US Laws, Codes, Statutes & Cases

To each volumetric flask, add 1 mL 0.6% sulfamic acid (Section 8.2.1), accurately pipet 2 mL 0.2% formaldehyde solution (Section 8.2.2), then add 5 mL pararosaniline solution (Section 8.2.13). Start a laboratory timer that has been set for 30 minutes. Bring all flasks to volume with recently boiled and cooled distilled water and mix thoroughly. The color must be developed (during the 30-minute period) in a temperature environment in the range of 20° to 30 °C, which is controlled to ±1 °C. For increased precision, a constant temperature bath is recommended during the color development step. After 30 minutes, determine the corrected absorbance of each standard at 548 nm against a distilled water reference (Section 10.1). Denote this absorbance as (A). Distilled water is used in the reference cell rather than the reagant blank because of the temperature sensitivity of the reagent blank. Calculate the total micrograms SO₂ in each solution:

where:

V_TCM/SO2 = volume of sulfite-TCM solution used, mL;

C_TCM/SO2 = concentration of sulfur dioxide in the working sulfite-TCM, µg SO₂/mL (from equation 4); and

D = dilution factor (D = 1 for the working sulfite-TCM solution; D = 0.1 for the diluted working sulfite-TCM solution).

A calibration equation is determined using the method of linear least squares (Section 12.1). The total micrograms SO₂ contained in each solution is the x variable, and the corrected absorbance (eq. 10) associated with each solution is the y variable. For the calibration to be valid, the slope must be in the range of 0.030 ±0.002 absorbance unit/µg SO₂, the intercept as determined by the least squares method must be equal to or less than 0.170 absorbance unit when the color is developed at 22 °C (add 0.015 to this 0.170 specification for each °C above 22 °C) and the correlation coefficient must be greater than 0.998. If these criteria are not met, it may be the result of an impure dye and/or an improperly standardized sulfite-TCM solution. A calibration factor (B_s) is determined by calculating the reciprocal of the slope and is subsequently used for calculating the sample concentration (Section 12.3).

10.3 Dynamic Calibration Procedures (Option 2). Atmospheres containing accurately known concentrations of sulfur dioxide are prepared using permeation devices. In the systems for generating these atmospheres, the permeation device emits gaseous SO₂ at a known, low, constant rate, provided the temperature of the device is held constant (±0.1 °C) and the device has been accurately calibrated at the temperature of use. The SO₂ permeating from the device is carried by a low flow of dry carrier gas to a mixing chamber where it is diluted with SO₂-free air to the desired concentration and supplied to a vented manifold. A typical system is shown schematically in Figure 4 and this system and other similar systems have been described in detail by O'Keeffe and Ortman; (19) Scaringelli, Frey, and Saltzman, (20) and Scaringelli, O'Keeffe, Rosenberg, and Bell. (21) Permeation devices may be prepared or purchased and in both cases must be traceable either to a National Bureau of Standards (NBS) Standard Reference Material (SRM 1625, SRM 1626, SRM 1627) or to an NBS/EPA-approved commercially available Certified Reference Material (CRM). CRM's are described in Reference 22, and a list of CRM sources is available from the address shown for Reference 22. A recommended protocol for certifying a permeation device to an NBS SRM or CRM is given in Section 2.0.7 of Reference 2. Device permeation rates of 0.2 to 0.4 µg/min, inert gas flows of about 50 mL/min, and dilution air flow rates from 1.1 to 15 L/min conveniently yield standard atmospheres in the range of 25 to 600 µg SO₂/m³ (0.010 to 0.230 ppm).

10.3.1 Calibration Option 2A (30-minute and 1-hour samples): Generate a series of six standard atmospheres of SO₂ (e.g., 0, 50, 100, 200, 350, 500, 750 µg/m³ ) by adjusting the dilution flow rates appropriately. The concentration of SO₂ in each atmosphere is calculated as follows:

where:

C_a = concentration of SO₂ at standard conditions, µg/m³ ;

P_r = permeation rate, µg/min;

Q_d = flow rate of dilution air, std L/min; and

Q_p = flow rate of carrier gas across permeation device, std L/min.

Be sure that the total flow rate of the standard exceeds the flow demand of the sample train, with the excess flow vented at atmospheric pressure. Sample each atmosphere using similar apparatus as shown in Figure 1 and under the same conditions as field sampling (i.e., use same absorbing reagent volume and sample same volume of air at an equivalent flow rate). Due to the length of the sampling periods required, this method is not recommended for 24-hour sampling. At the completion of sampling, quantitatively transfer the contents of each impinger to one of a series of 25-mL volumetric flasks (if 10 mL of absorbing solution was used) using small amounts of distilled water for rinse (<5mL). If >10 mL of absorbing solution was used, bring the absorber solution in each impinger to orginal volume with distilled H₂ O and pipet 10-mL portions from each impinger into a series of 25-mL volumetric flasks. If the color development steps are not to be started within 12 hours of sampling, store the solutions at 5° ±5 °C. Calculate the total micrograms SO₂ in each solution as follows:

where:

C_a = concentration of SO₂ in the standard atmosphere, µg/m³ ;

O_s = sampling flow rate, std L/min;

t=sampling time, min;

V_a = volume of absorbing solution used for color development (10 mL); and

V_b = volume of absorbing solution used for sampling, mL.

Add the remaining reagents for color development in the same manner as in Section 10.2 for static solutions. Calculate a calibration equation and a calibration factor (B_g) according to Section 10.2, adhering to all the specified criteria.

10.3.2 Calibration Option 2B (24-hour samples): Generate a standard atmosphere containing approximately 1,050 µg SO₂/m³ and calculate the exact concentration according to equation 12. Set up a series of six absorbers according to Figure 2 and connect to a common manifold for sampling the standard atmosphere. Be sure that the total flow rate of the standard exceeds the flow demand at the sample manifold, with the excess flow vented at atmospheric pressure. The absorbers are then allowed to sample the atmosphere for varying time periods to yield solutions containing 0, 0.2, 0.6, 1.0, 1.4, 1.8, and 2.2 µg SO₂/mL solution. The sampling times required to attain these solution concentrations are calculated as follows:

where:

t = sampling time, min;

V_b = volume of absorbing solution used for sampling (50 mL);

C_s = desired concentration of SO₂ in the absorbing solution, µg/mL;

C_a = concentration of the standard atmosphere calculated according to equation 12, µg/m³ ; and

Q_s = sampling flow rate, std L/min.

