Title 40—Protection of Environment–Volume 2

A standard wavelength filter traceable to the National Bureau of Standards is used to verify the wavelength calibration according to the procedure enclosed with the filter. The wavelength calibration must be verified upon initial receipt of the instrument and after each 160 hours of normal use or every 6 months, whichever occurs first.

7.3.2 Spectrophotometer cells: A set of 1-cm path length cells suitable for use in the visible region is used during analysis. If the cells are unmatched, a matching correction factor must be determined according to Section 10.1.

7.3.3 Temperature control device: The color development step during analysis must be conducted in an environment that is in the range of 20° to 30 °C and controlled to ±1 °C. Both calibration and sample analysis must be performed under identical conditions (within 1 °C). Adequate temperature control may be obtained by means of constant temperature baths, water baths with manual temperature control, or temperature controlled rooms.

7.3.4 Glassware: Class A volumetric glassware of various capacities is required for preparing and standardizing reagents and standards and for dispensing solutions during analysis. These included pipets, volumetric flasks, and burets.

7.3.5 TCM waste receptacle: A glass waste receptacle is required for the storage of spent TCM solution. This vessel should be stoppered and stored in a hood at all times.

8.0 Reagents.

8.1 Sampling.

8.1.1 Distilled water: Purity of distilled water must be verified by the following procedure:(18)

8.1.2 Absorbing reagent (0.04 M potassium tetrachloromercurate [TCM]): Dissolve 10.86 g mercuric chloride, 0.066 g EDTA, and 6.0 g potassium chloride in distilled water and dilute to volume with distilled water in a 1,000-mL volumetric flask. (Caution: Mercuric chloride is highly poisonous. If spilled on skin, flush with water immediately.) The pH of this reagent should be between 3.0 and 5.0 (10) Check the pH of the absorbing solution by using pH indicating paper or a pH meter. If the pH of the solution is not between 3.0 and 5.0, dispose of the solution according to one of the disposal techniques described in Section 13.0. The absorbing reagent is normally stable for 6 months. If a precipitate forms, dispose of the reagent according to one of the procedures described in Section 13.0.

8.2 Analysis.

8.2.1 Sulfamic acid (0.6%): Dissolve 0.6 g sulfamic acid in 100 mL distilled water. Perpare fresh daily.

8.2.2 Formaldehyde (0.2%): Dilute 5 mL formaldehyde solution (36 to 38 percent) to 1,000 mL with distilled water. Prepare fresh daily.

8.2.3 Stock iodine solution (0.1 N): Place 12.7 g resublimed iodine in a 250-mL beaker and add 40 g potassium iodide and 25 mL water. Stir until dissolved, transfer to a 1,000 mL volumetric flask and dilute to volume with distilled water.

8.2.4 Iodine solution (0.01 N): Prepare approximately 0.01 N iodine solution by diluting 50 mL of stock iodine solution (Section 8.2.3) to 500 mL with distilled water.

8.2.5 Starch indicator solution: Triturate 0.4 g soluble starch and 0.002 g mercuric iodide (preservative) with enough distilled water to form a paste. Add the paste slowly to 200 mL of boiling distilled water and continue boiling until clear. Cool and transfer the solution to a glass stopperd bottle.

8.2.6 1 N hydrochloric acid: Slowly and while stirring, add 86 mL of concentrated hydrochloric acid to 500 mL of distilled water. Allow to cool and dilute to 1,000 mL with distilled water.

8.2.7 Potassium iodate solution: Accurately weigh to the nearest 0.1 mg, 1.5 g (record weight) of primary standard grade potassium iodate that has been previously dried at 180 °C for at least 3 hours and cooled in a dessicator. Dissolve, then dilute to volume in a 500-mL volumetric flask with distilled water.

8.2.8 Stock sodium thiosulfate solution (0.1 N): Prepare a stock solution by dissolving 25 g sodium thiosulfate (Na2 S2 O3 ÷ 5H2 O) in 1,000 mL freshly boiled, cooled, distilled water and adding 0.1 g sodium carbonate to the solution. Allow the solution to stand at least 1 day before standardizing. To standardize, accurately pipet 50 mL of potassium iodate solution (Section 8.2.7) into a 500-mL iodine flask and add 2.0 g of potassium iodide and 10 mL of 1 N HCl. Stopper the flask and allow to stand for 5 minutes. Titrate the solution with stock sodium thiosulfate solution (Section 8.2.8) to a pale yellow color. Add 5 mL of starch solution (Section 8.2.5) and titrate until the blue color just disappears. Calculate the normality (Ns) of the stock sodium thiosulfate solution as follows:

8.2.9 Working sodium thiosulfate titrant (0.01 N): Accurately pipet 100 mL of stock sodium thiosulfate solution (Section 8.2.8) into a 1,000-mL volumetric flask and dilute to volume with freshly boiled, cooled, distilled water. Calculate the normality of the working sodium thiosulfate titrant (NT) as follows:

8.2.10 Standardized sulfite solution for the preparation of working sulfite-TCM solution: Dissolve 0.30 g sodium metabisulfite (Na2 S2 O5) or 0.40 g sodium sulfite (Na2 SO3) in 500 mL of recently boiled, cooled, distilled water. (Sulfite solution is unstable; it is therefore important to use water of the highest purity to minimize this instability.) This solution contains the equivalent of 320 to 400 µg SO2/mL. The actual concentration of the solution is determined by adding excess iodine and back-titrating with standard sodium thiosulfate solution. To back-titrate, pipet 50 mL of the 0.01 N iodine solution (Section 8.2.4) into each of two 500-mL iodine flasks (A and B). To flask A (blank) add 25 mL distilled water, and to flask B (sample) pipet 25 mL sulfite solution. Stopper the flasks and allow to stand for 5 minutes. Prepare the working sulfite-TCM solution (Section 8.2.11) immediately prior to adding the iodine solution to the flasks. Using a buret containing standardized 0.01 N thiosulfate titrant (Section 8.2.9), titrate the solution in each flask to a pale yellow color. Then add 5 mL starch solution (Section 8.2.5) and continue the titration until the blue color just disappears.

8.2.11 Working sulfite-TCM solution: Accurately pipet 5 mL of the standard sulfite solution (Section 8.2.10) into a 250-mL volumetric flask and dilute to volume with 0.04 M TCM. Calculate the concentration of sulfur dioxide in the working solution as follows:

This solution is stable for 30 days if kept at 5 °C. (16) If not kept at 5 °C, prepare fresh daily.

