40 CFR Appendix M to Part 51 - Recommended Test Methods for State Implementation Plans

TITLE 40 - PROTECTION OF ENVIRONMENT

CHAPTER I - ENVIRONMENTAL PROTECTION AGENCY

SUBCHAPTER C - AIR PROGRAMS

PART 51 - REQUIREMENTS FOR PREPARATION, ADOPTION, AND SUBMITTAL OF IMPLEMENTATION PLANS

subpart x - PROVISIONS FOR IMPLEMENTATION OF 8 - HOUR OZONE NATIONAL AMBIENT AIR QUALITY STANDARD

Appendix M to Part 51 - Recommended Test Methods for State Implementation Plans

Method 201Determination of PM10 Emissions (Exhaust Gas Recycle Procedure).

Method 201ADetermination of PM10 Emissions (Constant Sampling Rate Procedure).

Method 202Determination of Condensible Particulate Emissions From Stationary Sources Method 204Criteria for and Verification of a Permanent or Temporary Total Enclosure.

Method 204AVolatile Organic Compounds Content in Liquid Input Stream.

Method 204BVolatile Organic Compounds Emissions in Captured Stream.

Method 204CVolatile Organic Compounds Emissions in Captured Stream (Dilution Technique).

Method 204DVolatile Organic Compounds Emissions in Uncaptured Stream from Temporary Total Enclosure.

Method 204EVolatile Organic Compounds Emissions in Uncaptured Stream from Building Enclosure.

Method 204FVolatile Organic Compounds Content in Liquid Input Stream (Distillation Approach).

Method 205Verification of Gas Dilution Systems for Field Instrument Calibrations Presented herein are recommended test methods for measuring air pollutantemanating from an emission source. They are provided for States to use in their plans to meet the requirements of subpart KSource Surveillance.

The State may also choose to adopt other methods to meet the requirements of subpart K of this part, subject to the normal plan review process.

The State may also meet the requirements of subpart K of this part by adopting, again subject to the normal plan review process, any of the relevant methods in appendix A to 40 CFR part 60.

Method 201Determination of PM10 Emissions (exhaust gas recycle procedure) 1. Applicability and Principle 1.1 Applicability. This method applies to the in-stack measurement of particulate matter (PM) emissions equal to or less than an aerodynamic diameter of nominally 10 m (PM10) from stationary sources. The EPA recognizes that condensible emissions not collected by an in-stack method are also PM10, and that emissions that contribute to ambient PM10 levels are the sum of condensible emissions and emissions measured by an in-stack PM10 method, such as this method or Method 201A. Therefore, for establishing source contributions to ambient levels of PM10, such as for emission inventory purposes, EPA suggests that source PM10 measurement include both in-stack PM10 and condensible emissions. Condensible missions may be measured by an impinger analysis in combination with this method.

1.2 Principle. A gas sample is isokinetically extracted from the source.

An in-stack cyclone is used to separate PM greater than PM10, and an in-stack glass fiber filter is used to collect the PM10. To maintain isokinetic flow rate conditions at the tip of the probe and a constant flow rate through the cyclone, a clean, dried portion of the sample gas at stack temperature is recycled into the nozzle. The particulate mass is determined gravimetrically after removal of uncombined water.

2. Apparatus Note: Method 5 as cited in this method refers to the method in 40 CFR part 60, appendix A.

2.1 Sampling Train. A schematic of the exhaust of the exhaust gas recycle (EGR) train is shown in Figure 1 of this method.

2.1.1 Nozzle with Recycle Attachment. Stainless steel (316 or equivalent) with a sharp tapered leading edge, and recycle attachment welded directly on the side of the nozzle (see schematic in Figure 2 of this method). The angle of the taper shall be on the outside. Use only straight sampling nozzles. Gooseneck or other nozzle extensions designed to turn the sample gas flow 90, as in Method 5 are not acceptable.

Locate a thermocouple in the recycle attachment to measure the temperature of the recycle gas as shown in Figure 3 of this method. The recycle attachment shall be made of stainless steel and shall be connected to the probe and nozzle with stainless steel fittings. Two nozzle sizes, e.g., 0.125 and 0.160 in., should be available to allow isokinetic sampling to be conducted over a range of flow rates.

Calibrate each nozzle as described in Method 5, Section 5.1.

2.1.2 PM10 Sizer. Cyclone, meeting the specifications in Section 5.7 of this method.

2.1.3 Filter Holder. 63mm, stainless steel. An Andersen filter, part number SE274, has been found to be acceptable for the in-stack filter.

Note: Mention of trade names or specific products does not constitute endorsement by the Environmental Protection Agency.

2.1.4 Pitot Tube. Same as in Method 5, Section 2.1.3. Attach the pitot to the pitot lines with stainless steel fittings and to the cyclone in a configuration similar to that shown in Figure 3 of this method. The pitot lines shall be made of heat resistant material and attached to the probe with stainless steel fittings.

2.1.5 EGR Probe. Stainless steel, 15.9-mm ( 5/8-in.) ID tubing with a probe liner, stainless steel 9.53-mm ( 3/8-in.) ID stainless steel recycle tubing, two 6.35-mm ( 1/4-in.) ID stainless steel tubing for the pitot tube extensions, three thermocouple leads, and one power lead, all contained by stainless steel tubing with a diameter of approximately 51 mm (2.0 in.). Design considerations should include minimum weight construction materials sufficient for probe structural strength. Wrap the sample and recycle tubes with a heating tape to heat the sample and recycle gases to stack temperature.

2.1.6 Condenser. Same as in Method 5, Section 2.1.7.

2.1.7 Umbilical Connector. Flexible tubing with thermocouple and power leads of sufficient length to connect probe to meter and flow control console.

2.1.8 Vacuum Pump. Leak-tight, oil-less, noncontaminating, with an absolute filter, HEPA type, at the pump exit. A Gast Model 0522V103 G18DX pump has been found to be satisfactory.

2.1.9 Meter and Flow Control Console. System consisting of a dry gas meter and calibrated orifice for measuring sample flow rate and capable of measuring volume to 2 percent, calibrated laminar flow elements (LFE's) or equivalent for measuring total and sample flow rates, probe heater control, and manometers and magnehelic gauges (as shown in Figures 4 and 5 of this method), or equivalent. Temperatures needed for calculations include stack, recycle, probe, dry gas meter, filter, and total flow. Flow measurements include velocity head (p), orifice differential pressure (H), total flow, recycle flow, and total back-pressure through the system.

2.1.10 Barometer. Same as in Method 5, Section 2.1.9.

2.1.11 Rubber Tubing. 6.35-mm ( 1/4-in.) ID flexible rubber tubing.

2.2 Sample Recovery.

2.2.1 Nozzle, Cyclone, and Filter Holder Brushes. Nylon bristle brushes property sized and shaped for cleaning the nozzle, cyclone, filter holder, and probe or probe liner, with stainless steel wire shafts and handles.

2.2.2 Wash Bottles, Glass Sample Storage Containers, Petri Dishes, Graduated Cylinder and Balance, Plastic Storage Containers, and Funnels.

Same as Method 5, Sections 2.2.2 through 2.2.6 and 2.2.8, respectively.

2.3 Analysis. Same as in Method 5, Section 2.3.

3. Reagents The reagents used in sampling, sample recovery, and analysis are the same as that specified in Method 5, Sections 3.1, 3.2, and 3.3, respectively.

4. Procedure 4.1 Sampling. The complexity of this method is such that, in order to obtain reliable results, testers should be trained and experienced with the test procedures.

4.1.1 Pretest Preparation. Same as in Method 5, Section 4.1.1.

4.1.2 Preliminary Determinations. Same as Method 5, Section 4.1.2, except use the directions on nozzle size selection in this section. Use of the EGR method may require a minimum sampling port diameter of 0.2 m (6 in.). Also, the required maximum number of sample traverse points at any location shall be 12.

4.1.2.1 The cyclone and filter holder must be in-stack or at stack temperature during sampling. The blockage effects of the EGR sampling assembly will be minimal if the cross-sectional area of the sampling assembly is 3 percent or less of the cross-sectional area of the duct and a pitot coefficient of 0.84 may be assigned to the pitot. If the cross-sectional area of the assembly is greater than 3 percent of the cross-sectional area of the duct, then either determine the pitot coefficient at sampling conditions or use a standard pitot with a known coefficient in a configuration with the EGR sampling assembly such that flow disturbances are minimized.

4.1.2.2 Construct a setup of pressure drops for various p's and temperatures. A computer is useful for these calculations. An example of the output of the EGR setup program is shown in Figure 6 of this method, and directions on its use are in section 4.1.5.2 of this method.

Computer programs, written in IBM BASIC computer language, to do these types of setup and reduction calculations for the EGR procedure, are available through the National Technical Information Services (NTIS), Accession number PB90500000, 5285 Port Royal Road, Springfield, VA 22161.

4.1.2.3 The EGR setup program allows the tester to select the nozzle size based on anticipated average stack conditions and prints a setup sheet for field use. The amount of recycle through the nozzle should be between 10 and 80 percent. Inputs for the EGR setup program are stack temperature (minimum, maximum, and average), stack velocity (minimum, maximum, and average), atmospheric pressure, stack static pressure, meter box temperature, stack moisture, percent 02, and percent CO2 in the stack gas, pitot coefficient (Cp), orifice H2, flow rate measurement calibration values [slope (m) and y-intercept (b) of the calibration curve], and the number of nozzles available and their diameters.

4.1.2.4 A less rigorous calculation for the setup sheet can be done manually using the equations on the example worksheets in Figures 7, 8, and 9 of this method, or by a Hewlett-Packard HP41 calculator using the program provided in appendix D of the EGR operators manual, entitled Applications Guide for Source PM10 Exhaust Gas Recycle Sampling System.

This calculation uses an approximation of the total flow rate and agrees within 1 percent of the exact solution for pressure drops at stack temperatures from 38 to 260 C (100 to 500 F) and stack moisture up to 50 percent. Also, the example worksheets use a constant stack temperature in the calculation, ingoring the complicated temperature dependence from all three pressure drop equations. Errors for this at stack temperatures 28 C (50 F) of the temperature used in the setup calculations are within 5 percent for flow rate and within 5 percent for cyclone cut size.

4.1.2.5 The pressure upstream of the LFE's is assumed to be constant at 0.6 in. Hg in the EGR setup calculations.

4.1.2.6 The setup sheet constructed using this procedure shall be similar to Figure 6 of this method. Inputs needed for the calculation are the same as for the setup computer except that stack velocities are not needed.

4.1.3 Preparation of Collection Train. Same as in Method 5, Section 4.1.3, except use the following directions to set up the train.

4.1.3.1 Assemble the EGR sampling device, and attach it to probe as shown in Figure 3 of this method. If stack temperatures exceed 260 C (500 F), then assemble the EGR cyclone without the O-ring and reduce the vacuum requirement to 130 mm Hg (5.0 in. Hg) in the leak-check procedure in Section 4.1.4.3.2 of this method.

4.1.3.2 Connect the proble directly to the filter holder and condenser as in Method 5. Connect the condenser and probe to the meter and flow control console with the umbilical connector. Plug in the pump and attach pump lines to the meter and flow control console.

4.1.4 Leak-Check Procedure. The leak-check for the EGR Method consists of two parts: the sample-side and the recycle-side. The sample-side leak-check is required at the beginning of the run with the cyclone attached, and after the run with the cyclone removed. The cyclone is removed before the post-test leak-check to prevent any disturbance of the collected sample prior to analysis. The recycle-side leak-check tests the leak tight integrity of the recycle components and is required prior to the first test run and after each shipment.

4.1.4.1 Pretest Leak-Check. A pretest leak-check of the entire sample-side, including the cyclone and nozzle, is required. Use the leak-check procedure in Section 4.1.4.3 of this method to conduct a pretest leak-check.

4.1.4.2 Leak-Checks During Sample Run. Same as in Method 5, Section 4.1.4.1.

4.1.4.3 Post-Test Leak-Check. A leak-check is required at the conclusion of each sampling run. Remove the cyclone before the leak-check to prevent the vacuum created by the cooling of the probe from disturbing the collected sample and use the following procedure to conduct a post-test leak-check.

4.1.4.3.1 The sample-side leak-check is performed as follows: After removing the cyclone, seal the probe with a leak-tight stopper. Before starting pump, close the coarse total valve and both recycle valves, and open completely the sample back pressure valve and the fine total valve.

After turning the pump on, partially open the coarse total valve slowly to prevent a surge in the manometer. Adjust the vacuum to at least 381 mm Hg (15.0 in. Hg) with the fine total valve. If the desired vacuum is exceeded, either leak-check at this higher vacuum or end the leak-check as shown below and start over.

Caution: Do not decrease the vacuum with any of the valves. This may cause a rupture of the filter.

Note: A lower vacuum may be used, provided that it is not exceeded during the test.

4.1.4.3.2 Leak rates in excess of 0.00057 m 3 /min (0.020 ft 3 /min) are unacceptable. If the leak rate is too high, void the sampling run.

4.1.4.3.3 To complete the leak-check, slowly remove the stopper from the nozzle until the vacuum is near zero, then immediately turn off the pump. This procedure sequence prevents a pressure surge in the manometer fluid and rupture of the filter.

4.1.4.3.4 The recycle-side leak-check is performed as follows: Close the coarse and fine total valves and sample back pressure valve. Plug the sample inlet at the meter box. Turn on the power and the pump, close the recycle valves, and open the total flow valves. Adjust the total flow fine adjust valve until a vacuum of 25 inches of mercury is achieved. If the desired vacuum is exceeded, either leak-check at this higher vacuum, or end the leak-check and start over. Minimum acceptable leak rates are the same as for the sample-side. If the leak rate is too high, void the sampling run.

4.1.5 EGR Train Operation. Same as in Method 5, Section 4.1.5, except omit references to nomographs and recommendations about changing the filter assembly during a run.

4.1.5.1 Record the data required on a data sheet such as the one shown in Figure 10 of this method. Make periodic checks of the manometer level and zero to ensure correct H and p values. An acceptable procedure for checking the zero is to equalize the pressure at both ends of the manometer by pulling off the tubing, allowing the fluid to equilibrate and, if necessary, to re-zero. Maintain the probe temperature to within 11 C (20 F) of stack temperature.

4.1.5.2 The procedure for using the example EGR setup sheet is as follows: Obtain a stack velocity reading from the pitot manometer (p), and find this value on the ordinate axis of the setup sheet. Find the stack temperature on the abscissa. Where these two values intersect are the differential pressures necessary to achieve isokineticity and 10 m cut size (interpolation may be necessary).

4.1.5.3 The top three numbers are differential pressures (in. H2 O), and the bottom number is the percent recycle at these flow settings. Adjust the total flow rate valves, coarse and fine, to the sample value (H) on the setup sheet, and the recycle flow rate valves, coarse and fine, to the recycle flow on the setup sheet.

4.1.5.4 For startup of the EGR sample train, the following procedure is recommended. Preheat the cyclone in the stack for 30 minutes. Close both the sample and recycle coarse valves. Open the fine total, fine recycle, and sample back pressure valves halfway. Ensure that the nozzle is properly aligned with the sample stream. After noting the p and stack temperature, select the appropriate H and recycle from the EGR setup sheet. Start the pump and timing device simultaneously. Immediately open both the coarse total and the coarse recycle valves slowly to obtain the approximate desired values. Adjust both the fine total and the fine recycle valves to achieve more precisely the desired values. In the EGR flow system, adjustment of either valve will result in a change in both total and recycle flow rates, and a slight iteration between the total and recycle valves may be necessary. Because the sample back pressure valve controls the total flow rate through the system, it may be necessary to adjust this valve in order to obtain the correct flow rate.

Note: Isokinetic sampling and proper operation of the cyclone are not achieved unless the correct H and recycle flow rates are maintained.

4.1.5.5 During the test run, monitor the probe and filter temperatures periodically, and make adjustments as necessary to maintain the desired temperatures. If the sample loading is high, the filter may begin to blind or the cyclone may clog. The filter or the cyclone may be replaced during the sample run. Before changing the filter or cyclone, conduct a leak-check (Section 4.1.4.2 of this method). The total particulate mass shall be the sum of all cyclone and the filter catch during the run.

Monitor stack temperature and p periodically, and make the necessary adjustments in sampling and recycle flow rates to maintain isokinetic sampling and the proper flow rate through the cyclone. At the end of the run, turn off the pump, close the coarse total valve, and record the final dry gas meter reading. Remove the probe from the stack, and conduct a post-test leak-check as outlined in Section 4.1.4.3 of this method.

4.2 Sample Recovery. Allow the probe to cool. When the probe can be safely handled, wipe off all external PM adhering to the outside of the nozzle, cyclone, and nozzle attachment, and place a cap over the nozzle to prevent losing or gaining PM. Do not cap the nozzle tip tightly while the sampling train is cooling, as this action would create a vacuum in the filter holder. Disconnect the probe from the umbilical connector, and take the probe to the cleanup site. Sample recovery should be conducted in a dry indoor area or, if outside, in an area protected from wind and free of dust. Cap the ends of the impingers and carry them to the cleanup site. Inspect the components of the train prior to and during disassembly to note any abnormal conditions. Disconnect the pitot from the cyclone. Remove the cyclone from the probe. Recover the sample as follows: 4.2.1 Container Number 1 (Filter). The recovery shall be the same as that for Container Number 1 in Method 5, Section 4.2.

4.2.2 Container Number 2 (Cyclone or Large PM Catch). The cyclone must be disassembled and the nozzle removed in order to recover the large PM catch. Quantitatively recover the PM from the interior surfaces of the nozzle and the cyclone, excluding the turn around cup and the interior surfaces of the exit tube. The recovery shall be the same as that for Container Number 2 in Method 5, Section 4.2.

4.2.3 Container Number 3 (PM10). Quantitatively recover the PM from all of the surfaces from cyclone exit to the front half of the in-stack filter holder, including the turn around cup and the interior of the exit tube. The recovery shall be the same as that for Container Number 2 in Method 5, Section 4.2.

4.2.4 Container Number 4 (Silica Gel). Same as that for Container Number 3 in Method 5, Section 4.2.

4.2.5 Impinger Water. Same as in Method 5, Section 4.2, under Impinger Water.

4.3 Analysis. Same as in Method 5, Section 4.3, except handle EGR Container Numbers 1 and 2 like Container Number 1 in Method 5, EGR Container Numbers 3, 4, and 5 like Container Number 3 in Method 5, and EGR Container Number 6 like Container Number 3 in Method 5. Use Figure 11 of this method to record the weights of PM collected.

4.4 Quality Control Procedures. Same as in Method 5, Section 4.4.

4.5 PM10 Emission Calculation and Acceptability of Results. Use the EGR reduction program or the procedures in section 6 of this method to calculate PM10 emissions and the criteria in section 6.7 of this method to determine the acceptability of the results.

5. Calibration Maintain an accurate laboratory log of all calibrations.

5.1 Probe Nozzle. Same as in Method 5, Section 5.1.

5.2 Pitot Tube. Same as in Method 5, Section 5.2.

5.3 Meter and Flow Control Console.

5.3.1 Dry Gas Meter. Same as in Method 5, Section 5.3.

5.3.2 LFE Gauges. Calibrate the recycle, total, and inlet total LFE gauges with a manometer. Read and record flow rates at 10, 50, and 90 percent of full scale on the total and recycle pressure gauges. Read and record flow rates at 10, 20, and 30 percent of full scale on the inlet total LFE pressure gauge. Record the total and recycle readings to the nearest 0.3 mm (0.01 in.). Record the inlet total LFE readings to the nearest 3 mm (0.1 in.). Make three separate measurements at each setting and calculate the average. The maximum difference between the average pressure reading and the average manometer reading shall not exceed 1 mm (0.05 in.). If the differences exceed the limit specified, adjust or replace the pressure gauge. After each field use, check the calibration of the pressure gauges.

5.3.3 Total LFE. Same as the metering system in Method 5, Section 5.3.

5.3.4 Recycle LFE. Same as the metering system in Method 5, Section 5.3, except completely close both the coarse and fine recycle valves.

5.4 Probe Heater. Connect the probe to the meter and flow control console with the umbilical connector. Insert a thermocouple into the probe sample line approximately half the length of the probe sample line. Calibrate the probe heater at 66C (150F), 121C (250F), and 177C (350F). Turn on the power, and set the probe heater to the specified temperature. Allow the heater to equilibrate, and record the thermocouple temperature and the meter and flow control console temperature to the nearest 0.5C (1F). The two temperatures should agree within 5.5C (10F). If this agreement is not met, adjust or replace the probe heater controller.

5.5 Temperature Gauges. Connect all thermocouples, and let the meter and flow control console equilibrate to ambient temperature. All thermocouples shall agree to within 1.1C (2.0F) with a standard mercury-in-glass thermometer. Replace defective thermocouples.

5.6 Barometer. Calibrate against a standard mercury-in-glass barometer.

5.7 Probe Cyclone and Nozzle Combinations. The probe cyclone and nozzle combinations need not be calibrated if the cyclone meets the design specifications in Figure 12 of this method and the nozzle meets the design specifications in appendix B of the Application Guide for the Source PM10 Exhaust Gas Recycle Sampling System, EPA/600/388058. This document may be obtained from Roy Huntley at (919) 5411060. If the nozzles do not meet the design specifications, then test the cyclone and nozzle combination for conformity with the performance specifications (PS's) in Table 1 of this method. The purpose of the PS tests is to determine if the cyclone's sharpness of cut meets minimum performance criteria. If the cyclone does not meet design specifications, then, in addition to the cyclone and nozzle combination conforming to the PS's, calibrate the cyclone and determine the relationship between flow rate, gas viscosity, and gas density. Use the procedures in Section 5.7.5 of this method to conduct PS tests and the procedures in Section 5.8 of this method to calibrate the cyclone. Conduct the PS tests in a wind tunnel described in Section 5.7.1 of this method and using a particle generation system described in Section 5.7.2 of this method. Use five particle sizes and three wind velocities as listed in Table 2 of this method. Perform a minimum of three replicate measurements of collection efficiency for each of the 15 conditions listed, for a minimum of 45 measurements.

5.7.1 Wind Tunnel. Perform calibration and PS tests in a wind tunnel (or equivalent test apparatus) capable of establishing and maintaining the required gas stream velocities within 10 percent.

5.7.2 Particle Generation System. The particle generation system shall be capable of producing solid monodispersed dye particles with the mass median aerodynamic diameters specified in Table 2 of this method. The particle size distribution verification should be performed on an integrated sample obtained during the sampling period of each test. An acceptable alternative is to verify the size distribution of samples obtained before and after each test, with both samples required to meet the diameter and monodispersity requirements for an acceptable test run.

5.7.2.1 Establish the size of the solid dye particles delivered to the test section of the wind tunnel using the operating parameters of the particle generation system, and verify the size during the tests by microscopic examination of samples of the particles collected on a membrane filter. The particle size, as established by the operating parameters of the generation system, shall be within the tolerance specified in Table 2 of this method. The precision of the particle size verification technique shall be at least 0.5 m, and the particle size determined by the verification technique shall not differ by more than 10 percent from that established by the operating parameters of the particle generation system.

5.7.2.2 Certify the monodispersity of the particles for each test either by microscopic inspection of collected particles on filters or by other suitable monitoring techniques such as an optical particle counter followed by a multichannel pulse height analyzer. If the proportion of multiplets and satellites in an aerosol exceeds 10 percent by mass, the particle generation system is unacceptable for purposes of this test.

Multiplets are particles that are agglomerated, and satellites are particles that are smaller than the specified size range.

5.7.3 Schematic Drawings. Schematic drawings of the wind tunnel and blower system and other information showing complete procedural details of the test atmosphere generation, verification, and delivery techniques shall be furnished with calibration data to the reviewing agency.

5.7.4 Flow Rate Measurement. Determine the cyclone flow rates with a dry gas meter and a stopwatch, or a calibrated orifice system capable of measuring flow rates to within 2 percent.

