United States
^—""e"c,hn Control Technology Center
EPA-600 /R- 64~ 211 December 1994
SEPA
EVALUATION OF A LIQUID CHEMICAL SCRUBBER
SYSTEM FOR STYRENE REMOVAL
control £ technology center
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TECHNICAL REPORT DATA
(Phase read InUruaions on the reverse before completing
1.REPORTNO
UFA-600 /R-94-211
2.
3. RE
4 TIT;~E AND SUBTlTl.C
Evaluation of a Liquid Chemical Scrubber
System for
5 REPORT DATE
December 1994
btyrene Removal
6. PERFORMING ORGANIZATION CODE
7 ALTHORlS)
Larry I55%. Manufac-
turing processes that involve the spraying of styrene-based resins have been identi-
fied as a possible significant source of volatile organic compound emissions that may
affect human health and contribute to the ozone nonattainment problem. Until recent-
ly, no known cost-effective technology has been demonstrated to control such styrene
emissions, and this short-term field evaluation was carried out to characterize the
styrene removal efficiency of a pilot-scale version of the liquid chemical scrubbing
process.- This test was carried out at a facility (Eljer Plumbingware in Wilson, NC)
that manufactures polyester bathtubs and shower stalls by spraying styrene-based
resins onto molds in vented, open spray booths. A side stream of air, exhausted
from one of the spray booths in the gel coating part of the process, was used for the
test.
17.
KEY WORDS AND DOCUMENT ANALYSIS
a. DESCRIPTORS
b.IDENTIFIERS/OPEN ENDED TERMS
c. COSATI Field/Group
Pollution
Styrene Resins
Spray Coating
Industrial Processes
Scrubbers
Pollution Control
Stationary Sources
Bathtubs
Shower Stalls
13 B
in, ii j
13H
07A, 131
18. distribution statement
19. SECURITY CLASS (This Report)
Unclassified
21. NO. OF PAGES
104
Release to Public
20. SECURITY CLASS (This page)
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
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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/R-84-2U
December 1994
EVALUATION OF A LIQUID CHEMICAL SCRUBBER
SYSTEM FOR STYRENE REMOVAL
Prepared by:
Larry Felix, Randy Merritt, and Ashley Williamson
Southern Research Institute
Environmental Sciences Research Department
P. O. Box 55305
Birmingham, AL 35255-5305
EPA Contract Number 68-D2-0062
Task No. 12, Phase 2
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
Manufacturing processes that involve the spraying of styrene-based resins have 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. Until recently, no known technology has
been demonstrated to control such emissions of styrene. Now, several processes have been developed
to control styrene emissions and a short-term field evaluation was planned to characterize the styrene
removal efficiency of a pilot-scale version of a liquid chemical scrubbing process. This test was carried
out at a facility (Eljer Plumbingware in Wilson, NC) that manufactures polyester bathtubs and shower
stalls by spraying styrene-based resins onto molds in vented, open, spray booths. A side stream of air
exhausted from one of the spray booths in the gel coating part of the process was used for this test.
In this study the styrene removal efficiency of a pilot-scale version of the QUAD Chemtact™
scrubber was quantified by continuously measuring the total hydrocarbon (THC) content of spray booth
exhaust air entering and exiting the device with THC analyzers and, for some tests, by collecting NIOSH
EPA Method 18 samples (adsorption tube procedure) at the inlet and exit of the device. Twenty-five
different combinations and strengths of scrubber chemicals (test conditions) were identified, and for
each test condition, average styrene removal efficiency was determined. Average styrene removal
efficiency approached but was never greater than 55% for any test condition.
This work was performed 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.
ii
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TABLE OF CONTENTS
Abstract ii
List of Figures iv
List of Tables v
Acknowledgments vi
Preface vii
Metric to Nonmetric Conversions viii
Section Paoe
1. Introduction 1
2. Project Description 3
2.1 Experimental Approach 3
2.2 Eljer Plumbingware Facility 4
2.3 The Liquid Chemical Scrubbing Process 7
2.3.1 Pilot-Scale Liquid Chemical Scrubbing Device 10
2.3.2 Specific Test Conditions 12
2.4 Experimental Apparatus 16
2.4.1 Connection lo the Pilot-Scale Liquid Chemical Scrubber 16
2.4.2 Sampling Van 16
2.5 Experimental Methods and Procedures 21
2.5.1 Total Hydrocarbon Analyzers 21
2.5.2 Collection of EPA Method 18 Samples 22
2.5.3 Collection of Scrubber Liquid Samples 24
2.5.4 Total Flow Rate Measurements 25
3. Data, Results, and Discussion 26
3.1 Total Hydrocarbon Analyzer Data 26
3.1.1 Inlet Data 26
3.1.2 Outlet Data 36
3.1.3 Efficiency Data 36
3.1.4 Estimated Styrene Emissions from Gel Coat Booth #2 44
3.2 EPA Method 18 Data 46
3.3 Analysis of Recovered Scrubber Liquid Samples 48
3.4 Total Flow Rate Data 51
4. Summary and Conclusions 53
4.1 Economics 54
5. References 56
Appendix A NIOSH Method 1501 57
Appendix B Quality Control Evaluation Report 65
Appendix C Total Hydrocarbon Analyzer Daily Results 77
Appendix D Results of Chemical Analyses of Water and Scrubber Liquid Samples 89
iii
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LIST OF FIGURES
Figure Page
1. Layout of the Eljer Plumbingware Facility 5
2. Diagrammatic representation of the liquid chemical scrubbing process 9
3. Diagram of the pilot-scale liquid chemical scrubber tested at Eljer Plumbingware 11
4. Overall arrangement for sampling at the Eljer Plumbingware Facility 17
5. Equipment arrangement used for sampling with THC analyzers 18
6. Equipment arrangement used for EPA Method 18 sampling 19
7. Inlet and outlet hydrocarbon emissions, 0830 to 1015, June 22,1993 27
8. Inlet and outlet hydrocarbon emissions, 1015 to 1200, June 22,1993 28
9. Inlet and outlet hydrocarbon emissions, 1230 to 1400, June 22,1993 29
10. Inlet and outlet hydrocarbon emissions, 0700 to 1030, June 23,1993 30
11. Inlet and outlet hydrocarbon emissions, 1030 to 1215, June 23,1993 31
12. Inlet and outlet hydrocarbon emissions, 1230 to 1415, June 23,1993 32
13. Inlet and outlet hydrocarbon emissions. 0730 to 1030, June 24,1993 33
14. Inlet and outlet hydrocarbon emissions, 1030 to 1215, June 24,1993 34
15. Inlet and outlet hydrocarbon emissions, 1230 to 1400, June 24,1993 35
16. Hydrocarbon removal efficiency, June 22,1993 41
17. Hydrocarbon removal efficiency, June 23,1993 42
18. Hydrocarbon removal efficiency, June 24, 1993 43
iv
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LIST OF TABLES
Table Page
1. Daily Test Conditions 12
2. Summary of Test Conditions for June 22,1993 13
3. Summary of Test Conditions for June 23,1993 14
4. Summary of Test Conditions for June 24,1993 15
5. Inlet and Outlet Styrene Level and Efficiency of Styrene Removal for each Mold
Sprayed and for each Test Condition, June 22,1993 38
6. Inlet and Outlet Styrene Level and Efficiency of Styrene Removal for each Mold
Sprayed and for each Test Condition, June 23,1993 39
7. Inlet and Outlet Styrene Level and Efficiency of Styrene Removal for each Mold
Sprayed and for each Test Condition, June 24,1993 40
8. Hydrocarbon Emissions from Direct Spraying in Gel Coat Booth #2, THC Data 45
9. Total Hydrocarbon Emissions from Gei Coat Booth #2, THC Data 45
10. Sampling Conditions for Adsorption Tube Measurements made at Eljer Plumbingware,
June 22-24,1993. EPA Method 18 Sampling 47
11. Results of Adsorption Tube and THC Measurements made at Eljer Plumbingware,
June 22-24,1993. EPA Method 18 Sampling 48
12. Summary of Test Conditions During Which Scrubber Liquid Samples were Taken 50
13. Results of Analyses Carried out on Scrubber Liquid Samples and a Process Water Sample 50
14. Flow Rate Measurements at the Inlet of the Liquid Chemical Scrubber 51
15. Design and Cost Specification for a Full-Scale Liquid Chemical Scrubber 55
B-1. Results of SRI Analyses of EPA Performance Evaluation Audit Sample 70
B-2. Results of SRI Analyses of Matheson Calibration Gas 70
B-3. Data Quality Indicator Goals for Critical Measurements Estimated in QAPP 73
B-4. Data Quality Indicator Values for EPA Method 18 (NIOSH Method 1501)
Measurements Made at Eljer Plumbingware 73
B-5. Data Quality Indicator Values for THC Analyzer Measurements Made at Eljer Plumbingware 74
B-6. Comparability of Method 18 and THC Analyzer Measurements 76
C-1. THC Analyzer Results from June 22, 1993, First Period of Spraying 78
C-2. THC Analyzer Results from June 22,1993, Second Period of Spraying 79
C-3. THC Analyzer Results from June 22,1993, Third Period of Spraying 80
C-4. THC Analyzer Results from June 23,1993, First Period of Spraying 81
C-5. THC Analyzer Results from June 23,1993, Second Period of Spraying 83
C-6. THC Analyzer Results from June 23, 1993, Third Period of Spraying 84
C-7. THC Analyzer Results from June 24,1993, First Period of Spraying 85
C-8. THC Analyzer Results from June 24,1993, Second Period of Spraying 87
C-9. THC Analyzer Results from June 24,1993, Third Period of Spraying 88
D-1. Analysis of Sample from Scrubber Chamber #1,6/23/93 at 1340 hours 90
D-2. Analysis of Sample from Scrubber Chamber #2, 6/23/93 at 1340 hours 91
D-3. Analysis of Sample from Scrubber Chamber #1, 6/24/93 at 1040 hours 92
D-4. Analysis of Sample from Scrubber Chamber #2, 6/24/93 at 1040 hours 93
D-5. Analysis of Sample from Scrubber Chamber #3, 6/24/93 at 1040 hours 94
D-6. Analysis of Sample of Tap Water, 6/24/93 at 1015 hours 95
v
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ACKNOWLEDGMENTS
The authors would like to thank J. N. Eason, Plant Manager at Eljer Plumbingware in Wilson,
NC, for providing a site to carry out this evaluation and Rollie Nagel, Manager of Safety and
Environmental Health at Eljer, for his support and help during the test. The authors would also like to
thank Harold J. Rafson of QUAD Technologies, Inc. in Chicago, IL for providing the pilot scale liquid
chemical scrubber system used in these tests. Finally, the authors would like to thank EPA Task Officer
Bobby Daniel of the EPA Air and Energy Engineering Research Laboratory for his help, support, and
coordination throughout this work.
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 or 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 Multiplier Yields Nonmetric
kPa
1450.38
psig
kPa
4.0145
in. H20
°C
1.8T + 32
°F
cm
0.3937
in.
m
3.2808
ft
m2
10.7639
ft2
m3
35.3134
ft3
mmHg
0.03937
in. Hg
kg
2.2026
to
1000 kg
0.90802
ton
I
0.2643
gal.
m3/min
35.3134
ft3/min
viii
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SECTION 1
INTRODUCTION
The control of styrene is a major concern for many areas of the country. Up to the time of this
evaluation, The Control Technology Center (CTC) had received over 30 calls on the topic. One area of
styrene emissions is in the manufacture of shower stalls and bathtubs. There are approximately 200 of
these plants operating in the U.S. emitting uncontrolled styrene to the atmosphere. Until recently, no
known cost-effective technology had been demonstrated to control the emission of styrene.
After being contacted by one supplier of a styrene removal technology, the CTC attempted to
find other vendors of control technology for styrene removal. One other vendor was found and the CTC
contacted this vendor, QUAD Technologies Inc., of Chicago, IL, to propose the evaluation of their
chemical scrubber process (the QUAD Chemtact™ System) on a source of styrene emissions. This
process utilizes liquid chemical scrubbing technology to remove styrene by spraying fine droplets (a
mist) of a diluted chemical solution into a contaminated air stream as it is injected tangentially into the
top of a hollow cylindrical reaction chamber. Styrene is apparently oxidized and absorbed into the mist
of water and scrubber liquor which is continuously collected and exhausted through the chamber drain.
The treated air is then exhausted tangentially through the bottom of the reaction chamber.
The CTC initiated a proposed project to evaluate processes for controlling styrene emissions at
a representative fiberglass shower stall and bath tub manufacturing plant. Eljer Incorporated of Wilson,
North Carolina was selected as a possible site and was visited by representatives of EPA in August of
1992 and later, in October, by representatives of EPA, SRI, and QUAD. A test was planned for
November, 1992. However, due to scheduling constraints and equipment problems, this test was
canceled. Later, in 1993, the test was rescheduled for June as part of a styrene emissions evaluation.
1
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In May of 1993 a second site visit occurred and plans were finalized for the test in June. The week of
June 21, 1993 was selected for the test.
This facility was selected because at this site Eljer manufactures both fiberglass shower stalls
and bathtubs by spraying styrene-based resins onto various mold shapes in individual spray booths that
are vented to the atmosphere. During the May visit, a tentative agreement was reached to test the
Chemtact process on a representative source of styrene emissions from the shower stall/bathtub
construction process.
Vent air from the spray booths used for mold-coating that is exhausted to the atmosphere is the
major point source of emissions from the manufacture of fiberglass shower stalls and bathtubs. Thus,
the number of manufacturing steps that involve the spraying of styrene-based resins and the number of
individual spray booths in operation at a particular facility determine the level of styrene emitted to the
atmosphere.
Any fiberglass product that during its manufacture requires the spraying of styrene is a source of
organic vapors that could affect human health both directly and indirectly. The results of this evaluation
will provide information to state and local agencies for use in responding to public concerns.
2
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SECTION 2
PROJECT DESCRIPTION
2.1 EXPERIMENTAL APPROACH
Styrene is an integral part of the industrial process that produces fiberglass bath tubs and
shower stalls. In the first step of this manufacturing process, styrene is mixed with polyester resin and a
pigment to create a "gel coat" that is sprayed onto a previously prepared mold. Molds are typically
reusable and before each use the moid is waxed and coated with a mold-release agent that also helps
to provide a high gloss to the finished product. In subsequent manufacturing steps, styrene and
polyester resin are mixed with inert fillers and sprayed onto the previously coated mold along with
chopped fiberglass. Between each application the coated mold is set aside while the resin is allowed to
cure. Because curing is an exothermic process, the next manufacturing step is usually not carried out
until the coated mold has cooled. Fiberglass provides structural support for the finished article, styrene
and polyester resin act as a glue to hold the matrix together, and the inert fillers provide additional
structural support and can also serve as a fire retardant. The final step of manufacture is to separate
the finished fiberglass product from the moid and prepare the product for shipment.
The purpose of this project was to evaluate the performance of a pilot-scale liquid chemical
scrubber designed to control styrene emissions. During this evaluation, the pilot-scale control device
was configured to treat a portion of the air exhaust from a gelcoat booth at a fiberglass shower stall and
bath tub manufacturing plant operated by Eljer Plumbingware located in Wilson, North Carolina.
To measure the styrene removal efficiency of the pilot-scale liquid chemical scrubber, total
hydrocarbon (THC) analyzers equipped with flame ionization detectors (FID) were used to determine
total hydrocarbon levels at the inlet and outlet of the device on a continuous basis while charcoal-filled
sampling tubes were used to collect samples of volatile organic compounds (VOC's) at the inlet and
outlet of the device over time periods of approximately one-half hour. Styrene levels in the inlet and
outlet gas streams were quantified by subsequent chromatographic analysis (with FID detection) of the
VOC's retained in the charcoal-filled sampling tubes.
3
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2.2 ELJER PLUMBINGWARE FACILITY
The Eljer Plumbingware facility, diagrammatically shown in Figure 1, is located in Wilson, North
Carolina In this figure the location of the pilot-scale scrubber is shown along with the location of the van
used for sampling. During this evaluation, the workday started at 0700. Breaks in production occurred
at 1000 hours (15 minute morning break) and 1200 hours (30 minute lunch break). The workday ended
at 1400.
Each stage of manufacture except for mold separation or "pulling" begins in a spray booth. At
the Eljer facility the spray booths were not constructed in place but are prefabricated units manufactured
by Binks, Inc. Each spray booth is approximately 3.05 m (10 ft) high, 4.11 m (13.5) ft wide, and
approximately 3.66 m (12 ft) deep. The booths are approximately 1 m deeper but 3.66 m back from the
mouth of the booth an expanded metal grate is mounted across the width and height of the booth on
which a large sheet of air conditioning-type filter material is mounted. The filter material is usually
changed every other day.
Each spray booth is continuously vented with air from the interior of the plant that is pulled into
the booth entrance, through the air conditioning filter mat, and a five-blade fan unit mounted
approximately 2m below the roof of the building. Air pulled into the fan exits through ductwork that
reenters the side of the building and exhausts vertically through a 0.91 m (3 ft) diameter stack mounted
on the roof of the facility. Each exhaust fan has a nominal rated flow of 411 m3/min (14,500 acfm).
There are three distinct manufacturing steps that are required to produce a fiberglass shower
stall or bath tub at the Eljer facility. First, a prepared mold is mounted on a cart and wheeled into one of
the three gelcoat spray booths located in the mold repair shop. In the spray booth, the mold and cart
are designed to slide onto the arm of a permanently mounted pedestal assembly that can be
hydraulically elevated above the floor of the spray booth. The mold and cart are also designed to rotate
on the arm of the pedestal so that all parts of the mold are accessible for spraying. This mounting
system is duplicated in every spray booth at the Eljer facility.
Gel coat is a mixture of styrene monomer, polyester resin, and pigment (32.2% styrene by
analysis) and is purchased as a prepared mix in 55 gallon drums and, during this test, contained no
4
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-190 ftr
EXHAUST
FAN
t
RESIN
MIXING
ROOM
/
FILT1R MAT
SUPPORT
GEICOAT
STAGING
AREA
T
13.$ ft
SERVICE
ACCESS
!
FIBERGLASS
ROVING FEEDER
r
BACK-UP
BOOTVt tZ
A BACK-UP
T booth #1
LAY-UP
BOOTH M
X LAY-UP
Y BOOTH *6
[Si
A LAY-UP
W BOOTH I
^ LAY-UP
BOOTH #3
LAY-UP
BOOTH #2
£ LAY-UP
BOOTH •!
PUMPS
ROCF EXHAUST
VENT STACK
UNUSED
BOOTH
UNUSED
BOOTH
~
jt
MOLD SEPARATING
STATION
UNUSED
BOOTH
fSELCOAT
BOOTH «3
Sampling
Van
BOOTH »2
GELCOAT
BOOTH #1
Pilot-Scale Liquid
Chemical Scrubber
LANT
265 ft.
MOLD REPAIR SHOP
EXHAUST FANS
I I I
Figure 1. Layout of Eljer Rumbhgware Facility
5
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additive to suppress styrene vapor emissions. At the time of this test at least four colors of pigment
were observed: white, off white, pink, and blue. However, plant records only keep track of white and
colored gel coat usage.
About two to three minutes are required to coat a bath tub mold (approximately 2.5 m2) with gel
coal and five minutes are required to coat a large shower stall mold (7-8 m2) with gelcoat. When
spraying is complete, the mold is oriented upright and the pedestal is lowered until the wheeled cart
mounted to the mold contacts the floor. The mold and cart are then wheeled out of the booth to await
the next stage of manufacture. Between each stage of manufacture the coated mold is set aside to cure
and harden for about an hour. Curing generates heat so there is a time interval between sprayings to
allow the coated mold to cool.
The second stage of manufacture is called the "first lay-up" or "initial laminating" step and
occurs in two parts. In this stage, the mold is conveyed to one of the first lay-up booths and, as with the
first step of manufacture, mounted on a pedestal and prepared for spraying. The mix sprayed in this
stage is composed of a powdered inert filler added to a mixture of styrene monomer and polyester resin
to form a slurry that contains approximately 50% solids (21.4% styrene by analysis). The lay-up mix is
prepared in the resin mix room shown in Figure 1 and is pumped to the point of delivery.
Two coats of this slurry are sprayed onto the mold in this stage and during spraying, chopped
fiberglass roving (3 to 4 cm long) is also blown at about a 30° angle into the stream of spray as It exits
the spray nozzle. The spray mixes with the strands of chopped fiberglass and forms an entangled mat
of resin-impregnated fiberglass on the surface of the mold. The inert filler and the chopped fiberglass
help provide structural support to the finished product. Between sprayings, the mold is left in the booth
while from two to four workers quickly compact and flatten or "roll" the matted surface of the mold with
small, hand held rollers. After the second spraying, the mold is wheeled from the booth and rolled again.
The total time for both sprayings usually takes two to three minutes and rolling can take another one to
two minutes. However, because one person is used to operate the sprayer in the three lay-up booths,
the time between sprayings averages from seven to ten minutes while other molds are being sprayed in
the other lay-up booths. As with the first stage of manufacture, this step is brief and requires only three
6
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to five minutes to complete. When this step is completed the coated mold Is once again set aside to
cure.
The third, and final, spraying step is called the "second lay-up" or "back up" step and takes
place in one of the two second lay-up booths shown in the upper left comer of Figure 1 (Back-Up Booth
#1 or Back-Up Booth #2). In this step, a blend of powdered inert filler (incorporating a fire retardant) is
added to a mixture of styrene monomer and polyester resin to form a sluny that contains approximately
50% solids (20.9% styrene by analysis). As with the lay-up mix, the back-up mix is prepared in the resin
mix room shown in Figure 1 and is pumped to the point of delivery.
This back-up mixture is also sprayed with chopped fiberglass fibers and forms the final two
layers of the mold. As with the second stage of manufacture, the mold is first moved into the back-up
booth where a fresh layer of the back-up slurry/chopped fiberglass mix is sprayed onto the mold. The
mold is then moved out in front of the booth where precut chipboard and corrugated paper supports are
pressed and molded into the wet slurry/fiberglass layer on the sides and bottom of the mold. The mold
is then moved back Into the booth for a final spraying that covers all of the chipboard and heavy
corrugated paper supports. After the mold emerges from the back-up booth for the second time it is
manually rolled and set aside to cure for the last time.
The final stage of manufacture is "pulling" or separation of the mold from the completed shower
stall or bath tub. After the finished fiberglass piece is trimmed and inspected, it is prepared for
shipment.
2.3 THE LIQUID CHEMICAL SCRUBBING PROCESS
The liquid chemical scrubbing process that was the subject of this evaluation was originally
developed for odor control.1 Subsequent to this development, it was determined by the manufacturer
that a system of this type could be used to control VOC emissions. The following description of the
liquid chemical scrubbing process is taken from general information supplied by the manufacturer on the
operation of the liquid chemical scrubbing process. No specific information was provided that described
how a full-scale version of this system operates or how a full-scale system differs from the pilot-scale
7
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This technology takes advantage of a patented absorption technique based on the mass
transfer equation that provides enhanced chemical reactivity with an atomized mist. The manufacturer
asserts that mist provides a large surface area where gas-liquid phase reactions take place that result in
the elimination of gaseous contaminants.