At the completion of sampling, bring the absorber solutions to original volume with distilled water. Pipet a 10-mL portion from each absorber into one of a series of 25-mL volumetric flasks. If the color development steps are not to be started within 12 hours of sampling, store the solutions at 5° ±5 °C. Add the remaining reagents for color development in the same manner as in Section 10.2 for static solutions. Calculate the total µg SO₂ in each standard as follows:

where:

V_a = volume of absorbing solution used for color development (10 mL).

All other parameters are defined in equation 14.

Calculate a calibration equation and a calibration factor (B_t) according to Section 10.2 adhering to all the specified criteria.

11.0 Sample Preparation and Analysis.

11.1 Sample Preparation. Remove the samples from the shipping container. If the shipment period exceeded 12 hours from the completion of sampling, verify that the temperature is below 10 °C. Also, compare the solution level to the temporary level mark on the absorber. If either the temperature is above 10 °C or there was significant loss (more than 10 mL) of the sample during shipping, make an appropriate notation in the record and invalidate the sample. Prepare the samples for analysis as follows:

1. For 30-minute or 1-hour samples: Quantitatively transfer the entire 10 mL amount of absorbing solution to a 25-mL volumetric flask and rinse with a small amount (<5 mL) of distilled water.

2. For 24-hour samples: If the volume of the sample is less than the original 50-mL volume (permanent mark on the absorber), adjust the volume back to the original volume with distilled water to compensate for water lost to evaporation during sampling. If the final volume is greater than the original volume, the volume must be measured using a graduated cylinder. To analyze, pipet 10 mL of the solution into a 25-mL volumetric flask.

11.2 Sample Analysis. For each set of determinations, prepare a reagent blank by adding 10 mL TCM absorbing solution to a 25-mL volumetric flask, and two control standardscontainingapproximately5and 15 µg SO₂, respectively. The control standards are prepared according to Section 10.2 or 10.3. The analysis is carried out as follows:

1. Allow the sample to stand 20 minutes after the completion of sampling to allow any ozone to decompose (if applicable).

2. To each 25-mL volumetric flask containing reagent blank, sample, or control standard, add 1 mL of 0.6% sulfamic acid (Section 8.2.1) and allow to react for 10 min.

3. Accurately pipet 2 mL of 0.2% formaldehyde solution (Section 8.2.2) and then 5 mL of pararosaniline solution (Section 8.2.13) into each flask. Start a laboratory timer set at 30 minutes.

4. Bring each flask to volume with recently boiled and cooled distilled water and mix thoroughly.

5. During the 30 minutes, the solutions must be in a temperature controlled environment in the range of 20° to 30 °C maintained to ±1 °C. This temperature must also be within 1 °C of that used during calibration.

6. After 30 minutes and before 60 minutes, determine the corrected absorbances (equation 10) of each solution at 548 nm using 1-cm optical path length cells against a distilled water reference (Section 10.1). (Distilled water is used as a reference instead of the reagent blank because of the sensitivity of the reagent blank to temperature.)

7. Do not allow the colored solution to stand in the cells because a film may be deposited. Clean the cells with isopropyl alcohol after use.

8. The reagent blank must be within 0.03 absorbance units of the intercept of the calibration equation determined in Section 10.

11.3 Absorbance range. If the absorbance of the sample solution ranges between 1.0 and 2.0, the sample can be diluted 1:1 with a portion of the reagent blank and the absorbance redetermined within 5 minutes. Solutions with higher absorbances can be diluted up to sixfold with the reagent blank in order to obtain scale readings of less than 1.0 absorbance unit. However, it is recommended that a smaller portion (<10 mL) of the original sample be reanalyzed (if possible) if the sample requires a dilution greater than 1:1.

11.4 Reagent disposal. All reagents containing mercury compounds must be stored and disposed of using one of the procedures contained in Section 13. Until disposal, the discarded solutions can be stored in closed glass containers and should be left in a fume hood.

12.0 Calculations.

12.1 Calibration Slope, Intercept, and Correlation Coefficient. The method of least squares is used to calculate a calibration equation in the form of:

where:

y = corrected absorbance,

m = slope, absorbance unit/µg SO₂,

x = micrograms of SO₂,

b = y intercept (absorbance units).

The slope (m), intercept (b), and correlation coefficient (r) are calculated as follows:

where n is the number of calibration points.

A data form (Figure 5) is supplied for easily organizing calibration data when the slope, intercept, and correlation coefficient are calculated by hand.

12.2 Total Sample Volume. Determine the sampling volume at standard conditions as follows:

where:

V_std = sampling volume in std L,

Q_i = standard flow rate determined at the initiation of sampling in std L/min,

Q_f = standard flow rate determined at the completion of sampling is std L/min, and

t = total sampling time, min.

12.3 Sulfur Dioxide Concentration. Calculate and report the concentration of each sample as follows:

where:

A = corrected absorbance of the sample solution, from equation (10);

A_o = corrected absorbance of the reagent blank, using equation (10);

B_X = calibration factor equal to B_s, B_g, or B_t depending on the calibration procedure used, the reciprocal of the slope of the calibration equation;

V_a = volume of absorber solution analyzed, mL;

V_b = total volume of solution in absorber (see 11.1–2), mL; and

V_std = standard air volume sampled, std L (from Section 12.2).

Σ x=___  Σ y=___  Σ x² =___  Σxy___  Σy² ___  

n=___ (number of pairs of coordinates.)

Figure 5. Data form for hand calculations.

12.4 Control Standards. Calculate the analyzed micrograms of SO₂ in each control standard as follows:

where:

C_q = analyzed µg SO₂ in each control standard,

A = corrected absorbance of the control standard, and

A_o = corrected absorbance of the reagent blank.

The difference between the true and analyzed values of the control standards must not be greater than 1 µg. If the difference is greater than 1 µg, the source of the discrepancy must be identified and corrected.

12.5 Conversion of µg/m³ to ppm (v/v). If desired, the concentration of sulfur dioxide at reference conditions can be converted to ppm SO₂ (v/v) as follows:

13.0 The TCM absorbing solution and any reagents containing mercury compounds must be treated and disposed of by one of the methods discussed below. Both methods remove greater than 99.99 percent of the mercury.

