OAR Box 1500 

Prepped by Ollie Stewart 

Document Number: 

78) ll-C-104 

Docket Number: 

A-94-52 

Printed 8/5/2008 1:51:30 PM Sheet 78 of 343 

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P.2 

..«the Ji 

Wb *1r, 

if Sm. 

IS} PACIFIC ENVIRONMENTAL SERVICES, INC. 

A-94-52 

\\-C~lo-f 

Central Park West 

5001 South Miami Boulevard, Suite 300 

P.O. Box 12077 

Research Triangle Park, NC 27709-2077 

(919)941-0333 

FAX (919) 941-0234 

Mr. Bob James 

Enduro Systems, Inc. 

7100 Old Katy Road 

Houston, TX 77024 

Dear Mr. James: 

The purpose of this letter is to provide you with information pertaining to the measurement 

of styrene emissions from pultrusion operations. Dr. Madeleine Strum ofthe U.S. EPA agreed to 

provide you with this information during our October 5,1998 conference call regarding the Enduro 

facility in Freeport, Texas (Vesca Plastics). The information attached to this letter includes copies 

ofthe following documents: 

-Method 204 - Criteria for and Verification of a Permanent or Temporary Total Enclosure 

-Method 25 A - Determination of Total Gaseous Organic Concentration Using a Flame Ionization 

Analyzer 

-Title V Styrene Emission Factor Test Report: Glasforms, Inc. (Non-Confidential Version) 

The first two documents discuss EPA reference test methods that your facility may employ 

to capture and measure styrene emissions (.after discussion with the appropriate permitting 

authorities). The third document is a test report for styrene emissions testing conducted at a facility 

in San Jose, California. This facility is owned and operated by Glasforms, Inc. Methods similar to 

EPA reference methods 204 and 25A were used in the measurement of styrene emissions from a 

single pultrusion line at this facility. 

If you have any questions about the attached information, please do not hesitate to contact 

me at (919) 941-0333 or Dr. Madeleine Strum at (919) 541-2383. 

Sincerely, 

PACIFIC ENVIRONMENTAL SERVICES, INC. 

Robert M. Jemison 

Environmental Consultant 

cc: Madeleine Strum, EPA 

Attachments (3) 

WASHINGTON, D.C. • RESEARCH TRIANQLE PARK, NC • LOS ANGELES. CA • CINCINNATI. OH 

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EMISSION MEASUREMENT TECHNICAL INFORMATION CENTER 

NSPS TEST METHOD 

METHOD 25A-DETERMINATI0N OF TOTAL GASEOUS ORGANIC 

CONCENTRATION USING A FLAME IONIZATION ANALYZER 

1. Applicability and Principle 

1.1 Applicability. This method applies to the measurement of total gaseous 

organic concentration of vapors consisting primarily of alkanes, alkenes, and/or 

arenes (aromatic hydrocarbons). The concentration is expressed in terms of 

propane (or other appropriate organic calibration gas) or in terms of carbon. 

1.2 Principle. A gas sample is extracted from the source through a heated 

sample line, if necessary, and glass fiber filter to a flame ionization analyzer 

(FIA). Results are reported as volume concentration equivalents of the 

calibration gas or as carbon equivalents. 

2. Definitions 

2.1 Measurement Systems. The total equipment required for the determination 

of the gas concentration. The system consists of the following major subsystems: 

2.1.1 Sample Interface. That portion of the system that is used for one or more 

of the following: sample acquisition, sample transportation, sample 

conditioning, or protection of the analyzer from the effects of the stack 

effluent. 

2.1.2 Organic Analyzer. That portion of the system that senses organic 

concentration and generates an output proportional to the gas concentration. 

2.2 Span Value. The upper limit of a gas concentration measurement range that 

is specified for affected source categories in the applicable part of the 

regulations. The span value is established in the applicable regulation and is 

usually 1.5 to 2.5 times the applicable emission limit. If no span value is 

provided, use a span value equivalent to 1.5 to 2.5 times the expected 

concentration. For convenience, the span value should correspond to 100 percent 

of the recorder scale. 

2.3 Calibration Gas. A known concentration of a gas in an appropriate diluent 

gas. 

2.4 Zero Drift. The difference in the measurement system response to a zero 

level calibration gas before and after a stated period of operation during which 

no unscheduled maintenance, repair, or adjustment took place. 

