.9
253.4
632.9
105.7
284.4
74.3
331.2
49.1
52.4
62.4
283.4
35.1
0.000 0.0
0.980 2498.1
1.117 2847.9
• 0.000 0.0
0.030 75.8
0.117 298.9
0.044 1 12.5
0.625 1592.6
0.000 0.0
0.083 211.1
0.089 226.0
0.263 670.7
0.771 1966.2
0.000 0.0
0.332 845.3
0.163 415.7
0.341 869.6
0.084 212.9
0.349 889.7
0.062 157.5
0.065 164.8
0.063 159.8
0.172 439.5
0.026 67.5
(continued)
-------
TABLE 34 QUANTITATION AND EMISSION SUMMARY OF COMPOUNDS IDENTIFIED IN VOST SAMPLES: DAY 1 SHRED CONDITION
(concluded)1,2
1 SET1
1
BURN RATE
-t.3kg/h
1 VOL SAMP- 0.02225 m3
1
COMPOUND IDENTIFIED
ETHENYL.METllYL BENZENE
METHYL.METHTLETHYL C.H.
UMONENE 1
METHYL.METH1LETHYL BENZENE
ISOCYANO BENZENE
DIHYDROINDENE
METHYUPROPH. BENZENZE
TETRAMETHYL BENZENE
ETHYNYL,METHyL BENZENE
METHYL.METHYJ.ETHYL BENZENE
METHYUMETHYLETHENYL BENZENE
ETHENYL.DIMETOYL BENZENE
TETRAMETHYL BENZENE
METHYL INDENEj
METHYL INDENE
METHYLENEINDIENE
DIMETHYLOIHYDJ*) INDENE
DIMETHYL.METH H.PROPYL BENZENE
NAPTHALENE
BENZOTHIOPHEME
BENZODIAZINE
METHYL NAPTHA.ENE
METHYL NAPTHA.ENE
TOTALS
AVERAGE
GASEOUS
CONCENTRATION
(mg/lm3)
0.000
0.080
0.379
0.082
0.312
0.022
0.031
0.204
0.000
0.067
0.424
0.000
0.043
0.000
0.050
0.015
0.000
0.014
0.458
0.007
0.016
0.057
0.041
7.583
ESTIMATED
EMISSIONS
(mgfag TIRE)
0.0
126.0
595.2
128.7
489.3
34.4
48.2
320.3
0.0
104.8
664.7
0.0
68.0
0.0
79.0
23.6
0.0
22.1
718.0
11.1
24.6
88.8
64.6
11894.4
SET 2
BURN RATE
-1.4kg/h
VOL SAMP- 0.02043 m3
AVERAGE
GASEOUS
CONCENTRATION
(mg/m3)
0.012
0.080
0.502
0.091
0.143
0.024
0.019
0.000
0.405
0.071
0.411
0.000
0.036
0.027
0.053
0.019
0.013
0.013
0.889
0.019
0.018
0.112
0.063
8.516
ESTIMATED
EMISSIONS
(mg/kgTIRE)
18.1
116.2
731.4
132.2
208.4
35.3
27.7
0.0
590.3
103.6
598.9
0.0
51.8
39.3
77.7
27.6
18.3
18.9
1295.4
27.9
25.6
163.2
91.6
12403.2
SETS
BURN RATE - .8 kg/h
VOL. SAMP .
AVERAGE
GASEOUS
CONCENTRATION
(mg/m3)
0.016
0.180
0.760
0.056
0.060
0.045
0.045
0.169
0.000
0.126
0.649
0.018
0.076
0.027
0.071
0.023
0.021
0.020
0.224
0.000
0.000
0.067
0.043
8.493
0.01896 m3
ESTIMATED
EMISSIONS
(mg/kg TIRE)
40.5
458.8
1936.1
143.9
203.6
115.1
114.2
430.7
0.0
320.4
1655.3
46.2
194.9
68.5
180.7
57.8
54.3
50.9
571.4
0.0
0.0
170.5
110.8
21646.6
1 Concentration s determined using system response to toluene.
2 Average gase aus concentrations and estimated emissions are based on controlled dilution of pit emissions. It is unknown how well this dilution
represents amb ent air exchange under actual conditions.
-------
TABLE 3-10.! QUANTITATION AND EMISSION SUMMARY OF COMPOUND IDENTIFIED IN VOST SAMPLE: DAY 2 SHRED CONDITION1 -2
SET1
BURN RATE -
SET 2
1.5k0/h
VOL SAMP -0.0191 2 m3
COMPOUND IDENTIFIED
BUTADIENE
PENTADIENE
BENZENE
THIOPHENE
METHYL CYCLOHEXENE
METHYL HEXADIENE
HEPTADIENE
METHYL BENZENE
METHYL THIOPHENE
DIMETHYL HEXADIENE
ETHENYL CYCLOHEXENE
ETHYL BENZENE
DIMETHYL BENZENE
ETHYNYL BENZENE
ETHENYL BENZENE
METHYLETHYL BENZENE
CYCLIC ALKENE
ETHENYLDIMETHYLCYCLOHEXENe
PROPYL BENZENE
ETHYUMETHYL BENZENE
TRIMETHYL BENZENE
METHYL.ETHENYL BENZENE
BENZALDEHYDE
ETHENYLMETHYL BENZENE
AVERAGE
GASEOUS
CONCENTRATION
(mgAn3)
0.077
0.956
1.509
0.032
0.020
0.067
0.043
0.692
0.010
0.047
0.084
0.209
0.543
0.094
0.470
0.081
0.074
0.213
0.047
0.224
0.037
0.057
0.210
0.035
ESTIMATED
EMISSIONS
(ma/kg TIRE)
104.7
1296.9
2051.2
43.3
26.7
91.2
58.6
940.2
14.3
63.7
114.8
283.7
737.8
128.4
638.6
110.7
100.5
289.9
64.1
304.7
51.0
77.6
285.2
47.8
BURN RATE
-2.3(<8Jh
VOL SAMP- 0.01946 m3
AVERAGE
GASEOUS
CONCENTRATION
(mg/m3)
0.044
0.399
1.662
0.031
0.016
0.045
0.019
1.112
0.000
0.029
0.051
0.149
0.543
0.308
0.569
0.051
0.034
0.065
0.024
0.167
0.034
0.035
0.369
0.046
ESTIMATED
EMISSIONS
(mg/Kg TIRE)
38.7
353.8
1668.8
27.8
14.0
39.5
17.3
965.9
0.0
25.3
44.9
131.7
481.2
273.2
504.2
45.4
30.2
67.6
20.9
139.5
29.8
30.9
327.3
40.5
SETS
BURN RATE
-.9kgvti
VOL SAMP. 0.0213 m3
AVERAGE
GASEOUS
CONCENTRATION
(mg/m3)
0.163
0.306
1.039
0.000
0.026
0.066
0.042
0.587
0.011
0.055
0.073
0.160
0.535
0.000
0.236
0.090
0.056
0.112
0.037
0.260
0.045
0.032
0.148
0.000
ESTIMATED
EMISSIONS
(mg/kg TIRE)
370.2
693.6
2352.8
0.0
58.4
194.6
95.2
1330.8
25.9
124.7
165.4
407.4
1211.1
0.0
534.5
203.0
127.3
253.9
64.5
589.1
101.1
72.2
334.7
0.0
(continued)
-------
TABLE 3-10. QUANTITAT1ON AND EMISSION SUMMARY OF COMPOUND IDENTIFIED IN VOST SAMPLE: DAY 2 SHRED CONDITION
(concluded)1.2
SET1
BURNRATE-1.5kg/h
COMPOUND IDENTIFIED
ETHENYL.METHYL BENZENE
METHYUMETHYLETHYL C.H.