13.1 Disposal of Mercury-Containing Solutions.

13.2 Method for Forming an Amalgam.

1. Place the waste solution in an uncapped vessel in a hood.

2. For each liter of waste solution, add approximately 10 g of sodium carbonate until neutralization has occurred (NaOH may have to be used).

3. Following neutralization, add 10 g of granular zinc or magnesium.

4. Stir the solution in a hood for 24 hours. Caution must be exercised as hydrogen gas is evolved by this treatment process.

5. After 24 hours, allow the solution to stand without stirring to allow the mercury amalgam (solid black material) to settle to the bottom of the waste receptacle.

6. Upon settling, decant and discard the supernatant liquid.

7. Quantitatively transfer the solid material to a container and allow to dry.

8. The solid material can be sent to a mercury reclaiming plant. It must not be discarded.

13.3 Method Using Aluminum Foil Strips.

1. Place the waste solution in an uncapped vessel in a hood.

2. For each liter of waste solution, add approximately 10 g of aluminum foil strips. If all the aluminum is consumed and no gas is evolved, add an additional 10 g of foil. Repeat until the foil is no longer consumed and allow the gas to evolve for 24 hours.

3. Decant the supernatant liquid and discard.

4. Transfer the elemental mercury that has settled to the bottom of the vessel to a storage container.

5. The mercury can be sent to a mercury reclaiming plant. It must not be discarded.

14.0 References for SO₂ Method.

1. Quality Assurance Handbook for Air Pollution Measurement Systems, Volume I, Principles. EPA–600/9–76–005, U.S. Environmental Protection Agency, Research Triangle Park, NC 27711, 1976.

2. Quality Assurance Handbook for Air Pollution Measurement Systems, Volume II, Ambient Air Specific Methods. EPA–600/4–77–027a, U.S. Environmental Protection Agency, Research Triangle Park, NC 27711, 1977.

3. Dasqupta, P. K., and K. B. DeCesare. Stability of Sulfur Dioxide in Formaldehyde and Its Anomalous Behavior in Tetrachloromercurate (II). Submitted for publication in Atmospheric Environment, 1982.

4. West, P. W., and G. C. Gaeke. Fixation of Sulfur Dioxide as Disulfitomercurate (II) and Subsequent Colorimetric Estimation. Anal. Chem., 28:1816, 1956.

5. Ephraim, F. Inorganic Chemistry. P. C. L. Thorne and E. R. Roberts, Eds., 5th Edition, Interscience, 1948, p. 562.

6. Lyles, G. R., F. B. Dowling, and V. J. Blanchard. Quantitative Determination of Formaldehyde in the Parts Per Hundred Million Concentration Level. J. Air. Poll. Cont. Assoc., Vol. 15(106), 1965.

7. McKee, H. C., R. E. Childers, and O. Saenz, Jr. Collaborative Study of Reference Method for Determination of Sulfur Dioxide in the Atmosphere (Pararosaniline Method). EPA-APTD-0903, U.S. Environmental Protection Agency, Research Triangle Park, NC 27711, September 1971.

8. Urone, P., J. B. Evans, and C. M. Noyes. Tracer Techniques in Sulfur—Air Pollution Studies Apparatus and Studies of Sulfur Dioxide Colorimetric and Conductometric Methods. Anal. Chem., 37: 1104, 1965.

9. Bostrom, C. E. The Absorption of Sulfur Dioxide at Low Concentrations (pphm) Studied by an Isotopic Tracer Method. Intern. J. Air Water Poll., 9:333, 1965.

10. Scaringelli, F. P., B. E. Saltzman, and S. A. Frey. Spectrophotometric Determination of Atmospheric Sulfur Dioxide. Anal. Chem., 39: 1709, 1967.

11. Pate, J. B., B. E. Ammons, G. A. Swanson, and J. P. Lodge, Jr. Nitrite Interference in Spectrophotometric Determination of Atmospheric Sulfur Dioxide. Anal. Chem., 37:942, 1965.

12. Zurlo, N., and A. M. Griffini. Measurement of the Sulfur Dioxide Content of the Air in the Presence of Oxides of Nitrogen and Heavy Metals. Medicina Lavoro, 53:330, 1962.

13. Rehme, K. A., and F. P. Scaringelli. Effect of Ammonia on the Spectrophotometric Determination of Atmospheric Concentrations of Sulfur Dioxide. Anal. Chem., 47:2474, 1975.

14. McCoy, R. A., D. E. Camann, and H. C. McKee. Collaborative Study of Reference Method for Determination of Sulfur Dioxide in the Atmosphere (Pararosaniline Method) (24-Hour Sampling). EPA–650/4–74–027, U.S. Environmental Protection Agency, Research Triangle Park, NC 27711, December 1973.

15. Fuerst, R. G. Improved Temperature Stability of Sulfur Dioxide Samples Collected by the Federal Reference Method. EPA–600/4–78–018, U.S. Environmental Protection Agency, Research Triangle Park, NC 27711, April 1978.

16. Scaringelli, F. P., L. Elfers, D. Norris, and S. Hochheiser. Enhanced Stability of Sulfur Dioxide in Solution. Anal. Chem., 42:1818, 1970.

17. Martin, B. E. Sulfur Dioxide Bubbler Temperature Study. EPA–600/4–77–040, U.S. Environmental Protection Agency, Research Triangle Park, NC 27711, August 1977.

18. American Society for Testing and Materials. ASTM Standards, Water; Atmospheric Analysis. Part 23. Philadelphia, PA, October 1968, p. 226.

19. O'Keeffe, A. E., and G. C. Ortman. Primary Standards for Trace Gas Analysis. Anal. Chem., 38:760, 1966.

20. Scaringelli, F. P., S. A. Frey, and B. E. Saltzman. Evaluation of Teflon Permeation Tubes for Use with Sulfur Dioxide. Amer. Ind. Hygiene Assoc. J., 28:260, 1967.

21. Scaringelli, F. P., A. E. O'Keeffe, E. Rosenberg, and J. P. Bell, Preparation of Known Concentrations of Gases and Vapors With Permeation Devices Calibrated Gravimetrically. Anal. Chem., 42:871, 1970.

22. A Procedure for Establishing Traceability of Gas Mixtures to Certain National Bureau of Standards Standard Reference Materials. EPA–600/7–81–010, U.S. Environmental Protection Agency, Environmental Monitoring Systems Laboratory (MD–77), Research Triangle Park, NC 27711, January 1981.

