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8.4.2.1.4 After all washings have been collected in the appropriate sample container(s), tighten the lid(s) on the container(s) to prevent leakage during shipment to the laboratory. Mark the height of the fluid level to allow subsequent determination of whether leakage has occurred during transport. Label each container to identify its contents clearly.
8.4.3 Container No. 2 (Silica Gel). Same as Method 5, Section 8.7.6.3.
8.4.4 Container No. 3 (Filter). If a filter was used, carefully remove it from the filter holder, place it in a 100-ml glass sample bottle, and add 20 to 40 ml of absorbing solution. If it is necessary to fold the filter, be sure that the particulate cake is inside the fold. Carefully transfer to the 100-ml sample bottle any particulate matter and filter fibers that adhere to the filter holder gasket by using a dry Nylon bristle brush and a sharp-edged blade. Seal the container. Label the container to identify its contents clearly. Mark the height of the fluid level to allow subsequent determination of whether leakage has occurred during transport.
8.4.5 Container No. 4 (Filter Blank). If a filter was used, treat an unused filter from the same filter lot as that used for sampling according to the procedures outlined in Section 8.4.4.
8.4.6 Container No. 5 (Absorbing Solution Blank). Place 650 ml of 4 percent KMnO4 absorbing solution in a 1000-ml sample bottle. Seal the container.
8.4.7 Container No. 6 (HCl Rinse Blank). Place 200 ml of water in a 1000-ml sample bottle, and add 25 ml of 8 N HCl carefully with stirring. Seal the container. Only one blank sample per 3 runs is required.
9.0 Quality Control
9.1 Miscellaneous Quality Control Measures.
------------------------------------------------------------------------
Quality control
Section measure Effect
------------------------------------------------------------------------
8.0, 10.0..................... Sampling Ensure accuracy and
equipment leak- precision of
checks and sampling
calibration. measurements.
10.2.......................... Spectrophotometer Ensure linearity of
calibration. spectrophotometer
response to
standards.
11.3.3........................ Check for matrix Eliminate matrix
effects. effects.
------------------------------------------------------------------------
9.2 Volume Metering System Checks. Same as Method 5, Section 9.2.
10.0 Calibration and Standardization
Same as Method 101, Section 10.0, with the following exceptions:
10.1 Optical Cell Heating System Calibration. Same as in Method 101, Section 10.4, except use a-25 ml graduated cylinder to add 25 ml of water to the bottle section of the aeration cell.
10.2 Spectrophotometer and Recorder Calibration.
10.2.1 The Hg response may be measured by either peak height or peak area.
Note: The temperature of the solution affects the rate at which elemental Hg is released from a solution and, consequently, it affects the shape of the absorption curve (area) and the point of maximum absorbance (peak height). To obtain reproducible results, all solutions must be brought to room temperature before use.
10.2.2 Set the spectrophotometer wave length at 253.7 nm, and make certain the optical cell is at the minimum temperature that will prevent water condensation. Then set the recorder scale as follows: Using a 25-ml graduated cylinder, add 25 ml of water to the aeration cell bottle. Add three drops of Antifoam B to the bottle, and then pipet 5.0 ml of the working Hg standard solution into the aeration cell.
Note: Always add the Hg-containing solution to the aeration cell after the 25 ml of water.
10.2.3 Place a Teflon-coated stirring bar in the bottle. Add 5 ml of absorbing solution to the aeration bottle, and mix well. Before attaching the bottle section to the bubbler section of the aeration cell, make certain that (1) the aeration cell exit arm stopcock (Figure 101–3 of Method 101) is closed (so that Hg will not prematurely enter the optical cell when the reducing agent is being added) and (2) there is no flow through the bubbler. If conditions (1) and (2) are met, attach the bottle section to the bubbler section of the aeration cell. Add sodium chloride-hydroxylamine in 1 ml increments until the solution is colorless. Now add 5 ml of tin (II) solution to the aeration bottle through the side arm, and immediately stopper the side arm. Stir the solution for 15 seconds, turn on the recorder, open the aeration cell exit arm stopcock, and immediately initiate aeration with continued stirring. Determine the maximum absorbance of the standard, and set this value to read 90 percent of the recorder full scale.
11.0 Analytical Procedure
11.1 Sample Loss Check. Check the liquid level in each container to see if liquid was lost during transport. If a noticeable amount of leakage occurred, either void the sample or use methods subject to the approval of the Administrator to account for the losses.
11.2 Sample Preparation. Treat sample containers as follows:
11.2.1 Containers No. 3 and No. 4 (Filter and Filter Blank).
11.2.1.1 If a filter is used, place the contents, including the filter, of Containers No. 3 and No. 4 in separate 250-ml beakers, and heat the beakers on a steam bath until most of the liquid has evaporated. Do not heat to dryness. Add 20 ml of concentrated HNO3 to the beakers, cover them with a watch glass, and heat on a hot plate at 70 °C (160 °F) for 2 hours. Remove from the hot plate.
11.2.1.2 Filter the solution from digestion of the Container No. 3 contents through Whatman No. 40 filter paper, and save the filtrate for addition to the Container No. 1 filtrate as described in Section 11.2.2. Discard the filter paper.
11.2.1.3 Filter the solution from digestion of the Container No. 4 contents through Whatman No. 40 filter paper, and save the filtrate for addition to Container No. 5 filtrate as described in Section 11.2.3 below. Discard the filter paper.