LIMONENE
METHYUMETHYLETHYL BENZENE
ISOCYANO BENZENE
DIHYDROINDENE
METHYUPROPYL BENZENZE
TETRAMETHYL BENZENE
ETHYNYUMETHYL BENZENE
METHYUMETHYLETHYL BENZENE
PHENOL
METHYUMETHYLETHENYL BENZENE
ETHENYUOIMETHYL BENZENE
TETRAMETHYL BENZENE
METHYL INDENE
METHYL INDENE
METHYLENE INDENE
DIMETHYLDIHYDRO INDENE
NAPTHALENE
BENZOTHIOPHENE
BENZODJAZINE
METHYL NAPTHALENE
METHYL NAPTHALENE
TOTALS
VOL SAMP
AVERAGE
GASEOUS
CONCENTRATION
(mg/lm3)
0.022
0.060
0.631
0.060
0.155
0.000
0.000
0.000
0.264
0.074
0.000
0.376
0.023
0.039
0.033
0.066
0.022
0.000
0.661
0.024
0.017
0.060
0.068
8.547
- 0.01912 m3
ESTIMATED
EMISSIONS
(mg/kg TIRE)
30.5
108.5
658.4
81.0
210.3
0.0
0.0
0.0
358.3
100.9
0.0
511.2
31.1
53.6
45.0
69.5
29.5
0.0
890.1
32.2
22.9
108.9
120.2
11618.2
SET2
BURN RATE - 2.3 kg/h
VOL SAMP.
AVERAGE
GASEOUS
CONCENTRATION
(mgAn3)
0.038
0.000
0.433
0.122
0.292
0.000
0.000
0.000
0.720
0.047
0.099
0.121
0.025
0.037
0.062
0.072
0.040
0.000
1.294
0.020
0.035
0.164
0.084
9.715
0.01 946 m3
ESTIMATED
EMISSIONS
(mg/kg TIRE)
33.4
0.0
384.1
108.2
259.1
0.0
0.0
0.0
637.9
42.1
87.9
107.1
22.0
33.1
55.0
63.5
35.4
0.0
1147.1
17.9
31.4
145.0
74.4
8613.0
SETS
BURN RATE - .9 kg/h
VOL SAMP.
AVERAGE
GASEOUS
CONCENTRATION
(mgftn3)
0.000
0.100
0.414
0.118
0.149
0.032
0.027
0.116
0.000
0.074
0.000
0.275
0.020
0.050
0.024
0.044
0.015
0.016
0.153
0.000
0.000
0.013
0.014
5.771
0.0213 m3
ESTIMATED
EMISSIONS
(mg/kg TIRE)
0.0
225.6 '
936.8
266.4
336.8
73.4
60.4
263.5
0.0
168.6
0.0
622.1
45.4
112.3
55.3
96.9
35.1
35.6
345.6
0.0
0.0
30.6
32.0
13074.8
1 Concentrations determined using system response to toluene.
2 Average gaseous concentrations and estimated emissions are based on controlled dilution of pit emissions. It is unknown how well this dilution
represents ambient air exchange under actual conditions.
-------
the amount of tire material combusted in a specific period by that amount of time (in minutes) and
normalizing it to an hourly basis. The resultant value is an emission estimate of the amount of compound
emUed at a specific bum rate. An example calculation follows:
The amount of ethenyl benzene (styrene) found to be in the first sample collected on the
second day of the "CHUNK" condition was determined to be 0.01961 mg. The sample
represented 0.0186 m3 of gas stream collected over a 42.1 min continuous period.
During this time, 5.4 Ib of tire material were consumed through combustion. The volume
of air introduced into the bum hut equalled 1,200 cfm. This equals 2,039 m3/h.
The average gaseous concentration - 0.01961 mg/0.0186 m3 = 1.054 mg/rrfl
The bum rate - (5.4 lb/42.1 min) (60 min/h)» 7.7 b/h = 3.5 kg/h
The estimated emissions »(1.054 mg/m3) (2039 m3/h)/ 3.5 kg/h - 614.0 mg of
styrene/kg of tire combusted.
3.4 SEMI-VOLATILE ORGANICS
As with the volatile organic analyses, the MS analysis of the XAD-2 extracts produced the
identification of the same types of compounds. Table 3-11 lists the 60 compounds identified and
indicates that substituted mono- and poly-aromatics were again the predominant products of incomplete
combustion. Many of the compounds collected and identified by the VOST technique were also found in
the XAD-2 extracts. Table 3-12 shows that similar ambient-loading and emission-rate values were
reaized from the XAD-2 extracts. The emission rate for many compounds increased with decreasing
bum rate, but not for all. The emission of napthalene, for example, was much greater at higher bum
rates, as evidenced during the "CHUNK" condition. In addition, the average gaseous concentration is
ateo greater in this situation. This finding contrasts with the trends observed in the VOST samples.
The paniculate filters located upstream of the XAD-2 canisters contained considerable quantities
of oiganics. The majority of compounds found in the paniculate have boiling points exceeding 300 °C.