[47 FR 54899, Dec. 6, 1982; 48 FR 17355, Apr. 22, 1983]

top

1.0 Applicability.

1.1 This method provides a measurement of the mass concentration of total suspended particulate matter (TSP) in ambient air for determining compliance with the primary and secondary national ambient air quality standards for particulate matter as specified in §50.6 and §50.7 of this chapter. The measurement process is nondestructive, and the size of the sample collected is usually adequate for subsequent chemical analysis. Quality assurance procedures and guidance are provided in part 58, appendixes A and B, of this chapter and in References 1 and 2.

2.0 Principle.

2.1 An air sampler, properly located at the measurement site, draws a measured quantity of ambient air into a covered housing and through a filter during a 24-hr (nominal) sampling period. The sampler flow rate and the geometry of the shelter favor the collection of particles up to 25–50 µm (aerodynamic diameter), depending on wind speed and direction.(3) The filters used are specified to have a minimum collection efficiency of 99 percent for 0.3 µm (DOP) particles (see Section 7.1.4).

2.2 The filter is weighed (after moisture equilibration) before and after use to determine the net weight (mass) gain. The total volume of air sampled, corrected to EPA standard conditions (25 °C, 760 mm Hg [101 kPa]), is determined from the measured flow rate and the sampling time. The concentration of total suspended particulate matter in the ambient air is computed as the mass of collected particles divided by the volume of air sampled, corrected to standard conditions, and is expressed in micrograms per standard cubic meter (µg/std m³ ). For samples collected at temperatures and pressures significantly different than standard conditions, these corrected concentrations may differ substantially from actual concentrations (micrograms per actual cubic meter), particularly at high elevations. The actual particulate matter concentration can be calculated from the corrected concentration using the actual temperature and pressure during the sampling period.

3.0 Range.

3.1 The approximate concentration range of the method is 2 to 750 µg/std m³ . The upper limit is determined by the point at which the sampler can no longer maintain the specified flow rate due to the increased pressure drop of the loaded filter. This point is affected by particle size distribution, moisture content of the collected particles, and variability from filter to filter, among other things. The lower limit is determined by the sensitivity of the balance (see Section 7.10) and by inherent sources of error (see Section 6).

3.2 At wind speeds between 1.3 and 4.5 m/sec (3 and 10 mph), the high-volume air sampler has been found to collect particles up to 25 to 50 µm, depending on wind speed and direction.(3) For the filter specified in Section 7.1, there is effectively no lower limit on the particle size collected.

4.0 Precision.

4.1 Based upon collaborative testing, the relative standard deviation (coefficient of variation) for single analyst precision (repeatability) of the method is 3.0 percent. The corresponding value for interlaboratory precision (reproducibility) is 3.7 percent.(4)

5.0 Accuracy.

5.1 The absolute accuracy of the method is undefined because of the complex nature of atmospheric particulate matter and the difficulty in determining the “true” particulate matter concentration. This method provides a measure of particulate matter concentration suitable for the purpose specified under Section 1.0, Applicability.

6.0 Inherent Sources of Error.

6.1 Airflow variation. The weight of material collected on the filter represents the (integrated) sum of the product of the instantaneous flow rate times the instantaneous particle concentration. Therefore, dividing this weight by the average flow rate over the sampling period yields the true particulate matter concentration only when the flow rate is constant over the period. The error resulting from a nonconstant flow rate depends on the magnitude of the instantaneous changes in the flow rate and in the particulate matter concentration. Normally, such errors are not large, but they can be greatly reduced by equipping the sampler with an automatic flow controlling mechanism that maintains constant flow during the sampling period. Use of a contant flow controller is recommended.*

6.2 Air volume measurement. If the flow rate changes substantially or nonuniformly during the sampling period, appreciable error in the estimated air volume may result from using the average of the presampling and postsampling flow rates. Greater air volume measurement accuracy may be achieved by (1) equipping the sampler with a flow controlling mechanism that maintains constant air flow during the sampling period,* (2) using a calibrated, continuous flow rate recording device to record the actual flow rate during the samping period and integrating the flow rate over the period, or (3) any other means that will accurately measure the total air volume sampled during the sampling period. Use of a continuous flow recorder is recommended, particularly if the sampler is not equipped with a constant flow controller.

6.3 Loss of volatiles. Volatile particles collected on the filter may be lost during subsequent sampling or during shipment and/or storage of the filter prior to the postsampling weighing.(5) Although such losses are largely unavoidable, the filter should be reweighed as soon after sampling as practical.

6.4 Artifact particulate matter. Artifact particulate matter can be formed on the surface of alkaline glass fiber filters by oxidation of acid gases in the sample air, resulting in a higher than true TSP determination.(6 7) This effect usually occurs early in the sample period and is a function of the filter pH and the presence of acid gases. It is generally believed to account for only a small percentage of the filter weight gain, but the effect may become more significant where relatively small particulate weights are collected.

6.5 Humidity. Glass fiber filters are comparatively insensitive to changes in relative humidity, but collected particulate matter can be hygroscopic.(8) The moisture conditioning procedure minimizes but may not completely eliminate error due to moisture.

6.6 Filter handling. Careful handling of the filter between the presampling and postsampling weighings is necessary to avoid errors due to loss of fibers or particles from the filter. A filter paper cartridge or cassette used to protect the filter can minimize handling errors. (See Reference 2, Section 2).

6.7 Nonsampled particulate matter. Particulate matter may be deposited on the filter by wind during periods when the sampler is inoperative. (9) It is recommended that errors from this source be minimized by an automatic mechanical device that keeps the filter covered during nonsampling periods, or by timely installation and retrieval of filters to minimize the nonsampling periods prior to and following operation.

6.8 Timing errors. Samplers are normally controlled by clock timers set to start and stop the sampler at midnight. Errors in the nominal 1,440-min sampling period may result from a power interruption during the sampling period or from a discrepancy between the start or stop time recorded on the filter information record and the actual start or stop time of the sampler. Such discrepancies may be caused by (1) poor resolution of the timer set-points, (2) timer error due to power interruption, (3) missetting of the timer, or (4) timer malfunction. In general, digital electronic timers have much better set-point resolution than mechanical timers, but require a battery backup system to maintain continuity of operation after a power interruption. A continuous flow recorder or elapsed time meter provides an indication of the sampler run-time, as well as indication of any power interruption during the sampling period and is therefore recommended.