11.2.2 Container No. 1 (Impingers, Probe, and Filter Holder) and, if applicable, No. 1A (HCl rinse).
11.2.2.1 Filter the contents of Container No. 1 through Whatman No. 40 filter paper into a 1 liter volumetric flask to remove the brown manganese dioxide (MnO2) precipitate. Save the filter for digestion of the brown MnO2 precipitate. Add the sample filtrate from Container No. 3 to the 1-liter volumetric flask, and dilute to volume with water. If the combined filtrates are greater than 1000 ml, determine the volume to the nearest ml and make the appropriate corrections for blank subtractions. Mix thoroughly. Mark the filtrate as analysis Sample No. A.1 and analyze for Hg within 48 hr of the filtration step. Place the saved filter, which was used to remove the brown MnO2 precipitate, into an appropriate sized container. In a laboratory hood, add 25 ml of 8 N HCl to the filter and allow to digest for a minimum of 24 hours at room temperature.
11.2.2.2 Filter the contents of Container 1A through Whatman No. 40 filter paper into a 500-ml volumetric flask. Then filter the digestate of the brown MnO2 precipitate from Container No. 1 through Whatman No. 40 filter paper into the same 500-ml volumetric flask, and dilute to volume with water. Mark this combined 500 ml dilute solution as analysis Sample No. A.2. Discard the filters.
11.2.3 Container No. 5 (Absorbing Solution Blank) and No. 6 (HCl Rinse Blank).
11.2.3.1 Treat Container No. 5 as Container No. 1 (as described in Section 11.2.2), except substitute the filter blank filtrate from Container No. 4 for the sample filtrate from Container No. 3, and mark as Sample A.1 Blank.
11.2.3.2 Treat Container No. 6 as Container No. 1A, (as described in Section 11.2.2, except substitute the filtrate from the digested blank MnO2 precipitate for the filtrate from the digested sample MnO2 precipitate, and mark as Sample No. A.2 Blank.
Note: When analyzing samples A.1 Blank and HCl A.2 Blank, always begin with 10 ml aliquots. This applies specifically to blank samples.
11.3 Analysis. Calibrate the analytical equipment and develop a calibration curve as outlined in Section 10.0.
11.3.1 Mercury Samples. Then repeat the procedure used to establish the calibration curve with appropriately sized aliquots (1 to 10 ml) of the samples (from Sections 11.2.2 and 11.2.3) until two consecutive peak heights agree within 3 percent of their average value. If the 10 ml sample is below the detectable limit, use a larger aliquot (up to 20 ml), but decrease the volume of water added to the aeration cell accordingly to prevent the solution volume from exceeding the capacity of the aeration bottle. If the peak maximum of a 1.0 ml aliquot is off scale, further dilute the original sample to bring the Hg concentration into the calibration range of the spectrophotometer. If the Hg content of the absorbing solution and filter blank is below the working range of the analytical method, use zero for the blank.
11.3.2 Run a blank and standard at least after every five samples to check the spectrophotometer calibration; recalibrate as necessary.
11.3.3 Check for Matrix Effects (optional). Same as Method 101, Section 11.3.3.
12.0 Data Analysis and Calculations
Note: Carry out calculations, retaining at least one extra decimal significant figure beyond that of the acquired data. Round off figures only after the final calculation. Other forms of the equations may be used as long as they give equivalent results.
12.1 Nomenclature.
C(fltr)Hg = Total ng of Hg in aliquot of KMnO4 filtrate and HNO3 digestion of filter analyzed (aliquot of analysis Sample No. A.1).
C(fltr blk)Hg = Total ng of Hg in aliquot of KMnO4 blank and HNO3 digestion of blank filter analyzed (aliquot of analysis Sample No. A.1 blank).
C(HC1 blk)Hg = Total ng of Hg analyzed in aliquot of the 500-ml analysis Sample No. HCl A.2 blank.
C(HCl)Hg = Total ng of Hg analyzed in the aliquot from the 500-ml analysis Sample No. HCl A.2.
DF = Dilution factor for the HCl-digested Hg-containing solution, Analysis Sample No. “HCl A.2.”
DFblk = Dilution factor for the HCl-digested Hg containing solution, Analysis Sample No. “HCl A.2 blank.” (Refer to sample No. “HCl A.2” dilution factor above.)
m(fltr)Hg = Total blank corrected µg of Hg in KMnO4 filtrate and HNO3 digestion of filter sample.
m(HCl)Hg = Total blank corrected µg of Hg in HCl rinse and HCl digestate of filter sample.
mHg = Total blank corrected Hg content in each sample, µg.
S = Aliquot volume of sample added to aeration cell, ml.
Sblk = Aliquot volume of blank added to aeration cell, ml.
Vf(blk) = Solution volume of blank sample, 1000 ml for samples diluted as described in Section 11.2.2.
Vf(fltr) = Solution volume of original sample, normally 1000 ml for samples diluted as described in Section 11.2.2.
Vf(HCl) = Solution volume of original sample, 500 ml for samples diluted as described in Section 11.2.1.
10-3 = Conversion factor, µg/ng.
12.2 Average Dry Gas Meter Temperature and Average Orifice Pressure Drop, Dry Gas Volume, Volume of Water Vapor Condensed, Moisture Content, Isokinetic Variation, and Stack Gas Velocity and Volumetric Flow Rate. Same as Method 5, Sections 12.2 through 12.5, 12.11, and 12.12, respectively.