Table 3-13 contains a summary of semi-volatile organic emission data from all 4 test conditions. The total
organics from respective boiling-point-based analyses are presented for each component of the sampling
media. The emission rate data presented show that from 12-50 g of semi-volatile organics can be
emJied for every kilogram of tire burned. It appears that as bum rate decreased, the amount of organics
39
-------
TABLE 3-11. COMPOUNDS IDENTIFIED BY GC/MS FROM XAD-2 EXTRACTS
Compound Identified Formula
METHYL BENZENE C7H8
CYCLOPENTANONE
DIMETHYL CYCLOHEXENE
ETHENYL CYCLOHEXENE
ETHYL BENZENE
DIMETHYL BENZENE
HEXANENITRILE
ETHYNYL BENZENE
STYRENE
NONANE CgH20
PROPENYL CYCLOHEXANE CgHie
METHYLETHYL BENZENE CgHi2
PROPYLBENZENE CgHi2
BENZALDEHYDE CyHeO
TRIMETHYL BENZENE CgHi2
PHENOL CeHsO
CYANOBENZENE C?H5N
PROPENYLBENZENE CgHio
METHYL.ETHENYL BENZENE
METHYL.METHYLETHYL BENZENE
LIMONENE CiQHi6
DIHYDRO INDENE
HYDROXY BENZALDEHYDE
INDENE CgHs
TETRAMETHYL BENZENE
ETHYL.DIMETHYL BENZENE
METHYL PHENOL
METHYL BENZALDEHYDE
METHYL.(METHYLETHYL) BENZENE
PROPENYL.METHYL BENZENE CioHi2
UNDECANE CnH24
(DIMETHYLPROPYL) BENZENE Ci 1 HI 6
DIMETHYL,(METHYLETHYL) BENZENE CnHie
BUTYNYL BENZENE
METHYL INDENE
AZULENE
NAPHTHALENE
BENZO[B]THIOPHENE
BENZISOTHIAZOLE CyHsNS
HEXAHYDRO AZEPINONE
DiHYDRO.METHYL NAPHTHALENE
BUTYLJRIMETHYL BENZENE C13H20
METHYL NAPHTHALENE CnHiQ
BIPHENYL C12H10
DIMETHYL NAPHTHALENE C12H12
DIHYDRO ACENAPHTHALENE C12H10
(continued)
40
-------
TABLE 3-11. COMPOUNDS IDENTIFIED BY GC/MS FROM XAD-2 EXTRACTS (concluded)
Compound Identified Formula
ACENAPHTHALENE C-|2H8
(DIMETHYL,HEXENYL),METHYL BENZENE C14H20
PENTADECANE CisH32
1,1'BIPHENYL. METHYL C13H12
ISOCYANO NAPHTHALENE CnH?N
NAPHTHALENECARBOXALDEHYDE Ci 1 HaO
PROPENYL NAPHTHALENE C13H12
THIMETHYL NAPHTHALENE C13H14
1HFLUORENE CisHio
DIMETHYL BIPHENYL C14H14
DIBENZOTHIOPHENE C12H10S
PHENANTHRENE C14H1Q
9H FLUORENE, METHYLENE C14H10
PHENYLNAPHTHALENE
41
-------
TABLE 3-12. QUANTITATION AND EMISSION SUMMARY OF COMPOUNDS IDENTIFIED IN XAD-2 EXTRACTS1-2
DAY 1 CHUNK CONDITION
VOL SAMP-12.98 m3
BURN RATE
DAY 2 CHUNK CONDITION
VOL SAMP-12.76 mfl/m3
BURNRATE-1.7kg/h
DAY 1 SHRED CONDITION
VOL SAMP-13.77 m&m*
BURN RATE -1.1 kg/h
DAY 2 SHRED CONDITION
VOL SAMP-12.43 mg/m3
BURNRATE-1.3kg/h
COMPOUND IDENTIFIED
AVERAGE AVERAGE AVERAGE AVERAGE
GASEOUS ESTIMATED GASEOUS ESTIMATED GASEOUS ESTIMATED GASEOUS ESTIMATED
CONCENTRATION EMISSIONS CONCENTRATION EMISSIONS CONCENTRATION EMISSIONS CONCENTRATION EMISSIONS
(mg/m3) (mg/KgTIRE) (mg/m3) (mg/kgTIRE) (mgttrfl) (mo/kg TIRE) (mg/m3) (mgAgTIRE)
METHYL BENZENE
ETHYL BENZENE
DIMETHYL BENZENE
ETHYNYL BENZENE
STYRENE
METHYLETHYL BENZENE
PROPYL BENZENE
BENZALDEHYDE
TRIMETHYL BENZENE
PHENOL
CYANOBENZENE
TRIMETHYL BENZENE
METHYL.METHYLETHYL BENZENE
UMONENE
INDENE
TETRAMETHYL BENZENE
ETHYL.DIMETHYL BENZENE
METHYL BENZALDEHYDE
ETHYL.DIMETHYL BENZENE
PROPENYL.METHYL BENZENE
METHYL INDENE
METHYL INDENE
NAPHTHALENE
BENZO(B]THIOPHENE
BENZISOTHIAZOLE
HEXAHYDRO AZEPINONE
0.716
0.074
0.000
0.185
0.419
0.000
0.000
0.111
0.000
0.180
0.095
0.127
0.000
0.000
0.325
0.000
0.000
0.000
0.000
0.000
0.000
0.000
1.230
0.099
0.000
0.000
634.8
65.8
0.0
163.6
371.5
0.0
0.0
08.6
0.0
168.3
84.3
112.8
0.0
0.0
288.5
0.0
0.0
0.0
0.0
0.0
0.0
0.0
1090.4
87.6
0.0
0.0
1.500
0.289
0.513
0.325
0.795
0.081
0.000
0.327
0.000
0.473
0.305
0.256
0.215
0.094
0.602
0.000
0.000
0.000
0.000
0.000
0.188
0.000
1.931
0.000
0.000
0.126
1799.5
347.1
615.3
390.0
953.3
97.4
0.0
392.1
0.0
566.9
365.5
307.6
258.1
113.2
722.0
0.0
0.0
0.0
0.0
0.0
225.6
0.0
2315.9
0.0
0.0
151.4
0.731
0.192
0.554
0.078
0.332
0.142
0.136
0.343
0.156
0.360
0.307
0.195
0.926
1.402
0.156
0.094
0.000
0.089
0.162
0.537
0.223
0.000
O.S16
0.000
0.1 7J>
0.345
1354.9
355.0
1026.1
144.2
614.6
263.5
251.2
635.3
289.9
667.2
569.3
361.5
1716.1
2599.2
289.9
174.8
0.0
164.7
300.0
996.2
413.7
0.0
957.2
0.0
330.9
638.9
0.911
0.203
0.532
0.150
0.433
0.122
0.118
0.000
0.351
0.470
0.292
0.199
0.704
1.316
0.251
0.000
0.154
0.000
0.000
0.000
0.114
0.132
0.843
0.000
0.000
0.555
1429.0
318.3
834.2
235.2
679.8
191.0
184.6
0.0
549.9
736.8
458.6
312.2
1104.9
2064.5
393.9
0.0
241.8
0.0
0.0
0.0
179.2
207.3
1322.8
0.0
0.0
869.9
(continued)
-------
TABLE 3-12. QUANTITATION AND EMISSION SUMMARY OF COMPOUNDS IDENTIFIED IN XAD-2 EXTRACTS (concluded)1'2
DAY 1 CHUNK CONDITION
VOL SAMP-12.06 m3
BURN RATE- 2.3 kg/h
DAY 2 CHUNK CONDITION
VOL SAMP-12.76 mgM»3
BURNRATE-1.7ko/h
DAY 1 SHRED CONDITION
VOL SAMP -
BURN RATE-1.1
DAY 2 SHRED CONDITION
VOL SAMP - 12.43 mg/m3
BURNRATE-1.3ko/h
COMPOUND IDENTIFIED
AVERAGE AVERAGE AVERAGE AVERAGE
GASEOUS ESTIMATED GASEOUS ESTIMATED GASEOUS ESTIMATED GASEOUS ESTIMATED
CONCENTRATION EMISSIONS CONCENTRATION EMISSIONS CONCENTRATION EMISSIONS CONCENTRATION EMISSIONS
(mg/m3) (mg/kgTIRE) (mg/m3) (mg/kgTIRE) (mg/ta3) (mg/kg TIRE) (mgfnfl) (mg/kgTIRE)
