United States
control Technology Center
EPA-600/2-91-061
November 1991
EVALUATION OF VOC EMISSIONS FROM HEATED
ROOFING ASPHALT
control ig technology center
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RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The nine series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
6. Scientific and Technical Assessment Reports (STAR)
7. Interagency Energy-Environment Research and Development
8. "Special" Reports
9. Miscellaneous Reports
This report has been assigned to the ENVIRONMENTAL PROTECTION TECH-
NOLOGY series. This series describes research performed to develop and dem-
onstrate instrumentation, equipment, and methodology to repair or prevent en-
vironmental degradation from point and non-point sources of pollution. This work
provides the new or improved technology required for the control and treatment
of pollution sources to meet environmental quality standards.
EPA REVIEW NOTICE
This report has been reviewed by the U.S. Environmental Protection Agency, and
approved for publication. Approval does not signify that the contents necessarily
reflect the views and policy of the Agency, nor does mention of trade names or
commercial products constitute endorsement or recommendation for use.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
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EPA-600/2-91-061
November 1991
EVALUATION OF VOC EMISSIONS FROM
HEATED ROOFING ASPHALT
Prepared by:
Peter Kariher, Michael Tufts, and Larry Hamel
Acurex Corporation
Environmental Systems Division
4915 Prospectus Drive
P.O. Box 13109
Research Triangle Park, NC 27709
EPA Contract Number: 68-DO-0141
Task No. 91-001
Task Officer: Bobby E. Daniel
Air and Energy Engineering Research Laboratory
U.S. Environmental Protection Agency
Research Triangle Park, NC 27711
Prepared for:
Control Technology Center
U.S. Environmental Protection Agency
Research Triangle Park, NC 27711
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CONTROL TECHNOLOGY CENTER
Sponsored by:
Emission Standards Division
Office of Air Quality Planning and Standards
U.S. Environmental Protection Agency
Research Triangle Park, NC 27711
Air and Energy Engineering Research Laboratory
U.S. Environmental Protection Agency
Research Triangle Park, NC 27711
Center for Environmental Research Information
Office of Research and Development
U.S. Environmental Protection Agency
Cincinnati, OH 45268
ABSTRACT
A short-term, in-house project to characterize emissions from a simulated asphalt roofing kettle was
performed at EPA/AEERL. Hot asphalt surfacing and resurfacing has been identified as a possible
significant source of volatile organic compound (VOC) emissions that may affect human health and
contribute to the ozone non-attainment problem.
The purpose of the study was to collect, identify, and semi-quantitate as many of the compounds
as possible that are discharged during the open heating of roofing asphalt and relate them to the amount
volatilized into the air.
Types 1, 2, and 3 mopping grade asphalts were chosen for this study. They constitute more than
90 percent of roofing asphalt used. Samples of each type of asphalt were placed in a simulated roofing
kettle, heated to predetermined temperatures, and sampled for volatile and semi-volatile organic emissions.
Compounds identified during this study were alkanes, aromatics, a ketone, and an aldehyde.
This work was done at the request of the Control Technology Center (CTC) steering committee to
provide information to state and local agencies for use in responding to public concerns.
11
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TABLE OF CONTENTS
Abstract ii
List of Figures iv
List of Tables v
Acknowledgements vi
Preface vii
Metric to Nonmetric Conversions viii
Section Page
1. Introduction 1
2. Project Description 3
2.1 Experimental Approach 3
2.2 Experimental Apparatus 4
2.2.1 Bum Hut 4
2.2.2 Sample Shed 6
2.3 Experimental Methods and Procedures 10
2.3.1 Simulation of Open Air Asphalt Kettle Heating 10
2.3.2 Volatile Organics Collection 10
2.3.3 Semi-volatile Organics and Paniculate Collection 15
3. Data, Results, and Discussion 19
3.1 Volatile Organic Emission Data 19
3.2 Semi-Volatile Organic Emissions Data 36
4. Summary and Conclusions 48
5. References 49
Appendix A. Quality Control Evaluation Report 50
HI
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LIST OF FIGURES
Figure Page
1. Sampling Buildings 5
2. Heating Apparatus in "Bum Hut" 7
3. Diagram of Sampling System Used 8
4. Schematic of Volatile Organic Sampling Train 9
5. AEERL/OCB (Organics Control Branch) Sample Log 12
6. VOST Field Data Sheet 13
7. Semi-volatile Sampling Worksheet 16
8. TOO Mass Data 34
9. GRAV Mass Data 35
iv
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LIST OF TABLES
Table Page
1. Compounds Identified by GC/MS from VOST Runs 20
2. D-Benzene Data 20
3. Type 1 (VOST) Condition 1 21
4. Type 1 (VOST) Condition 2 22
5. Type 1 (VOST) Condition 3 23
6. Type 2 (VOST) Condition 1 24
7. Type 2 (VOST) Condition 2 25
8. Type 2 (VOST) Condition 3 26
9. Type 3 (VOST) Condition 1 27
10. Type 3 (VOST) Condition 2 28
11. Type 3 (VOST) Condition 3 29
12. Sampling Data 30
13. Background Data (VOST) 31
14. Blank Data (VOST) 33
15. GRAV Mass Data 36
16. Compounds Identified by MS from XAD and Filter Extract Runs 37
17. Type 1 (TCO) Condition 1 38
18. Type 1 (TCO) Condition 2 39
19. Type 1 (TCO) Condition 3 40
20. Type 2 (TCO) Condition 1 41
21. Type 2 (TCO) Condition 2 42
22. Type 2 (TCO) Condition 3 43
23. Type 3 (TCO) Condition 1 44
24. Type 3 (TCO) Condition 2 45
25. Type 3 (TCO) Condition 3 46
26. ASTM Standards 47
A-1. Percent Bias For VOST PEAs 52
A-2. Results of External Audit 54
A-3. Accuracy and Precision Data for Semi-Volatiles 54
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ACKNOWLEDGEMENTS
The authors would like to recognize EPA/AEERL's Ray Steiber for his expertise in identifying
compounds. The authors would like to thank Ken Krebs of Acurex for his analytical support and Ray
Thomas of Acurex for his sampling support.
VI
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PREFACE
The Control Technology Center (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 engineering assistance projects, such as this one, focus on topics of national or regional
interest that are identified through contact with state and local agencies.
VII
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Metric to Nonmetric Conversions
Readers more familiar with nonmetric units may use the following factors to convert to that
system.
Metric
Times
Yields Nonmetric
°C
m3
mmHg
kg
m3/min
1.8T + 32
35.336
0.03937
2.2026
35.714
°F
ft3
in. Hg
Ib
cfm
viii
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SECTION 1
INTRODUCTION
The Control Technology Center (CTC) and its Air Research Information Service Center (AIR
RISC) information support system have received numerous calls on the health effects of asphalt roofing
fumes. In response to these calls, the CTC steering committee initiated a parametric study of the
emissions profile from asphalt roofing techniques.
Asphalt is produced near the end of the fractional distillation of crude oil. Roofing asphalt is
produced by blowing air through the asphalt flux at different temperatures to derive the adhesives used
for roof surfacing or resurfacing. Types 1, 2, and 3 were chosen for this study. They cover the roof
range levels from flat to a 25 percent slope and constitute more than 90 percent of roofing asphalt used
for mopping operations.1
The asphalt can be delivered to the site in two ways. It is either heated and transported in a
tanker truck or heated in a container (kettle) on site. When the heated kettle method is used, the
asphalt is purchased in paper-covered sections of approximately 45-kg* blocks. The blocks are
chopped into sections and added to the kettle as needed.
Several emissions sources exist from the on site asphalt roofing process, but the heating kettle
has been identified as a major point of emissions. A simulated heated roofing kettle was constructed
and placed in a building (bum hut) used for similar projects. In-house testing was performed to
* A conversion table has been provided!for convenience on page viii.
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characterize emissions from the simulated kettle. The data from this project can then be used to
estimate the amount of organic compound volatilized into the air.
Previous work done by AEERL in this area included a cursory examination of emissions during
reroofing of the Environmental Research Center, RTF, NC, in 1989. Although minimal compound
identification was performed, the analytes detected included alkanes, alkenes, aromatics, alcohols,
aldehydes, and a ketone.2
Asphalt roofing operations are a source of organic vapors that could affect human health both
directly and indirectly. This study will provide information to state and local agencies for use in
responding to public concerns.
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SECTION 2
PROJECT DESCRIPTION
2.1 EXPERIMENTAL APPROACH
Asphalt roofing cement is used as a sealing medium for many buildings with relatively level
roofs. The method of application of this material is to use a torch to heat the side of the kettle, until it
reaches a viscosity that allows it to be mopped onto the roof surface. This viscosity is defined as the
equiviscous temperature (EVT). The normal procedure is to heat the asphalt to temperatures
considerably higher than needed to ensure EVT after the asphalt is transported to the point of
application.3
The purpose of this study was to collect, identify, and estimate the quantities of as many of the
compounds as possible that were discharged during the small-scale, open heating of roofing asphalt
and relate them to the amount of roofing asphalt volatilized. A predetermined amount of one of the
grades of roofing asphalt was placed in the heating kettle and heated with a torch applied to the bottom
of the kettle. The first temperature condition was defined by the melting of the asphalt. At this
temperature, the asphalt was not liquid enough to be applied with a mop, but was no longer a solid
block. The temperature was recorded and heating was regulated to maintain a constant temperature in
the asphalt. Samples were taken to determine the emissions at this condition. The second
temperature condition was the EVT condition where the asphalt was the right consistency to mop onto
a surface. The temperature was monitored and stabilized at this condition, and samples were taken.
The third temperature was approximately 66 °C higher than the second condition. Heating the asphalt
to this temperature is a common practice prior to transporting the asphalt to the application site. The
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same heating procedure was used for all three asphalt types. The temperatures inside the bum hut
and sample transport duct also were monitored periodically. The asphalt block was replaced after each
test after a significant weight toss was recorded. A baseline test using the torch, but no asphalt, was to
determine background compounds.
