This method does not include all of the specifications (e.g., equipment and supplies) and procedures (e.g., sampling and analytical) essential to its performance. Some material is incorporated by reference from other methods in this part. Therefore, to obtain reliable results, persons using this method should have a thorough knowledge of at least the following additional test methods: Method 1, Method 2, Method 3, Method 5, and Method 6.
This method is applicable for the determination of H2SO4 (including H2SO4 mist and SO3) and gaseous SO2 emissions from stationary sources.
Filterable particulate matter may be determined along with H2SO4 and SO2 (subject to the approval of the Administrator) by inserting a heated glass fiber filter between the Probe and isopropanol impinger (see Section 6.1.1 of Method 6). If this option is chosen, particulate analysis is gravimetric only; sulfuric acid is not determined separately.
Adherence to the requirements of this method will enhance the quality of the data obtained from air pollutant sampling methods.
A gas sample is extracted isokinetically from the stack. The H2SO4 and the SO2 are separated, and both fractions are measured separately by the barium-thorin titration method.
4.1 Possible interfering agents of this method are fluorides, free ammonia, and dimethyl aniline. If any of these interfering agents is present (this can be determined by knowledge of the process), alternative methods, subject to the approval of the Administrator, are required.
This method may involve hazardous materials, operations, and equipment. This test method may not address all of the safety problems associated with its use. It is the responsibility of the user of this test method to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to performing this test method.
Same as Method 6, Section 5.2.
Same as Method 5, Section 6.1, with the following additions and exceptions:
6.1.1 Sampling train. A schematic of the sampling train used in this method is shown in Figure 8-1; it is similar to the Method 5 sampling train, except that the filter position is different, and the filter holder does not have to be heated. See Method 5, Section 6.1.1, for details and guidelines on operation and maintenance.
188.8.131.52 Probe liner. Borosilicate or quartz glass, with a heating system to prevent visible condensation during sampling. Do not use metal Probe liners.
184.108.40.206 Filter holder. Borosilicate glass, with a glass frit filter support and a silicone rubber gasket. Other gasket materials (e.g., Teflon or Viton) may be used, subject to the approval of the Administrator. The holder design shall provide a positive seal against leakage from the outside or around the filter. The filter holder shall be placed between the first and second impingers. Do not heat the filter holder.
220.127.116.11 impingers. Four, of the Greenburg-Smith design, as shown in Figure 8-1. The first and third impingers must have standard tips. The second and fourth impingers must be modified by replacing the insert with an approximately 13-mm (1/2-in.) ID glass tube, having an unconstricted tip located 13 mm (1/2 in.) from the bottom of the impinger. Similar collection systems, subject to the approval of the Administrator, may be used.
18.104.22.168 temperature sensor. Thermometer, or equivalent, to measure the temperature of the gas leaving the impinger train to within 1 C (2 F).
The following items are required for sample recovery:
6.2.1 Wash Bottles. Two polyethylene or glass bottles, 500-ml.
6.2.2 Graduated Cylinders. Two graduated cylinders (volumetric flasks may be used), 250-ml, 1-liter.
6.2.3 Storage Bottles. Leak-free polyethylene bottles, 1-liter size (two for each sampling run).
6.2.4 Trip Balance. 500-g capacity, to measure to ± 0.5 g (necessary only if a moisture content analysis is to be done).
The following items are required for sample analysis:
6.3.1 Pipettes. Volumetric 10-ml, 100-ml.
6.3.2 Burette. 50-ml.
6.3.3 Erlenmeyer Flask. 250-ml (one for each sample, blank, and standard).
6.3.4 Graduated Cylinder. 100-ml.
6.3.5 Dropping Bottle. To add indicator solution, 125-ml size.
Unless otherwise indicated, all reagents are to conform to the specifications established by the Committee on Analytical Reagents of the American Chemical Society, where such specifications are available. Otherwise, use the best available grade.