2-M6THYL NAPHTHALENE
1-METHYL NAPHTHALENE
BIPHENYL
DIMETHYL NAPHTHALENE
ACENAPHTHALENE
1.V BIPHENYL. METHYL
ISOCYANO NAPHTHALENE
PROPENYL NAPHTHALENE
TRIMETHYL NAPHTHALENE
1HFLUORENE
PHENANTHRENE
TOTALS
0.164
0.124
0.063
0.000
0.390
0.025
0.021
0.053
0.000
0.067
0.152
4.670
145.6
109.9
73.5
0.0
345.6
22.1
18.7
46.6
0.0
76.9
135.0
4140.4
0.466
0.463
0.290
0.069
0.773
0.000
0.000
0.000
0.000
0.288
0.194
12672.8
559.4
555.3
347.8
83.0
927.0
0.0
0.0
0.0
0.0
346.0
233.2
9.367
0.202
0.122
0.180
0.183
0.217
0.000
0.000
0.000
0.169
0.141
0.000
17362.2
373.9
225.7
333.6
338.8
402.2
0.0
0.0
0.0
312.9
260.8
0.0
9.633
0.313
0.146
0.208
0.000
0.430
0.000
0.000
0.000
0.203
0.230
0.251
15108.7
490.5
229.7
326.3
0.0
673.8
0.0
0.0
0.0
319.1
361.2
394.2
10.566
1 Concentrations determined using system response to TCO calibration mix.
2 Average gaseous concentrations and estimated emissions are based on controlled dilution of pit emissions. It is unknown how well this dilution
represents ambient air exchange under actual conditions.
-------
Y
TABLE 3-13. ORGANIC EMISSION SUMMARY
SAMPLE WEIGHT
SAMPLE TIME CHANGE
PORTION (min) (kg)
XAD-2 140 5.4
FILTER 1 11 1.7
FILTER 2 129 3.7
FILTER TOTAL 140 5.4
AVG VOLUME
BURN RATE SAMP
(kg/h) (m3)
DAY
2.3
9.4
1.7
2.3
1 CHUNK CONDITION
12.98
0.93
12.05
12.98
AVERAGE GASEOUS
CONCENTRATION
TCO GRAV
(mg/m3) (mg/m3)
6.067 0.698
0.043 33.634
0.066 4.823
0.065 6.888
TOTAL
ESTIMATED EMISSIONS
TCO GRAV
(mg/kg TIRE)
5379
9
79
58
5436
619
7296
5785
6106
6725 12161
DAY 2 CHUNK CONDITION
XAD-2 152 4.3
FILTER 1 42 2.4
FILTER 2 110 1.8
FILTER TOTAL 152 4.3
XAD-2 182 3.2
FILTER 182 3.2
XAD-2 183 4.0
FILTER 183 4.0
1.7
3.5
1.0
1.7
DAY
1.1
1.1
DAY
1.3
1.3
12.76
3.3
9.45
12.76
1 SHRED CONDITION
13.77
13.77
2 SHRED CONDITION
12.43
12.43
11.398 0.749
0.018 18.498
0.53 10.219
0.398 12.359
TOTAL
20.658 0.89
0.141 6.822
TOTAL
15.65 1.099
0.173 8.771
13671
11
1081
477
14148
38292
261
38554
24546
271
898
10776
20837
14824
. 15722 29870
1650
12646
14295 52849
1724
13757
TOTAL
24818
16481
40290
-------
emitted, particularly in the TOO range, Increased. There did not seem to be any significant variation in
GRAV range organic emissions when related to bum rate.
A polycydic aromatic hydrocarbon (PAH) analysis was performed on the liquid extractions of the
XAD-2 and filter components. The results of the analyses are presented in TaWes 3-14 through 3-17.
The list of 16 PAHs contain several compounds known to be carcinogenic. In particular, the presence of
benzo(a)pyrene (BAP) is of major importance. It is a highly scrutinized compound when evaluating
combustion processes. Although no trend in concentration related to bum rate exists, the magnitude of
the emissions warrants concern.
The PAH analysis reveals that only roughly 10 percent of the GRAV range organics could be
accounted for. It was not possible to identify the remaining portion because of equipment limitations. The
GC/MS system used was not set up for high temperature applications, so this area remains unexplored.
tt may be posstote that carbon black, a major constituent of tire material, may exist as sub .45 urn
particles that passed through the filter during cleanup of the paniculate extraction. It may also be
possble that some of the discrepancy between the PAH and GRAV results may be due to suspected low
sample recoveries for the PAH analysis.
3.5 PARTICULATE LOADING
The collection of paniculate was performed using three separate systems. Paniculate was
captured with the semi-volatile organic system, with the airborne metals paniculate collection system, and
with a medium volume PMio sampler located in the bum hut. Table 3-18 contains a summary of the
paniculate loading values of these three systems for the 4 test conditions. For total average gaseous
concentration there seems to be good agreement between the organic paniculate and the metals
paniculate systems during each test condition. Moreover, average gaseous concentration increased with
increased bum rate. As the bum rate decreased, the percent of organics extracted increased. This
finding is important because, although under reduced average gaseous concentration, the amount of
organic material that the paniculate contains is greater. Comparing bum rate to paniculate estimated
emissions shows that the emission rate of paniculate decreased with lower bum rates, although nearly
100 g of partfculate were emitted for every kilogram of tire combusted.
45
-------
TABLE 3-14. PAH QUANTITATION AND EMISSION SUMMARY: DAY 1 CHUNK CONDITION1
XAD-2 EXTRACT
VOL SAMP -12.98m3
BURN RATE- 2.3 kg/h
1ST PART FILTER
VOL SAMP-0.93 m3
BURN RATE-9.4kg/h
2ND PART FILTER
VOL SAMP-12.06 m3
BURN RATE- 1.7 kg/h
FILTER TOTALS
VOL SAMP-12.96 m3
BURN RATE - 2.3 kg/h
COMPOUND IDENTIFIED
AVERAGE AVERAGE AVERAGE AVERAGE
GASEOUS ESTIMATED GASEOUS ESTIMATED GASEOUS ESTIMATED GASEOUS ESTIMATED
CONCENTRATION EMISSIONS CONCENTRATION EMISSIONS CONCENTRATION EMISSIONS CONCENTRATION EMISSIONS
(mg/m3) (ing/Kg TIRE) (mg/m3) (mg/VgTIRE) (mg/m3) (mg/KgTIRE) (mg/m3) (mg/kgTIRE)
NAPHTHALENE
ACENAPHTHYLENE
ACENAPHTHENE
FLOURENE
PHENANTHRENE
ANTHRACENE
FLOURANTHENE
PYRENE
BENZ(A)ANTHRACENE
CHRYSENE
BENZO(B)FLOURANTHENE
BENZO(K)FLOURANTHENE
BENZO(A)PYRENE
DIBENZ(A.H)ANTHRACENE
BENZCKO.H.OPERYLENE
INDENO(1 .2.3-CDJPYRENE
TOTALS
0.810
0.628
0.120
0.185
0.157
0.027
0.076
0.000
0.001
0.000
0.000
0.000
0.000
0.000
0.000
0.000
2.004
718.2
556.5
106.4
163.9
139.5
24.2
67.3
0.0
0.5
0.0
0.0
0.0
0.0
0.0
0.0
0.0
1776.5
0.000
0.000
1.027
0.059
0.099
0.000
0.473
0.124
0.226
0.368
0.344
0.328
0.481
0.000
0.441
0.312
4.262
0.0
0.0
222.7
12.8
21.6
0.0
102.6
26.8
49.0
79.9
74.8
71.1
104.4
0.0
95.6
67.6
928.9
0.000
0.017
0.114
0.007
0.045
0.015
0.224
0.000
0.041
0.038
0.025
0.027
0.034
0.000
0.000
0.019
0.606
0.0
19.9
137.0
9.0
54.3
17.6
268.7
0.0
48.8
45.4
29.9
32.8
40.8
0.0
0.0
22.5
726.6
0.000
0.015
0.180
0.011
0.049
0.014
0.242
0.009
0.054
0.062
0.048
0.049
0.066
0.000
0.032
0.040
0.869
0.0
13.7
159.2
9.9
43.6
12.0
2145
7.9
47.8
54.5
42.3
43.4
58.6
0.0
28.0
35.2
770.6
1 Average gaseous concentrations and estimated emissions are based on controlled dilution of pit emissions. It is unknown now well this dilution
represents ambient air exchange under actual conditions.