6.9 Recirculation of sampler exhaust. Under stagnant wind conditions, sampler exhaust air can be resampled. This effect does not appear to affect the TSP measurement substantially, but may result in increased carbon and copper in the collected sample. (10) This problem can be reduced by ducting the exhaust air well away, preferably downwind, from the sampler.

7.0 Apparatus.

(See References 1 and 2 for quality assurance information.)

Note: Samplers purchased prior to the effective date of this amendment are not subject to specifications preceded by (†).

7.1 Filter. (Filters supplied by the Environmental Protection Agency can be assumed to meet the following criteria. Additional specifications are required if the sample is to be analyzed chemically.)

7.1.1 Size: 20.3±0.2×25.4±0.2 cm (nominal 8×10 in).

7.1.2 Nominal exposed area: 406.5 cm² (63 in² ).

7.1.3. Material: Glass fiber or other relatively inert, nonhygroscopic material. (8)

7.1.4 Collection efficiency: 99 percent minimum as measured by the DOP test (ASTM–2986) for particles of 0.3 µm diameter.

7.1.5 Recommended pressure drop range: 42–54 mm Hg (5.6–7.2 kPa) at a flow rate of 1.5 std m³ /min through the nominal exposed area.

7.1.6 pH: 6 to 10. (11)

7.1.7 Integrity: 2.4 mg maximum weight loss. (11)

7.1.8 Pinholes: None.

7.1.9 Tear strength: 500 g minimum for 20 mm wide strip cut from filter in weakest dimension. (See ASTM Test D828–60).

7.1.10 Brittleness: No cracks or material separations after single lengthwise crease.

7.2 Sampler. The air sampler shall provide means for drawing the air sample, via reduced pressure, through the filter at a uniform face velocity.

7.2.1 The sampler shall have suitable means to:

a. Hold and seal the filter to the sampler housing.

b. Allow the filter to be changed conveniently.

c. Preclude leaks that would cause error in the measurement of the air volume passing through the filter.

d. (†) Manually adjust the flow rate to accommodate variations in filter pressure drop and site line voltage and altitude. The adjustment may be accomplished by an automatic flow controller or by a manual flow adjustment device. Any manual adjustment device must be designed with positive detents or other means to avoid unintentional changes in the setting.

7.2.2 Minimum sample flow rate, heavily loaded filter: 1.1 m³ /min (39 ft³ /min).‡

7.2.3 Maximum sample flow rate, clean filter: 1.7 m³ /min (60 ft³ /min).‡

7.2.4 Blower Motor: The motor must be capable of continuous operation for 24-hr periods.

7.3 Sampler shelter.

7.3.1 The sampler shelter shall:

a. Maintain the filter in a horizontal position at least 1 m above the sampler supporting surface so that sample air is drawn downward through the filter.

b. Be rectangular in shape with a gabled roof, similar to the design shown in Figure 1.

c. Cover and protect the filter and sampler from precipitation and other weather.

d. Discharge exhaust air at least 40 cm from the sample air inlet.

e. Be designed to minimize the collection of dust from the supporting surface by incorporating a baffle between the exhaust outlet and the supporting surface.

7.3.2 The sampler cover or roof shall overhang the sampler housing somewhat, as shown in Figure 1, and shall be mounted so as to form an air inlet gap between the cover and the sampler housing walls. ^† This sample air inlet should be approximately uniform on all sides of the sampler. ^† The area of the sample air inlet must be sized to provide an effective particle capture air velocity of between 20 and 35 cm/sec at the recommended operational flow rate. The capture velocity is the sample air flow rate divided by the inlet area measured in a horizontal plane at the lower edge of the cover. ^† Ideally, the inlet area and operational flow rate should be selected to obtain a capture air velocity of 25 ±2 cm/sec.

7.4 Flow rate measurement devices.

7.4.1 The sampler shall incorporate a flow rate measurement device capable of indicating the total sampler flow rate. Two common types of flow indicators covered in the calibration procedure are (1) an electronic mass flowmeter and (2) an orifice or orifices located in the sample air stream together with a suitable pressure indicator such as a manometer, or aneroid pressure gauge. A pressure recorder may be used with an orifice to provide a continuous record of the flow. Other types of flow indicators (including rotameters) having comparable precision and accuracy are also acceptable.

7.4.2 † The flow rate measurement device must be capable of being calibrated and read in units corresponding to a flow rate which is readable to the nearest 0.02 std m³ /min over the range 1.0 to 1.8 std m³ /min.

7.5 Thermometer, to indicate the approximate air temperature at the flow rate measurement orifice, when temperature corrections are used.

7.5.1 Range: −40° to +50 °C (223–323 K).

7.5.2 Resolution: 2 °C (2 K).

7.6 Barometer, to indicate barometric pressure at the flow rate measurement orifice, when pressure corrections are used.

7.6.1 Range: 500 to 800 mm Hg (66–106 kPa).

7.6.2 Resolution: ±5 mm Hg (0.67 kPa).

7.7 Timing/control device.

7.7.1 The timing device must be capable of starting and stopping the sampler to obtain an elapsed run-time of 24 hr ±1 hr (1,440 ±60 min).

7.7.2 Accuracy of time setting: ±30 min, or better. (See Section 6.8).

7.8 Flow rate transfer standard, traceable to a primary standard. (See Section 9.2.)

7.8.1 Approximate range: 1.0 to 1.8 m³ /min.

7.8.2 Resolution: 0.02 m³ /min.

7.8.3 Reproducibility: ±2 percent (2 times coefficient of variation) over normal ranges of ambient temperature and pressure for the stated flow rate range. (See Reference 2, Section 2.)

7.8.4 Maximum pressure drop at 1.7 std m³ /min; 50 cm H₂ O (5 kPa).

7.8.5 The flow rate transfer standard must connect without leaks to the inlet of the sampler and measure the flow rate of the total air sample.

7.8.6 The flow rate transfer standard must include a means to vary the sampler flow rate over the range of 1.0 to 1.8 m³ /min (35–64 ft³ /min) by introducing various levels of flow resistance between the sampler and the transfer standard inlet.