12.3 Total Mercury.
12.3.1 For each source sample, correct the average maximum absorbance of the two consecutive samples whose peak heights agree within 3 percent of their average for the contribution of the blank. Use the calibration curve and these corrected averages to determine the final total weight of Hg in ng in the aeration cell for each source sample.
12.3.2 Correct for any dilutions made to bring the sample into the working range of the spectrophotometer.
Note: This dilution factor applies only to the intermediate dilution steps, since the original sample volume [(Vf)HCL] of “HCl A.2” has been factored out in the equation along with the sample aliquot (S). In Eq. 101A–1, the sample aliquot, S, is introduced directly into the aeration cell for analysis according to the procedure outlined in Section 11.3.1. A dilution factor is required only if it is necessary to bring the sample into the analytical instrument's calibration range.
Note: The maximum allowable blank subtraction for the HCl is the lesser of the two following values: (1) the actual blank measured value (analysis Sample No. HCl A.2 blank), or (2) 5% of the Hg content in the combined HCl rinse and digested sample (analysis Sample No. HCl A.2).
Note: The maximum allowable blank subtraction for the HCl is the lesser of the two following values: (1) the actual blank measured value (analysis Sample No. “A.1 blank”), or (2) 5% of the Hg content in the filtrate (analysis Sample No. “A.1”).
12.3 Mercury Emission Rate. Same as Method 101, Section 12.3.
12.4 Determination of Compliance. Same as Method 101, Section 12.4.
13.0 Method Performance
13.1 Precision. Based on eight paired-train tests, the intra-laboratory standard deviation was estimated to be 4.8 µg/ml in the concentration range of 50 to 130 µg/m3.
13.2 Bias. [Reserved]
13.3 Range. After initial dilution, the range of this method is 20 to 800 ng Hg/ml. The upper limit can be extended by further dilution of the sample.
14.0 Pollution Prevention [Reserved]
15.0 Waste Management [Reserved]
16.0 References
Same as Section 16.0 of Method 101, with the addition of the following:
1. Mitchell, W.J., et al. Test Methods to Determine the Mercury Emissions from Sludge Incineration Plants. U.S. Environmental Protection Agency. Research Triangle Park, NC. Publication No. EPA–600/4–79–058. September 1979.
2. Wilshire, Frank W., et al. Reliability Study of the U.S. EPA's Method 101A—Determination of Particulate and Gaseous Mercury Emissions. U.S. Environmental Protection Agency. Research Triangle Park, NC. Report No. 600/D–31/219 AREAL 367, NTIS Acc No. PB91–233361.
3. Memorandum from William J. Mitchell to Roger T. Shigehara discussing the potential safety hazard in Section 7.2 of Method 101A. February 28, 1990.
17.0 Tables, Diagrams, Flowcharts, And Validation Data [Reserved]
Method 102—Determination of Particulate and Gaseous Mercury Emissions From Chlor-Alkali Plants (Hydrogen Streams)
Note: 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 and in appendix A to 40 CFR part 60. 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 101.
1.0 Scope and Application
1.1 Analytes.
------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
Mercury (Hg)................... 7439-97-6 Dependent upon recorder
and spectrophotometer.
------------------------------------------------------------------------
1.2 Applicability. This method is applicable for the determination of Hg emissions, including both particulate and gaseous Hg, from chlor-alkali plants and other sources (as specified in the regulations) where the carrier-gas stream in the duct or stack is principally hydrogen.
1.3 Data Quality Objectives. Adherence to the requirements of this method will enhance the quality of the data obtained from air pollutant sampling methods.
2.0 Summary of Method
2.1 Particulate and gaseous Hg emissions are withdrawn isokinetically from the source and collected in acidic iodine monochloride (ICl) solution. The Hg collected (in the mercuric form) is reduced to elemental Hg, which is then aerated from the solution into an optical cell and measured by atomic absorption spectrophotometry.
3.0 Definitions [Reserved]
4.0 Interferences
Same as Method 101, Section 4.2.
5.0 Safety
5.1 Disclaimer. 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.
5.2 Corrosive Reagents. Same as Method 101, Section 5.2.
5.3 Explosive Mixtures. The sampler must conduct the source test under conditions of utmost safety because hydrogen and air mixtures are explosive. Since the sampling train essentially is leakless, attention to safe operation can be concentrated at the inlet and outlet. If a leak does occur, however, remove the meter box cover to avoid a possible explosive mixture. The following specific precautions are recommended:
5.3.1 Operate only the vacuum pump during the test. The other electrical equipment, e.g., heaters, fans, and timers, normally are not essential to the success of a hydrogen stream test.
5.3.2 Seal the sample port to minimize leakage of hydrogen from the stack.
5.3.3 Vent sampled hydrogen at least 3 m (10 ft) away from the train. This can be accomplished by attaching a 13-mm (0.50-in.) ID Tygon tube to the exhaust from the orifice meter.
Note: A smaller ID tubing may cause the orifice meter calibration to be erroneous. Take care to ensure that the exhaust line is not bent or pinched.
6.0 Equipment and Supplies
Same as Method 101, Section 6.0, with the exception of the following:
6.1 Probe Heating System. Do not use, unless otherwise specified.
6.2 Glass Fiber Filter. Do not use, unless otherwise specified.
7.0 Reagents and Standards
Same as Method 101, Section 7.0.