8.2.12 Purified pararosaniline (PRA) stock solution (0.2% nominal):

8.2.12.1 Dye specifications—

8.2.12.2 Preparation of stock PRA solution—A specially purified (99 to 100 percent pure) solution of pararosaniline, which meets the above specifications, is commercially available in the required 0.20 percent concentration (Harleco Co.). Alternatively, the dye may be purified, a stock solution prepared, and then assayed according to the procedure as described below.(10)

8.2.12.3 Purification procedure for PRA—

1. Place 100 mL each of 1-butanol and 1 N HCl in a large separatory funnel (250-mL) and allow to equilibrate. Note: Certain batches of 1-butanol contain oxidants that create an SO2 demand. Before using, check by placing 20 mL of 1-butanol and 5 mL of 20 percent potassium iodide (KI) solution in a 50-mL separatory funnel and shake thoroughly. If a yellow color appears in the alcohol phase, redistill the 1-butanol from silver oxide and collect the middle fraction or purchase a new supply of 1-butanol.

2. Weigh 100 mg of pararosaniline hydrochloride dye (PRA) in a small beaker. Add 50 mL of the equilibrated acid (drain in acid from the bottom of the separatory funnel in 1.) to the beaker and let stand for several minutes. Discard the remaining acid phase in the separatory funnel.

3. To a 125-mL separatory funnel, add 50 mL of the equilibrated 1-butanol (draw the 1-butanol from the top of the separatory funnel in 1.). Transfer the acid solution (from 2.) containing the dye to the funnel and shake carefully to extract. The violet impurity will transfer to the organic phase.

4. Transfer the lower aqueous phase into another separatory funnel, add 20 mL of equilibrated 1-butanol, and extract again.

5. Repeat the extraction procedure with three more 10-mL portions of equilibrated 1-butanol.

6. After the final extraction, filter the acid phase through a cotton plug into a 50-mL volumetric flask and bring to volume with 1 N HCl. This stock reagent will be a yellowish red.

7. To check the purity of the PRA, perform the assay and adjustment of concentration (Section 8.2.12.4) and prepare a reagent blank (Section 11.2); the absorbance of this reagent blank at 540 nm should be less than 0.170 at 22 °C. If the absorbance is greater than 0.170 under these conditions, further extractions should be performed.

8.2.12.4 PRA assay procedure—The concentration of pararosaniline hydrochloride (PRA) need be assayed only once after purification. It is also recommended that commercial solutions of pararosaniline be assayed when first purchased. The assay procedure is as follows:(10)

1. Prepare 1 M acetate-acetic acid buffer stock solution with a pH of 4.79 by dissolving 13.61 g of sodium acetate trihydrate in distilled water in a 100-mL volumetric flask. Add 5.70 mL of glacial acetic acid and dilute to volume with distilled water.

2. Pipet 1 mL of the stock PRA solution obtained from the purification process or from a commercial source into a 100-mL volumetric flask and dilute to volume with distilled water.

3. Transfer a 5–mL aliquot of the diluted PRA solution from 2. into a 50–mL volumetric flask. Add 5mL of 1 M acetate-acetic acid buffer solution from 1. and dilute the mixture to volume with distilled water. Let the mixture stand for 1 hour.

4. Measure the absorbance of the above solution at 540 nm with a spectrophotometer against a distilled water reference. Compute the percentage of nominal concentration of PRA by

8.2.13 Pararosaniline reagent: To a 250–mL volumetric flask, add 20 mL of stock PRA solution. Add an additional 0.2 mL of stock solution for each percentage that the stock assays below 100 percent. Then add 25 mL of 3 M phosphoric acid and dilute to volume with distilled water. The reagent is stable for at least 9 months. Store away from heat and light.

9.0 Sampling Procedure.

9.1 General Considerations. Procedures are described for short-term sampling (30-minute and 1-hour) and for long-term sampling (24-hour). Different combinations of absorbing reagent volume, sampling rate, and sampling time can be selected to meet special needs. For combinations other than those specifically described, the conditions must be adjusted so that linearity is maintained between absorbance and concentration over the dynamic range. Absorbing reagent volumes less than 10 mL are not recommended. The collection efficiency is above 98 percent for the conditions described; however, the efficiency may be substantially lower when sampling concentrations below 25 µγSO2/m
3.(8,9)

9.2 30-Minute and 1-Hour Sampling. Place 10 mL of TCM absorbing reagent in a midget impinger and seal the impinger with a thin film of silicon stopcock grease (around the ground glass joint). Insert the sealed impinger into the sampling train as shown in Figure 1, making sure that all connections between the various components are leak tight. Greaseless ball joint fittings, heat shrinkable Teflon ® tubing, or Teflon ® tube fittings may be used to attain leakfree conditions for portions of the sampling train that come into contact with air containing SO2. Shield the absorbing reagent from direct sunlight by covering the impinger with aluminum foil or by enclosing the sampling train in a light-proof box. Determine the flow rate according to Section 9.4.2. Collect the sample at 1 ±0.10 L/min for 30-minute sampling or 0.500 ±0.05 L/min for 1-hour sampling. Record the exact sampling time in minutes, as the sample volume will later be determined using the sampling flow rate and the sampling time. Record the atmospheric pressure and temperature.

9.3 24-Hour Sampling. Place 50 mL of TCM absorbing solution in a large absorber, close the cap, and, if needed, apply the heat shrink material as shown in Figure 3. Verify that the reagent level is at the 50 mL mark on the absorber. Insert the sealed absorber into the sampling train as shown in Figure 2. At this time verify that the absorber temperature is controlled to 15 ±10 °C. During sampling, the absorber temperature must be controlled to prevent decomposition of the collected complex. From the onset of sampling until analysis, the absorbing solution must be protected from direct sunlight. Determine the flow rate according to Section 9.4.2. Collect the sample for 24 hours from midnight to midnight at a flow rate of 0.200 ±0.020 L/min. A start/stop timer is helpful for initiating and stopping sampling and an elapsed time meter will be useful for determining the sampling time.

9.4 Flow Measurement.

9.4.1 Calibration: Flow measuring devices used for the on-site flow measurements required in 9.4.2 must be calibrated against a reliable flow or volume standard such as an NBS traceable bubble flowmeter or calibrated wet test meter. Rotameters or critical orifices used in the sampling train may be calibrated, if desired, as a quality control check, but such calibration shall not replace the on-site flow measurements required by 9.4.2. In-line rotameters, if they are to be calibrated, should be calibrated in situ, with the appropriate volume of solution in the absorber.