7.8.7 The conventional type of flow transfer standard consists of: An orifice unit with adapter that connects to the inlet of the sampler, a manometer or other device to measure orifice pressure drop, a means to vary the flow through the sampler unit, a thermometer to measure the ambient temperature, and a barometer to measure ambient pressure. Two such devices are shown in Figures 2a and 2b. Figure 2a shows multiple fixed resistance plates, which necessitate disassembly of the unit each time the flow resistance is changed. A preferable design, illustrated in Figure 2b, has a variable flow restriction that can be adjusted externally without disassembly of the unit. Use of a conventional, orifice-type transfer standard is assumed in the calibration procedure (Section 9). However, the use of other types of transfer standards meeting the above specifications, such as the one shown in Figure 2c, may be approved; see the note following Section 9.1.

7.9 Filter conditioning environment

7.9.1 Controlled temperature: between 15° and 30 °C with less than ±3 °C variation during equilibration period.

7.9.2 Controlled humidity: Less than 50 percent relative humidity, constant within ±5 percent.

7.10 Analytical balance.

7.10.1 Sensitivity: 0.1 mg.

7.10.2 Weighing chamber designed to accept an unfolded 20.3×25.4 cm (8×10 in) filter.

7.11 Area light source, similar to X-ray film viewer, to backlight filters for visual inspection.

7.12 Numbering device, capable of printing identification numbers on the filters before they are placed in the filter conditioning environment, if not numbered by the supplier.

8.0 Procedure.

(See References 1 and 2 for quality assurance information.)

8.1 Number each filter, if not already numbered, near its edge with a unique identification number.

8.2 Backlight each filter and inspect for pinholes, particles, and other imperfections; filters with visible imperfections must not be used.

8.3 Equilibrate each filter in the conditioning environment for at least 24-hr.

8.4 Following equilibration, weigh each filter to the nearest milligram and record this tare weight (W_i) with the filter identification number.

8.5 Do not bend or fold the filter before collection of the sample.

8.6 Open the shelter and install a numbered, preweighed filter in the sampler, following the sampler manufacturer's instructions. During inclement weather, precautions must be taken while changing filters to prevent damage to the clean filter and loss of sample from or damage to the exposed filter. Filter cassettes that can be loaded and unloaded in the laboratory may be used to minimize this problem (See Section 6.6).

8.7 Close the shelter and run the sampler for at least 5 min to establish run-temperature conditions.

8.8 Record the flow indicator reading and, if needed, the barometric pressure (P³ ₃) and the ambient temperature (T³ ₃) see NOTE following step 8.12). Stop the sampler. Determine the sampler flow rate (see Section 10.1); if it is outside the acceptable range (1.1 to 1.7 m³ /min [39–60 ft³ /min]), use a different filter, or adjust the sampler flow rate. Warning: Substantial flow adjustments may affect the calibration of the orifice-type flow indicators and may necessitate recalibration.

8.9 Record the sampler identification information (filter number, site location or identification number, sample date, and starting time).

8.10 Set the timer to start and stop the sampler such that the sampler runs 24-hrs, from midnight to midnight (local time).

8.11 As soon as practical following the sampling period, run the sampler for at least 5 min to again establish run-temperature conditions.

8.12 Record the flow indicator reading and, if needed, the barometric pressure (P³ ₃) and the ambient temperature (T³ ₃).

Note: No onsite pressure or temperature measurements are necessary if the sampler flow indicator does not require pressure or temperature corrections (e.g., a mass flowmeter) or if average barometric pressure and seasonal average temperature for the site are incorporated into the sampler calibration (see step 9.3.9). For individual pressure and temperature corrections, the ambient pressure and temperature can be obtained by onsite measurements or from a nearby weather station. Barometric pressure readings obtained from airports must be station pressure, not corrected to sea level, and may need to be corrected for differences in elevation between the sampler site and the airport. For samplers having flow recorders but not constant flow controllers, the average temperature and pressure at the site during the sampling period should be estimated from weather bureau or other available data.

8.13 Stop the sampler and carefully remove the filter, following the sampler manufacturer's instructions. Touch only the outer edges of the filter. See the precautions in step 8.6.

8.14 Fold the filter in half lengthwise so that only surfaces with collected particulate matter are in contact and place it in the filter holder (glassine envelope or manila folder).

8.15 Record the ending time or elapsed time on the filter information record, either from the stop set-point time, from an elapsed time indicator, or from a continuous flow record. The sample period must be 1,440 ±60 min. for a valid sample.

8.16 Record on the filter information record any other factors, such as meteorological conditions, construction activity, fires or dust storms, etc., that might be pertinent to the measurement. If the sample is known to be defective, void it at this time.

8.17 Equilibrate the exposed filter in the conditioning environment for at least 24-hrs.

8.18 Immediately after equilibration, reweigh the filter to the nearest milligram and record the gross weight with the filter identification number. See Section 10 for TSP concentration calculations.

9.0 Calibration.

9.1 Calibration of the high volume sampler's flow indicating or control device is necessary to establish traceability of the field measurement to a primary standard via a flow rate transfer standard. Figure 3a illustrates the certification of the flow rate transfer standard and Figure 3b illustrates its use in calibrating a sampler flow indicator. Determination of the corrected flow rate from the sampler flow indicator, illustrated in Figure 3c, is addressed in Section 10.1

Note: The following calibration procedure applies to a conventional orifice-type flow transfer standard and an orifice-type flow indicator in the sampler (the most common types). For samplers using a pressure recorder having a square-root scale, 3 other acceptable calibration procedures are provided in Reference 12. Other types of transfer standards may be used if the manufacturer or user provides an appropriately modified calibration procedure that has been approved by EPA under Section 2.8 of appendix C to part 58 of this chapter.

9.2 Certification of the flow rate transfer standard.

9.2.1 Equipment required: Positive displacement standard volume meter traceable to the National Bureau of Standards (such as a Roots meter or equivalent), stop-watch, manometer, thermometer, and barometer.

9.2.2 Connect the flow rate transfer standard to the inlet of the standard volume meter. Connect the manometer to measure the pressure at the inlet of the standard volume meter. Connect the orifice manometer to the pressure tap on the transfer standard. Connect a high-volume air pump (such as a high-volume sampler blower) to the outlet side of the standard volume meter. See Figure 3a.

9.2.3 Check for leaks by temporarily clamping both manometer lines (to avoid fluid loss) and blocking the orifice with a large-diameter rubber stopper, wide cellophane tape, or other suitable means. Start the high-volume air pump and note any change in the standard volume meter reading. The reading should remain constant. If the reading changes, locate any leaks by listening for a whistling sound and/or retightening all connections, making sure that all gaskets are properly installed.