5.7.5 Performance Specification Procedure. Establish the test particle generator operation and verify the particle size microscopically. If mondispersity is to be verified by measurements at the beginning and the end of the run rather than by an integrated sample, these measurements may be made at this time.

5.7.5.1 The cyclone cut size (D50) is defined as the aerodynamic diameter of a particle having a 50 percent probability of penetration.

Determine the required cyclone flow rate at which D50 is 10 m. A suggested procedure is to vary the cyclone flow rate while keeping a constant particle size of 10 m. Measure the PM collected in the cyclone (mc), exit tube (mt), and filter (mf). Compute the cyclone efficiency (Ec) as follows: (image) 5.7.5.2 Perform three replicates and calculate the average cyclone efficiency as follows: (image) where E1, E2, and E3 are replicate measurements of Ec.

5.7.5.3 Calculate the standard deviation () for the replicate measurements of Ec as follows: (image) if exceeds 0.10, repeat the replicate runs.

5.7.5.4Using the cyclone flow rate that produces D50 for 10 m, measure the overall efficiency of the cyclone and nozzle, Eo, at the particle sizes and nominal gas velocities in Table 2 of this method using this following procedure.

5.7.5.5Set the air velocity in the wind tunnel to one of the nominal gas velocities from Table 2 of this method. Establish isokinetic sampling conditions and the correct flow rate through the sampler (cyclone and nozzle) using recycle capacity so that the D50 is 10 m. Sample long enough to obtain 5 percent precision on the total collected mass as determined by the precision and the sensitivity of the measuring technique. Determine separately the nozzle catch (mn), cyclone catch (mc), cyclone exit tube catch (mt), and collection filter catch (mf).

5.7.5.6Calculate the overall efficiency (Eo) as follows: (image) 5.7.5.7 Do three replicates for each combination of gas velocities and particle sizes in Table 2 of this method. Calculate Eo for each particle size following the procedures described in this section for determining efficiency. Calculate the standard deviation () for the replicate measurements. If exceeds 0.10, repeat the replicate runs.

5.7.6 Criteria for Acceptance. For each of the three gas stream velocities, plot the average Eo as a function of particle size on Figure 13 of this method. Draw a smooth curve for each velocity through all particle sizes. The curve shall be within the banded region for all sizes, and the average Ec for a D50 for 10 m shall be 50 0.5 percent.

5.8 Cyclone Calibration Procedure. The purpose of this section is to develop the relationship between flow rate, gas viscosity, gas density, and D50. This procedure only needs to be done on those cyclones that do not meet the design specifications in Figure 12 of this method.

5.8.1 Calculate cyclone flow rate. Determine the flow rates and D50's for three different particle sizes between 5 m and 15 m, one of which shall be 10 m. All sizes must be within 0.5 m. For each size, use a different temperature within 60 C (108 F) of the temperature at which the cyclone is to be used and conduct triplicate runs. A suggested procedure is to keep the particle size constant and vary the flow rate.

Some of the values obtained in the PS tests in Section 5.7.5 may be used.

5.8.1.1 On log-log graph paper, plot the Reynolds number (Re) on the abscissa, and the square root of the Stokes 50 number [(STK50)1/2] on the ordinate for each temperature. Use the following equations: (image) (image) where: Qcyc = Cyclone flow rate cm 3 /sec.

= Gas density, g/cm 3 .

dcyc = Diameter of cyclone inlet, cm.

cyc = Viscosity of gas through the cyclone, poise.

D50 = Cyclone cut size, cm.

5.8.1.2 Use a linear regression analysis to determine the slope (m), and the y-intercept (b). Use the following formula to determine Q, the cyclone flow rate required for a cut size of 10 m. (image) where: Q = Cyclone flow rate for a cut size of 10 m, cm 3 /sec.

Ts = Stack gas temperature, K, d = Diameter of nozzle, cm.

K1 = 4.077103.

5.8.2. Directions for Using Q. Refer to Section 5 of the EGR operators manual for directions in using this expression for Q in the setup calculations.

6. Calculations 6.1 The EGR data reduction calculations are performed by the EGR reduction computer program, which is written in IBM BASIC computer language and is available through NTIS, Accession number PB90-500000, 5285 Port Royal Road, Springfield, Virginia 22161. Examples of program inputs and outputs are shown in Figure 14 of this method.

6.1.1 Calculations can also be done manually, as specified in Method 5, Sections 6.3 through 6.7, and 6.9 through 6.12, with the addition of the following: 6.1.2 Nomenclature.

Bc = Moisture fraction of mixed cyclone gas, by volume, dimensionless.

C1 = Viscosity constant, 51.12 micropoise for K (51.05 micropoise for R).

C2 = Viscosity constant, 0.372 micropoise/K (0.207 micropoise/ R).

C3 = Viscosity constant, 1.05104 micropoise/K 2 (3.24105 micropoise/ R 2 ).

C4 = Viscosity constant, 53.147 micropoise/fraction O2.

C5 = Viscosity constant, 74.143 micropoise/fraction H2 O.

D50 = Diameter of particles having a 50 percent probability of penetration, m.

f02 = Stack gas fraction O2 by volume, dry basis.

K1 = 0.3858 K/mm Hg (17.64 R/in. Hg).

Mc = Wet molecular weight of mixed gas through the PM10 cyclone, g/g-mole (lb/lb-mole).

Md = Dry molecular weight of stack gas, g/g-mole (lb/lb-mole).

Pbar = Barometer pressure at sampling site, mm Hg (in. Hg).

Pin1 = Gauge pressure at inlet to total LFE, mm H2 O (in. H2 O).

P3 = Absolute stack pressure, mm Hg (in. Hg).

Q2 = Total cyclone flow rate at wet cyclone conditions, m 3 /min (ft 3 /min).

Qs(std) = Total cyclone flow rate at standard conditons, dscm/min (dscf/min).

Tm = Average temperature of dry gas meter, K (R).

Ts = Average stack gas temperature, K (R).

Vw(std) = Volume of water vapor in gas sample (standard conditions), scm (scf).

XT = Total LFE linear calibration constant, m 3 /[(min)(mm H2 O]) { ft 3 /[(min)(in. H2 O)]}.

YT = Total LFE linear calibration constant, dscm/min (dscf/min).

PT = Pressure differential across total LFE, mm H2 O, (in. H2 O).

= Total sampling time, min.

cyc = Viscosity of mixed cyclone gas, micropoise.

LFE = Viscosity of gas laminar flow elements, micropoise.

std = Viscosity of standard air, 180.1 micropoise.

6.2 PM10 Particulate Weight. Determine the weight of PM10 by summing the weights obtained from Container Numbers 1 and 3, less the acetone blank.

6.3 Total Particulate Weight. Determine the particulate catch for PM greater than PM10 from the weight obtained from Container Number 2 less the acetone blank, and add it to the PM10 particulate weight.

6.4 PM10 Fraction. Determine the PM10 fraction of the total particulate weight by dividing the PM10 particulate weight by the total particulate weight.

6.5 Total Cyclone Flow Rate. The average flow rate at standard conditions is determined from the average pressure drop across the total LFE and is calculated as follows: (image) The flow rate, at actual cyclone conditions, is calculated as follows: (image) The flow rate, at actual cyclone conditions, is calculated as follows: (image) 6.6 Aerodynamic Cut Size. Use the following procedure to determine the aerodynamic cut size (D50).

6.6.1 Determine the water fraction of the mixed gas through the cyclone by using the equation below. (image) 6.6.2 Calculate the cyclone gas viscosity as follows: cyc = C1 + C2 Ts + C3 Ts2 + C4 f02 C5 Bc 6.6.3 Calculate the molecular weight on a wet basis of the cyclone gas as follows: Mc = Md(1 Bc) + 18.0(Bc) 6.6.4 If the cyclone meets the design specification in Figure 12 of this method, calculate the actual D50 of the cyclone for the run as follows: (image) where 1 = 0.1562.

6.6.5If the cyclone does not meet the design specifications in Figure 12 of this method, then use the following equation to calculate D50.

(image) where: m = Slope of the calibration curve obtained in Section 5.8.2.

b = y-intercept of the calibration curve obtained in Section 5.8.2.

6.7 Acceptable Results. Acceptability of anisokinetic variation is the same as Method 5, Section 6.12.

6.7.1 If 9.0 m D50 11 m and 90 I 110, the results are acceptable. If D50 is greater than 11 m, the Administrator may accept the results. If D50 is less than 9.0 m, reject the results and repeat the test.

7. Bibliography 1. Same as Bibliography in Method 5.

2. McCain, J.D., J.W. Ragland, and A.D. Williamson. Recommended Methodology for the Determination of Particles Size Distributions in Ducted Sources, Final Report. Prepared for the California Air Resources Board by Southern Research Institute. May 1986.

3. Farthing, W.E., S.S. Dawes, A.D. Williamson, J.D. McCain, R.S.

Martin, and J.W. Ragland. Development of Sampling Methods for Source PM10 Emissions. Southern Research Institute for the Environmental Protection Agency. April 1989.

4. Application Guide for the Source PM10 Exhaust Gas Recycle Sampling System, EPA/600/388058. (image) (image) (image) (image) (image) EXAMPLE EMISSION GAS RECYCLE SETUP SHEET VERSION 3.1 MAY 1986 TEST I.D.: SAMPLE SETUP RUN DATE: 11/24/86 LOCATION: SOURCE SIM OPERATOR(S): RH JB NOZZLE DIAMETER (IN): .25 STACK CONDITIONS: AVERAGE TEMPERATURE (F): 200.0 AVERAGE VELOCITY (FT/SEC): 15.0 AMBIENT PRESSURE (IN HG): 29.92 STACK PRESSURE (IN H20): .10 GAS COMPOSITION: H20=10.0% MD=28.84 O2=20.9% MW=27.75 CO2=.0% (LB/LB MOLE) TARGET PRESSURE DROPS TEMPERATURE (F) DP(PTO) 150....................................... 161 172 183 194 206 217 228 0.026 SAMPLE.................................... .49 .49 .48 .47 .46 .45 .45 TOTAL..................................... 1.90 1.90 1.91 1.92 1.92 1.92 1.93 RECYCLE................................... 2.89 2.92 2.94 2.97 3.00 3.02 3.05 % RCL..................................... 61% 61% 62% 62% 63% 63% 63% .031 .58....................................... .56 .55 .55 .55 .54 .53 .52 1.88...................................... 1.89 1.89 1.90 1.91 1.91 1.91 1.92 2.71...................................... 2.74 2.77 2.80 2.82 2.85 2.88 2.90 57%....................................... 57% 58% 58% 59% 59% 60% 60% .035 .67....................................... .65 .64 .63 .62 .61 .670 .59 1.88...................................... 1.88 1.89 1.89 1.90 1.90 1.91 1.91 2.57...................................... 2.60 2.63 2.66 2.69 2.72 2.74 2.74 54%....................................... 55% 55% 56% 56% 57% 57% 57% .039 .75....................................... .74 .72 .71 .70 .69 .67 .66 1.87...................................... 1.88 1.88 1.89 1.89 1.90 1.90 1.91 2.44...................................... 2.47 2.50 2.53 2.56 2.59 2.62 2.65 51%....................................... 52% 52% 53% 53% 54% 54% 55% Figure 6. Example EGR setup sheet.

Barometric =............................................... __ pressure, Pbar, _ in. Hg Stack static =............................................... __ pressure, Pg, _ in. H2 O Average stack =............................................... __ temperature, ts, _ F Meter =............................................... __ temperature, tm, _ F Gas analysis: %CO2........... =............................................... __ _ %O2............ =............................................... __ _ %N2+%CO........ =............................................... __ _ Fraction =............................................... __ moisture _ content, Bws.

Calibration data: Nozzle =............................................... __ diameter, Dn _ in.

Pitot =............................................... __ coefficient, _ Cp.

H2, in. =............................................... __ H2O. _ Molecular weight of stack gas, dry basis: Md=0.44 (%CO2)+0.32 =............................................... lb/ lb mo le (%O2)+0.28 (%N2+%CO) Molecular weight of stack gas, wet basis: Mw=Md (1- =............................................... __ lb/lb Bws)+18Bws. _ mole Absolute stack pressure: Ps=Pbar+(Pg/ =............................................... __ in. Hg 13.6) _ (image) Desired meter orifice pressure (H) for velocity head of stack gas (p): (image) Figure 7. Example worksheet 1, meter orifice pressure head calculation.

Barometric =............................. __ pressure, Pbar, _ in. Hg Absolute stack =............................. __ pressure, Ps, _ in. Hg Average stack =............................. __ temperature, Ts, _ R Meter =............................. __ temperature, Tm, _ R Molecular weight =............................. __ of stack gas, _ wet basis, Md lb/ lb mole Pressure upstream =............................. 0.

of LFE, in. Hg 6 Gas analysis: %O2............ =............................. __ _ Fraction =............................. __ moisture _ content, Bws.

Calibration data: Nozzle =............................. __ diameter, Dn, _ in.

Pitot =............................. __ coefficient, _ Cp.

Total LFE =............................. __ calibration _ constant, Xt.

Total LFE =............................. __ calibration _ constant, Tt.

Absolute pressure upstream of LFE: PLFE=Pbar+0.6.. =............................. __ in. Hg _ Viscosity of gas in total LFE: LFE=152. =............................. __ 418+0.2552 _ Tm+3.2355x10-5 Tm2+0.53147 (%O2).

Viscosity of dry stack gas: d=152.41 =............................. __ 8+0.2552 _ Ts+3.2355x10-5 Ts2+0.53147 (%O2).

Constants: (image) (image) (image) (image) (image) Total LFE pressure head: (image) Figure 8. Example worksheet 1, meter orifice pressure head calculation.

Barometric =............................. __ pressure, Pbar, _ in. Hg Absolute stack =............................. __ pressure, Ps, _ in. Hg Average stack =............................. __ temperature, Ts, _ R Meter =............................. __ temperature, Tm, _ R Molecular weight =............................. __ of stack gas, _ dry basis, Md lb/ lb mole Viscosity of LFE =............................. __ gasLFE,po _ ise Absolute pressure =............................. __ upstream of LFE, _ PPLEin. Hg Calibration data: Nozzle =............................. __ diameter, Dn, _ in.

Pitot =............................. __ coefficient, _ Cp.

Recycle LFE =............................. __ calibration _ constant, Xt Recycle LFE =............................. __ calibration _ constant, Yt (image) (image) (image) (image) (image) Pressure head for recycle LFE: (image) Figure 9. Example worksheet 3, recycle LFE pressure head. (image) Plant____________________ Date____________________ Run no.____________________ Filter no.____________________ Amount liquid lost during transport____________________ Acetone blank volume, ml____________________ Acetone wash volume, ml (2)(3)____________________ Acetone blank conc., mg/mg (Equation 54, Method 5)____________________ Acetone wash blank, mg (Equation 55, Method 5)____________________ ------------------------------------------------------------------------ Weight of particulate matter, mg Container number -------------------------- Final Tare Weight weight weight gain ------------------------------------------------------------------------ 1............................................ ....... ....... .......

3............................................ ....... ....... .......

Total...................................... ....... ....... .......

-------- Less acetone blank......................... ....... ....... .......

-------- Weight of PM10............................. ....... ....... .......

2............................................ ....... ....... .......

-------- Less acetone blank......................... ....... ....... .......

-------- Total particulate weight................... ....... ....... .......

-------- ------------------------------------------------------------------------ Figure 11. EGR method analysis sheet. (image) Table 1_Performance Specifications for Source PM10 Cyclones and Nozzle Combinations ------------------------------------------------------------------------ Parameter Units Specification ------------------------------------------------------------------------ 1. Collection efficiency........ Percent........... Such that collection efficiency falls within envelope specified by Section 5.7.6 and Figure 13.

2. Cyclone cut size (D50)....... m.......... 10 1 m aerodynamic diameter.

------------------------------------------------------------------------ Table 2_Particle Sizes and Nominal Gas Velocities for Efficiency ------------------------------------------------------------------------ Target gas velocities (m/sec) -------------------------------------- Particle size (m)a 7 15 25 1.0 1.5 2.5 ------------------------------------------------------------------------ 5 0.5.................... ........... ........... ...........

7 0.5.................... ........... ........... ...........

10 0.5................... ........... ........... ...........

14 1.0................... ........... ........... ...........

20 1.0................... ........... ........... ...........

------------------------------------------------------------------------ (a) Mass median aerodynamic diameter.

(image) Emission Gas Recycle, Data Reduction, Version 3.4MAY 1986 Test ID. Code: Chapel Hill 2.

Test Location: Baghouse Outlet.

Test Site: Chapel Hill.

Test Date: 10/20/86.

Operators(s): JB RH MH.

Entered Run Data Temperatures: T(STK)....... 251.0 F T(RCL)....... 259.0 F T(LFE)....... 81.0 F T(DGM)....... 76.0 F System Pressures: DH(ORI)...... 1.18 INWG DP(TOT)...... 1.91 INWG P(INL)....... 12.15 INWG DP(RCL)...... 2.21 INWG DP(PTO)...... 0.06 INWG Miscellanea: P(BAR)....... 29.99 INWG DP(STK)...... 0.10 INWG V(DGM)....... 13.744 FT3 TIME......... 60.00 MIN % CO2........ 8.00 % O2......... 20.00 NOZ (IN)..... 0.2500 Water Content: Estimate..... 0.0% or Condenser.... 7.0 ML Column....... 0.0 GM Raw Masses: Cyclone 1.... 21.7 MG Filter....... 11.7 MG Impinger 0.0 MG Residue.

Blank Values: CYC Rinse.... 0.0 MG Filter Holder 0.0 MG Rinse.

Filter Blank. 0.0 MG Impinger 0.0 MG Rinse.

Calibration Values: CP(PITOT).... 0.840 DH@(ORI)..... 10.980 M(TOT LFE)... 0.2298 B(TOT LFE)... -.0058 M(RCL LFE)... 0.0948 B(RCL LFE)... -.0007 DGM GAMMA.... 0.9940 Reduced Data Stack Velocity 15.95 (FT/SEC) Stack Gas 2.4 Moisture (%) Sample Flow Rate 0.3104 (ACFM) Total Flow Rate 0.5819 (ACFM) Recycle Flow Rate 0.2760 (ACFM) Percent Recycle 46.7 Isokinetic Ratio 95.1 (%) ---------------------------------------------------------------------------------------------------------------- (Particulate) ------------------ (LB/DSCF) (X (% (MG/DNCM) (GR/ACF) (GR/DCF) 1E6) (UM) Method 201ADetermination of PM10 Emissions (Constant Sampling Rate Procedure) 1. Applicability and Principle 1.1 Applicability. This method applies to the in-stack measurement of particulate matter (PM) emissions equal to or less than an aerodynamic diameter of nominally 10 (PM10) from stationary sources. The EPA recognizes that condensible emissions not collected by an in-stack method are also PM10, and that emissions that contribute to ambient, PM10 levels are the sum of condensible emissions and emissions measured by an in-stack PM10 method, such as this method or Method 201. Therefore, for establishing source contributions to ambient levels of PM10, such as for emission inventory purposes, EPA suggests that source PM10 measurement include both in-stack PM10 and condensible emissions. Condensible emissions may be measured by an impinger analysis in combination with this method.

1.2 Principle. A gas sample is extracted at a constant flow rate through an in-stack sizing device, which separates PM greater than PM10.

Variations from isokinetic sampling conditions are maintained within well-defined limits. The particulate mass is determined gravimetrically after removal of uncombined water.

2. Apparatus Note: Methods cited in this method are part of 40 CFR part 60, appendix A.

2.1 Sampling Train. A schematic of the Method 201A sampling train is shown in Figure 1 of this method. With the exception of the PM10 sizing device and in-stack filter, this train is the same as an EPA Method 17 train.

2.1.1 Nozzle. Stainless steel (316 or equivalent) with a sharp tapered leading edge. Eleven nozzles that meet the design specification in Figure 2 of this method are recommended. A larger number of nozzles with small nozzle increments increase the likelihood that a single nozzle can be used for the entire traverse. If the nozzles do not meet the design specifications in Figure 2 of this method, then the nozzles must meet the criteria in Section 5.2 of this method.

2.1.2 PM10 Sizer. Stainless steel (316 or equivalent), capable of determining the PM10 fraction. The sizing device shall be either a cyclone that meets the specifications in Section 5.2 of this method or a cascade impactor that has been calibrated using the procedure in Section 5.4 of this method.

2.1.3 Filter Holder. 63-mm, stainless steel. An Andersen filter, part number SE274, has been found to be acceptable for the in-stack filter.

Note: Mention of trade names or specific products does not constitute endorsement by the Environmental Protection Agency.

2.1.4 Pitot Tube. Same as in Method 5, Section 2.1.3. The pitot lines shall be made of heat resistant tubing and attached to the probe with stainless steel fittings.

2.1.5 Probe Liner. Optional, same as in Method 5, Section 2.1.2.

2.1.6 Differential Pressure Gauge, Condenser, Metering System, Barometer, and Gas Density Determination Equipment. Same as in Method 5, Sections 2.1.4, and 2.1.7 through 2.1.10, respectively.

2.2 Sample Recovery.

2.2.1 Nozzle, Sizing Device, Probe, and Filter Holder Brushes. Nylon bristle brushes with stainless steel wire shafts and handles, properly sized and shaped for cleaning the nozzle, sizing device, probe or probe liner, and filter holders.

2.2.2 Wash Bottles, Glass Sample Storage Containers, Petri Dishes, Graduated Cylinder and Balance, Plastic Storage Containers, Funnel and Rubber Policeman, and Funnel. Same as in Method 5, Sections 2.2.2 through 2.2.8, respectively.

2.3 Analysis. Same as in Method 5, Section 2.3.

3. Reagents The reagents for sampling, sample recovery, and analysis are the same as that specified in Method 5, Sections 3.1, 3.2, and 3.3, respectively.

4. Procedure 4.1 Sampling. The complexity of this method is such that, in order to obtain reliable results, testers should be trained and experienced with the test procedures.

4.1.1 Pretest Preparation. Same as in Method 5, Section 4.1.1.

4.1.2 Preliminary Determinations. Same as in Method 5, Section 4.1.2, except use the directions on nozzle size selection and sampling time in this method. Use of any nozzle greater than 0.16 in. in diameter requires a sampling port diameter of 6 inches. Also, the required maximum number of traverse points at any location shall be 12.

4.1.2.1 The sizing device must be in-stack or maintained at stack temperature during sampling. The blockage effect of the CSR sampling assembly will be minimal if the cross-sectional area of the sampling assembly is 3 percent or less of the cross-sectional area of the duct.

If the cross-sectional area of the assembly is greater than 3 percent of the cross-sectional area of the duct, then either determine the pitot coefficient at sampling conditions or use a standard pitot with a known coefficient in a configuration with the CSR sampling assembly such that flow disturbances are minimized.

4.1.2.2 The setup calculations can be performed by using the following procedures.

4.1.2.2.1 In order to maintain a cut size of 10 m in the sizing device, the flow rate through the sizing device must be maintained at a constant, discrete value during the run. If the sizing device is a cyclone that meets the design specifications in Figure 3 of this method, use the equations in Figure 4 of this method to calculate three orifice heads (H): one at the average stack temperature, and the other two at temperatures 28 C (50 F) of the average stack temperature. Use H calculated at the average stack temperature as the pressure head for the sample flow rate as long as the stack temperature during the run is within 28 C (50 F) of the average stack temperature. If the stack temperature varies by more than 28 C (50 F), then use the appropriate H.

4.1.2.2.2 If the sizing device is a cyclone that does not meet the design specifications in Figure 3 of this method, use the equations in Figure 4 of this method, except use the procedures in Section 5.3 of this method to determine Qs, the correct cyclone flow rate for a 10 m size.