Figure 2 shows a schematic diagram of a vertically-configured liquid chemical scrubbing device
that incorporates all of the equipment necessary to operate as a stand-alone unit. Because of design
considerations, the components of a full-scale unit would probably be arranged in a horizontal
configuration. The major components of such a system are an air compressor, a continuous monitor for
pH control of the scrubber liquor, a water softening unit, scrubber chemicals with chemical metering
pumps, the scrubber reaction chamber with its associated spray nozzle, the exhaust fan, and the outlet
stack. This is a once-through process. Thus, spent scrubber liquids are disposed of and are not
regenerated. Literature supplied by the manufacturer does not indicate if the liquid effluents generated
by this process require special handling for their disposal.
Styrene Is removed by spraying fine droplets of a diluted chemical solution into a contaminated
air stream as it passes through a hollow, cylindrical reaction chamber. Spray nozzles are situated within
the chamber so that a fog of chemical-containing droplets mixes with the incoming contaminated air and
flows in the same direction toward the outlet. The mixing process in the chamber is enhanced by the
tangential inlet that forces a swirling motion within the chamber. As the mixture travels through the
reaction chamber, the chemical-containing droplets solubilize or absorb and react with VOC's in the
contaminated air stream. Treated air is exhausted tangentially from the bottom of the chamber. It then
proceeds to another chamber (not shown in Figure 2) or to the exhaust stack. After solubilization or
reaction has taken place, unevaporated droplets that are large enough to be captured on the sides of the
reaction chamber collect at the drain opening in the floor of the chamber and are discharged. A pH
sensor located in the drain piping is used as a control input to maintain the pH of the liquid effluent's at a
preset value. In a large unit suction pressure is usually maintained at 0.25 kPa (1 in. H2O). These units
are constructed from PVC or fiberglass.
8
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CONTROLS
INLET
WATER
SUPPLY
LIQUID
METERING
PANEL
metering
CONTROLS
—SOFTENED WATER
SOFT
WATER
WATER
SOFTENER
STORAGE
J
£
a n
CHEMICAL
CRUM
CfCMCAL
DRUM
&
INLET
NOZZLE
REACTION
CHAMBER
EXHAUST
Figure 2. Diagrammatic representation of the liquid chemical scrubbing process.
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2.3.1 Pilot-Scale Liquid Chemical Scrubbing Device
A diagram of the pilot unit is shown in Figure 3. In this figure, styrene-laden air enters at the top
right, and successively passes through each of the three reaction chambers. The chambers and all
interconnecting tubing are constructed of PVC plastic. The reaction chambers are nominally 1.07 m (3.5
ft) in diameter and 1.83 m (6 ft) high. Interconnecting PVC piping has a nominal inside diameter of 8.9
cm (3.5 in.). In each reaction chamber, contaminated air enters tangentially at the top of the chamber
and mixes with a mist of the scrubbing liquor that is sprayed from three titanium spray nozzles within the
chamber. The tangential inlet forces air and mist to swirl together while B transits the chamber. The air
and mist exit through a similar tangential outlet at the bottom of the chamber and flow through two 90°
bends before entering at the top of the next reaction chamber. Each reaction chamber has a bottom
drain that, for this test, was exhausted into a plastic bucket. At the exit of the last reaction chamber the
mist and air stream pass through a 90° bend upward to an exhaust fan that is vented to the atmosphere.
The atomizing nozzles are designed to operate at choked flow (sonic velocity) when supplied
with compressed air at a pressure of 413.7 kPa (60 pslg). As Figure 3 shows, the pilot unit was
equipped with three identical reaction chambers (in series) that have tangential top inlets and tangential
outlets at three vertical elevations. Only the bottom outlets were used during this test. Also shown in
Figure 3 are the locations used to obtain inlet and outlet gas samples as well as the location of the
pressure taps used to measure system pressure drop.
Each reaction chamber was fed by a separate chemical metering pump so that a contaminated
air stream could be treated with up to three different chemical solutions as it passed through the device.
Separate five gallon plastic buckets were used to mix and hold the chemical solutions that were supplied
to each metering pump.
The manufacturer states that most of the fine droplets collect at the drain opening cast into the
floor of each reaction chamber where the collected liquid is exhausted. Thus, there should be little liquid
carryover. This was observed to be the case during testing.
10
-------
OUTLET
Sampling Point for
Outlet Emissions and
AP measurement
UQUtO 2
UQUID3
UQUtO 1
AIR
B <¦
NOZZLES
S3
to
NOZZLES
INLET
NOZZLES
FAN SPEED
CONTROLS
C«M:CA.
METERING
PUMPS
REACTION
CHAMBER #3
REACTION
CHAMBER #2
REACTION
CHAMBER #1
ouQ
DRAIN
DRAIN
(a) SIDE VIEW
REACTION REACTION REACTION
CHAMBER #3 CHAMBER #2 CHAMBER #1
O NOZZLES
O NOZZLES
fan
LIQUID »3
PUMP
FAN S«EB
CONTROLS
Sampling Point for
inlet Emissions and
AP measurement
OUTLET
(b) TOP VIEW
Figure 3. Diagram of the pilot-scale Squid chemical scrubber tested at Bjer Plumbingware.
11
-------
2.3.2 Specific Test Conditions
Throughout this evaluation the pilot unit was operated at a slight negative pressure , from 0.8 to
0.9 kPa (3.2 to 3.6 in. H2O} at a nominal flow rate of 2.0 m3/min (70 acfm). Laundry bleach (NaCIO),
hydrogen peroxide (H2O2), sulfuric acid (H2SO4), and ethylene glycol (antifreeze) along with a variety of
surfactants were evaluated for styrene removal.
Table 1 presents the overall conditions encountered for the three days of testing. Tables 2
through 4 delineate the specific test conditions, scrubber additives, and flows used in each reaction
chamber of the liquid chemical scrubber for each day of testing, June 22 through June 24,1993. Entries
in Tables 2 though 4 are listed in chronological order, starting with the first mold that was sprayed while
the liquid chemical scrubber was operational through to the end of the day of testing. As can be seen
from an inspection of these tables, a number of test conditions were tried. This was because styrene
removal efficiency across the liquid chemical scrubber was never very great, which led to the trial of a
variety of scrubber additives, and because it was easy to change from one scrubber additive to another
for a particular reaction chamber.
It is difficult to comment on the choice of scrubber additives and surfactants used by the
scrubber manufacturer, particularly because the manufacturer has not provided any information as to
why the additives and surfactants that were used were chosen for testing. Given the relatively poor
performance that was observed, the matter was not pursued.
Table 1. Daily Test Conditions
Oate
Time
Inlet Air Temp.
Rel. Humidity
Bar. Pressure
System AP
Air Flow Rate
(°C)
(%>
(kPa)
(kPa)
(m3/min)
June 22
0810
26.7
82
101.1
0.80
2.01
June 23
0734
21.1
72
101.4
0.80
1.86
1345
37.8
42
102.2
0.80
1.88
June 24
0719
22.2
80
102.2
0.87
1.97
1217
37.8
40
102.9
0.90
1.64
12
-------
Table 2. Summary of Test Conditions for June 22,1993
Scrubber
Addition Rate
Scrubber
Addition Rite
Scrubber
Addition Rate
Test
Mold
Start
End
Reaction
Additive
Water
Reaction
Additive
Water
Reaction
Additive
Water
Cond.
#
Time
Time
Chamber #1
flph)
flph)
Chamber #2
flph)
-------
Table 3. Summary of Test Conditions for June 23,1993
Scrubber
Addition Rate
Scrubber
Addition Rate
Scrubber
Addition Rate
Test
Mold
Start
End
Ruction
Additive
Water
Reaction
Additive
Water
Reaction
Additive
Water
Cond.
#
Tim*
Tim#
Chamber #1
(W
(Iph)
Chamber #2
m
ft*)
Chamber #3
(iph)
(W
1
1
0712
0718
H20
0.00
34.07
H2O
0.00
34.07
HjOOnly
0.00
34.07
2
2
0734
0737
H2S04 (2%)
1.50
34.07
H2SO4 (2%)
2.56
34.07
H20 Onty
0.00
34.07
3
0742
0747
H2S04 (2%)
1.50
34.07
H2S04 (2%)
2.56
34.07
H20 Only
0.00
34.07
3
4
0750
0757
H2S04 (2%)
1.50
34.07
NaCIO (5.25%)
2.56
34.07
H20 Only
000
34.07
5
0759
0808
HjS04 (2%)
1.50
34.07
NaCIO (5.25%)
2.56
34.07
HjO Only
0.00
34.07
4
6
0814
0823
H2SO< (2%)
0.90
34.07
NaCIO (5.25%) ~
H2SO4 (2%)
to Raach pH >7
1.70
34.07
HjOOnly
0.00
34.07
7
0825
0829
H2S04 (2*)
0.90
34.07
NaCIO (5.25%) ~
H2SO4 (2%)
to Reach pH =7
1.70
34.07
HjO Only
0.00
34.07
8
0834
0840
H2SO4 (2%)
0.90
34.07
NaCIO (5.25%) ~
1.70
34 07
H20 Only
0.00
34.07
H2SO4 (2%)
to Reach pH =7
5
9
0845
0854
NaCIO (5.25%) ~
H2S04 (2%)
to Reach pH *7,
Surfactant "B"
0.90
34.07
NaCIO (5.25%) ~
H2S04 (2%)
to Reach pH «7,
Surfactant "B"
1.70
34.07
H20 Only
0.00
34.07
10
0910
0917
NaCIO (5.25%) +
H2SO4 (2%)
to Reach pH =7,
Surfactant "8"
0.90
34.07
NaCIO (5 25%) ~
H2SO4 (2%)
to Reach pH =7,
Surfactant "B"
1.70
34.07
H20 Only
0.00
34.07
11
0917
0923
NaCIO (5.25%) ~
H2SO4 (2%)
to Reach pH =7,
Surfactant "B"
0.90
34.07
NaCIO (5 25%) ~
HzS04 (2%)
to Reach pH »7,
Surfactant "B"
1.70
34.07
HjOOnty
0.00
34.07
12
0939
0946
NaCIO (5 25%) +
H2S04 (2%)
to Reach pH =7,
Surfactant "B"
090
34.07
NaCIO (5 25%) ~
H2SO4 (2%)
to Reach pH =7,
Surfactant "B"
1.70
34.07
HjOOnly
0.00
34.07
6
13
0948
0955
H2SO4 (2%).
Surfactant "A"
090
3407
H2SO, (2%),
Surfactant "A"
1.70
34.07
H20 Only
0.00
34.07
7
14
1031
1036
H2SO4 (2%),
Surfactant "E"
0.90
34.07
H2S04 (2%),
Surfactant "E"
1.70
34.07
H20 Only
1.89
34.07
8
15
1039
1048
H2SO4 (2%),
Surfactant "E"
0.90
34.07
H2SO« (2%),
Surfactant "E"
1.70
34.07
Surfactant "F"
180
34.07
16
1049
1057
H2SO4 (2%),
Surfactant "E"
0.90
34.07
H2SO4 (2%).
Surfactant "E"
1.70
34 07
Surfactant "P
1.89
34.07
9
17
1101
1105
H2SO4 (2%),
Surfactant "E"
0.90
34.07
HjSO* (2%),
Surfactant "E"
1.70
34.07
Surfactant "D"
1.89
34.07
18
1112
1120
H2SO« (2%).
Surfactant "E"
0.90
34.07
H2S04 (2%),
Surfactant "E"
1.70
34.07
Surfactant "D"
1 89
34.07
10
19
1124
1137
H2SO4 (2%)
0.90
34.07
H2SO4 (2%)
1.70
34.07
H2SO4 (2%)
1.89
34.07
20
1144
1154
H2SO4 (2%)
0.90
34.07
H2SO4 (2%)
1.70
34.07
H2S04 (2%)
1.89
34.07
21
1157
12:03
H2SO4 (2%)
0.90
34.07
HJS04 (2%)
1.70
34.07
H2SO4 (2%)
1.69
34.07
11
22
1242
1254
NaCIO (5.25%),
Surfactant "E"
0.90
34.07
NaCIO (5.25%),
Surfactant "E"
1.70
34.07
H20 Only
0.00
34.07
12
23
1259
1306
NaCIO (5.25%),
Cold Da. Water
0.90
34.07
NaCIO (5.25%),
Coid Oil Water
1.70
34.07
HjOOnly
0.00
34.07
24
1308
1313
NaCIO (5.25%),
Cotd Dil. Water
0.90
34 07
NaCIO (5 25%),
Cold CM. Water
1.70
34.07
H2OOn»y
0.00
34.07
25
1317
1322
NaCIO (5.25%),
Cotd DH. Water
0.90
34.07
NaCIO (5.25%),
Coid DH. Water
1.70
34.07
H20 Only
0.00
34 07
13
26
1324
1327
H2SO4 (2%),
Surfactant "E"
0.60
34.07
NaCIO (5.25%)
2.56
34.07
H2O Only
0.00
34.07
27
1332
1337
H2SO4 (2%),
Surfactant "E"
0.60
34.07
NaCIO (5.25%)
256
34.07
HjOOnly
0.00
34.07
28
1340
1344
H2S04 (2%),
Surfactant "E"
0.60
34.07
NaCIO (5.25%)
256
34.07
HjO Only
0.00
34.07
29
1352
1356
H2SO4 (2%),
Surfactant "E"
0.60
34.07
NaCIO (5.25%)
2.56
34.07
H20 Only
000
34.07
30
1357
1403
H2SO« (2%),
Surfactant "E"
0.60
34.07
NaCIO (5 25%)
2.56
34.07
HjOOnly
0.00
34.07
14
-------
Table 4. Summary of Test Conditions for June 24,1993
Scrubber
Addition Rate
Scrubber
Addition Rate
Scrubber
Addition Rate
Test
Mold
Start
End
Reaction
Additive
Water
Reaction
Additive
Water
Reaction
Additive
Water
Cond
#
Time
Time
Chamber #1
(Iph)
(Iph)
Chamber #2
(Iph)
(Iph)
Chamber #3
(Iph)
(Iph)
1
1
0742
0748
H202 (3%)
106
34.07
H2O2 (3%)
1.26
34.07
HiCb (3%)
1.14
34.07
2
0754
0801
H2O2 (3%)
1.06
34.07
H2Oj (3%)
1.28
34.07
HzOj (3%)
1.14
34.07
2
3
0805
0809
Dilute MEKP
1.0C
34.07
Water
0.00
34 07
Water
0.00
34.07
4
0813
08108
Dilute MEKP
1.06
34.07
Water
0.00
34.07
Water
0.00
34.07
5
0822
08208
Dilute MEKP
1.06
34.07
Water
0.00
34.07
Water
0.00
34.07
3
6
0837
0842
H2S04 (2%),
Surfactant "E"
1.05
34.07
H202 (3%)
1.70
34.07
H2O2 (3%)
1.32
34.07
7
0847
0853
HaSCX, (2%),
Surfactant "E"
1.05
34.07
HjOj(3%>
1.70
34.07
H2O2 (3%)
1.32
34.07
e
0857
0903
H2SO4 (2%),
Surfactant "E"
1.05
34.07
H202<3%)
1.70
34.07
H2O2 (3%)
132
34.07
9
0905
0911
HjSO< (2%),
Surfactant "E"
1.05
34.07
H2O2 (3%)
1.70
34.07
HjOj<3%)
1.32
34.07
10
0912
0920
H2SO< (2%),
Surfactant "E"
1.05
34.07
HjO: (3%)
1.70
34.07
HjOjO*)
1.32
34.07
11
0932
0937
H2S04 (2%),
Surfactant "E"
1.05
34.07
Hj02 (3%)
1.70
34.07
HzOj (3%)
1.32
34.07
12
0940
0948
H2SO4 (2%),
Surfactant "E"
1.05
34.07
H202 (3%)
1.70
34.07
H202 (3%)
1.32
34.07
13
0953
1000
H2SO4 (2%),
Surfactant "E"
1.05
34.07
H202 (3%)
1.70
34.07
Hj02 (3%)
1.32
34.07
14
1034
1039
H2S04 (2%).
Surfactant "E"
1.05
34.07
H2O2 (3%)
1.70
34.07
H202<3%)
1.32
34 07
15
1044
1053
H2SO< (2%),
Surfactant "E"
1.05
34.07
H202 (3%)
1.70
34.07
HzOj (3%)
1.32
34.07
16
1054
1101
H2S04 (2%),
Surfactant "E"
1.05
34.07
H202 (3%)
1.70
34.07
H202 (3%)
1.32
34.07
17
1106
1112
H2S04 (2%),
Surfactant "E"
1.05
34.07
h2o2 (3%;
1.70
34.07
H2O2 (3%)
1.32
34.07
18
1118
1124
H2S04 (2%),
Surfactant "E"
1.05
34.07
H202 (3%)
1.70
34.07
H202 (3%)
1.32
34.07
19
1128
1134
H2S04 (2%),
Surfactant "E"
1.05
34.07
H202{3%)
1.70
34.07
HzOj (3%)
1.32
34.07
20
1138
1141
HjS04 (2%).
Surfactant "E"
1.05
34.07
H202 (3%)
1.70
34.07
H202 (3%)
1.32
34.07
21-
1146
1153
H2S04 (2%),
Surfactant "E"
1.05
34.07
H202 (3%)
1.70
34.07
Hz02 (3%)
1 32
34.07
22
1156
1206
H2S04 (2%).
Surfactant "E"
1.05
34.07
H202 (3%)
1.70
34.07
H202<3%)
1.32
34.07
23
1244
1247
H2SO4 (2%).
Surfactant *E"
1.05
34.07
H2Oj (3%)
1.70
34.07
H2O2 (3%)
1.32
34.07
24
1252
1257
HzSCU (2%).
Surfactant "E"
1.05
34.07
Hj02 (3%)
1.70
34.07
(3%)
1.32
34.07
25
1333
1338
H2SO4 (2%),
Surfactant "E"
1.05
34.07
H20j(3%)
1.70
34.07
HzOj (3%)
1.32
34.07
26
1339
1344
H2S04 (2%),
Surfactant "E"
1 05
34.07
HjOjP*)
1.70
34.07
H2O2 (3%)
1.32
34.07
27
1346
1350
H2SO4 (2%).
Surfactant "E"
1.05
34.07
H202 (3%)
1.70
34.07
H202(3%)
1.32
34.07
28
1352
1353
HzSO, (2%),
Surfactant "E"
1.05
34.07
HjOj (3%)
1.70
34.07
H202(3%)
1.32
34.07
15
-------
2.4 EXPERIMENTAL APPARATUS
2 4.1 Connection to the Pilot-Scale Liquid Chemical Scrubber
The pilot-scale device was situated as close as possible to the outlet of Gel Coat booth #2
located on the roof of the facility. A 15.24 cm (6 in.) diameter flexible aluminum sampling line was used
to convey a sample of air exiting the spray booth. This line was approximately 17.1 m (56 ft) long. This
sampling line was not heat-traced because local ambient temperatures averaged near 38°C (100°F)
during most of the testing. At the exit of the last reaction chamber but before the exhaust fan a tee was
connected to the nominal 10.2 cm (4 in.) diameter PVC exhaust line to obtain outlet air samples.
Because saturated air and some mist exited the last reaction chamber, the outlet sample line contained
a liquid drop out section that was drained as needed. Figure 4 shows how the pilot unit and the van
containing the sampling equipment were situated.
At the pilot unit inlet and outlet single 9.53mm (0.375 in.) diameter heated Teflon® sample lines
were used to carry gas samples to the sample van for analysis. The inlet sample line was about 2.13 m
(7 ft) long. The outlet sample line was approximately 3.66 m (12 ft) long with the condensate trap placed
midway in the line at its lowest point.
The EPA Quality Assurance Handbook applicable to Method 18 sampling indicates that it is
proper to maintain sampling lines above the local ambient temperature if the compound being sampled
could condense within the sample lines.® Thus, to avoid the possibility of styrene loss and to minimize
condensation of water from the saturated air in the outlet sampling line, the sample lines were heated to
at least 11°C (20°F) above the local ambient temperature. Because the local afternoon temperature
averaged near 38°C (100°F) during the test, all sample lines were kept at 49°C (120°F)-
2.4.2 Sampling Van
Figures 5 and 6 show how the gas sampling equipment was connected within the van used to
house the sampling equipment. Two equivalent systems were constructed so that concurrent samples
could be obtained at the inlet and the outlet of the liquid chemical scrubber. Thus, the description that
follows applies to either system.
16
-------
ROOF OF ELJER FACILITY
OOWbT®
FACILITY
VENTILATION
FANS
OL18RATDN
AND PUB. GAS
GELCOAT
BOOTH #3
EXHAUST
chapt
RECORDER
THC
ANALYZERS
SAMPLE
PUMPS
OUTLET
w I \
^-7^^0 s. / o / 0 r"
\o O J \ 0 o /\ o o J
p
PUOT-SCALE SCRUBBER
GELCOAT
BOOTH #2
EXHAUST
GELCOAT
BOOTH #1
EXHAUST
Figure 4. O/eraP arrangement for sampling at the Eljer Plumbingware Faclity
17
-------
TO HEATED
SAMPLING LINE
i-5.
TO EPA METHOD 18
(NiOSH METHOD 1501)
SAMPLING APPARATUS
(Used for Other Sampling)
OUTPUT TO DAS AND
CHART RECORDER
J.U.M. VE-7
THC Analyzer
EXHAUST
H2/He
FUEL
GAS
n2
PURGE
GAS
TO OTHER THC ANALYZER
(X)
ZERO
AIR
<8>
2 2
ppm
39
ppm
jar
171
ppm
STYRENE CALIBRATION GAS
TO OTHER THC
ANALYZER
Figure 5. Equipment Arrangement Used for Sampling with THC Analyzers
18
-------
INLET OR OUTLET
HEATED SAMPLING LINE
- TO THC ANALYZER
DRYING TUBE. ONLY
FOR OUTLET RUNS
CHARCOAL TUBE
EXHAUST
SAMPLING
PUMP
J
VOST TRAIN SAMPLER
PUMP BOX
Figure 6. Equipment arrangement used for EPA Method 18 sampling.
19
-------
Shortly after each 9.53mm diameter sample line entered the sampling van it was divided into
two 6.35 mm (0.25 in.) diameter sample lines less than 10 cm in length. The smaller sampling lines
were not heat traced. One line was connected to a J.U.M. Instruments VE-7 THC analyzer and the
other line was connected to a Swagelock™ "Tee" connector with a shut off-valve from which samples of
gas could be withdrawn into charcoal-filled adsorption tubes (EPA Method 18, Section 7.4 or NIOSH
Method 1501). Outlet charcoal tube samples were preceded by an anhydrous sodium sulfate-filled
drying tube to remove water vapor. Sample flow was maintained at 3 1/m by the THC analyzer. When
EPA Method 18 samples were taken this flow was increased by 0.2 l/m at the inlet and 0.5 l/m at the
outlet. With the short sample lines this flow rate was more than sufficient to assure that residence times
in the sample lines were low (between 2 and 3 seconds for the longest sample line).
Figure 5 shows the calibration gas system used for the THC analyzers. Three mixtures of
styrene in nitrogen were used for calibration (171 ppm, 39 ppm, and 2.2 ppm), in addition to zero air
(less than 0.1 ppm THC). The bottles of calibration gas were interconnected with positive shut-off valves
to a common manifold that was itself connected to the span gas port on both THC analyzers. This
system allowed both THC analyzers to be calibrated from the same calibration gases.