9.2.4 After satisfactorily completing the leak check as described above, unclamp both manometer lines and zero both manometers.

9.2.5 Achieve the appropriate flow rate through the system, either by means of the variable flow resistance in the transfer standard or by varying the voltage to the air pump. (Use of resistance plates as shown in Figure 1a is discouraged because the above leak check must be repeated each time a new resistance plate is installed.) At least five different but constant flow rates, evenly distributed, with at least three in the specified flow rate interval (1.1 to 1.7 m³ /min [39–60 ft³ /min]), are required.

9.2.6 Measure and record the certification data on a form similar to the one illustrated in Figure 4 according to the following steps.

9.2.7 Observe the barometric pressure and record as P₁ (item 8 in Figure 4).

9.2.8 Read the ambient temperature in the vicinity of the standard volume meter and record it as T₁ (item 9 in Figure 4).

9.2.9 Start the blower motor, adjust the flow, and allow the system to run for at least 1 min for a constant motor speed to be attained.

9.2.10 Observe the standard volume meter reading and simultaneously start a stopwatch. Record the initial meter reading (V_i) in column 1 of Figure 4.

9.2.11 Maintain this constant flow rate until at least 3 m³ of air have passed through the standard volume meter. Record the standard volume meter inlet pressure manometer reading as ΔP (column 5 in Figure 4), and the orifice manometer reading as ΔH (column 7 in Figure 4). Be sure to indicate the correct units of measurement.

9.2.12 After at least 3 m³ of air have passed through the system, observe the standard volume meter reading while simultaneously stopping the stopwatch. Record the final meter reading (V_f) in column 2 and the elapsed time (t) in column 3 of Figure 4.

9.2.13 Calculate the volume measured by the standard volume meter at meter conditions of temperature and pressures as V_m=V_f−V_i. Record in column 4 of Figure 4.

9.2.14 Correct this volume to standard volume (std m³ ) as follows:

where:

V_std = standard volume, std m³ ;

V_m = actual volume measured by the standard volume meter;

P₁ = barometric pressure during calibration, mm Hg or kPa;

ΔP = differential pressure at inlet to volume meter, mm Hg or kPa;

P_std = 760 mm Hg or 101 kPa;

T_std = 298 K;

T₁ = ambient temperature during calibration, K.

Calculate the standard flow rate (std m³ /min) as follows:

where:

Q_std = standard volumetric flow rate, std m³ /min

t = elapsed time, minutes.

Record Q_std to the nearest 0.01 std m³ /min in column 6 of Figure 4.

9.2.15 Repeat steps 9.2.9 through 9.2.14 for at least four additional constant flow rates, evenly spaced over the approximate range of 1.0 to 1.8 std m³ /min (35–64 ft³ /min).

9.2.16 For each flow, compute

√ΔΔH (P₁/P_std)(298/T₁)

(column 7a of Figure 4) and plot these value against Q_std as shown in Figure 3a. Be sure to use consistent units (mm Hg or kPa) for barometric pressure. Draw the orifice transfer standard certification curve or calculate the linear least squares slope (m) and intercept (b) of the certification curve:

√ΔΔH (P₁/P_std)(298/T₁)

=mQ_std+b. See Figures 3 and 4. A certification graph should be readable to 0.02 std m³ /min.

9.2.17 Recalibrate the transfer standard annually or as required by applicable quality control procedures. (See Reference 2.)

9.3 Calibration of sampler flow indicator.

Note: For samplers equipped with a flow controlling device, the flow controller must be disabled to allow flow changes during calibration of the sampler's flow indicator, or the alternate calibration of the flow controller given in 9.4 may be used. For samplers using an orifice-type flow indicator downstream of the motor, do not vary the flow rate by adjusting the voltage or power supplied to the sampler.

9.3.1 A form similar to the one illustrated in Figure 5 should be used to record the calibration data.

9.3.2 Connect the transfer standard to the inlet of the sampler. Connect the orifice manometer to the orifice pressure tap, as illustrated in Figure 3b. Make sure there are no leaks between the orifice unit and the sampler.

9.3.3 Operate the sampler for at least 5 minutes to establish thermal equilibrium prior to the calibration.

9.3.4 Measure and record the ambient temperature, T₂, and the barometric pressure, P₂, during calibration.

9.3.5 Adjust the variable resistance or, if applicable, insert the appropriate resistance plate (or no plate) to achieve the desired flow rate.

9.3.6 Let the sampler run for at least 2 min to re-establish the run-temperature conditions. Read and record the pressure drop across the orifice (ΔH) and the sampler flow rate indication (I) in the appropriate columns of Figure 5.

9.3.7 Calculate √ΔΔH(P₂/P_std)(298/T₂) and determine the flow rate at standard conditions (Q_std) either graphically from the certification curve or by calculating Q_std from the least square slope and intercept of the transfer standard's transposed certification curve: Q_std=1/m √ΔH(P₂/P_std)(298/T₂)−b. Record the value of Q_std on Figure 5.

9.3.8 Repeat steps 9.3.5, 9.3.6, and 9.3.7 for several additional flow rates distributed over a range that includes 1.1 to 1.7 std m³ /min.

9.3.9 Determine the calibration curve by plotting values of the appropriate expression involving I, selected from table 1, against Q_std. The choice of expression from table 1 depends on the flow rate measurement device used (see Section 7.4.1) and also on whether the calibration curve is to incorporate geographic average barometric pressure (P_a) and seasonal average temperature (T_a) for the site to approximate actual pressure and temperature. Where P_a and T_a can be determined for a site for a seasonal period such that the actual barometric pressure and temperature at the site do not vary by more than ±60 mm Hg (8 kPa) from P_a or ±15 °C from T_a, respectively, then using P_a and T_a avoids the need for subsequent pressure and temperature calculation when the sampler is used. The geographic average barometric pressure (P_a) may be estimated from an altitude-pressure table or by making an (approximate) elevation correction of −26 mm Hg (−3.46 kPa) for each 305 m (1,000 ft) above sea level (760 mm Hg or 101 kPa). The seasonal average temperature (T_a) may be estimated from weather station or other records. Be sure to use consistent units (mm Hg or kPa) for barometric pressure.