4.1.2.2.3 To select a nozzle, use the equations in Figure 5 of this method to calculate pmin and pmax for each nozzle at all three temperatures. If the sizing device is a cyclone that does not meet the design specifications in Figure 3 of this method, the example worksheets can be used.

4.1.2.2.4 Correct the Method 2 pitot readings to Method 201A pitot readings by multiplying the Method 2 pitot readings by the square of a ratio of the Method 201A pitot coefficient to the Method 2 pitot coefficient. Select the nozzle for which pmin and pmax bracket all of the corrected Method 2 pitot readings. If more than one nozzle meets this requirement, select the nozzle giving the greatest symmetry. Note that if the expected pitot reading for one or more points is near a limit for a chosen nozzle, it may be outside the limits at the time of the run.

4.1.2.2.5 Vary the dwell time, or sampling time, at each traverse point proportionately with the point velocity. Use the equations in Figure 6 of this method to calculate the dwell time at the first point and at each subsequent point. It is recommended that the number of minutes sampled at each point be rounded to the nearest 15 seconds.

4.1.3 Preparation of Collection Train. Same as in Method 5, Section 4.1.3, except omit directions about a glass cyclone.

4.1.4 Leak-Check Procedure. The sizing device is removed before the post-test leak-check to prevent any disturbance of the collected sample prior to analysis.

4.1.4.1 Pretest Leak-Check. A pretest leak-check of the entire sampling train, including the sizing device, is required. Use the leak-check procedure in Method 5, Section 4.1.4.1 to conduct a pretest leak-check.

4.1.4.2 Leak-Checks During Sample Run. Same as in Method 5, Section 4.1.4.1.

4.1.4.3 Post-Test Leak-Check. A leak-check is required at the conclusion of each sampling run. Remove the cyclone before the leak-check to prevent the vacuum created by the cooling of the probe from disturbing the collected sample and use the procedure in Method 5, Section 4.1.4.3 to conduct a post-test leak-check.

4.1.5 Method 201A Train Operation. Same as in Method 5, Section 4.1.5, except use the procedures in this section for isokinetic sampling and flow rate adjustment. Maintain the flow rate calculated in Section 4.1.2.2.1 of this method throughout the run provided the stack temperature is within 28 C (50 F) of the temperature used to calculate H. If stack temperatures vary by more than 28 C (50 F), use the appropriate H value calculated in Section 4.1.2.2.1 of this method.

Calculate the dwell time at each traverse point as in Figure 6 of this method.

4.2 Sample Recovery. If a cascade impactor is used, use the manufacturer's recommended procedures for sample recovery. If a cyclone is used, use the same sample recovery as that in Method 5, Section 4.2, except an increased number of sample recovery containers is required.

4.2.1 Container Number 1 (In-Stack Filter). The recovery shall be the same as that for Container Number 1 in Method 5, Section 4.2.

4.2.3 Container Number 2 (Cyclone or Large PM Catch). This step is optional. The anisokinetic error for the cyclone PM is theoretically larger than the error for the PM10 catch. Therefore, adding all the fractions to get a total PM catch is not as accurate as Method 5 or Method 201. Disassemble the cyclone and remove the nozzle to recover the large PM catch. Quantitatively recover the PM from the interior surfaces of the nozzle and cyclone, excluding the turn around cup and the interior surfaces of the exit tube. The recovery shall be the same as that for Container Number 2 in Method 5, Section 4.2.

4.2.4 Container Number 3 (PM10). Quantitatively recover the PM from all of the surfaces from the cyclone exit to the front half of the in-stack filter holder, including the turn around cup inside the cyclone and the interior surfaces of the exit tube. The recovery shall be the same as that for Container Number 2 in Method 5, Section 4.2.

4.2.6 Container Number 4 (Silica Gel). The recovery shall be the same as that for Container Number 3 in Method 5, Section 4.2.

4.2.7 Impinger Water. Same as in Method 5, Section 4.2, under Impinger Water.

4.3 Analysis. Same as in Method 5, Section 4.3, except handle Method 201A Container Number 1 like Container Number 1, Method 201A Container Numbers 2 and 3 like Container Number 2, and Method 201A Container Number 4 like Container Number 3. Use Figure 7 of this method to record the weights of PM collected. Use Figure 53 in Method 5, Section 4.3, to record the volume of water collected.

4.4 Quality Control Procedures. Same as in Method 5, Section 4.4.

4.5 PM10 Emission Calculation and Acceptability of Results. Use the procedures in section 6 to calculate PM10 emissions and the criteria in section 6.3.5 to determine the acceptability of the results.

5. Calibration Maintain an accurate laboratory log of all calibrations.

5.1 Probe Nozzle, Pitot Tube, Metering System, Probe Heater Calibration, Temperature Gauges, Leak-check of Metering System, and Barometer. Same as in Method 5, Section 5.1 through 5.7, respectively.

5.2 Probe Cyclone and Nozzle Combinations. The probe cyclone and nozzle combinations need not be calibrated if both meet design specifications in Figures 2 and 3 of this method. If the nozzles do not meet design specifications, then test the cyclone and nozzle combinations for conformity with performance specifications (PS's) in Table 1 of this method. If the cyclone does not meet design specifications, then the cylcone and nozzle combination shall conform to the PS's and calibrate the cyclone to determine the relationship between flow rate, gas viscosity, and gas density. Use the procedures in Section 5.2 of this method to conduct PS tests and the procedures in Section 5.3 of this method to calibrate the cyclone. The purpose of the PS tests are to conform that the cyclone and nozzle combination has the desired sharpness of cut. Conduct the PS tests in a wind tunnel described in Section 5.2.1 of this method and particle generation system described in Section 5.2.2 of this method. Use five particle sizes and three wind velocities as listed in Table 2 of this method. A minimum of three replicate measurements of collection efficiency shall be performed for each of the 15 conditions listed, for a minimum of 45 measurements.

5.2.1 Wind Tunnel. Perform the calibration and PS tests in a wind tunnel (or equivalent test apparatus) capable of establishing and maintaining the required gas stream velocities within 10 percent.

5.2.2 Particle Generation System. The particle generation system shall be capable of producing solid monodispersed dye particles with the mass median aerodynamic diameters specified in Table 2 of this method.

Perform the particle size distribution verification on an integrated sample obtained during the sampling period of each test. An acceptable alternative is to verify the size distribution of samples obtained before and after each test, with both samples required to meet the diameter and monodispersity requirements for an acceptable test run.

5.2.2.1 Establish the size of the solid dye particles delivered to the test section of the wind tunnel by using the operating parameters of the particle generation system, and verify them during the tests by microscopic examination of samples of the particles collected on a membrane filter. The particle size, as established by the operating parameters of the generation system, shall be within the tolerance specified in Table 2 of this method. The precision of the particle size verification technique shall be at least 0.5, m, and particle size determined by the verification technique shall not differ by more than 10 percent from that established by the operating parameters of the particle generation system.

5.2.2.2 Certify the monodispersity of the particles for each test either by microscopic inspection of collected particles on filters or by other suitable monitoring techniques such as an optical particle counter followed by a multichannel pulse height analyzer. If the proportion of multiplets and satellites in an aerosol exceeds 10 percent by mass, the particle generation system is unacceptable for the purpose of this test.

Multiplets are particles that are agglomerated, and satellites are particles that are smaller than the specified size range.

5.2.3 Schematic Drawings. Schematic drawings of the wind tunnel and blower system and other information showing complete procedural details of the test atmosphere generation, verification, and delivery techniques shall be furnished with calibration data to the reviewing agency.

5.2.4 Flow Measurements. Measure the cyclone air flow rates with a dry gas meter and a stopwatch, or a calibrated orifice system capable of measuring flow rates to within 2 percent.

5.2.5 Performance Specification Procedure. Establish test particle generator operation and verify particle size microscopically. If monodisperity is to be verified by measurements at the beginning and the end of the run rather than by an integrated sample, these measurements may be made at this time.

5.2.5.1 The cyclone cut size, or D50, of a cyclone is defined here as the particle size having a 50 percent probability of penetration.

Determine the cyclone flow rate at which D50 is 10 m. A suggested procedure is to vary the cyclone flow rate while keeping a constant particle size of 10 m. Measure the PM collected in the cyclone (mc), the exit tube (mt), and the filter (mf). Calculate cyclone efficiency (Ec) for each flow rate as follows: (image) 5.2.5.2.Do three replicates and calculate the average cyclone efficiency [Ec(avg)] as follows: (image) Where E1, E2, and E3 are replicate measurements of Ec.

5.2.5.3Calculate the standard deviation () for the replicate measurements of Ec as follows: (image) If exceeds 0.10, repeat the replicated runs.

5.2.5.4 Measure the overall efficiency of the cyclone and nozzle, Eo, at the particle sizes and nominal gas velocities in Table 2 of this method using the following procedure.

5.2.5.5 Set the air velocity and particle size from one of the conditions in Table 2 of this method. Establish isokinetic sampling conditions and the correct flow rate in the cyclone (obtained by procedures in this section) such that the D50 is 10 m. Sample long enough to obtain 5 percent precision on total collected mass as determined by the precision and the sensitivity of measuring technique.

Determine separately the nozzle catch (mn), cyclone catch (mc), cyclone exit tube (Mt), and collection filter catch (mf) for each particle size and nominal gas velocity in Table 2 of this method. Calculate overall efficiency (Eo) as follows: (image) 5.2.5.6 Do three replicates for each combination of gas velocity and particle size in Table 2 of this method. Use the equation below to calculate the average overall efficiency [Eo(avg)] for each combination following the procedures described in this section for determining efficiency. (image) Where E1, E2, and E3 are replicate measurements of Eo.

5.2.5.7 Use the formula in Section 5.2.5.3 to calculate for the replicate measurements. If exceeds 0.10 or if the particle sizes and nominal gas velocities are not within the limits specified in Table 2 of this method, repeat the replicate runs.

5.2.6 Criteria for Acceptance. For each of the three gas stream velocities, plot the Eo(avg) as a function of particle size on Figure 8 of this method. Draw smooth curves through all particle sizes. Eo(avg) shall be within the banded region for all sizes, and the Ec(avg) shall be 50 0.5 percent at 10 m.

5.3 Cyclone Calibration Procedure. The purpose of this procedure is to develop the relationship between flow rate, gas viscosity, gas density, and D50.

5.3.1 Calculate Cyclone Flow Rate. Determine flow rates and D50's for three different particle sizes between 5 m and 15 m, one of which shall be 10 m. All sizes must be determined within 0.5 m. For each size, use a different temperature within 60 C (108 F) of the temperature at which the cyclone is to be used and conduct triplicate runs. A suggested procedure is to keep the particle size constant and vary the flow rate.

5.3.1.1 On log-log graph paper, plot the Reynolds number (Re) on the abscissa, and the square root of the Stokes 50 number [(Stk50)12] on the ordinate for each temperature. Use the following equations to compute both values: (image) (image) where: Qcyc = Cyclone flow rate, cm 3 /sec.

= Gas density, g/cm 3 .

dcyc = Diameter of cyclone inlet, cm.

s = Viscosity of stack gas, micropoise.

D50 = Aerodynamic diameter of a particle having a 50 percent probability of penetration, cm.

5.3.1.2 Use a linear regression analysis to determine the slope (m) and the Y-intercept (b). Use the following formula to determine Q, the cyclone flow rate required for a cut size of 10 m. (image) where: m = Slope of the calibration line.

b = y-intercept of the calibration line.

Qs = Cyclone flow rate for a cut size of 10 m, cm 3 /sec.

d = Diameter of nozzle, cm.

Ts = Stack gas temperature, · R.

Ps = Absolute stack pressure, in. Hg.

Mw = Wet molecular weight of the stack gas, lb/1b-mole.

K1 = 4.077103.

5.3.1.3 Refer to the Method 201A operators manual, entitled Application Guide for Source PM10 Measurement with Constant Sampling Rate, for directions in the use of this equation for Q in the setup calculations.

5.4 Cascade Impactor. The purpose of calibrating a cascade impactor is to determine the empirical constant (STK50), which is specific to the impactor and which permits the accurate determination of the cut size of the impactor stages at field conditions. It is not necessary to calibrate each individual impactor. Once an impactor has been calibrated, the calibration data can be applied to other impactors of identical design.

5.4.1 Wind Tunnel. Same as in Section 5.2.1 of this method.

5.4.2 Particle Generation System. Same as in Section 5.2.2 of this method.

5.4.3 Hardware Configuration for Calibrations. An impaction stage constrains an aerosol to form circular or rectangular jets, which are directed toward a suitable substrate where the larger aerosol particles are collected. For calibration purposes, three stages of the cascade impactor shall be discussed and designated calibration stages 1, 2, and 3. The first calibration stage consists of the collection substrate of an impaction stage and all upstream surfaces up to and including the nozzle. This may include other preceding impactor stages. The second and third calibration stages consist of each respective collection substrate and all upstream surfaces up to but excluding the collection substrate of the preceding calibration stage. This may include intervening impactor stages which are not designated as calibration stages. The cut size, or D50, of the adjacent calibration stages shall differ by a factor of not less than 1.5 and not more than 2.0. For example, if the first calibration stage has a D50 of 12 m, then the D50 of the downstream stage shall be between 6 and 8 m.

5.4.3.1 It is expected, but not necessary, that the complete hardware assembly will be used in each of the sampling runs of the calibration and performance determinations. Only the first calibration stage must be tested under isokinetic sampling conditions. The second and third calibration stages must be calibrated with the collection substrate of the preceding calibration stage in place, so that gas flow patterns existing in field operation will be simulated.

5.4.3.2 Each of the PM10 stages should be calibrated with the type of collection substrate, viscid material (such as grease) or glass fiber, used in PM10 measurements. Note that most materials used as substrates at elevated temperatures are not viscid at normal laboratory conditions.

The substrate material used for calibrations should minimize particle bounce, yet be viscous enough to withstand erosion or deformation by the impactor jets and not interfere with the procedure for measuring the collected PM.

5.4.4 Calibration Procedure. Establish test particle generator operation and verify particle size microscopically. If monodispersity is to be verified by measurements at the beginning and the end of the run rather than by an integrated sample, these measurements shall be made at this time. Measure in triplicate the PM collected by the calibration stage (m) and the PM on all surfaces downstream of the respective calibration stage (m') for all of the flow rates and particle size combinations shown in Table 2 of this method. Techniques of mass measurement may include the use of a dye and spectrophotometer. Particles on the upstream side of a jet plate shall be included with the substrate downstream, except agglomerates of particles, which shall be included with the preceding or upstream substrate. Use the following formula to calculate the collection efficiency (E) for each stage.

5.4.4.1 Use the formula in Section 5.2.5.3 of this method to calculate the standard deviation () for the replicate measurements. If exceeds 0.10, repeat the replicate runs.

5.4.4.2 Use the following formula to calculate the average collection efficiency (Eavg) for each set of replicate measurements.

Eavg=(E1+E2+E3)/3 where E1, E2, and E3 are replicate measurements of E.

5.4.4.3 Use the following formula to calculate Stk for each Eavg.

(image) where: D = Aerodynamic diameter of the test particle, cm (g/cm 3 )1/2.

Q = Gas flow rate through the calibration stage at inlet conditions, cm 3 /sec.

= Gas viscosity, micropoise.

A = Total cross-sectional area of the jets of the calibration stage, cm2.

dj = Diameter of one jet of the calibration stage, cm.

5.4.4.4 Determine Stk50 for each calibration stage by plotting Eavg versus Stk on log-log paper. Stk50 is the Stk number at 50 percent efficiency. Note that particle bounce can cause efficiency to decrease at high values of Stk. Thus, 50 percent efficiency can occur at multiple values of Stk. The calibration data should clearly indicate the value of Stk50 for minimum particle bounce. Impactor efficiency versus Stk with minimal particle bounce is characterized by a monotonically increasing function with constant or increasing slope with increasing Stk.

5.4.4.5 The Stk50 of the first calibration stage can potentially decrease with decreasing nozzle size. Therefore, calibrations should be performed with enough nozzle sizes to provide a measured value within 25 percent of any nozzle size used in PM10 measurements.

5.4.5 Criteria For Acceptance. Plot Eavg for the first calibration stage versus the square root of the ratio of Stk to Stk50 on Figure 9 of this method. Draw a smooth curve through all of the points. The curve shall be within the banded region.

6. Calculations Calculations are as specified in Method 5, sections 6.3 through 6.7, and 6.9 through 6.11, with the addition of the following: 6.1 Nomenclature.

Bws=Moisture fraction of stack, by volume, dimensionless.

C1=Viscosity constant, 51.12 micropoise for K (51.05 micropoise for R).

C2=Viscosity constant, 0.372 micropoise/ K (0.207 micropoise/R).

C3=Viscosity constant, 1.05104 micropoise/ K2 (3.24105 micropoise/R2).

C4=Viscosity constant, 53.147 micropoise/fraction O2.

C5=Viscosity constant, 74.143 micropoise/fraction H2O.

D50=Diameter of particles having a 50 percent probability of penetration, m.

fo=Stack gas fraction O2, by volume, dry basis.

K1=0.3858 K/mm Hg (17.64 R/in. Hg).

Mw=Wet molecular weight of stack gas, g/g-mole (lb/lb-mole).

Md=Dry molecular weight of stack gas, g/g-mole (1b/1b-mole).

Pbar=Barometric pressure at sampling site, mm Hg (in. Hg).

Ps=Absolute stack pressure, mm Hg (in. Hg).

Qs=Total cyclone flow rate at wet cyclone conditions, m 3 /min (ft 3 /min).

Qs(std)=Total cyclone flow rate at standard conditions, dscm/min (dscf/min).

Tm=Average absolute temperature of dry meter, K (R).

Ts=Average absolute stack gas temperature, K (R).

Vw(std)=Volume of water vapor in gas sample (standard conditions), scm (scf).

=Total sampling time, min.

s=Viscosity of stack gas, micropoise.

6.2 Analysis of Cascade Impactor Data. Use the manufacturer's recommended procedures to analyze data from cascade impactors.

6.3 Analysis of Cyclone Data. Use the following procedures to analyze data from a single stage cyclone.

6.3.1 PM10 Weight. Determine the PM catch in the PM10 range from the sum of the weights obtained from Container Numbers 1 and 3 less the acetone blank.

6.3.2 Total PM Weight (optional). Determine the PM catch for greater than PM10 from the weight obtained from Container Number 2 less the acetone blank, and add it to the PM10 weight.

6.3.3 PM10 Fraction. Determine the PM10 fraction of the total particulate weight by dividing the PM10 particulate weight by the total particulate weight.

6.3.4 Aerodynamic Cut Size. Calculate the stack gas viscosity as follows: s=C1+C2Ts+C3Ts2+C4f02-C5Bws 6.3.4.1 The PM10 flow rate, at actual cyclone conditions, is calculated as follows: (image) 6.3.4.2 Calculate the molecular weight on a wet basis of the stack gas as follows: (image) 6.3.4.3 Calculate the actual D50 of the cyclone for the given conditions as follows: (image) where 1=0.027754 for metric units (0.15625 for English units).

6.3.5 Acceptable Results. The results are acceptable if two conditions are met. The first is that 9.0 m D50 11.0 m. The second is that no sampling points are outside pmin and pmax, or that 80 percent I 120 percent and no more than one sampling point is outside pmin and pmax. If D50 is less than 9.0 m, reject the results and repeat the test.

7. Bibliography 1. Same as Bibliography in Method 5.

2. McCain, J.D., J.W. Ragland, and A.D. Williamson. Recommended Methodology for the Determination of Particle Size Distributions in Ducted Sources, Final Report. Prepared for the California Air Resources Board by Southern Research Institute. May 1986.

3. Farthing, W.E., S.S. Dawes, A.D. Williamson, J.D. McCain, R.S.

Martin, and J.W. Ragland. Development of Sampling Methods for Source PM10 Emissions. Southern Research Institute for the Environmental Protection Agency. April 1989. NTIS PB 89 190375, EPA/600/388056.

4. Application Guide for Source PM10 Measurement with Constant Sampling Rate, EPA/600/388057. (image) (image) (image) Barometric pressure, Pbar, in. Hg= ___ Stack static pressure, Pg, in. H2 O= ___ Average stack temperature, ts, F= ___ Meter temperature, tm, F= ___ Orifice H2, in. H2 O= ___ Gas analysis: %CO2= ___ %O2= ___ %N2+%CO= ___ Fraction moisture content, Bws= ___ Molecular weight of stack gas, dry basis: Md=0.44 (%CO2)+0.32 (%O2)+0.28 (%N2+%CO)= ___ lb/lb mole Molecular weight of stack gas, wet basis: Mw=Md (1Bws)+18 (Bws)= ___ lb/lb mole Absolute stack pressure: (image) Viscosity of stack gas: s=152.418+0.2552 ts+3.2355105 ts2+0.53147 (%02)-74.143 Bws= ___ micropoise Cyclone flow rate: (image) Figure 4. Example worksheet 1, cyclone flow rate and H.

Orifice pressure head (H) needed for cyclone flow rate: (image) Calculate H for three temperatures: ------------------------------------------------------------------------ ts, F ------------------------------------------------------------------------ H, in. H2O ------------------------------------------------------------------------ Stack viscosity, s, micropoise = ___ Absolute stack pressure, Ps, in. Hg = ___ Average stack temperature, ts, F = ___ Meter temperature, tm, F = ___ Method 201A pitot coefficient, Cp = ___ Cyclone flow rate, ft 3 /min, Qs = ___ Method 2 pitot coefficient, Cp = ___ Molecular weight of stack gas, wet basis, Mw = ___ Nozzle diameter, Dn, in. = ___ Nozzle velocity: (image) (image) (image) Maximum and minimum velocities: Calculate Rmin (image) If Rmin is less than 0.5, or if an imaginary number occurs when calculating Rmin, use Equation 1 to calculate vmin. Otherwise, use Equation 2.

Eq. 1 vmin = vn (0.5) = __ ft/sec Eq. 2 vmin =vn Rmin = __ ft/sec Calculate Rmax. (image) If Rmax is greater than 1.5, use Equation 3 to calculate vmax.

Otherwise, use Equation 4.

Eq. 3 vmax = vn (1.5) = __ ft/sec Eq. 4 vmax =vn Rmax = __ ft/sec Figure 5. Example worksheet 2, nozzle selection.

Maximum and minimum velocity head values: (image) (image) ------------------------------------------------------------------------ Nozzle No.

------------------------------------------------------------------------ Dn, in.............................................. ... ... ... ...

vn, ft/sec.......................................... ... ... ... ...

vmin, ft/sec........................................ ... ... ... ...

vmax, ft/sec........................................ ... ... ... ...

pmin, in. H2O................................ ... ... ... ...

pmax, in. H2O................................ ... ... ... ...

------------------------------------------------------------------------ Velocity traverse data: (image) Total run time, minutes = ___ Number of traverse points = (image) where: t1 = dwell time at first traverse point, minutes.

p1 = the velocity head at the first traverse point (from a previous traverse), in. H20.

pavg = the square of the average square root of the p's (from a previous velocity traverse), in. H20.

At subsequent traverse points, measure the velocity p and calculate the dwell time by using the following equation: (image) where: tn = dwell time at traverse point n, minutes.

pn = measured velocity head at point n, in. H20.

p1 = measured velocity head at point 1 in. H20.

Figure 6. Example worksheet 3, dwell time.

---------------------------------------------------------------------------------------------------------------- Port Point No. ------------------------------------------------------------------------------------------------ p t p t p t p t ---------------------------------------------------------------------------------------------------------------- 1 ............ ......... ........... ......... ........... ......... ........... .........

2 ............ ......... ........... ......... ........... ......... ........... .........

3 ............ ......... ........... ......... ........... ......... ........... .........

4 ............ ......... ........... ......... ........... ......... ........... .........

5 ............ ......... ........... ......... ........... ......... ........... .........

6 ............ ......... ........... ......... ........... ......... ........... .........