It should be noted that after all testing had been completed, concentrations of the styrene gases
used for calibration standards during testing (from the vendor that supplied the gases, Matheson Gas
Products, Inc.) were found to be in substantial error. The values quoted above were determined
separately as part of a process that established that the vendor-supplied calibrations were in error.
Appendix B, the Quality Control Evaluation Report for this work, details this process and the method
used to correct the field THC data.
The 0 -10 V output signal from each THC analyzer was fed to one channel of a two-channel
chart recorder. The output signal from each THC analyzer was also recorded on 1.44 Mb floppy disks
with a dedicated PC-based datalogger. Output from each THC analyzer was logged once every second.
The software used to log the data (Quicklog PC™) was configured to display the last 50 minutes of data
20
-------
(last 3000 data values) from both channels on the PC monitor. Output from the inlet THC analyzer was
displayed on a 0 to 1000 ppm scale and output from the outlet THC analyzer was displayed on a 0 to
100 ppm scale.
Previously it had been determined that virtually all (99%) of the organic material exhausted from
the gelcoat spray booths was styrene monomer.' In this case, as for previous testing at this facility, the
primary intent of these measurements was to establish time-averaged levels of styrene at the inlet and
outlet of the pilot-scale styrene control device to determine the styrene removal efficiency. As with
previous measurements, EPA Method 18 (adsorption tube procedure, equivalent to NIOSH Method
1501) was followed in obtaining these samples (see Appendix A).'
Figure 6 shows the equipment arrangement used for the EPA Method 18 sampling. The same
basic arrangement was used to obtain Inlet and outlet samples except that at the outlet each adsorption
tube was preceded by a drying tube that contained anhydrous sodium sulfate. It was necessary to
provide dry, or relatively dry, air to the charcoal adsorption tubes used in this test because the
adsorption efficiency of styrene (on charcoal) drops off sharply as absolute humidity increases (see
Appendix A). Anhydrous sodium sulfate is widely used for this type of sampling and does not collect
styrene. The samples were obtained with a single volatile organic sampling train (VOST) sampling
pump connected to a manifold that, in turn, was connected to a standard small charcoal-filled tube.
Flow was set before each measurement to approximately 0.2 l/m for inlet samples and 0.5 l/m for outlet
samples.
2.5 EXPERIMENTAL METHODS AND PROCEDURES
2.5.1 Total Hydrocarbon Analyzers
J.U.M. Instruments Model VE-7 total hydrocarbon (THC) analyzers equipped with flame
ionization detectors (FID) were used to obtain a continuous measurement of the total hydrocarbon
content in air that entered (air exhaust from gelcoat booth #2) and exited ihe pilot-scale liquid chemical
scrubber. This analyzer extracts approximately 3 l/m of sample with an internal sample pump
21
-------
and sends from 17 to 20 cm3/m of thai sample to an onboard FID. The FID's in these instruments were
set up to use a 60% helium- 40% hydrogen (helifuel) mixture as a fuel. Two of these THC analyzers
were used for the duration of testing. These instruments were inspected and were zeroed and
calibrated with THC-free air and the styrene span gases respectively before testing.
The JUM VE-7 provides five decade output ranges that can be manually selected from 0-10
ppm to 0-100,000 ppm. A 0-10V signal is output at the rear of the instrument that corresponds to the
decade range selected. The instrument used to sample air from the inlet of the liquid chemical scrubber
was set to measure in the 0-1000 ppm range and the instrument used to monitor air exhausted from the
device was set to measure in the 0-100 ppm range. As indicated above, the output from each of these
instruments was recorded on a two-channel chart recorder and also logged on a dedicated PC-based
data acquisition system.
These instruments are normally calibrated with propane. However, for this test they were
calibrated with three mixtures of styrene in nitrogen (171 ppm, 39 ppm, and 2.2 ppm) in addition to zero
air (less than 0.1 ppm hydrocarbons). When the instruments were zeroed on zero air, Instrument
response was linear with the three calibration gases.
The instruments were calibrated and operated according to the manufacturer's instruction
manual. Calibration and zero gas connections on the back panel of the instrument were not used, rather
calibration and zero gas were routed to the sample gas input (common field practice), and calibration
and zero gas pressures were maintained at sample gas input pressure levels. Fuel gas (helifuel)
pressure was maintained at 1.5 bar (21 psig). Internal instrument sample pressure was maintained at
200 mbar (3 psig). Full calibrations (all span gases, zero gas) were performed on both THC analyzers
at the beginning and middle of each day and instrument calibration was checked at the end of each day
of testing.
2.5.2 Collection of EPA Method 18 Samples
The Adsorption Tube Procedure defined in Section 7.4 of EPA Method 18 (equivalent to NIOSH
Method 1501) was followed to obtain samples of VOCs from air that entered the liquid chemical
scrubber (air exhaust from gelcoat booth #2), air that exited the device, and from the low and midrange
22
-------
styrene calibration standards. EPA Method 18 (Adsorption Tube Procedure) specifies that an applicable
NIOSH Method be followed for the analysis of such samples. A copy of the proper NIOSH procedure
(NIOSH Method 1501) is included in Appendix A.
As shown in Figure 6, the heated inlet and outlet sampling lines were divided after reaching the
van housing the sampling equipment. One side was directed to a THC analyzer and the other side to a
VOST sample pump through a stainless steel fitting where VOC samples were taken. Flow through the
VOST pump was set at 0.2 I /m for Inlet samples and at 0.5 l/m for outlet samples. Thus, total sample
flow was 3.2 I /m at the inlet and 3.5 I /m at the outlet. A higher sample flow was used at the outlet to be
sure that sufficient styrene would be captured in the adsorption tube for proper analysis. Sample times
ranged from 19 to 32 minutes and were governed by process stability. Originally It was planned to take
many more samples than were obtained. However, this was prevented due to difficulties encountered in
the operation of the pilot-scale liquid chemical scrubber and the large number of short-duration test
conditions.
Because air at ihe outlet of the pilot-scale device was saturated with water, provision had to be
made to remove water from air samples before the air reached the charcoal-filled adsorption tubes (SKC
Model 226-01 coconut charcoal-filled tube, NIOSH approved, Lot 120). This is because the styrene
collection efficiency of the coconut charcoal in the adsorption tubes is severely degraded by the
presence of water vapor under conditions of high humidity (see Appendix A). Therefore, the charcoal-
filled adsorption tubes were preceded by standard drying tubes filled with 9 grams of anhydrous sodium
sulfate (SKC Catalog No. 226-44-02). Anhydrous sodium sulfate does not adsorb or react with styrene
vapor. Large-capacity tubes were used to insure that all of the water in the incoming air stream would
be removed and because the other size available (250 mg) did not provide a sufficient margin of safety
for water vapor removal. One of the large-capacity tubes can remove all of the water from
approximately 2001 of 35°C (95°F) saturated air. In this sampling effort these drying tubes were used
once and then discarded. Sample volume never exceeded 161.
Samples of the styrene calibration gases were taken directly from the gas cylinders. For these
samples, flow was measured with a Buck Model M-5 primary gas flow standard bubble flow meter.
23
-------
Sample volumes and total styrene loadings were kept within the ranges established by EPA Method 18
and NIOSH Method 1501 (see Appendix A).
To prevent contamination, all sample tubes are made of glass and are designed so that a small
glass seal on either end of the tube must be broken off before a gas sample can be pulled through the
tube. Samples were taken over time periods ranging from 19 to 32 minutes. When sampling ended
each tube was sealed with a plastic cap prowled by the manufacturer. Previous experience at SRI has
shown that when styrene is sampled, these tubes do not require refrigeration to preserve the sample
prior to analysis. Thus, the tubes were kept at room temperature until their contents were extracted for
analysis. Previous experience at SRI has also shown that these tubes can await extraction for up to
three weeks with no noticeable degradation in sample recovery and that such samples do not require
refrigeration while analysis is pending. However, all of the charcoal sample tubes taken for this study
were analyzed well within three weeks after they were obtained.
The charcoal-filled sample tubes from this evaluation were returned to SRI's laboratories in
Birmingham, Alabama for analysis. Analysis consisted of desorption of VOC's adsorbed on the charcoal
with carbon disulfide (according to the EPA Method 18 mandated NIOSH procedure that is proper for
styrene detection, NIOSH Method 1501, reproduced in Appendix A) followed by injection into a gas
chromatograph (GC) coupled to an FID. In addition, styrene standards were used to spike randomly
selected charcoal-filled tubes and these samples were analyzed to determine a desorption efficiency
specific to this lot of charcoal-filled tubes (in this case, 90.25%). From this analysis, styrene present in
the samples was quantified. Knowledge of the amount of styrene present, the sample time, and the
sample gas flow rate allowed the determination of a time averaged value for the styrene present at the
inlet and outlet of the control device that could be compared with data from the THC analyzers.
2.5.3 Collection of Scrubber Liquid Samples
Samples of spent scrubber liquid were obtained from the first two reaction chambers on June 23
(at 1340) and from all three reaction chambers on June 24 (at 1040). On June 23, only water was
injected in the third reaction chamber so no liquid sample was taken. In addition, a sample of the lap
(process) water used to dilute the chemicals used for scrubbing was obtained on June 24 (at 1015). All
24
-------
liquid samples were preserved in 250 ml glass sample bottles with Teflon-sealed caps. The samples
were kept at room temperature, away from light.
The liquid samples were brought back to SRI's Birmingham, Alabama laboratories where,
according to the standard operating procedure for water samples, they were refrigerated until they could
be analyzed (refrigeration was not required in the field). Each Hquid sample was diluted and subjected to
chromatographic analysis for the presence of volatile and semivolatile organic compounds. The results
of these analyses are shown in Appendix D. Some of these analyses were complicated by surfactants
(intended to improve droplet dispersion) that were present in the scrubber liquid samples. During
analysis these surfactants tended to produce copious amounts of foam.
2.5.4 Total Flow Rate Measurements
It was planned to make daily measurements of the total flow rate into the pilot-scale liquid
chemical scrubber with a standard pitot tube according to EPA Method 1 A. However, the flow rate into
this device was determined to be much lower than was expected, too low to measure accurately with a
standard pitot. Thus, on June 22, after it was determined that the standard pitot would not be useable,
arrangements were made to obtain a thermal anemometer that had been calibrated in a wind tunnel at
SRI's laboratories in Birmingham, Alabama. On the morning of June 24 measurements were made near
the inlet of the liquid chemical scrubber at the end of a long section of straight ducting (2.5 to 3 m in
length). The inside diameter of the flexible aluminum ducting was measured and found to be 14.6 cm
(5 75 in.) which corresponds to an area of 167.5 cm2 (0.180 ft2).
To measure air velocity, two four-point, equal-area traverses were made at points spaced 90°
apart across the duct diameter. The air velocity measurement was then converted to a volumetric flow
measurement. The result of this measurement (a flow rate of 1.97 m3/min) is shown in Table 1. From
this measurement, and knowledge of the exact trans# time of styrene-laden air through the liquid
chemical scrubber (from inspection of the THC analyzer output recorded at the inlet and outlet of the
pilot-scale scrubber), it was possible to accurately determine the total air flow rate into the pilot-scale
scrubber during each period of testing. More information on these measurements is presented in
Section 3.4 of this report.
-------
SECTION 3
DATA, RESULTS, AND DISCUSSION
3.1 TOTAL HYDROCARBON ANALYZER DATA
The THC's were operated continuously through the three days of testing. No operational
problems were encountered with the THC monitors other than an infrequent flame-out of one of the
FID's and occasional losses of power due to circuit breaker overload or accidental disconnection of
power by plant personnel. Because these periods were short and because the instruments were
monitored closely, no significant data were lost.
3.1.1 Inlet Data
VOC emissions from the spraying process can be characterized as being quite variable. At the
inlet of the pilot-scale liquid chemical scrubber instantaneous hydrocarbon emissions (essentially 100%
styrene) ranged from as low as 50 ppm to as high as 250 ppm during spraying in the gelcoat booth.
While molds were being removed from the spray booth or installed in the spray booth hydrocarbon
emission levels ranged from 12 to 25 ppm. During midday lunch breaks in the production process,
hydrocarbon levels decreased to approximately 5 ppm.
Figures 7 through 15 show output from the inlet THC analyzer that was recorded on the
datalogger for the three days of testing, June 22 through 24,1993. THC data taken during periods of
calibration are not shown. For comparison purposes, data from the outlet THC analyzer are also shown
on these figures. Outlet data will be discussed in Section 3.1.2, below.
These figures show that there are three distinct "periods" of spraying per day. The first period
lasts from the start of spraying in the morning (from as early as 0700) and ends when the plant
employees have a 15 minute break at approximately 1000 hours. The second period starts at
approximately 1015 and lasts until the lunch break at noon. The final period starts around 1230 and
lasts until approximately 1400. Spraying can end earlier than 1400 if daily production quotas are met.
These figures show the variability and the periodic nature of the emissions from this process.
Because of the variety of molds (with different surface areas) that are sprayed and because of the
26
-------
250
Inlet
Outlet (Shifted)
200
150 —
100 —
50 —
0845
0915
0930
0945
1000
1015
0830
0900
Time of Day, June 22,1993
Figure 7. Inlet and outlet hydrocarbon emissions, 0830 to 1015, June 22, 1993
-------
300
Inlet
Outlet (Shifted)
250 —
200 —
150 —
100 —
x>
>»
50 —
1015
1030
1045
1100
1115
1130
1145
1200
Time of Day, June 22,1993
Figure 8. Inlet and outlet hydrocarbon emissions, 1015 to 1200, June 22,1993
-------
300
Inlet
Outlet (Shifted)
250 —
| 200 —
Q.
150
100 —
50 —
1230
1245
1300
1315
1330
1345
1400
1415
Time of Day, June 22, 1993
Figure 9. Inlet and outlet hydrocarbon emissions, 1230 to 1400, June 22,1993
-------
250
Inlet
Outlet (Shifted)
200 —
I
Q.
150
100 —
TJ
>\
50 —
CMC*
THC
Z«a
0700
0730
0800
0830
0900
0930
1000
1030
Time of Day, June 23,1993
Figure 10. Inlet and outlet hydrocarbon emissions, 0700 to 1030, June 23,1993
-------
250
Inlet
Outlet (Shifted)
200
i
CL
150
100
1030
1045
1100
1115
1130
1145
1200
1215
Time of Day, June 23,1993
Figure 11. Inlet and outlet hydrocarbon emissions, 1030 to 1215, June 23,1993
-------
300
Inlet
Outlet (Shifted)
250 —
I 200 —
Ql
150
100 —
¦o
>»
50 —
M
1230
1245
1300
1315
1350
1375
1400
1415
1430
Time of Day, June 23,1993
Figure 12. Inlet and outlet hydrocarbon emissions, 1230 to 1415, June 23,1993
-------
250
Inlet
Outlet (Shifted)
200 —
150 —
100 —
50
1030
1000
0930
0900
0830
0800
0730
Time of Day, June 24,1993
Figure 13. Inlet and outlet hydrocarbon emissions, 0730 to 1030, June 24,1993
-------
350
Inlet
Outlet (Shifted)
300 —
250 —
200 —
150 —
100 —
50 —
1030
1045
1100
1115
1130
1145
1200
1215
Time of Day, June 24,1993
Figure 14. Inlet and outlet hydrocarbon emissions, 1030 to 1215, June 24,1993
-------
300
Inlet
250 —
Outlet (Shifted)
200
Q.
CL
150 —
100
50 —
1230
1245
1300
1315
1330
1345
1400
Time of Day, June 24,1993
Figure 15. Inlet and outlet hydrocarbon emissions, 1230 to 1400, June 24,1993
-------
nature of the spraying process, it is difficult to determine if differences from one spraying period to
another are due to differences in the type of mold (bath tub versus shower stall) or to the approach used
by the operator. Because the periodic nature of these emissions have been observed in the past,5
spraying activity in gel coat booth #2 was recorded on a video camera and the surface area of each
mold was determined so that it would be possible to determine the level of styrene emissions as a
function of the surface area sprayed.
Figures 7 through 15 also show output from the outlet THC analyzer that was recorded on the
datalogger for the three days of testing, June 22 through 24,1993. These data have been shifted to
align with the inlet data. The amount of time that the data were shifted so that inlet and outlet peaks in
styrene concentration align is equal to the transit time through the device. Transit times ranged from
1.70 minutes to 2.08 minutes. As with THC data from the inlet, periods of calibration are not shown.
Also not shown are data from most periods when water was emptied from the outlet sampling line or
when an FID flame-out occurred.
These data show that outlet emissions from the pilot scale liquid scrubber are closely coupled to
inlet emissions. This behavior should be expected because of the relatively constant transit time for
emissions to pass through the device. Thus, outlet emissions rose and fell with inlet emissions.
Generally, peak outlet emissions ranged between 50 and 100 ppm (depending on the test condition) and
between sprayings usually fell to levels equal to those measured at the inlet to the device at such times
(5 to 30 ppm).
3.1.3 Efficiency Data
During each period of spraying, styrene removal efficiency was determined by comparing average
inlet and outlet THC measurements recorded by the dedicated PC-based data logger. In order to isolate
periods of spraying activity in gel coat booth #2 from periods when no spraying was taking place in that
booth, data were segregated into periods of time when inlet hydrocarbon emissions were greater than
30 ppm (which coincided with spraying) and periods when hydrocarbon emissions were equal to or lower
than 30 ppm (which coincided with periods between spraying) 30 ppm was selected as a break point
-------
from inspection of the data. After this segregation was made, outlet data (shifted to remove the effect of
transit time through the pilot-scale scrubber, as shown in Figures 7 through 15) were averaged over the
same time periods used for the inlet data and these averages were used to determine hydrocarbon (as
styrene) removal efficiency for each mold that was sprayed. The results of these calculations are
presented in Tables 5 through 7. These tables present average inlet and outlet THC emissions data and
hydrocarbon removal efficiency averaged over each period of mold spraying and each test condition.
Figures 16 through 18 present the efficiency averages from Tables 5 through 7 in the form of bar graphs
showing hydrocarbon removal efficiency for each period of mold spraying (as individual bars) and for
test condition (as thick horizontal lines over the time period of the test condition).
Raw averages of inlet and outlet THC data for periods during which inlet emissions were greater
than 30 ppm and for periods when inlet emissions were less than or equal to 30 ppm are shown in
Appendix C. These data were used to generate the results shown in Tables 5 through 7. In this
appendix, population standard deviations and 95% confidence intervals are also included for each
average. Because the inlet THC data were analyzed to determine periods during which hydrocarbon
emissions were greater or less than 30 ppm, no attempt was made in Appendix C to segregate the
results into groups corresponding to the test conditions shown in Tables 2 through 4. Therefore, the
tables presented in Appendix C are organized by spraying periods (three per day).
These figures also show that the liquid chemical scrubber was not able to exceed an average
hydrocarbon removal efficiency of greater than 55% for any of the 25 test conditions. When water was
sprayed (only in reaction chamber 1), in the absence of any other chemical, the hydrocarbon removal
efficiency averaged 33% (Test Condition 1 on 6/22). Indeed, when the liquid chemical scrubber was off
line because of a water line rupture (with flow still maintained through the device), a hydrocarbon
removal efficiency of 30% was measured! Thus, the greatest effect of any chemical additive was to
increase average hydrocarbon removal efficiency by 26% over that obtained with water or 29% over that
obtained by using the liquid chemical scrubber as a settling chamber.
37
-------
Table 5. Inlet and Outlet Styrene Level and Efficiency of Styrene Removal
for each Mold Sprayed and for each Test Condition, June 22, 1993.
Test
Mold
Irvl&t ChirAnA 1 aiiaI
— Average Efficiency —
Cond
Moid
Mold
Spray
For Each Mold
Test Condition
For Each Mold
Test Condition
Per
Test Condition
#
*
Area
Time
Average
Sid. Dev.
Average
Std. Dev.
Average
Std. Dev.
Average
Std. Dev.
Mold
Average
Std. Dev.
(m3)
(tec)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(PPm)
(ppm)
(ppm)
<*>
<%)
(*)
1
1
7.80
260
103 0
37.0
66.8
12.5
351
2
613
344
938
41.8
63.3
16.0
32.5
3
7.80
409
85.8
43.7
59.6
19.5
305
4
530
262
89.7
44 9
92.3
42.2
58.6
13.3
61.9
16.1
34.6
32.8
2.1
2
5
5.85
482
68.7
43 5
47.9
15.5
30.3
6
7.99
313
103.7
38.0
82.5
41.5
64.9
12.7
54.6
14.4
37.4
331
5.0
3
7
7.99
680
69.8
28.6
47.7
11.4
31.6
8
780
543
85.1
29.8
54.0
11.9
366
9
5.85
285
99.7
51 4
80.9
34.5
60.4
13.3
52.3
12.0
394
349
4.0
4
10
6 13
354
113.3
48.0
85.9
20.0
24 1
11
5 30
272
1068
54.4
67.6
18.7
367
12
7 80
520
102.7
46.3
71.2
18.8
30.6
13
1.39
385
775
49.3
99.5
49.0
54.4
14.5
69.7
18.1
29.8
30.0
5.2
5
14
7.99
434
106.7
49.5
71 3
175
33.2
15
7.80
303
1239
53.1
78.4
17.3
36.8
16
7.99
511
103.7
54.6
65.7
21.9
36.7
17
7.80
464
101.1
524
107 4
52.5
63.3
21.0
68.7
19.8
374
360
1.9
6
18
5.30
197
1009
39 6
100.9
N/A
49,4
7.6
49.4
N/A
51.1
51.1
N/A
7
19
799
357
126.4
43.8
71.7
14.7
43.3
20
530
261
107.1
42.4
118.2
43.2
60.8
11.3
67.1
13.4
43.2
433
01
8
21
5.30
302
1007
51 2
59.7
13.2
40.8
22
7.80
345
113.9
46.4
107.8
48.7
62.8
14.2
61.4
13.7
44.8
42.9
2.9
9
23
585
212
112.7
49.3
49.5
10.8
56 1
24
7 99
314
112.2
34.4
112.4
41.0
78.5
13.5
66.8
12.5
30 0
40.5
18.4
38
-------
Table 6. Inlet and Outlet Styrene Level and Efficiency of Styrene Removal
for each Mold Sprayed and for each Test Condition, June 23,1993.
Test
Mold
Outlet Styrene Level
— Average Efficiency —
Cond.
Mold
Moid
Spray
For Each Mold
Test Condition
For Each Moid
Test Condition
Per
Test Condition
*
*
Area
Time
Average
Std. Dev.
Average
Std. Dev.
Average
Std. Dev.
Average
Std Dev.
Motd
Average
Std. Dev.