8.0 Sample Collection, Preservation, Transport, and Storage
Same as Method 101, Section 8.0, with the exception of the following:
8.1 Setting of Isokinetic Rates.
8.1.1 If a nomograph is used, take special care in the calculation of the molecular weight of the stack gas and in the setting of the nomograph to maintain isokinetic conditions during sampling (Sections 8.1.1.1 through 8.1.1.3 below).
8.1.1.1 Calibrate the meter box orifice. Use the techniques described in APTD–0576 (see Reference 9 in Section 17.0 of Method 5). Calibration of the orifice meter at flow conditions that simulate the conditions at the source is suggested. Calibration should either be done with hydrogen or with some other gas having similar Reynolds Number so that there is similarity between the Reynolds Numbers during calibration and during sampling.
8.1.1.2 The nomograph described in APTD–0576 cannot be used to calculate the C factor because the nomograph is designed for use when the stack gas dry molecular weight is 29 ±4. Instead, the following calculation should be made to determine the proper C factor:
Where:
Bws = Fraction by volume of water vapor in the stack gas.
Cp = Pitot tube calibration coefficient, dimensionless.
Md = Dry molecular weight of stack gas, lb/lb-mole.
Ps = Absolute pressure of stack gas, in. Hg.
Pm = Absolute pressure of gas at the meter, in. Hg.
Tm = Absolute temperature of gas at the orifice, °R.
?H@ = Meter box calibration factor obtained in Section 8.1.1.1, in. H2O.
0.00154 = (in. H2O/°R).
Note: This calculation is left in English units, and is not converted to metric units because nomographs are based on English units.
8.1.1.3 Set the calculated C factor on the operating nomograph, and select the proper nozzle diameter and K factor as specified in APTD–0576. If the C factor obtained in Section 8.1.1.2 exceeds the values specified on the existing operating nomograph, expand the C scale logarithmically so that the values can be properly located.
8.1.2 If a calculator is used to set isokinetic rates, it is suggested that the isokinetic equation presented in Reference 13 in Section 17.0 of Method 101 be consulted.
8.2 Sampling in Small (<12-in. Diameter) Stacks. When the stack diameter (or equivalent diameter) is less than 12 inches, conventional pitot tube-probe assemblies should not be used. For sampling guidelines, see Reference 14 in Section 17.0 of Method 101.
9.0 Quality Control
Same as Method 101, Section 9.0.
10.0 Calibration and Standardizations
Same as Method 101, Section 10.0.
11.0 Analytical Procedure
Same as Method 101, Section 11.0.
12.0 Data Analysis and Calculations
Same as Method 101, Section 12.0.
13.0 Method Performance
Same as Method 101, Section 13.0.
13.1 Analytical Range. After initial dilution, the range of this method is 0.5 to 120 µg Hg/ml. The upper limit can be extended by further dilution of the sample.
14.0 Pollution Prevention. [Reserved]
15.0 Waste Management. [Reserved]
16.0 References
Same as Method 101, Section 16.0.
17.0 Tables, Diagrams, Flowcharts, and Validation Data. [Reserved]
Method 103—Beryllium Screening Method
1.0 Scope and Application
1.1 Analytes.
------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
Beryllium (Be)................. 7440-41-7 Dependent upon
analytical procedure
used.
------------------------------------------------------------------------
1.2 Applicability. This procedure details guidelines and requirements for methods acceptable for use in determining Be emissions in ducts or stacks at stationary sources.
1.3 Data Quality Objectives. Adherence to the requirements of this method will enhance the quality of the data obtained from air pollutant sampling methods.
2.0 Summary of Method
2.1 Particulate Be emissions are withdrawn isokinetically from three points in a duct or stack and are collected on a filter. The collected sample is analyzed for Be using an appropriate technique.
3.0 Definitions. [Reserved]
4.0 Interferences. [Reserved]
5.0 Safety
5.1 Disclaimer. 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.
5.2 Hydrochloric Acid (HCl). Highly corrosive and toxic. Vapors are highly irritating to eyes, skin, nose, and lungs, causing severe damage. May cause bronchitis, pneumonia, or edema of lungs. Exposure to concentrations of 0.13 to 0.2 percent can be lethal to humans in a few minutes. Provide ventilation to limit exposure. Reacts with metals, producing hydrogen gas. Personal protective equipment and safe procedures are useful in preventing chemical splashes. If contact occurs, immediately flush with copious amounts of water at least 15 minutes. Remove clothing under shower and decontaminate. Treat residual chemical burn as thermal burn.
6.0 Equipment and Supplies
6.1 Sample Collection. A schematic of the required sampling train configuration is shown in Figure 103–1 in Section 17.0. The essential components of the train are as follows:
6.1.1 Nozzle. Stainless steel, or equivalent, with sharp, tapered leading edge.
6.1.2 Probe. Sheathed borosilicate or quartz glass tubing.
6.1.3 Filter. Millipore AA, or equivalent, with appropriate filter holder that provides a positive seal against leakage from outside or around the filter. It is suggested that a Whatman 41, or equivalent, be placed immediately against the back side of the Millipore filter as a guard against breakage of the Millipore. Include the backup filter in the analysis. To be equivalent, other filters shall exhibit at least 99.95 percent efficiency (0.05 percent penetration) on 0.3 micron dioctyl phthalate smoke particles, and be amenable to the Be analysis procedure. The filter efficiency tests shall be conducted in accordance with ASTM D 2986–71, 78, 95a (incorporated by reference—see §61.18). Test data from the supplier's quality control program are sufficient for this purpose.