---------------------------------------------------------------------------------------------------------------- Plant ___ Date ___ Run no. ___ Filter no. ___ Amount of liquid lost during transport ___ Acetone blank volume, ml ___ Acetone wash volume, ml (4) ___ (5) ___ Acetone blank conc., mg/mg (Equation 54, Method 5) ___ Acetone wash blank, mg (Equation 55, Method 5) ___ ------------------------------------------------------------------------ Weight of PM10 (mg) ----------------------------- Container No. Final Tare Weight weight weight gain ------------------------------------------------------------------------ 1......................................... ........ ........ ........

3......................................... ........ ........ ........

--------- Total................................. ........ ........ ........

--------- Less acetone blank.................... ........ ........ ........

--------- Weight of PM10........................ ........ ........ ........

------------------------------------------------------------------------ Figure 7. Method 201A analysis sheet.

Table 1_Performance Specifications for Source PM10 Cyclones and Nozzle Combinations ------------------------------------------------------------------------ Parameter Units Specifications ------------------------------------------------------------------------ 1. Collection efficiency......... Percent......... Such that collection efficiency falls within envelope specified by Section 5.2.6 and Figure 8.

2. Cyclone cut size (D50)........ m........ 10 1 m aerodynamic diameter.

------------------------------------------------------------------------ Table 2_Particle Sizes and Nominal Gas Velocities for Efficiency ------------------------------------------------------------------------ Target gas velocities (m/sec) -------------------------------------- Particle size (m)a 7 15 25 1.0 1.5 2.5 ------------------------------------------------------------------------ 5 0.5.................... ........... ........... ...........

7 0.5.................... ........... ........... ...........

10 0.5................... ........... ........... ...........

14 1.0................... ........... ........... ...........

20 1.0................... ........... ........... ...........

------------------------------------------------------------------------ (a) Mass median aerodynamic diameter. (image) (image) Method 202Determination of Condensible Particulate Emissions From Stationary Sources 1. Applicability and Principle 1.1 Applicability.

1.1.1 This method applies to the determination of condensible particulate matter (CPM) emissions from stationary sources. It is intended to represent condensible matter as material that condenses after passing through a filter and as measured by this method (Note: The filter catch can be analyzed according to the appropriate method).

1.1.2 This method may be used in conjunction with Method 201 or 201A if the probes are glass-lined. Using Method 202 in conjunction with Method 201 or 201A, only the impinger train configuration and analysis is addressed by this method. The sample train operation and front end recovery and analysis shall be conducted according to Method 201 or 201A.

1.1.3 This method may also be modified to measure material that condenses at other temperatures by specifying the filter and probe temperature. A heated Method 5 out-of-stack filter may be used instead of the in-stack filter to determine condensible emissions at wet sources.

1.2 Principle.

1.2.1 The CPM is collected in the impinger portion of a Method 17 (appendix A, 40 CFR part 60) type sampling train. The impinger contents are immediately purged after the run with nitrogen (N2) to remove dissolved sulfur dioxide (SO2) gases from the impinger contents. The impinger solution is then extracted with methylene chloride (MeCl2). The organic and aqueous fractions are then taken to dryness and the residues weighed. The total of both fractions represents the CPM.

1.2.2 The potential for low collection efficiency exist at oil-fired boilers. To improve the collection efficiency at these type of sources, an additional filter placed between the second and third impinger is recommended.

2. Precision and Interference 2.1 Precision. The precision based on method development tests at an oil-fired boiler and a catalytic cracker were 11.7 and 4.8 percent, respectively.

2.2 Interference. Ammonia. In sources that use ammonia injection as a control technique for hydrogen chloride (HC1), the ammonia interferes by reacting with HC1 in the gas stream to form ammonium chloride (NH4 C1) which would be measured as CPM. The sample may be analyzed for chloride and the equivalent amount of NH4 C1 can be subtracted from the CPM weight. However, if NH4 C1 is to be counted as CPM, the inorganic fraction should be taken to near dryness (less than 1 ml liquid) in the oven and then allowed to air dry at ambient temperature to prevent any NH4 C1 from vaporizing.

3. Apparatus 3.1 Sampling Train. Same as in Method 17, section 2.1, with the following exceptions noted below (see Figure 2021). Note: Mention of trade names or specific products does not constitute endorsement by EPA.

3.1.1 The probe extension shall be glass-lined or Teflon.

3.1.2 Both the first and second impingers shall be of the Greenburg-Smith design with the standard tip.

3.1.3 All sampling train glassware shall be cleaned prior to the test with soap and tap water, water, and rinsed using tap water, water, acetone, and finally, MeCl2. It is important to completely remove all silicone grease from areas that will be exposed to the MeCl2 during sample recovery.

3.2 Sample Recovery. Same as in Method 17, section 2.2, with the following additions: 3.2.1 N2 Purge Line. Inert tubing and fittings capable of delivering 0 to 28 liters/min of N2 gas to the impinger train from a standard gas cylinder (see Figure 2022). Standard 0.95 cm ( 3/8-inch) plastic tubing and compression fittings in conjunction with an adjustable pressure regulator and needle valve may be used.

3.2.2 Rotameter. Capable of measuring gas flow at 20 liters/min.

3.3 Analysis. The following equipment is necessary in addition to that listed in Method 17, section 2.3: 3.3.1 Separatory Funnel. Glass, 1-liter.

3.3.2 Weighing Tins. 350-ml.

3.3.3 Dry Equipment. Hot plate and oven with temperature control.

3.3.4 Pipets. 5-ml.

3.3.5 Ion Chromatograph. Same as in Method 5F, Section 2.1.6.

4. Reagents Unless otherwise indicated, all reagents must conform to the specifications established by the Committee on Analytical Reagents of the American Chemical Society. Where such specifications are not available, use the best available grade.

4.1 Sampling. Same as in Method 17, section 3.1, with the addition of deionized distilled water to conform to the American Society for Testing and Materials Specification D 119374, Type II and the omittance of section 3.1.4.

4.2 Sample Recovery. Same as in Method 17, section 3.2, with the following additions: 4.2.1 N2 Gas. Zero N2 gas at delivery pressures high enough to provide a flow of 20 liters/min for 1 hour through the sampling train.

4.2.2 Methylene Chloride, ACS grade. Blanks shall be run prior to use and only methylene chloride with low blank values (0.001 percent) shall be used.

4.2.3 Water. Same as in section 4.1.

4.3 Analysis. Same as in Method 17, section 3.3, with the following additions: 4.3.1 Methylene Chloride. Same as section 4.2.2.

4.3.2 Ammonium Hydroxide. Concentrated (14.8 M) NH4 OH.

4.3.3 Water. Same as in section 4.1.

4.3.4 Phenolphthalein. The pH indicator solution, 0.05 percent in 50 percent alcohol.

5. Procedure 5.1 Sampling. Same as in Method 17, section 4.1, with the following exceptions: 5.1.1 Place 100 ml of water in the first three impingers.

5.1.2 The use of silicone grease in train assembly is not recommended because it is very soluble in MeCl2 which may result in sample contamination. Teflon tape or similar means may be used to provide leak-free connections between glassware.

5.2 Sample Recovery. Same as in Method 17, section 4.2 with the addition of a post-test N2 purge and specific changes in handling of individual samples as described below.

5.2.1 Post-test N2 Purge for Sources Emitting SO2. (Note: This step is recommended, but is optional. With little or no SO2 is present in the gas stream, i.e., the pH of the impinger solution is greater than 4.5, purging has been found to be unnecessary.) As soon as possible after the post-test leak check, detach the probe and filter from the impinger train. Leave the ice in the impinger box to prevent removal of moisture during the purge. If necessary, add more ice during the purge to maintain the gas temperature below 20 C. With no flow of gas through the clean purge line and fittings, attach it to the input of the impinger train (see Figure 2022). To avoid over- or under-pressurizing the impinger array, slowly commence the N2 gas flow through the line while simultaneously opening the meter box pump valve(s). When using the gas cylinder pressure to push the purge gas through the sample train, adjust the flow rate to 20 liters/min through the rotameter. When pulling the purge gas through the sample train using the meter box vacuum pump, set the orifice pressure differential to H2 and maintain an overflow rate through the rotameter of less than 2 liters/min. This will guarantee that the N2 delivery system is operating at greater than ambient pressure and prevents the possibility of passing ambient air (rather than N2) through the impingers. Continue the purge under these conditions for 1 hour, checking the rotameter and H value(s) periodically. After 1 hour, simultaneously turn off the delivery and pumping systems.

5.2.2 Sample Handling.

5.2.2.1 Container Nos. 1, 2, and 3. If filter catch is to be determined, as detailed in Method 17, section 4.2.

5.2.2.2 Container No. 4 (Impinger Contents). Measure the liquid in the first three impingers to within 1 ml using a clean graduated cylinder or by weighing it to within 0.5 g using a balance. Record the volume or weight of liquid present to be used to calculate the moisture content of the effluent gas. Quantitatively transfer this liquid into a clean sample bottle (glass or plastic); rinse each impinger and the connecting glassware, including probe extension, twice with water, recover the rinse water, and add it to the same sample bottle. Mark the liquid level on the bottle.

5.2.2.3 Container No. 5 (MeCl2 Rinse). Follow the water rinses of each impinger and the connecting glassware, including the probe extension with two rinses of MeCl2; save the rinse products in a clean, glass sample jar. Mark the liquid level on the jar.

5.2.2.4 Container No. 6 (Water Blank). Once during each field test, place 500 ml of water in a separate sample container.

5.2.2.5 Container No. 7 (MeCl2 Blank). Once during each field test, place in a separate glass sample jar a volume of MeCl2 approximately equivalent to the volume used to conduct the MeCl2 rinse of the impingers.

5.3 Analysis. Record the data required on a sheet such as the one shown in Figure 2023. Handle each sample container as follows: 5.3.1 Container Nos. 1, 2, and 3. If filter catch is analyzed, as detailed in Method 17, section 4.3.

5.3.2 Container Nos. 4 and 5. Note the level of liquid in the containers and confirm on the analytical data sheet whether leakage occurred during transport. If a noticeable amount of leakage has occurred, either void the sample or use methods, subject to the approval of the Administrator, to correct the final results. Measure the liquid in Container No. 4 either volumetrically to 1 ml or gravimetrically to 0.5 g. Remove a 5-ml aliquot and set aside for later ion chromatographic (IC) analysis of sulfates. (Note: Do not use this aliquot to determine chlorides since the HCl will be evaporated during the first drying step; Section 8.2 details a procedure for this analysis.) 5.3.2.1 Extraction. Separate the organic fraction of the sample by adding the contents of Container No. 4 (MeCl2) to the contents of Container No. 4 in a 1000-ml separatory funnel. After mixing, allow the aqueous and organic phases to fully separate, and drain off most of the organic/MeCl2 phase. Then add 75 ml of MeCl2 to the funnel, mix well, and drain off the lower organic phase. Repeat with another 75 ml of MeCl2.

This extraction should yield about 250 ml of organic extract. Each time, leave a small amount of the organic/MeCl2 phase in the separatory funnel ensuring that no water is collected in the organic phase. Place the organic extract in a tared 350-ml weighing tin.

5.3.2.2 Organic Fraction Weight Determination (Organic Phase from Container Nos. 4 and 5). Evaporate the organic extract at room temperature and pressure in a laboratory hood. Following evaporation, desiccate the organic fraction for 24 hours in a desiccator containing anhydrous calcium sulfate. Weigh to a constant weight and report the results to the nearest 0.1 mg.

5.3.2.3 Inorganic Fraction Weight Determination. (Note: If NH4 Cl is to be counted as CPM, the inorganic fraction should be taken to near dryness (less than 1 ml liquid) in the oven and then allow to air dry at ambient temperature. If multiple acid emissions are suspected, the ammonia titration procedure in section 8.1 may be preferred.) Using a hot plate, or equivalent, evaporate the aqueous phase to approximately 50 ml; then, evaporate to dryness in a 105 C oven. Redissovle the residue in 100 ml of water. Add five drops of phenolphthalein to this solution; then, add concentrated (14.8 M) NH4 OH until the sample turns pink. Any excess NH2 OH will be evaporated during the drying step.

Evaporate the sample to dryness in a 105 C oven, desiccate the sample for 24 hours, weigh to a constant weight, and record the results to the nearest 0.1 mg. (Note: The addition of NH4 OH is recommended, but is optional when little or no SO2 is present in the gas stream, i.e., when the pH of the impinger solution is greater than 4.5, the addition of NH4 OH is not necessary.) 5.3.2.4 Analysis of Sulfate by IC to Determine Ammonium Ion (NH4+) Retained in the Sample. (Note: If NH4 OH is not added, omit this step.) Determine the amount of sulfate in the aliquot taken from Container No.

4 earlier as described in Method 5F (appendix A, 40 CFR part 60). Based on the IC SO42 analysis of the aliquot, calculate the correction factor to subtract the NH4+ retained in the sample and to add the combined water removed by the acid-base reaction (see section 7.2).

5.3.3 Analysis of Water and MeCl2 Blanks (Container Nos. 6 and 7).

Analyze these sample blanks as described above in sections 5.3.2.3 and 5.3.2.2, respectively.

5.3.4 Analysis of Acetone Blank (Container No. 8). Same as in Method 17, section 4.3.

6. Calibration Same as in Method 17, section 5, except for the following: 6.1 IC Calibration. Same as Method 5F, section 5.

6.2 Audit Procedure. Concurrently, analyze the audit sample and a set of compliance samples in the same manner to evaluate the technique of the analyst and the standards preparation. The same analyst, analytical reagents, and analytical system shall be used both for compliance samples and the EPA audit sample. If this condition is met, auditing of subsequent compliance analyses for the same enforcement agency within 30 days is not required. An audit sample set may not be used to validate different sets of compliance samples under the jurisdiction of different enforcement agencies, unless prior arrangements are made with both enforcement agencies.

6.3 Audit Samples. Audit Sample Availability. Audit samples will be supplied only to enforcement agencies for compliance tests. The availability of audit samples may be obtained by writing: Source Test Audit Coordinator (MD77B), Quality Assurance Division, Atmospheric Research and Exposure Assessment Laboratory, U.S.

Environmental Protection Agency, Research Triangle, Park, NC 27711 or by calling the Source Test Audit Coordinator (STAC) at (919) 5417834.

The request for the audit sample must be made at least 30 days prior to the scheduled compliance sample analysis.

6.4 Audit Results. Calculate the audit sample concentration according to the calculation procedure described in the audit instructions included with the audit sample. Fill in the audit sample concentration and the analyst's name on the audit response form included with the audit instructions. Send one copy to the EPA Regional Office or the appropriate enforcement agency and a second copy to the STAC. The EPA Regional Office or the appropriate enforcement agency will report the results of the audit to the laboratory being audited. Include this response with the results of the compliance samples in relevant reports to the EPA Regional Office or the appropriate enforcement agency.

7. Calculations Same as in Method 17, section 6, with the following additions: 7.1 Nomenclature. Same as in Method 17, section 6.1 with the following additions.

Ccpm=Concentration of the CPM in the stack gas, dry basis, corrected to standard conditions, g/dscm (g/dscf).

CSO4=Concentration of SO42 in the sample, mg/ml.

mb=Sum of the mass of the water and MeCl2 blanks, mg.

mc=Mass of the NH4+ added to sample to form ammonium sulfate, mg.

mi=Mass of inorganic CPM matter, mg.

mo=Mass of organic CPM, mg.

mr=Mass of dried sample from inorganic fraction, mg.

Vb=Volume of aliquot taken for IC analysis, ml.

Vic=Volume of impinger contents sample, ml.

7.2 Correction for NH4+ and H2O. Calculate the correction factor to subtract the NH4+ retained in the sample based on the IC SO42 and if desired, add the combined water removed by the acid-base reaction.

(image) =0.1840, when only correcting for NH4+.

7.3Mass of Inorganic CPM. (image) 7.4 Concentration of CPM. (image) 8. Alternative Procedures 8.1 Determination of NH4+ Retained in Sample by Titration.

8.1.1 An alternative procedure to determine the amount of NH4+ added to the inorganic fraction by titration may be used. After dissolving the inorganic residue in 100 ml of water, titrate the solution with 0.1 N NH4 OH to a pH of 7.0, as indicated by a pH meter. The 0.1 N NH4 OH is made as follows: Add 7 ml of concentrated (14.8 M) NH4 OH to 1 liter of water. Standardize against standardized 0.1 N H2 SO4 and calculate the exact normality using a procedure parallel to that described in section 5.5 of Method 6 (appendix A, 40 CFR part 60). Alternatively, purchase 0.1 N NH4 OH that has been standardized against a National Institute of Standards and Technology reference material.

8.1.2 Calculate the concentration of SO42 in the sample using the following equation. (image) where N = Normality of the NH4OH, mg/ml.

Vt = Volume of NH4 OH titrant, ml.

48.03 = mg/meq.

100 = Volume of solution, ml.

8.3.1 Calculate the CPM as described in section 7.

8.2 Analysis of Chlorides by IC. At the conclusion of the final weighing as described in section 5.3.2.3, redissolve the inorganic fraction in 100 ml of water. Analyze an aliquot of the redissolved sample for chlorides by IC using techniques similar to those described in Method 5F for sulfates. Previous drying of the sample should have removed all HCl.

Therefore, the remaining chlorides measured by IC can be assumed to be NH4 Cl, and this weight can be subtracted from the weight determined for CPM.

8.3 Air Purge to Remove SO2 from Impinger Contents. As an alternative to the post-test N2 purge described in section 5.2.1, the tester may opt to conduct the post-test purge with air at 20 liter/min. Note: The use of an air purge is not as effective as a N2 purge.

8.4 Chloroform-ether Extraction. As an alternative to the methylene chloride extraction described in section 5.3.2.1, the tester may opt to conduct a chloroform-ether extraction. Note: The Chloroform-ether was not as effective as the MeCl2 in removing the organics, but it was found to be an acceptable organic extractant. Chloroform and diethylether of ACS grade, with low blank values (0.001 percent), shall be used.

Analysis of the chloroform and diethylether blanks shall be conducted according to Section 5.3.3 for MeCl2.

8.4.1 Add the contents of Container No. 4 to a 1000-ml separatory funnel. Then add 75 ml of chloroform to the funnel, mix well, and drain off the lower organic phase. Repeat two more times with 75 ml of chloroform. Then perform three extractions with 75 ml of diethylether.

This extraction should yield approximately 450 ml of organic extraction.

Each time, leave a small amount of the organic/MeCl2 phase in the separatory funnel ensuring that no water is collected in the organic phase.

8.4.2 Add the contents of Container No. 5 to the organic extraction.

Place approximately 300 ml of the organic extract in a tared 350-ml weighing tin while storing the remaining organic extract in a sample container. As the organic extract evaporates, add the remaining extract to the weighing tin.

8.4.3 Determine the weight of the organic phase as described in Section 5.3.2.2.

8.5 Improving Collection Efficiency. If low impinger collection efficiency is suspected, the following procedure may be used.

8.5.1 Place an out-of-stock filter as described in Method 8 between the second and third impingers.

8.5.2 Recover and analyze the filter according to Method 17, Section 4.2. Include the filter holder as part of the connecting glassware and handle as described in sections 5.2.2.2 and 5.2.2.3.

8.5.3 Calculate the Concentration of CPM as follows: (image) where: mf = amount of CPM collected on out-of-stack filter, mg.

8.6 Wet Source Testing. When testing at a wet source, use a heated out-of-stack filter as described in Method 5.

9. Bibliography 1. DeWees, W.D., S.C. Steinsberger, G.M. Plummer, L.T. Lay, G.D.

McAlister, and R.T. Shigehara. Laboratory and Field Evaluation of the EPA Method 5 Impinger Catch for Measuring Condensible Matter from Stationary Sources. Paper presented at the 1989 EPA/AWMA International Symposium on Measurement of Toxic and Related Air Pollutants. Raleigh, North Carolina. May 15, 1989.

2. DeWees, W.D. and K.C. Steinsberger. Method Development and Evaluation of Draft Protocol for Measurement of Condensible Particulate Emissions.

Draft Report. November 17, 1989.

3. Texas Air Control Board, Laboratory Division. Determination of Particulate in Stack Gases Containing Sulfuric Acid and/or Sulfur Dioxide. Laboratory Methods for Determination of Air Pollutants.

Modified December 3, 1976.

4. Nothstein, Greg. Masters Thesis. University of Washington. Department of Environmental Health. Seattle, Washington.

5. Particulate Source Test Procedures Adopted by Puget Sound Air Pollution Control Agency Board of Directors. Puget Sound Air Pollution Control Agency, Engineering Division. Seattle, Washington. August 11, 1983.

6. Commonwealth of Pennsylvania, Department of Environmental Resources.

Chapter 139, Sampling and Testing (Title 25, Rules and Regulations, Part I, Department of Environmental Resources, Subpart C, Protection of Natural Resources, Article III, Air Resources). January 8, 1960.

7. Wisconsin Department of Natural Resources. Air Management Operations Handbook, Revision 3. January 11, 1988. (image) (image) Moisture Determination Volume or weight of liquid in impingers: ___ ml or g Weight of moisture in silica gel: ___ g Sample Preparation (Container No. 4) Amount of liquid lost during transport: ___ ml Final volume: ___ ml pH of sample prior to analysis: ___ Addition of NH4 OH required: ___ Sample extracted 2X with 75 ml MeCl2?: ___ For Titration of Sulfate Normality of NH2 OH: ___ N Volume of sample titrated: ___ ml Volume of titrant: ___ ml Sample Analysis ------------------------------------------------------------------------ Weight of condensible particulate, mg Container number -------------------------- Final Tare Weight weight weight gain ------------------------------------------------------------------------ 4 (Inorganic)................................ ....... ....... .......

4 & 5 (Organic).......................... ....... ....... .......

------------------------------------------------------------------------ Total: ___ Less Blank: ___ Weight of Consensible Particulate: Figure 2023. Analytical data sheet.

Method 204Criteria 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 3.1Natural 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.

3.2Permanent 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.

3.3Temporary Total Enclosure (TTE). A temporarily installed enclosure that completely surrounds a source of 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.

3.4Building 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 5.1Any NDO shall be at least four equivalent opening diameters from each VOC emitting point unless otherwise specified by the Administrator.

5.2Any exhaust point from the enclosure shall be at least four equivalent duct or hood diameters from each NDO.

5.3The total area of all NDO's shall not exceed 5 percent of the surface area of the enclosure's four walls, floor, and ceiling.

5.4The 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.

5.5All 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 process.

6. Criteria for a Permanent Total Enclosure 6.1Same as sections 5.1 and 5.3 through 5.5.

6.2All VOC emissions must be captured and contained for discharge through a control device.

7. Quality Control 7.1The 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.

7.2Estimate 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 2041 or the following equation may be used as an aid. (image) 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 2041 or Equation 2041 to determine the volumetric flow rate of the uncaptured gas stream (QF).

An exhaust fan that has a variable flow control is desirable.

7.3Monitor 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.

7.4After 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.

7.5Monitor 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 measurements do not agree, adjust the ventilation rate from the TTE until they agree within 10 percent.

8. Procedure 8.1Determine 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.

8.2Measure 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: (image) The NEAR must be 10.05.

8.3Measure 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: (image) where: QO = the sum of the volumetric flow from all gas streams exiting the enclosure through an exhaust duct or hood.

QI = 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. H2O) corresponds to an FV of 3,600 m/hr (200 fpm).

8.4Verify 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 (image) View or download PDF Method 204AVolatile Organic Compounds Content in Liquid Input Stream 1. Scope and Application 1.1Applicability. This procedure is applicable for determining the input of volatile organic compounds (VOC). It is intended to be used in the development of liquid/gas protocols for determining VOC capture efficiency (CE) for surface coating and printing operations.

1.2Principle. The amount of VOC introduced to the process (L) is the sum of the products of the weight (W) of each VOC containing liquid (ink, paint, solvent, etc.) used and its VOC content (V).