For each test, a selected representative roofing asphalt was heated in a controlled outbuilding
designed for the simulation of the open burning or heating of similar products. To perform each test, a
stainless steel bowl was filled with about 7 kg of asphalt, and the specific weight of the asphalt was
measured. After the asphalt was melted, the diameter of the bowl was measured at the asphalt line,
and sampling began. Volatile organic samples were collected with volatile organic sampling train
(VOST) tubes, and the semi-volatile organics and particulates were collected with XAD-2 and Pallflex
142-mm filters. After each test was performed, the final weight of the asphalt was recorded. The
volatile organic samples collected were analyzed by an adsorption and thermal description gas
chromatograph/mass selective detector(GC/MSD) system. The semi-volatile organics were analyzed
using GC/MSD for compound identification and a gas chromatograph/flame ionization detector (GC/FID)
for compound quantitation. A total chromatographable organics (TOO) analysis provided the total
organics in the boiling point range of 100-300 °C. A gravimetric (GRAY) analysis indicated the amount
of organic material possessing boiling points greater than 300 °C. Both the VOST and TOO samples
were analyzed by GC/MSD to provide compound class and compound specific identification. A
representative portion of the identified compounds were semi-quantitated. The semi-quantitative
information was coupled with collected sample volumes and material mass displacement to estimate
gaseous emission concentrations and mass emissions based on total material volatilized.
2.2 EXPERIMENTAL APPARATUS
2.2.1 Burn Hut
The burn hut is an 2.4-m x 2.4-m x 2.4-m outbuilding modified for small-scale combustion
experiments (Figure 1). The building has a cooled, dilution air handling system capable of delivering
nominally 34.0 m3/min. A deflector shield was located 1.2 m over the pit to protect the ceiling and
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Sample Shed
"Burn" Hut
(Arrows indicate air flow)
Figure 1. Sampling buildings.
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enhance ambient mixing. The sample duct, a 20.3-cm pipe, was located to the side of the deflector
shield (Figure 2). Since the sample air was mixed thoroughly by the deflector shield and the air
conditioner flow, the sample duct transported a representative portion (Figure 2) of the gaseous,
paniculate-containing sample to the sampling shed located adjacent to the burn hut (Figure 1). The
portion of the gas transported through the sample duct was assumed to be representative of all the gas
in the hut as was proven in previous experiments performed in the same shed.4 The unheated duct
was insulated when it exited the burn hut to minimize heat loss and condensation of organics. The
door and window were open several inches to allow ventilation of the flow from the air conditioner and
the mixed air. This allowed the sample duct to work at a slight negative pressure rather than at the
pressure from the air conditioners that were supplying sample gas.
2.2.2 Sample Shed
The sample shed contained the majority of the associated sampling equipment: the volatile
organic sampling train (VOST) system, the semi-volatile organics/particulate sample collection systems,
and the paniculate removal system.
All gaseous samples were extracted from a sampling manifold within the duct. The manifold
consisted of 9.5-mm stainless steel probes positioned in the sample transport duct so the probe orifice
faced the direction of sample flow. All samples were obtained at the same location (Figure 3). The
sample stream was pulled from the burn hut into the sample shed under slight negative pressure by an
induced draft (ID) fan located downstream of the sample manifold.
Volatile organics were collected using the Nutech Model 280 VOST system (Figure 4). For this
application, the heated probe was not used. Other changes included the absence of the glass-lined
probe. The connection from the sample manifold to the sampling train was made with an insulated
section of 6.4-mm Teflon tubing.
Semi-volatile organics and paniculate were collected using a sample system modified for use in
this study. A 9.5-mm stainless steel tube was connected from the manifold to a paniculate filter
assembly. Paniculate was collected on a 142-mm, Teflon-coated, glass fiber filter located in the filter
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Figure 2. Heating Apparatus in "Burn Hut"
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Duct Cross Section
Flow
From Burn Hut
142mmTFE
Coated Filter
XAD-2
Canister
t
Vent
lut ^ f
*W»PV* OO TTi it*:**** / ^"v
DFar
6.4 mm TFE Tubing (Insulated)
VOST System
Condensers,
Meters, Pumps
©
Dry Gas
Meter
Vacuum Pump
Vent
Figure 3. Diagram of sampling system used.
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housing. This filter housing was connected to a XAD-2 canister that held roughly 150 g of the organic
sorbent material. The exit of the canister was connected to a pump and metering system.
2.3 EXPERIMENTAL METHODS AND PROCEDURES
2.3.1 Simulation of Open Air Asphalt Kettle Heating
Asphalt was obtained from local sources. Asphalt types 1 and 3 were supplied by Morton J.R.
Company of Raleigh, NC. Type 2 asphalt was obtained from Bob Lyerly of Owens-Corning Fiberglass,
Morehead City, NC. All three asphalt types were made by the Trumbull Asphalt Division of Owens-
Corning Fiberglass Corporation. The asphalt was supplied in 45-kg cardboard or tin containers and
required chopping before the asphalt could be put into the kettle. A known amount of asphalt was
placed in the kettle and heated until melted but unmoppable. This temperature was determined to be
unmoppable because the asphalt appeared to have a high viscosity but had just lost the solid
appearance. This temperature was maintained and recorded as the first condition. The second
temperature condition was the EVT condition where the asphalt was the right consistency to mop onto
a surface. At this temperature the asphalt easily flowed and had a much lower viscosity than the first
melting temperature. The third temperature was approximately 66 °C higher than the second condition.
For each condition, once the desired temperature was obtained, the asphalt was maintained at that
V
temperature and the sampling was performed. The conditions are listed in Table 15.
2.3.2 Volatile Organics Collection
Volatile organics were collected using a modified VOST technique. Organics were collected in
triplicate on pairs of Tenax-GC-containing glass tubes. The VOST system was operated as described in
EPA-600/8-84-007.5 These tests were performed using a short section of 6.4-mm Teflon tubing to
transport the gas sample from the sample duct to the VOST train. Sample flow rates and total volumes
were determined during the shakedown tests. These tests included heating a sample of asphalt to
determine asphalt sample sizes and sample volumes. A sample flow rate of 0.5 L/min for 10 min was
determined to be optimum for the VOST tubes. These shakedown test samples were analyzed to
prevent instrument overbad on the GC/MSD.
10
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The Tenax tubes were conditioned at 230 °C for at least 12 hr prior to use. At least 50 percent
of the pairs of tubes were quality-control-checked (QC'd). The tubes were checked for organic
contamination by GC/FID with a QC rejection of 100 ng total organics per set (based on system
response to toluene) and an individual peak rejection of 50 ng. Following conditioning and QC, the
tubes were sealed in pairs in a Teflon bag. The conditioned tubes were refrigerated at 4 °C until use.
Following use, the tubes were returned to the Teflon bag, reseated and placed into a cryo-freezer until
they were analyzed. The tubes were stored in two separate freezers to prevent contamination of
conditioned tubes by the sampled tubes. All sampling information was collected on standardized data
collection sheets (Figures 5 & 6).
The VOST collected samples were analyzed using an adsorption and thermal desorption
GC/MSD system. The analytical method used in this study is found in EPA-600/8-84-0075. Our goal
was to identify and semi-quantitate unknown compounds.
Collected VOST samples were analyzed in pairs. Three pairs were collected for each sample. The
samples were desorbed in a clamshell heater at 190 °C for 10 min. Helium carried the vaporized
analytes onto a cryogenically cooled trap at -150 °C. This trap focuses the sample prior to injection.
The trap was rapidly heated to 225 °C with the sample directed onto a 30-m x 0.32-mm I.D. DB-624
capillary column. The oven temperature program was initially operated at 20 °C for 5 min, then heated
at 3 °C/min until reaching 150 °C. The oven was then ramped at 5 °C/min until reaching 260 °C at
which it was held for 15 min. All detector temperatures on the GC were held at 260 °C.
Simultaneous detection by the MSD and FID was attempted by using a splitter apparatus
installed between the column exit and detectors. It was determined that the FID was unusable because
the flame was extinguished on most of the samples. The MSD acquired sufficient spectral data such
that each chromatographic peak was sampled at least 5 times over a 45-420 atomic mass unit (AMU)
range. The resulting chromatogram was digitally stored for data interpretation. The MSD was
calibrated for mass linearity using perfluorotributylamine (PFTBA). Several criteria were used to assist
11
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AEERUOCB SAMPLE LOG
Samples transferred by
Signature of transferor _
Samples received by
Signature of transferee
Date
Date
ro
Project Analysis required
Date
Sample ID Sample contents/description Collected
Date
Prepped
For further Wbmation contact at ( i
Figure 5. AEERL/OCB sample log.
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Plant
Data
Locatlon_
Op«rator_
Maid Blank l.D.i T»n*«_
THna«/Oiarco« 1
Stack Mo.
Prol>a •*>.
WOST Mo.
M>tanalar f*>
Dry Caa Hetar Ho.
Mir
H*.a
Laak
diack
•
Cartridge 1.0.
Tana*
Vanaa/
Oiarcoal
totaaatar
Madlaf
ll/aslnl
Tl>
Initial
la
Final
•aapllng
Ourailon
|a>l»|
froba
Ta*p.
I*C|
Baroaiatf Ic
Praaaura
tin «( H<|l
Oonilanaei
Ou 1 1 c t
Trip.
I'CI
(°C)
Hctac
T«ap.
(Out 1 at )
(liters)
Ui r <*** Halai
Initial
Final
Caa
Voluaia
Illtaral
CiMvanta
Saapla) 1.0.
Cowanta
ilolors to sample collucbon on one pair of Tenax/charcoal traps.
Figure 6. VOST field data sheet.