(m1)
(sec)
(ppm)
(PPm)
(ppm)
(PPm)
(PPm)
(ppm)
(ppm)
(ppm)
(*)
w
(%)
1
1
7.B0
393
74.8
333
74.8
N/A
41.4
10.9
41.4
N/A
44.7
44.7
N/A
2
2
5.30
207
81.6
30.1
33.6
5.8
588
3
6.69
315
82.8
31.5
82.3
31.0
40.3
8.4
37.7
7.5
51.3
54.3
5.3
3
4
7.80
386
80.8
31.7
399
9.4
50.6
5
7.80
562
72.0
32.1
75.6
31.9
38.4
11.0
39.0
10.4
467
48.3
2.8
4
6
7.25
540
72.2
35.9
37.8
12.3
47.6
7
5.30
238
86.1
32.7
41.6
61
51.7
8
780
404
83.3
36.1
78.8
35.3
44.4
9.6
40.8
10.4
46.7
48.1
2.7
5
9
780
548
77.5
34.3
40.2
126
48.1
10
5.85
426
720
36.5
37.9
8.9
47.3
11
5.30
317
87.4
41.5
45.3
10.4
48.2
12
780
431
864
33 6
80.2
36.1
42.9
10.9
41.2
10.9
503
48.5
1.3
6
13
780
402
109.9
39.1
109.9
N/A
55.0
11.2
550
N/A
50.0
50.0
N/A
7
14
530
322
869
41 4
86.9
N/A
41.0
9.3
41.0
N/A
528
528
N/A
6
15
7 80
550
91 1
51.2
53.0
17.5
41.8
16
7.80
469
99.9
429
95.1
47.5
59.3
14.7
55.9
16.3
40.6
41.2
08
9
17
530
269
106 7
458
55.7
10.0
47.8
18
799
438
1104
46 2
109.0
46.0
63.0
153
602
13.6
42.9
44.8
3.5
10
19
7.99
760
80 1
42 5
46.8
18.0
41.6
20
7 99
592
96 9
46.5
56.6
19.5
41 6
21
585
315
1106
433
91.8
44.1
606
13.2
52.9
17.7
45.2
42.3
2.1
11
22
7.99
719
85 4
50.8
85.4
N/A
49.9
20.0
49.9
N/A
41.5
41.5
N/A
12
23
7.99
374
100.4
36.2
52.9
135
47.4
24
5 30
289
865
38.1
47.0
9.3
45.7
25
6.69
277
104.3
32.6
97.3
35.8
52.9
95
51.1
11.2
49.3
47.4
1.8
13
26
1.11
185
58.5
26 1
25.5
3.1
564
27
7.80
318
105.2
33.6
47.1
95
55.3
28
6.69
260
153.6
50.6
71.0
104
53.8
29
7 80
262
109.0
41.7
48.7
11.0
553
30
567
331
93.0
41.3
105.9
40.0
44.1
79
483
9.0
526
54.5
1.5
39
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Table 7. Inlet and Outlet Styrene Level and Efficiency of Styrene Removal
for each Mold Sprayed and for each Test Condition, June 24,1993.
Test
Mold
Outlet Styrene Level
— Aware Efficiency —
Cond.
Mold
Mold
Spray
For Each Mold
Test Condition
For Each Mold
Test Condition
Per
Test Condition
•
#
Area
Time
Average
Std. D»v.
Average
Std. Dev.
Average
Std. Dev.
Average
Std. Dev.
Mold
Average
Std. Dev.
(m3)
(sec)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(PP»")
(ppm)
(%)
<%>
W
1
1
7.99
371
85.7
27.8
47.8
9.8
443
2
7.99
437
87.8
32.9
66.8
30.7
49.4
124
48.6
11.3
43.7
44.0
0.4
2
3
5.85
244
91.2
349
435
8.5
523
4
6.13
334
91.7
39.9
56.8
24.1
38.0
5
6.13
341
950
43.2
92.8
39.9
77.7
8.2
61.1
16.2
18.1
34.4
17.1
3
6
5.85
263
922
40.9
68.4
7.1
258
7
7.99
387
103.2
44.8
67.8
14 4
34.3
8
780
374
91.5
39.6
56.7
11.0
380
9
7.25
331
114.2
47.2
64.0
10.6
44.0
10
7.99
492
97.1
442
593
15.4
389
11
799
295
104.1
42.8
63.0
133
39.5
12
7.99
500
83.8
32 5
51.6
6.4
38.4
13
6.69
435
876
41.6
55.0
14 1
37.2
14
5.85
312
104.3
469
552
13.5
47 1
15
7.99
519
97.6
59 0
587
22.4
399
16
7 80
439
125.0
61.7
71.3
200
430
17
7.99
359
131.9
581
71 6
184
45.7
18
530
364
104.3
58 4
54.4
15.0
478
19
3.25
350
96.0
63.2
496
107
484
20
2.23
165
88 8
480
39 1
4.9
56.0
21
7.80
444
123.6
61.6
62.2
175
49.6
22
7.99
578
81 8
37 5
406
23.6
50.4
23
5 30
211
117.0
55.9
56.2
12.5
52.0
24
7.80
304
132 4
60,2
68.4
14.4
483
25
7.80
299
129.4
52.8
649
127
49.8
26
5.85
274
1091
51.5
55.1
6.8
494
27
6.69
298
114.8
49.6
60.5
107
47.3
28
5.30
113
122.8
389
1049
50.2
51 2
3.2
58.5
15.1
58.3
438
7.4
40
-------
T*s! Condition Average
Test Conditions
0800
0900
1000
1100
1200
1300
1400
Time of Day, June 22, 1993
Figure 16. Hydrocarbon removal efficiency, June 22,1993.
-------
•b.
to
70
60
50
40
30
20
10
Test Condition Average
Test Conditions
12 3 4
10
11 12
13
0700
0800
0900
1000
1100
1200
1300
1400
Time of Day, June 23,1993
Figure 17. Hydrocarbon removal efficiency, June 23,1993
-------
Test Coil (fit ton Average
Test Conditions
1 2
r^_r
r~"T"
0700 0800 0900 1000 1100 1200 1300 1400
Time of Day, June 24, 1993
Figure 18. Hydrocarbon removal efficiency, June 24,1993
-------
As Indicated above, a wide variety of chemical additives and surfactants were tested. While the
reasons for the choice of these exact chemicals has not been addressed in any literature supplied by the
scrubber manufacturer, before the test, the manufacturer indicated that solutions of both sodium
hypochlorite and sodium hydroxide (along with a surfactant to aid in dispersion) would be evaluated for
styrene removal. It is reasonable to expect that a bleach would react with styrene to break it down into
benzoic acid. Why the other chemicals were evaluated has not been addressed by the manufacturer.
3.1.4 Estimated Stvrene Emissions from Gel Coat Booth »2
It is possible to estimate styrene emissions to the atmosphere from the shower stall and bath tub
gel coating process from THC data taken at the inlet of the liquid chemical scrubber device. Using the
methodology described above, THC data from each day of testing were inspected to determine times
during which bath tubs or shower stall molds were sprayed. VOC emissions (assumed to be 100%
styrene) were averaged over the time required to spray each bath tub or shower stall mold and
multiplied by the time required to spray the mold to determine the emissions rate in milligrams of styrene
per cubic meter per second of air flow. This value was multiplied by the flow rate of the gelcoat booth
exhaust fan to obtain a mass emissions rate of styrene to the atmosphere for each bath tub or shower
stall The air flow through the outlet stack on gel coat booth #2 was measured to be 6.23 m3/s (dry, or
13,193 dscfm) on 6/17/93 as part of Phase 1 of this Work Assignment. Tables 8 and 9 shows the results
of these calculations.
Table 8 summarizes hydrocarbon emissions during periods of mold spraying. Over the three days
of testing sufficient data were acquired to estimate styrene mass emissions for a total of 82 separate
mold sprayings. On the average, 6.2 ± 2.1 minutes were required to spray a mold and during that time
approximately 0.144 ± 0.043 kg of styrene per square meter of mold surface was vented to the
atmosphere, assuming that the average flow rate of the exhaust fan in gel coat booth #2 equaled the
flow rate measured on 6/17/93. In terms of emissions per mold, the 82 molds sprayed represented
552.2 m2 (5944 ft2) of mold area or an average of 6.73 m2 (72.5 ft2) per mold. Thus, during spraying,
approximately 0.97 ± 0.29 kg of styrene were emitted to the atmosphere for every mold that was
sprayed. The fairly high standard deviations for these numbers are most likely due to the fact that many
-------
Table 8. Hydrocarbon Emissions from Direct Spraying in Gel Coat Booth #2, THC Data
Date
Start
End
Molds
Mold
—Spray
Time —
— Styrene
Emissions
Time
Time
Sprayed
Area
Average
Std. Dev.
Average
Std. Dev
Average
Std. Dev.
-------
different types molds were sprayed and that bath tub enclosures require a longer time to spray (with
higher emissions) than smaller shower stalls.
It should be emphasized that the above numbers are strictly for periods of spraying (hydrocarbon
emissions greater than 30 ppm). Overall emissions are somewhat higher than shown in Table 8
because during any given period, total emissions to the atmosphere, through gel coat booth #2, are a
sum of the emissions that occur during the spraying of a mold and the emissions swept into the booth
between sprayings. Emissions not directly associated with spraying can come from molds that have
been sprayed and not yet removed from the booth, coated molds that are left outside the mouth of the
booth while an adjacent booth is being cleared, or from recently sprayed molds passing in front of the
booth. Total hydrocarbon emissions are shown in Table 9. Thus, for the three days of testing, total
emissions averaged approximately 0.17 ± 0.02 kg of styrene for every square meter of mold that was
sprayed. Likewise, for every mold that was sprayed, the total emissions of styrene to the atmosphere
averaged 1.12 ± 0.11 kg of styrene. Comparing the emissions directly associated with spraying to total
emissions, it appears that, on the average, approximately 13% of all the emissions are not directly
associated with spraying.
3.2 EPA METHOD 18 DATA
EPA Method 18, Adsorption Tube Procedure, was followed to obtain charcoal tube samples at the
inlet and outlet of the liquid chemical scrubber situated at gel coat booth #2. Due to the nature of the
adsorption tube sampling procedure, the desire to sample process emissions over an extended period,
and expected inlet and outlet hydrocarbon emissions levels, sample times of from one to one and one-
half hours were planned. Unfortunately, because test conditions frequently lasted for short times as one
or another scrubber additive was evaluated to improve scrubber performance it was only possible to
complete two concurrent sampling runs at the inlet and outlet of the liquid chemical scrubber.
On June 22, a sample of the 39 ppm styrene calibration standard was taken with an adsorption
tube and on June 23, a sample of the 2.2 ppm styrene calibration standard was taken with an adsorption
lube. At the liquid chemical scrubber, concurrent inlet and outlet adsorption tube samples were obtained
-------
on the last day of sampling, June 24, during test condition #3. One run was made in the morning (from
1052 to 1125) and the other run was made in the afternoon, from 1332 to 1351. During both of these
runs three molds were sprayed. No sampling problems were encountered during any erf these runs.
Table 10 shows the sample times and sampling parameters that were used to take these
samples and Table 11 presents the results of these measurements. Also shown in this table are results
of measurements recorded with the inlet and outlet THC monitors that were averaged over the time
period during which the adsorption tube samples were obtained. Standard deviations are not shown for
these THC measurements because, in this case, they would quantify the effect of concentration
variations due to normal process changes (spray guns being cycled from off to on to off) over the time
that the adsorption tube sample was obtained rather than provide an overall uncertainty in the average
emissions level.
Table 10. Sampling Conditions for Adsorption Tube Measurements made at
Eljer Plumbingware, June 22-24,1993. EPA Method 18 Sampling
Date
Sample
Sample
Start
End
Sample
Sample
Sample
ID No.
Time
Time
Time
Flow Rate
Volume
(min)
(liters/min)
(liters)
6/22/93
Midrange Calibration Standard
1
0900
1000
60
0.210
12.62
6/23/93
Low Range Calibration Standard
2
1035
1140
65
0.306
19.90
6/24/93
Inlet. Liquid Chemical Scrubber
3
1052
1125
33
0.196
6.35
Outlet, Liquid Chemical Scrubber
4
1052
1125
33
0.481
15.54
Inlet, Liquid Chemical Scrubber
5
1332
1351
19
0.174
3.30
Outlet, Liquid Chemical Scrubber
6
1332
1351
19
0.507
9.64
With the exception of the low range calibration standard, the results shown in Table 11 indicate
that the Method 18 measurements are lower than concurrent measurements made with the THC
analyzers. Percentage differences (difference divided by average expressed as a percent) for the four
concentration determinations that could be compared to THC measurements ranged from approximately
13% to 15% below the THC averages with the afternoon scrubber inlet measurement approximately
22% below the averaged THC value. Only styrene was detected in the analyses of these samples
47
-------
Table 11. Results of Adsorption Tube and THC Measurements made at
Eljer Plumbingware, June 22-24,1993. EPA Method 18 Sampling.
Sample
Sample
Start
End
Styrene Concentration
Difference
Efficiency
ID No.
Time
Time
Method 18
From THC
THC-Method 18
Meth. 18/THC
(ppm)
(ppm)
(%)
(%>
Midrange Calibration Standard
1
0900
1000
35.8
39.1*
8.8
Low Range Calibration Standard
2
1035
1140
2.28
2.2*
-3.6
Inlet, Liquid Chemical Scrubber
3
1052
1125
70.5
80.0
12.6
Outlet, Liquid Chemical Scrubber
4
1052
1125
41.3
48.1
15.2
41.4/39.9
Inlet, Liquid Chemical Scrubber
5
1332
1351
76.2
94.7
21.7
Outlet, Liquid Chemical Scrubber
6
1332
1351
42.5
49.3
14.8
44.4 / 47.9
* Concentration determined for styrene calibration standard.
With respect to styrene removal efficiency, both methods yielded efficiencies between 40 and
50%. There is no clear reason for the differences observed between the THC and Method
measurements, and agreement to within ± 10% was expected (see Appendix B). The fact that the THC
measurements were consistently greater than the EPA Method 18 measurements points to the need for
a larger set of Method 18 samples so that a better comparison could be made.
3.3 ANALYSIS OF RECOVERED SCRUBBER LIQUID SAMPLES
All samples were taken at reaction chamber drains. Samples of spent scrubber liquid were
obtained from the first two reaction chambers on June 23 (at 1340) and from all three reaction chambers
on June 24 (at 1040). On June 23, only water was injected in the third reaction chamber so no liquid
sample was taken. In addition, a sample of the process water used to dilute the chemicals used for
scrubbing was obtained on June 24 (at 1015). All liquid samples were preserved in 250 ml glass sample
bottles with Teflon-sealed caps. It was originally intended to obtain more scrubber liquid samples.
Unfortunately, because so many test conditions were tried, it was difficult to isolate a set of operating
conditions (where reasonable styrene removal was obtained) that persisted for a long enough period to
obtain a set of scrubber samples that were not contaminated by additives from a previous test condition.
48
-------
The samples were kept at room temperature, away from light until they could be brought back to
SRI's Birmingham, Alabama laboratories for analysis. The samples were returned to SRI on June 27
and, according to standard operating procedure, were placed in refrigerated storage until they could be
analyzed. The samples were analyzed on August 25 and 26 according to EPA SW-846 Method 8240
using a Hewlett-Packard Model 5890 Series II Gas Chromatograph with a Hewlett-Packard Model
5971A Mass Selective Detector. This analysis employs & purge and trap procedure, and scrubber liquid
samples from June 23 (Reaction Chamber's #1 and #2) and June 24 (Reaction Chamber #1) contained
enough of the surfactant that was added to improve droplet dispersion that the samples generated a
vigorous foam when they were purged. This required that the samples be diluted to the point where the
level of foaming did not affect the analysis. The effect of this dilution was to reduce the sample size
from 5 ml to 0.01 ml to 0.05 ml, depending on the sample, which significantly increased the detection
limit for semivolatile and volatile organic compounds present in these samples (see Appendix D).
Table 12 summarizes the test conditions under which the samples were obtained and Table 13
presents the results of the analyses carried out on these samples. As Table 12 shows, the same
additive was used in Reaction Chamber #1 during both of the test conditions for which liquid samples
were obtained. However, on June 24, the rate of addition of the scrubber additive (2% H2S04 and
surfactant "E") was approximately 1.75 times that used on June 23. The same additives were not used
in the other reaction chambers. On June 23, a 5.25% solution of NaCIO was added to Reaction
Chamber #2 and water atone was added to Reaction Chamber #3. On June 24, 3% H,Oa was added to
both Reaction Chamber #2 and #3.
As Table 13 shows, styrene was detected in only the sample from Reaction Chamber #1 on
June 24. This is not surprising, because styrene present in the liquid sample would continue to react
with scrubber additives (such as sodium hypochlorite) within the reaction chamber, in the chamber drain
system, and possibly after the sample was acquired before it was analyzed. Also, Table 13 shows that
in all but one of the scrubber liquid samples, acetone and chloroform were detected. The presence of
chloroform in liquid collected from Reaction Chambers #1 and #2 at 13:40 on June 23 could be
explained by the use of sodium hypochlorite in both of these chambers earlier in the day. Acetone was
49
-------
probably not detected in the one sample (Reaction Chamber #1, 6/23) because this sample had to be
heavily diluted (0.01 ml in water as opposed to a 5 ml sample with no water dilution) to reduce foaming
caused by the surfactant present in the sample. The sample from Reaction Chamber #1 taken on June
24 also had to be diluted to reduce foaming from the surfactant, but by much less (0.05 ml in water to
make a 5 ml sample). Less dilution along with the fact that the additive flow rate to Reaction Chamber
#1 on June 24 was 1.75 times that used on June 23, makes it probable that more compounds would be
detected in that sample (e.g. acetone, carbon disulfide, and unreacted styrene) than in the sample
obtained on June 23.
Table 12. Summary of Test Conditions During Which Scrubber Liquid Samples were Taken
Scrubber
Addition Rate
Scrubber
Addition Rate
Scrubber
Addition Rate
Date
Test
Cond
Start
Time
End
Time
Sample
Time
Reaction
Chamber #1
Additive
(Iph)
Water
(Iph)
Reaction
Chamber #2
Additive
(Iph)
Water
(Iph)
Reaction
Chamber #3
Additive
(Iph)
Water
(Iph)
6/23
13
1324
1403
1340
HjSO. (2%),
Surfactant "E"
0.60
34.07
NaCIO (5.25%)
2.56
34 07
HjO Only
0.00
34.07
6/24
3
637
1353
1040
HjSO« (2%),
Surfactant "E"
1.05
34.07
H:Oj(3%)
1.70
34.07
H2O2 (3%)
1.32
34.07
Table 13. Results of Analyses Carried out on Scrubber Liquid Samples
and a Process Water Sample
Date
Time
Origin
Compound
Concentration
Detection Limit
(H9")
(H9/I)
6/23
1340
Reaction Chamber #1
Chloroform
23300
410
Reaction Chamber #2
Acetone
709
364
Chloroform
39400
41
6/24
1040
Reaction Chamber #1
Acetone
1910
728
Carbon Disulfide
104
280*
2-Butanone
53400
1460
Chloroform
230
82
Styrene
1022
141
Reaction Chamber #2
Acetone
2440
7.28
2-Butanone
367
14.6
Chloroform
1.65
0.82
Reaction Chamber #3
Acetone
7.41
7.28
Chloroform
7.31
0.82
6/24
1015
Process Water
Chloroform
55
0.82
Bromodichloromethane
12.2
2.37
* Conservative estimate of detection limit based on previous measurements of similar water samples.
50
-------
The presence of 2-butanone in the sample from Reaction Chamber #1 on 6/24 is explained
because MEKP, the peroxide of 2-butanone, was used in this chamber earlier in the day. It is possible
that residual MEKP remained in Reaction Chamber #1 and that it was present in the sample collected on
that day. It could have hydrolized before or after collection.
3.4 Total Flow Rate Data
Following the methodology described in Section 2.5.4, air flow into the liquid chemical scrubber
was measured on the morning of June 24 with a thermal anemometer that had been calibrated in a wind
tunnel at SRI's Birmingham, Alabama facility. As was indicated earlier, because the flow rate was lower
than initially expected flow could not be measured according to EPA Method 1A with a standard pitot
probe. Method 1A indicates that the minimum number of traverse points for round ducts between 0.1
and 0.3 m diameter is 8, providing that there are no flow disturbances within 10 duct diameters upstream
and 8 duct diameters downstream. These criteria were satisfied and 8 traverse points were used, four
each on two diameters, 90° apart. Table 14 presents the results of these measurements. The flow
measurements made on June 24 (at 0845) were the actual flows used for testing.
Table 14. Flow Rate Measurements at the Inlet of the Liquid Chemical Scrubber
Date and Time
Traverse Point
Port A
Port B
Average
Traverse
Traverse
Flow Rate*
m/min
m/min
m3/min
6/24/93, 0845
1
109.7
108.2
2
121.9
128.0
3
123.4
125.0
4
106.7
115.8
Average
1.966
* The duct diameter was 14.6 cm
As indicated above, because it was found that flow into the liquid chemical scrubber was too tow
to allow the use a standard pitot to measure flow rate, it was not possible to measure flow into the
51
-------
device until a thermal anemometer could be received late on June 23. To determine the flow rate
through the liquid chemical scrubber for the two earlier days of testing, the value for flow rate determined
on June 24 was scaled according to the ratio of the transit time measured through the scrubber on June
22 and 23 compared to that measured for June 24. This is because the coordinated THC measurements
made at the inlet and outlet of the liquid chemical scrubber allowed the transit time of styrene-laden air
through the device to be determined. Once the transit time was known, flow could be scaled relative to
the transit time and flow rate measurement made on the morning of June 24.
52
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SECTION 4
SUMMARY AND CONCLUSIONS
The purpose of this study was to evaluate the liquid chemical scrubbing process for controlling
styrene emissions at a representative fiberglass shower stall and bath tub manufacturing plant. This
process was evaluated with the aid of a small, transportable pilot-scale liquid chemical scrubber unit
supplied by the manufacturer of full-scale devices that utilize this technology. The evaluation was
carried out from June 22-24,1993 at the Eljer Plumbingware facility located in Wilson, NC.
The liquid chemical scrubbing process takes advantage of a patented absorption technique based
on the mass transfer equation that provides enhanced chemical reactivity with an atomized mist. The
manufacturer asserts thai the mist provides a large surface area where gas-liquid phase reactions take
place that result in the removal of gaseous contaminants.
The major components of the pilot-scale system tested in this study included the three-chamber
scrubber equipped with three spray nozzles and separate chemical metering pumps for each chamber,
internal ducting to allow the chambers to be connected in a variety of configurations, and a variable
speed exhaust fan. The pilot-scale unit is mounted on a large trailer for ease of transport.
This is a once-through process. Thus, spent scrubber liquids were disposed of and were not
regenerated While no attempt was made to address issues associated with the disposal of spent
scrubber liquids, the chemical analyses reported in Appendix C suggest that such disposal is
straightforward.
The pilot-scale liquid chemical scrubber was not able to achieve styrene removal efficiencies
greater than 55% over a period of mold spraying although a number of additives were tried (including
sodium hypochlorite, ethylene glycol, sulfuric acid, methyl ethyl ketone peroxide, hydrogen peroxide, and
water). In the three days of testing 25 separate test conditions were completed.
In addition to the evaluation of the liquid chemical scrubbing process, it was possible to quantify
styrene emissions in the spray booth exhaust to which the pilot-scale device was connected. These
measurements showed that styrene was the only volatile organic compound present in the spray booth
53
-------
exhausts at this facility and that time-averaged concentrations of styrene ranged from 0.14 kg of styrene
per square meter of mold sprayed (during periods of active mold spraying) to 0.17 kg of styrene per
square meter of mold sprayed when all of the emissions entering the spray booth (over a day of
spraying) were accounted for.