1.3Sampling Requirements. A CE test shall consist of at least three sampling runs. Each run shall cover at least one complete production cycle, but shall be at least 3 hours long. The sampling time for each run need not exceed 8 hours, even if the production cycle has not been completed. Alternative sampling times may be used with the approval of the Administrator.

2. Summary of Method The amount of VOC containing liquid introduced to the process is determined as the weight difference of the feed material before and after each sampling run. The VOC content of the liquid input material is determined by volatilizing a small aliquot of the material and analyzing the volatile material using a flame ionization analyzer (FIA). A sample of each VOC containing liquid is analyzed with an FIA to determine V.

3. Safety Because this procedure is often applied in highly explosive areas, caution and care should be exercised in choosing, installing, and using the appropriate equipment.

4. Equipment and Supplies Mention of trade names or company products does not constitute endorsement. All gas concentrations (percent, ppm) are by volume, unless otherwise noted.

4.1Liquid Weight.

4.1.1Balances/Digital Scales. To weigh drums of VOC containing liquids to within 0.2 lb or 1.0 percent of the total weight of VOC liquid used.

4.1.2Volume Measurement Apparatus (Alternative). Volume meters, flow meters, density measurement equipment, etc., as needed to achieve the same accuracy as direct weight measurements.

4.2VOC Content (FIA Technique). The liquid sample analysis system is shown in Figures 204A1 and 204A2. The following equipment is required: 4.2.1Sample Collection Can. An appropriately-sized metal can to be used to collect VOC containing materials. The can must be constructed in such a way that it can be grounded to the coating container.

4.2.2Needle Valves. To control gas flow.

4.2.3Regulators. For carrier gas and calibration gas cylinders.

4.2.4Tubing. Teflon or stainless steel tubing with diameters and lengths determined by connection requirements of equipment. The tubing between the sample oven outlet and the FIA shall be heated to maintain a temperature of 120 5 C.

4.2.5Atmospheric Vent. A tee and 0- to 0.5-liter/min rotameter placed in the sampling line between the carrier gas cylinder and the VOC sample vessel to release the excess carrier gas. A toggle valve placed between the tee and the rotameter facilitates leak tests of the analysis system.

4.2.6Thermometer. Capable of measuring the temperature of the hot water bath to within 1 C.

4.2.7Sample Oven. Heated enclosure, containing calibration gas coil heaters, critical orifice, aspirator, and other liquid sample analysis components, capable of maintaining a temperature of 120 5 C.

4.2.8Gas Coil Heaters. Sufficient lengths of stainless steel or Teflon tubing to allow zero and calibration gases to be heated to the sample oven temperature before entering the critical orifice or aspirator.

4.2.9Water Bath. Capable of heating and maintaining a sample vessel temperature of 100 5 C.

4.2.10Analytical Balance. To measure 0.001 g.

4.2.11Disposable Syringes. 2-cc or 5-cc.

4.2.12Sample Vessel. Glass, 40-ml septum vial. A separate vessel is needed for each sample.

4.2.13Rubber Stopper. Two-hole stopper to accommodate 3.2-mm ( 1/8-in.) Teflon tubing, appropriately sized to fit the opening of the sample vessel. The rubber stopper should be wrapped in Teflon tape to provide a tighter seal and to prevent any reaction of the sample with the rubber stopper. Alternatively, any leak-free closure fabricated of nonreactive materials and accommodating the necessary tubing fittings may be used.

4.2.14Critical Orifices. Calibrated critical orifices capable of providing constant flow rates from 50 to 250 ml/min at known pressure drops. Sapphire orifice assemblies (available from O'Keefe Controls Company) and glass capillary tubing have been found to be adequate for this application.

4.2.15Vacuum Gauge. Zero to 760-mm (0- to 30-in.) Hg U-Tube manometer or vacuum gauge.

4.2.16Pressure Gauge. Bourdon gauge capable of measuring the maximum air pressure at the aspirator inlet (e.g., 100 psig).

4.2.17Aspirator. A device capable of generating sufficient vacuum at the sample vessel to create critical flow through the calibrated orifice when sufficient air pressure is present at the aspirator inlet. The aspirator must also provide sufficient sample pressure to operate the FIA. The sample is also mixed with the dilution gas within the aspirator.

4.2.18Soap Bubble Meter. Of an appropriate size to calibrate the critical orifices in the system.

4.2.19Organic Concentration Analyzer. An FIA with a span value of 1.5 times the expected concentration as propane; however, other span values may be used if it can be demonstrated that they would provide more accurate measurements. The FIA instrument should be the same instrument used in the gaseous analyses adjusted with the same fuel, combustion air, and sample back-pressure (flow rate) settings. The system shall be capable of meeting or exceeding the following specifications: 4.2.19.1Zero Drift. Less than 3.0 percent of the span value.

4.2.19.2Calibration Drift. Less than 3.0 percent of the span value.

4.2.19.3Calibration Error. Less than 5.0 percent of the calibration gas value.

4.2.20Integrator/Data Acquisition System. An analog or digital device or computerized data acquisition system used to integrate the FIA response or compute the average response and record measurement data. The minimum data sampling frequency for computing average or integrated values is one measurement value every 5 seconds. The device shall be capable of recording average values at least once per minute.

4.2.21Chart Recorder (Optional). A chart recorder or similar device is recommended to provide a continuous analog display of the measurement results during the liquid sample analysis.

5. Reagents and Standards 5.1Calibration and Other Gases. Gases used for calibration, fuel, and combustion air (if required) are contained in compressed gas cylinders.

All calibration gases shall be traceable to National Institute of Standards and Technology standards and shall be certified by the manufacturer to 1 percent of the tag value. 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, dilution systems calibrated using Method 205 may be used. Alternative methods for preparing calibration gas mixtures may be used with the approval of the Administrator.

5.1.1Fuel. The FIA manufacturer's recommended fuel should be used. A 40 percent H2/60 percent He or 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. Other mixtures may be used provided the tester can demonstrate to the Administrator that there is no oxygen synergism effect.

5.1.2Carrier Gas. High purity air with less than 1 ppm of organic material (as propane) or less than 0.1 percent of the span value, whichever is greater.

5.1.3FIA Linearity Calibration Gases. Low-, mid-, and high-range gas mixture standards with nominal propane concentrations of 2030, 4555, and 7080 percent of the span value in air, respectively. Other calibration values and other span values may be used if it can be shown to the Administrator's satisfaction that equally accurate measurements would be achieved.

5.1.4System Calibration Gas. Gas mixture standard containing propane in air, approximating the undiluted VOC concentration expected for the liquid samples.

6. Sample Collection, Preservation and Storage 6.1Samples must be collected in a manner that prevents or minimizes loss of volatile components and that does not contaminate the coating reservoir.

6.2Collect a 100-ml or larger sample of the VOC containing liquid mixture at each application location at the beginning and end of each test run. A separate sample should be taken of each VOC containing liquid added to the application mixture during the test run. If a fresh drum is needed during the sampling run, then obtain a sample from the fresh drum.

6.3When collecting the sample, ground the sample container to the coating drum. Fill the sample container as close to the rim as possible to minimize the amount of headspace.

6.4After the sample is collected, seal the container so the sample cannot leak out or evaporate.

6.5Label the container to clearly identify the contents.

7. Quality Control 7.1Required instrument quality control parameters are found in the following sections: 7.1.1The FIA system must be calibrated as specified in section 8.1.

7.1.2The system drift check must be performed as specified in section 8.2.

7.2Audits.

7.2.1Audit Procedure. Concurrently, analyze the audit sample and a set of compliance samples in the same manner to evaluate the technique of the analyst and the standards preparation. The same analyst, analytical reagents, and analytical system shall be used both for compliance samples and the EPA audit sample. If this condition is met, auditing of subsequent compliance analyses for the same enforcement agency within 30 days is not required. An audit sample set may not be used to validate different sets of compliance samples under the jurisdiction of different enforcement agencies, unless prior arrangements are made with both enforcement agencies.

7.2.2Audit Samples and Audit Sample Availability. Audit samples will be supplied only to enforcement agencies for compliance tests. The availability of audit samples may be obtained by writing: Source Test Audit Coordinator (STAC) (MD77B), Quality Assurance Division, Atmospheric Research and Exposure Assessment Laboratory, U.S.

Environmental Protection Agency, Research Triangle Park, NC 27711 or by calling the STAC at (919) 5417834. The request for the audit sample must be made at least 30 days prior to the scheduled compliance sample analysis.

7.2.3Audit Results. Calculate the audit sample concentration according to the calculation procedure described in the audit instructions included with the audit sample. Fill in the audit sample concentration and the analyst's name on the audit response form included with the audit instructions. Send one copy to the EPA Regional Office or the appropriate enforcement agency, and a second copy to the STAC. The EPA Regional Office or the appropriate enforcement agency will report the results of the audit to the laboratory being audited. Include this response with the results of the compliance samples in relevant reports to the EPA Regional Office or the appropriate enforcement agency.

8. Calibration and Standardization 8.1FIA Calibration and Linearity Check. Make necessary adjustments to the air and fuel supplies for the FIA and ignite the burner. Allow the FIA to warm up for the period recommended by the manufacturer. Inject a calibration gas into the measurement system and adjust the back-pressure regulator to the value required to achieve the flow rates specified by the manufacturer. Inject the zero- and the high-range calibration gases and adjust the analyzer calibration to provide the proper responses.

Inject the low- and mid-range gases and record the responses of the measurement system. The calibration and linearity of the system are acceptable if the responses for all four gases are within 5 percent of the respective gas values. If the performance of the system is not acceptable, repair or adjust the system and repeat the linearity check.

Conduct a calibration and linearity check after assembling the analysis system and after a major change is made to the system.

8.2Systems Drift Checks. After each sample, repeat the system calibration checks in section 9.2.7 before any adjustments to the FIA or measurement system are made. If the zero or calibration drift exceeds 3 percent of the span value, discard the result and repeat the analysis.

Alternatively, recalibrate the FIA as in section 8.1 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). The data that results in the lowest CE value shall be reported as the results for the test run.

8.3Critical Orifice Calibration.

8.3.1Each critical orifice must be calibrated at the specific operating conditions under which it will be used. Therefore, assemble all components of the liquid sample analysis system as shown in Figure 204A3.

A stopwatch is also required.

8.3.2Turn on the sample oven, sample line, and water bath heaters, and allow the system to reach the proper operating temperature. Adjust the aspirator to a vacuum of 380 mm (15 in.) Hg vacuum. Measure the time required for one soap bubble to move a known distance and record barometric pressure.

8.3.3Repeat the calibration procedure at a vacuum of 406 mm (16 in.) Hg and at 25-mm (1-in.) Hg intervals until three consecutive determinations provide the same flow rate. Calculate the critical flow rate for the orifice in ml/min at standard conditions. Record the vacuum necessary to achieve critical flow.

9. Procedure 9.1Determination of Liquid Input Weight.

9.1.1Weight Difference. Determine the amount of material introduced to the process as the weight difference of the feed material before and after each sampling run. In determining the total VOC containing liquid usage, account for: (a) The initial (beginning) VOC containing liquid mixture.

(b) Any solvent added during the test run.

(c) Any coating added during the test run.

(d) Any residual VOC containing liquid mixture remaining at the end of the sample run.

9.1.1.1Identify all points where VOC containing liquids are introduced to the process. To obtain an accurate measurement of VOC containing liquids, start with an empty fountain (if applicable). After completing the run, drain the liquid in the fountain back into the liquid drum (if possible) and weigh the drum again. Weigh the VOC containing liquids to 0.5 percent of the total weight (full) or 1.0 percent of the total weight of VOC containing liquid used during the sample run, whichever is less. If the residual liquid cannot be returned to the drum, drain the fountain into a preweighed empty drum to determine the final weight of the liquid.

9.1.1.2If it is not possible to measure a single representative mixture, then weigh the various components separately (e.g., if solvent is added during the sampling run, weigh the solvent before it is added to the mixture). If a fresh drum of VOC containing liquid is needed during the run, then weigh both the empty drum and fresh drum.

9.1.2Volume Measurement (Alternative). If direct weight measurements are not feasible, the tester may use volume meters or flow rate meters and density measurements to determine the weight of liquids used if it can be demonstrated that the technique produces results equivalent to the direct weight measurements. If a single representative mixture cannot be measured, measure the components separately.

9.2Determination of VOC Content in Input Liquids 9.2.1 Assemble the liquid VOC content analysis system as shown in Figure 204A1.

9.2.2Permanently identify all of the critical orifices that may be used.

Calibrate each critical orifice under the expected operating conditions (i.e., sample vacuum and temperature) against a volume meter as described in section 8.3.

9.2.3Label and tare the sample vessels (including the stoppers and caps) and the syringes.

9.2.4Install an empty sample vessel and perform a leak test of the system. Close the carrier gas valve and atmospheric vent and evacuate the sample vessel to 250 mm (10 in.) Hg absolute or less using the aspirator. Close the toggle valve at the inlet to the aspirator and observe the vacuum for at least 1 minute. If there is any change in the sample pressure, release the vacuum, adjust or repair the apparatus as necessary, and repeat the leak test.

9.2.5Perform the analyzer calibration and linearity checks according to the procedure in section 5.1. Record the responses to each of the calibration gases and the back-pressure setting of the FIA.

9.2.6Establish the appropriate dilution ratio by adjusting the aspirator air supply or substituting critical orifices. Operate the aspirator at a vacuum of at least 25 mm (1 in.) Hg greater than the vacuum necessary to achieve critical flow. Select the dilution ratio so that the maximum response of the FIA to the sample does not exceed the high-range calibration gas.

9.2.7Perform system calibration checks at two levels by introducing compressed gases at the inlet to the sample vessel while the aspirator and dilution devices are operating. Perform these checks using the carrier gas (zero concentration) and the system calibration gas. If the response to the carrier gas exceeds 0.5 percent of span, clean or repair the apparatus and repeat the check. Adjust the dilution ratio as necessary to achieve the correct response to the upscale check, but do not adjust the analyzer calibration. Record the identification of the orifice, aspirator air supply pressure, FIA back-pressure, and the responses of the FIA to the carrier and system calibration gases.

9.2.8After completing the above checks, inject the system calibration gas for approximately 10 minutes. Time the exact duration of the gas injection using a stopwatch. Determine the area under the FIA response curve and calculate the system response factor based on the sample gas flow rate, gas concentration, and the duration of the injection as compared to the integrated response using Equations 204A2 and 204A3.

9.2.9Verify that the sample oven and sample line temperatures are 120 5 C and that the water bath temperature is 100 5 C.

9.2.10Fill a tared syringe with approximately 1 g of the VOC containing liquid and weigh it. Transfer the liquid to a tared sample vessel. Plug the sample vessel to minimize sample loss. Weigh the sample vessel containing the liquid to determine the amount of sample actually received. Also, as a quality control check, weigh the empty syringe to determine the amount of material delivered. The two coating sample weights should agree within 0.02 g. If not, repeat the procedure until an acceptable sample is obtained.

9.2.11Connect the vessel to the analysis system. Adjust the aspirator supply pressure to the correct value. Open the valve on the carrier gas supply to the sample vessel and adjust it to provide a slight excess flow to the atmospheric vent. As soon as the initial response of the FIA begins to decrease, immerse the sample vessel in the water bath.

(Applying heat to the sample vessel too soon may cause the FIA response to exceed the calibrated range of the instrument and, thus, invalidate the analysis.) 9.2.12Continuously measure and record the response of the FIA until all of the volatile material has been evaporated from the sample and the instrument response has returned to the baseline (i.e., response less than 0.5 percent of the span value). Observe the aspirator supply pressure, FIA back-pressure, atmospheric vent, and other system operating parameters during the run; repeat the analysis procedure if any of these parameters deviate from the values established during the system calibration checks in section 9.2.7. After each sample, perform the drift check described in section 8.2. If the drift check results are acceptable, calculate the VOC content of the sample using the equations in section 11.2. Alternatively, recalibrate the FIA as in section 8.1 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). The data that results in the lowest CE value shall be reported as the results for the test run. Integrate the area under the FIA response curve, or determine the average concentration response and the duration of sample analysis.

10. Data Analysis and Calculations 10.1Nomenclature.

AL=area under the response curve of the liquid sample, area count.

AS=area under the response curve of the calibration gas, area count.

CS=actual concentration of system calibration gas, ppm propane.

K=1.830 109 g/(ml-ppm).

L=total VOC content of liquid input, kg.

ML=mass of liquid sample delivered to the sample vessel, g.

q = flow rate through critical orifice, ml/min.

RF=liquid analysis system response factor, g/area count.

S=total gas injection time for system calibration gas during integrator calibration, min.

VFj=final VOC fraction of VOC containing liquid j.

VIj=initial VOC fraction of VOC containing liquid j.

VAj=VOC fraction of VOC containing liquid j added during the run.

V=VOC fraction of liquid sample.

WFj=weight of VOC containing liquid j remaining at end of the run, kg.

WIj=weight of VOC containing liquid j at beginning of the run, kg.

WAj=weight of VOC containing liquid j added during the run, kg.

10.2Calculations 10.2.1Total VOC Content of the Input VOC Containing Liquid. (image) 10.2.2Liquid Sample Analysis System Response Factor for Systems Using Integrators, Grams/Area Count. (image) 10.2.3VOC Content of the Liquid Sample. (image) 11. Method Performance The measurement uncertainties are estimated for each VOC containing liquid as follows: W = 2.0 percent and V = 4.0 percent. Based on these numbers, the probable uncertainty for L is estimated at about 4.5 percent for each VOC containing liquid.

12. Diagrams (image) View or download PDF (image) View or download PDF (image) View or download PDF Method 204BVolatile Organic Compounds Emissions in Captured Stream 1. Scope and Application 1.1Applicability. This procedure is applicable for determining the volatile organic compounds (VOC) content of captured gas streams. It is intended to be used in the development of a gas/gas protocol for determining VOC capture efficiency (CE) for surface coating and printing operations. The procedure may not be acceptable in certain site-specific situations [e.g., when: (1) direct-fired heaters or other circumstances affect the quantity of VOC at the control device inlet; and (2) particulate organic aerosols are formed in the process and are present in the captured emissions].

1.2Principle. The amount of VOC captured (G) is calculated as the sum of the products of the VOC content (CGj), the flow rate (QGj), and the sample time (C) from each captured emissions point.

1.3Sampling Requirements. A CE test shall consist of at least three sampling runs. Each run shall cover at least one complete production cycle, but shall be at least 3 hours long. The sampling time for each run need not exceed 8 hours, even if the production cycle has not been completed. Alternative sampling times may be used with the approval of the Administrator.

2. Summary of Method A gas sample is extracted from the source though a heated sample line and, if necessary, a glass fiber filter to a flame ionization analyzer (FIA).

3. Safety Because this procedure is often applied in highly explosive areas, caution and care should be exercised in choosing, installing, and using the appropriate equipment.

4. Equipment and Supplies Mention of trade names or company products does not constitute endorsement. All gas concentrations (percent, ppm) are by volume, unless otherwise noted.

4.1Gas VOC Concentration. A schematic of the measurement system is shown in Figure 204B1. The main components are as follows: 4.1.1Sample Probe. Stainless steel or equivalent. The probe shall be heated to prevent VOC condensation.

4.1.2Calibration Valve Assembly. Three-way valve assembly at the outlet of the sample probe to direct the zero and calibration gases to the analyzer. Other methods, such as quick-connect lines, to route calibration gases to the outlet of the sample probe are acceptable.

4.1.3Sample Line. Stainless steel or Teflon tubing to transport the sample gas to the analyzer. The sample line must be heated to prevent condensation.

4.1.4Sample Pump. A leak-free pump, to pull the sample gas through the system at a flow rate sufficient to minimize the response time of the measurement system. The components of the pump that contact the gas stream shall be constructed of stainless steel or Teflon. The sample pump must be heated to prevent condensation.

4.1.5Sample Flow Rate Control. A sample flow rate control valve and rotameter, or equivalent, to maintain a constant sampling rate within 10 percent. The flow rate control valve and rotameter must be heated to prevent condensation. A control valve may also be located on the sample pump bypass loop to assist in controlling the sample pressure and flow rate.

4.1.6Organic Concentration Analyzer. An FIA with a span value of 1.5 times the expected concentration as propane; however, other span values may be used if it can be demonstrated to the Administrator's satisfaction that they would provide equally accurate measurements. The system shall be capable of meeting or exceeding the following specifications: 4.1.6.1Zero Drift. Less than 3.0 percent of the span value.

4.1.6.2Calibration Drift. Less than 3.0 percent of the span value.

4.1.6.3Calibration Error. Less than 5.0 percent of the calibration gas value.

4.1.6.4Response Time. Less than 30 seconds.

4.1.7Integrator/Data Acquisition System. An analog or digital device, or computerized data acquisition system used to integrate the FIA response or compute the average response and record measurement data. The minimum data sampling frequency for computing average or integrated values is one measurement value every 5 seconds. The device shall be capable of recording average values at least once per minute.

4.2Captured Emissions Volumetric Flow Rate.

4.2.1Method 2 or 2A Apparatus. For determining volumetric flow rate.

4.2.2Method 3 Apparatus and Reagents. For determining molecular weight of the gas stream. An estimate of the molecular weight of the gas stream may be used if approved by the Administrator.

4.2.3Method 4 Apparatus and Reagents. For determining moisture content, if necessary.

5. Reagents and Standards 5.1Calibration and Other Gases. Gases used for calibration, fuel, and combustion air (if required) are contained in compressed gas cylinders.

All calibration gases shall be traceable to National Institute of Standards and Technology standards and shall be certified by the manufacturer to 1 percent of the tag value. 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, dilution systems calibrated using Method 205 may be used. Alternative methods for preparing calibration gas mixtures may be used with the approval of the Administrator.

5.1.1Fuel. The FIA manufacturer's recommended fuel should be used. A 40 percent H2/60 percent He or 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. Other mixtures may be used provided the tester can demonstrate to the Administrator that there is no oxygen synergism effect.

5.1.2Carrier Gas. High purity air with less than 1 ppm of organic material (as propane or carbon equivalent) or less than 0.1 percent of the span value, whichever is greater.

5.1.3FIA Linearity Calibration Gases. Low-, mid-, and high-range gas mixture standards with nominal propane concentrations of 2030, 4555, and 7080 percent of the span value in air, respectively. Other calibration values and other span values may be used if it can be shown to the Administrator's satisfaction that equally accurate measurements would be achieved.

5.2Particulate 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 must be heated to prevent any condensation unless it can be demonstrated that no condensation occurs.

6. Quality Control 6.1Required instrument quality control parameters are found in the following sections: 6.1.1The FIA system must be calibrated as specified in section 7.1.

6.1.2The system drift check must be performed as specified in section 7.2.

6.1.3The system check must be conducted as specified in section 7.3.

6.2Audits.

6.2.1Analysis Audit Procedure. Immediately before each test, analyze an audit cylinder as described in section 7.2. The analysis audit must agree with the audit cylinder concentration within 10 percent.

6.2.2Audit Samples and Audit Sample Availability. Audit samples will be supplied only to enforcement agencies for compliance tests. The availability of audit samples may be obtained by writing: Source Test Audit Coordinator (STAC) (MD77B), Quality Assurance Division, Atmospheric Research and Exposure Assessment Labortory, U.S.

Environmental Protection Agency, Research Triangle Park, NC 27711 or by calling the STAC at (919) 5417834. The request for the audit sample must be made at least 30 days prior to the scheduled compliance sample analysis.

6.2.3Audit Results. Calculate the audit sample concentration according to the calculation procedure described in the audit instructions included with the audit sample. Fill in the audit sample concentration and the analyst's name on the audit response form included with the audit instructions. Send one copy to the EPA Regional Office or the appropriate enforcement agency, and a second copy to the STAC. The EPA Regional Office or the appropriate enforcement agency will report the results of the audit to the laboratory being audited. Include this response with the results of the compliance samples in relevant reports to the EPA Regional Office or the appropriate enforcement agency.