9.4.2 Determination of flow rate at sampling site: For short-term samples, the standard flow rate is determined at the sampling site at the initiation and completion of sample collection with a calibrated flow measuring device connected to the inlet of the absorber. For 24-hour samples, the standard flow rate is determined at the time the absorber is placed in the sampling train and again when the absorber is removed from the train for shipment to the analytical laboratory with a calibrated flow measuring device connected to the inlet of the sampling train. The flow rate determination must be made with all components of the sampling system in operation (e.g., the absorber temperature controller and any sample box heaters must also be operating). Equation 6 may be used to determine the standard flow rate when a calibrated positive displacement meter is used as the flow measuring device. Other types of calibrated flow measuring devices may also be used to determine the flow rate at the sampling site provided that the user applies any appropriate corrections to devices for which output is dependent on temperature or pressure.

If a barometer is not available, the following equation may be used to determine the barometric pressure:

If the initial flow rate (Qi) differs from the flow rate of the critical orifice or the flow rate indicated by the flowmeter in the sampling train (Qc) by more than 5 percent as determined by equation (8), check for leaks and redetermine Qi.

Invalidate the sample if the difference between the initial (Qi) and final (Qf) flow rates is more than 5 percent as determined by equation (9):

9.5 Sample Storage and Shipment. Remove the impinger or absorber from the sampling train and stopper immediately. Verify that the temperature of the absorber is not above 25 °C. Mark the level of the solution with a temporary (e.g., grease pencil) mark. If the sample will not be analyzed within 12 hours of sampling, it must be stored at 5° ±5 °C until analysis. Analysis must occur within 30 days. If the sample is transported or shipped for a period exceeding 12 hours, it is recommended that thermal coolers using eutectic ice packs, refrigerated shipping containers, etc., be used for periods up to 48 hours. (17) Measure the temperature of the absorber solution when the shipment is received. Invalidate the sample if the temperature is above 10 °C. Store the sample at 5° ±5 °C until it is analyzed.

10.0 Analytical Calibration.

10.1 Spectrophotometer Cell Matching. If unmatched spectrophotometer cells are used, an absorbance correction factor must be determined as follows:

1. Fill all cells with distilled water and designate the one that has the lowest absorbance at 548 nm as the reference. (This reference cell should be marked as such and continually used for this purpose throughout all future analyses.)

2. Zero the spectrophotometer with the reference cell.

3. Determine the absorbance of the remaining cells (Ac) in relation to the reference cell and record these values for future use. Mark all cells in a manner that adequately identifies the correction.

The corrected absorbance during future analyses using each cell is determining as follows:

10.2 Static Calibration Procedure (Option 1). Prepare a dilute working sulfite-TCM solution by diluting 10 mL of the working sulfite-TCM solution (Section 8.2.11) to 100 mL with TCM absorbing reagent. Following the table below, accurately pipet the indicated volumes of the sulfite-TCM solutions into a series of 25-mL volumetric flasks. Add TCM absorbing reagent as indicated to bring the volume in each flask to 10 mL.

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:

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 (Bs) 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/m
3 (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/m
3) by adjusting the dilution flow rates appropriately. The concentration of SO2 in each atmosphere is calculated as follows:

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 (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:

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 (Bg) 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/m
3 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:

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:

Calculate a calibration equation and a calibration factor (Bt) 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 (

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 standards containing approximately 5 and 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 (

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:

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

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:

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

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

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/m
3 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.

Appendix B to Part 50—Reference Method for the Determination of Suspended Particulate Matter in the Atmosphere (High-Volume Method)

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 m
3). 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 m
3. 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.)

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 cm
2 (63 in
2).

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 m
3/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 m
3/min (39 ft
3/min).‡

7.2.3 Maximum sample flow rate, clean filter: 1.7 m
3/min (60 ft
3/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 m
3/min over the range 1.0 to 1.8 std m
3/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 m
3/min.

7.8.2 Resolution: 0.02 m
3/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 m
3/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 m
3/min (35–64 ft
3/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 (Wi) 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 (P
33) and the ambient temperature (T
33) 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 m
3/min [39–60 ft
3/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 (P
33) and the ambient temperature (T
33).

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

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 m
3/min [39–60 ft
3/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 (Vi) in column 1 of Figure 4.

9.2.11 Maintain this constant flow rate until at least 3 m
3 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 m
3 of air have passed through the system, observe the standard volume meter reading while simultaneously stopping the stopwatch. Record the final meter reading (Vf) 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 Vm = Vf−Vi. Record in column 4 of Figure 4.

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

Record Qstd to the nearest 0.01 std m
3/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 m
3/min (35–64 ft
3/min).

9.2.16 For each flow, compute

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.

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/Pstd)(298/T2) and determine the flow rate at standard conditions (Qstd) either graphically from the certification curve or by calculating Qstd from the least square slope and intercept of the transfer standard’s transposed certification curve: Qstd = 1/m √ΔH(P2/Pstd)(298/T2)−b. Record the value of Qstd 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 m
3/min.

9.3.9 Determine the calibration curve by plotting values of the appropriate expression involving I, selected from table 1, against Qstd. 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 (Pa) and seasonal average temperature (Ta) for the site to approximate actual pressure and temperature. Where Pa and Ta 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 Pa or ±15 °C from Ta, respectively, then using Pa and Ta avoids the need for subsequent pressure and temperature calculation when the sampler is used. The geographic average barometric pressure (Pa) 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 (Ta) 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]= mQstd + b. See Figures 3 and 5. Calibration curves should be readable to 0.02 std m
3/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 Qstd for the initial flow rate from the sampler calibration curve, either graphically or from the transposed regression equation:

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 Qstd from the sampler calibration curve, either graphically or from the transposed regression equation:

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 Qstd.

10.2 Calculate the total air volume sampled as:

10.3 Calculate and report the particulate matter concentration as:

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

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.