4.1 ECONOMICS
The liquid chemical scrubber manufacturer was asked to provide a quotation for a full-scale
system suitable for the Eljer facility. That system is described in Table 15. For such a full-scale device
the installed cost was quoted to be $475,000 with an hourly operating cost of $10.01. Assuming an
average styrene inlet concentration of 110 ppm, as was used in the previous economic analysis of the
Polyad* FB system,3 a system flow rate of 145,000 scfm, and a 50% styrene removal efficiency, the total
cost depreciated over a nine year lifetime is $9.04/scfm or $563/ton of styrene removed.
54
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Table 15. Design and Cost Specification for a Full-Scale Liquid Chemical Scrubber
DESIGN ASSUMPTIONS AND COSTS
Air Capacity
Inlet Temperature
Inlet Styrene Concentration
Total System Efficiency
Hours of Operation per Year
Period of Depreciation
Cost of Operation
Cost of Electrical Power
Sodium Hypochlorite
Surface Active Agent
Installed Cost
Total Cost
145,000 scfm
75 °F
110 ppm (250 ppm maximum)
50 %
2000 hours
9 years
10.01 $/hr
0.07 $/kWh
0.37 $/lb (dry)
10 $/gallon
475,000.00 $
563.36 $/ton of styrene removed (over 9 year life)
9.04 $/scfm (over 9 year life)
LIQUID CHEMICAL SCRUBBER DESIGN
Layout
Inlet Duct
Exhaust
Stack Height
Horizontal
Openings into Plenum from Spraybooths
14 x 7 ft (into Horizontal Construction)
28 ft
Reaction Chamber
Number
Reaction Time
1 Chamber
10 Seconds
Effective Chamber Volume 24,167 ft3
Dimensions 14x14x135 ft (with Plenum)
14x7x129 ft (Chamberwithout Plenum)
EXHAUST FAN
CHEMICAL SUPPLY SYSTEM
LIQUID DISTRIBUTION SYSTEM
Number of Nozzles
Flow Rate
Compressed Air
Flow Rate
Pressure
ELECTRICAL CONTROLS
ACCESSORY EQUIPMENT
Existing
Single Stage / 2 Chemicals
15 (Model No. Q-1)
0.75 gal/min (per Nozzle)
11.25 gal/min (Total)
60 scfm (per Nozzle)
900 scfm (Total)
80 psig
Standard, per Local Code
Air Compressor, 180 hp
55
-------
SECTION 5
REFERENCES
1. Mist Scrubbing Technology developed by QUAD Technologies, Inc. for odor control at rendering
plants, flavor houses, landfill gas, composting, and other municipal applications. Mist Scrubbing
Technology is protected by several United States and foreign patents, and patent applications.
Among these are patent numbers 4,125,589,4,225,566, B1-4,238,461, 4,302,226,4,308,040,
4,416,861, arid 4,844,874. Other patent applications are pending. The chemistry of compost
scrubbing is covered by U.S patent 4,994,245 for which QUAD has an exclusive license.
2. Quality Assurance Handbook for Air Pollution Measurement Systems: Volume 111. Stationary
Sources Specific Methods, Section 3.16. U. S. Environmental Protection Agency, Research
Triangle Park, NC, EPA Report EPA/600/4-77/027b (NTIS PB 80-112303), May, 1989.
3. Felix, L., Merritt, R , Williamson, A., Evaluation ot the Polyad* FB Air Purification and Solvent
Recovery Process for Styrene Removal, U. S. Environmental Protection Agency, Office of
Research and Development, Air and Engineering Research Laboratory, Research Triangle Park,
NC, EPA Report EPA-6Q0/R-93-212 {NTIS PB94-130317), November, 1993.
56
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APPENDIX A
NIOSH METHOD 1501
57
-------
FORMULA: las
le 1
HYDROCARBONS, AROMATIC
M.U.: Table
1
BETHDD: 1501
ISSUED: 2/15/84
0SHA, NI0SH,
ACSIH: Table 2
PROPERTIES: Table I
COMPOUNDS:
(Synonyms
in Table 1)
benzene
p-ter*-butv1 to1uene
caneme a-
-------
HYCROCARBCNS. AROMATIC HETVCO: ISA!
REAGENTS:
EQUIPMENT:
1.
Eluent: Carbon disulfide*.
1.
Sampler: glass tube, 7 an long, 8 as 00, 4 im> ID,
Chromatographic quality containing
flame-sealed ends, containing two sections of
(optional) suitable internal
activated (600 *C) coconut shell charcoal (front
standard.
» 100 mg, back » 50 mg) separated by a 2-«n urethane
2.
Analytes, reagent grade*
foam plug. A silylated glass wool plug precedes the
3.
Nitrogen or heliun, purified
front section and a 3-mn urethane foam plug follows
4.
Hydrogen, prepurified.
the back section. Pressure drop across the tube at
S.
Air, filtered.
1 L/min airflow sust be less than 3.4 kPa. Tubes
6.
naphthalene calibration stock
are connercially available.
solution, 0.40 g/mL in C^.
2.
Personal sampling punps, 0.01 to 1 l/fcrin
(Table 3), with flexible connecting
tubing.
•See Soecial Precautions.
3.
Gas chrcmatograph, PIS, Integrator, and colum
(page 1S01-1).
4.
vials, glass, 1-«L, with PTFE-lined caps.
5.
Pipet, 1-«L, and pipet bulb.
6.
Syringes, 5-, 10-, 25- and 100-uL.
7.
Volunetric flasks, 10-at.
SPECIAL PRECAUTIONS: Carton disulfide is toxic and extremely flanrnable (flash point * -30 *C);
benzene is a suspect carcinogen. Prepare samples and standards in a yell-ventilated hood.
SAW'.IMG.
1. Calibrate each personal sanpling purp with a representative sansler in line.
2. Break the ends of the sanpler imnediately before sanpling. Attach saroler to personal
sampling pure with flexible tubing.
3. Sarole at an accurately known flw rate between 0.01 and 0.2 L/min (to 1 L/min for
naonthalene or styrene) for a total sanple size as shown in Taale 3.
4. Cap the samplers with plastic (not rubber) caps and pack securely for shipment.
SAMPLE PREPARATION:
5. Place the front and back sorbent sections of the sanpler tube in separate vials. Discard
the glass wool and foam plugs.
6. Acd 1.0 mL eluent to each vial. Attach crimp cap to each vial immediately.
7. Allow to stand at least 30 mitt with occasional agitation.
CALIBRATION AND QUALITY CONTROL:
8. Calibrate daily with at least five working standards over the appropriate range (ca. 0.01
to 10 mg analyte per saople; see Table 4).
a. Add known amounts of analyte (calibration stock solution far naphthalene) to eluent In
10-tU. vol line trie flasks and dilute to the nark.
b. Analyze together with samples and blanks (steps 11, 12 and 13).
c. Prepare calibration graph (peak area of analyte vs. ng analyte).
2/15/84 1501-2
59
-------
WETHOO: ISO!
HYpaOCAftBONS. APOHATTP
9. Oeter-mne desorption efficiency (0E5 at least once for each batch of charcoal used for
sanpling in the calibration range (step B). Prepare three tubes at each of five levels
plus three media blanks.
a. Remove and discard bade sorbent section of a media blank sampler.
b. Inject a known amount of analyte (calibration stock solution for naphthalene) directly
onto front sartent section with a microliter syringe.
c. Cap the tube. Allow to stand overnight.
d. Oesort (steps 5 through 7) and analyze together with working standards (steps 11, 12
and 13).
e. Prepare a graph of OE vs. ng analyte recovered.
10. Analyze three quality control blind spikes and three analyst spikes to insure that the
calibration graph and OE graph are in control.
MEASUREMENT:
11. Set gas chrcmatograph according to manufacturer's recommendations and to conditions given
on page 1501-1. Select appropriate colunn t«rn>erature:
Approximate Retention Time (win). at Indicated Colirr Twcerature
Substance3
50 *C
100 *c
150 *C
ProQr*rmeti°
benzene
2.5
2.5
toluene
4.3
1.1
4.2
xylene (para)
7.0
1.4
5.2
ethylbenzene
7.0
1.4
5.5
xylene (metal
7.2
1.5
5.S
cimene
8.3
1.6
6.0
xylene (orthc)
10
1.9
6.S
styrene
16
2.6
7.6
a-methy1styrene
3.2
1.0
a.i
vinyl toluene (mela)
3.3
1.2
a.5
naphthalene
25
4.3
12
*Oata not availaole for jj-tert-butyltoluene and £-«inyltoluene.
^Temperature program: 50 *C for 3 ain, then 15 *C'min to 200 *C.
NOTE: Alternatively, colum and tanperature may be taken from Table 4.
12. Inject sample aliquot manually using solvent flush technique or with autosampler.
NOTE: If peak area is above the linear range of the working standards, dilute with eluent,
reanalyze and apply the appropriate dilution factor in calculations.
13. Measure peak area.
CALCULATIONS:
14. Determine the mass, mg (corrected for 0E) of analyte found in the sanple front (Uf) and
back (W^) sorbent sections, and in the average aedia blank front (Bf) and back (3^)
sorfcent sections.
MOTE: If > Wf/10, report breakthrough and possible sacple loss.
2/15/84 1501-3
60
-------
HYSSOCAflSCNS. aBCWATIC
gTXIP; 1SQ1
15. Calculate concentration, c, of analyte in the air '/olune sampled, V (I):
ng/m3
V
EVALUATION OF HETHCO:
Precisions and biases listed in Table 3 were determined by analyzing generated atacspheres
containing one-half, one, and two times the OSHA standard. Generated concentrations were
independently verified. Breakthrough capacities were determined in dry air. Storage Stability
was not assessed. Measurement precisions given in Table 4 were determined by spiking sampling
media with amounts corresponding to one-half, one, and tao times the OSHA standard for naninal
air volunes. Oesorption efficiencies for spiked samplers conuining oily one ccipound exceeded
7SV Reference [12] provides more specific information.
REFERENCES:
[1] User check, U8Tl. nIOSH Sequence #4121-$ (unpublished, Oecweer 7, 1983).
[2] NIOSH Manual of Analytical Methods, 2nd. ed., V. 1, PSCAA 127, U.S. Oeparttnent of Health,
Education, and Welfare. Publ. (NIOSH) 77-157^V (1977).
[3] Ibid. V. 2. S22, $23. S25, S26. $29, S30. U.S. Department of Health. Education, and
Welfare. Publ. (NIOSH) 77-157-8 (1977).
[4] Ibid. V. 3. S292. S31', S318, S3d3, U.S. Oepartwnt of Health, Education, and Welfare,
Publ. (NIQS'ri) 77-1S7-C (1977).
[5] R. 0. Oreisbach. "Physical Properties of Chemica' Ccspounds"; Advances in CiHiristry
Series, *c. 15; American Chemical Society, Washington (1955).
[6] Code of receral Regulations; Title 29 (Labor), Parts 1900 to 1910; U.S. Government
Printing Office, Washington (1980); 29 CFR 191Q.1000.
[7] Update Criteria and Recarmenaations for a Revised Benzene Standard, U.S. Department of
Health, Education, and welfare, (August 1976).
[8] Criteria for a Reccmnended Standard Occupational Exposure to Toluene, U.S. Department
of Health,, Education, and Welfare, Publ. (NIOSH) 73-11023 (1973).
[9] Criteria for a Recarmended Standard... .Occupational Exposure to Xylene, U.S. Department of
Health, Education, and Welfare, Publ. (NIOSH) 75-168 (1975).
^0] TLVs - Threshold litnit Values for Chemical Substances and Physical Agents in the work
Erw'ranment with Intended Chances for 1983-34. ACIH, Cincinnati, OH (1983).
[11] Criteria for a Recommended Standard.. .Occupational Exposure to Styrene, U.S. Oepartaient of
Health and Hunan Services, Publ. (NIOSH) 83-119 (1983).
[12] Oocunentat'.cn of the NIOSH validation Tests, S22, S23, S25, S26, S29, S30, S292, S311,
S318, S3<52, U.S. Department of Health, Education, and Welfare; Publ. (NIOSH) 77-185 (1977).
HE7KCD REVISED BY: R. Alan Lunsford, Ph.D., and Julie R. Okenfuss; based on results of NIOSH
Contract CDC-99-74-45.
2/15/94 1501-
61
-------
HETHGO: ISO 1 HYDROCARBONS. ABOHATTf-
Table 1. Synonyms, formula, molecular* weight, properties [5].
Holec- toiling Vapor Pressure Density
Empirical ular Point 3 25 *C # 20 *C
Wame/SynerMTS Structure Formula Weight (*C) (trm Hq) (kPa) Co/ml)
benzene ^ 78.11 80.1 95.2 12.7 0.879
CAS *71-13-2
(OS ( CnH16 148.25 192.3 0.7 0.09 0.961
CAS *98-51-1 \
1-tert-butvl-4-methylbenzene
cunene CgH^ 120.20 152.4 4.7 0.62 0.362
CAS #98-82-3 \
iscprcpylbenzene
ethylbenzene i VlO 106-n ,38-2 9-s ,-2B °-a&1
CAS 1100-11-4
©~\
a-methy 1 styrene CgH^ 118.18 165.4 2.5 0.33 0.911
CAS #98-33-9 NS-V V«
i sopropenylbenzene
(1 -methy 1 etheny 1) -benzene
naphthalene |^)TOl C'0H8 123,18 80-2* °'2 0-03 1-025
CAS #91-20-3
styrene ^8 104-15 14S-2 °-31 °-906
CAS S100-42-5 \^l/ V-
vinyl benzene
toluene CjHg 92.14 110.6 28.4 3.79 0.867
CAS #108-38-3 ^C=7
¦ethylbenzene
vinyl toluene5 CgHlo
CAS #25013-15-4 \^7 ^
methylstyrene (j-vinyitoluene)
methy1viny1benzene
xylenec /TVi ^0 106JT
CAS #1330-20-7 \W/
dimethylbenzene (^-xylene)
118.18
167.7
1.6
0.22
0.396
(metal
171.6
1.9
0.26
0.911
(para)
172.8
1.8
0.24
0.911
(ortho)
169.8
1.8
0.24
0.904
(ortho)
144.4
6.7
0.89
0.880
(metal
139.1
8.4
1.12
0.864
(para)
138.4
8.8
1.18
0.861
'ttelting point.
bCcnmercial mixture of meta and para isaners.
fixture of isaners.
2/15/84
1501—S
62
-------
HVQROCAflBCxS. ARCWATIC
WETHOO: l«;rn
Table 2. Permissible exposure limits, ppra [6-11],
05HA
HI0SH
ACGIH
mg/m3
oer oom
Substance
TUA
C
Peak
M
C
Tiv
5TEL
benzene
10
25
SO*
1
10** 25**
3.19
p-tert-butv1 to1uene
10
10
20
6.06
oxnene
50
(Skin)
50
75 (skin)
4.91
•thylbenzene
100
100
125
4.34
a-iwthy 1 Styrene
100
50
100
4.33
naphthalene
10
10
15
5.24
styrene
100
200
SQCp
50
100
50
100
4.26
toluene
200
300
500*
100
200*
100
150 (skin)
3.77
vinyltoluene
10C
50
100
4.83
xylene
100
100
200*
100
150
4.34
'ttaximun duration 10 nin in 9
ftr.
suspec
:t carcinogen [10].
* 10-min sanple.
Table 3. Sanpling f!o*ratea, volune, capacity, range, overall bias and precision [3,4,12].
Breakthrough flange
Sanplino Volune a at Overall
Flowrate vol ire (11 Concentration VOl-*C* Bias Precision
Substance (l/min) VCl-JJO VOU-HAXb (L) £mg/m3} (mg/m3) (V, (sr)
benzene
£0.20
2C
30
>45
149
42- 16=
0.8
0.0S9
p-tert-buty1 to 1uene
<0.20
10
29
44
112
29- 119
-10.4
0.071d
cmene
£0.20
10
30
>45
480
120- 48C
4.6
0.059
ethylbenzene
£0.20
10
24
3S
917
222- 884
-8.1
0.089d
a-methyIstyrene
£0.20
3f
30
>45
940
226- 943
-10.8
0.061**
naphtha 1enee
£1.0
200
200
>240
ai
19- 83
-0.5
0.055
Styrene
£1.0
53
14
21
1710
426-1710
-10.7
0.053d
toluene
£0.20
2«
8
12
2294
548-2190
3.8
0.052
vinyl toluene
£0.20
10
24
36
952
256- 970
-9.5
0.061d
xylene
£0.20
12
23
35
870
218- 870
-2.1
0.060
'tlininun recsmnended flow is 0.01 L/min.
"Approximately tao-thirds tfte breakthrough volune, except for naphthalene.
HO-min sample.
^Corrected value, calculated from data in Reference 12.
•naphthalene shows poor desorption efficiency at low loading; 100-1 nininua vol una is
reccnmended.
^15-min sample.
95-min sanple.
2/15/84 1501-5
63
-------
HE^OO: 1S01
HYOROCWSONS, ABOWATtC
TaPle 4. Measurement
range, precision and conditions* [3,4,12].
Oesorption Measurement Carrier
Colum Parameters'5
Volune
Range Precision
Mow
t
Length
Substance
(mt)
(mg)
(sr3
(mL/min)
CC)
(n)
Pacfcingc
benzene
1.0
0.09- 0.35
0.036
50
US
0.9
A
p-tert-butv1 toIuene
0.5
0.27- 1.09
0.021^
50
115
3.0
8
etnene
0.5
0.86- 3.46
0.01Q
50
99
3.0
8
•thylbenzene
0.5
2.17- B.67
0.010
50
85
3.0
8
a-aiethylstyrene
0.5
0.S9- 3.57
0.011
50
115
3.0
8
naphthalene
1.0
4.96-19.7
0.019
30
125
3.0
C
styrene
0.5
2.17- 8.49
0.013d
50
109
3.0
8
toluene
1.0
1.13- 4.51
0.011
50
155
0.9
0
vinyl toluene
0.5
2.41- 9.S4
0.008
50
120
3.0
8
xylene
1.0
2.60-10.4
0.010
SO
180
0.9
0
'injection volune, 5.0 yi.; nitrogen carrier gas.
''All ealims stainless steel, 3.2 on outside diameter.
CA, 50/80 mesh Porapak P; 3, 101 FFAP an 30/100 nesh Oil mmorb W AU-OHCS;
C, 101 OV—101 on 100/120 mesh Supelraport; D, 50/90 nesh Porapak Q.
•^Corrected value, calculated fran data in [12].
2/15/84
1501-7
64
-------
APPENDIX B
QUALITY CONTROL EVALUATION REPORT
65
-------
SUMMARY
A Quality Assurance Project Plan (QAPP) was written and approved for this project. No field
audits were planned or performed. However, as stated in the QAPP, certified calibration gases (nominal
values of 5, 50, and 200 ppmv of styrene in nitrogen and zero air with less than 0.1 ppm THC content)
served as field performance audit samples for EPA Method 18 (NIOSH Method 1501) and THC
sampling. Unfortunately, as documented below, the concentrations of the styrene calibration gases
were incorrectly determined by the vendor, Matheson Gas Products, Inc. Actual concentrations were
determined to be 2.2, 39.1, and 170.8 ppmv of styrene, respectively.
EPA personnel were on site to oversee diagnostic measurements. In the field, QC was
addressed by strict adherence to standard sampling protocols either as specified for EPA Method 18
(NIOSH Method 1501) or by following a standard operating procedure (modified as needed for this
particular sampling task) with the THC analyzers as specified in the THC instruction manual.
In SRI's Analytical Chemistry facilities, QC is addressed by strict adherence to standard
operating procedures (SOP) previously defined and implemented. Pertinent SOP's for the analyses
required on this project were included in the QAPP. While random audits can occur while the field
samples from any project are being analyzed, and audits are regularly performed by the QA officer at
this facility, no audit was planned or performed as part of this project.
For the most part, the data quality indicator (DQI) goals for this project were achieved.
However, significant problems were encountered with the calibration gases purchased for this test and
these problems could have compromised virtually all of the data. These difficulties are discussed below.
SIGNIFICANT QA/QC PROBLEMS
One significant QA/QC problem was encountered. After sampling for both phases of the Work
Assignment had been completed, samples of the nominal 3 and 52 ppmv styrene cylinder gas standards
taken in the field on June 24 with Method 18 (Section 7.4, Absorption Tube Procedure, equivalent to
NIOSH Method 1501) were analyzed to verify sample recovery for the second phase of this Work
Assignment. These samples were analyzed on July 7.1993. Styrene concentrations of 2.3 and 35.8
66
-------
ppmv were determined corresponding to vendor-certified values of 3 and 52 ppmv. Such large
discrepancies between the styrene concentrations certified by Matheson Gas Products and the styrene
concentrations measured with the adsorption tubes suggested that the vendor-certified concentrations of
these calibration gases were in error or that some part of the laboratory analysis performed by SRI was
incorrect. Therefore, a two-pronged investigation followed that focused on the possibility that the
styrene calibration gases were in error, that SRI made incorrect determinations of the styrene content in
the calibration gases, or a combination of the two possibilities occurred.
With respect to the calibration gases, two bottles each of the low styrene concentration (nominal
5 ppmv styrene in nitrogen) and intermediate styrene concentration (nominal 50 ppmv styrene in
nitrogen) calibration gases were ordered from Matheson Gas Products for this test on May 13,1993 and
were received in early June. As indicated above, Matheson Gas Products certified that the styrene
content in the two bottles of low concentration gas were actually 3 ppmv while the styrene concentration
in one of the intermediate calibration standards was 52 ppmv (used in Phase 2 of this Work Assignment
as the calibration standard) and the other intermediate concentration standard was 54 ppmv. Two
cylinders of the high calibration standard (nominal 200 ppmv styrene in nitrogen) were ordered on
September 30, 1992 for an earlier EPA-sponsored test at the Eljer facility. These gases were received
in mid-October, 1992. One cylinder of this gas was not used during that test and was taken on this test
for use as a high styrene concentration calibration gas. Matheson certified that the styrene content was
195 ppmv for this cylinder. Matheson Gas Products was contacted and a representative indicated that
as far as their records indicated, the cylinders were property prepared and passivated and that stable
styrene concentrations were determined in their laboratory (and were recorded on the calibration tags
supplied with each cylinder) when the gases were shipped to SRI.