2.5 Calibration drift. The difference in the measurement system response to 

a midlevel calibration gas before and after a stated period of operation during 

which no unscheduled maintenance, repair or adjustment took place. 

2.6 Response Time. The time interval from a step change in pollutant 

Prepared by Emission Measurement Branch EMTIC TM-25A 

Technical Support Division, OAQPS, EPA June 23, 1993 

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EMTIC TM-25A EMTIC NSPS TEST METHOD Page 2 

concentration at the inlet to the emission measurement system to the time at 

which 95 percent of the corresponding final value is reached as displayed on the 

recorder. 

2.7 Calibration Error. The difference between the gas concentration indicated 

by the measurement system and the known concentration of the calibration gas. 

3. Apparatus. 

A schematic of an acceptable measurement system is shown in Figure 25A-1. 

The essential components of the measurement system are described below: 

3.1 Organic Concentration Analyzer. A flame ionization analyzer (FIA) capable 

of meeting or exceeding the specifications in this method. 

3.2 Sample Probe. Stainless steel, or equivalent, three-hole rake type. 

Sample holes shall be 4 mm in diameter or smaller and located at 16.7, 50, and 

83.3 percent of the equivalent stack diameter. Alternatively, a single opening 

probe may be used so that a gas sample is collected from the centrally located 

10 percent area of the stack cross-section. 

3.3 Sample Line. Stainless steel or Teflon * tubing to transport the sample 

gas to the analyzer. The sample line should be heated, if necessary, to prevent 

condensation in the line. 

3.4 Calibration Valve Assembly. A three way valve assembly to direct the zero 

and calibration gases to the analyzers is recommended. Other methods, such as 

quick-connect lines, to route calibration gas to the analyzers are applicable. 

3.5 Particulate Filter. An in-stack or an out-of-stack glass fiber filter is 

recommended if exhaust gas particulate loading is significant. An out-of-stack 

filter should be heated to prevent any condensation. 

* Mention of trade names or specific products does not constitute 

endorsement by the Environmental Protection Agency. 

3.6 Recorder. A strip-chart recorder, analog computer, or digital recorder for 

recording measurement data. The minimum data recording requirement is one 

measurement value per minute, Note: This method is often applied in highly 

explosive areas. Caution and care should be exercised in choice of equipment and 

installation. 

4. Calibration and Other Gases. 

Gases used for calibrations, fuel, and combustion air (if required) are 

contained in compressed gas cylinders. Preparation of calibration gases shall 

be done according to the procedure in Protocol No. 1, listed in Citation 2 of 

Bibliography. Additionally, the manufacturer of the cylinder should provide a 

recommended shelf life for each calibration gas cylinder over which the 

concentration does not change more than ±2 percent from the certified value. For 

calibration gas values not generally available (i.e., organics between 1 and 10 

percent by volume), alternative methods for preparing calibration gas mixtures, 

such as dilution systems, may be used with prior approval of the Administrator. 

Calibration gases usually consist of propane in air or nitrogen and are 

determined in terms of the span value. Organic compounds other than propane can 

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EMTIC TM-25A EMTIC NSPS TEST METHOD Page 3 

be used following the above guidelines and making the appropriate corrections for 

response factor. 

4.1 Fuel. A 40 percent H2/60 percent N2 gas mixture is recommended to avoid 

an oxygen synergism effect that reportedly occurs when oxygen concentration 

varies significantly from a mean value. 

4.2 Zero Gas. High purity air with less than 0.1 parts per million by volume 

(ppmv) of organic material (propane or carbon equivalent) or less than 0.1 

percent of the span value, whichever is greater. 

4.3 Low-level Calibration Gas. An organic calibration gas with a concentration 

equivalent to 25 to 35 percent of the applicable span value. 

4.4 Mid-level Calibration Gas. An organic calibration gas with a concentration 

equivalent to 45 to 55 percent of the applicable span value. 

4.5 High-level Calibration Gas. An organic calibration gas with a 

concentration equivalent to 80 to 90 percent of the applicable span value. 