Appendix C to Part 50—Measurement Principle and Calibration Procedure for the Measurement of Carbon Monoxide in the Atmosphere (Non-Dispersive Infrared Photometry)

1.0 Applicability

1.1 This non-dispersive infrared photometry (NDIR) Federal Reference Method (FRM) provides measurements of the concentration of carbon monoxide (CO) in ambient air for determining compliance with the primary and secondary National Ambient Air Quality Standards (NAAQS) for CO as specified in § 50.8 of this chapter. The method is applicable to continuous sampling and measurement of ambient CO concentrations suitable for determining 1-hour or longer average measurements. The method may also provide measurements of shorter averaging times, subject to specific analyzer performance limitations. Additional CO monitoring quality assurance procedures and guidance are provided in part 58, appendix A, of this chapter and in reference 1 of this appendix C.

2.1 Measurements of CO in ambient air are based on automated measurement of the absorption of infrared radiation by CO in an ambient air sample drawn into an analyzer employing non-wavelength-dispersive, infrared photometry (NDIR method). Infrared energy from a source in the photometer is passed through a cell containing the air sample to be analyzed, and the quantitative absorption of energy by CO in the sample cell is measured by a suitable detector. The photometer is sensitized specifically to CO by employing CO gas in a filter cell in the optical path, which, when compared to a differential optical path without a CO filter cell, limits the measured absorption to one or more of the characteristic wavelengths at which CO strongly absorbs. However, to meet measurement performance requirements, various optical filters, reference cells, rotating gas filter cells, dual-beam configurations, moisture traps, or other means may also be used to further enhance sensitivity and stability of the photometer and to minimize potential measurement interference from water vapor, carbon dioxide (CO2), or other species. Also, various schemes may be used to provide a suitable zero reference for the photometer, and optional automatic compensation may be provided for the actual pressure and temperature of the air sample in the measurement cell. The measured infrared absorption, converted to a digital reading or an electrical output signal, indicates the measured CO concentration.

2.2 The measurement system is calibrated by referencing the analyzer’s CO measurements to CO concentration standards traceable to a National Institute of Standards and Technology (NIST) primary standard for CO, as described in the associated calibration procedure specified in section 4 of this reference method.

2.3 An analyzer implementing this measurement principle will be considered a reference method only if it has been designated as a reference method in accordance with part 53 of this chapter.

2.4 Sampling considerations. The use of a particle filter in the sample inlet line of a CO FRM analyzer is optional and left to the discretion of the user unless such a filter is specified or recommended by the analyzer manufacturer in the analyzer’s associated operation or instruction manual.

3.1 The NDIR measurement principle is potentially susceptible to interference from water vapor and CO2, which have some infrared absorption at wavelengths in common with CO and normally exist in the atmosphere. Various instrumental techniques can be used to effectively minimize these interferences.

4.1 Principle. Either of two methods may be selected for dynamic multipoint calibration of FRM CO analyzers, using test gases of accurately known CO concentrations obtained from one or more compressed gas cylinders certified as CO transfer standards:

4.1.1 Dilution method: A single certified standard cylinder of CO is quantitatively diluted as necessary with zero air to obtain the various calibration concentration standards needed.

4.1.2 Multiple-cylinder method: Multiple, individually certified standard cylinders of CO are used for each of the various calibration concentration standards needed.

4.1.3 Additional information on calibration may be found in Section 12 of reference 1.

4.2 Apparatus. The major components and typical configurations of the calibration systems for the two calibration methods are shown in Figures 1 and 2. Either system may be made up using common laboratory components, or it may be a commercially manufactured system. In either case, the principal components are as follows:

4.2.1 CO standard gas flow control and measurement devices (or a combined device) capable of regulating and maintaining the standard gas flow rate constant to within ±2 percent and measuring the gas flow rate accurate to within ±2 percent, properly calibrated to a NIST-traceable standard.

4.2.2 For the dilution method (Figure 1), dilution air flow control and measurement devices (or a combined device) capable of regulating and maintaining the air flow rate constant to within ±2 percent and measuring the air flow rate accurate to within ±2 percent, properly calibrated to a NIST-traceable standard.

4.2.3 Standard gas pressure regulator(s) for the standard CO cylinder(s), suitable for use with a high-pressure CO gas cylinder and having a non-reactive diaphragm and internal parts and a suitable delivery pressure.

4.2.4 Mixing chamber for the dilution method of an inert material and of proper design to provide thorough mixing of CO standard gas and diluent air streams.

4.2.5 Output sampling manifold, constructed of an inert material and of sufficient diameter to ensure an insignificant pressure drop at the analyzer connection. The system must have a vent designed to ensure nearly atmospheric pressure at the analyzer connection port and to prevent ambient air from entering the manifold.

4.3.1 CO gas concentration transfer standard(s) of CO in air, containing an appropriate concentration of CO suitable for the selected operating range of the analyzer under calibration and traceable to a NIST standard reference material (SRM). If the CO analyzer has significant sensitivity to CO2, the CO standard(s) should also contain 350 to 400 ppm CO2 to replicate the typical CO2 concentration in ambient air. However, if the zero air dilution ratio used for the dilution method is not less than 100:1 and the zero air contains ambient levels of CO2, then the CO standard may be contained in nitrogen and need not contain CO2.

4.3.2 For the dilution method, clean zero air, free of contaminants that could cause a detectable response on or a change in sensitivity of the CO analyzer. The zero air should contain
4.4 Procedure Using the Dilution Method

4.4.1 Assemble or obtain a suitable dynamic dilution calibration system such as the one shown schematically in Figure 1. Generally, all calibration gases including zero air must be introduced into the sample inlet of the analyzer. However, if the analyzer has special, approved zero and span inlets and automatic valves to specifically allow introduction of calibration standards at near atmospheric pressure, such inlets may be used for calibration in lieu of the sample inlet. For specific operating instructions, refer to the manufacturer’s manual.

4.4.2 Ensure that there are no leaks in the calibration system and that all flowmeters are properly and accurately calibrated, under the conditions of use, if appropriate, against a reliable volume or flow rate standard such as a soap-bubble meter or wet-test meter traceable to a NIST standard. All volumetric flow rates should be corrected to the same temperature and pressure such as 298.15 K (25 °C) and 760 mm Hg (101 kPa), using a correction formula such as the following:

4.4.3 Select the operating range of the CO analyzer to be calibrated. Connect the measurement signal output of the analyzer to an appropriate readout instrument to allow the analyzer’s measurement output to be continuously monitored during the calibration. Where possible, this readout instrument should be the same one used to record routine monitoring data, or, at least, an instrument that is as closely representative of that system as feasible.