The following reagents are required for sample collection:
7.1.1 Filters and Silica Gel. Same as in Method 5, Sections 7.1.1 and 7.1.2, respectively.
7.1.2 Water. Same as in Method 6, Section 7.1.1.
7.1.3 Isopropanol, 80 Percent by Volume. Mix 800 ml of isopropanol with 200 ml of water.
Check for peroxide impurities using the procedure outlined in Method 6, Section 22.214.171.124.
7.1.4 Hydrogen Peroxide (H2O2), 3 Percent by Volume. Dilute 100 ml of 30 percent H2O2 to 1 liter with water. Prepare fresh daily.
The reagents and standards required for sample recovery are:
7.2.1 Water. Same as in Section 7.1.2.
7.2.2 Isopropanol, 80 Percent. Same as in Section 7.1.3.
Same as Method 6, Section 7.3.
7.3.1 Quality Assurance Audit Samples. When making compliance determinations, and upon availability, audit samples may be obtained from the appropriate EPA Regional Office or from the responsible enforcement authority.
The responsible enforcement authority should be notified at least 30 days prior to the test date to allow sufficient time for sample delivery.
Same as Method 5, Section 8.1, except that filters should be inspected but need not be desiccated, weighed, or identified. If the effluent gas can be considered dry (i.e., moisture-free), the silica gel need not be weighed.
Same as Method 5, Section 8.2.
Same as Method 5, Section 8.3, with the following exceptions:
8.3.1 Use Figure 8-1 instead of Figure 5-1.
8.3.2 Replace the second sentence of Method 5, Section 8.3.1 with: Place 100 ml of 80 percent isopropanol in the first impinger, 100 ml of 3 percent H2O2 in both the second and third impingers; retain a portion of each reagent for use as a blank solution. Place about 200 g of silica gel in the fourth impinger.
8.3.3 Ignore any other statements in Section 8.3 of Method 5 that are obviously not applicable to the performance of Method 8.
If moisture content is to be determined by impinger analysis, weigh each of the first three impingers (plus absorbing solution) to the nearest 0.5 g, and record these weights. Weigh also the silica gel (or silica gel plus container) to the nearest 0.5 g, and record.)
Same as Method 5, Section 8.4.1.
Follow the basic procedure in Method 5, Section 8.4.2, noting that the Probe heater shall be adjusted to the minimum temperature required to prevent condensation, and also that verbiage such as "...plugging the inlet to the filter holder..." found in Section 126.96.36.199 of Method 5 shall be replaced by "...plugging the inlet to the first impinger...". The pretest leak-check is recommended, but is not required.
Follow the basic procedures in Method 5, Section 8.5, in conjunction with the following special instructions:
8.6.1 Record the data on a sheet similar to that shown in Figure 8-2 (alternatively, Figure 5-2 in Method 5 may be used). The sampling rate shall not exceed 0.030 m3/min (1.0 cfm) during the run. Periodically during the test, observe the connecting line between the Probe and first impinger for signs of condensation. If condensation does occur, adjust the Probe heater setting upward to the minimum temperature required to prevent condensation. If component changes become necessary during a run, a leak-check shall be performed immediately before each change, according to the procedure outlined in Section 8.4.3 of Method 5 (with appropriate modifications, as mentioned in Section 8.5 of this method); record all leak rates. If the leakage rate(s) exceeds the specified rate, the tester shall either void the run or plan to correct the sample volume as outlined in Section 12.3 of Method 5. Leak-checks immediately after component changes are recommended, but not required. If these leak-checks are performed, the procedure in Section 8.4.2 of Method 5 (with appropriate modifications) shall be used.
8.6.2 After turning off the pump and recording the final readings at the conclusion of each run, remove the Probe from the stack. Conduct a post-test (mandatory) leak-check as outlined in Section 8.4.4 of Method 5 (with appropriate modifications), and record the leak rate. If the post-test leakage rate exceeds the specified acceptable rate, either correct the sample volume, as outlined in Section 12.3 of Method 5, or void the run.