5. Measurement System Performance Specifications 

5.1 Zero Drift. Less than ±3 percent of the span value. 

5.2 Calibration Drift. Less than ±3 percent of span value. 

5.3 Calibration Error. Less than ±5 percent of the calibration gas value. 

6. Pretest Preparations 

6.1 Selection of Sampling Site. The location of the sampling site is generally 

specified by the applicable regulation or purpose of the test; i.e., exhaust 

stack, inlet line, etc. The sample port shall be located at least 1.5 meters or 

2 equivalent diameters upstream of the gas discharge to the atmosphere. 

6.2 Location of Sample Probe. Install the sample probe so that the probe is 

centrally located in the stack, pipe, or duct and is sealed tightly at the stack 

port connection. 

6.3 Measurement System Preparation. Prior to the emission test, assemble the 

measurement system following the manufacturer's written instructions in preparing 

the sample interface and the organic analyzer. Make the system operable. 

FIA equipment can be calibrated for almost any range of total organics 

concentrations. For high concentrations of organics (>1.0 percent by volume as 

propane) modifications to most commonly available analyzers are necessary. One 

accepted method of equipment modification is to decrease the size of the sample 

to the analyzer through the use of a smaller diameter sample capillary. Direct 

and continuous measurement of organic concentration is a necessary consideration 

when determining any modification design. 

6.4 Calibration Error Test. Immediately prior to the test series, (within 2 

hours of the start of the test) introduce zero gas and high-level calibration gas 

at the calibration valve assembly. Adjust the analyzer output to the appropriate 

levels, if necessary. Calculate the predicted response for the low-level and 

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EMTIC TM-25A EMTIC NSPS TEST METHOD Page 4 

mid-level gases based on a linear response line between the zero and high-level 

responses. Then introduce low-level and mid-level calibration gases successively 

to the measurement system. Record the analyzer responses for low-level and midlevel calibration gases and determine the differences between the measurement 

system responses and the predicted responses. These differences must be less 

than 5 percent of the respective calibration gas value. If not, the measurement 

system is not acceptable and must be replaced or repaired prior to testing. No 

adjustments to the measurement system shall be conducted after the calibration 

and before the drift check (Section 7.3). If adjustments are necessary before 

the completion of the test series, perform the drift checks prior to the required 

adjustments and repeat the calibration following the adjustments. If multiple 

electronic ranges are to be used, each additional range must be checked with a 

mid-level calibration gas to verify the multiplication factor. 

6.5 Response Time Test. Introduce Zero gas into the measurement system at the 

calibration valve assembly. When the system output has stabilized, switch 

quickly to the high-level calibration gas. Record the time from the 

concentration change to the measurement system response equivalent to 95 percent 

of the step change. Repeat the test three times and average the results. 

7. Emission Measurement Test Procedure 

7.1 Organic Measurement. Begin sampling at the start of the test period, 

recording time and any required process information as appropriate. In 

particular, note on the recording chart periods of process interruption or cyclic 

operation. 

7.2 Drift Determination. Immediately following the completion of the test 

period and hourly during the test period, reintroduce the zero and mid-level 

calibration gases, one at a time, to the measurement system at the calibration 

valve assembly. (Make no adjustments to the measurement system until after both 

the zero and calibration drift checks are made.) Record the analyzer response. 

If the drift.values exceed the specified limits, invalidate the test results 

preceding the check and repeat the test following corrections to the measurement 

system. Alternatively, recalibrate the test measurement system as in Section 6.4 

and report the results using both sets of calibration data (i.e., data determined 

prior to the test period and data determined following the test period). 

8. Organic Concentration calculations 

Determine the average organic concentration in terms of ppmv as propane or 

other calibration gas. The average shall be determined by the integration of the 

output recording over the period specified in the applicable regulation. If 

results are required in terms of ppmv as carbon, adjust measured concentrations 

using Equation 25A-1. 

C C = KCmeas Eq. 25A-1 

Where: 

Cc = Organic concentration as carbon, ppmv. 

Cmoas= Organic concentration as measured, ppmv. 

K = Carbon equivalent correction factor. 

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EMTIC TM-25A EMTIC NSPS TEST METHOD Page 5 

K = 2 for ethane. 

K = 3 for propane. 

K = 4 for butane. 

K = Appropriate response factor for other organic calibration 

gases. 

9. Bibliography 

1. Measurement of Volatile Organic Compounds-Guideline Series. U.S. 

Environmental Protection Agency. Research Triangle Park, NC. 