4.4.4 Connect the inlet of the CO analyzer to the output-sampling manifold of the calibration system.

4.4.5 Adjust the calibration system to deliver zero air to the output manifold. The total air flow must exceed the total demand of the analyzer(s) connected to the output manifold to ensure that no ambient air is pulled into the manifold vent. Allow the analyzer to sample zero air until a stable response is obtained. After the response has stabilized, adjust the analyzer zero reading.

4.4.6 Adjust the zero air flow rate and the CO gas flow rate from the standard CO cylinder to provide a diluted CO concentration of approximately 80 percent of the measurement upper range limit (URL) of the operating range of the analyzer. The total air flow rate must exceed the total demand of the analyzer(s) connected to the output manifold to ensure that no ambient air is pulled into the manifold vent. The exact CO concentration is calculated from:

4.4.7 Generate several additional concentrations (at least three evenly spaced points across the remaining scale are suggested to verify linearity) by decreasing FCO or increasing FD. Be sure the total flow exceeds the analyzer’s total flow demand. For each concentration generated, calculate the exact CO concentration using equation (2). Record the concentration and the analyzer’s stable response for each concentration. Plot the analyzer responses (vertical or y-axis) versus the corresponding CO concentrations (horizontal or x-axis). Calculate the linear regression slope and intercept of the calibration curve and verify that no point deviates from this line by more than 2 percent of the highest concentration tested.

4.5 Procedure Using the Multiple-Cylinder Method. Use the procedure for the dilution method with the following changes:

4.5.1 Use a multi-cylinder, dynamic calibration system such as the typical one shown in Figure 2.

4.5.2 The flowmeter need not be accurately calibrated, provided the flow in the output manifold can be verified to exceed the analyzer’s flow demand.

4.5.3 The various CO calibration concentrations required in Steps 4.4.5, 4.4.6, and 4.4.7 are obtained without dilution by selecting zero air or the appropriate certified standard cylinder.

4.6 Frequency of Calibration. The frequency of calibration, as well as the number of points necessary to establish the calibration curve and the frequency of other performance checking, will vary by analyzer. However, the minimum frequency, acceptance criteria, and subsequent actions are specified in reference 1, appendix D, “Measurement Quality Objectives and Validation Template for CO” (page 5 of 30). The user’s quality control program should provide guidelines for initial establishment of these variables and for subsequent alteration as operational experience is accumulated. Manufacturers of CO analyzers should include in their instruction/operation manuals information and guidance as to these variables and on other matters of operation, calibration, routine maintenance, and quality control.

1. QA Handbook for Air Pollution Measurement Systems—Volume II. Ambient Air Quality Monitoring Program. U.S. EPA. EPA–454/B–08–003 (2008).

Appendix D to Part 50—Reference Measurement Principle and Calibration Procedure for the Measurement of Ozone in the Atmosphere (Chemiluminescence Method)

1.0 Applicability.

1.1 This chemiluminescence method provides reference measurements of the concentration of ozone (O3) in ambient air for determining compliance with the national primary and secondary ambient air quality standards for O3 as specified in 40 CFR part 50. This automated method is applicable to the measurement of ambient O3 concentrations using continuous (real-time) sampling and analysis. Additional quality assurance procedures and guidance are provided in 40 CFR part 58, appendix A, and in Reference 14.

2.0 Measurement Principle.

2.1 This reference method is based on continuous automated measurement of the intensity of the characteristic chemiluminescence released by the gas phase reaction of O3 in sampled air with either ethylene (C2H4) or nitric oxide (NO) gas. An ambient air sample stream and a specific flowing concentration of either C2H4 (ET–CL method) or NO (NO–CL method) are mixed in a measurement cell, where the resulting chemiluminescence is quantitatively measured by a sensitive photo-detector. References 8–11 describe the chemiluminescence measurement principle.

2.2 The measurement system is calibrated by referencing the instrumental chemiluminescence measurements to certified O3 standard concentrations generated in a dynamic flow system and assayed by photometry to be traceable to a National Institute of Standards and Technology (NIST) standard reference photometer for O3 (see Section 4, Calibration Procedure, below).

2.3 An analyzer implementing this measurement principle is shown schematically in Figure 1. Designs implementing this measurement principle must include: an appropriately designed mixing and measurement cell; a suitable quantitative photometric measurement system with adequate sensitivity and wavelength specificity for O3; a pump, flow control, and sample conditioning system for sampling the ambient air and moving it into and through the measurement cell; a sample air dryer as necessary to meet the water vapor interference limit requirement specified in subpart B of part 53 of this chapter; a means to supply, meter, and mix a constant, flowing stream of either C2H4 or NO gas of fixed concentration with the sample air flow in the measurement cell; suitable electronic control and measurement processing capability; and other associated apparatus as may be necessary. The analyzer must be designed and constructed to provide accurate, repeatable, and continuous measurements of O3 concentrations in ambient air, with measurement performance that meets the requirements specified in subpart B of part 53 of this chapter.

2.4 An analyzer implementing this measurement principle and calibration procedure will be considered a federal reference method (FRM) only if it has been designated as a reference method in accordance with part 53 of this chapter.

2.5 Sampling considerations. The use of a particle filter on the sample inlet line of a chemiluminescence O3 FRM analyzer is required to prevent buildup of particulate matter in the measurement cell and inlet components. This filter must be changed weekly (or at least often as specified in the manufacturer’s operation/instruction manual), and the sample inlet system used with the analyzer must be kept clean, to avoid loss of O3 in the O3 sample air prior to the concentration measurement.

3.0 Interferences.

3.1 Except as described in 3.2 below, the chemiluminescence measurement system is inherently free of significant interferences from other pollutant substances that may be present in ambient air.

3.2 A small sensitivity to variations in the humidity of the sample air is minimized by a sample air dryer. Potential loss of O3 in the inlet air filter and in the air sample handling components of the analyzer and associated exterior air sampling components due to buildup of airborne particulate matter is minimized by filter replacement and cleaning of the other inlet components.