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in compound identification. A mass spectral library (National Institute of Standards and Technology*)
matching program was used extensively. The program was written so that, lor each integrated peak,
spectra were obtained both at the point of maximum intensity (peak top) and at the peak start
(baseline). This baseline or background spectrum was subtracted from the peak spectra. This
background-subtracted spectrum was compared to spectra in the library. The top five matches were
presented and compared. An expert experienced in mass spectral interpretation evaluated the
matches. In addition, several samples were prepared containing an alkane mix. This mix was
analyzed by injection onto the adsorption media and then thermally desorbed. The elution order was
used to generate a retention index that aided in compound identification and individual peak
referencing. Standards were prepared for eight of the tentatively identified compounds to confirm
identification and provide semi-quantitation.
Quantitation of volatile organics was performed from the MSD integration data. Response
factors were calculated by dividing the known mass of a single compound by the area counts assigned
to that compound from a 5-point calibration standard. Calibration checks were performed daily. The
compounds in the 5-point calibration standard included benzene, toluene, xylene, decane, dodecane,
tetradecane, and heptadecane. Because of the large number of compounds, quantitation based on
individual standard calibrations was not possible. To accommodate this problem, calculated response
factors from the standards were used for the compounds that were identified. A trend was seen in the
response factors for the standards; the response factors were seen to increase as the retention time
increased. This trend was used to assign response factors to those compounds that were not found in
the standard calibration. Following analysis and compound identification, several standards were
prepared to represent the alkane and aromatic compound classes. The response factors were
calculated from the standard mix. The response factors were used to quantitate identified compounds
in each compound class. Prior to sampling, the Tenax tube pairs were spiked with a known quantity of
Formerly the National Bureau of Standards.
14
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deuterated benzene (06), an internal standard. Five mL of 48.8-ng/mL deuterated benzene in air was
injected onto the pair of Tenax tubes. Recovery of the deuterated benzene from the samples varied
considerably. The values ranged from 39 to 174 percent for the deuterated benzene.
2.3.3 Semi-volatile Oroanics and Paniculate Collection
The sampling system used for the collection of semi-volatile organics and paniculate was a
modified system specifically fabricated for use on this project (Figure 3). Overall, the system was very
similar in nature to that of the Source Assessment Sampling System (SASS) equipment used for stack
sampling. A short length of 0.95-cm O.D. stainless steel tubing was used to connect the sample
manifold to the filter assembly. The filter assembly held a 142-mm diameter, Teflon-coated, glass fiber
filter. The filter assembly was connected to an XAD-2-filled stainless steel canister. This canister
contained roughly 150 g of the organic sorbent material. A drying tube containing silica gel was
connected after the canister for moisture removal before being attached to the dry gas meter. The dry
gas meter was connected to the canister to measure total volume sampled. A sample pump was
connected to the end of the dry gas meter and vented outside the shed.
The system was operated at a nominal sample rate of 0.06 m3/min for 3 hr. The system was
leak-checked up to the exit of the filter assembly before and after each sample period. All sampling
information was recorded on standardized data collection sheets (Figure 7). Upon completion of the
sample period, the train was dismantled and brought to the laboratory for sample retrieval.
The XAD-2 was packed in the canisters, capped, sealed in Teflon bags, and refrigerated at
4 °C until used. After use, the canisters were returned to the Teflon bag, reseated, and refrigerated in
a cryo-freezer at -80 °C until extracted. The paniculate filters were desiccated, tared, and stored in
labeled aluminum foil envelopes until used. Following sampling, the filters were placed back in the foil
envelopes with the loaded side facing upward. The filters were desiccated (with the foil open), weighed
and stored in a desiccator until extracted.
The paniculate filter and XAD-2 samples from each sample were extracted separately.
Following sampling, the filters were extracted with methylene chloride in an ultrasonic bath. The XAD-2
15
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SEMI-VOLATILE SAMPLING WORKSHEET
Run*
Date
Tamb
Conditions
(°C/°F) Pbar
(mm Ho/in Hg)
XAD-2 Run Canister #
XAD-2 Field Blank*
DGMI.D.tf
Filter Field Blank #
Correction Factor
Filter Start Stop
I.D. i Time ' Time
DGM Temp
°C/0F
j
Time
Orifice
delta P
i
Start
DGM
*
f. •*£ f
t
% f
f %
Stop
DGM
Totals
"" f \
"„" *' V*
.:•
.•
Total
Time (min)
Total
DGM(ft3)
f "- j
-••, , <>,
f •. f
f "• f "•
i* s •• "
Corrected tt^
ft3/min
Std tt3/min
Std m3/min
Comments:
Figure 7. Semi-volatile sampling worksheet
16
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canisters were extracted with methylene chloride by pump through elution. The paniculate filter and
XAD-2 extracts from the same samples were combined. The combined extracts were concentrated and
filtered with a 0.45-mm filter and brought to a stock volume of 10 ml_. Crystals were found in the
concentrated samples after being stored in the cryo-freezer (-80 °C). The crystals had the appearance
of frozen water. A 5-mL aliquot of each sample was passed through a bed of Na2SO4 to remove any
residual water. The bed was then rinsed with methylene chloride. The rlnsate was then concentrated
to 5 ml_. Crystallization still occurred in the samples when returned to the cryo-freezer, but the crystals
appeared to be organic in nature.
A portion of sample solution was analyzed for TCO using a GC/FID analytical method. The
TCO analysis determines the amount of organic material with boiling points between 100 and 300 °C
based on the average system response to an alkane standard mix. The analysis was conducted using
a reduced temperature ramp from the specified temperature program (5 °C/min as opposed to
20 °C/min) to obtain the greater peak separation needed for individual compound quantitation.
Compounds possessing boiling points greater than 300 °C were quantified using GRAV
analysis. This procedure gravimetrically measures the organic material remaining after an aliquot of the
liquid sample is allowed to evaporate in an aluminum pan.
Compound identification was performed by GC/MSD. The conditions were almost identical to
those used in the TCO analysis. The compounds were separated using a 0.32-mm I.D. x 30-m DB-5
column with 5 °C/min temperature ramping program. This column was the same length used for the
TCO analysis. Compounds were identified using a spectral library matching program similar to that
used for volatile organics identification. These compound matches were examined and verified by an
expert mass spectroscopist. Again, an alkane standard mix for establishing retention indices
information was used to aid compound identification.
Quantitation of identified compounds was based on response factors calculated from a standard
mix. The response factors were calculated from a 5-point calibration. Calibration checks were run
before and after the samples were analyzed. The compounds in these calibration standards included
17
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heptane, decane, dodecane, tetradecane, and heptadecane. Compounds were quantitated by using
response factors from the standard mix and assigning the values to compounds with similar retention
indices or the specific compound. The data from the standard mix combined with identification data
from the MSD provided retention indices for the sample compounds. The retention indices were
established from the alkane standards and were used to mark elution orders both from the MSD and
FID runs, allowing cross-referencing of quantitative reports.
18
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SECTION 3
DATA, RESULTS, AND DISCUSSION
3.1 VOLATILE ORGANIC EMISSION DATA
Problems keeping the FID flame lit resulted in the loss of data for several VOST tubes.
Because the FID and the MSD acquired data simultaneously, it was possible to use only the MSD
integration data to quantify. Most of the compounds from the VOST tubes were identified by the
GC/MSD instrument. The majority of these compounds were alkanes, aromatics, and aldehydes (Table
1). This was expected because of the petroleum-type chemicals used in the manufacture of asphalt.
The alkanes ranged from heptane to heptadecane and included all the straight chain alkanes between
these two ranges. The aromatic compounds found were benzene, toluene, xylene, and substituted
naphthalenes. The only aldehyde found was benzaldehyde, and a ketone (1-phenyl-ethanone), both of
which may be contaminants from the oxidation of Tenax. Large concentrations of dichloromethane
were found in the samples and may be attributed to the XAD-2 solvent wash. Because the outlet of the
XAD-2 canister was flowing into the sampling shed, the methylene chloride may have contaminated the
Tenax tubes during exchanging. Because of the large variations in recovery for the dueterated
benzene, the sample concentrations were not scaled. Table 2 presents the data for the average
deuterated benzene areas for the three pairs of VOST tubes collected for each condition.
The data tables are arranged so each asphalt type may be examined at each temperature. In
each category, the average gaseous concentration, estimated emissions, and emissions per area of the
kettle are presented (Tables 3-11). Sampling data also are available in Table 12.
19
-------
TABLE 1. COMPOUNDS IDENTIFIED BY GC/MS FROM VOST RUNS
Compound Identified
Formula
Methane, dichloro-
Benzene
Heptane
Benzene, methyl-
Octane
Benzene, dimethyl-
Nonane
Decane
Benzene, trimethyl-
Benzaldehyde
Undecane
Benzene, tetramethyl-
Ethanone, 1-phenyl-
Dodecane
Undecane, dimethyl-
Naphthalene
Tridecane
Tetradecane
Naphthalene, dimethyl-
Pentadecane
Hexadecane
Heptadecane
Naphthalene, trimethyl-
CH2CI
C8H18
C8H10
C9H20
C10H22
C9H12
C7H60
C11H24
C10H14
C8H80
C12H26
C13H28
C10H8
C13H28
C14H30
C11H10
C15H32
C16H34
C17H36
C13H14
TABLE 2. D-BENZENE DATA
Nanograms of Deuterated Benzene
Type 1 Type 2 Type 3
Condition 1
2
3
230
96
140
426
362
180
111
225
205
Average
Standard Deviation
Actual
219 ng
104ng
244 ng
20
-------
TABLE 3. TYPE 1 (VOST) CONDITION 1
Type 1 Asphalt (VOST)
Condition 1
Compound
Methane, dichloro
Benzene
Heptane
Benzene, methyl
Octane
Benzene, dimethyl
Nonane
Decane
Benzene, trimethyl
Benzaldehyde
Undecane
Benzene, tetramethyl
Ethanone, 1-phenyl
Dodecane
Undecane, dimethyl
Naphthalene
Tridecane
Tetradecane
Naphthalene, dimethyl
Pentadecane
Hexadecane
Heptadecane
Naphthalene, trimethyl
Compound
Mass
(ng)
0
0
0
13
0
0
0
21
0
30
0
0
0
25
0
0
147
0
0
0
0
0
0
Weight Loss (kg)
Time (h)
Temperature (C)
Sample Volume (L)
Average
Gaseous Cone.