With respect to SRI's laboratory procedures, while conversations were being held with Matheson
Gas Products, two other samples of the 3 and 52 ppmv styrene calibration gases were taken on July 13
and analyzed to check the procedures followed during the earlier analyses. In addition, different high-
purity liquid laboratory standards for styrene (from two different suppliers, Aldrich and Chem Service)
were used to prepare independent calibration standards that were checked against one another on the
-------
same GC-FID used for both sets of analyses. Approximately six calibration standards (of different
concentrations below, centered about, and above those measured from the earlier analyses of the
adsorption tubes) were prepared by adding a known quantity of each high-purity liquid styrene standard
to a known quantity of high-purity carbon disulfide. Known microliter volumes of these liquid mixtures
were then injected into the GC-FID used for the adsorption tube analyses and the peak areas were
recorded and averaged. No statistically different result was determined for the two liquid styrene
standards and the analyses of these two adsorption tube samples were consistent with the earlier
results. To make a definitive assessment of the actual styrene content of the Matheson-certlfied 3 and
52 ppmv styrene calibration gases, on July 29 and 30, four adsorption tube samples each were taken
from each calibration gas cylinder (using EPA Method 18, Adsorption Tube Procedure). Two adsorption
tube samples of each styrene calibration standard were taken inside (at an average laboratory
temperature of 22°C) and two adsorption tube samples were taken outside with the calibration gas
bottles in the direct sun (an average temperature of 38°C). The reason samples were taken at
laboratory conditions and al conditions that mimicked ambient field temperatures experienced at the
Eljer facility was to determine if styrene gas was condensed within the sampling apparatus at room
temperature - a possible explanation for the apparent low recovery based on Matheson's certified
values. The adsorption tubes (from the same lot used at Eljer: SKC, Inc. catalog # 226-01, coconut
charcoal, Lot 120) were analyzed by removing the charcoal from the tubes and desorbing the styrene
into high-purity carbon disulfide. As part of the analytical procedure, the desorption efficiency of styrene
from this lot of coconut charcoal is separately determined each time a sample or set of samples is
analyzed. The desorption efficiency was determined to be 90.25%, equal to the value that has been
determined in the past. The results of these analyses, carried out during the first week of August, was
that no difference could be detected between samples obtained inside or outside the laboratory and that
the Matheson-certified 3 ppmv styrene gas was 2.69 ppmv with an RSD of 3.55% while the Matheson-
certified 52 ppmv styrene gas was 39.1 ppmv with an RSD of 0.55%. No error was found in the
analytical procedures followed in these analyses, in the preparation of the two sets of calibration
standards, or in the behavior or operation of the GC-FID used for these analyses.
68
-------
Next, a performance evaluation audit standard was requested from EPA to determine with
certainty if the error was due to our analytical procedures. The cylinder was sent to SRI on September
17 and the results of SRI's triplicate analysis (using the Method 18, Adsorption Tube Procedure) of the
styrene content in the cylinder was reported to the EPA on September 21. After it was determined that
SRI's analysis was within 96.6% of the actual styrene concentration of 58.6 ppmv (with an accuracy of ±
2.2%), it was concluded that the concentrations reported on Matheson's analysis of all the gas samples
provided for this test were in error. The results of the tests of the EPA performance evaluation audit
sample are shown in Table B-1. Table B-2 shows the results of tests performed to determine the actual
styrene content of these gases. No other corrective actions were required or taken during the collection
of samples and data or during subsequent analysis of samples collected during testing.
The values reported In Table B-2 were obtained by two separate methods. First, as part of the
investigation discussed above, EPA Method 18, Adsorption Tube Procedure (equivalent to NIOSH
Method 1501). was used to make triplicate determinations of the styrene content of each of the nominal
3, 52, 54, and 195 ppm styrene calibration gases. All of these determinations were completed by
September 14. Second, on September 29, a JUM VE-7 THC analyzer (one of the THC analyzers used
in the sampling van) was allowed to stabilize for 24 hours on filtered ambient laboratory air and was then
spanned with 10.7 ppm ± 1% propane (unfortunately, other propane standards were not available when
these measurements were performed) and zeroed with a THC-free zero air standard (s 0.1 ppm of
hydrocarbon compounds). The THC analyzer was then used to sample the 58.6 ppm EPA audit
standard, as well as the nominal 3, 54, and 195 ppm styrene calibration gases (at this time the cylinder
containing the 52 ppm calibration gas had been exhausted). Styrene content was determined based on
the response of each of the calibration gases to the value measured for the EPA audit standard. Zero
and span checks performed at the beginning, middle and at the end of the THC measurements
confirmed instrumental stability.
These results required that, at best, all of the data be scaled to reflect the true concentrations of
styrene present in the gas cylinders obtained from Matheson Gas Products that were used for field
calibrations. At worst, the data could be completely compromised because the styrene within the
-------
Table B-1. Results of SRI Analyses of EPA Performance Evaluation Audit Sample*
Sample"
Measured (ppm)
Actual (ppm)
Rel % Difference
1.
55.6
58.6
-5.1
2.
57.0
58.6
-2.7
3.
57.1
58.6
-2.6
Average ± RSD
56.6 ± 1.5%
58.6 ± 2.2%
-3.4
* Cylinder CLM 008308. Specified as containing styrene at a concentration
under 100 ppm with the balance gas being nitrogen. Content later quoted by
EPA to be 58.6 ppm ± 2.2% RSD.
** Analysis by EPA Method 18, Absorption Tube Procedure, with GC/FID.
Aside from the diluent (CS2), styrene was the only material detected.
Table B-2. Results of SRI Analyses of Matheson Calibration Gas
Matheson Analysis*
SRI Method 18 Analysis"
SRI THC Analysis'
Comparability
(ppm)
(ppm)
RSD (%)
(ppm)
RSD (%)
(% Diff.)
3
2.69
3.55
2.16
0.25
21.9
52
39.1
0.55
N/A"
--
-•
54
37.B
2.07
39.45
0.12
-4.3
195
176.8
4.06
170.8
0.18
3.5
* As indicated on gas cylinder, ppm stymie in nitrogen.
** Absorption Tube Procedure using charcoal tubes.
1 THC calibrated with 10.7 ppm propane in nitrogen. Response referred to styrene by
analysis of EPA performance evaluation audit sample (58.6 ppm styrene measured
151 06 ± 0.24 ppm with propane-based calibration).
n Cylinder exhausted before THC measurements could be made.
cylinders supplied by Matheson could have been slowly polymerizing since the cylinders were prepared
and the styrene concentrations measured after the test would not represent styrene concentrations
present in the cylinders at the time of the test. The latter eventuality was explored with Matheson in the
initial conversations that were directed toward determining the source of the disagreement. As indicated
above, Matheson Gas Products asserted that the cylinders were properly prepared and passivated.
While Matheson was unable to explain why the concentrations were so far from those determined by
70
-------
their original in-house analysis, they did maintain that if the temperature indicating strips on the sides of
the cylinders had not changed color (indicating exposure to temperatures that could degrade the
sample), styrene concentrations within the cylinders should have remained stable through the time
period of the test and our subsequent determination of the actual styrene concentrations within the
cylinders. Because none of the temperature indicating strips on the sides of the cylinders had changed
color (indicating the temperature of the cylinder had reached or exceeded 125°F). we proceeded to
correct the data assuming that styrene concentrations in the calibration cylinders measured after the test
were representative of styrene concentrations present during testing.
Correction of the THC data was straightforward. During the test, only the nominal 52 ppm
styrene calibration gas (actually 39.1 ppm by later analysis) was used to calibrate the THC analyzers.
Because the cylinder of this gas was emptied before the THC measurements reported in Table B-2
could be made, results obtained with these analyzers were scaled by a ratio of 0.7519 (or 39.1/52).
DATA QUALITY
The following procedures were used to determine how well data quality indicator (DQI) goals
were met:
• Precision is expressed as percent coefficient of variation:
% CV = 100 x (Sx^Xgvg)
where Sx is the standard deviation of x number of data values from the data set and
Xgvg is the mean or average of the x number of data values from the data set.
• Bias is expresses as a difference or percent difference between measured and known
values:
Bias = (X-T)
71
-------
%RPD = 100 x [(X-TVTl
where T is the true value (reference standard) and X is the mean sample
concentration. %RPD is the relative percent difference.
• Completeness is expressed as a percent between successful analyses and total
attempts:
Completeness = 100 x S/A
where S is the number of successful analyses and A is the total number of attempts.
• Comparability is expressed as a percent difference (%Diff) between the results for two
methods:
%Diff = 100 x (R1-R2)/[(Ri+R2)/2]
where R-| is the result for one method and R2 is the result for the second method.
Table B-3 shows the DQI goals that were estimated for critical measurements in the QAPP.
Table B-4 shows DQI values for measurements carried out with charcoal tubes (EPA Method 18,
Adsorption Tube Procedure, equivalent to NIOSH Method 1501) and Table B-5 shows DQI values for
THC analyzer measurements. Below, the precision, accuracy, and completeness of the data that were
obtained in this project are reviewed.
72
-------
Precision
Precision could not be established for the EPA Method 18 (NIOSH Method 1501) field
measurements because a sufficient number of measurements could not be made to define a standard
deviation (due to the short duration of all but three of the test conditions and the time lost waiting for
acceptable performance). With respect to measurements obtained with the THC analyzers, precision
was determined by the repetitive sampling of calibration gases. Table B-5 shows that the precision
obtained with these devices was generally well below the initial estimate of ± 10% listed in Table B-3.
Table B-3. Data Quality Indicator Goals for Critical Measurements Estimated in QAPP
Method and
Reference
Measurement
Parameter
Experimental
Condition
Expected
Precision
(Rel. Std. Dev.. %)
Expected
Accuracy
(% Bias)
Completeness
(%)
NIOSH 1501
Styrene
Content
1. Inlet and Outlet
of control
device,
2. Calibration gas
samples.
5. 8'
-10.7*
90
Total
Hydrocarbon
Analyzer with
FID. "
Hydrocarbon
compounds in
air.
1. Inlet and Outlet
of control
device,
2.Calibration gas
samples.
±10'
±5f
90
* Precision and bias for sampling with charcoal-filled adsorption tube.
" J.U.M. Model VE-7 THC Analyzer.
T Estimated values. Precision and bias will be determined for each instrument
Table B-4. Data Quality Indicator Values for EPA Method 18 (NIOSH
Method 1501) Measurements Made at Eljer Plumbingware*
Method and
Reference
Measurement
Parameter
Experimental
Condition
Measured Value
(ppm)
Accuracy
Bias)
Completeness
(%)
EPA 18
Styrene
39.1 ppm cal gas
35.8
-8.4
33
or
Content
5.6
NIOSH 1501
2.16 ppm cal gas
2.28
33
Precision undetermined. Single samples
73
-------
Table B-5. Data Quality Indicator Values for THC Analyzer
Measurements Made at Eljer Plumbingware*
INLET THC ANALYZER
Cal Gas/% Bias
2.16 ppm
Bias
39.1 ppm
Bias
170.8 ppm
Bias
Styrene Cal Gas
Styrene Cal Gas
Styrene Cal Gas
(THC Value)
w
(THC Value)
(%)
(THC Value)
(%)
6/22/93
2.13
-1.3
37.46 .
-4.2
150.33
-12.0
37.46
-4.2
38.96
-0.4
37.95
-3.0
6/23/93
2.11
-2.2
37.69
-3.6
148.80
-12.9
38.63
-1.2
6/24/93
39.24
0.4
37.28
-4.7
Average
2.12
-1.7
38.08
-2.6
149.56
-12.4
Precision (%CV)
0.7
2.0
0.7
OUTLET THC ANALYZER
Cal Gas/% Bias
2.16 ppm
Bias
39.1 ppm
Bias
170.8 ppm
Bias
Styrene Cal Gas
Styrene Cal Gas
Styrene Cal Gas
(THC Value)
(%)
(THC Value)
(%)
(THC Value}
(%)
6/22/93
2.21
2.2
36.42
-6.9
151.76
-11.1
36.42
-6.9
39.18
0.2
39.05
-0.1
6/23/93
2.05
36.01
149.96
37.89
6/24/93
37.08
37.26
Average
2.13
22
37.41
-3.4
150.86
-111
Precision (%CV)
5.2
3.2
0.8
* Completeness was 99.6% for both THC analyzers.
Bias
For Method 18 each measurement of bias was less than the -10.7% DQI goal cited in Table B-3.
Thus, this DQI goal was met, although only two samples were taken. For the THC analyzers, bias was
determined for each measurement of the 2.16 and 170.8 ppm calibration gases and for the 39.1 ppm
74
-------
primary calibration gas before each calibration (before instrument span was set to 39.1 ppm). The DQI
goal of ± 5% were easily met for the 2.16 and 39.1 ppm calibration gases but were not met for the 170.8
ppm calibration gas. In this case, One losses could be partly at fault because some condensation of
styrene within a Teflon sample line had been observed in the past with this particular calibration gas.
Cpmpieteness
For the NIOSH Method 1501 samples taken at the inlet and outlet of the Polyad FB device,
completeness was 100% because every sample that was attempted was successfully analyzed.
For THC analyzer measurements, completeness was near 100%. Minuscule amounts of data
were lost during FID flame-outs and some data was lost during a short power failure. Out of
approximately 14.7 hours of data (at one data point per second) less than 3 minutes worth of data were
lost due to FID flame-outs or power failures (completeness of 99.6%).
Representativeness
The design of the pilot-scale liquid chemical scrubber dictated much of the sampling strategy
and sampling methodology practiced during this evaluation to obtain representative samples. The use
of a large, flexible aluminum sampling line avoided contamination from plasticizers in a flexible plastic
line. Location of the sampling line inlet (within the vent exhaust duct) and flow velocity into the Polyad
FB unit (nominally 2 m/sec) assured that the sample extracted from the gel coat booth #2 exhaust was
representative. Following the sample methodology recommended in Section 7.4 of EPA Method 18
(equivalent to NIOSH Method 1501) also assured that representative samples were obtained.
Comparability
The sampling plan for this project made provision for simultaneous sampling using the two
measurement methods of this study which would allow comparison of the results when suitably
averaged over the same sampling period. While fewer EPA Method 18 samples were obtained than
were planned, two concurrent inlet outlet Method 18 runs were made that can be compared to THC
measurements averaged over the time that the Method 18 samples were taken. Table B-6 shows this
comparison.
75
-------
Considering that the expected bias for the Method 18 measurements is -10.7% and that the
expected bias for the THC measurements was ± 5%, three of the four measurements lie within 15.7% of
each other. The other measurement lies considerably outside of the acceptable range. These is no
explanation for this difference, other than it would have been desirable to have had many more Method
18 samples to compare with concurrent THC measurements.
Table B-6. Comparability of Method 18 and THC Analyzer Measurements
Sample
Start
End
Styrene Concentration
Comparability
Time
Time
Method 18
From THC
THC-Method 18
(PPm)
(ppm)
{%)
Inlet, Liquid Chemical Scrubber
10S2
1125
70.5
80.0
12.6
Outlet, Liquid Chemical Scrubber
1052
1125
41.3
48.1
15.2
Inlet. Liquid Chemical Scrubber
1332
1351
76.2
94.7
21.7
Outlet, Liquid Chemical Scrubber
1332
1351
42.5
49.3
14.8
76
-------
APPENDIX C
TOTAL HYDROCARBON ANALYZER DAILY RESULTS
77
-------
Table C-1. THC Analyzer Results from June 22,1993, First Period of Spraying
«VJ
CIa ^ m jJ
m m FT THC 1
tFUItV C.
ciapsiQ
inuc i i nv twu
">
Start
End
Time
Average
Population
95% Conf.
Average
Population
95% Conf.
Time
Time
(seconds)
Std. Dev.
Interval
Std Dev.
Interval
0630 00
0834:12
253
16.76
4 97
0.61
20.59
629
0.78
0834 13
0834:52
40
67.67
23.76
7.36
39.20
5.74
1.78
0834:55
0839:14
260
103.01
36.96
4.49
66.81
12.50
1.52
0839:15
0844:36
322
17.31
6.30
0.69
21.67
7.25
0.79
0844 37
0850:20
344
93.81
41.84
4.42
63.33
16.04
1.70
0850:21
0853:07
167
21.16
3.01
0.46
24 36
3.95
0.60
0853:08
0859:56
409
85.78
43.67
4.23
59.59
19.49
1.89
0859:57
0859:59
3
28.92
0.33
0.37
26 56
0.12
0.14
0900:00
0900:07
8
32.07
1.10
077
25.83
0.30
0.21
0900 08
0903:25
198
18.69
3.65
0.51
21.66
7.37
1.03
0903 26
0907:47
262
89.67
44.93
5.44
58 64
13.35
1.62
0907:48
0908:03
16
28.56
0.63
0.31
31.51
0.68
0.33
0906:04
0908:10
7
31.71
0.96
0.71
29.90
0.26
0.19
0908:11
0908:14
4
29.48
022
0.21
29.22
0.11
0.11
0908:15
0908:23
9
32.26
0.87
0.57
28.46
0.25
0.16
0908:24
0908:27
4
29 71
0.28
0.28
27.86
0.14
0.14
0908:29
0908:39
11
29.21
0.57
0.34
27.17
0.25
0.15
0908 40
0916:41
482
68.66
43.55
3.89
47 87
15.49
1.38
091642
0916:46
5
29.38
0.31
0.27
34 50
0.04
004
0916:47
0918:20
94
49.23
21.63
4.37
33 02
1.59
0.32
091821
0918:23
3
29.92
0.09
0.10
29.49
0.09
0.11
0918:24
0918:29
6
30 96
049
0.39
29.12
0.13
0.10
0918:34
0918:36
3
29 53
044
0.50
26 31
0.06
0.06
0918 38
0918:42
5
28.49
0.73
0.64
27.87
0.14
0.13
0918:43
0918:48
6
31 78
1.19
0.95
27 39
0.14
0.12
0918:49
0920:18
90
22.93
2.68
0.55
28 86
3.29
0.68
0920 19
0925:31
313
103.70
38.04
421
6491
1267
1.40
0925:33
0925 37
5
30.60
0.29
0.25
40.73
0.44
0.39
0925:38
0S26.08
31
24.01
2.25
0.79
35.97
2.13
0.75
0926:09
0926:11
3
30.82
0.46
0.52
32.00
0.18
0.20
0926:12
0926:14
3
29.59
0.35
0.39
31.33
0.13
0.14
0926:17
0926:20
4
29.40
0.41
0.41
30 45
0.19
0.19
0926:21
0926:38
18
32 73
201
0.93
28 41
0.81
0.38
0926:39
0931 02
264
20.27
3.97
0.48
24.94
3.57
0.43
0931:03
0942:22
680
69 77
28.59
215
47.70
11.38
0.86
0942:25
0942:27
3
30.74
0.41
0.46
28.90
0.05
0.05
0942:28
0942:30
3
29 29
0.42
0.48
28.76
0.02
0.02
0942:35
0942:41
7
28.11
0.84
0.62
28.42
0.11
0.08
0942:44
0943:10
27
23 33
283
1.07
28.02
0.14
0.05
0943:11
0944 23
73
41.57
5.07
1.16
25.70
1.49
0.34
0944:24
0947 39
196
17.31
2.75
0.39
19.22
2.83
0.40
0947:40
0956 42
543
85.07
29.84
2.51
53.95
11.91
1.00
0956:43
0956:49
7
29.30
0.45
033
38.85
0.47
0.35
0956:50
0956 54
5
31.42
033
0.29
40.52
0.34
0.30
0956:55
0956:58
4
2915
045
0 44
41.84
0.28
0.27
0956:59
0957:06
8
32.39
1.38
0.95
43.88
0.62
0.43
0957:07
095716
10
27 22
1.38
0.86
47.47
1.25
0.77
0957:17
1002 01
285
99 66
51.41
5.97
60 35
13.31
1.55
1002:02
1002:06
5
29.75
0.25
0.22
33.42
0.24
0.21
1002:07
1002:17
11
31.03
0.50
0.29
31.99
0.53
0.31
1002:20
1002:23
4
30.65
0.24
0.24
30.69
0.19
0.19
1002:24
1002 33
10
29.35
0.55
0.34
29 57
0.37
0.23
1002:34
1002:42
9
31.01
065
0.43
28 34
0.38
025
1002:43
1003:12
30
27.66
1.14
0.41
25.90
0.98
0.35
1003:15
1019:59
1005
9.57
5.72
035
12.37
3.54
0.22
Emissions
>30 PPM
3887
82 02
54.27
Emissions
<30 PPM
1432
2019
24.03
All
Emissions
5319
65.36
4613
73.1% of time spent spraying, 0834 • 1003
• Outlier, from periods at the beginning and end ot spraying
78
-------
Table C-2. THC Analyzer Results from June 22,1993, Second Period of Spraying
June Z
2,1993
Elapsed
INLET THC (pp
m)
OUTLET THC (
ppm)
Start
End
Time
Average
Population
95% Conf.
Average
Population
95% Conf.
Time
Time
(seconds)
Sid Dev.
Interval
Std. Dev.
Interval
1020:00
1032:45
766
8.46
5.77
0.41
15.37
1065
0.75
1032:46
1038:39
354
113.27
4805
5.00
85.93
20.01
208
1038:40
1038 44
5
29.38
0.32
0.28
39.58
0.36
0.31
1036:46
1043:09
264
18.96
4.54
0.55
27.22
9.83
1.19
1043:10
1043:17
B
4207
7.11
4.93
58.88
0.92
0.64
1043:18
1043:23
6
24.86
1.99
1.59
62 20
0.73
0.58
1043:24
1047:55
272
106.83
54.41
6.47
67.58
18.72
223
1047:56
1047:58
3
29.43
0.30
0.34
33.00
0.22
0.25
1047:59
1048 09
11
33.68
2.03
1.20
31.69
0.46
0.27
1048:10
1049:10
61
26.03
1.49
0.37
26.98
217
0.54
1049:11
104915
5
30 66
0.33
0.29
23.36
0.13
0.11
1049:16
1051:27
132
23 34
3.89
0.68
26.77
7.40
1.26
1051:28
1051:36
9
31.92
1.03
0.67
46.35
0.71
0.46
1051:37
1051:39
3
29 68
0.26
0.29
47.79
0.12
0.13
1051:40
1051:44
5
31.60
0.73
0.64
48.31
0.21
0.19
1051:45
1051:48
4
28.64
0.22
0.22
49.00
0.29
0.29
1051:49
1100:28
520
102.67
46.25
3.98
71.21
18.79
1.61
1100:29
1100:33
5
28 99
0.57
0.50
32.99
0.06
0.05
1100:34
1100:38
5
31 60
0.75
0.66
33.56
0.29
0.25
1100:39
1100:48
10
25 71
1.91
1.19
35.03
0.62
0.39
1100:49
1100:51
3
31.21
0.46
0.52
36.65
0.19
0.21
1100:52
1101:56
65
20 58
3.26
0.79
42.12
2.17
0.53
1101:57
1103:43
107
69.62
38.05
7.21
49.21
785
1.49
1103:44
1103:51
a
29 20
0.57
0.40
67.32
1.01
0.70
1103:52
110821
270
82.01
49.27
5.88
56.06
14.48
1.73
1108:23
1109 07
45
34.29
2.26
0.66
31.49
098
0.29
1109 08
1109-10
3
29.29
0.17
0.19
29.96
0.05
0.06
1109:11
1109:20
10
32.85
1.55
0.96
29.71
0.09
006
1109:21
1110:08
48
27 97
1.28
0.36
28.41
0.67
0.19
1110:11
1110:26
16
27.55
1.61
0.79
26.68
0.24
0.12
1110:27
1110:47
21
39 67
6.56
2.80
25.71
0.33
0.14
1110:48
1110 53
6
29.08
0.57
0.46
24.97
0.10
0.08
1110:54
1110 56
3
30.79
0.34
0.39
24.72
003
0.04
1110:57
1117 28
392
16.80
4.81
0.48
19.55
6.63
0.66
1117:29
1119:39
131
77.71
37.85
6.48
44.54
547
0.94
1119:41
1119 44
4
30 71
0.39
0.38
59.90
0.43
0.42
1119:49
1119:52
4
29 37
0.28
0.28
63.04
0.59
0.58
1119:55
1119:58
4
29.73
0.08
0.08
65.71
0.49
0.48
1119:59
1124 49
291
122.96
49.46
5.68
83.75
17.54
2.01
1124:50
1130:11
322
10.97
13.63
1.49
21.47
20.58
2.25
1130:12
1135:19
303
123.95
53.08
5.98
78.39
17.27
1.94
1135:20
1135:49
30
2611
1.67
0.60
37.13
2.10
0.75
1135:50
1136:12
23
36 09
5.99
2.45
31 38
1.22
0.50
1136:13
1136:17
5
27 28
1.32
1.15
28.97
0.21
0.16
1136:18
1136 24
7
36 47
3.87
2.87
28.06
028
0.21
1136:25
1136:57
33
27.42
1.33
0.45
25.79
0.82
0.28
1136:58
1137:03
6
32.17
1.15
0.92
25.24
0.14
0.11
1137:04
1138 13
70
25.10
2.10
0.49
34.62
6.42
1.50
1138:14
1146:44
511
103.73
54.63
4.74
65.69
21.85
1.89
1146:45
1147:27
43
1812
6.34
1.90
42.34
4.79
1.43
1147:28
115511
464
101.12
52.44
4.77
63.31
21.04
1.91
1155:12
1100:12
301
16.56
324
0.37
11.32
8.75
0.99
1200:16
1200:19
4
43.19
8.05
7.89
0.57
000
0.00
1200:20
1216:03
791
0.72
1.37
0.10
5.87
12.99
0.91
Emissions
>30 PPM
3404
100.43
67.40
Emissions
<30 PPM
1831
18.37
2362
All
Emissions
5235
71.73
52.09
65.0 % of bme spent spraying, 1032 -1200
* Outlier. from periods at the beginning and end of spraying.