4.0 Calibration Procedure.

4.1 Principle. The calibration procedure is based on the photometric assay of O3 concentrations in a dynamic flow system. The concentration of O3 in an absorption cell is determined from a measurement of the amount of 254 nm light absorbed by the sample. This determination requires knowledge of (1) the absorption coefficient (α) of O3 at 254 nm, (2) the optical path length (l) through the sample, (3) the transmittance of the sample at a nominal wavelength of 254 nm, and (4) the temperature (T) and pressure (P) of the sample. The transmittance is defined as the ratio I/I0, where I is the intensity of light which passes through the cell and is sensed by the detector when the cell contains an O3 sample, and I0 is the intensity of light which passes through the cell and is sensed by the detector when the cell contains zero air. It is assumed that all conditions of the system, except for the contents of the absorption cell, are identical during measurement of I and I0. The quantities defined above are related by the Beer-Lambert absorption law,

A stable O3 generator is used to produce O3 concentrations over the required calibration concentration range. Each O3 concentration is determined from the measurement of the transmittance (I/I0) of the sample at 254 nm with a photometer of path length l and calculated from the equation,

The calculated O3 concentrations must be corrected for O3 losses, which may occur in the photometer, and for the temperature and pressure of the sample.

4.2 Applicability. This procedure is applicable to the calibration of ambient air O3 analyzers, either directly or by means of a transfer standard certified by this procedure. Transfer standards must meet the requirements and specifications set forth in Reference 12.

4.3 Apparatus. A complete UV calibration system consists of an O3 generator, an output port or manifold, a photometer, an appropriate source of zero air, and other components as necessary. The configuration must provide a stable O3 concentration at the system output and allow the photometer to accurately assay the output concentration to the precision specified for the photometer (4.3.1). Figure 2 shows a commonly used configuration and serves to illustrate the calibration procedure, which follows. Other configurations may require appropriate variations in the procedural steps. All connections between components in the calibration system downstream of the O3 generator must be of glass, Teflon, or other relatively inert materials. Additional information regarding the assembly of a UV photometric calibration apparatus is given in Reference 13. For certification of transfer standards which provide their own source of O3, the transfer standard may replace the O3 generator and possibly other components shown in Figure 2; see Reference 12 for guidance.

4.3.1 UV photometer. The photometer consists of a low-pressure mercury discharge lamp, (optional) collimation optics, an absorption cell, a detector, and signal-processing electronics, as illustrated in Figure 2. It must be capable of measuring the transmittance, I/I0, at a wavelength of 254 nm with sufficient precision such that the standard deviation of the concentration measurements does not exceed the greater of 0.005 ppm or 3% of the concentration. Because the low-pressure mercury lamp radiates at several wavelengths, the photometer must incorporate suitable means to assure that no O3 is generated in the cell by the lamp, and that at least 99.5% of the radiation sensed by the detector is 254 nm radiation. (This can be readily achieved by prudent selection of optical filter and detector response characteristics.) The length of the light path through the absorption cell must be known with an accuracy of at least 99.5%. In addition, the cell and associated plumbing must be designed to minimize loss of O3 from contact with cell walls and gas handling components. See Reference 13 for additional information.

4.3.2 Air flow controllers. Air flow controllers are devices capable of regulating air flows as necessary to meet the output stability and photometer precision requirements.

4.3.3 Ozone generator. The ozone generator used must be capable of generating stable levels of O3 over the required concentration range.

4.3.4 Output manifold. The output manifold must be constructed of glass, Teflon, or other relatively inert material, and should be of sufficient diameter to insure a negligible pressure drop at the photometer connection and other output ports. The system must have a vent designed to insure atmospheric pressure in the manifold and to prevent ambient air from entering the manifold.

4.3.5 Two-way valve. A manual or automatic two-way valve, or other means is used to switch the photometer flow between zero air and the O3 concentration.

4.3.6 Temperature indicator. A device to indicate temperature must be used that is accurate to ±1 °C.

4.3.7 Barometer or pressure indicator. A device to indicate barometric pressure must be used that is accurate to ±2 torr.

4.4 Reagents.

4.4.1 Zero air. The zero air must be free of contaminants which would cause a detectable response from the O3 analyzer, and it must be free of NO, C2H4, and other species which react with O3. A procedure for generating suitable zero air is given in Reference 13. As shown in Figure 2, the zero air supplied to the photometer cell for the I0 reference measurement must be derived from the same source as the zero air used for generation of the O3 concentration to be assayed (I measurement). When using the photometer to certify a transfer standard having its own source of O3, see Reference 12 for guidance on meeting this requirement.

4.5 Procedure.

4.5.1 General operation. The calibration photometer must be dedicated exclusively to use as a calibration standard. It must always be used with clean, filtered calibration gases, and never used for ambient air sampling. A number of advantages are realized by locating the calibration photometer in a clean laboratory where it can be stationary, protected from the physical shock of transportation, operated by a responsible analyst, and used as a common standard for all field calibrations via transfer standards.

4.5.2 Preparation. Proper operation of the photometer is of critical importance to the accuracy of this procedure. Upon initial operation of the photometer, the following steps must be carried out with all quantitative results or indications recorded in a chronological record, either in tabular form or plotted on a graphical chart. As the performance and stability record of the photometer is established, the frequency of these steps may be reduced to be consistent with the documented stability of the photometer and the guidance provided in Reference 12.

4.5.2.1 Instruction manual. Carry out all set up and adjustment procedures or checks as described in the operation or instruction manual associated with the photometer.

4.5.2.2 System check. Check the photometer system for integrity, leaks, cleanliness, proper flow rates, etc. Service or replace filters and zero air scrubbers or other consumable materials, as necessary.

4.5.2.3 Linearity. Verify that the photometer manufacturer has adequately established that the linearity error of the photometer is less than 3%, or test the linearity by dilution as follows: Generate and assay an O3 concentration near the upper range limit of the system or appropriate calibration scale for the instrument, then accurately dilute that concentration with zero air and re-assay it. Repeat at several different dilution ratios. Compare the assay of the original concentration with the assay of the diluted concentration divided by the dilution ratio, as follows

The linearity error must be less than 5%. Since the accuracy of the measured flow-rates will affect the linearity error as measured this way, the test is not necessarily conclusive. Additional information on verifying linearity is contained in Reference 13.

4.5.2.4 Inter-comparison. The photometer must be inter-compared annually, either directly or via transfer standards, with a NIST standard reference photometer (SRP) or calibration photometers used by other agencies or laboratories.

4.5.2.5 Ozone losses. Some portion of the O3 may be lost upon contact with the photometer cell walls and gas handling components. The magnitude of this loss must be determined and used to correct the calculated O3 concentration. This loss must not exceed 5%. Some guidelines for quantitatively determining this loss are discussed in Reference 13.