-------
TABLE 3-18. PAH QUANTITATION AND EMISSION SUMMARY: DAY 2 CHUNK CONDITION1
XAD-2 EXTRACT
VOL SAMP-12.78 n3
BURN RATE-1.
1ST PART FILTER
VOL SAMP-3.30 m3
BURN RATE • 9.5 kg/h
2ND PART FILTER
VOL SAMP-0.45 m3
BURN RATE. 1.0ko/h
FILTER TOTAL
VOL SAMP. 12.76 m3
BURN RATE-1.
COMPOUND IDENTIFIED
AVERAGE AVERAGE AVERAGE AVERAGE
GASEOUS ESTIMATED GASEOUS ESTIMATED GASEOUS ESTIMATED GASEOUS ESTIMATED
CONCENTRATION EMISSIONS CONCENTRATION EMISSIONS CONCENTRATION EMISSIONS CONCENTRATION EMISSIONS
(mg/m3) (ma/Kg TIRE) (mg/m3) (mg/kgTIRE) (mg/m3) (mfl/kgTIRE) (m&nfl) (mo/kg TIRE)
NAPHTHALENE
ACENAPHTHYLENE
ACENAPHTHENE
FLOURENE
PHENANTHRENE
ANTHRACENE
FLOURANTHENE
PYRENE
BENZ(A)ANTHRACENE
CHRYSENE
BENZO(D)FLOURANTHENE
BENZO
-------
TABLE 3-16. PAH QUANTITAT1ON AND EMISSION SUMMARY: DAY 1 SHRED CONDITION1
XAD-2 EXTRACT
VOL SAMP - 13.77 m3
BURN RATE »1.1kg/h
PART FILTER
VOL SAMP «13.77 m3
BURN RATE - 1.1 kg/h
AVERAGE
GASEOUS ESTIMATED
CONCENTRATION EMISSIONS
PAH (mg/m3) (mg/kg TIRE)
NAPHTHALENE
ACENAPHTHYLENE
ACENAPHTHENE
FLOURENE
PHENANTHRENE
ANTHRACENE
FLOURANTHENE
PYRENE
BENZ(A)ANTHRACENE
CHRYSENE
BEN2O(B)FLOURANTHENE
BENZO{K)FLOURANTHENE
BENZO(A)PYRENE
CMBENZ(A,H) ANTHRACENE
BENZO
-------
TABLE 3-17. PAH QUANTITATION AND EMISSION SUMMARY: DAY 2 SHRED CONDITION1
XAD-2 EXTRACT
VOL SAMP -12.43 m3
BURNRATE«1.3kg/h
PART FILTER
VOL SAMP. 12.43 m3
BURNRATE-1.3kg/h
AVERAGE
GASEOUS ESTIMATED
CONCENTRATION EMISSIONS
PAH (mg/m3) (mg/kg TIRE)
NAPHTHALENE
ACENAPHTHYLENE
ACENAPHTHENE
FLOURENE
PHENANTHRENE
ANTHRACENE
FLOURANTHENE
PYRENE
BENZ( A) ANTHRACENE
CHRYSENE
BENZO(B)FLOURANTHENE
BENZO(K)FLOURANTHENE
BENZO(A)PYRENE
WBENZ(A,H) ANTHRACENE
BENZO(G,H,I)PERYLENE
WDENO{1 5Ł-CD)PYRENE
TOTALS
0.347
0.406
0.941
0.137
0.143
0.025
0.133
0.013
0.008
0.001
0.000
0.000
0.000
0.000
0.000
0.000
2.155
544.7
6375
1476.3
2145
225.0
39.5
208.6
20.4
12.6
1.3
0.0
0.0
0.0
0.0
0.0
0.0
33805
AVERAGE
GASEOUS ESTIMATED
CONCENTRATION EMISSIONS
(mg/m3) (mg/kg TIRE)
0.000
0.000
0.158
0.003
0.020
0.007
0.200
0.097
0.068
0.082
0.062
0.070
0.082
0.000
0.113
0.062
1.023
0.0
0.0
2485
4.6
30.8
10.8
314.1
152.8
106.1
129.0
97.0
109.5
129.0
0.0
176.7
96.6
16055
1 Average gaseous concentrations and estimated emissions are based on controlled dilution of pit
emissions. R is unknown how well this dilution represents ambient air exchange under actual conditions.
-------
TABLE 3-18. PARTICULATE COLLECTION SUMMARY1
VOLUME
SAMPLE SAMP
PORTION (m3)
BURN
RATE
(kBVh)
AVERAGE
GASEOUS
CONCEN.
(mg/mS)
ESTIMATED
EMISSIONS
(mgftgTIRE)
EXTRORQ SAMPLE
% PORTION
VOLUME
SAMP
(m3)
CHUNK DAY 1
OROPARTFILT1
OROPARTRLT2
TOTAL
MET PART FILT1
METPARTRLT2
TOTAL
PM10 FILTER
0.03
12.06
12.06
5.10
7.07
13.16
0.53
0.4
1.7
2.3
4.0
1.3
2.7
14
750.6
41.1
91.0
260
38.4
120.3
810.6
162816.3
40205:8
81471.3
111036.0
60228.0
07645.4
110368.0
4.5 ORQ PART FILT1
11.0 ORQPARTFILT2
7.6 TOTAL
MET PART FILT1
METPARTFILT2
TOTAL
PM102
3.3
0.45
12.75
2.86
9.08
11.04
5.38
SHRED DAY 1
ORQ PART FILTER
MET PART FILTER
PM10
13.77
13.20
5.4
1.1
1.1
0.85
34
35.7
74.5
63023.6
66174.8
178712.4
22.6 ORQ PART FILTER
MET PART FILTER
PM10
12.43
15.56
3.45
BURN
RATE
(Kfl/h)
AVERAGE
GASEOUS
CONCEN.