Publication No. EPA-450/2-78-041. June 1978. p. 46-54. 

2. Traceability Protocol for Establishing True Concentrations of Gases 

Used for Calibration and Audits of Continuous Source Emission 

Monitors (Protocol No. 1). U.S. Environmental Protection Agency, 

Environmental Monitoring and Support Laboratory. Research Triangle 

Park, NC. June 1978. 

3. Gasoline Vapor Emission Laboratory Evaluation-Part 2. U.S. 

Environmental Protection Agency, Office of Air Quality Planning and 

Standards. Research Triangle Park, NC. EMB Report No. 75-GAS-6. 

August 1975. 

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EMTIC TM-25A EMTIC NSPS TEST METHOD Page 6 

no Heated 

Sample 

Line 

bJ 

Pump 

Stack 

Figure 25A-1. Organic Concentration Measurement System. 

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METHOD 204--CRITERIA FOR AND VERIFICATION OF A PERMANENT OR 

TEMPORARY TOTAL ENCLOSURE 

1. SCOPE AND APPLICATION 

This procedure is used to determine whether a permanent or 

temporary enclosure meets the criteria for a total enclosure. An 

existing building may be used as a temporary or permanent' 

enclosure as long as it meets the appropriate criteria described 

in this method. 

2. SUMMARY OF METHOD 

An enclosure is evaluated against a set of criteria. If the 

criteria are met and if all the exhaust gases from the enclosure 

are ducted to a control device, then the volatile organic 

compounds (VOC) capture efficiency (CE) is assumed to be 

100 percent, and CE need not be measured. However, if part of 

the exhaust gas stream is not ducted to a control device, CE must 

be determined. 

3. DEFINITIONS 

3.1 Natural Draft Opening (NDO). Any permanent opening in 

the enclosure that remains open during operation of the facility 

and is not connected to a duct in which a fan is installed. 

3.2 Permanent Total Enclosure (PE). A permanently 

installed enclosure that completely surrounds a source of 

emissions such that all VOC emissions are captured and contained 

for discharge to a control device. 

3.3 Temporary Total Enclosure (TTE). A temporarily 

installed enclosure that completely surrounds a source of 

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•s 

emissions such that all VOC emissions that are not directed 

through the control device (i.e. uncaptured) are captured by the 

enclosure and contained for discharge through ducts that allow 

for the accurate measurement of the uncaptured VOC emissions. 

3.4 Building Enclosure (BE). An existing building that is 

used as a TTE. 

4. SAFETY 

An evaluation of the proposed building materials and the 

design for.the enclosure is recommended to minimize any potential 

hazards. 

5. CRITERIA FOR TEMPORARY TOTAL ENCLOSURE 

5.1 Any NDO shall be at least four equivalent opening 

diameters from each VOC emitting point unless otherwise .specified 

by the Administrator. 

5.2 Any exhaust point from the enclosure shall be at least 

four equivalent duct or hood diameters from each NDO. 

5.3 The total area of all NDO's shall not exceed 5 percent 

of the surface area of the enclosure's four walls, floor, and 

ceiling. 

5.4 The average facial velocity (FV) of air through all 

NDO's shall be at least 3,600 m/hr (200 fpm). The direction of 

air flow through all NDO's shall be into the enclosure. 

5.5 All access doors and windows whose areas are not 

included in section 5.3 and are not included in the calculation 

in section 5.4 shall be closed during routine operation of the 
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process. 

6 CRITERIA FOR A PERMANENT TOTAL ENCLOSURE 

6.1 Same as sections 5.1 and 5.3 through 5.5. 

6.2 All VOC emissions must be captured and contained for 

discharge through a control device. 

7. QUALITY CONTROL 

7.1 The success of this method lies in designing the TTE to 

simulate the conditions that exist without the TTE (i.e., the 

effect of the TTE on the normal flow patterns around the affected 

facility or the amount of uncaptured VOC emissions should be 

minimal). The TTE must enclose the application stations, coating 

reservoirs, and all areas from the application station to the 

oven. The oven does not have to be enclosed if it is under 

negative pressure. The NDO's of the temporary enclosure and an 

exhaust fan must be properly sized and placed. 