6.1.4 Meter-Pump System. Any system that will maintain isokinetic sampling rate, determine sample volume, and is capable of a sampling rate of greater than 14 lpm (0.5 cfm).
6.2 Measurement of Stack Conditions. The following equipment is used to measure stack conditions:
6.2.1 Pitot Tube. Type S, or equivalent, with a constant coefficient (±5 percent) over the working range.
6.2.2 Inclined Manometer, or Equivalent. To measure velocity head to ±10 percent of the minimum value.
6.2.3 Temperature Measuring Device. To measure stack temperature to ±1.5 percent of the minimum absolute stack temperature.
6.2.4 Pressure Measuring Device. To measure stack pressure to ±2.5 mm Hg (0.1 in. Hg).
6.2.5 Barometer. To measure atmospheric pressure to ±2.5 mm Hg (0.1 in. Hg).
6.2.6 Wet and Dry Bulb Thermometers, Drying Tubes, Condensers, or Equivalent. To determine stack gas moisture content to ±1 percent.
6.3 Sample Recovery.
6.3.1 Probe Cleaning Equipment. Probe brush or cleaning rod at least as long as probe, or equivalent. Clean cotton balls, or equivalent, should be used with the rod.
6.3.2 Leakless Glass Sample Bottles. To contain sample.
6.4 Analysis. All equipment necessary to perform an atomic absorption, spectrographic, fluorometric, chromatographic, or equivalent analysis.
7.0 Reagents and Standards
7.1 Sample Recovery.
7.1.1 Water. Deionized distilled, to conform to ASTM D 1193–77, 91 (incorporated by reference—see §61.18), Type 3.
7.1.2 Acetone. Reagent grade.
7.1.3 Wash Acid, 50 Percent (V/V) Hydrochloric Acid (HCl). Mix equal volumes of concentrated HCl and water, being careful to add the acid slowly to the water.
7.2 Analysis. Reagents and standards as necessary for the selected analytical procedure.
8.0 Sample Collection, Preservation, Transport, and Storage
Guidelines for source testing are detailed in the following sections. These guidelines are generally applicable; however, most sample sites differ to some degree and temporary alterations such as stack extensions or expansions often are required to insure the best possible sample site. Further, since Be is hazardous, care should be taken to minimize exposure. Finally, since the total quantity of Be to be collected is quite small, the test must be carefully conducted to prevent contamination or loss of sample.
8.1 Selection of a Sampling Site and Number of Sample Runs. Select a suitable sample site that is as close as practicable to the point of atmospheric emission. If possible, stacks smaller than one foot in diameter should not be sampled.
8.1.1 Ideal Sampling Site. The ideal sampling site is at least eight stack or duct diameters downstream and two diameters upstream from any flow disturbance such as a bend, expansion or contraction. For rectangular cross sections, use Equation 103–1 in Section 12.2 to determine an equivalent diameter, De.
8.1.2 Alternate Sampling Site. Some sampling situations may render the above sampling site criteria impractical. In such cases, select an alternate site no less than two diameters downstream and one-half diameter upstream from any point of flow disturbance. Additional sample runs are recommended at any sample site not meeting the criteria of Section 8.1.1.
8.1.3 Number of Sample Runs Per Test. Three sample runs constitute a test. Conduct each run at one of three different points. Select three points that proportionately divide the diameter, or are located at 25, 50, and 75 percent of the diameter from the inside wall. For horizontal ducts, sample on a vertical line through the centroid. For rectangular ducts, sample on a line through the centroid and parallel to a side. If additional sample runs are performed per Section 8.1.2, proportionately divide the duct to accommodate the total number of runs.
8.2 Measurement of Stack Conditions. Using the equipment described in Section 6.2, measure the stack gas pressure, moisture, and temperature to determine the molecular weight of the stack gas. Sound engineering estimates may be made in lieu of direct measurements. Describe the basis for such estimates in the test report.
8.3 Preparation of Sampling Train.
8.3.1 Assemble the sampling train as shown in Figure 103–1. It is recommended that all glassware be precleaned by soaking in wash acid for two hours.
8.3.2 Leak check the sampling train at the sampling site. The leakage rate should not be in excess of 1 percent of the desired sample rate.
8.4 Sampling Train Operation.
8.4.1 For each run, measure the velocity at the selected sampling point. Determine the isokinetic sampling rate. Record the velocity head and the required sampling rate. Place the nozzle at the sampling point with the tip pointing directly into the gas stream. Immediately start the pump and adjust the flow to isokinetic conditions. At the conclusion of the test, record the sampling rate. Again measure the velocity head at the sampling point. The required isokinetic rate at the end of the period should not have deviated more than 20 percent from that originally calculated. Describe the reason for any deviation beyond 20 percent in the test report.
8.4.2 Sample at a minimum rate of 14 liters/min (0.5 cfm). Obtain samples over such a period or periods of time as are necessary to determine the maximum emissions which would occur in a 24-hour period. In the case of cyclic operations, perform sufficient sample runs so as to allow determination or calculation of the emissions that occur over the duration of the cycle. A minimum sampling time of two hours per run is recommended.