(mflfimS)
ESTIMATED
EMISSIONS
(mgTfcgTIRE)
EXTR.ORQ.
%
CHUNK DAY 2
3.5
1
1.7
3.5
1
1.7
1.3
274.2
31.2
04.1
201.7
35.3
03.8
68.68
150741.1
63616.8
112664.6
160036.1
71076.7
112504.8
107721.0
6.8
34.5
13.6
SHRED DAY 2
1.3
1.3
1.0
53.5
40.1
111.2
83912.7
62895.3
110335.2
16.7
1 Average gaseous concentrations and estimated emissions are based on controlled dilution of pit emissions. It is unknown how well this dilution
represents ambient air exchange under actual conditions.
-------
The PMiQ sampler was used to assess the amount of paniculate found In the 10 urn or less
range. Surface area is an important criterion when determining paniculate emission standards and
assessment. Paniculate of this size, once airborne, tend to persist in the atmosphere for long periods
and to become an inhalation problem. Owing to the nature of the sampler and the application to this
study, several problems were encountered during data collection. The ambient sampler was designed to
operate constantly at 4 cfm. This relatively high flow rate was difficult to maintain because of the rapid
loading of the paniculate filter. As the loading increased, the flow rate through the system decreased until
the required flow rate could no longer be obtained. The 4 cfm flow rate was required to maintain the
specific cut-off point for paniculate sizing. As the flow rate decreased, the size of paniculate reaching the
filter increased; therefore, the data presented may not be valid because the required flow rate was not
maintained.
3.6 AIRBORNE METALS
A separate paniculate collection system was operated in order to verify and quantify the presence
of metals collected from ambient emissions. Seventeen target metals reportedly found in tires were
isolated.9 The list was compiled from information on combusted tire-ash residues. Table 3-19 shows the
results of the metal analyses. The results from the method blank are also included to demonstrate the
marginal differences between the blank and collected samples. Many of the analyses are at or near
instrument detection levels. The only significant differences between the blank and sample were found
with lead and zinc. The lead results are extremely dose to the instrument detection level of the element.
The major difference was found in the zinc analyses. Tables 3-20 and 3-21 contain average gaseous
concentration and emission rate estimates of the quantified metals for each bum condition. Many of the
estimates are based on the detection levels themselves and are presented as "less than" quantities. The
zinc data suggest that both average gaseous concentration and estimated emissions increased with
increased bum rates.
51
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TABLE 3-19. AIRBORNE PARTICULATE METALS ANALYSIS SUMMARY
METAL
ALUMINUM
ARSENIC
BARIUM
CALCIUM
CHROMIUM
COPPER
IRON
MAGNESIUM
SODIUM
NICKEL
LEAD
ANTIMONY
SELENIUM
SILICON
TITANIUM
VANADIUM
ZINC
BLANK
FILTER
TOTAL
(mg)
0.02
<0.0005
<0.01
0.03
0.01
<0.002
0.06
0.004
0.02
0.01
<0.0005
<0.02
<0.0005
0.13
<0.05
<0.05
0.01
CHUNK DAY 1
FILTER 1
TOTAL
(mg)
0.03
<0.0005
<0.01
0.07
0.03
«0.002
0.16
0.01
0.06
0.02
0.002
<0.02
<0.0005
0.49
-------
TABLE 3-20. AIRBORNE PARTICULATE METALS QUANTITATION AND EMISSION SUMMARY: "CHUNK" CONDITION1
METAL
CHUNK DAY 1
CHUNK DAY 2
2ND PART FILTER
VOL SAMP * 7.97 m3
BURN RATE = 1.4 kg/h
1ST PART FILTER
VOL SAMP. 2.86 m3
BURN RATE « 3.5 kg/h
2ND PART FILTER
VOL SAMP . 9.08 m3
BURN RATE = 1.0 kg/h
1ST PART FILTER
VOL SAMP-5.19 m3
BURN RATE-4.9 kg/h
AVERAGE AVERAGE AVERAGE AVERAGE
GASEOUS ESTIMATED GASEOUS ESTIMATED GASEOUS ESTIMATED GASEOUS ESTIMATED
CONCENTRATION EMISSIONS CONCENTRATION EMISSIONS CONCENTRATION EMISSIONS CONCENTRATION EMISSIONS
{mg/m3) (mg/kgTIRE) (mg/m3) (mg/kgTIRE) (mg/m3) (mg/kgTIRE) (mg/m3) (mg/kg TIRE)
ALUMINUM
ARSENIC
BARIUM
CALCIUM
CHROMIUM
COPPER
IRON
MAGNESIUM
SODIUM
NICKEL
LEAD
ANTIMONY
SELENIUM
SILICON
TITANIUM
VANADIUM
ZINC
TOTALS
0.0058
<0.0001
<0.0019
0.0135
0.0058
<0.0004
0.0308
0.0019
0.0116
0.0039
0.0004
<0.0039
<0.0001
0.0944
<0.0096
<0.0096
0.0848
<0.2784
2.4
0.0
<0.8
5.6
2.4
<0.2
12.8
0.8
4.8
1.6
0.2
<1.6
0.0
39.3
<4.0
<4.0
35.3
<115.8
0.0013
0.0000
<0.0013
0.0050
0.0009
<0.0003
0.0050
0.0006
0.0050
0.0013
0.0003
<0.0025
<0.0001
0.0188
<0.0063
<0.0063
0.0176
<0.0725
V.8
0.0
<1.9
7.3
1.3
<0.4
7.3
0.9
7.3
1.8
0.4
<3.6
<0.1
27.4
<9.2
<9.2
25.6
<105.6
0.0070
<0.0002
<0.0035
0.0140
0.0035
<0.0007
0.0245
0.0021
0.0175
0.0070
0.0007
<0.0070
<0.0002
0.0874
<0.01V5
<0.0175
0.1259
<0.3361
4.1
<0.1
<2.0
8.1
2.0
<0.4
14.3
1.2
10.2
4.1
0.4
<4.1
<0.1
50.9
<10.2
<10.2
73.3
< 195.8
0.0022
<0.0001
<0.0011
0.0055
0.0003
<0.0002
0.0022
0.0009
0.0066
0.0004
0.0003
<0.0022
<0.0001
0.0165
<0.0055
<0.0055
0.0099
<0.0596
4.5
<0.2
<2.2
11.2
0.7
<0.4
4.5
18
13.5
0.9
0.7
<4.5
<0.2
33.7
<11.2
<11 2
20.2
<12,.6
SAMPLE FILTERS CONTAINED IN ALUMINUM FOIL—POSSIBLE ALUMINUM CONTAMINATION
SAMPLE FILTERS MADE OF QUARTZ—POSSIBLE SILICON CONTAMINATION
1 Average gaseous concentrations and estimated emissions are based on controlled dilution of pit emissions. It is unknown how well this dilution
represents ambient air exchange under actual conditions.
-------
TABLE 3-21. AIRBORNE PARTICULATE METALS QUANTITATION AND EMISSION SUMMARY:
"SHRED" CONDITION!