7.2 Estimate the ventilation rate of the TTE that best 

simulates the conditions that exist without the TTE (i.e., the 

effect of the TTE on the normal flow patterns around the affected 

facility or the amount of uncaptured VOC emissions should be 

minimal). Figure 204-1 or the following equation may be used as 

an aid. 

C£_ QGCG Eq. 204-1 

QGCG

+QI£F 

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Measure the concentration (CG) and flow rate (QG) of the captured 

gas stream, specify a safe concentration (CF) for the uncaptured 

gas stream, estimate the CE, and then use the plot in Figure 204-

1 or Equation 204-1 to determine the volumetric flow rate of the 

uncaptured gas stream (QF) . An exhaust fan that has a variable 

flow control is desirable. 

7.3 Monitor the VOC concentration of the captured gas steam 

in the duct before the capture device without the TTE. To 

minimize the effect of temporal variation on the captured 

emissions, the baseline measurement should be made over as long a 

time period as practical. However, the process conditions must 

be the same for the measurement in section 7.5 as they are for 

this baseline measurement. This may require short measuring 

times for this quality control check before and after the 

construction of the TTE. 

7.4 After the TTE is constructed, monitor the VOC 

concentration inside the TTE. This concentration should not 

continue to increase, and must not exceed the safe level 

according to Occupational Safety and Health Administration 

requirements for permissible exposure limits. An increase 

in VOC concentration indicates poor TTE design. 

7.5 Monitor the VOC concentration of the captured gas 

stream in the duct before the capture device with the TTE. To 

limit the effect of the TTE on the process, the VOC concentration 

with and without the TTE must be within 10 percent. If the 

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measurements do not agree, adjust the ventilation rate from the 

TTE until they agree within 10 percent. 

8. PROCEDURE 

8.1 Determine the equivalent diameters of the NDO's and 

determine the distances from each VOC emitting point to all 

NDO's. Determine the equivalent diameter of each exhaust duct or 

hood and its distance to all NDO's. Calculate the distances in 

terms of equivalent diameters. The number of equivalent 

diameters shall be at least four. 

8.2 Measure the total surface area (AT) of the enclosure 

and the total area (AN) of all NDO's in the enclosure. Calculate 

the NDO to enclosure area ratio (NEAR) as follows: 

NEAR = - £ Eq. 204-2 

/\rp 

The NEAR must be £0.05. 

8.3 Measure the volumetric flow rate, corrected to standard 

conditions, of each gas stream exiting the enclosure through an 

exhaust duct or hood using EPA Method 2. In some cases (e.g., 

when the building is the enclosure), it may be necessary to 

measure the volumetric flow rate, corrected to standard 

conditions, of each gas stream entering the enclosure through a 

forced makeup air duct using Method 2. Calculate FV using the 

following equation: 

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FV = Eq. 204-3 

where: 

Q0 = the sum of the volumetric flow from all gas streams 

exiting the enclosure through an exhaust duct or hood. 

Qx = the sum of the volumetric flow from all gas streams 

into the enclosure through a forced makeup air duct; 

zero, if there is no forced makeup air into the 

enclosure. 

AN = total area of all NDO's in enclosure. 

The FV shall be at least 3,600 m/hr (200 fpm). 

Alternatively,' measure the pressure differential across 

the enclosure. A pressure drop of 0.013 mm Hg (0.007 in. H20) 

corresponds to an FV of 3,600 m/hr (200. fpm). 

8.4 Verify that the direction of air flow through all NDO's 

is inward. If FV is less than 9,000 m/hr (500 fpm), the 

continuous inward flow of air shall be verified using streamers, 

smoke tubes, or tracer gases. Monitor the direction of air flow 

for at least 1 hour, with checks made no more than 10 minutes 

apart. If FV is greater than 9,000 m/hr (500 fpm), the direction 

of air flow through the NDOs shall be presumed to be inward at 

all times without verification. 

9. DIAGRAMS 

/ * 
j i i i i i 

o.s 1.0 

Volumetric FlowratP of ruoitiv* Missions Exhaust Stream , i £ 

Volumetric Flowrate of Gas Stream Delivered to the Control Oevica qG 

Figure 204-1. The crumpler chart. 

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The Title V Styrene Emission Factor Test Report may be found in docket number A-94-52, 

item II-B-17, section 2 of Attachment VI.