(mg/cu m)
0.0000
0.0000
0.0000
0.0027
0.0000
0.0000
0.0000
0.0043
0.0000
0.0062
0.0000
0.0000
0.0000
0.0052
0.0000
0.0000
0.0306
0.0000
0.0000
0.0000
0.0000
0.0000
0.0000
Total
0.0010
4.0167
117
4.79
Estimated
Emissions
(g/kg)
0
0
0
23
0
0
0
37
0
53
0
0
0
44
0
0
260
0
0
0
0
0
0
417
Emissions
per Area
(mg/sq m h)
0
0
0
42
0
0
0
66
0
95
0
0
0
80
0
0
470
0
0
0
0
0
0
21
-------
TABLE 4. TYPE 1 (VOST) CONDITION 2
Type 1 Asphalt (VOST)
Condition 2
Compound
Methane, dichloro
Benzene
Heptane
Benzene, methyl
Octane
Benzene, dimethyl
Nonane
Decane
Benzene, trimethyl
Benzaldehyde
Undecane
Benzene, tetramethyl
Ethanone, 1-phenyl
Dodecane
Undecane, dimethyl
Naphthalene
Tridecane
Tetradecane
Naphthalene, dimethyl
Pentadecane
Hexadecane
Heptadecane
Naphthalene, trimethyl
Compound
Mass
(ng)
1545
94
0
0
0
0
0
15
0
53
31
55
0
28
0
0
11
0
0
33
31
0
0
Weight Loss (kg)
Time (h)
Temperature (C)
Sample Volume (L)
Average
Gaseous Cone.
(mg/cu m)
0.3385
0.0205
0.0000
0.0000
0.0000
0.0000
0.0000
0.0032
0.0000
0.0117
0.0068
0.0120
0.0000
0.0061
0.0000
0.0000
0.0024
0.0000
0.0000
0.0073
0.0068
0.0000
0.0000
Total
0.0020
3.5833
163
4.57
Estimated
Emissions
(g/kg)
1285*
78
0
0
0
0
0
12
0
44
26
46
0
23
0
0
9
0
0
28
26
0
0
292"
Emissions
per Area
(mg/sq m h)
5200
315
0
0
0
0
0
49
0
180
104
185
0
93
0
0
38
0
0
112
105
0
0
* Contaminant
** Dichloro methane not included
22
-------
TABLE 5. TYPE 1 (VOST) CONDITION 3
Type 1 Asphalt (VOST)
Condtion 3
Compound
Methane, dichloro
Benzene
Heptane
Benzene, methyl
Octane
Benzene, dimethyl
Nonane
Decane
Benzene, trimethyl
Benzaldehyde
Undecane
Benzene, tetramethyl
Ethanone, 1-phenyl
Dodecane
Undecane, dimethyl
Naphthalene
Tridecane
Tetradecane
Naphthalene, dimethyl
Pentadecane
Hexadecane
Heptadecane
Naphthalene, trimethyl
Compound
Mass
(ng)
451
155
97
111
94
115
111
167
0
278
201
87
0
258
0
0
258
296
452
739
359
0
286
Weight Loss (kg)
Time (h)
Temperature (C)
Sample Volume (L)
Average
Gaseous Cone.
(mg/cu m)
0.0943
0.0324
0.0203
0.0233
0.0196
0.0242
0.0232
0.0350
0.0000
0.0581
0.0421
0.0182
0.0000
0.0541
0.0000
0.0000
0.0541
0.0619
0.0947
0.1547
0.0751
0.0000
0.0598
Total
0.0337
3.133333
246
4.77
Estimated
Emissions
(g/kg)
19
6
4
5
4
5
5
7
0
11
8
4
0
11
0
0
11
12
19
30
15
0
12
188
Emissions
per Area
(mg/sq m h)
1449
498
312
358
301
371
357
538
0
893
647
279
0
831
0
0
831
951
1454
2376
1153
0
919
23
-------
TABLE 6. TYPE 2 (VOST) CONDITION 1
Type 2 Asphalt (VOST)
Condition 1
Compound
Methane, dichloro
Benzene
Heptane
Benzene, methyl
Octane
Benzene, dimethyl
Nonane
Decane
Benzene, trimethyl
Benzaldehyde
Undecane
Benzene, tetramethyl
Ethanone, 1-phenyl
Dodecane
Undecane, dimethyl
Naphthalene
Tridecane
Tetradecane
Naphthalene, dimethyl
Pentadecane
Hexadecane
Heptadecane
Naphthalene, trimethyl
Compound
Mass
(ng)
94
0
0
23
0
0
0
0
0
111
54
0
28
61
0
0
51
61
27
22
74
24
45
Weight Loss (kg)
Time (h)
Temperature (C)
Sample Volume (L)
Average
Gaseous Cone.
(mg/cu m)
0.0197
0.0000
0.0000
0.0049
0.0000
0.0000
0.0000
0.0000
0.0000
0.0232
0.0113
0.0000
0.0059
0.0128
0.0000
0.0000
0.0107
0.0129
0.0056
0.0046
0.0154
0.0051
0.0094
Total
0.0015
3.9667
132
4.77
Estimated
Emissions
(g/kg)
111
0
0
27
0
0
0
0
0
130
63
0
33
72
0
0
60
72
32
26
87
28
53
794
Emissions
per Area
(mg/sq m h)
303
0
0
75
0
0
0
0
0
356
173
0
90
197
0
0
164
198
87
70
237
78
145
24
-------
TABLE 7. TYPE 2 (VOST) CONDITION 2
Type 2 Asphalt (VOST)
Condition 2
Compound
Methane, dichloro
Benzene
Heptane
Benzene, methyl
Octane
Benzene, dimethyl
Nonane
Decane
Benzene, trimethyl
Benzaldehyde
Undecane
Benzene, tetramethyl
Ethanone, 1-phenyl
Dodecane
Undecane, dimethyl
Naphthalene
Tridecane
Tetradecane
Naphthalene, dimethyl
Pentadecane
Hexadecane
Heptadecane
Naphthalene, trimethyl
Compound
Mass
(ng)
401
204
0
197
0
143
0
143
0
357
133
208
121
267
0
83
235
157
34
91
89
0
0
Weight Loss (kg)
Time (h)
Temperature (C)
Sample Volume (L)
Average
Gaseous Cone.
(mg/cu m)
0.0788
0.0400
0.0000
0.0386
0.0000
0.0282
0.0000
0.0281
0.0000
0.0701
0.0261
0.0409
0.0238
0.0524
0.0000
0.0162
0.0460
0.0308
0.0066
0.0178
0.0174
0.0000
0.0000
Total
0.0138
3.3667
170
5.10
Estimated
Emissions
(g/kg)
41
21
0
20
0
15
0
15
0
36
14
21
12
27
0
8
24
16
3
9
9
0
0
291
Emissions
per Area
(mg/sq m h)
1210
614
0
593
0
433
0
432
0
1077
401
628
365
805
0
249
707
473
102
274
267
0
0
25
-------
TABLE 8. TYPE 2 (VOST) CONDITION 3
Type 2 Asphalt (VOST)
Condtion 3
Compound
Methane, dichloro
Benzene
Heptane
Benzene, methyl
Octane
Benzene, dimethyl
Nonane
Decane
Benzene, trimethyl
Benzaldehyde
Undecane
Benzene, tetramethyl
Ethanone, 1-phenyl
Dodecane
Undecane, dimethyl
Naphthalene
Tridecane
Tetradecane
Naphthalene, dimethyl
Pentadecane
Hexadecane
Heptadecane
Naphthalene, trimethyl
Compound
Mass
(ng)
1141
0
62
82
69
65
98
109
0
248
137
39
0
183
65
0
124
0
21
110
98
51
19
Weight Loss (kg)
Time (h)
Temperature (C)
Sample Volume (L)
Average
Gaseous Cone.
(mg/cu m)
0.2287
0.0000
0.0124
0.0165
0.0139
0.0130
0.0196
0.0218
0.0000
0.0497
0.0275
0.0078
0.0000
0.0367
0.0130
0.0000
0.0249
0.0000
0.0043
0.0220
0.0196
0.0101
0.0039
Total
0.0297
4.05
246
4.99
Estimated
Emissions
(g/kg)
66
0
4
5
4
4
6
6
0
14
8
2
0
11
4
0
7
0
1
6
6
3
1
158
Emissions
per Area
(mg/sq m h)
3512
0
190
254
214
200
301
335
0
764
422
120
0
564
200
0
382
0
66
338
301
156
60
26
-------
TABLE 9. TYPE 3 (VOST) CONDITION 1
Type 3 Asphalt (VOST)
Condition 1
Compound
Methane, dichloro
Benzene
Heptane
Benzene, methyl
Octane
Benzene, dimethyl
Nonane
Decane
Benzene, trimethyl
Benzaldehyde
Undecane
Benzene, tetramethyl
Ethanone, 1-phenyl
Dodecane
Undecane, dimethyl
Naphthalene
Tridecane
Tetradecane
Naphthalene, dimethyl
Pentadecane
Hexadecane
Naphthalene, trimethyl
Compound
Mass
(ng)
1044
843
58
200
45
64
57
79
0
311
97
0
395
118
0
61
64
49
0
28
0
0
Weight Loss (kg)
Time (h)
Temperature (C)
Sample Volume (L)
Average
Gaseous Cone.