9.3.10 Draw the sampler calibration curve or calculate the linear least squares slope (m), intercept (b), and correlation coefficient of the calibration curve: [Expression from table 1]= mQ_std+b. See Figures 3 and 5. Calibration curves should be readable to 0.02 std m³ /min.

9.3.11 For a sampler equipped with a flow controller, the flow controlling mechanism should be re-enabled and set to a flow near the lower flow limit to allow maximum control range. The sample flow rate should be verified at this time with a clean filter installed. Then add two or more filters to the sampler to see if the flow controller maintains a constant flow; this is particularly important at high altitudes where the range of the flow controller may be reduced.

9.4 Alternate calibration of flow-controlled samplers. A flow-controlled sampler may be calibrated solely at its controlled flow rate, provided that previous operating history of the sampler demonstrates that the flow rate is stable and reliable. In this case, the flow indicator may remain uncalibrated but should be used to indicate any relative change between initial and final flows, and the sampler should be recalibrated more often to minimize potential loss of samples because of controller malfunction.

9.4.1 Set the flow controller for a flow near the lower limit of the flow range to allow maximum control range.

9.4.2 Install a clean filter in the sampler and carry out steps 9.3.2, 9.3.3, 9.3.4, 9.3.6, and 9.3.7.

9.4.3 Following calibration, add one or two additional clean filters to the sampler, reconnect the transfer standard, and operate the sampler to verify that the controller maintains the same calibrated flow rate; this is particularly important at high altitudes where the flow control range may be reduced.

10.0 Calculations of TSP Concentration.

10.1 Determine the average sampler flow rate during the sampling period according to either 10.1.1 or 10.1.2 below.

10.1.1 For a sampler without a continuous flow recorder, determine the appropriate expression to be used from table 2 corresponding to the one from table 1 used in step 9.3.9. Using this appropriate expression, determine Q_std for the initial flow rate from the sampler calibration curve, either graphically or from the transposed regression equation:

Q_std =

1/m ([Appropriate expression from table 2]−b)

Similarly, determine Q_std from the final flow reading, and calculate the average flow Q_std as one-half the sum of the initial and final flow rates.

10.1.2 For a sampler with a continuous flow recorder, determine the average flow rate device reading, I, for the period. Determine the appropriate expression from table 2 corresponding to the one from table 1 used in step 9.3.9. Then using this expression and the average flow rate reading, determine Q_std from the sampler calibration curve, either graphically or from the transposed regression equation:

Q_std =

1/m ([Appropriate expression from table 2]−b)

If the trace shows substantial flow change during the sampling period, greater accuracy may be achieved by dividing the sampling period into intervals and calculating an average reading before determining Q_std.

10.2 Calculate the total air volume sampled as:

V−Q_std×t

where:

V = total air volume sampled, in standard volume units, std m³ /;

Q_std = average standard flow rate, std m³ /min;

t = sampling time, min.

10.3 Calculate and report the particulate matter concentration as:

where:

TSP = mass concentration of total suspended particulate matter, µg/std m³ ;

W_i = initial weight of clean filter, g;

W_f = final weight of exposed filter, g;

V = air volume sampled, converted to standard conditions, std m³ ,

10⁶ = conversion of g to µg.

10.4 If desired, the actual particulate matter concentration (see Section 2.2) can be calculated as follows:

(TSP)_a=TSP (P₃/P_std)(298/T₃)

where:

(TSP)_a = actual concentration at field conditions, µg/m³ ;

TSP = concentration at standard conditions, µg/std m³ ;

P₃ = average barometric pressure during sampling period, mm Hg;

P_std = 760 mn Hg (or 101 kPa);

T₃ = average ambient temperature during sampling period, K.

11.0 References.

1. Quality Assurance Handbook for Air Pollution Measurement Systems, Volume I, Principles. EPA–600/9–76–005, U.S. Environmental Protection Agency, Research Triangle Park, NC 27711, 1976.

2. Quality Assurance Handbook for Air Pollution Measurement Systems, Volume II, Ambient Air Specific Methods. EPA–600/4–77–027a, U.S. Environmental Protection Agency, Research Triangle Park, NC 27711, 1977.

3. Wedding, J. B., A. R. McFarland, and J. E. Cernak. Large Particle Collection Characteristics of Ambient Aerosol Samplers. Environ. Sci. Technol. 11:387–390, 1977.

4. McKee, H. C., et al. Collaborative Testing of Methods to Measure Air Pollutants, I. The High-Volume Method for Suspended Particulate Matter. J. Air Poll. Cont. Assoc., 22 (342), 1972.

5. Clement, R. E., and F. W. Karasek. Sample Composition Changes in Sampling and Analysis of Organic Compounds in Aerosols. The Intern. J. Environ. Anal. Chem., 7:109, 1979.

6. Lee, R. E., Jr., and J. Wagman. A Sampling Anomaly in the Determination of Atmospheric Sulfuric Concentration. Am. Ind. Hygiene Assoc. J., 27:266, 1966.

7. Appel, B. R., et al. Interference Effects in Sampling Particulate Nitrate in Ambient Air. Atmospheric Environment, 13:319, 1979.

8. Tierney, G. P., and W. D. Conner. Hygroscopic Effects on Weight Determinations of Particulates Collected on Glass-Fiber Filters. Am. Ind. Hygiene Assoc. J., 28:363, 1967.

9. Chahal, H. S., and D. J. Romano. High-Volume Sampling Effect of Windborne Particulate Matter Deposited During Idle Periods. J. Air Poll. Cont. Assoc., Vol. 26 (885), 1976.

10. Patterson, R. K. Aerosol Contamination from High-Volume Sampler Exhaust. J. Air Poll. Cont. Assoc., Vol. 30 (169), 1980.

11. EPA Test Procedures for Determining pH and Integrity of High-Volume Air Filters. QAD/M–80.01. Available from the Methods Standardization Branch, Quality Assurance Division, Environmental Monitoring Systems Laboratory (MD–77), U.S. Environmental Protection Agency, Research Triangle Park, NC 27711, 1980.

12. Smith, F., P. S. Wohlschlegel, R. S. C. Rogers, and D. J. Mulligan. Investigation of Flow Rate Calibration Procedures Associated with the High-Volume Method for Determination of Suspended Particulates. EPA–600/4–78–047, U.S. Environmental Protection Agency, Research Triangle Park, NC, June 1978.

[47 FR 54912, Dec. 6, 1982; 48 FR 17355, Apr. 22, 1983]