7. Calibration and Standardization 7.1FIA Calibration and Linearity Check. Make necessary adjustments to the air and fuel supplies for the FIA and ignite the burner. Allow the FIA to warm up for the period recommended by the manufacturer. Inject a calibration gas into the measurement system and adjust the back-pressure regulator to the value required to achieve the flow rates specified by the manufacturer. Inject the zero-and the high-range calibration gases and adjust the analyzer calibration to provide the proper responses.

Inject the low- and mid-range gases and record the responses of the measurement system. The calibration and linearity of the system are acceptable if the responses for all four gases are within 5 percent of the respective gas values. If the performance of the system is not acceptable, repair or adjust the system and repeat the linearity check.

Conduct a calibration and linearity check after assembling the analysis system and after a major change is made to the system.

7.2Systems Drift Checks. Select the calibration gas that most closely approximates the concentration of the captured emissions for conducting the drift checks. Introduce the zero and calibration gases at the calibration valve assembly and verify that the appropriate gas flow rate and pressure are present at the FIA. Record the measurement system responses to the zero and calibration gases. The performance of the system is acceptable if the difference between the drift check measurement and the value obtained in section 7.1 is less than 3 percent of the span value. Alternatively, recalibrate the FIA as in section 7.1 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). The data that results in the lowest CE value shall be reported as the results for the test run. Conduct the system drift checks at the end of each run.

7.3System Check. Inject the high-range calibration gas at the inlet of the sampling probe and record the response. The performance of the system is acceptable if the measurement system response is within 5 percent of the value obtained in section 7.1 for the high-range calibration gas. Conduct a system check before and after each test run.

8. Procedure 8.1.Determination of Volumetric Flow Rate of Captured Emissions.

8.1.1Locate all points where emissions are captured from the affected facility. Using Method 1, determine the sampling points. Be sure to check each site for cyclonic or swirling flow.

8.1.2Measure the velocity at each sampling site at least once every hour during each sampling run using Method 2 or 2A.

8.2Determination of VOC Content of Captured Emissions.

8.2.1Analysis Duration. Measure the VOC responses at each captured emissions point during the entire test run or, if applicable, while the process is operating. If there are multiple captured emission locations, design a sampling system to allow a single FIA to be used to determine the VOC responses at all sampling locations.

8.2.2Gas VOC Concentration.

8.2.2.1Assemble the sample train as shown in Figure 204B1. Calibrate the FIA according to the procedure in section 7.1.

8.2.2.2Conduct a system check according to the procedure in section 7.3.

8.2.2.3Install 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.

8.2.2.4Inject zero gas at the calibration valve assembly. Allow the measurement system response to reach zero. Measure the system response time as the time required for the system to reach the effluent concentration after the calibration valve has been returned to the effluent sampling position.

8.2.2.5Conduct a system check before, and a system drift check after, each sampling run according to the procedures in sections 7.2 and 7.3.

If the drift check following a run indicates unacceptable performance (see section 7.3), the run is not valid. Alternatively, recalibrate the FIA as in section 7.1 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). The data that results in the lowest CE value shall be reported as the results for the test run. The tester may elect to perform system drift checks during the run not to exceed one drift check per hour.

8.2.2.6Verify that the sample lines, filter, and pump temperatures are 120 5 C.

8.2.2.7Begin sampling at the start of the test period and continue to sample during the entire run. Record the starting and ending times and any required process information as appropriate. If multiple captured emission locations are sampled using a single FIA, sample at each location for the same amount of time (e.g., 2 minutes) and continue to switch from one location to another for the entire test run. Be sure that total sampling time at each location is the same at the end of the test run. Collect at least four separate measurements from each sample point during each hour of testing. Disregard the measurements at each sampling location until two times the response time of the measurement system has elapsed. Continue sampling for at least 1 minute and record the concentration measurements.

8.2.3Background Concentration.

Note: Not applicable when the building is used as the temporary total enclosure (TTE).

8.2.3.1Locate all natural draft openings (NDO's) of the TTE. A sampling point shall be at the center of each NDO, unless otherwise specified by the Administrator. If there are more than six NDO's, choose six sampling points evenly spaced among the NDO's.

8.2.3.2Assemble the sample train as shown in Figure 204B2. Calibrate the FIA and conduct a system check according to the procedures in sections 7.1 and 7.3.

Note: This sample train shall be separate from the sample train used to measure the captured emissions.

8.2.3.3Position the probe at the sampling location.

8.2.3.4Determine the response time, conduct the system check, and sample according to the procedures described in sections 8.2.2.4 through 8.2.2.7.

8.2.4Alternative Procedure. The direct interface sampling and analysis procedure described in section 7.2 of Method 18 may be used to determine the gas VOC concentration. The system must be designed to collect and analyze at least one sample every 10 minutes. If the alternative procedure is used to determine the VOC concentration of the captured emissions, it must also be used to determine the VOC concentration of the uncaptured emissions.

9. Data Analysis and Calculations 9.1Nomenclature.

Ai=area of NDO i, ft 2 .

AN=total area of all NDO's in the enclosure, ft 2 .

CBi=corrected average VOC concentration of background emissions at point i, ppm propane.

CB=average background concentration, ppm propane.

CGj=corrected average VOC concentration of captured emissions at point j, ppm propane.

CDH=average measured concentration for the drift check calibration gas, ppm propane.

CDO=average system drift check concentration for zero concentration gas, ppm propane.

CH=actual concentration of the drift check calibration gas, ppm propane.

Ci=uncorrected average background VOC concentration measured at point i, ppm propane.

Cj=uncorrected average VOC concentration measured at point j, ppm propane.

G=total VOC content of captured emissions, kg.

K1=1.830106 kg/(m 3 -ppm).

n=number of measurement points.

QGj=average effluent volumetric flow rate corrected to standard conditions at captured emissions point j, m 3 /min.

C=total duration of captured emissions.

9.2Calculations.

9.2.1Total VOC Captured Emissions. (image) 9.2.2VOC Concentration of the Captured Emissions at Point j. (image) 9.2.3Background VOC Concentration at Point i. (image) 9.2.4Average Background Concentration. (image) Note: If the concentration at each point is within 20 percent of the average concentration of all points, then use the arithmetic average.

10. Method Performance The measurement uncertainties are estimated for each captured or uncaptured emissions point as follows: QGj=5.5 percent and CGj=5.0 percent. Based on these numbers, the probable uncertainty for G is estimated at about 7.4 percent.

11. Diagrams (image) View or download PDF (image) View or download PDF Method 204CVolatile Organic Compounds Emissions in Captured Stream (Dilution Technique) 1. Scope and Application 1.1Applicability. This procedure is applicable for determining the volatile organic compounds (VOC) content of captured gas streams. It is intended to be used in the development of a gas/gas protocol in which uncaptured emissions are also measured for determining VOC capture efficiency (CE) for surface coating and printing operations. A dilution system is used to reduce the VOC concentration of the captured emissions to about the same concentration as the uncaptured emissions. The procedure may not be acceptable in certain site-specific situations [e.g., when: (1) direct-fired heaters or other circumstances affect the quantity of VOC at the control device inlet; and (2) particulate organic aerosols are formed in the process and are present in the captured emissions].

1.2Principle. The amount of VOC captured (G) is calculated as the sum of the products of the VOC content (CGj), the flow rate (QGj), and the sampling time (C) from each captured emissions point.

1.3Sampling Requirements. A CE test shall consist of at least three sampling runs. Each run shall cover at least one complete production cycle, but shall be at least 3 hours long. The sampling time for each run need not exceed 8 hours, even if the production cycle has not been completed. Alternative sampling times may be used with the approval of the Administrator.

2. Summary of Method A gas sample is extracted from the source using an in-stack dilution probe through a heated sample line and, if necessary, a glass fiber filter to a flame ionization analyzer (FIA). The sample train contains a sample gas manifold which allows multiple points to be sampled using a single FIA.

3. Safety Because this procedure is often applied in highly explosive areas, caution and care should be exercised in choosing, installing, and using the appropriate equipment.

4. Equipment and Supplies Mention of trade names or company products does not constitute endorsement. All gas concentrations (percent, ppm) are by volume, unless otherwise noted.

4.1Gas VOC Concentration. A schematic of the measurement system is shown in Figure 204C1. The main components are as follows: 4.1.1Dilution System. A Kipp in-stack dilution probe and controller or similar device may be used. The dilution rate may be changed by substituting different critical orifices or adjustments of the aspirator supply pressure. The dilution system shall be heated to prevent VOC condensation. Note: An out-of-stack dilution device may be used.

4.1.2Calibration Valve Assembly. Three-way valve assembly at the outlet of the sample probe to direct the zero and calibration gases to the analyzer. Other methods, such as quick-connect lines, to route calibration gases to the outlet of the sample probe are acceptable.

4.1.3Sample Line. Stainless steel or Teflon tubing to transport the sample gas to the analyzer. The sample line must be heated to prevent condensation.

4.1.4Sample Pump. A leak-free pump, to pull the sample gas through the system at a flow rate sufficient to minimize the response time of the measurement system. The components of the pump that contact the gas stream shall be constructed of stainless steel or Teflon. The sample pump must be heated to prevent condensation.

4.1.5Sample Flow Rate Control. A sample flow rate control valve and rotameter, or equivalent, to maintain a constant sampling rate within 10 percent. The flow control valve and rotameter must be heated to prevent condensation. A control valve may also be located on the sample pump bypass loop to assist in controlling the sample pressure and flow rate.

4.1.6Sample Gas Manifold. Capable of diverting a portion of the sample gas stream to the FIA, and the remainder to the bypass discharge vent.

The manifold components shall be constructed of stainless steel or Teflon. If captured or uncaptured emissions are to be measured at multiple locations, the measurement system shall be designed to use separate sampling probes, lines, and pumps for each measurement location and a common sample gas manifold and FIA. The sample gas manifold and connecting lines to the FIA must be heated to prevent condensation.

Note: Depending on the number of sampling points and their location, it may not be possible to use only one FIA. However to reduce the effect of calibration error, the number of FIA's used during a test should be keep as small as possible.

4.1.7Organic Concentration Analyzer. An FIA with a span value of 1.5 times the expected concentration as propane; however, other span values may be used if it can be demonstrated to the Administrator's satisfaction that they would provide equally accurate measurements. The system shall be capable of meeting or exceeding the following specifications: 4.1.7.1Zero Drift. Less than 3.0 percent of the span value.

4.1.7.2Calibration Drift. Less than 3.0 percent of the span value.

4.1.7.3Calibration Error. Less than 5.0 percent of the calibration gas value.

4.1.7.4Response Time. Less than 30 seconds.

4.1.8Integrator/Data Acquisition System. An analog or digital device or computerized data acquisition system used to integrate the FIA response or compute the average response and record measurement data. The minimum data sampling frequency for computing average or integrated values is one measurement value every 5 seconds. The device shall be capable of recording average values at least once per minute.

4.2Captured Emissions Volumetric Flow Rate.

4.2.1Method 2 or 2A Apparatus. For determining volumetric flow rate.

4.2.2Method 3 Apparatus and Reagents. For determining molecular weight of the gas stream. An estimate of the molecular weight of the gas stream may be used if approved by the Administrator.

4.2.3Method 4 Apparatus and Reagents. For determining moisture content, if necessary.

5. Reagents and Standards 5.1Calibration and Other Gases. Gases used for calibration, fuel, and combustion air (if required) are contained in compressed gas cylinders.

All calibration gases shall be traceable to National Institute of Standards and Technology standards and shall be certified by the manufacturer to 1 percent of the tag value. 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, dilution systems calibrated using Method 205 may be used. Alternative methods for preparing calibration gas mixtures may be used with the approval of the Administrator.

5.1.1Fuel. The FIA manufacturer's recommended fuel should be used. A 40 percent H2/60 percent He or 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. Other mixtures may be used provided the tester can demonstrate to the Administrator that there is no oxygen synergism effect 5.1.2Carrier Gas and Dilution Air Supply. High purity air with less than 1 ppm of organic material (as propane or carbon equivalent), or less than 0.1 percent of the span value, whichever is greater.

5.1.3FIA Linearity Calibration Gases. Low-, mid-, and high-range gas mixture standards with nominal propane concentrations of 2030, 4555, and 7080 percent of the span value in air, respectively. Other calibration values and other span values may be used if it can be shown to the Administrator's satisfaction that equally accurate measurements would be achieved.

5.1.4Dilution Check Gas. Gas mixture standard containing propane in air, approximately half the span value after dilution.

5.2Particulate 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 must be heated to prevent any condensation unless it can be demonstrated that no condensation occurs.

6. Quality Control 6.1Required instrument quality control parameters are found in the following sections: 6.1.1The FIA system must be calibrated as specified in section 7.1.

6.1.2The system drift check must be performed as specified in section 7.2.

6.1.3The dilution factor must be determined as specified in section 7.3.

6.1.4The system check must be conducted as specified in section 7.4.

6.2Audits.

6.2.1Analysis Audit Procedure. Immediately before each test, analyze an audit cylinder as described in section 7.2. The analysis audit must agree with the audit cylinder concentration within 10 percent.

6.2.2Audit Samples and Audit Sample Availability. Audit samples will be supplied only to enforcement agencies for compliance tests. The availability of audit samples may be obtained by writing: Source Test Audit Coordinator (STAC) (MD77B), Quality Assurance Division, Atmospheric Research and Exposure Assessment Laboratory, U.S.

Environmental Protection Agency, Research Triangle Park, NC 27711 or by calling the STAC at (919) 5417834. The request for the audit sample must be made at least 30 days prior to the scheduled compliance sample analysis.

6.2.3Audit Results. Calculate the audit sample concentration according to the calculation procedure described in the audit instructions included with the audit sample. Fill in the audit sample concentration and the analyst's name on the audit response form included with the audit instructions. Send one copy to the EPA Regional Office or the appropriate enforcement agency, and a second copy to the STAC. The EPA Regional Office or the appropriate enforcement agency will report the results of the audit to the laboratory being audited. Include this response with the results of the compliance samples in relevant reports to the EPA Regional Office or the appropriate enforcement agency.

7. Calibration and Standardization 7.1FIA Calibration and Linearity Check. Make necessary adjustments to the air and fuel supplies for the FIA and ignite the burner. Allow the FIA to warm up for the period recommended by the manufacturer. Inject a calibration gas into the measurement system after the dilution system and adjust the back-pressure regulator to the value required to achieve the flow rates specified by the manufacturer. Inject the zero-and the high-range calibration gases and adjust the analyzer calibration to provide the proper responses. Inject the low-and mid-range gases and record the responses of the measurement system. The calibration and linearity of the system are acceptable if the responses for all four gases are within 5 percent of the respective gas values. If the performance of the system is not acceptable, repair or adjust the system and repeat the linearity check. Conduct a calibration and linearity check after assembling the analysis system and after a major change is made to the system.

7.2Systems Drift Checks. Select the calibration gas that most closely approximates the concentration of the diluted captured emissions for conducting the drift checks. Introduce the zero and calibration gases at the calibration valve assembly, and verify that the appropriate gas flow rate and pressure are present at the FIA. Record the measurement system responses to the zero and calibration gases. The performance of the system is acceptable if the difference between the drift check measurement and the value obtained in section 7.1 is less than 3 percent of the span value. Alternatively, recalibrate the FIA as in section 7.1 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). The data that results in the lowest CE value shall be reported as the results for the test run. Conduct the system drift check at the end of each run.

7.3Determination of Dilution Factor. Inject the dilution check gas into the measurement system before the dilution system and record the response. Calculate the dilution factor using Equation 204C3.

7.4System Check. Inject the high-range calibration gas at the inlet to the sampling probe while the dilution air is turned off. Record the response. The performance of the system is acceptable if the measurement system response is within 5 percent of the value obtained in section 7.1 for the high-range calibration gas. Conduct a system check before and after each test run.

8. Procedure 8.1Determination of Volumetric Flow Rate of Captured Emissions 8.1.1Locate all points where emissions are captured from the affected facility. Using Method 1, determine the sampling points. Be sure to check each site for cyclonic or swirling flow.

8.2.2Measure the velocity at each sampling site at least once every hour during each sampling run using Method 2 or 2A.

8.2Determination of VOC Content of Captured Emissions 8.2.1Analysis Duration. Measure the VOC responses at each captured emissions point during the entire test run or, if applicable, while the process is operating. If there are multiple captured emissions locations, design a sampling system to allow a single FIA to be used to determine the VOC responses at all sampling locations.

8.2.2Gas VOC Concentration.

8.2.2.1Assemble the sample train as shown in Figure 204C1. Calibrate the FIA according to the procedure in section 7.1.

8.2.2.2Set the dilution ratio and determine the dilution factor according to the procedure in section 7.3.

8.2.2.3Conduct a system check according to the procedure in section 7.4.

8.2.2.4Install 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.

8.2.2.5Inject zero gas at the calibration valve assembly. Measure the system response time as the time required for the system to reach the effluent concentration after the calibration valve has been returned to the effluent sampling position.

8.2.2.6Conduct a system check before, and a system drift check after, each sampling run according to the procedures in sections 7.2 and 7.4.

If the drift check following a run indicates unacceptable performance (see section 7.4), the run is not valid. Alternatively, recalibrate the FIA as in section 7.1 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). The data that results in the lowest CE value shall be reported as the results for the test run. The tester may elect to perform system drift checks during the run not to exceed one drift check per hour.

8.2.2.7Verify that the sample lines, filter, and pump temperatures are 120 5 C.

8.2.2.8Begin sampling at the start of the test period and continue to sample during the entire run. Record the starting and ending times and any required process information as appropriate. If multiple captured emission locations are sampled using a single FIA, sample at each location for the same amount of time (e.g., 2 min.) and continue to switch from one location to another for the entire test run. Be sure that total sampling time at each location is the same at the end of the test run. Collect at least four separate measurements from each sample point during each hour of testing. Disregard the measurements at each sampling location until two times the response time of the measurement system has elapsed. Continue sampling for at least 1 minute and record the concentration measurements.

8.2.3Background Concentration.

Note: Not applicable when the building is used as the temporary total enclosure (TTE).

8.2.3.1Locate all natural draft openings (NDO's) of the TTE. A sampling point shall be at the center of each NDO, unless otherwise approved by the Administrator. If there are more than six NDO's, choose six sampling points evenly spaced among the NDO's.

8.2.3.2Assemble the sample train as shown in Figure 204C2. Calibrate the FIA and conduct a system check according to the procedures in sections 7.1 and 7.4.

8.2.3.3Position the probe at the sampling location.

8.2.3.4Determine the response time, conduct the system check, and sample according to the procedures described in sections 8.2.2.4 through 8.2.2.8.

8.2.4Alternative Procedure. The direct interface sampling and analysis procedure described in section 7.2 of Method 18 may be used to determine the gas VOC concentration. The system must be designed to collect and analyze at least one sample every 10 minutes. If the alternative procedure is used to determine the VOC concentration of the captured emissions, it must also be used to determine the VOC concentration of the uncaptured emissions.

9. Data Analysis and Calculations 9.1Nomenclature.

Ai=area of NDO i, ft2.

AN=total area of all NDO's in the enclosure, ft2.

CA = actual concentration of the dilution check gas, ppm propane.

CBi=corrected average VOC concentration of background emissions at point i, ppm propane.

CB=average background concentration, ppm propane.

CDH=average measured concentration for the drift check calibration gas, ppm propane.

CD0=average system drift check concentration for zero concentration gas, ppm propane.

CH=actual concentration of the drift check calibration gas, ppm propane.

Ci=uncorrected average background VOC concentration measured at point i, ppm propane.

Cj=uncorrected average VOC concentration measured at point j, ppm propane.

CM=measured concentration of the dilution check gas, ppm propane.

DF=dilution factor.

G=total VOC content of captured emissions, kg.

K1=1.830106 kg/(m 3 ppm).

n=number of measurement points.

QGj=average effluent volumetric flow rate corrected to standard conditions at captured emissions point j, m 3 /min.

C=total duration of CE sampling run, min.

9.2Calculations.

9.2.1Total VOC Captured Emissions. (image) 9.2.2VOC Concentration of the Captured Emissions at Point j. (image) 9.2.3Dilution Factor. (image) 9.2.4Background VOC Concentration at Point i. (image) 9.2.5Average Background Concentration. (image) Note: If the concentration at each point is within 20 percent of the average concentration of all points, then use the arithmetic average.

10. Method Performance The measurement uncertainties are estimated for each captured or uncaptured emissions point as follows: QGj=5.5 percent and CGj= 5 percent. Based on these numbers, the probable uncertainty for G is estimated at about 7.4 percent.

11. Diagrams (image) View or download PDF (image) View or download PDF Method 204DVolatile Organic Compounds Emissions in Uncaptured Stream From Temporary Total Enclosure 1. Scope and Application 1.1Applicability. This procedure is applicable for determining the uncaptured volatile organic compounds (VOC) emissions from a temporary total enclosure (TTE). It is intended to be used as a segment in the development of liquid/gas or gas/gas protocols for determining VOC capture efficiency (CE) for surface coating and printing operations.

1.2Principle. The amount of uncaptured VOC emissions (F) from the TTE is calculated as the sum of the products of the VOC content (CFj), the flow rate (QFj) from each uncaptured emissions point, and the sampling time (F).

1.3Sampling Requirements. A CE test shall consist of at least three sampling runs. Each run shall cover at least one complete production cycle, but shall be at least 3 hours long. The sampling time for each run need not exceed 8 hours, even if the production cycle has not been completed. Alternative sampling times may be used with the approval of the Administrator.

2. Summary of Method A gas sample is extracted from the uncaptured exhaust duct of a TTE through a heated sample line and, if necessary, a glass fiber filter to a flame ionization analyzer (FIA).

3. Safety Because this procedure is often applied in highly explosive areas, caution and care should be exercised in choosing, installing, and using the appropriate equipment.

4. Equipment and Supplies Mention of trade names or company products does not constitute endorsement. All gas concentrations (percent, ppm) are by volume, unless otherwise noted.

4.1Gas VOC Concentration. A schematic of the measurement system is shown in Figure 204D1. The main components are as follows: 4.1.1Sample Probe. Stainless steel or equivalent. The probe shall be heated to prevent VOC condensation.

4.1.2Calibration Valve Assembly. Three-way valve assembly at the outlet of the sample probe to direct the zero and calibration gases to the analyzer. Other methods, such as quick-connect lines, to route calibration gases to the outlet of the sample probe are acceptable.

4.1.3Sample Line. Stainless steel or Teflon tubing to transport the sample gas to the analyzer. The sample line must be heated to prevent condensation.

4.1.4Sample Pump. A leak-free pump, to pull the sample gas through the system at a flow rate sufficient to minimize the response time of the measurement system. The components of the pump that contact the gas stream shall be constructed of stainless steel or Teflon. The sample pump must be heated to prevent condensation.

4.1.5Sample Flow Rate Control. A sample flow rate control valve and rotameter, or equivalent, to maintain a constant sampling rate within 10 percent. The flow control valve and rotameter must be heated to prevent condensation. A control valve may also be located on the sample pump bypass loop to assist in controlling the sample pressure and flow rate.

4.1.6Sample Gas Manifold. Capable of diverting a portion of the sample gas stream to the FIA, and the remainder to the bypass discharge vent.

The manifold components shall be constructed of stainless steel or Teflon. If emissions are to be measured at multiple locations, the measurement system shall be designed to use separate sampling probes, lines, and pumps for each measurement location and a common sample gas manifold and FIA. The sample gas manifold and connecting lines to the FIA must be heated to prevent condensation.

4.1.7Organic Concentration Analyzer. An FIA with a span value of 1.5 times the expected concentration as propane; however, other span values may be used if it can be demonstrated to the Administrator's satisfaction that they would provide more accurate measurements. The system shall be capable of meeting or exceeding the following specifications: 4.1.7.1Zero Drift. Less than 3.0 percent of the span value.