8.5 Sample Recovery.
8.5.1 It is recommended that all glassware be precleaned as in Section 8.3. Sample recovery should also be performed in an area free of possible Be contamination. When the sampling train is moved, exercise care to prevent breakage and contamination. Set aside a portion of the acetone used in the sample recovery as a blank for analysis. The total amount of acetone used should be measured for accurate blank correction. Blanks can be eliminated if prior analysis shows negligible amounts.
8.5.2 Remove the filter (and backup filter, if used) and any loose particulate matter from filter holder, and place in a container.
8.5.3 Clean the probe with acetone and a brush or long rod and cotton balls. Wash into the container with the filter. Wash out the filter holder with acetone, and add to the same container.
9.0 Quality Control. [Reserved]
10.0 Calibration and Standardization
10.1 Sampling Train. As a procedural check, compare the sampling rate regulation with a dry gas meter, spirometer, rotameter (calibrated for prevailing atmospheric conditions), or equivalent, attached to the nozzle inlet of the complete sampling train.
10.2 Analysis. Perform the analysis standardization as suggested by the manufacturer of the instrument, or the procedures for the analytical method in use.
11.0 Analytical Procedure
Make the necessary preparation of samples and analyze for Be. Any currently acceptable method (e.g., atomic absorption, spectrographic, fluorometric, chromatographic) may be used.
12.0 Data Analysis and Calculations
12.1 Nomenclature.
As(avg) = Stack area, m 2 (ft 2 ).
L = Length.
R = Be emission rate, g/day.
Vs(avg) = Average stack gas velocity, m/sec (ft/sec).
Vtotal = Total volume of gas sampled, m 3 (ft 3 ).
W = Width.
Wt = Total weight of Be collected, mg.
10-6 = Conversion factor, g/µg.
86,400 = Conversion factor, sec/day.
12.2 Calculate the equivalent diameter, De, for a rectangular cross section as follows:
12.3 Calculate the Be emission rate, R, in g/day for each stack using Equation 103–2. For cyclic operations, use only the time per day each stack is in operation. The total Be emission rate from a source is the summation of results from all stacks.
12.4 Test Report. Prepare a test report that includes as a minimum: A detailed description of the sampling train used, results of the procedural check described in Section 10.1 with all data and calculations made, all pertinent data taken during the test, the basis for any estimates made, isokinetic sampling calculations, and emission results. Include a description of the test site, with a block diagram and brief description of the process, location of the sample points in the stack cross section, and stack dimensions and distances from any point of disturbance.
13.0 Method Performance. [Reserved]
14.0 Pollution Prevention. [Reserved]
15.0 Waste Management. [Reserved]
16.0 References. [Reserved]
17.0 Tables, Diagrams, Flow Charts, and Validation Data
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Method 104—Determination of Beryllium Emissions From Stationary Sources
Note: 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 methods in appendix A to 40 CFR part 60. 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, and Method 5 in appendix A, part 60.
1.0 Scope and Application
1.1 Analytes.
------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
Beryllium (Be)................. 7440-41-7 Dependent upon
recorder and
spectrophotometer.
------------------------------------------------------------------------
1.2 Applicability. This method is applicable for the determination of Be emissions in ducts or stacks at stationary sources. Unless otherwise specified, this method is not intended to apply to gas streams other than those emitted directly to the atmosphere without further processing.
1.3 Data Quality Objectives. Adherences to the requirements of this method will enhance the quality of the data obtained from air pollutant sampling methods.
2.0 Summary of Method
2.1 Particulate and gaseous Be emissions are withdrawn isokinetically from the source and are collected on a glass fiber filter and in water. The collected sample is digested in an acid solution and is analyzed by atomic absorption spectrophotometry.
3.0 Definitions [Reserved]
4.0 Interferences
4.1 Matrix Effects. Analysis for Be by flame atomic absorption spectrophotometry is sensitive to the chemical composition and to the physical properties (e.g., viscosity, pH) of the sample. Aluminum and silicon in particular are known to interfere when present in appreciable quantities. The analytical procedure includes (optionally) the use of the Method of Standard Additions to check for these matrix effects, and sample analysis using the Method of Standard Additions if significant matrix effects are found to be present (see Reference 2 in Section 16.0).
5.0 Safety
5.1 Disclaimer. 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.
5.2 Corrosive reagents. The following reagents are hazardous. Personal protective equipment and safe procedures are useful in preventing chemical splashes. If contact occurs, immediately flush with copious amounts of water at least 15 minutes. Remove clothing under shower and decontaminate. Treat residual chemical burn as thermal burn.
5.2.1 Hydrochloric Acid (HCl). Highly toxic. Vapors are highly irritating to eyes, skin, nose, and lungs, causing severe damage. May cause bronchitis, pneumonia, or edema of lungs. Exposure to concentrations of 0.13 to 0.2 percent can be lethal to humans in a few minutes. Provide ventilation to limit exposure. Reacts with metals, producing hydrogen gas.
5.2.2 Hydrogen Peroxide (H2O2). Irritating to eyes, skin, nose, and lungs.
5.2.3 Nitric Acid (HNO3). Highly corrosive to eyes, skin, nose, and lungs. Vapors cause bronchitis, pneumonia, or edema of lungs. Reaction to inhalation may be delayed as long as 30 hours and still be fatal. Provide ventilation to limit exposure. Strong oxidizer. Hazardous reaction may occur with organic materials such as solvents.