8.6.3 Drain the ice bath and, with the Probe disconnected, purge the remaining part of the train by drawing clean ambient air through the system for 15 minutes at the average flow rate used for sampling.
Clean ambient air can be provided by passing air through a charcoal filter. Alternatively, ambient air (without cleaning) may be used.
Same as Method 5, Section 8.6.
8.8.1 Container No. 1.
188.8.131.52 If a moisture content analysis is to be performed, clean and weigh the first impinger (plus contents) to the nearest 0.5 g, and record this weight.
184.108.40.206 Transfer the contents of the first impinger to a 250-ml graduated cylinder. Rinse the Probe, first impinger, all connecting glassware before the filter, and the front half of the filter holder with 80 percent isopropanol. Add the isopropanol rinse solution to the cylinder. Dilute the contents of the cylinder to 225 ml with 80 percent isopropanol, and transfer the cylinder contents to the storage container. Rinse the cylinder with 25 ml of 80 percent isopropanol, and transfer the rinse to the storage container. Add the filter to the solution in the storage container and mix. Seal the container to protect the solution against evaporation. Mark the level of liquid on the container, and identify the sample container.
8.8.2 Container No. 2.
220.127.116.11 If a moisture content analysis is to be performed, clean and weigh the second and third impingers (plus contents) to the nearest 0.5 g, and record the weights. Also, weigh the spent silica gel (or silica gel plus impinger) to the nearest 0.5 g, and record the weight.
18.104.22.168 Transfer the solutions from the second and third impingers to a 1-liter graduated cylinder. Rinse all connecting glassware (including back half of filter holder) between the filter and silica gel impinger with water, and add this rinse water to the cylinder. Dilute the contents of the cylinder to 950 ml with water. Transfer the solution to a storage container. Rinse the cylinder with 50 ml of water, and transfer the rinse to the storage container. Mark the level of liquid on the container. Seal and identify the sample container.
Same as Method 5, Section 9.2.
10.1 Sampling equipment. Same as Method 5, Section 10.0.
10.2 Barium Standard Solution. Same as Method 6, Section 10.5.
Same as Method 6, Section 11.1.
11.2.1 Container No. 1. Shake the container holding the isopropanol solution and the filter. If the filter breaks up, allow the fragments to settle for a few minutes before removing a sample aliquot. Pipette a 100-ml aliquot of this solution into a 250-ml Erlenmeyer flask, add 2 to 4 drops of thorin indicator, and titrate to a pink endpoint using 0.0100 N barium standard solution. Repeat the titration with a second aliquot of sample, and average the titration values. Replicate titrations must agree within 1 percent or 0.2 ml, whichever is greater.
11.2.2 Container No. 2. Thoroughly mix the solution in the container holding the contents of the second and third impingers. Pipette a 10-ml aliquot of sample into a 250-ml Erlenmeyer flask. Add 40 ml of isopropanol, 2 to 4 drops of thorin indicator, and titrate to a pink endpoint using 0.0100 N barium standard solution. Repeat the titration with a second aliquot of sample, and average the titration values. Replicate titrations must agree within 1 percent or 0.2 ml, whichever is greater.
11.2.3 Blanks. Prepare blanks by adding 2 to 4 drops of thorin indicator to 100 ml of 80 percent isopropanol. Titrate the blanks in the same manner as the samples.
11.3.1 When the method is used to analyze samples to demonstrate compliance with a source emission regulation, EPA audit samples must be analyzed, subject to availability.
11.3.2 Concurrently analyze audit samples and the compliance samples in the same manner to evaluate the technique of the analyst and the standards preparation.
It is recommended that known quality control samples be analyzed prior to the compliance and audit sample analyses to optimize the system accuracy and precision. These quality control samples may be obtained by contacting the appropriate EPA regional Office or the responsible enforcement authority.