4.1.7.2Calibration Drift. Less than 3.0 percent of the span value.

4.1.7.3Calibration Error. Less than 5.0 percent of the calibration gas value.

4.1.7.4Response Time. Less than 30 seconds.

4.1.8Integrator/Data Acquisition System. An analog or digital device or computerized data acquisition system used to integrate the FIA response or compute the average response and record measurement data. The minimum data sampling frequency for computing average or integrated values is one measurement value every 5 seconds. The device shall be capable of recording average values at least once per minute.

4.2Uncaptured Emissions Volumetric Flow Rate.

4.2.1Method 2 or 2A Apparatus. For determining volumetric flow rate.

4.2.2Method 3 Apparatus and Reagents. For determining molecular weight of the gas stream. An estimate of the molecular weight of the gas stream may be used if approved by the Administrator.

4.2.3Method 4 Apparatus and Reagents. For determining moisture content, if necessary.

4.3Temporary Total Enclosure. The criteria for designing an acceptable TTE are specified in Method 204.

5. Reagents and Standards 5.1Calibration and Other Gases. Gases used for calibration, fuel, and combustion air (if required) are contained in compressed gas cylinders.

All calibration gases shall be traceable to National Institute of Standards and Technology standards and shall be certified by the manufacturer to 1 percent of the tag value. 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, dilution systems calibrated using Method 205 may be used. Alternative methods for preparing calibration gas mixtures may be used with the approval of the Administrator.

5.1.1Fuel. The FIA manufacturer's recommended fuel should be used. A 40 percent H2/60 percent He or 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. Other mixtures may be used provided the tester can demonstrate to the Administrator that there is no oxygen synergism effect.

5.1.2Carrier Gas. High purity air with less than 1 ppm of organic material (as propane or carbon equivalent) or less than 0.1 percent of the span value, whichever is greater.

5.1.3FIA Linearity Calibration Gases. Low-, mid-, and high-range gas mixture standards with nominal propane concentrations of 2030, 4555, and 7080 percent of the span value in air, respectively. Other calibration values and other span values may be used if it can be shown to the Administrator's satisfaction that equally accurate measurements would be achieved.

5.2Particulate 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 must be heated to prevent any condensation unless it can be demonstrated that no condensation occurs.

6. Quality Control 6.1Required instrument quality control parameters are found in the following sections: 6.1.1The FIA system must be calibrated as specified in section 7.1.

6.1.2The system drift check must be performed as specified in section 7.2.

6.1.3The system check must be conducted as specified in section 7.3.

6.2Audits.

6.2.1Analysis Audit Procedure. Immediately before each test, analyze an audit cylinder as described in section 7.2. The analysis audit must agree with the audit cylinder concentration within 10 percent.

6.2.2Audit Samples and Audit Sample Availability. Audit samples will be supplied only to enforcement agencies for compliance tests. The availability of audit samples may be obtained by writing: Source Test Audit Coordinator (STAC) (MD77B) Quality Assurance Division, Atmospheric Research and Exposure Assessment Laboratory, U.S. Environmental Protection Agency, Research Triangle Park, NC 27711 or by calling the STAC at (919) 5417834. The request for the audit sample must be made at least 30 days prior to the scheduled compliance sample analysis.

6.2.3Audit Results. Calculate the audit sample concentration according to the calculation procedure described in the audit instructions included with the audit sample. Fill in the audit sample concentration and the analyst's name on the audit response form included with the audit instructions. Send one copy to the EPA Regional Office or the appropriate enforcement agency, and a second copy to the STAC. The EPA Regional Office or the appropriate enforcement agency will report the results of the audit to the laboratory being audited. Include this response with the results of the compliance samples in relevant reports to the EPA Regional Office or the appropriate enforcement agency.

7. Calibration and Standardization 7.1FIA Calibration and Linearity Check. Make necessary adjustments to the air and fuel supplies for the FIA and ignite the burner. Allow the FIA to warm up for the period recommended by the manufacturer. Inject a calibration gas into the measurement system and adjust the back-pressure regulator to the value required to achieve the flow rates specified by the manufacturer. Inject the zero-and the high-range calibration gases and adjust the analyzer calibration to provide the proper responses.

Inject the low-and mid-range gases and record the responses of the measurement system. The calibration and linearity of the system are acceptable if the responses for all four gases are within 5 percent of the respective gas values. If the performance of the system is not acceptable, repair or adjust the system and repeat the linearity check.

Conduct a calibration and linearity check after assembling the analysis system and after a major change is made to the system.

7.2Systems Drift Checks. Select the calibration gas concentration that most closely approximates that of the uncaptured gas emissions concentration to conduct the drift checks. Introduce the zero and calibration gases at the calibration valve assembly and verify that the appropriate gas flow rate and pressure are present at the FIA. Record the measurement system responses to the zero and calibration gases. The performance of the system is acceptable if the difference between the drift check measurement and the value obtained in section 7.1 is less than 3 percent of the span value. Alternatively, recalibrate the FIA as in section 7.1 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). The data that results in the lowest CE value shall be reported as the results for the test run. Conduct a system drift check at the end of each run.

7.3System Check. Inject the high-range calibration gas at the inlet of the sampling probe and record the response. The performance of the system is acceptable if the measurement system response is within 5 percent of the value obtained in section 7.1 for the high-range calibration gas. Conduct a system check before each test run.

8. Procedure 8.1Determination of Volumetric Flow Rate of Uncaptured Emissions 8.1.1 Locate all points where uncaptured emissions are exhausted from the TTE. Using Method 1, determine the sampling points. Be sure to check each site for cyclonic or swirling flow.

8.1.2Measure the velocity at each sampling site at least once every hour during each sampling run using Method 2 or 2A.

8.2Determination of VOC Content of Uncaptured Emissions.

8.2.1Analysis Duration. Measure the VOC responses at each uncaptured emission point during the entire test run or, if applicable, while the process is operating. If there are multiple emission locations, design a sampling system to allow a single FIA to be used to determine the VOC responses at all sampling locations.

8.2.2Gas VOC Concentration.

8.2.2.1Assemble the sample train as shown in Figure 204D1. Calibrate the FIA and conduct a system check according to the procedures in sections 7.1 and 7.3, respectively.

8.2.2.2Install 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.

8.2.2.3Inject zero gas at the calibration valve assembly. Allow the measurement system response to reach zero. Measure the system response time as the time required for the system to reach the effluent concentration after the calibration valve has been returned to the effluent sampling position.

8.2.2.4Conduct a system check before, and a system drift check after, each sampling run according to the procedures in sections 7.2 and 7.3.

If the drift check following a run indicates unacceptable performance (see section 7.3), the run is not valid. Alternatively, recalibrate the FIA as in section 7.1 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). The data that results in the lowest CE value shall be reported as the results for the test run. The tester may elect to perform system drift checks during the run not to exceed one drift check per hour.

8.2.2.5Verify that the sample lines, filter, and pump temperatures are 120 5 C.

8.2.2.6Begin sampling at the start of the test period and continue to sample during the entire run. Record the starting and ending times and any required process information, as appropriate. If multiple emission locations are sampled using a single FIA, sample at each location for the same amount of time (e.g., 2 min.) and continue to switch from one location to another for the entire test run. Be sure that total sampling time at each location is the same at the end of the test run. Collect at least four separate measurements from each sample point during each hour of testing. Disregard the response measurements at each sampling location until 2 times the response time of the measurement system has elapsed. Continue sampling for at least 1 minute and record the concentration measurements.

8.2.3Background Concentration.

8.2.3.1Locate all natural draft openings (NDO's) of the TTE. A sampling point shall be at the center of each NDO, unless otherwise approved by the Administrator. If there are more than six NDO's, choose six sampling points evenly spaced among the NDO's.

8.2.3.2Assemble the sample train as shown in Figure 204D2. Calibrate the FIA and conduct a system check according to the procedures in sections 7.1 and 7.3.

8.2.3.3Position the probe at the sampling location.

8.2.3.4Determine the response time, conduct the system check, and sample according to the procedures described in sections 8.2.2.3 through 8.2.2.6.

8.2.4Alternative Procedure. The direct interface sampling and analysis procedure described in section 7.2 of Method 18 may be used to determine the gas VOC concentration. The system must be designed to collect and analyze at least one sample every 10 minutes. If the alternative procedure is used to determine the VOC concentration of the uncaptured emissions in a gas/gas protocol, it must also be used to determine the VOC concentration of the captured emissions. If a tester wishes to conduct a liquid/gas protocol using a gas chromatograph, the tester must use Method 204F for the liquid steam. A gas chromatograph is not an acceptable alternative to the FIA in Method 204A.

9. Data Analysis and Calculations 9.1Nomenclature.

Ai=area of NDO i, ft 2 .

AN=total area of all NDO's in the enclosure, ft 2 .

CBi=corrected average VOC concentration of background emissions at point i, ppm propane.

CB=average background concentration, ppm propane.

CDH=average measured concentration for the drift check calibration gas, ppm propane.

CD0=average system drift check concentration for zero concentration gas, ppm propane.

CFj=corrected average VOC concentration of uncaptured emissions at point j, ppm propane.

CH=actual concentration of the drift check calibration gas, ppm propane.

Ci=uncorrected average background VOC concentration at point i, ppm propane.

Cj=uncorrected average VOC concentration measured at point j, ppm propane.

F=total VOC content of uncaptured emissions, kg.

K1=1.830106 kg/(m 3 -ppm).

n=number of measurement points.

QFj=average effluent volumetric flow rate corrected to standard conditions at uncaptured emissions point j, m 3 /min.

F=total duration of uncaptured emissions sampling run, min.

9.2Calculations.

9.2.1Total Uncaptured VOC Emissions. (image) 9.2.2VOC Concentration of the Uncaptured Emissions at Point j. (image) 9.2.3Background VOC Concentration at Point i. (image) 9.2.4Average Background Concentration. (image) Note: If the concentration at each point is within 20 percent of the average concentration of all points, use the arithmetic average.

10. Method Performance The measurement uncertainties are estimated for each uncaptured emission point as follows: QFj=5.5 percent and CFj=5.0 percent. Based on these numbers, the probable uncertainty for F is estimated at about 7.4 percent.

11. Diagrams (image) View or download PDF (image) View or download PDF Method 204EVolatile Organic Compounds Emissions in Uncaptured Stream From Building Enclosure 1. Scope and Application 1.1Applicability. This procedure is applicable for determining the uncaptured volatile organic compounds (VOC) emissions from a building enclosure (BE). It is intended to be used in the development of liquid/gas or gas/gas protocols for determining VOC capture efficiency (CE) for surface coating and printing operations.

1.2Principle. The total amount of uncaptured VOC emissions (FB) from the BE is calculated as the sum of the products of the VOC content (CFj) of each uncaptured emissions point, the flow rate (QFj) at each uncaptured emissions point, and time (F).

1.3Sampling Requirements. A CE test shall consist of at least three sampling runs. Each run shall cover at least one complete production cycle, but shall be at least 3 hours long. The sampling time for each run need not exceed 8 hours, even if the production cycle has not been completed. Alternative sampling times may be used with the approval of the Administrator.

2. Summary of Method A gas sample is extracted from the uncaptured exhaust duct of a BE through a heated sample line and, if necessary, a glass fiber filter to a flame ionization analyzer (FIA).

3. Safety Because this procedure is often applied in highly explosive areas, caution and care should be exercised in choosing, installing, and using the appropriate equipment.

4. Equipment and Supplies Mention of trade names or company products does not constitute endorsement. All gas concentrations (percent, ppm) are by volume, unless otherwise noted.

4.1Gas VOC Concentration. A schematic of the measurement system is shown in Figure 204E1. The main components are as follows: 4.1.1Sample Probe. Stainless steel or equivalent. The probe shall be heated to prevent VOC condensation.

4.1.2Calibration Valve Assembly. Three-way valve assembly at the outlet of the sample probe to direct the zero and calibration gases to the analyzer. Other methods, such as quick-connect lines, to route calibration gases to the outlet of the sample probe are acceptable.

4.1.3Sample Line. Stainless steel or Teflon tubing to transport the sample gas to the analyzer. The sample line must be heated to prevent condensation.

4.1.4Sample Pump. A leak-free pump, to pull the sample gas through the system at a flow rate sufficient to minimize the response time of the measurement system. The components of the pump that contact the gas stream shall be constructed of stainless steel or Teflon. The sample pump must be heated to prevent condensation.

4.1.5Sample Flow Rate Control. A sample flow rate control valve and rotameter, or equivalent, to maintain a constant sampling rate within 10 percent. The flow rate control valve and rotameter must be heated to prevent condensation. A control valve may also be located on the sample pump bypass loop to assist in controlling the sample pressure and flow rate.

4.1.6Sample Gas Manifold. Capable of diverting a portion of the sample gas stream to the FIA, and the remainder to the bypass discharge vent.

The manifold components shall be constructed of stainless steel or Teflon. If emissions are to be measured at multiple locations, the measurement system shall be designed to use separate sampling probes, lines, and pumps for each measurement location, and a common sample gas manifold and FIA. The sample gas manifold must be heated to prevent condensation.

4.1.7Organic Concentration Analyzer. An FIA with a span value of 1.5 times the expected concentration as propane; however, other span values may be used if it can be demonstrated to the Administrator's satisfaction that they would provide equally accurate measurements. The system shall be capable of meeting or exceeding the following specifications: 4.1.7.1Zero Drift. Less than 3.0 percent of the span value.

4.1.7.2Calibration Drift. Less than 3.0 percent of the span value.

4.1.7.3Calibration Error. Less than 5.0 percent of the calibration gas value.

4.1.7.4Response Time. Less than 30 seconds.

4.1.8Integrator/Data Acquisition System. An analog or digital device or computerized data acquisition system used to integrate the FIA response or compute the average response and record measurement data. The minimum data sampling frequency for computing average or integrated values is one measurement value every 5 seconds. The device shall be capable of recording average values at least once per minute.

4.2Uncaptured Emissions Volumetric Flow Rate.

4.2.1Flow Direction Indicators. Any means of indicating inward or outward flow, such as light plastic film or paper streamers, smoke tubes, filaments, and sensory perception.

4.2.2Method 2 or 2A Apparatus. For determining volumetric flow rate.

Anemometers or similar devices calibrated according to the manufacturer's instructions may be used when low velocities are present.

Vane anemometers (Young-maximum response propeller), specialized pitots with electronic manometers (e.g., Shortridge Instruments Inc., Airdata Multimeter 860) are commercially available with measurement thresholds of 15 and 8 mpm (50 and 25 fpm), respectively.

4.2.3Method 3 Apparatus and Reagents. For determining molecular weight of the gas stream. An estimate of the molecular weight of the gas stream may be used if approved by the Administrator.

4.2.4Method 4 Apparatus and Reagents. For determining moisture content, if necessary.

4.3Building Enclosure. The criteria for an acceptable BE are specified in Method 204.

5. Reagents and Standards 5.1Calibration and Other Gases. Gases used for calibration, fuel, and combustion air (if required) are contained in compressed gas cylinders.

All calibration gases shall be traceable to National Institute of Standards and Technology standards and shall be certified by the manufacturer to 1 percent of the tag value. 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, dilution systems calibrated using Method 205 may be used. Alternative methods for preparing calibration gas mixtures may be used with the approval of the Administrator.

5.1.1Fuel. The FIA manufacturer's recommended fuel should be used. A 40 percent H2/60 percent He or 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. Other mixtures may be used provided the tester can demonstrate to the Administrator that there is no oxygen synergism effect.

5.1.2Carrier Gas. High purity air with less than 1 ppm of organic material (propane or carbon equivalent) or less than 0.1 percent of the span value, whichever is greater.

5.1.3FIA Linearity Calibration Gases. Low-, mid-, and high-range gas mixture standards with nominal propane concentrations of 2030, 4555, and 7080 percent of the span value in air, respectively. Other calibration values and other span values may be used if it can be shown to the Administrator's satisfaction that equally accurate measurements would be achieved.

5.2Particulate 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 must be heated to prevent any condensation unless it can be demonstrated that no condensation occurs.

6. Quality Control 6.1Required instrument quality control parameters are found in the following sections: 6.1.1The FIA system must be calibrated as specified in section 7.1.

6.1.2The system drift check must be performed as specified in section 7.2.

6.1.3The system check must be conducted as specified in section 7.3.

6.2Audits.

6.2.1Analysis Audit Procedure. Immediately before each test, analyze an audit cylinder as described in section 7.2. The analysis audit must agree with the audit cylinder concentration within 10 percent.

6.2.2Audit Samples and Audit Sample Availability. Audit samples will be supplied only to enforcement agencies for compliance tests. The availability of audit samples may be obtained by writing: Source Test Audit Coordinator (STAC) (MD77B), Quality Assurance Division, Atmospheric Research and Exposure Assessment Laboratory, U.S.

Environmental Protection Agency, Research Triangle Park, NC 27711 or by calling the STAC at (919) 5417834. The request for the audit sample must be made at least 30 days prior to the scheduled compliance sample analysis.

6.2.3Audit Results. Calculate the audit sample concentration according to the calculation procedure described in the audit instructions included with the audit sample. Fill in the audit sample concentration and the analyst's name on the audit response form included with the audit instructions. Send one copy to the EPA Regional Office or the appropriate enforcement agency, and a second copy to the STAC. The EPA Regional Office or the appropriate enforcement agency will report the results of the audit to the laboratory being audited. Include this response with the results of the compliance samples in relevant reports to the EPA Regional Office or the appropriate enforcement agency.

7. Calibration and Standardization 7.1FIA Calibration and Linearity Check. Make necessary adjustments to the air and fuel supplies for the FIA and ignite the burner. Allow the FIA to warm up for the period recommended by the manufacturer. Inject a calibration gas into the measurement system and adjust the back-pressure regulator to the value required to achieve the flow rates specified by the manufacturer. Inject the zero-and the high-range calibration gases, and adjust the analyzer calibration to provide the proper responses.

Inject the low-and mid-range gases and record the responses of the measurement system. The calibration and linearity of the system are acceptable if the responses for all four gases are within 5 percent of the respective gas values. If the performance of the system is not acceptable, repair or adjust the system and repeat the linearity check.

Conduct a calibration and linearity check after assembling the analysis system and after a major change is made to the system.

7.2Systems Drift Checks. Select the calibration gas that most closely approximates the concentration of the captured emissions for conducting the drift checks. Introduce the zero and calibration gases at the calibration valve assembly and verify that the appropriate gas flow rate and pressure are present at the FIA. Record the measurement system responses to the zero and calibration gases. The performance of the system is acceptable if the difference between the drift check measurement and the value obtained in section 7.1 is less than 3 percent of the span value. Alternatively, recalibrate the FIA as in section 7.1 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). The data that results in the lowest CE value shall be reported as the results for the test run. Conduct a system drift check at the end of each run.

7.3System Check. Inject the high-range calibration gas at the inlet of the sampling probe and record the response. The performance of the system is acceptable if the measurement system response is within 5 percent of the value obtained in section 7.1 for the high-range calibration gas. Conduct a system check before each test run.

8. Procedure 8.1Preliminary Determinations. The following points are considered exhaust points and should be measured for volumetric flow rates and VOC concentrations: 8.1.1Forced Draft Openings. Any opening in the facility with an exhaust fan. Determine the volumetric flow rate according to Method 2.

8.1.2Roof Openings. Any openings in the roof of a facility which does not contain fans are considered to be exhaust points. Determine volumetric flow rate from these openings. Use the appropriate velocity measurement devices (e.g., propeller anemometers).

8.2Determination of Flow Rates.

8.2.1Measure the volumetric flow rate at all locations identified as exhaust points in section 8.1. Divide each exhaust opening into nine equal areas for rectangular openings and into eight equal areas for circular openings.

8.2.2Measure the velocity at each site at least once every hour during each sampling run using Method 2 or 2A, if applicable, or using the low velocity instruments in section 4.2.2.

8.3Determination of VOC Content of Uncaptured Emissions.

8.3.1Analysis Duration. Measure the VOC responses at each uncaptured emissions point during the entire test run or, if applicable, while the process is operating. If there are multiple emissions locations, design a sampling system to allow a single FIA to be used to determine the VOC responses at all sampling locations.

8.3.2Gas VOC Concentration.

8.3.2.1Assemble the sample train as shown in Figure 204E1. Calibrate the FIA and conduct a system check according to the procedures in sections 7.1 and 7.3, respectively.

8.3.2.2Install 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.

8.3.2.3Inject zero gas at the calibration valve assembly. Allow the measurement system response to reach zero. Measure the system response time as the time required for the system to reach the effluent concentration after the calibration valve has been returned to the effluent sampling position.

8.3.2.4Conduct a system check before, and a system drift check after, each sampling run according to the procedures in sections 7.2 and 7.3.

If the drift check following a run indicates unacceptable performance (see section 7.3), the run is not valid. Alternatively, recalibrate the FIA as in section 7.1 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). The data that results in the lowest CE value shall be reported as the results for the test run. The tester may elect to perform drift checks during the run, not to exceed one drift check per hour.

8.3.2.5Verify that the sample lines, filter, and pump temperatures are 120 5 C.

8.3.2.6Begin sampling at the start of the test period and continue to sample during the entire run. Record the starting and ending times, and any required process information, as appropriate. If multiple emission locations are sampled using a single FIA, sample at each location for the same amount of time (e.g., 2 minutes) and continue to switch from one location to another for the entire test run. Be sure that total sampling time at each location is the same at the end of the test run.

Collect at least four separate measurements from each sample point during each hour of testing. Disregard the response measurements at each sampling location until 2 times the response time of the measurement system has elapsed. Continue sampling for at least 1 minute, and record the concentration measurements.

8.4Alternative Procedure. The direct interface sampling and analysis procedure described in section 7.2 of Method 18 may be used to determine the gas VOC concentration. The system must be designed to collect and analyze at least one sample every 10 minutes. If the alternative procedure is used to determine the VOC concentration of the uncaptured emissions in a gas/gas protocol, it must also be used to determine the VOC concentration of the captured emissions. If a tester wishes to conduct a liquid/gas protocol using a gas chromatograph, the tester must use Method 204F for the liquid steam. A gas chromatograph is not an acceptable alternative to the FIA in Method 204A.

9. Data Analysis and Calculations 9.1Nomenclature.

CDH=average measured concentration for the drift check calibration gas, ppm propane.

CD0=average system drift check concentration for zero concentration gas, ppm propane.

CFj=corrected average VOC concentration of uncaptured emissions at point j, ppm propane.

CH=actual concentration of the drift check calibration gas, ppm propane.

Cj=uncorrected average VOC concentration measured at point j, ppm propane.

FB=total VOC content of uncaptured emissions from the building, kg.

K1=1.830 106 kg/(m 3 ppm).

n=number of measurement points.

QFj=average effluent volumetric flow rate corrected to standard conditions at uncaptured emissions point j, m 3 /min.

F=total duration of CE sampling run, min.

9.2Calculations 9.2.1Total VOC Uncaptured Emissions from the Building. (image) 9.2.2VOC Concentration of the Uncaptured Emissions at Point j. (image) 10. Method Performance The measurement uncertainties are estimated for each uncaptured emissions point as follows: QFj=10.0 percent and CFj=5.0 percent. Based on these numbers, the probable uncertainty for FB is estimated at about 11.2 percent.

11. Diagrams (image) View or download PDF Method 204FVolatile Organic Compounds Content in Liquid Input Stream (Distillation Approach) 1.Introduction 1.1Applicability. This procedure is applicable for determining the input of volatile organic compounds (VOC). It is intended to be used as a segment in the development of liquid/gas protocols for determining VOC capture efficiency (CE) for surface coating and printing operations.

1.2Principle. The amount of VOC introduced to the process (L) is the sum of the products of the weight (W) of each VOC containing liquid (ink, paint, solvent, etc.) used, and its VOC content (V), corrected for a response factor (RF).