5.2.4 Sodium Hydroxide (NaOH). Causes severe damage to eyes and skin. Inhalation causes irritation to nose, throat, and lungs. Reacts exothermically with limited amounts of water.
5.3 Beryllium is hazardous, and precautions should be taken to minimize exposure.
6.0 Equipment and Supplies
6.1 Sample Collection. Same as Method 5, Section 6.1, with the exception of the following:
6.1.1 Sampling Train. Same as Method 5, Section 6.1.1, with the exception of the following:
6.1.2 Probe Liner. Borosilicate or quartz glass tubing. A heating system capable of maintaining a gas temperature of 120 ±14 °C (248 ±25 °F) at the probe exit during sampling to prevent water condensation may be used.
Note: Do not use metal probe liners.
6.1.3 Filter Holder. Borosilicate glass, with a glass frit filter support and a silicone rubber gasket. Other materials of construction (e.g., stainless steel, Teflon, 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 holder shall be attached immediately at the outlet of the probe. A heating system capable of maintaining the filter at a minimum temperature in the range of the stack temperature may be used to prevent condensation from occurring.
6.1.4 Impingers. Four Greenburg-Smith impingers connected in series with leak-free ground glass fittings or any similar leak-free noncontaminating fittings. For the first, third, and fourth impingers, use impingers that are modified by replacing the tip with a 13 mm-ID (0.5 in.) glass tube extending to 13 mm (0.5 in.) from the bottom of the flask may be used.
6.2 Sample Recovery. The following items are needed for sample recovery:
6.2.1 Probe Cleaning Rod. At least as long as probe.
6.2.2 Glass Sample Bottles. Leakless, with Teflon-lined caps, 1000 ml.
6.2.3 Petri Dishes. For filter samples, glass or polyethylene, unless otherwise specified by the Administrator.
6.2.4 Graduated Cylinder. 250 ml.
6.2.5 Funnel and Rubber Policeman. To aid in transfer of silica gel to container; not necessary if silica gel is weighed in the field.
6.2.6 Funnel. Glass, to aid in sample recovery.
6.2.7 Plastic Jar. Approximately 300 ml.
6.3 Analysis. The following items are needed for sample analysis:
6.3.1 Atomic Absorption Spectrophotometer. Perkin-Elmer 303, or equivalent, with nitrous oxide/acetylene burner.
6.3.2 Hot Plate.
6.3.3 Perchloric Acid Fume Hood.
7.0 Reagents and Standards
Note: Unless otherwise indicated, it is intended that all reagents 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.
7.1 Sample Collection. Same as Method 5, Section 7.1, including deionized distilled water conforming to ASTM D 1193–77 or 91 (incorporated by reference—see §61.18), Type 3. The Millipore AA filter is recommended.
7.2 Sample Recovery. Same as Method 5 in appendix A, part 60, Section 7.2, with the addition of the following:
7.2.1 Wash Acid, 50 Percent (V/V) Hydrochloric Acid (HCl). Mix equal volumes of concentrated HCl and water, being careful to add the acid slowly to the water.
7.3 Sample Preparation and Analysis. The following reagents and standards and standards are needed for sample preparation and analysis:
7.3.1 Water. Same as in Section 7.1.
7.3.2. Perchloric Acid (HClO4). Concentrated (70 percent V/V).
7.3.3 Nitric Acid (HNO3). Concentrated.
7.3.4 Beryllium Powder. Minimum purity 98 percent.
7.3.5 Sulfuric Acid (H2SO4) Solution, 12 N. Dilute 33 ml of concentrated H2SO4 to 1 liter with water.
7.3.6 Hydrochloric Acid Solution, 25 Percent HCl (V/V).
7.3.7 Stock Beryllium Standard Solution, 10 µg Be/ml. Dissolve 10.0 mg of Be in 80 ml of 12 N H2SO4 in a 1000-ml volumetric flask. Dilute to volume with water. This solution is stable for at least one month. Equivalent strength Be stock solutions may be prepared from Be salts such as BeCl2 and Be(NO3)2 (98 percent minimum purity).
7.3.8 Working Beryllium Standard Solution, 1 µg Be/ml. Dilute a 10 ml aliquot of the stock beryllium standard solution to 100 ml with 25 percent HCl solution to give a concentration of 1 mg/ml. Prepare this dilute stock solution fresh daily.
8.0 Sample Collection, Preservation, Transport, and Storage
The amount of Be that is collected is generally small, therefore, it is necessary to exercise particular care to prevent contamination or loss of sample.
8.1 Pretest Preparation. Same as Method 5, Section 8.1, except omit Section 8.1.3.
8.2 Preliminary Determinations. Same as Method 5, Section 8.2, with the exception of the following:
8.2.1 Select a nozzle size based on the range of velocity heads to assure that it is not necessary to change the nozzle size in order to maintain isokinetic sampling rates below 28 liters/min (1.0 cfm).
8.2.2 Obtain samples over a period or periods of time that accurately determine the maximum emissions that occur in a 24-hour period. In the case of cyclic operations, perform sufficient sample runs for the accurate determination of the emissions that occur over the duration of the cycle. A minimum sample time of 2 hours per run is recommended.
8.3 Preparation of Sampling Train. Same as Method 5, Section 8.3, with the exception of the following:
8.3.1 Prior to assembly, clean all glassware (probe, impingers, and connectors) by first soaking in wash acid for 2 hours, followed by rinsing with water.
