US EPA Method 204a--Volatile Organic Compounds Content In Liquid Input Stream
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.
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).
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
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 a FIA to determine V.
Because this procedure is often applied in highly explosive areas, caution and care should be exercised in choosing, installing, and using the appropriate equipment.
Mention of trade names or company products does not constitute endorsement. All gas concentrations (percent, ppm) are by volume, unless otherwise noted.
To weigh drums of VOC containing liquids to within 0.2 lb or 1.0 percent of the total weight of VOC liquid used.
Volume meters, flow meters, density measurement equipment, etc., as needed to achieve the same accuracy as direct weight measurements.
The liquid sample analysis system is shown in Figures 204A-1 and 204A-2. The following equipment is required:
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.
To control gas flow.
For carrier gas and calibration gas cylinders.
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 ± 5C.
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.
Capable of measuring the temperature of the hot water bath to within 1C.
Heated enclosure, containing calibration gas coil heaters, critical orifice, aspirator, and other liquid sample analysis components, capable of maintaining a temperature of 120 ± 5C.
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.
Capable of heating and maintaining a sample vessel temperature of 100 ± 5C.
To measure ± 0.001 g.
2-cc or 5-cc.
glass, 40-ml septum vial. A separate vessel is needed for each sample.
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 non-reactive materials and accommodating the necessary tubing fittings may be used.
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.
Zero to 760-mm (0- to 30-in.) Hg U-Tube manometer or vacuum gauge.
Bourdon gauge capable of measuring the maximum air pressure at the aspirator inlet (e.g., 100 psig).
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.
Of an appropriate size to calibrate the critical orifices in the system.
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:
22.214.171.124 Zero Drift.
Less than ±3.0 percent of the span value.
126.96.36.199 calibration Drift.
Less than ±3.0 percent of the span value.
188.8.131.52 calibration Error.
Less than ±5.0 percent of the calibration gas value.
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.
A chart recorder or similar device is recommended to provide a continuous analog display of the measurement results during the liquid sample analysis.
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.
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.
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.
Low-, mid-, and high-range gas mixture standards with nominal propane concentrations of 20-30, 45-55, and 70-80 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.
Gas mixture standard containing propane in air, approximating the undiluted VOC concentration expected for the liquid samples.
6.1 Samples must be collected in a manner that prevents or minimizes loss of volatile components and that does not contaminate the coating reservoir.
6.2 Collect 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.
6.3 When 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.
6.4 After the sample is collected, seal the container so the sample cannot leak out or evaporate.
6.5 Label the container to clearly identify the contents.
Required instrument quality control parameters are found in the following sections:
7.1.1 The FIA system must be calibrated as specified in section 8.1.
7.1.2 The system drift check must be performed as specified in section 8.2.
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.
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) (MD-77B)
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) 541-7834. The request for the audit sample must be made at least 30 days prior to the scheduled compliance sample analysis.
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.
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.
After each sample, repeat the system calibration checks insection 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.
8.3.1 Each 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 204A-3. A stopwatch is also required.
8.3.2 Turn 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.
8.3.3 Repeat 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.
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.
184.108.40.206 Identify 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 pre-weighed empty drum to determine the final weight of the liquid.
220.127.116.11 If 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.
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.
9.2.1 Assemble the liquid VOC content analysis system as shown in Figure 204A-1.
9.2.2 Permanently 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.
9.2.3 Label and tare the sample vessels (including the stoppers and caps) and the syringes.
9.2.4 Install 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.
9.2.5 Perform 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.
9.2.6 Establish 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.
9.2.7 Perform 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.
9.2.8 After 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 204A-2 and 204A-3.
9.2.9 Verify that the sample oven and sample line temperatures are 120 ± 5C and that the water bath temperature is 100 ± 5C.
9.2.10 Fill 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.
9.2.11 Connect 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.)
9.2.12 Continuously 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.
10.2.1 Total VOC Content of the Input VOC Containing Liquid.
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.