11.3.3 The same analyst, analytical reagents, and analytical system shall be used for the compliance samples and the EPA audit samples. If this condition is met, duplicate auditing of subsequent compliance analyses for the same enforcement agency within a 30-day period is waived. Audit samples may not be used to validate different compliance samples under the jurisdiction of separate enforcement agencies, unless prior arrangements have been made with both enforcement agencies.
11.4.1 Calculate the audit sample concentrations in mg/dscm and submit results using the instructions provided with the audit samples.
11.4.2 Report the results of the audit samples and the compliance determination samples along with their identification numbers, and the analyst's name to the responsible enforcement authority. Include this information with reports of any subsequent compliance analyses for the same enforcement authority during the 30-day period.
11.4.3 The concentrations of the audit samples obtained by the analyst shall agree within 5 percent of the actual concentrations. If the 5 percent specification is not met, reanalyze the compliance and audit samples, and include initial and reanalysis values in the test report.
11.4.4 Failure to meet the 5 percent specification may require retests until the audit problems are resolved. However, if the audit results do not affect the compliance or noncompliance status of the affected facility, the Administrator may waive the reanalysis requirement, further audits, or retests and accept the results of the compliance test. While steps are being taken to resolve audit analysis problems, the Administrator may also choose to use the data to determine the compliance or noncompliance status of the affected facility.
Carry out calculations retaining at least one extra significant figure beyond that of the acquired data. Round off figures after final calculation.
Same as Method 5, Section 12.1, with the following additions and exceptions:
Ca = Actual concentration of SO2 in audit sample, mg/dscm.
Cd = Determined concentration of SO2 in audit sample, mg/dscm.
CH2SO4 = Sulfuric acid (including SO3) concentration, g/dscm (lb/dscf).
CSO2 = Sulfur dioxide concentration, g/dscm (lb/dscf).
N = Normality of barium perchlorate titrant, meq/ml.
RE = Relative error of QA audit sample analysis, percent
Va = Volume of sample aliquot titrated, 100 ml for H2SO4 and 10 ml for SO2.
Vsoln = Total volume of solution in which the sample is contained, 250 ml for the SO2 sample and 1000 ml for the H2SO4
Vt = Volume of barium standard solution titrant used for the sample, ml.
Vtb = Volume of barium standard solution titrant used for the blank, ml.
See data sheet (Figure 8-2).
Same as Method 5, Section 12.3.
Calculate the volume of water vapor using Equation 5-2 of Method 5; the weight of water collected in the impingers and silica gel can be converted directly to milliliters (the specific gravity of water is 1 g/ml). Calculate the moisture content of the stack gas (Bws) using Equation 5-3 of Method 5. The NOTE in Section 12.5 of Method 5 also applies to this method. Note that if the effluent gas stream can be considered dry, the volume of water vapor and moisture content need not be calculated.
K3 = 0.04904 g/meq for metric units,
= 1.081 x 10-4 lb/meq for English units.
K4 = 0.03203 g/meq for metric units,
= 7.061 x 10-5 lb/meq for English units.
Same as Method 5, Section 12.11.
Calculate the average stack gas velocity and volumetric flow rate, if needed, using data obtained in this method and the equations in Sections 12.6 and 12.7 of Method 2.
Same as Method 6, Section 12.4.
Collaborative tests have shown that the minimum detectable limits of the method are 0.06 mg/m3 (4 x 10-9 lb/ft3) for H2SO4 and 1.2 mg/m3 (74 x 10-9 lb/ft3) for SO2. No upper limits have been established. Based on theoretical calculations for 200 ml of 3 percent H2O2 solution, the upper concentration limit for SO2 in a 1.0 m3 (35.3 ft3) gas sample is about 12,000 mg/m3 (7.7 x 10-4 lb/ft3). The upper limit can be extended by increasing the quantity of peroxide solution in the impingers.