(mg/cu m)
0.0547
0.0442
0.0030
0.0105
0.0024
0.0033
0.0030
0.0042
0.0000
0.0163
0.0051
0.0000
0.0207
0.0062
0.0000
0.0032
0.0034
0.0026
0.0000
0.0014
0.0000
0.0000
Total
0.0010
2.7333
163
19.09*
Estimated
Emissions
(0*0)
317
256
18
61
14
19
17
24
0
94
30
0
120
36
0
18
19
15
0
8
0
0
1066
Emissions
per Area
(mg/sq m h)
840
679
47
161
36
51
46
64
0
251
78
0
318
95
0
49
52
39
0
22
0
0
'Sample volume different because initial volumes were still being determined
27
-------
TABLE 10. TYPE 3 (VOST) CONDITION 2
Type 3 Asphalt (VOST)
Condition 2
Compound
Methane, dichloro
Benzene
Heptane
Benzene, methyl
Octane
Benzene, dimethyl
Nonane
Decane
Benzene, trimethyl
Benzaldehyde
Undecane
Benzene, tetramethyl
Ethanone, 1-phenyl
Dodecane
Undecane, dimethyl
Naphthalene
Tridecane
Tetradecane
Naphthalene, dimethyl
Pentadecane
Hexadecane
Heptadecane
Naphthalene, trimethyl
Compound
Mass
(ng)
2153
20
57
159
53
83
89
106
27
353
222
0
156
170
52
0
738
122
70
120
0
0
0
Weight Loss (kg)
Time (h,
Temperature (C)
Sample Volume (L)
Average
Gaseous Cone.
(mg/cu m)
0.4429
0.0041
0.0117
0.0327
0.0109
0.0171
0.0183
0.0218
0.0056
0.0726
0.0456
0.0000
0.0320
0.0351
0.0107
0.0000
0.1519
0.0251
0.0145
0.0247
0.0000
0.0000
0.0000
Total
0.0134
3.9833
218
4.83
Estimated
Emissions
(g/kg)
279
3
7
21
7
11
12
14
4
46
29
0
20
22
7
0
96
16
9
16
0
0
0
619
Emissions
per Area
(mg/sq m h)
6803
63
180
503
168
262
281
335
86
1116
701
0
492
539
165
0
2334
386
223
380
0
0
0
28
-------
TABLE 11. TYPE 3 (VOST) CONDITION 3
Type 3 Asphalt (VOST)
Condtion 3
Compound
Methane, dichloro
Benzene
Heptane
Benzene, methyl
Octane
Benzene, dimethyl
Nonane
Decane
Benzene, trimethyl
Benzaldehyde
Undecane
Benzene, tetramethyl
Ethanone, 1-phenyl
Dodecane
Undecane, dimethyl
Naphthalene
Tridecane
Tetradecane
Naphthalene, dimethyl
Pentadecane
Hexadecane
Heptadecane
Naphthalene, trimethyl
Compound
Mass
(ng)
2623
148
351
354
325
567
437
175
817
0
539
438
0
618
233
0
332
239
156
226
0
0
0
Weight Loss (kg)
Time (h)
Temperature (C)
Sample Volume (L)
Average
Gaseous Cone.
(mg/cu m)
0.5126
0.0289
0.0686
0.0692
0.0635
0.1108
0.0854
0.0342
0.1596
0.0000
0.1053
0.0856
0.0000
0.1207
0.0455
0.0000
0.0648
0.0467
0.0305
0.0442
0.0000
0.0000
0.0000
Total
0.1180
4.0333
288
5.12
Estimated
Emissions
(g/kg)
37
2
5
5
5
8
6
2
12
0
8
6
0
9
3
0
5
3
2
3
0
0
0
121
Emissions
per Area
(mg/sq m h)
7873
444
1054
1063
975
1702
1311
526
2452
0
1618
1315
0
1855
699
0
996
718
469
680
0
0
0
29
-------
TABLE 12. SAMPLING DATA
Date
10-24-90
10-25-90
11-9-90
11-13-90
11-19-90
11-20-90
11-21-90
11-27-90
11-28-90
11-29-90
Asphalt Type
3
3
3
2
2
2
1
1
1
Condition
Background
1
2
3
3
1
2
1
2
3
Ambient Temp (C)
24
22
35
33
35
28
32
24
29
34
Barometric
Pressure(mmHg)
752
753
757
759
751
761
759
763
779
768
The original experiments were conducted while the experimental setup measuring the weight
under the simulated kettle was malfunctioning, rendering the weights uncertain. In an effort to verify the
weight data, several run conditions were reported with weights taken before and after the runs. Runs
are numbered as: type 1 condition 3, type 2 conditions 2 and 5, and type 3 conditions 2 and 3.
The retested weights were used to produce the results of the calculations presented on the
following pages. The average gaseous concentrations were found by dividing the milligrams of
compound by the volume of sample drawn through the VOST tubes. The masses of compounds found
in the background were subtracted from the masses found in samples. The background was sampled
before the test. The average gaseous concentrations for the compounds found in the background
samples are presented in Table 13. The blanks were not incorporated into the data since they
contained the same compounds in the background in roughly the same concentrations except for
dichtoro methane. Table 14 provides the data for the blanks so that the data may be compared with
the results of the samples. The estimated emissions were found by multiplying the average gaseous
concentrations by the amount of air introduced to the bum hut by the air conditioners. This value was
multiplied by the time of sampling, then divided by the weight toss of the asphalt. The air conditioner
system flow rate was measured twice, and the velocity was assumed to be constant for the entire
30
-------
TABLE 13. BACKGROUND DATA (VOST)
Compound
Methane, dichloro
Benzene
Benzene, methyl
Benzaldehyde
Ethanone, 1-phenyl
Area
40803473
2015041
1905582
9070293
15010602
Rf
0.000005
0.000005
0.000004
0.000005
0.000005
Mass (ng)
224
11
9
51
84
Average
Gaseous Cone.
(mg/cu m)
0.011758
0.000580
0.000449
0.002661
0.004404
sampling period. The measurement for the air conditioner flow was performed using a pitot tube
traverse. The weight loss of the asphalt was calculated by subtracting the final weight from the
beginning weight on the load cell. The TCO and GRAV masses are presented in Figures 8 and 9 and
in Table 15.
The emissions per area were calculated by multiplying the average gaseous concentration by
the air conditioner flow rate and dividing by the surface area of the kettle. The average diameter of the
bowl at the asphalt level was found to be 419 mm. This value allows the calculation of the emissions
for a specific compound for a kettle with a known surface area over a period of time. The emission
rates also allow the calculation of emissions for each of the asphalt grades and temperature conditions.
Example calculation:
This calculation is for type 1 asphalt, condition 1, for toluene. The air conditioner flow rate was
2119 m3/h, the surface area of the kettle was 0.1380 m2. the weight toss was 0.0010 kg, and the time
of sampling was 4.0167 h. There was 13 ng of toluene found in the VOST tubes and 4.79 L of air was
sampled.
Average Gaseous Concentration • VOST Tube Cone. / Sampling Volume
Average Gaseous Concentration - 13 ng/ 4.79 L = 0.0027 mg/m3
Emission Rate = Weight Loss / Sampling Time
Emission Rate = (0.0010 kg)/ (4.0167 h) = 0.00025 kg/h
31
-------
Estimated Emissions «(Average Gaseous Conc.)(AC Flow Rate)/(Emission Rate)
Estimated Emissions - (0.0027 mg/m3)(2H9 m3/ti)/(0.00025 kg/h) - 22885 mg of toluene
emitted/kg of asphalt tost
Emissions per Area « (Average Gaseous Conc.)(AC Flow rate)/(Surface Area of Kettle)
Emissions per Area • (0.0027 mg/m3)(2119 m3/h)/(0.1380 m2) » 41.5 mg/h m2
32
-------
TABLE 14. BLANK DATA (VOST)
Nanograms of Compound in Blank VOST Tubes
Compound
Methane, dtehtoro
Benzene
Benzene, methyl
BenzakJehyde
Ethanone, 1-phenyl
T1 C1
6106
0
0
0
0
T1 C2
502
0
0
58
45
T1C3
5171
0
0
0
0
T2C1
7657
0
0
0
0
T2C2
7884
0
0
NM*
NM*
Average Gaseous Concentration in Blank
Compound
Methane, dichtoro
Benzene
Benzene, methyl
BenzaWehyde
Ethanone, 1-phenyl
T1 C1
1.2746
0.0000
0.0000
0.0000
0.0000
T1 C2
0.1099
0.0000
0.0000
0.0127
0.0098
T1 C3
1.0823
0.0000
0.0000
0.0000
0.0000
T2C1
1.6043
0.0000
0.0000
0.0000
0.0000
T2C2
1.5474
0.0000
0.0000
NM*
NM*
T2C3
0
0
0
0
0
VOST Tubes
T2C3
0.0000
0.0000
0.0000
0.0000
0.0000
T3C1
7994
74
41
322
728
(mg/cu m)
T3C1
0.4188
0.0039
0.0021
0.0169
0.0381
T3C2
10358
0
0
0
0
T3C2
2.1310
0.0000
0.0000
0.0000
0.0000
T3C3
12111
0
0
0
0
T3C3
2.3668
0.0000
0.0000
0.0000
0.0000
NM - Not measured (Compound present but integrator not working)
-------
16
14
O
O)
en
CO
CD
O
O
12
10
100
A
150
200
250
Asphalt Temp (deg. C)
Type 1 Type 2 Type 3
D A O
A conversion table is provided on page viii
Figures. TOO mass data.
34
300
-------
400
^ ^^
O) 300
C/D
O)
03
200
DC
O
100
O
A I
A
100
150
200
A
250
Asphalt Temp (deg. C)
Type 1 Type 2 Type 3
D A O
Figure 9. GRAV mass data.