8.3.2 Save a portion of the water for a blank analysis.
8.3.3 Procedures relating to the use of metal probe liners are not applicable.
8.3.4 Probe and filter heating systems are needed only if water condensation is a problem. If this is the case, adjust the heaters to provide a temperature at or above the stack temperature. However, membrane filters such as the Millipore AA are limited to about 107 °C (225 °F). If the stack gas is in excess of about 93 °C (200 °F), consideration should be given to an alternate procedure such as moving the filter holder downstream of the first impinger to insure that the filter does not exceed its temperature limit. After the sampling train has been assembled, turn on and set the probe heating system, if applicable, at the desired operating temperature. Allow time for the temperatures to stabilize. Place crushed ice around the impingers.
Note: An empty impinger may be inserted between the third impinger and the silica gel to remove excess moisture from the sample stream.
8.4 Leak Check Procedures, Sampling Train Operation, and Calculation of Percent Isokinetic. Same as Method 5, Sections 8.4, 8.5, and 8.6, respectively.
8.5 Sample Recovery. Same as Method 5, Section 8.7, except treat the sample as follows: Transfer the probe and impinger assembly to a cleanup area that is clean, protected from the wind, and free of Be contamination. Inspect the train before and during this assembly, and note any abnormal conditions. Treat the sample as follows: Disconnect the probe from the impinger train.
8.5.1 Container No. 1. Same as Method 5, Section 8.7.6.1.
8.5.2 Container No. 2. Place the contents (measured to 1 ml) of the first three impingers into a glass sample bottle. Use the procedures outlined in Section 8.7.6.2 of Method 5, where applicable, to rinse the probe nozzle, probe fitting, probe liner, filter holder, and all glassware between the filter holder and the back half of the third impinger with water. Repeat this procedure with acetone. Place both water and acetone rinse solutions in the sample bottle with the contents of the impingers.
8.5.3 Container No. 3. Same as Method 5, Section 8.7.6.3.
8.6 Blanks.
8.6.1 Water Blank. Save a portion of the water as a blank. Take 200 ml directly from the wash bottle being used and place it in a plastic sample container labeled “H2O blank.”
8.6.2 Filter. Save two filters from each lot of filters used in sampling. Place these filters in a container labeled “filter blank.”
8.7 Post-test Glassware Rinsing. If an additional test is desired, the glassware can be carefully double rinsed with water and reassembled. However, if the glassware is out of use more than 2 days, repeat the initial acid wash procedure.
9.0 Quality Control
9.1 Miscellaneous Quality Control Measures.
------------------------------------------------------------------------
Quality control
Section measure Effect
------------------------------------------------------------------------
8.4, 10.1..................... Sampling Ensure accuracy and
equipment leak precision of
checks and sampling
calibration. measurements.
10.2.......................... Spectrophotometer Ensure linearity of
calibration. spectrophotometer
response to
standards.
11.5.......................... Check for matrix Eliminate matrix
effects. effects.
11.6.......................... Audit sample Evaluate analyst's
analysis. technique and
standards
preparation.
------------------------------------------------------------------------
9.2 Volume Metering System Checks. Same as Method 5, Section 9.2.
10.0 Calibration and Standardization
Note: Maintain a laboratory log of all calibrations.
10.1 Sampling Equipment. Same as Method 5, Section 10.0.
10.2 Preparation of Standard Solutions. Pipet 1, 3, 5, 8, and 10 ml of the 1.0 µg Be/ml working standard solution into separate 100 ml volumetric flasks, and dilute to the mark with water. The total amounts of Be in these standards are 1, 3, 5, 8, and 10 µg, respectively.
10.3 Spectrophotometer and Recorder. The Be response may be measured by either peak height or peak area. Analyze an aliquot of the 10-µg standard at 234.8 nm using a nitrous oxide/acetylene flame. Determine the maximum absorbance of the standard, and set this value to read 90 percent of the recorder full scale.
10.4 Calibration Curve.
10.4.1 After setting the recorder scale, analyze an appropriately sized aliquot of each standard and the BLANK (see Section 11) until two consecutive peaks agree within 3 percent of their average value.
10.4.3 Subtract the average peak height (or peak area) of the blank—which must be less than 2 percent of recorder full scale—from the averaged peak heights of the standards. If the blank absorbance is greater than 2 percent of full-scale, the probable cause is Be contamination of a reagent or carry-over of Be from a previous sample. Prepare the calibration curve by plotting the corrected peak height of each standard solution versus the corresponding total Be weight in the standard (in µg).
10.5 Spectrophotometer Calibration Quality Control. Calculate the least squares slope of the calibration curve. The line must pass through the origin or through a point no further from the origin than ±2 percent of the recorder full scale. Multiply the corrected peak height by the reciprocal of the least squares slope to determine the distance each calibration point lies from the theoretical calibration line. The difference between the calculated concentration values and the actual concentrations (i.e., 1, 3, 5, 8, and 10 µg Be) must be less than 7 percent for all standards.
11.0 Analytical Procedure
11.1 Sample Loss Check. Prior to analysis, check the liquid level in Container No. 2. Note on the analytical data sheet whether leakage occurred during transport. If a noticeable amount of leakage occurred, either void the sample or take steps, subject to the approval of the Administrator, to adjust the final results. (continued)