TOTALS
SHRED DAY 1
PART FILTER
VOL SAMP = 13.29 m3
BURN RATE = 1.1 kg/h
SHRED DAY 2
PART FILTER
VOL SAMP = 15.56
BURN RATE =1.3 kg/h
METAL
ALUMINUM
ARSENIC
BARIUM
CALCIUM
CHROMIUM
COPPER
IRON
MAGNESIUM
SODIUM
NICKEL
LEAD
ANTIMONY
SELENIUM
SILICON
TITANIUM
VANADIUM
ZINC
AVERAGE
GASEOUS
CONCENTRATION
(mg/m3)
0.0015
<0.0001
<0.0008
0.0030
0.0015
<0.0002
0.0075
0.0005
0.0030
0.0008
0.0001
<0.0015
<0.0001
0.0150
<0.0038
<0.0038
0.0105
ESTIMATED
EMISSIONS
(mg/kg TIRE)
2.8
<0.2
<1.5
5.6
2.8
<0.4
13.9
0.8
5.6
1.4
0.1
<2.8
<0.2
27.9
<7.0
<7.0
19.5
AVERAGE
GASEOUS
CONCENTRATION
(mg/m3)
0.0013
<0.0001
<0.0006
0.0026
0.0005
<0.0001
0.0019
0.0004
0.0039
0.0005
0.0001
<0.0013
<0.0001
0.0174
<0.0032
<0.0032
0.0186
ESTIMATED
EMISSIONS
(mg/kg TIRE)
2.0
<0.2
<0.9
4.0
0.8
<0.2
3.0
0.7
6.0
0.8
0.1
<2.0
<0.2
27.2
<5.0
<5.0
29.2
<0.0537
<99.5
<0.0558
<87.5
1 Average gaseous concentrations and estimated emissions are based on controlled dilution of pit
emissions. It is unknown how well this dilution represents ambient air exchange under actual conditions.
54
-------
SECTION 4
SUMMARY AND CONCLUSIONS
The primary goal of this project was to characterize potently harmful emissions from the
simulated open ouming of scrap tires. The simulation was necessarily crude, because it would be
extremely difficult to match the burning of the equivalent of two tires with a 6 million tire, full-scale,
stockpile fire. Nevertheless, the study allowed the investigators to identify and measure gaseous
emissions and directly relate this information to a mass bum rate. This task was accomplished by
accurately measuring dilution volumes, sample volumes, and weights of tire material combusted.
It is unknown how well the concentrations obtained from this study represent those at an actual
tire fire. The dilution air added to the bum hut was used not only to control known volumes introduced,
but to simulate ambient conditions as well. It is probable that the same types of compounds identified
during this study are emitted during an actual fire, but whether the average gaseous concentrations and
estimated emissions are comparable is uncertain. A comparison with limited data collected at the
Winchester, Virginia fire by NIOSH.1 1 indicates that reasonable agreement exists within several
measurement areas. Many of the same compounds were identified in actual plume samples. Particularly
good agreement exists in PAH plume measurements. NIOSH reported ambient concentrations of total
PAHs are generally within the same order of magnitude as average gaseous concentrations obtained
during testing. Measurements of CO also indicate similar agreement as well as do metals
measurements. Both the lead and zinc measurements show similar values both in gaseous concentration
and relative concentration between the two metals. It may be reasonable to assume that the estimates
obtained during this study may be within an order of magnitude of emissions realized from actual stock
p3e fires.
The results of this study pose a variety of pertinent topics and questions regarding tire fires. How
far does the paniculate from a stockpile fire carry? Are evacuation procedures for populations in the
55
-------
proximity of stockpile (ires sufficient? Is it good policy to continue to let tire fires bum themselves out? A
greater potential for harmful organic emissions seems to exist at lower bum rates; thus a smoldering tire
fire may be more harmful than one that is burning out of control. The identification of significant quantities
of benzo(a)pyrene in the paniculate extracts warrants serious concern. High emissions of other noxious
compounds, particularly benzene, with concentrations often exceeding 1 ppm, suggest that uncontrolled
scrap tire combustion poses significant health risks.
The results from the airborne metals portion of the study were inconclusive. Maximum values
were presented, often based on detection levels. Emissions of lead and zinc may reach significant
quantities. Chemical analysis of ash residues reveals that zinc comprises nearly 50 percent of the total
residue.9 Evidently, the other metals known to be contained in tires remain in the ash residue. Although
no attempt was made to analyze ash residue, significant quantities of metals present in the ash could
potentially be leached out into groundwater systems, posing another major problem.
The values obtained by the on-line analyzers for normal combustion gases showed that as bum
rate increased, the amount of CO, SO2, and unbumed hydrocarbons also increased. High bum rate
conditions were not fuOy evaluated, so greater quantities of these gases, particularly SOa, may be emitted
during a stockpile fire. Tires contain a significant amount of sulfur, so high emissions of SOa, while Ifcely
only a minor contributor to the acid rain problem, could have significant local consequences.
This study was designed to identify the potential chemical hazards from tire fires on a small-scale,
simulation basis. The study reveals the potential for the emission of great amounts of organic
compounds, primarily aromatics, some of which may be extremely harmful. Although the estimates of
average gaseous concentrations and estimated emissions are crude, the trends presented in regard to
bum rate may be helpful in directing further research and control efforts. The fact that the "SHRED"
condition resulted in a lower bum rate indicates that the gaps between the tire material provide the major
avenue of oxygen transport. Oxygen transport appears to be a major if not the controlling mechanism for
sustaining the combustion process. This fact could have advantageous implications for those attempting
to combat tire fires. It may be possible to fill the gaps between tires with a foam inhtoitor, potentially
suffocating the fire from within.
56
-------
SECTION 5
REFERENCES
1. Sladek, Thomas A. Workshop on Disposal Techniques with Energy Recovery for Scrapped
Vehicle Tires. City and County of Denver, The Energy Task Force of the Urban Consortium for
Technology Initiatives, U.S. Department of Energy, Denver, CO, February, 1987,101 pp.
2. Haverfield, L.E. and B.L Hoffman 1966. "Used tires as a Means of Dispersal of Aedes aeovpti in
Texas." Mosq. News. 26:433-5.
3. Miller, Robert D. "Managing Scrap Tires: What Role Should State and Local Government Play?"
In Workshop on Disposal Techniques with Energy Recovery for Scrapped Vehicle Tires. City and
County of Denver, The Energy Task Force of the Urban Consortium for Technology Initiatives,
U.S. Department of Energy, Denver, CO, February, 1987.
4. Wolfson, D.E., JA Beckman. J.G. Walters, and D.J. Bennet. Destructive Distillation of Scrap
Tires. Bureau of Mines Report of Investigations #7302, Sept. 1969.
5. Method 0030 SW-846 in Test Methods for Evaluating Solid Wastes. Vol. II, Field Manual
PhysfcaVChemfcal Methods, EPA, November, 1986.
6. Method 5040 SW-846 in Test Methods for Evaluating Solid Wastes. Vol. II, Laboratory Manual
Physical/Chemical Methods, EPA, November, 1986.