O
300
35
-------
TABLE 15. GRAV MASS DATA
Sample Identification
Type 1 Condition 1
Type 1 Condition 2
Type 1 Condition 3
Type 2 Condition 1
Type 2 Condition 2
Type 2 Condition 3
Type 3 Condition 1
Type 3 Condition 2
Type 3 Condition 3
Asphalt
Temp (°C)
117
163
246
132
170
246
163
218
288
1 00-300 °C
TCO Mass
(mg)
0.04
0.03
3.48
0.13
2.08
2.34
0.03
0.34
13.91
>300 °C
GRAV Mass
(mg)
0.5
1.6
223.8
0.9
7.9
113.6
1.8
41.0
355.4
Total Mass
(mg)
1.0
1.6
227.3
1.0
10.0
115.9
1.8
41.3
369.3
Real Weight
Loss (kg)
0.001
0.002
0.034
0.002
0.014
0.030
0.001
0.013
0.018
3.2 SEMI-VOLATILE ORGANIC EMISSIONS DATA
Compounds were identified by the same identification program as the volatile organics. The
identification data showed only straight chain alkanes (Table 16). The alkanes started from nonane and
progressed through hentriacontane. Because the method used to extract the filters and XAD-2 samples
had been proven to have excellent recoveries, it was assumed that all the compounds were extracted,
although some of the compounds above C-24 may have had less recovery. Aromatics and aldehydes
were not found in any of the samples. Quantitation was made from weight data. The calibration check
of the GC/FID was done by analyzing a calibration standard as the first and last sample. The data
between the two were compared for continuity, and response factors were computed from this data and
the 5-point calibration. The MSD data were used only for compound identification. The masses of
compounds found in the background were subtracted from the masses found in samples for the TCOs.
The GRAV background weight was not subtracted because the weight was below detection limits.
Compounds were then matched by retention time and retention indices. The average gaseous
concentration increased as the temperature increased (Tables 17-25). The average gaseous
concentration, emission rate, and emissions per area were calculated using the same formulas as the
volatile organics. The sample time for the canisters and filters was 3 hours and is reflected in the
36
-------
TABLE 16. COMPOUNDS IDENTIFIED BY MS FROM XAD AND FILTER EXTRACT RUNS
Compound Name Formula
Nonane C9H20
Decane cioH22
Undecane cnH24
Dodecane C12H26
Tridecane ciaH28
Tetradecane ci4Hso
Pentadecane cisH32
Hexadecane cieH34
Octadecane Ci8H38
Nonadecane cigH4o
Icosane C20H42
Henicosane C21H44
Docosane ^22^46
Tricosane ^23H48
Tetracosane ^24^50
Pentacosane C25H52
Hexacosane ^26^54
Heptacosane C27H56
Octacosane C2B^5s
Nonacosane C29Heo
Triacontane C3oH62
Hentriacontane C31H64
calculations. Table 26 presents the ASTM standards for roofing asphalt.
37
-------
TABLE 17. TYPE 1 (TOO) CONDITION 1
Type 1 Asphalt (TOO)
Condition 1
Compound
Nonane
Decane
Undecane
Dodecane
Tridecane
Tetradecane
Pentadecane
Hexadecane
Heptadecane
Octadecane
Nonadecane
Icosane
Henicosane
Docosane
Tricosane
Tetracosane
Pentacosane
Hexacosane
Heptacosane
Octacosane
Nonaoosane
Triacontane
Hentriacontane
Compound
Mass
(ng)
0
0
0
0
0
0
0
6895
10996
8710
508
0
0
0
0
12354
0
0
0
0
0
0
0
Weight Loss (kg)
Temperature (C)
Sample Volume (ou m)
Average
Gaseous Cone.
(mg/cu m)
O.OOe+00
O.OOe+00
O.OOe+00
O.OOe+00
O.OOe+00
O.OOe+00
O.OOe+00
7.27e-04
1.16e-03
9.186-04
5.366-05
O.OOe+00
O.OOe+00
O.OOe+00
O.OOe+00
1.30e-03
O.OOe+00
O.OOe+00
O.OOe+00
O.OOe+00
O.OOe+00
O.OOe+00
O.OOe+00
Total
0.0010
117
9.49
Estimated
Emissions
(g/kg)
0
0
0
0
0
0
0
5
7
6
0
0
0
0
0
8
0
0
0
0
0
0
0
26
Emissions
per Area
(mg/sq m h)
0
0
0
0
0
0
0
11
18
14
1
0
0
0
0
20
0
0
0
0
0
0
0
38
-------
TABLE 18. TYPE 1 (TOO) CONDITION 2
Type 1 Asphalt (TOO)
Condition 2
Compound
Nonane
Decane
Undecane
Dodecane
Tridecane
Tetradecane
Pentadecane
Hexadecane
Heptadecane
Octadecane
Nonadecane
Icosane
Henicosane
Docosane
Tricosane
Tetracosane
Pentacosane
Hexacosane
Heptacosane
Octacosane
Nonacosane
Triacontane
Nonane
Compound
Mass
(ng)
VV^^^^^^^^^^^B^_H^^W^^^^^^^^^^^^H
0
0
0
0
0
0
0
0
2667
918
174
78
646
0
0
923
0
0
0
0
0
0
0
Weight Loss (kg)
Temperature (C)
Sample Volume (cu m)
Average
Gasmous Cone.
(mg/cu m)
^^^^-^•"••'••••^^^^MM1M*^^MIHM«V«IVV^^H<^«_IV^K^^^^^^^^
O.OOe+00
O.OOe+00
O.OOe+00
O.OOe+00
O.OOe+00
O.OOe+00
O.OOe+00
O.OOe+00
2.78e-03
9.586-04
1.826-04
8.156-05
6.746-04
O.OOe+00
O.OOe+00
9.636-04
O.OOe+00
O.OOe+00
O.OOe+00
O.OOe+00
O.OOe+00
O.OOe+00
O.OOe+00
Total
0.0020
163
9.58
Estimated
Emissions
(gfcg)
^^^^•^•AA^^^^^^^MPW^BWIW^^WV
0
0
0
0
0
0
0
0
9
3
1
0
2
0
0
3
0
0
0
0
0
0
0
18
Emissions
per Area
(mg/sq m h)
^^^^^^^^— ^1M^^H^^«M>W«*»*M>»
0
0
0
0
0
0
0
0
43
15
3
1
10
0
0
15
0
0
0
0
0
0
0
39
-------
TABLE 19. TYPE 1 (TCO) CONDITION 3
Type 1 Asphalt (TCO)
Condtk>n3
Compound
Nonane
Decane
Undecane
Dodecane
Tridecane
Tetradecane
Pentadecane
Hexadecane
Heptadecane
Octadecane
Nonadecane
Icosane
Henicosane
Docosane
Tricosane
Tetracosane
Pentacosane
Hexacosane
Heptacosane
Octacosane
Nonacosane
Triacontane
Nonane
Compound
Mass
(ng)
5592
5353
5171
5237
5563
7948
11620
14912
19259
19459
27406
55778
64582
61621
59342
66264
67365
67031
45177
50389
32859
23600
21066
Weight Loss (kg)
Temperature (C)
Sample Volume (cu m)
Average
Gaseous Cone.
(mg/cu m)
5.83e-03
5.58e-03
5.396-03
5.45e-03
5.806-03
8.286-03
1.216-02
1.556-02
2.016-02
2.036-02
2.856-02
5.816-02
6.736-02
6.426-02
6.186-02
6.906-02
7.026-02
6.986-02
4.716-02
5.256-02
3.426-02
2.466-02
2.196-02
Total
0.0337
246
9.60
Estimated
Emissions
(g/kg)
1
1
1
1
1
2
2
3
4
4
5
11
13
12
12
13
13
13
9
10
6
5
4
146
Emissions
per Area
(mg/sq m h)
89
86
83
84
89
127
186
239
308
311
439
892
1033
986
949
1060
1078
1073
723
806
526
378
337
40
-------
TABLE 20. TYPE 2 (TCO) CONDITION 1
Type 2 Asphalt (TCO)
Condition 1
Compound
Nonane
Decane
Undecane
Dodecane
Tridecane
Tetradecane
Pentadecane
Hexadecane
Heptadecane
Octadecane
Nonadecane
Icosane
Henicosane
Docosane
Tricosane
Tetracosane
Pentacosane
Hexacosane
Heptacosane
Octacosane
Nonacosane
Triacontane
Hentriacontane
Compound
Mass
(no)
0
0
0
301
385
472
530
1034
991
624
0
0
0
0
0
1079
0
0
0
0
0
0
0
Weight Loss (kg)
Temperature (C)
Sample Volume (cu m)
Average
Gaseous Cone.
(mg/cu m)
O.OOe+00
O.OOe+00
O.OOe+00
3.20e-04
4.09e-04
5.026-04
5.646-04
1.106-03
1.056-03
6.646-04
O.OOe+00
O.OOe+00
O.OOe+00
O.OOe+00
O.OOe+00
1.15e-03
O.OOe+00
O.OOe+00
O.OOe+00
O.OOe+00
O.OOe+00
O.OOe+00
O.OOe+00
Total
0.0015
132
9.40
Estimated
Emissions
(g/kg)
0
0
0
1
2
2
2
5
4
3
0
0
0
0
0
5
0
0
0
0
0
0
0
24
Emissions
per Area
(mg/sq m h)
0
0
0
5
6
8
9
17
16
10
0
0
0
0
0
18
0
0
0
0
0
0
0
41
-------
TABLE 21. TYPE 2 (TOO) CONDITION 2
Type 2 Asphalt (TOO)
Condition 2
Compound
Nonane
Decane
Undecane
Dodecane
Tridecane
Tetradecane
Pentadecane
Hexadecane
Heptadecane
Octadecane
Nonadecane
Icosane
Henicosane
Docosane
Tricosane
Tetracosane
Pentacosane
Hexacosane
Heptacosane
Octacosane
Nonacosane
Triacontane
Hentriaoontane
Compound
Mass
(ng)
2279
2544
3110
3781
4602
6017
7879
8300
5483
2990
1444
1818
2073
746
0
1470
0
0
0
0
0
0
0
Weight Loss (kg)
Temperature (C)
Sample Volume (cu m)
Average
Gaseous Cone.