79
-------
Table C-3. THC Analyzer Results from June 22,1993, Third Period of Spraying
i. nn 4 AA4
Ik It Tl 1/^ /___\
r\i ST1 CT Tun l
cwpsvo
I Mb i i nw
Start
End
Time
Average
Population
95% Conf.
Average
Population
95% Conf,
Time
Time
(seconds)
Std. Dev.
Interval
Std. Dev.
Interval
1222:40
1239:46
1027
5.29
1.51
0.09
4.59
4.28
0.26
1239:47
1243:03
197
100.87
39.63
5.53
49 35
7.62
1.06
1243:04
1252:34
571
16.37
5.24
0.43
13.93
6.97
0.57
1252:35
1252:38
4
31.25
0.46
0.45
13.68
0.08
0.08
12S2:39
1252:48
10
25.30
2.68
1.66
14.05
0.14
0.09
1252 49
1253:01
13
32.48
1.65
0.89
14.74
025
0.14
1253:02
1253 07
6
27.92
1.00
0.80
15.35
0.10
0.08
1253:08
1253:28
21
31.98
1.63
0.70
16.13
0.35
0.15
1253:29
1253:57
29
24.64
2.85
1.04
17.43
0.35
0.13
1254:00
1254:04
5
17.73
9.19
8.05
18.27
0.08
0.07
1254:05
1254:15
11
32.42
1.22
0.72
18.54
0.12
0.07
1254:16
1254:18
3
29.15
0.17
0.19
18.77
0.04
0.04
1254:19
1255:13
55
35.65
2.49
0.66
1894
0.08
0.02
1255:14
125530
17
27.01
1.22
0.58
18.54
0.15
0.07
1255:31
125549
19
33.28
1.52
0.68
17.90
0.23
0.10
1255:50
1256:30
41
21.80
3.18
0.97
16.78
0.46
014
1256:31
1256:33
3
31 48
0.49
0.55
15.91
0.02
002
1256:34
1259:47
194
19.18
1.88
0.26
19.58
7.31
1.03
1259:48
1305:44
357
126 35
43 84
4.55
71.65
14.65
1.52
1305:45
1308:30
166
22 21
3.23
0.49
35.00
6.95
1.06
1308:31
1312:51
261
107.15
42 39
5.14
60.85
11.34
1.38
1312:52
1313:22
31
27.28
1.72
0.61
34.37
1.46
0.51
1313:25
1313:51
27
28.97
0.68
0.26
3242
0.72
0.27
1313 52
1318:53
302
100.74
51.19
5.77
59.68
13.23
1.49
1318:54
1320:54
121
22.94
2.01
0.36
26.39
5.21
0 93
1320:55
1321:03
9
34 02
1.89
1.23
18.95
0.21
0.14
1321:04
1322:44
101
22.08
2.34
0.46
22.28
4.32
0.84
1322:45
1328:29
345
113.89
46.42
4.90
62 84
14.19
1.50
1328:30
1330 58
149
1749
4.72
0.76
23 57
7.07
1.13
1331:01
1337:31
391
16.10
3.47
0.34
1058
0.86
0.09
1337:32
1337:36
5
31.32
0.61
0.53
11.36
0.08
0.07
1337:37
1338:14
38
24.33
2.83
0.90
14.16
1.87
0.59
1338 15
1338:22
8
33.74
1.99
1.38
18.02
0.45
0.31
1338 23
1338:55
33
21.44
2.49
0.85
22.63
2.34
0.80
1338 56
1342:27
212
112.73
49.26
6.63
49.49
10.83
1.46
1342:28
1351:01
514
14.38
4.79
0.41
21.75
5.97
0.52
1351:02
1356:15
314
112.20
34.37
3.80
78.50
13.51
1.49
1356:16
1357:27
72
23.34
2.26
052
55 83
719
1.66
1357:28
1357:30
3
31.41
0.14
0.16
44.77
0.20
0.23
1357:31
1405:00
450
3.14
4.62
0.43
21.95
7.16
0.66
Emissions
>30 PPM
2139
106.07
60.19
Emissions
<30 PPM
2519
18.13
20 23
All
Emissions
4658
58.51
38 58
46.9% of time spent spraying, 1239 -1357
" Outlier, from periods at the beginning and and of spraying.
80
-------
Table C-4. THC Analyzer Results from June 23,1993, First Period of Spraying
June 23. 1993
Elapsed
ot
TLET THC (
ppm)
Hi -¦
Start
End
Time
Average
Population
95% Conf.
Average
Population
95% Conf.
Tune
Time
(seconds)
Std. Dev.
Interval
Std. Dev.
Interval
0703:30
0712:13
524
4.59
1.54
0.13
3.68
2.99
0.26
0712:14
0712:42
29
59.33
13.87
5.05
23.85
2.72
0.99
0712:43
0712:54
12
24.30
3.89
2.20
30.48
1 03
0.58
0712:55
0718:46
352
77.75
33.26
3.47
43.17
10.90
1.14
0718:49
0719:02
14
37.94
4.41
2.31
19.42
0.63
0.33
0719:03
0734:32
930
7.41
2.87
0.18
5.41
3.74
0.24
0734 33
0737:59
207
81 58
30.09
4.10
33.62
5.79
0.79
0738:00
0742:12
253
14.29
3.91
0.48
14.02
4.89
0.60
0742:13
0747:27
315
82.84
31.52
3.48
40.33
8 44
0.93
0747:28
0749:03
96
20.86
4.48
0.90
19.36
2.14
0.43
0749:04
0749:41
38
37.34
2.90
092
14.66
0.63
0.20
0749:42
0750 52
71
14.42
4.17
0.97
17.40
2.71
0.63
0750:53
0757:18
386
80.80
31.69
3.16
39.92
9.37
0.93
0757:19
0757:31
13
27.98
1.09
0.59
23.20
033
0.18
0757:32
0757:43
12
34.79
329
1.86
22.13
0.34
0.19
0757:44
0757:51
8
26 41
1.79
1.24
21.32
0.21
0.15
0757:52
0758:03
12
33 51
1 73
0.98
20.70
0.14
0.08
0758:06
0758:13
8
3219
098
0.68
20.51
0.03
0.02
0758:14
0758:27
14
26 94
1.62
0.85
20.61
0.09
0.05
0758:28
0758:34
7
32.56
0.99
0.74
20.92
0.13
0.10
0758:35
0758:38
4
2910
0.55
0.54
21 24
0.09
0.09
0758,39
0758 47
9
30.34
0.20
0.13
21.51
0.18
0.12
0758:48
0759:21
34
22.03
3.93
1.32
24.19
1.65
0.56
0759:22
0808:43
562
71.97
32.12
2.66
38.37
10.98
0.91
0808:44
0811:05
142
1865
3.25
0.53
15.26
1.78
0.29
0811:06
0811:12
7
34 70
1.87
1.39
12.69
0.10
0.07
0811:13
0814 52
220
17.79
336
0.44
12.39
3.94
0.52
0814:53
0823 52
540
72 20
35.88
303
37.83
12.34
1.04
0823:53
0823 56
4
28.16
1.02
1.00
18 92
0.04
0.04
0823:58
0824:14
17
27.92
.1.43
0.68
1849
0.13
0.06
0824:15
0824:21
7
31.04
0.36
0.27
18.48
0.05
0.04
0824:22
0825:05
44
25.76
3.06
0.90
21.58
225
067
0825:07
0825:33
27
25.54
3.38
1.28
29.73
1.95
0.74
082534
0829:31
238
86.08
32.73
4.16
41.58
6.11
0.78
0829:34
0829:59
26
3610
271
1.04
26.40
1.10
0.42
0830:01
0830:43
43
32.15
1.40
0.42
21.88
1.30
0.39
0830:44
0830 47
4
29.09
0.44
0.43
19.91
0.10
0.10
0830:48
0830:53
6
30.68
0.34
0.27
19.54
016
0.13
0830:54
0830:58
5
29 63
0.17
0.15
18.89
0.17
0.15
0830 59
0831:02
4
30.49
023
0.23
18.48
0.08
0.08
0831:03
0831:11
9
28 47
0.72
0.47
17.89
0.24
0.16
0831:12
0831:17
6
31.15
0.58
0.46
17.23
0.14
0.11
0831:18
0834:11
174
17.76
2 49
0.37
15.02
292
0.43
0834:12
0840:55
404
83.27
36.06
3.52
44.40
960
0.94
0840:56
0845:03
248
15.93
3.55
0.44
17.94
4.52
0.56
0845:04
0854:11
548
77.49
34.33
2.87
40.18
12.57
1.05
0854:14
0854:21
8
31.34
0.68
0.47
19.71
0.11
0.08
0854:22
0854 45
24
2775
0.90
0.36
19.07
0.38
0.15
0854:46
0854:49
4
31.31
0.62
061
1851
0.15
0.14
0854:50
0855:12
23
27.30
1.96
0.80
18.05
0.30
0.12
0855:13
0855:16
4
30.87
0.45
0.44
17.59
0.06
0.06
0855:19
0855:25
7
30.96
0.67
0.50
17.20
0.07
0.05
0855:30
0855:38
9
28.27
068
0.44
16.82
0.09
0.06
0855:39
0855 41
3
31.16
0.17
0.19
16.62
0.02
0.02
0855:42
0856 16
35
26.05
224
0.74
16.33
0.35
0.12
0856:17
0856:19
3
30 77
0.26
0.30
1577
0.02
0.02
0856:20
0910:43
864
17 29
4.07
027
11.16
335
0.22
0910:44
0917:49
426
72,01
36.52
3.47
37.93
8.89
0.84
0917:51
0923:07
317
87.40
41.52
4.57
45.27
10.42
1.15
0923:09
0923 17
9
33.14
2.03
1.33
24.61
0.30
0.19
(Continued)
81
-------
Table C-4 Continued
h 10Q1
m !l ETT TUr 1 I _ .
ni in ft tup i
CldpSVU
! muuy
"1
lVrn;
Start
End
Thna
A wage
Population
95% Conf.
Avaraga
Population
95% Conf.
Tim*
Tmt
fsacondsl
Std. D«v
Interval
Std. Dav.
Interval
0923:18
0923:28
11
25.22
2.10
1.24
23.59
0.47
0.28
0923:29
0924:17
49
36.10
4.57
1.28
20.41
1.39
039
0924.16
0926:28
131
18.82
2.39
0.41
17.22
2.22
0.38
0905 06
0935:37
32
38.65
3.85
1.33
20.68
0.42
0.14
0935:38
0935:44
7
28.84
0.64
0.47
20.06
0.40
0.30
0935:45
0936:24
40
32.28
1.58
049
18.84
0.78
0.24
0936 25
0936:31
7
28.60
0.64
0.47
17.24
0.15
0.11
0936:32
0936:40
9
30.89
0.26
0.17
1668
0.17
0.11
0936:43
0936:54
12
32.75
1.61
0.91
15.88
0.21
0.12
0936:55
0939:15
141
19.72
3.75
0.62
17.00
4.06
0.67
0939:16
0946:26
431
86.39
33.59
3.17
42.91
10.91
1.03
0946:27
0948:35
129
20 91
2.56
0.44
21.87
4.48
0.77
0948:36
0955:17
402
109.67
39.12
3.82
54.97
11.16
1.09
095518
0957:16
119
20.40
3.33
0.60
11.19
11.17
2.01
Emissions
>30 PPM
5536
78.04
39.99
Emissions
<30 PPM
3829
15.83
13 22
Alt
Emissions
9365
52.60
29.05
59.1% of time spent spraying, 0712 • 0957
* Outlier, from a period at tha beginning of spraying.
82
-------
Table C-5. THC Analyzer Results from June 23,1993, Second Period of Spraying
June 2
3, 1993
Elapsed
INLET THC (pp
in)
Ol
TLETTHC (
ppm)
Start
End
Tim*
Average
Population
95V. Conf.
Average
Population
95% Conf.
Tim#
Tim#
(seconds)
Std. Dev
Interval
Std. Dev.
Interval
1030:00
1031:02
63
9.01
2.28
0.56
1399
5.22
1.29
1031:03
1036:24
322
86.88
41.41
4.52
41.03
925
1.01
1036:25
1039:32
163
18.05
3.49
0.54
20.30
5.65
0.87
1039:40
1048:57
550
91.13
51.17
4.28
53.05
17.47
1.46
1048:58
1049:47
SO
19.82
4.73
1.31
35 54
3 43
0.95
1049:48
1057:36
469
99.86
42.90
3.88
59.33
14.72
1.33
1057:37
1057:46
10
27.82
1.26
0.77
28.30
0.41
0.25
1057:47
1057:49
3
30.79
0.08
0.09
27.41
0.12
0.14
1057:50
1101:19
210
19.10
3.69
0.50
21.71
4.46
0.60
1101:20
1105:48
269
106.69
45.78
547
55.71
10.03
1.20
1105:49
1111:22
334
19.01
4.13
044
19 77
7.18
0.77
1111:23
1112:27
65
66.77
29.17
7.09
26.64
3.61
0.88
1112:28
1112:50
23
27.99
1.00
0.41
36.80
1.80
0.74
1112:51
1120:08
438
110.37
46.20
4.33
63.02
15.33
1.44
1120:09
1124:37
269
18.13
2.42
0.29
18.36
4.75
0.57
1124:38
1137:17
760
80.14
42.52
3.02
46.78
17.98
1.28
1137:18
1137:30
13
26 49
1.56
0.85
1995
0.33
0.18
1137:32
1144:44
433
16.83
3.88
037
13.26
4.99
0.47
1144:45
1154:36
592
96.86
46.51
3.75
56.61
19.45
1.57
1154:37
1154:57
21
25.04
3.07
1.31
21 90
0.61
0.26
1154:58
1155:03
6
31.96
0.78
0.62
20 60
0.18
0.14
1155:04
1157:51
168
18.74
3.22
0.49
1906
4.95
0.75
1157:52
1203:07
316
110.56
43.34
4.78
60.62
13.21
1.46
1203:08
1203:12
5
28.79
0.70
0.61
37.11
0.34
0.30
Emissions
>30 PPM
3790
94.93
53.55
Emissions
<30 PPM
1762
18 22
18.75
Ail
Emissions
5552
70 58
42.51
68 3 % of time spent spraying. 1030 • 1203
83
-------
Table C-6. THC Analyzer Results from June 23,1993, Third Period of Spraying
June 23, 1993
Elapsed
-INLET THC (ppi
m)
Ol
TLET THC (
ppm)
Start
End
Time
Average
Population
95% Conf.
Average
Population
95% Conf.
Time
Time
(seconds)
Std. Dev.
Interval
Std. Dev.
Interval
1220:37
1242:06
1290
4.64
2.57
0.14
10.33
11.15
0.61
1242:07
1243:15
69
73.26
30.12
7.11
24.78
2.13
0.50
1243:18
1243:25
8
31.32
0.54
0.38
30.95
0.69
0.48
1243 26
1243:57
32
25.77
1.91
0.66
36.83
2.94
1.02
1243:58
1254.07
610
90.64
50 85
4.03
53.72
19.99
1.58
1254:09
1254:28
20
32.95
1.41
0.62
22.44
0.57
0.25
1254:29
1254:44
ie
27.68
097
0.48
20.85
0.37
0.18
1254:45
1254:53
9
30.95
0.53
0.35
19.79
0.21
0.14
1254:54
1259:18
265
17 37
3.90
0.47
14.98
3.46
042
1259:19
1306:18
374
100.41
36 24
3.67
52.86
13.53
1.37
1306:19
1306:22
4
29.76
0.17
0.16
31.41
0.10
0.10
1306:23
1306:58
36
36.29
3.84
1.25
28.31
1.54
0.50
1306:59
1307:02
4
29.32
0.28
0.28
25.56
0.26
0.26
1307:05
1307:16
12
2S.19
0.45
0.26
24.07
0.45
0.25
1307:17
1307:23
7
31.54
0.76
0.56
22.91
0.23
0.17
1307:25
1307:41
17
35.27
3.16
1.50
21.99
0.25
0.12
1307:42
1308:51
70
18.53
4.09
0.96
28.57
5.11
1.20
1308:52
1313:40
289
86.49
38.12
4.39
46.99
9.29
1.07
1313:41
1317:31
231
19.07
3.66
0.47
19.46
5.12
0.66
1317:32
1322 08
277
104.34
32.59
3.84
52.88
9.51
1.12
1322:09
1322:11
3
29.27
0.27
0.31
33.93
0.21
0.24
1322:12
1322:19
8
32.19
1.24
0.86
32.62
058
0.40
1322:20
1324:09
110
20.62
4.37
0.62
24.37
2.68
0.50
1324:12
1324:33
22
23 39
2.58
1.08
25.15
0.65
0.27
1324:34
1327:38
185
58 51
26 09
3.76
25.52
3.06
0.44
1327:39
1332:29
291
1956
487
0.56
13.72
3.49
0.40
1332:30
1337:47
318
105.16
33.60
369
47.05
9.54
1.05
1337:49
1340:05
137
55 69
10 28
1.72
39.03
5.40
0.90
1340:07
1344 26
260
153.61
50.59
6.15
71.00
10.36
1.26
1344:27
1344 38
12
25.30
1.68
0.95
44.06
1 09
0.62
1344:39
1344 42
4
32.26
0.93
0.91
41 19
0.50
0.49
1344:43
1344:45
3
28.97
0.48
0.55
39.91
0.32
0.37
1344.46
1344 48
3
30.83
0.55
0.63
38.95
0.30
0.33
1344:49
1352:12
444
15.65
3.64
0.34
14.32
723
0.67
1352:13
1356.34
262
108.98
41.70
5.05
48.68
10.97
1.33
1356:35
1357:13
39
25.48
2.30
0.72
35.10
0.96
0.30
1357:16
1357:49
34
19.46
4.02
1.35
34.19
075
0.25
1357:50
1403:20
331
93.00
41.34
4.45
44.13
7.93
0.85
1403:21
1415:00
700
4.60
6.65
0.49
5.80
7.30
0.54
Emissions
> 30 PPM
3224
9515
48 48
Emissions
<30 PPM
1592
18.67
1844
All
Emissions
4816
69.87
38 55
66 9 % of tim« spent spraying, 1242 - 1415
* Outlier, from periods at the beginning and end of spraying.
84
-------
Table C-7. THC Analyzer Results from June 24,1993, First Period of Spraying
Jun« 24, 1993
Elapsed
tilt CT TUr> . _
|-\| in CT Tl_lf» /
IHU6 t mv IkV
jpill /
Start
End
Time
Average
Population
95% Corl
Average
Population
95% Conf
Tims
Tims
(seconds)
Std. Dev.
Interval
Std. Dev.
Interval
0712:00
0742:39
1802
5.45
2.17
0.10
3.77
4.06
0.19
0742:40
0743:18
39
62.84
18.42
5.78
26.19
3.43
1.08
0743 19
0743:28
10
28.13
1.44
089
33 07
0.67
0.41
0743:29
0748:50
322
90.27
27.84
304
50.85
9.79
1.07
0748 51
0754:11
321
12.12
2.68
0.29
14.14
6.06
0.66
0754:12
0754:48
37
64.97
19.12
6.16
28.61
3.35
1.08
0764:49
0754:54
6
28.14
0.94
0.75
35.03
0.41
0.33
0754:55
0801:28
394
90.81
32.88
3.25
51.54
12.45
1.23
0801:29
0805:30
242
12.18
2.69
0.34
15.00
5.00
0.63
0805:31
0809:34
244
91.16
34.86
4.37
43.53
8.49
1.07
0809:35
0813:20
226
14.19
2.83
0.37
21.08
7.78
1.01
0813:21
0818:54
334
91.73
39.89
4.28
56.84
24.08
158
0818:55
0822:44
230
15.40
296
0.38
21.39
19.84
2.56
0822 45
0828:25
341
94.96
43.20
4.58
77.74
9.20
0.98
0828:26
0828:31
6
26.94
1.03
0.82
65.82
0.24
0.19
082832
0829:32
61
37.52
4.20
1.05
62.43
1.65
0.41
0829 33
0829:35
3
29.38
0.34
0.39
59 44
0.07
0.08
0829:36
0829:48
13
31.92
0.91
0.49
59.17
0.33
0.18
0829 49
0829:52
4
29.60
0.30
0.30
58.30
0.14
0.14
0829:53
0830:05
13
34.26
2.23
1.21
57.62
0.26
0.14
0830:06
0830:09
4
28.69
066
0.65
57.05
0.04
0.04
0830:10
0830:19
10
33 36
1.47
0.91
56 70
0.19
0.11
0830:20
0830:23
4
28.68
0.82
080
56.33
0.04
0.04
0830:24
0830:44
21
33.62
1.96
0.84
55.61
0.37
0.16
0830:45
0830:50
6
27.37
1.19
0.95
54.87
0.11
0.09
0830:51
0830:54
4
30 49
024
0.24
55.19
0.50
0.49
0830:55
0831:34
40
28.33
0.87
0.27
54.09
0.70
022
0831:35
0831:37
3
31 20
060
0.68
53.07
0.04
0.05
0831:38
0831:59
22
26.49
1.60
0.67
52.73
0.21
0.09
0832 00
0832:11
12
33 25
1.98
1.12
5251
0.42
0.24
0832:12
0833:14
63
25 99
1.64
0.40
5047
0.79
0.19
0833:17
0833:20
4
29.19
0.40
0.39
49.04
0.05
0.05
0833 21
0833:23
3
30.65
0.22
025
48.87
0.05
0.06
0833:24
0837:49
266
12.93
2.87
0.35
46 80
3.09
0.37
0837:50
0842:12
263
92.19
40.92
4.95
68.43
714
0.86
0842:13
0847:00
288
1664
329
0.38
36.82
7.09
0.82
0847:01
0853:27
387
103.22
44.81
4.46
67 83
14.42
1.44
0853:28
0857:14
227
17.86
1.74
0.23
32.35
5.16
0.67
0857:15
0903:28
374
91.49
39.56
4.01
56.72
10.98
1.11
0903:29
0905 42
134
16.25
2.94
0.50
30.49
519
0.88
0905:43
0911:13
331
114.19
47.18
5.08
63.96
10.65
1.15
0911:14
0911:32
19
27 87
1.63
0.73
41.40
0.89
0.40
0911:33
0911:36
4
30.72
0.35
0.35
40.07
0.46
0.45
0911:37
0911:48
12
2824
0.76
0.43
40 33
0.40
0.23
0911:49
0912:09
21
38.02
3.25
1 39
40 66
0.62
0.27
0912:10
0912 35
26
21.99
3.79
1 46
41.54
0.80
0.31
0912:36
0920:47
492
97.09
44.23
3.91
59.30
15.40
1.36
0920:48
0924:39
232
14.99
2.77
0.36
8.11
8.35
1.07
0924:40
0924:59
20
33.52
1.48
0.65
1.08
0.04
0.02
0925:00
0925:03
4
29.51
0.21
0.21
1.01
0.02
0.02
0925:04
0925 28
25
34.40
1.76
0.69
2.29
1.46
0.57
0925:29
0932:07
399
13.21
2.25
0.22
13.38
7.04
0.69
0932:08
0937:02
295
104.13
42.75
4.88
62.99
13.29
1.52
0937:03
0940:39
217
17.31
3.12
0.41
26.11
5.72
0.76
0940:40
0948:59
500
83.77
32.49
2.85
51.59
6.44
0.56
0949:00
0953:15
256
16.74
371
0.45
25.03
7.12
0.87
0953 16
1000 30
435
87.61
41.58
3.91
54.99
14.05
1.32
(Continued)
85
-------
Table C-7 Continued
June 2
Start
Time
4, 1993
End
Time
Elapsed
Time
(seconds*
ir
Avar age
J LET THC (pp
Population
Std. Dev.
m)
95% Conf.