4.5.3 Assay of O3 concentrations. The operator must carry out the following steps to properly assay O3 concentrations.

4.5.3.1 Allow the photometer system to warm up and stabilize.

4.5.3.2 Verify that the flow rate through the photometer absorption cell, F, allows the cell to be flushed in a reasonably short period of time (2 liter/min is a typical flow). The precision of the measurements is inversely related to the time required for flushing, since the photometer drift error increases with time.

4.5.3.3 Ensure that the flow rate into the output manifold is at least 1 liter/min greater than the total flow rate required by the photometer and any other flow demand connected to the manifold.

4.5.3.4 Ensure that the flow rate of zero air, Fz, is at least 1 liter/min greater than the flow rate required by the photometer.

4.5.3.5 With zero air flowing in the output manifold, actuate the two-way valve to allow the photometer to sample first the manifold zero air, then Fz. The two photometer readings must be equal (I = I0).

4.5.3.6 Adjust the O3 generator to produce an O3 concentration as needed.

4.5.3.7 Actuate the two-way valve to allow the photometer to sample zero air until the absorption cell is thoroughly flushed and record the stable measured value of Io.

4.5.3.8 Actuate the two-way valve to allow the photometer to sample the O3 concentration until the absorption cell is thoroughly flushed and record the stable measured value of I.

4.5.3.9 Record the temperature and pressure of the sample in the photometer absorption cell. (See Reference 13 for guidance.)

4.5.3.10 Calculate the O3 concentration from equation 4. An average of several determinations will provide better precision.

4.5.3.11 Obtain additional O3 concentration standards as necessary by repeating steps 4.5.3.6 to 4.5.3.10 or by Option 1.

4.5.4 Certification of transfer standards. A transfer standard is certified by relating the output of the transfer standard to one or more O3 calibration standards as determined according to section 4.5.3. The exact procedure varies depending on the nature and design of the transfer standard. Consult Reference 12 for guidance.

4.5.5 Calibration of ozone analyzers. Ozone analyzers must be calibrated as follows, using O3 standards obtained directly according to section 4.5.3 or by means of a certified transfer standard.

4.5.5.1 Allow sufficient time for the O3 analyzer and the photometer or transfer standard to warm-up and stabilize.

4.5.5.2 Allow the O3 analyzer to sample zero air until a stable response is obtained and then adjust the O3 analyzer’s zero control. Offsetting the analyzer’s zero adjustment to +5% of scale is recommended to facilitate observing negative zero drift (if any). Record the stable zero air response as “Z”.

4.5.5.3 Generate an O3 concentration standard of approximately 80% of the desired upper range limit (URL) of the O3 analyzer. Allow the O3 analyzer to sample this O3 concentration standard until a stable response is obtained.

4.5.5.4 Adjust the O3 analyzer’s span control to obtain the desired response equivalent to the calculated standard concentration. Record the O3 concentration and the corresponding analyzer response. If substantial adjustment of the span control is necessary, recheck the zero and span adjustments by repeating steps 4.5.5.2 to 4.5.5.4.

4.5.5.5 Generate additional O3 concentration standards (a minimum of 5 are recommended) over the calibration scale of the O3 analyzer by adjusting the O3 source or by Option 1. For each O3 concentration standard, record the O3 concentration and the corresponding analyzer response.

4.5.5.6 Plot the O3 analyzer responses (vertical or Y-axis) versus the corresponding O3 standard concentrations (horizontal or X-axis). Compute the linear regression slope and intercept and plot the regression line to verify that no point deviates from this line by more than 2 percent of the maximum concentration tested.

4.5.5.7 Option 1: The various O3 concentrations required in steps 4.5.3.11 and 4.5.5.5 may be obtained by dilution of the O3 concentration generated in steps 4.5.3.6 and 4.5.5.3. With this option, accurate flow measurements are required. The dynamic calibration system may be modified as shown in Figure 3 to allow for dilution air to be metered in downstream of the O3 generator. A mixing chamber between the O3 generator and the output manifold is also required. The flow rate through the O3 generator (Fo) and the dilution air flow rate (FD) are measured with a flow or volume standard that is traceable to a NIST flow or volume calibration standard. Each O3 concentration generated by dilution is calculated from:

5.0 Frequency of Calibration.

5.1 The frequency of calibration, as well as the number of points necessary to establish the calibration curve, and the frequency of other performance checking will vary by analyzer; however, the minimum frequency, acceptance criteria, and subsequent actions are specified in Appendix D of Reference 14: Measurement Quality Objectives and Validation Templates. The user’s quality control program shall provide guidelines for initial establishment of these variables and for subsequent alteration as operational experience is accumulated. Manufacturers of analyzers should include in their instruction/operation manuals information and guidance as to these variables and on other matters of operation, calibration, routine maintenance, and quality control.

6.0 References.

Appendix E to Part 50 [Reserved]

Appendix F to Part 50—Measurement Principle and Calibration Procedure for the Measurement of Nitrogen Dioxide in the Atmosphere (Gas Phase Chemiluminescence)

Principle and Applicability

1. Atmospheric concentrations of nitrogen dioxide (NO2) are measured indirectly by photometrically measuring the light intensity, at wavelengths greater than 600 nanometers, resulting from the chemiluminescent reaction of nitric oxide (NO) with ozone (O3). (1,2,3) NO2 is first quantitatively reduced to NO(4,5,6) by means of a converter. NO, which commonly exists in ambient air together with NO2, passes through the converter unchanged causing a resultant total NOX concentration equal to NO + NO2. A sample of the input air is also measured without having passed through the converted. This latter NO measurement is subtracted from the former measurement (NO + NO2) to yield the final NO2 measurement. The NO and NO + NO2 measurements may be made concurrently with dual systems, or cyclically with the same system provided the cycle time does not exceed 1 minute.

2. Sampling considerations.

2.1 Chemiluminescence NO/NOX/NO2 analyzers will respond to other nitrogen containing compounds, such as peroxyacetyl nitrate (PAN), which might be reduced to NO in the thermal converter. (7) Atmospheric concentrations of these potential interferences are generally low relative to NO2 and valid NO2 measurements may be obtained. In certain geographical areas, where the concentration of these potential interferences is known or suspected to be high relative to NO2, the use of an equivalent method for the measurement of NO2 is recommended.

2.2 The use of integrating flasks on the sample inlet line of chemiluminescence NO/NOX/NO2 analyzers is optional and left to couraged. The sample residence time between the sampling point and the analyzer should be kept to a minimum to avoid erroneous NO2 measurements resulting from the reaction of ambient levels of NO and O3 in the sampling system.