1.3Sampling Requirements. A CE test shall consist of at least three sampling runs. Each run shall cover at least one complete production cycle, but shall be at least 3 hours long. The sampling time for each run need not exceed 8 hours, even if the production cycle has not been completed. Alternative sampling times may be used with the approval of the Administrator.

2.Summary of Method A sample of each coating used is distilled to separate the VOC fraction.

The distillate is used to prepare a known standard for analysis by a flame ionization analyzer (FIA), calibrated against propane, to determine its RF.

3.Safety Because this procedure is often applied in highly explosive areas, caution and care should be exercised in choosing, installing, and using the appropriate equipment.

4.Equipment and Supplies Mention of trade names or company products does not constitute endorsement. All gas concentrations (percent, ppm) are by volume, unless otherwise noted.

4.1Liquid Weight.

4.1.1Balances/Digital Scales. To weigh drums of VOC containing liquids to within 0.2 lb or 1.0 percent of the total weight of VOC liquid used.

4.1.2 Volume Measurement Apparatus (Alternative). Volume meters, flow meters, density measurement equipment, etc., as needed to achieve the same accuracy as direct weight measurements.

4.2 Response Factor Determination (FIA Technique). The VOC distillation system and Tedlar gas bag generation system apparatuses are shown in Figures 204F1 and 204F2, respectively. The following equipment is required: 4.2.1Sample Collection Can. An appropriately-sized metal can to be used to collect VOC containing materials. The can must be constructed in such a way that it can be grounded to the coating container.

4.2.2Needle Valves. To control gas flow.

4.2.3Regulators. For calibration, dilution, and sweep gas cylinders.

4.2.4Tubing and Fittings. Teflon and stainless steel tubing and fittings with diameters, lengths, and sizes determined by the connection requirements of the equipment.

4.2.5Thermometer. Capable of measuring the temperature of the hot water and oil baths to within 1 C.

4.2.6Analytical Balance. To measure 0.01 mg.

4.2.7Microliter Syringe. 10l size.

4.2.8Vacuum Gauge or Manometer. 0 to 760mm (0 to 30in.) Hg U-Tube manometer or vacuum gauge.

4.2.9Hot Oil Bath, With Stirring Hot Plate. Capable of heating and maintaining a distillation vessel at 110 3 C.

4.2.10Ice Water Bath. To cool the distillation flask.

4.2.11Vacuum/Water Aspirator. A device capable of drawing a vacuum to within 20 mm Hg from absolute.

4.2.12Rotary Evaporator System. Complete with folded inner coil, vertical style condenser, rotary speed control, and Teflon sweep gas delivery tube with valved inlet. Buchi Rotavapor or equivalent.

4.2.13Ethylene Glycol Cooling/Circulating Bath. Capable of maintaining the condenser coil fluid at 10 C.

4.2.14Dry Gas Meter (DGM). Capable of measuring the dilution gas volume within 2 percent, calibrated with a spirometer or bubble meter, and equipped with a temperature gauge capable of measuring temperature within 3 C.

4.2.15Activated Charcoal/Mole Sieve Trap. To remove any trace level of organics picked up from the DGM.

4.2.16Gas Coil Heater. Sufficient length of 0.125-inch stainless steel tubing to allow heating of the dilution gas to near the water bath temperature before entering the volatilization vessel.

4.2.17Water Bath, With Stirring Hot Plate. Capable of heating and maintaining a volatilization vessel and coil heater at a temperature of 100 5 C.

4.2.18Volatilization Vessel. 50ml midget impinger fitted with a septum top and loosely filled with glass wool to increase the volatilization surface.

4.2.19Tedlar Gas Bag. Capable of holding 30 liters of gas, flushed clean with zero air, leak tested, and evacuated.

4.2.20Organic Concentration Analyzer. An FIA with a span value of 1.5 times the expected concentration as propane; however, other span values may be used if it can be demonstrated that they would provide equally accurate measurements. The FIA instrument should be the same instrument used in the gaseous analyses adjusted with the same fuel, combustion air, and sample back-pressure (flow rate) settings. The system shall be capable of meeting or exceeding the following specifications: 4.2.20.1Zero Drift. Less than 3.0 percent of the span value.

4.2.20.2Calibration Drift. Less than 3.0 percent of the span value.

4.2.20.3Calibration Error. Less than 3.0 percent of the calibration gas value.

4.2.21Integrator/Data Acquisition System. An analog or digital device or computerized data acquisition system used to integrate the FIA response or compute the average response and record measurement data. The minimum data sampling frequency for computing average or integrated value is one measurement value every 5 seconds. The device shall be capable of recording average values at least once per minute.

4.2.22Chart Recorder (Optional). A chart recorder or similar device is recommended to provide a continuous analog display of the measurement results during the liquid sample analysis.

5.Reagents and Standards 5.1Zero Air. High purity air with less than 1 ppm of organic material (as propane) or less than 0.1 percent of the span value, whichever is greater. Used to supply dilution air for making the Tedlar bag gas samples.

5.2THC Free N2. High purity N2 with less than 1 ppm THC. Used as sweep gas in the rotary evaporator system.

5.3Calibration and Other Gases. Gases used for calibration, fuel, and combustion air (if required) are contained in compressed gas cylinders.

All calibration gases shall be traceable to National Institute of Standards and Technology standards and shall be certified by the manufacturer to 1 percent of the tag value. 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, dilution systems calibrated using Method 205 may be used. Alternative methods for preparing calibration gas mixtures may be used with the approval of the Administrator.

5.3.1Fuel. The FIA manufacturer's recommended fuel should be used. A 40 percent H2/60 percent He, or 40 percent H2/60 percent N2 mixture is recommended to avoid fuels with oxygen to avoid an oxygen synergism effect that reportedly occurs when oxygen concentration varies significantly from a mean value. Other mixtures may be used provided the tester can demonstrate to the Administrator that there is no oxygen synergism effect.

5.3.2Combustion Air. High purity air with less than 1 ppm of organic material (as propane) or less than 0.1 percent of the span value, whichever is greater.

5.3.3FIA Linearity Calibration Gases. Low-, mid-, and high-range gas mixture standards with nominal propane concentration of 2030, 4555, and 7080 percent of the span value in air, respectively. Other calibration values and other span values may be used if it can be shown that equally accurate measurements would be achieved.

5.3.4System Calibration Gas. Gas mixture standard containing propane in air, approximating the VOC concentration expected for the Tedlar gas bag samples.

6.Quality Control 6.1Required instrument quality control parameters are found in the following sections: 6.1.1The FIA system must be calibrated as specified in section 7.1.

6.1.2The system drift check must be performed as specified in section 7.2.

6.2Precision Control. A minimum of one sample in each batch must be distilled and analyzed in duplicate as a precision control. If the results of the two analyses differ by more than 10 percent of the mean, then the system must be reevaluated and the entire batch must be redistilled and analyzed.

6.3Audits.

6.3.1Audit Procedure. Concurrently, analyze the audit sample and a set of compliance samples in the same manner to evaluate the technique of the analyst and the standards preparation. The same analyst, analytical reagents, and analytical system shall be used both for compliance samples and the EPA audit sample. If this condition is met, auditing of subsequent compliance analyses for the same enforcement agency within 30 days is not required. An audit sample set may not be used to validate different sets of compliance samples under the jurisdiction of different enforcement agencies, unless prior arrangements are made with both enforcement agencies.

6.3.2Audit Samples. Audit Sample Availability. Audit samples will be supplied only to enforcement agencies for compliance tests. The availability of audit samples may be obtained by writing: Source Test Audit Coordinator (STAC) (MD77B), Quality Assurance Division, Atmospheric Research and Exposure Assessment Laboratory, U.S.

Environmental Protection Agency, Research Triangle Park, NC 27711 or by calling the STAC at (919) 5417834. The request for the audit sample must be made at least 30 days prior to the scheduled compliance sample analysis.

6.3.3Audit Results. Calculate the audit sample concentration according to the calculation procedure described in the audit instructions included with the audit sample. Fill in the audit sample concentration and the analyst's name on the audit response form included with the audit instructions. Send one copy to the EPA Regional Office or the appropriate enforcement agency, and a second copy to the STAC. The EPA Regional Office or the appropriate enforcement agency will report the results of the audit to the laboratory being audited. Include this response with the results of the compliance samples in relevant reports to the EPA Regional Office or the appropriate enforcement agency.

7.Calibration and Standardization 7.1FIA Calibration and Linearity Check. Make necessary adjustments to the air and fuel supplies for the FIA and ignite the burner. Allow the FIA to warm up for the period recommended by the manufacturer. Inject a calibration gas into the measurement system and adjust the back-pressure regulator to the value required to achieve the flow rates specified by the manufacturer. Inject the zero-and the high-range calibration gases and adjust the analyzer calibration to provide the proper responses.

Inject the low-and mid-range gases and record the responses of the measurement system. The calibration and linearity of the system are acceptable if the responses for all four gases are within 5 percent of the respective gas values. If the performance of the system is not acceptable, repair or adjust the system and repeat the linearity check.

Conduct a calibration and linearity check after assembling the analysis system and after a major change is made to the system. A calibration curve consisting of zero gas and two calibration levels must be performed at the beginning and end of each batch of samples.

7.2Systems Drift Checks. After each sample, repeat the system calibration checks in section 7.1 before any adjustments to the FIA or measurement system are made. If the zero or calibration drift exceeds 3 percent of the span value, discard the result and repeat the analysis.

Alternatively, recalibrate the FIA as in section 7.1 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). The data that results in the lowest CE value shall be reported as the results for the test run.

8.Procedures 8.1Determination of Liquid Input Weight 8.1.1Weight Difference. Determine the amount of material introduced to the process as the weight difference of the feed material before and after each sampling run. In determining the total VOC containing liquid usage, account for: (a) The initial (beginning) VOC containing liquid mixture; (b) any solvent added during the test run; (c) any coating added during the test run; and (d) any residual VOC containing liquid mixture remaining at the end of the sample run.

8.1.1.1Identify all points where VOC containing liquids are introduced to the process. To obtain an accurate measurement of VOC containing liquids, start with an empty fountain (if applicable). After completing the run, drain the liquid in the fountain back into the liquid drum (if possible), and weigh the drum again. Weigh the VOC containing liquids to 0.5 percent of the total weight (full) or 1.0 percent of the total weight of VOC containing liquid used during the sample run, whichever is less. If the residual liquid cannot be returned to the drum, drain the fountain into a preweighed empty drum to determine the final weight of the liquid.

8.1.1.2If it is not possible to measure a single representative mixture, then weigh the various components separately (e.g., if solvent is added during the sampling run, weigh the solvent before it is added to the mixture). If a fresh drum of VOC containing liquid is needed during the run, then weigh both the empty drum and fresh drum.

8.1.2Volume Measurement (Alternative). If direct weight measurements are not feasible, the tester may use volume meters and flow rate meters (and density measurements) to determine the weight of liquids used if it can be demonstrated that the technique produces results equivalent to the direct weight measurements. If a single representative mixture cannot be measured, measure the components separately.

8.2Determination of VOC Content in Input Liquids 8.2.1Collection of Liquid Samples.

8.2.1.1Collect a 1-pint or larger sample of the VOC containing liquid mixture at each application location at the beginning and end of each test run. A separate sample should be taken of each VOC containing liquid added to the application mixture during the test run. If a fresh drum is needed during the sampling run, then obtain a sample from the fresh drum.

8.2.1.2When collecting the sample, ground the sample container to the coating drum. Fill the sample container as close to the rim as possible to minimize the amount of headspace.

8.2.1.3After the sample is collected, seal the container so the sample cannot leak out or evaporate.

8.2.1.4Label the container to identify clearly the contents.

8.2.2Distillation of VOC.

8.2.2.1Assemble the rotary evaporator as shown in Figure 204F1.

8.2.2.2Leak check the rotary evaporation system by aspirating a vacuum of approximately 20 mm Hg from absolute. Close up the system and monitor the vacuum for approximately 1 minute. If the vacuum falls more than 25 mm Hg in 1 minute, repair leaks and repeat. Turn off the aspirator and vent vacuum.

8.2.2.3Deposit approximately 20 ml of sample (inks, paints, etc.) into the rotary evaporation distillation flask.

8.2.2.4Install the distillation flask on the rotary evaporator.

8.2.2.5Immerse the distillate collection flask into the ice water bath.

8.2.2.6Start rotating the distillation flask at a speed of approximately 30 rpm.

8.2.2.7Begin heating the vessel at a rate of 2 to 3 C per minute.

8.2.2.8After the hot oil bath has reached a temperature of 50 C or pressure is evident on the mercury manometer, turn on the aspirator and gradually apply a vacuum to the evaporator to within 20 mm Hg of absolute. Care should be taken to prevent material burping from the distillation flask.

8.2.2.9Continue heating until a temperature of 110 C is achieved and maintain this temperature for at least 2 minutes, or until the sample has dried in the distillation flask.

8.2.2.10Slowly introduce the N2 sweep gas through the purge tube and into the distillation flask, taking care to maintain a vacuum of approximately 400-mm Hg from absolute.

8.2.2.11Continue sweeping the remaining solvent VOC from the distillation flask and condenser assembly for 2 minutes, or until all traces of condensed solvent are gone from the vessel. Some distillate may remain in the still head. This will not affect solvent recovery ratios.

8.2.2.12Release the vacuum, disassemble the apparatus and transfer the distillate to a labeled, sealed vial.

8.2.3Preparation of VOC standard bag sample.

8.2.3.1Assemble the bag sample generation system as shown in Figure 204F2 and bring the water bath up to near boiling temperature.

8.2.3.2Inflate the Tedlar bag and perform a leak check on the bag.

8.2.3.3Evacuate the bag and close the bag inlet valve.

8.2.3.4Record the current barometric pressure.

8.2.3.5Record the starting reading on the dry gas meter, open the bag inlet valve, and start the dilution zero air flowing into the Tedlar bag at approximately 2 liters per minute.

8.2.3.6The bag sample VOC concentration should be similar to the gaseous VOC concentration measured in the gas streams. The amount of liquid VOC required can be approximated using equations in section 9.2. Using Equation 204F4, calculate CVOC by assuming RF is 1.0 and selecting the desired gas concentration in terms of propane, CC3. Assuming BV is 20 liters, ML, the approximate amount of liquid to be used to prepare the bag gas sample, can be calculated using Equation 204F2.

8.2.3.7Quickly withdraw an aliquot of the approximate amount calculated in section 8.2.3.6 from the distillate vial with the microliter syringe and record its weight from the analytical balance to the nearest 0.01 mg.

8.2.3.8Inject the contents of the syringe through the septum of the volatilization vessel into the glass wool inside the vessel.

8.2.3.9Reweigh and record the tare weight of the now empty syringe.

8.2.3.10Record the pressure and temperature of the dilution gas as it is passed through the dry gas meter.

8.2.3.11After approximately 20 liters of dilution gas have passed into the Tedlar bag, close the valve to the dilution air source and record the exact final reading on the dry gas meter.

8.2.3.12The gas bag is then analyzed by FIA within 1 hour of bag preparation in accordance with the procedure in section 8.2.4.

8.2.4Determination of VOC response factor.

8.2.4.1Start up the FIA instrument using the same settings as used for the gaseous VOC measurements.

8.2.4.2Perform the FIA analyzer calibration and linearity checks according to the procedure in section 7.1. Record the responses to each of the calibration gases and the back-pressure setting of the FIA.

8.2.4.3Connect the Tedlar bag sample to the FIA sample inlet and record the bag concentration in terms of propane. Continue the analyses until a steady reading is obtained for at least 30 seconds. Record the final reading and calculate the RF.

8.2.5Determination of coating VOC content as VOC (VIJ).

8.2.5.1Determine the VOC content of the coatings used in the process using EPA Method 24 or 24A as applicable.

9.Data Analysis and Calculations 9.1.Nomenclature.

BV=Volume of bag sample volume, liters.

CC3=Concentration of bag sample as propane, mg/liter.

CVOC=Concentration of bag sample as VOC, mg/liter.

K=0.00183 mg propane/(liter-ppm propane) L=Total VOC content of liquid input, kg propane.

ML=Mass of VOC liquid injected into the bag, mg.

MV=Volume of gas measured by DGM, liters.

PM=Absolute DGM gas pressure, mm Hg.

PSTD=Standard absolute pressure, 760 mm Hg.

RC3=FIA reading for bag gas sample, ppm propane.

RF=Response factor for VOC in liquid, weight VOC/weight propane.

RFJ=Response factor for VOC in liquid J, weight VOC/weight propane.

TM=DGM temperature, K.

TSTD=Standard absolute temperature, 293 K.

VIJ=Initial VOC weight fraction of VOC liquid J.

VFJ=Final VOC weight fraction of VOC liquid J.

VAJ=VOC weight fraction of VOC liquid J added during the run.

WIJ=Weight of VOC containing liquid J at beginning of run, kg.

WFJ=Weight of VOC containing liquid J at end of run, kg.

WAJ=Weight of VOC containing liquid J added during the run, kg.

9.2Calculations.

9.2.1Bag sample volume. (image) 9.2.2Bag sample VOC concentration. (image) 9.2.3Bag sample VOC concentration as propane. (image) 9.2.4Response Factor. (image) 9.2.5Total VOC Content of the Input VOC Containing Liquid. (image) 10. Diagrams (image) View or download PDF (image) View or download PDF Method 205Verification of Gas Dilution Systems for Field Instrument Calibrations 1. Introduction 1.1 Applicability. A gas dilution system can provide known values of calibration gases through controlled dilution of high-level calibration gases with an appropriate dilution gas. The instrumental test methods in 40 CFR part 60e.g., Methods 3A, 6C, 7E, 10, 15, 16, 20, 25A and 25Brequire on-site, multi-point calibration using gases of known concentrations. A gas dilution system that produces known low-level calibration gases from high-level calibration gases, with a degree of confidence similar to that for Protocol 1 gases, may be used for compliance tests in lieu of multiple calibration gases when the gas dilution system is demonstrated to meet the requirements of this method. The Administrator may also use a gas dilution system in order to produce a wide range of Cylinder Gas Audit concentrations when conducting performance specifications according to appendix F, 40 CFR part 60. As long as the acceptance criteria of this method are met, this method is applicable to gas dilution systems using any type of dilution technology, not solely the ones mentioned in this method.

1.2 Principle. The gas dilution system shall be evaluated on one analyzer once during each field test. A precalibrated analyzer is chosen, at the discretion of the source owner or operator, to demonstrate that the gas dilution system produces predictable gas concentrations spanning a range of concentrations. After meeting the requirements of this method, the remaining analyzers may be calibrated with the dilution system in accordance to the requirements of the applicable method for the duration of the field test. In Methods 15 and 16, 40 CFR part 60, appendix A, reactive compounds may be lost in the gas dilution system. Also, in Methods 25A and 25B, 40 CFR part 60, appendix A, calibration with target compounds other than propane is allowed. In these cases, a laboratory evaluation is required once per year in order to assure the Administrator that the system will dilute these reactive gases without significant loss.

Note: The laboratory evaluation is required only if the source owner or operator plans to utilize the dilution system to prepare gases mentioned above as being reactive.

2. Specifications 2.1 Gas Dilution System. The gas dilution system shall produce calibration gases whose measured values are within 2 percent of the predicted values. The predicted values are calculated based on the certified concentration of the supply gas (Protocol gases, when available, are recommended for their accuracy) and the gas flow rates (or dilution ratios) through the gas dilution system.

2.1.1 The gas dilution system shall be recalibrated once per calendar year using NIST-traceable primary flow standards with an uncertainty 0.25 percent. A label shall be affixed at all times to the gas dilution system listing the date of the most recent calibration, the due date for the next calibration, and the person or manufacturer who carried out the calibration. Follow the manufacturer's instructions for the operation and use of the gas dilution system. A copy of the manufacturer's instructions for the operation of the instrument, as well as the most recent recalibration documentation shall be made available for the Administrator's inspection upon request.

2.1.2 Some manufacturers of mass flow controllers recommend that flow rates below 10 percent of flow controller capacity be avoided; check for this recommendation and follow the manufacturer's instructions. One study has indicated that silicone oil from a positive displacement pump produces an interference in SO2 analyzers utilizing ultraviolet fluorescence; follow laboratory procedures similar to those outlined in Section 3.1 in order to demonstrate the significance of any resulting effect on instrument performance.

2.2 High-Level Supply Gas. An EPA Protocol calibration gas is recommended, due to its accuracy, as the high-level supply gas.

2.3 Mid-Level Supply Gas. An EPA Protocol gas shall be used as an independent check of the dilution system. The concentration of the mid-level supply gas shall be within 10 percent of one of the dilution levels tested in Section 3.2.

3. Performance Tests 3.1 Laboratory Evaluation (Optional). If the gas dilution system is to be used to formulate calibration gases with reactive compounds (Test Methods 15, 16, and 25A/25B (only if using a calibration gas other than propane during the field test) in 40 CFR part 60, appendix A), a laboratory certification must be conducted once per calendar year for each reactive compound to be diluted. In the laboratory, carry out the procedures in Section 3.2 on the analyzer required in each respective test method to be laboratory certified (15, 16, or 25A and 25B for compounds other than propane). For each compound in which the gas dilution system meets the requirements in Section 3.2, the source must provide the laboratory certification data for the field test and in the test report.

3.2 Field Evaluation (Required). The gas dilution system shall be evaluated at the test site with an analyzer or monitor chosen by the source owner or operator. It is recommended that the source owner or operator choose a precalibrated instrument with a high level of precision and accuracy for the purposes of this test. This method is not meant to replace the calibration requirements of test methods. In addition to the requirements in this method, all the calibration requirements of the applicable test method must also be met.

3.2.1 Prepare the gas dilution system according to the manufacturer's instructions. Using the high-level supply gas, prepare, at a minimum, two dilutions within the range of each dilution device utilized in the dilution system (unless, as in critical orifice systems, each dilution device is used to make only one dilution; in that case, prepare one dilution for each dilution device). Dilution device in this method refers to each mass flow controller, critical orifice, capillary tube, positive displacement pump, or any other device which is used to achieve gas dilution.

3.2.2 Calculate the predicted concentration for each of the dilutions based on the flow rates through the gas dilution system (or the dilution ratios) and the certified concentration of the high-level supply gas.

3.2.3 Introduce each of the dilutions from Section 3.2.1 into the analyzer or monitor one at a time and determine the instrument response for each of the dilutions.

3.2.4 Repeat the procedure in Section 3.2.3 two times, i.e., until three injections are made at each dilution level. Calculate the average instrument response for each triplicate injection at each dilution level. No single injection shall differ by more than 2 percent from the average instrument response for that dilution.

3.2.5 For each level of dilution, calculate the difference between the average concentration output recorded by the analyzer and the predicted concentration calculated in Section 3.2.2. The average concentration output from the analyzer shall be within 2 percent of the predicted value.

3.2.6 Introduce the mid-level supply gas directly into the analyzer, bypassing the gas dilution system. Repeat the procedure twice more, for a total of three mid-level supply gas injections. Calculate the average analyzer output concentration for the mid-level supply gas. The difference between the certified concentration of the mid-level supply gas and the average instrument response shall be within 2 percent.

3.3 If the gas dilution system meets the criteria listed in Section 3.2, the gas dilution system may be used throughout that field test. If the gas dilution system fails any of the criteria listed in Section 3.2, and the tester corrects the problem with the gas dilution system, the procedure in Section 3.2 must be repeated in its entirety and all the criteria in Section 3.2 must be met in order for the gas dilution system to be utilized in the test.

4. References 1. EPA Traceability Protocol for Assay and Certification of Gaseous Calibration Standards, EPA600/R93/224, Revised September 1993.

[55 FR 14249, Apr. 17, 1990; 55 FR 24687, June 18, 1990, as amended at 55 FR 37606, Sept. 12, 1990; 56 FR 6278, Feb. 15, 1991; 56 FR 65435, Dec. 17, 1991; 60 FR 28054, May 30, 1995; 62 FR 32502, June 16, 1997]