Interval
ot
Average
TLET THC (
Population
Std. Dev.
ppm)
95% Conl,
Interval
1000:31
1000:44
1001:01
Emission*
Emissions
All
1000:43
1001:00
1031:02
>30 PPM
<30 PPM
Emissions
13
17
1802
5015
3284
6299
28.53
32.96
7.48
91.24
15.67
6133
0.61
1.74
4.36
0.33
~.83
0.20
28.81
26.89
7.78
57.53
25.33
44.82
0.48
0.64
3.80
0.27
0.31
0.18
60.4 % o f time spent spraying, 0742 • 1001
* Outllftf. from periods at the beginning and and of spraying.
86
-------
Table C-8. THC Analyzer Results from June 24,1993, Second Period of Spraying
June 24, 1993
Elapsed
INLET THC (pp
pi)
OUTLET THC (
ppm)
Start
End
Time
Average
Population
95% Conf.
Average
Population
95% Conf.
Time
Time
(seconds!
Std. Dev.
Interval
Std. Dev.
Interval
1033 47
1034:34
48
8.98
2.74
0.77
0.95
0.05
0.01
1034 35
1039:46
312
104.28
46.95
5.21
55.19
13.52
1.50
1039:47
1039:50
4
2921
0.48
0.47
42.67
0.26
0.25
103951
1041:26
96
38.61
354
0.71
34.08
4.40
0.88
1041:27
1044:39
193
23.06
2.01
0.28
23.18
5.03
0.71
1044:41
1053:18
519
97.59
58 98
5.07
58.69
22.41
1.93
1053:19
1053:22
4
29.84
0.08
0.08
29.39
0.28
0.28
1053 23
1053:27
5
30.24
0.07
0.06
30 94
0.39
0.34
1053:28
1054:03
36
26.97
1.65
0.54
39.01
4.52
1.48
1054 04
1101:22
439
125.03
61.70
5.77
71.30
19.99
1.87
1101:23
1101:35
13
28.53
1.33
0.72
30.64
0.62
0.34
1101:36
1101:47
12
31.95
1.28
0.72
28.59
0.56
0.32
1101:51
1101:55
6
31.09
0.34
0.27
27.03
023
0.19
1101:56
1102:01
6
29 63
0.35
0.28
26.30
0.26
0.21
1102:02
1102:06
5
30 32
015
0.13
25.57
0.17
0.15
1102:07
1106:14
248
16.64
5.55
0.69
17.84
5,02
0.62
1106:15
1112:13
359
131.94
58.08
6.01
71.59
18.37
1.90
1112:15
1112:21
8
28.77
0.55
0.38
39 06
0.65
0 45
1112:22
1112:25
4
30.76
0.45
0.44
37.34
0.19
0.18
1112:26
1112:30
5
28.92
0.51
0.45
36.25
0.31
0.27
1112:31
1112:36
6
31 87
1.15
0.92
34.86
0.52
042
1112:37
1118:11
335
1949
5.20
0.56
17.91
6.67
071
1116:12
1124:15
364
10431
58.37
6.00
54.45
1505
1.55
1124:16
1124:19
4
29 75
0.25
0.25
27.79
0.15
0.15
1124:20
1124:42
23
33.76
1 69
0.69
25 98
0.90
0.37
1124:43
1125:11
29
27.81
1.30
0.47
23 23
0.65
0.24
112512
1125:15
4
30.30
0.07
0.06
22.29
0.06
0.06
1125 17
1125:28
12
31.52
0.70
0.39
21.67
0.24
0.14
1125:32
1125:45
15
31.68
0.64
0.32
21.06
0.17
0.09
1125:46
1126:00
15
27 38
1.17
0.59
20.34
0.25
012
1126:01
1126:23
23
34 38
'2.09
0.85
19.39
0.30
0.12
1126:24
1128:50
147
1964
3.92
0.63
18.77
3.74
0.60
1128:51
1130:21
91
81.65
45 55
9.36
31.48
2.58
0.53
1130:23
1130 46
25
25 81
2.57
1.01
42.34
2.34
0.92
1130.47
1134:40
234
109.15
63.24
8.10
57.42
10.67
1.37
1134:41
1134:47
7
27.72
1.30
0.96
33.93
0.54
0.40
1134:49
1135:31
43
27.11
1.11
0.33
28.91
2.13
0.64
1135:33
1135:41
9
29.30
0.36
0.23
25.05
0.32
0.21
1135:42
1136:22
41
34 63
207
0.63
22.61
1.13
0.35
1136:24
1136:45
23
28 66
064
0.26
2012
0.42
0.17
1136:46
1136 53
8
31 22
064
0.45
19.27
0.31
0.21
1136:54
1138 29
96
20.04
379
076
1822
2.70
0.54
1138:30
1141:14
165
88 60
48.02
7.33
39.09
4.93
0.75
1141:15
1141:36
22
28,03
1.10
0.46
31.21
1.23
0.52
1141:40
1141:47
8
30.43
0.16
0.11
28.01
0.37
0.2S
1141:48
1142:01
14
29 26
0.56
0.29
26.63
0.47
0.25
1142:02
1142:23
22
31.36
0.57
0.24
24.24
1.03
0.43
1142:24
1146:31
248
1963
4.28
0.53
16.60
4.62
0.57
1146:32
1153:55
123.56
61.56
5.73
62.24
17.48
1.63
1153:56
1156 22
147
21.92
273
0.44
1694
8.91
1.44
1156:23
1206:00
578
81.84
37.49
3.06
40.56
23 57
1.92
1206:01
1206.18
18
2914
0.90
0.42
24.78
052
0.24
1206:19
1206:26
8
30.86
0.51
0.35
23.51
0.18
0.12
1206:27
1207:15
49
25.07
2.44
0.68
21.18
1.08
0.30
1207:16
1207:18
3
30.51
0.19
022
19.27
0.09
0.10
1207:19
1209:45
147
19.55
3.98
0.64
8.94
8.37
1.35
Emissions
>30 PPM
3806
100.78
54.27
Emissions
<30 PPM
1796
20 94
19.86
All
Emissions
5602
7518
43 23
67.9 % of time spent spraying. 1034 - 1207
* Outlier, from periods at the beginning and end of spraying.
87
-------
Table C-9. THC Analyzer Results from June 24,1993, Third Period of Spraying
June 24, 1993
Elapsed
INLET THC (ppi
n)
-Ol
TLET THC (
?pm)
Start
End
Time
Average
Population
95% Con'
Average
Population
95% Conf.
Time
Time
(seconds)
Std. Dev.
Interval
Std. Dev.
Interval
1230:15
1244:15
841
5.45
263
0.1 a
6.16
3.09
0.21
1244:16
1247:46
211
116.96
55 88
7.54
56.16
12.45
1.68
1247:47
1251:57
251
21.52
4.05
0.50
24.12
9.35
1.16
1251:58
1252:01
4
30.95
0.48
0.47
21.41
0.38
0.37
1252:02
1252:36
35
22.89
2.23
0.74
30.28
4.92
1.63
1252:37
1257:40
304
132.39
60.19
6.77
68.41
14.37
1.62
1257:41
1304:26
406
20.10
5.03
0.49
17.88
7 43
0.72
1304:28
1305:25
59
36 62
3.40
0.87
15.53
087
0.22
1305:26
1305:42
17
29.15
0.83
0.39
17.65
0.33
0.16
1305.45
1305:52
a
29 36
0.29
0.20
18.73
0.19
0.13
1305:53
1305:57
5
30 90
0.46
0.41
19.22
0.18
0.16
1306:59
1306:10
13
26.14
1.47
0,80
19.79
0.22
0.12
1306:11
1307:25
75
43.30
7.09
1.60
19.98
1.06
0.24
1307:26
1333:06
1541
12.62
4.09
0.20
8.90
3.77
0.19
1333:07
1338:05
299
129.40
52.80
5.98
64.94
12.75
1.45
1338:06
1339.43
98
21.62
3.45
0.68
34.37
332
0.66
1339:44
1344:17
274
109.07
51 49
6.10
K.I 4
6.78
0.80
1344:18
1346:00
103
21.39
2.85
0.55
33.22
3.55
0.69
1346:01
1350:58
298
114.81
49 64
5.64
60.55
10.73
122
1350:59
1352:03
65
22 03
3.40
083
39.46
2.17
0.53
1352:04
1353:56
113
122.79
38 92
7.18
51.17
3.17
0.58
1353:57
1354:04
8
26.55
1.22
0.85
43.61
0.63
0.43
1354:05
1354:11
7
41.97
5.32
3.94
41.30
0.62
0.46
1354:12
1400:00
349
4.03
5.99
0.63
985
12.43
1.30
Emissions
>30 PPM
1649
113.75
56.93
Emissions
<30 PPM
2545
1605
15.13
All
Emissions
4194
54.46
31 56
39.3 % of time spent spraying. 1244 - 1354
* Outlier, from periods at the beginning and end of spraying.
88
-------
APPENDIX D
RESULTS OF CHEMICAL ANALYSES OF WATER AND SCRUBBER LIQUID SAMPLES
89
-------
Table D-1. Analysis of Sample from Scrubber Chamber #1,6/23/93 at 1340 houre
Date Sampled: Jun 23,1993 Sample ID:
Date Analyzed: Aug 25, 1993 SRI Run No.:
Sample Size: 0.01 ml Related Blank:
Scrubber Tank 1, Sample #5, H438-27-7
P03050
P02642 Surrogate
{% Recovery)
Amount
Concentration
or Det. Limt
Number
Compound
(NG)
(uG/L)
(HG/I)
17
1,2-dichloroethane-d4 SURR1
187
37.3
74.7
26
toluene-d8 SURR2
2S8
51.5
103
40
4-bromofluorobenzene SURR3
256
51.3
103
1
chloromethane
U
U
1255
2
vinyl chloride
U
U
885
3
bromomethane
u
u
3475
4
chloroethane
u
u
2510
5
1,1-dichloroelhene
u
u
2170
6
acetone
u
u
3640
7
methyl iodide
u
u
1600
8
carbon disulfide
u
u
1400
9
methylene chloride
u
u
2610
10
trans-1,2-dichloroethene
u
u
865
11
1,1-dichloroethane
u
u
2170
12
2-butanone
u
u
7300
13
bromochloromethane IS1
250
50
14
chloroform
233
23300
410
15
1,1,1-trichloroethane
U
U
7200
16
carbon tetrachloride
U
U
5300
18
benzene
U
U
795
19
1,2-dichloroethane
U
U
780
20
1,4-difluorobenzene IS2
250
50
21
trichloroethene
U
U
1425
22
1,2-dichloropropane
U
U
790
23
bromodichloromethane
U
U
1185
24
cis-1,3-dichloropropene
U
U
1225
25
2-hexanone
U
U
1545
27
toluene
U
U
1010
28
trans-1,3-dichloropropene
U
U
1320
29
1,1,2-trichloroethane
U
U
1660
30
tetrachloroethene
U
U
1440
31
4-methyl-2-pentanone
U
U
2065
32
dibromochloromethane
U
U
4425
33
chlorobenzene-dS IS3
250
50
34
chlorobenzene
U
U
1380
35
ethylbenzene
U
U
1085
36
m- & p-xylene
U
U
1020
37
o-xylene
U
U
945
38
styrene
U
U
705
39
bromoform
U
U
2545
41
1,1,2,2-tetrachloroethane
U
u
3135
U - Compound not detected or below detection limit
90
-------
Table D-2. Analysis of Sample from Scrubber Chamber #2, 6/23/93 at 1340 hours
Date Sampled: Jun 23,1993 Sample ID: Scrubber Tank 2, Sample #6, H438-28-1
Date Analyzed: Aug 25, 1993 SRI Run No.: P03051
Sample Size: 0.100 ml Related Blank: P02034 Surrogate
(% Recovery)
Amount
Concentration
or Det. Limt
Number
Compound
(NG)
(uG/L)
(nG/l)
17
1,2-dichioroethane-d4 SURR1
180
35.9
71.8
26
toluene-d8 SURR2
254
50.8
102
40
4-bromofluorobenzene SURR3
239
47.9
95.8
1
chloromethane
U
U
125.5
2
vinyl chloride
u
U
88.5
3
bromomethane
u
u
347.5
4
chloroethane
u
u
251.0
5
1,1-dichloroethene
u
u
217.0
6
acetone
70.9
709
364.0
7
methyl iodide
U
U
160.0
8
carbon disulfide
U
U
140.0
9
methylene chloride
U
U
261.0
10
trans-1,2-dichloroethene
U
U
86.5
11
1,1-dichloroethane
U
U
217.0
12
2-butanone
U
U
730.0
13
bromochloromethane IS 1
250
50
14
chloroform
3940
39400
41.0
15
1,1,1-trichloroethane
U
U
720.0
16
carbon tetrachloride
U
U
530.0
18
benzene
U
U
79.5
19
1,2-dichloroethane
U
U
78.0
20
1,4-difluorobenzene IS2
250
50
21
trichloroelhene
U
U
142.5
22
1,2-dichloropropane
U
U
79.0
23
bromodichloromethane
U
U
118.5
24
cis-1,3-dichloropropene
U
U
122.5
25
2-hexanone
U
U
154.5
27
toluene
U
U
101.0
28
trans-1,3-dichloropropene
U
U
132.0
29
1,1,2-trichloroethane
U
U
166.0
30
tetrachloroethene
U
U
144.0
31
4-methyl-2-pentanone
U
U
206.5
32
dibromochloromethane
U
U
442.5
33
chlorobenzene-dS IS3
250
50
34
chlorobenzene
u
U
138.0
35
ethylbenzene
u
U
108.5
36
m- & p-xylene
u
U
102.0
37
o-xylene
u
U
94.5
38
styrene
u
U
70.5
39
bromoform
u
u
254.5
41
1,1,2,2-tetrachIoroethane
u
u
313.5
U - Compound riot detected or below detection limit
91
-------
Table D-3. Analysis of Sample from Scrubber Chamber #1, 6/24/93 at 1040 hours
Date Sampled: Jun 24,1993 Sample ID:
Date Analyzed: Aug 25, 1993 SRI Run No.:
Sample Size: 0.05 ml Related Blank:
Scrubber Tank 1
P03052
P02642
Sample #7, H438-28-2
Surrogate
(% Recovery)
Amount
Concentration
or Det. Limt
Number
Compound
(NG)
(iiG/L)
(uG/L)
17
1,2-dichloroethane-d4 SURR1
190
38
76
26
toluene-d8 SURR2
260
52.1
104
40
4-bromofluorobenzene SURR3
248
49.5
99.1
1
chloromethane
U
U
251
2
vinyl chloride
U
U
177
3
bromomethane
u
u
695
4
chloroethane
u
u
502
5
1,1-dichloroethene
u
u
434
6
acetone
95.5
1910
728
7
methyl iodide
U
U
320
8
carton disulfide
5.2
104
280
9
methylene chloride
U
U
522
10
trans-1,2-dichloroethene
U
U
173
11
1,1-dichloroethane
U
U
434
12
2-butanone
2670
53400
1460
13
bromochloromethane IS1
250
50
14
chloroform
11.5
230
82
15
1,1,1-trichloroethane
U
U
1440
16
carbon tetrachloride
U
U
1060
18
benzene
U
U
159
19
1,2-dichloroethane
U
U
156
20
1,4-difluorobenzerte IS2
250
50
21
trichloroethene
U
U
285
22
1,2-dichloropropane
U
U
158
23
bromodichloromethane
U
U
237
24
cis-1,3-dichloropropene
U
U
245
25
2-hexanone
U
u
3090
27
toluene
U
u
202
28
trans-1,3-dichloropropene
U
u
264
29
1,1,2-trl chloroethane
U
u
332
30
tetrachloroethene
U
u
288
31
4-methyl-2-pentanone
u
u
4130
32
dibromochloromethane
u
u
885
33
chlorobenzene-dS IS3
250
50
34
chlorobenzene
U
U
276
35
ethylbenzene
U
U
217
36
m- & p-xylene
U
u
204
37
o-xylene
U
u
189
38
styrene
51.1
1022
141
39
bromoform
U
U
509
41
1,1,2,2-tetrachloroethane
U
U
627
U - Compound not detected or below detection limit
92
-------
Table D-4. Analysis of Sample from Scrubber Chamber #2, 6/24/93 at 1040 hours
Date Sampled: Jun 24, 1993 Sample ID: Scrubber Tank 2, Sample #8, H43B-29-3
Date Analyzed: Aug 26, 1993 SRI Run No.: P03060
Sample Size: 5 ml Related Blank: P02034 Surrogate
(% Recovery)
Amount
Concentration
or Det. Umt
Number
Compound
-------
Table D-5. Analysis of Sample from Scrubber Chamber #3,6/24/93 at 1040 hours
Date Sampled: Jun 24, 1993 Sample ID: Scrubber Tank 3, Sample #9, H438-29-2
Date Analyzed: Aug 26,1993 SRI Run No.: P03059
Sample Size: 5 ml Related Blank: P02034 Surrogate
(*A Recovery)
Amount
Concentration
or Det. limt
Number
Compound
(NG)
(nG/L)
(uG/L)
17
1,2-dichloroetharie-d4 SURR1
179
35.7
71.5
26
toluene-d8 SURR2
2S6
51.1
102
40
4-bromofluorobenzene SURR3
240
48
95.9
1
chloromethane
U
U
2.51
2
vinyl chloride
U
U
1.77
3
bromomethane
U
u
6.95
4
chloroethane
U
u
5.02
5
1,1-dichloroethene
U
u
4.34
6
acetone
37.1
7.41
7.28
7
methyl iodide
U
U
3.2
8
cartoon disulfide
U
U
2.8
9
methylene chloride
U
U
5.22
10
trans-1,2-dichloroethene
U
U
1.73
11
1,1-dichloroethane
U
U
4.34
12
2-butanone
u
U
14.6
13
bromochloromethane IS1
250
SO
14
chloroform
36.5
7.31
0.82
15
1,1,1-trichloroethane
U
U
14.4
16
carbon tetrachloride
U
U
10.6
18
benzene
U
U
1.59
19
1,2-dichloroethane
U
U
1.56
20
1,4-difluorobenzene IS2
250
50
21
trichloroethene
U
U
2.85
22
1,2-dichIoropropane
U
U
1.58
23
bromodichloromelhane
U
U
2.37
24
cis-1,3-dichloropropene
U
U
2.45
25
2-hexanone
U
U
30.9
27
toluene
U
U
2.02
28
trans-1,3-dichloropropene
U
U
2.64
29
1,1,2-trichloroethane
U
U
3.32
30
tetrachloroethene
U
u
2.88
31
4-methyl-2-pentanone
U
u
41.3
32
dibromochloromethane
U
u
8.85
33
chtorobenzene-dS IS3
250
50
34
chlorobenzene
U
U
2.76
35
ethylbenzene
U
U
2.17
36
m- & p-xylene
U
U
2.04
37
o-xylene
U
u
1.89
38
styrene
U
u
1.41
39
bromoform
U
u
5.09
41
1,1,2,2-tetra chloroethane
U
u
6.27
U - Compound not detected or below detection limit
94
-------
Table D-6. Analysis of Sample of Tap Water, 6/24/93 at 1015 hours
Sample ID: Scrubber Process H20, Sample #10, H438-27-6
SRI Run No.: P03049
Related Blank: P02034 Surrogate
(% Recovery)
Amount
Concentration
or Det. Umt
Number
Compound
(mG/L)
17
1,2-dichloroethane-d4 SURR1
186
37.2
74.5
26
toluene-dS SURR2
265
52.9
106
40
4-bromofluorobenzene SURR3
277
55.4
111
1
chloromethane
U
U
2.51
2
vinyl chloride
U
U
1.77
3
bromomethane
u
u
6.95
4
chloroethane
u
u
5.02
5
1,1-dichloroethene
u
u
4.34
6
acetone
u
u
7.28
7
methyl iodide
u
u
3.2
8
cartoon disulfide
u
u
2.8
9
methylene chloride
u
u
5.22
10
trans-1,2-dichloroethene
u
u
1.73
11
1,1-dichloroethane
u
u
4.34
12
2-butanone
u
u
14.6
13
bromochloromethane IS1
250
so
14
chloroform
275
55
0.82
15
1,1,1-trichloroethane
U
u
14.4
16
carbon tetrachloride
U
u
10.6
18
benzene
U
u
1.59
19
1,2-dichloroethane
U
u
1.56
20
1,4-difluorobenzene fS2
250
50
21
trichloroethene
U
U
2.85
22
1,2-dichloropropane
U
U
1.58
23
bromodichloromethane
60.8
12.2
2.37
24
cis-1,3-dichloropropene
U
U
2.45
25
2-hexanone
U
U
30.9
27
toluene
U
u
2.02
28
trans-1,3-dichloropropene
U
u
2.64
29
1,1,2-trichloroethane
U
u
3.32
30
tetrachloroethene
U
u
2.88
31
4-methyl-2-pentanone
U
u
41.3
32
dibromochloromethane
U
u
8.85
33
chlorobenzene-dS IS3
250
50
34
chlorobenzene
U
U
2.76
35
ethylbenzene
U
U
2.17
36
m- & p-xylene
u
U
2.04
37
o-xylene
u
u
1.89
38
styrene
u
u
1.41
39
bromoform
u
u
5.09
41
1,1,2,2-tetrachloroethane
u
u
6.27
U - Compound not detected or below detection limit
Date Sampled: Jun 24,1993
Date Analyzed: Aug 25,1993
Sample Size: 5 ml
95
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