7. Method 0010 Appendix B SW-846 in Test Methods for Evaluating Solid Wastes. Vol. II, Reid
Manual Physical/Chemical Methods, EPA, November, 1986..
8. Federal Register Part VIII. 40 CFR Part 136. Vol 49, No. 209, Friday October 26,1984, Rules and
Regulations, Method 610-Polynuclear Aromatic Hydrocarbons, pp. 43321.
9. Schulman, B.L. and PA White. "Pyrolysis of Scrap Tires Using the TOSCO II Progress - A
Progress Report." Reprint from the ACS Symposium Series, #76, Solid Wastes And Residues.
1978.
57
-------
10. Method 6010 SW-846 in Test Methods for Evaluating Solid Wastes. Vol. II, Laboratory Manual
Physical/Chemical Methods. EPA, November, 1986.
11. National Institute of Occupational Safety and Hearth (NIOSH), 1984, Hearth Hazard Evaluation
Report. Rhinehart Tire Fire. Winchester. Virginia. HETA 84-049-1441 (March).
58
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APPENDIX A
QUALITY CONTROL EVALUATION REPORT
The quality control measures taken during this study were performed to ensure that the data
collected adequately represented the simulation of the open burning of scrap tires. The data quality
objectives determined and procedures used during testing sampling and analysis are found in the Quality
Assurance Project Plan (QAPP) (QTRAK No. 89007, AEERL Category III).
Table A presents the data quality summary for accuracy, precision and completeness achieved
along with original goals for respective methods of measurement or analysis used during testing. As the
table indicates, all project goals were obtained with the exception of the SO2 measurements. As stated
earlier, the accuracy limits on Days 1 and 2 of the SHRED condition were exceeded during the day's end
span check. Although the limits were exceeded, the data were presented along with data collected during
vafid operating conditions. Since the problems associated with the operation of the instrument were
immediately noticeable, it was possible to isolate areas of likely valid data from obvious invalid data. In
addition, although the SO2 information is important, it is not critical. Determining the order of magnitude
of SO2 levels was adequate for this study, and this was obtained.
Prior to sampling, all dry gas meters were calibrated using an NBS traceable calibration system.
Correction factors were determined for each meter. The dilution air volumes were determined using a
p3ot measurement system.
The quantitation of volatile organic compounds was determined using the response factor
obtained during toluene caltoratton. The response of individual identified compounds in relation to toluene
was not determined. The quantitation of chromatographabte semi-volatile organic compounds was
determined using the response factor of the TCO standard calibrations. Again, responses of individual
identified compounds was not determined.
59
-------
TABLE A. DATA QUALITY SUMMARY FOR ACCURACY, PRECISION, AND COMPLETENESS
8
Measurement
02
CO
CO2
THC
SO2
Volatile Organlcs GC/MS
TCO GC/FID
GRAV
•With 2 failing points removed.
"Relative Percent Dilference
Accuracy (expressed
Di^o/^ 4 ti -i r»n t ovr»t*«*Q «*»!•
Accuracy (% Bias) Precision (% RSD) Completeness (%)
Goal No. Points Achieved (Avg.) Goal Achieved Planned Achieved
±20
±20
±20
±20
±20
±50
±15
±20
as percent
^ ao ri*»rr*on1
8
8
6
8
8
(6)*
9
9
2
bias) «
f- l-ol A 1" 1 VO
1.4 10
2.0 10
0 . 10
12.0 10
-10.7 10
(-1.2)*
-3.1 25
4.6 15
-1.5 20
measured - true
true
At-anH-arH HoviAt-innt «
2.6 >90
0.7 >90
4.1 >90
1.5 >90
38.4 >90
(3.9)*
7.9 >90
5.9 >90
1.7" >90
100
measured standard deviation
100
100
100
100
50
100
100
100
-
v i n
measured average
-------
Two performance evaluation audit samples were supplied by the Research Triangle Institute
(RTI): sample one, PAH-A. was used to evaluate just the instrument performance of PAHs in the SoRI
laboratories; the second sample, PAH-B, was used to evaluate the extraction efficiency of PAHs from
XAD-2, and the instrument performance. The results of the audit sample PAH-A indicate that a
systematic negative bias of approximately 60 percent existed. The results are being further analyzed
because of discrepancies in the dilution factors. The results of audit sample PAH-B show extraction
efficiencies ranging from 14-88 percent for four test analytes. No systematic bias was observed.
Because the major objective of the project is to qualitatively characterize the PAHs in the
emissions, the wide range of quantitative recoveries are not expected to affect the validity of the data.
In summary, the QA project objectives set forth have been obtained and the data collected from
this study is sufficient to meet project objectives.
61
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
i. REPORT NO.
EPA-600/2-89-054
2.
3. RECIPIENT'S ACCESSION-NO.
PS9G I 2 CO 04MS
4. TITLE AND SUBTITLE
Characterization of Emissions from the Simulated
Open Burning of Scrap Tires
5. REPORT DATE
October 1989
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
8. PERFORMING ORGANIZATION REPORT NO.
Jeffrey V. Ryan
9. PERFORMING ORGANIZATION NAME AND ADDRESS
10. PROGRAM ELEMENT NO.
Acurex Corporation
P.O. Box 13109
Research Triangle Park, North Carolina 27709
11. CONTRACT/GRANT NO.
68-02-4701, Task 88-41
13. SPONSORING AGENCY NAME AND ADDRESS
EPA, Office of Research and Development
Air and Energy Engineering Research Laboratory
Research Triangle Park, NC 27711
13. TYPE OF REPORT AND PERIOD COVERED
Task Final; 8/88 - 6/89
14. SPONSORING AGENCY CODE
EPA/600/13
is.SUPPLEMENTARY NOTES AEERL project officer is Paul M. Lemieux, Mail Drop 65, 919/
541-0962.
16. ABSTRACT
repOrt gives results of a. small-scale combustion study, designed to
collect, identify, and quantify products emitted during the simulated open burning
of scrap tires. Fixed combustion gas, volatile and semi-volatile organic, particu'r
late, and airborne metals data were collected under two burn conditions that varied
by the size of tire material. Burn rates, varied by material size, were used to esti-
mate potential emissions of identified products. Total estimated emissions of semi-
volatile organics ranged from 10 to 50 g/kg of tire material burned. Monoaromatic
and polyaromatic hydrocarbons were the predominant emission products identified.
The presence of benzo(a)pyrene (BAP) in particulate extracts is of particular conr"
cern because it is a known carcinogen. The presence of zinc in gaseous particulate
collection was also verified and quantified. Several trends were evaluated relating
emission products to burn rates.
7.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS
c. COSATI Field/Group
Pollution
Tires
Combustion
Emission
Pollution Control
Stationary Sources
Characterization
Scrap Tires
13B
13F
21B
14G
8. DISTRIBUTION STATEMENT
Release to Public
19. SECURITY CLASS (ThisReport)
Unclassified
21. NO. OF PAGES
20. SECURITY CLASS (Thispage)
Unclassified
69
22. PRICE
EPA Form 2220-1 O-73)
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