(mg/cu m)
2.346-03
2.626-03
3.206-03
3.896-03
4.736-03
6.196-03
8.106-03
8.546-03
5.646-03
3.086-03
1.496-03
1.876-03
2.136-03
7.67e-04
O.OOe+00
1.516-03
O.OOe+00
O.OOe+00
O.OOe+00
O.OOe+00
O.OOe+00
O.OOe+00
O.OOe+00
Total
0.0138
170
9.72
Estimated
Emissions
(g/kg)
1
1
1
2
2
3
4
4
3
1
1
1
1
0
0
1
0
0
0
0
0
0
0
26
Emissions
per Area
(mg/sq m h)
36
40
49
60
73
95
124
131
87
47
23
29
33
12
0
23
0
0
0
2
0
0
0
42
-------
TABLE 22. TYPE 2 (TCO) CONDITION 3
Type 2 Asphalt (TCO)
Condtton3
Compound
Nonane
Decane
Undecane
Dodecane
Tridecane
Tetradecane
Pentadecane
Hexadecane
Heptadecane
Octadecane
Nonadecane
Icosane
Henicosane
Docosane
Tricosane
Tetracosane
Pentacosane
Hexacosane
Heptacosane
Octacosane
Nonacosane
Triacontane
Hentriacontane
Compound
Mass
(ng)
5850
5335
5124
4877
4696
5995
7229
8481
8681
7360
9893
15769
17984
16039
13604
14583
16870
16607
13206
13440
14406
14555
15279
Weight Loss (kg)
Temperature (C)
Sample Volume (cu m)
Average
Gaseous Cone.
(mg/cu m)
5.97e-03
5.44e-03
5.23e-03
4.98e-03
4.796-03
6.126-03
7.386-03
8.656-03
8.866-03
7.516-03
1.016-02
1.616-02
1.846-02
1.646-02
1.396-02
1.496-02
.726-02
.696-02
.356-02
.376-02
.476-02
1.496-02
1.566-02
Total
0.0297
246
9.80
Estimated
Emissions
(g/kg)
1
1
1
1
1
1
2
2
2
2
2
3
4
4
3
3
4
4
3
3
3
3
3
56
Emissions
per Area
(mg/sq m h)
92
84
80
76
74
94
113
133
136
115
155
247
282
251
213
229
264
260
207
211
226
228
239
43
-------
TABLE 23. TYPE 3 (TCO) CONDITION 1
Type 3 Asphalt (TCO)
Condition 1
Compound
Nonane
Decane
Undecane
Dodecane
Tridecane
Tetradecane
Pentadecane
Hexadecane
Heptadecane
Octadecane
Nonadecane
Icosane
Henicosane
Docosane
Tricosane
Tetracosane
Pentacosane
Hexacosane
Heptacosane
Octacosane
Nonacosane
Triacontane
Hentriacontane
Compound
Mass
(ng)
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
760
0
0
0
0
0
0
0
Weight Loss (kg)
Temperature (C)
Sample Volume (cu m)
Average
Gaseous Cone.
(mg/cu m)
O.OOe+00
O.OOe+00
O.OOe+00
O.OOe+00
O.OOe+00
O.OOe+00
O.OOe+00
O.OOe+00
O.OOe+00
O.OOe+00
O.OOe+00
O.OOe+00
O.OOe+00
O.OOe+00
O.OOe+00
7.49e-04
O.OOe+00
O.OOe+00
O.OOe+00
O.OOe+00
O.OOe+00
O.OOe+00
O.OOe+00
Total
0.0010
163
10.14
Estimated
Emissions
(g/kg)
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
5
0
0
0
0
0
0
0
5
Emissions
per Area
(mg/sq m h)
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
12
0
0
0
0
0
0
0
44
-------
TABLE 24. TYPE 3 (TOO) CONDITION 2
Type 3 Asphalt (TOO)
Condition 2
Compound
Nonane
Decane
Undecane
Dodecane
Tridecane
Tetradecane
Pentadecane
Hexadecane
Heptadecane
Octadecane
Nonadecane
Icosane
Henicosane
Docosane
Tricosane
Tetracosane
Pentacosane
Hexacosane
Heptacosane
Octacosane
Nonacosane
Triacontane
Hentriacontane
Compound
Mass
(ng)
1172
1074
1230
1335
1455
1771
2094
2722
3633
3829
4050
9187
9379
7782
6617
7093
5503
4785
3855
3401
2528
1669
966
Weight Loss (kg)
Temperature (C)
Sample Volume (cu m)
Average
Gaseous Cone.
(mg/cu m)
1.21e-03
1.11e-03
1.276-03
1.386-03
1.516-03
1.836-03
2.176-03
2.826-03
3.766-03
3.966-03
4.196-03
9.506-03
9.706-03
8.056-03
6.856-03
7.346-03
5.696-03
4.956-03
3.996-03
3.526-03
2.616-03
1.736-03
9.996-04
Total
0.0134
218
9.67
Estimated
Emissions
(g/kg)
1
1
1
1
1
1
1
1
2
2
2
5
5
4
3
3
3
2
2
2
1
1
0
45
Emissions
per Area
(mg/sq m h)
19
17
20
21
23
28
33
43
58
61
64
146
149
124
105
113
87
76
61
54
40
27
15
45
-------
TABLE 25. TYPE 3 (TCO) CONDITION 3
Type 3 Asphalt (TCO)
Condtk>n3
Compound
Nonane
Decane
Undecane
Dodecane
Tridecane
Tetradecane
Pentadecane
Hexadecane
Heptadecane
Octadecane
Nonadecane
Icosane
Hentcosane
Docosane
Tricosane
Tetracosane
Pentacosane
Hexacosane
Heptacosane
Octacosane
Nonacosane
Triacontane
Hentriacontane
Compound
Mass
(ng)
17169
16047
14763
13355
12549
12872
11537
8760
9290
7182
10412
20150
19163
21364
23799
26128
31687
34520
29898
40861
36991
36785
38475
Weight Loss (kg)
Temperature (C)
Sample Volume (cu m)
Average
Gaseous Cone.
(mg/cu m)
1.73e-02
1.61e-02
1.486-02
1.346-02
1.266-02
1.296-02
1.166-02
8.816-03
9.346-03
7.226-03
1.056-02
2.036-02
1.936-02
2.156-02
2.396-02
2.636-02
3.196-02
3.47e-02
3.016-02
4.116-02
3.726-02
3.706-02
3.87e-02
Total
0.1180
288
9.95
Estimated
Emissions
(g/fcg)
1
1
1
1
1
1
1
0
1
0
1
1
1
1
1
1
2
2
2
2
2
2
2
28
Emissions
per Area
(mg/sq m h)
265
248
228
206
194
199
178
135
143
111
161
311
296
330
368
403
489
533
462
631
571
568
594
46
-------
TABLE 26. ASTM STANDARDS
ANSI Guidelines for Roofing Asphalt (ASTM D312-78)'
Type 1 includes asphalts that are relatively susceptible to flow at roof temperatures with good
adhesive and "self-healing" properties. They are generally used in slag- or gravel-surfaced roofs
on inclines up to 4.17 percent (V* in/ft) slope.
Type 2 includes asphalts that are moderately susceptible to flow at roof temperatures. They are
generally for use in built-up roof construction on inclines from approximately 4.17 percent (Vfe in/ft)
slope to 12.5 percent (1Vi> in/ft) slope.
Type 3 includes asphalts that are relatively nonsusceptible to flow at roof temperatures for use in
the construction of built-up roof construction on inclines from approximately 8.3 percent (1 in/ft)
slope to 25 percent (3 in/ft) slope.
Property
ANSI Physical Requirements of Asphalt in Roofing
Type 1 Type 2
Min
Max
Min
Max
Types
Min Max
Softening Point C (F) 57(135) 66(151)
Flash Point C (F) 225 (437)
Penetration Units
atOC(32F) ... 6
at 25 C (77 F) 18 60
at 46 C (115 F) 90 180
Ductility at 25 C (77 F) 10
cm
Solubility in Trichtoro- 99
ethytene, %
70 (158)
225 (437)
18
3
99
80(176)
6
40
100
85(185)
225 (437)
15
1.5
99
96(205)
35
90
Copyright ASTM. Reprinted with permission.
47
-------
SECTION 4
SUMMARY AND CONCLUSIONS
The purpose of this study was to characterize and semi-quantitate the volatile organic
emissions from a heated roofing asphalt kettle. The results show the types of emissions produced by
the three most common types of roofing asphalt used today. The data also show how the three types
of asphalt behave at the melting point, the equiviscous temperature, and an overheated temperature.
Compounds identified during this study were alkanes, aromatics, a ketone, and an aldehyde. Although
alcohols were found in the cursory study performed in 19892, the absence of these compounds may be
attributed to a difference in asphalt brand or a change in sampling procedures. The unheated sample
duct used in this study may have condensed the compounds before they reached the adsorbing
material.
By having the samples collected through an unheated duct several feet away from the asphalt
kettle, it may be possible to compare these results to the average gaseous concentrations of volatile
organics compounds found at a typical roofing asphalt project. These results show that, as the roofing
asphalt is heated through higher temperature ranges, more compounds are emitted at higher
concentrations. Useful emission factors also are provided in the data to help characterize the
emissions either by the mass of asphalt tost by heating or by the size of the kettle over a period of
time.
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SECTION 5
REFERENCES
1. Asphalt Roofing Manufacturing Industry-Background Information for Promulgated Standards.
EPA-450/3-80-021D (NTIS PB82-257726), July 1982.
2. Internal Communication with Bobby Daniel, 1990.
3. Health and Safety Guide for the Commercial Roofing Industry. OHEW (NIOSH) Publication No.
278-194. National Institute for Occupational Safety and Health. Cincinnati, Ohio. September
1978. pp.77.
4. Ryan, J.V., "Characterization of Emissions from the Simulated Open Burning of Scrap Tires,"
EPA-600/2-89-054 (NTIS PB90-126004), October 1989.
5. Hansen, E.M.. "Protocol for the Collection and Analysis of Volatile POHCs Using VOST," EPA-
600/8-84-007 (NTIS PB84-170042), March 1984.
6. ASTM D312-78, Annual Book of ASTM Standards, Part 15.
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APPENDIX A
QUALITY CONTROL EVALUATION REPORT
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ACCURACY AND PRECISION
Accuracy and precision were calculated using the following formulas:
Accuracy:
Percent bias • measure^ concentration - known concentration ^
known concentration
or
Percent recovery - meaaind
Precision:
known concentration
(C, -C2)
Relative precision data = * 100
(C1+C2)/2
Where: C1 = larger of the 2 measured values
C2 = smaller of the 2 measured values
or
_ . . , , , . . standard deviation of replicate measurements 1/v»
Relative standard deviation i— * 100
average of replicate measurements
[V; - average)
Standard deviation - V, _
>| ^ n
Where: V, = i* item
average - average of values
n = number of items
Two XAD-2 and one filter laboratory blank was run. The laboratory blanks included injecting an
internal standard on both the filter and the XAD-2 cartridges. The results of the extracts were
compared to those of a straight injection of the same compounds for either the TCO or the GRAV
analysis. It was determined that there was a recovery of 120 percent for the XAD-2 cartridges and 109
percent for the filter. This met the data quality objective (DQO) of 50-150 percent recovery.
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TABLE A-1 PERCENT BIAS FOR VOST PEAS
Compound True (ng) Measured (ng) Percent Bias
Benzene 122 142.5 +17
Toluene 147 196 +33
Ethyl Benzene 184 300.5 +63
Xylene 161 369 +129
VOLATILE ORGANIC DATA
Accuracy for this project was not assessed by spike recovery of the analyte for any of the
methods. However a measure of accuracy can be assessed by looking at the data for the internal
standard, deuterated benzene, in the VOST samples. A concentration of 244 ng of deuterated
benzene was spiked onto all the tubes before sampling. The average measured concentration was
219 ng for 27 samples. This gives a bias of 10.2 percent. Bias was also calculated by examining the
results of performance evaluation audit (PEA) samples from an external audit. Table A-1 shows the
results for benzene, toluene, xylene, and ethyl benzene.
As can be seen from Table A-1, there is increasing positive bias with increasing retention time.
This is probably caused by using a single response factor in calculating the analyte mass. This trend
was not taken into account when calculating the response factors for the PEAs. The actual asphalt
samples, however, were calculated on the basis of individual response factors from standards. The
DQO for quantitation accuracy for the volatile organics of ±50 percent was not met for ethyl benzene or
xylene, but was met for benzene and toluene.
The PEAs for the VOST tubes were also judged on the number of compounds identified
correctly. On average, 91 percent of the compounds were identified correctly meeting the DQO of
greater than 75 percent.
Precision for the volatile organics can be determined by the percent RSD of the internal
standard spikes for the VOST samples. The standard deviation for the deuterated benzene was 104
ng. The concentration of the compound was 244 ng.
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RSD * L * 100 = 47 percent
The DQO of 25 percent was not met for the samples in this project. Another measure of precision
were the external audits. These were submitted in duplicate with the results as seen in Table A-2.
These DQOs for precision of 25 percent were met 50 percent of the time for the PEAs. If the
DQO had been 50 percent, it would have been met. Under the circumstances of the project, in
consideration of the many sources of error, this may have been a more realistic goal. Same day
analysis or a different collection medium than Tenax may have allowed the project to meet the DQO.
Fifty percent is the normal error for VOST analysis.
The QC checks on the Tenax tubes all passed the parameters for clean tubes set forth in the
Quality Assurance Project Plan.
SEMI-VOLATILE DATA
The filters and XAD-2 cartridges were not spiked with an internal standard. The PEA filters
were spiked at too low a concentration to be measured. The QC check standards were run four times
a day with the TCOs. The data presented in Table A-3 provide the accuracy and precision for these
standards.
The values for accuracy met the DQO of 20 percent while the precision never met the DQO of
15 percent. Accuracy and precision data were calculated from the recovery data for the spiked
laboratory blanks. The replications called for in the QAPjP were not done, as agreed before sampling
began. The spiking solutions to characterize TOO and GRAV measurements were not used. QC
check samples as called for in the QAPjP for GRAV samples were not used. The deuterated
naphthalene internal standard as called for in the QAPjP was not used to determine the recovery for
the semi-volatiles from the XAD-2 resin.
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TABLE A-2. RESULTS OF EXTERNAL AUDIT
Compound
Benzene
Toluene
Ethyl Benzene
Xytene
Average (ng)
142.5
196
300.5
367
Standard
Deviation (ng)
60.1
2.8
85.6
46.7
Percent RSD
42.1
1.4
28.5
12.7
TABLE A-3. ACCURACY AND PRECISION DATA FOR SEMI-VOLATILES
Compound
Decane
Dodecane
Tetradecane
Heptadecane
True
(mg)
0.023949
0.023478
0.022179
0.021536
Measured
(mg)
0.021871
0.023322
0.025493
0.025376
Percent Bias
-8.67818
-0.66562
14.94403
17.83194
RPD*
24.42864
20.62726
19.98598
25.71266
* RPD » Relative Precision Data
COMPLETENESS
Completeness
Amount of valid data
Amount of planned data
Volatiles - 89 percent or 24 of 27 Blanks = 100 percent or 9 of 9
Semi-volatiles - 100 percent or 9 of 9 Blanks = 75 percent or 3 of 4
Three volatile samples were not analyzed because they were broken during analysis. DQO for
the volatiles was set at better than 75 percent, whereas the semi-volatiles were 100 percent. The
results of the volatile blanks are presented in Table 14 of the basic report. The decision not to run
semi-volatiles in duplicate was made before the project began. The semi-volatile field blank was not
collected although a background sample was collected. It was determined that there were no
compounds present in the background and that the GRAV mass was below detection limits.
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REPRESENTATIVENESS
The design of the bum hut and sampling shed ensured good mixing of the asphalt fumes with
ambient air before being sampled, ensuring representativeness. Using ambient pressures, air flows,
and temperatures ensured that the air reaching the sampling equipment was representative of possible
breathing zones. Also, studies in October 1989, "Characterization of Emissions from the Simulated
Open Burning of Scrap Tires," proved representative sampling using the same techniques performed in
this project.
COMPARABILITY
This study cannot be compared to studies of asphalt fumes in which sampling was done
directly over an open kettle. Those studies found significant concentrations of polyaromatic
hydrocarbons, for instance, which were not found in this study. This is thought to be due to the
circumstances of the sampling which was designed to simulate the compounds reaching the breathing
zones of people in the area of the kettle.
SUMMARY
It can be seen from the accuracy and precision data for the project that the DQOs for the
project may have been set for slightly unrealistic goals. An approved QAPjP was in place prior to data
collection thus stating the DQO. Several audits were performed during the course of the program.
These included a technical systems audit, performance evaluation audits, and an audit of data quality.
The technical systems audit evaluated the project organization and personnel, calibration procedures,
the facilities and equipment, the sample handling equipment, analytical procedures, quality control
procedures, data processing and validation procedures, and record keeping. The performance
evaluation audits included spiked samples for both the volatites and semi-volatiles. The results of both
are stated above. The data quality audit was performed by reviewing the data for proper data
recording, calculations, and discussion of data quality indicators. These audits were performed
externally by EPA/AEERL QA.
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After reviewing the data obtained form the load eel R was determined ths several of the run
conditions should be repeated for comparability. AN of the high temperatures (condition 3) and the
medium temperatures for types 2 and 3 were repeated. These tests were performed by heating a new -
block of asphalt to the desired temperature and maintaining it for a period of time. No air sampling was
repeated for these tests.
All of the audits were passed with minor recommendations although many of the DQOs were
not met. Since the margin by which the DQOs tailed was very small it could be seen that the DQOs for
the project may have been set unrealistically.
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
REPORT NO.
EPA-600/2-91-061
3. RECIPIENT'S ACCESSION NO.
TITLE AND SUBTITLE
Evaluation of VOC Emissions from Heated Roofing
Asphalt
5. REPORT DATE
November 1991
6. PERFORMING ORGANIZATION CODE
. AUTHOR(S)
Peter Kariher, Michael Tufts, and Larry Hamel
8. PERFORMING ORGANIZATION REPORT NO.
.PERFORMING ORGANIZATION NAME AND ADDRESS
A cur ex Corporation
P. O. Box 13109
Research Triangle Park, North Carolina 27709
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
68-DO-0141, Task 91-001
12. SPONSORING AGENCY NAME AND ADDRESS
EPA, Office of Research and Development
Air and Energy Engineering Research Laboratory
Research Triangle Park, North Carolina 27711
13. TYPE OF REPORT AND PERIOD COVERED
Task Final; 4/90 - 8/91
14. SPONSORING AGENCY CODE
EPA/600/13
is. SUPPLEMENTARY NOTES AEERL Task Officer is Bobby E. Daniel, Mail Drop 61, 919/541-
0908.
16. ABSTRACT
The report gives results of a short-term in-house project to characterize
emissions from a simulated asphalt roofing kettle, performed at EPA/AEERL. Hot
asphalt surfacing and resurfacing has been identified as a possible significant source
of volatile organic compound (VOC) emissions that may affect human health and con-
tribute to the ozone non- attainment problem. The purpose of the study was to col-
lect, identify, and semi-quantitate as many compounds as possible that are dischar-
ged during the open heating of roofing asphalt and relate them to the amount volatil-
ized into the air. Types 1, 2, and 3 mopping grade asphalts were chosen for this
study. They constitute more than 90% of roofing asphalt used. Samples of each type
of asphalt were placed in a simulated roofing kettle, heated to predetermined tem-
peratures, and sampled for volatile and semi-volatile organic emissions. Com-
pounds identified during the study were alkanes, aromatics, a ketone, and an alde-
hyde.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS
c. COSATI Field/Group
Pollution Aromatic Compounds
Asphalts Ketones
Organic Compounds Aldehydes
Volatility
Ozone
•Alkanes
18. DISTRIBUTION STATEMENT
Release to Public
Pollution Control
Stationary Sources
Volatile Organic Com-
pounds (VOCs)
19. SECURITY CLASS (ThisReport)
Unclassified
13B
08G, 13C
07 C
20M
07B
21. NO. OF PAGES
65
20. SECURITY CLASS (Thispage)
Unclassified
22. PRICE
EI>A Form 2220-1 (9-73)
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