2.3 The use of particulate filters on the sample inlet line of chemiluminescence NO/NOX/NO2 analyzers is optional and left to the discretion of the user or the manufacturer.

3. An analyzer based on this principle will be considered a reference method only if it has been designated as a reference method in accordance with part 53 of this chapter.

1. Alternative A—Gas phase titration (GPT) of an NO standard with O3.

Major equipment required: Stable O3 generator. Chemiluminescence NO/NOX/NO2 analyzer with strip chart recorder(s). NO concentration standard.

1.1 Principle. This calibration technique is based upon the rapid gas phase reaction between NO and O3 to produce stoichiometric quantities of NO2 in accordance with the following equation: (8)

1.2 Apparatus. Figure 1, a schematic of a typical GPT apparatus, shows the suggested configuration of the components listed below. All connections between components in the calibration system downstream from the O3 generator should be of glass, Teflon ®, or other non-reactive material.

1.2.1 Air flow controllers. Devices capable of maintaining constant air flows within ±2% of the required flowrate.

1.2.2 NO flow controller. A device capable of maintaining constant NO flows within ±2% of the required flowrate. Component parts in contact with the NO should be of a non-reactive material.

1.2.3 Air flowmeters. Calibrated flowmeters capable of measuring and monitoring air flowrates with an accuracy of ±2% of the measured flowrate.

1.2.4 NO flowmeter. A calibrated flowmeter capable of measuring and monitoring NO flowrates with an accuracy of ±2% of the measured flowrate. (Rotameters have been reported to operate unreliably when measuring low NO flows and are not recommended.)

1.2.5 Pressure regulator for standard NO cylinder. This regulator must have a nonreactive diaphragm and internal parts and a suitable delivery pressure.

1.2.6 Ozone generator. The generator must be capable of generating sufficient and stable levels of O3 for reaction with NO to generate NO2 concentrations in the range required. Ozone generators of the electric discharge type may produce NO and NO2 and are not recommended.

1.2.7 Valve. A valve may be used as shown in Figure 1 to divert the NO flow when zero air is required at the manifold. The valve should be constructed of glass, Teflon ®, or other nonreactive material.

1.2.8 Reaction chamber. A chamber, constructed of glass, Teflon ®, or other nonreactive material, for the quantitative reaction of O3 with excess NO. The chamber should be of sufficient volume (VRC) such that the residence time (tR) meets the requirements specified in 1.4. For practical reasons, tR should be less than 2 minutes.

1.2.9 Mixing chamber. A chamber constructed of glass, Teflon ®, or other nonreactive material and designed to provide thorough mixing of reaction products and diluent air. The residence time is not critical when the dynamic parameter specification given in 1.4 is met.

1.2.10 Output manifold. The output manifold should be constructed of glass, Teflon ®, or other non-reactive material and should be of sufficient diameter to insure an insignificant pressure drop at the analyzer connection. The system must have a vent designed to insure atmospheric pressure at the manifold and to prevent ambient air from entering the manifold.

1.3 Reagents.

1.3.1 NO concentration standard. Gas cylinder standard containing 50 to 100 ppm NO in N2 with less than 1 ppm NO2. This standard must be traceable to a National Bureau of Standards (NBS) NO in N2 Standard Reference Material (SRM 1683 or SRM 1684), an NBS NO2 Standard Reference Material (SRM 1629), or an NBS/EPA-approved commercially available Certified Reference Material (CRM). CRM’s are described in Reference 14, and a list of CRM sources is available from the address shown for Reference 14. A recommended protocol for certifying NO gas cylinders against either an NO SRM or CRM is given in section 2.0.7 of Reference 15. Reference 13 gives procedures for certifying an NO gas cylinder against an NBS NO2 SRM and for determining the amount of NO2 impurity in an NO cylinder.

1.3.2 Zero air. Air, free of contaminants which will cause a detectable response on the NO/NOX/NO2 analyzer or which might react with either NO, O3, or NO2 in the gas phase titration. A procedure for generating zero air is given in reference 13.

1.4 Dynamic parameter specification.

1.4.1 The O3 generator air flowrate (F0) and NO flowrate (FNO) (see Figure 1) must be adjusted such that the following relationship holds:

1.4.2 The flow conditions to be used in the GPT system are determined by the following procedure:

(a) Determine FT, the total flow required at the output manifold (FT = analyzer demand plus 10 to 50% excess).

(b) Establish [NO]OUT as the highest NO concentration (ppm) which will be required at the output manifold. [NO]OUT should be approximately equivalent to 90% of the upper range limit (URL) of the NO2 concentration range to be covered.

(c) Determine FNO as

(d) Select a convenient or available reaction chamber volume. Initially, a trial VRC may be selected to be in the range of approximately 200 to 500 scm
3.

(e) Compute FO as

(f) Compute tR as

(g) Compute the diluent air flowrate as

(h) If FO turns out to be impractical for the desired system, select a reaction chamber having a different VRC and recompute FO and FD.

1.5 Procedure.

1.5.1 Assemble a dynamic calibration system such as the one shown in Figure 1.

1.5.2 Insure that all flowmeters are calibrated under the conditions of use against a reliable standard such as a soap-bubble meter or wet-test meter. All volumetric flowrates should be corrected to 25 °C and 760 mm Hg. A discussion on the calibration of flowmeters is given in reference 13.

1.5.3 Precautions must be taken to remove O2 and other contaminants from the NO pressure regulator and delivery system prior to the start of calibration to avoid any conversion of the standard NO to NO2. Failure to do so can cause significant errors in calibration. This problem may be minimized by (1) carefully evacuating the regulator, when possible, after the regulator has been connected to the cylinder and before opening the cylinder valve; (2) thoroughly flushing the regulator and delivery system with NO after opening the cylinder valve; (3) not removing the regulator from the cylinder between calibrations unless absolutely necessary. Further discussion of these procedures is given in reference 13.

1.5.4 Select the operating range of the NO/NOX/NO2 analyzer to be calibrated. In order to obtain maximum precision and accuracy for NO2 calibration, all three channels of the analyzer should be set to the same range. If operation of the NO and NOX channels on higher ranges is desired, subsequent recalibration of the NO and NOX channels on the higher ranges is recommended.

1.5.5 Connect the recorder output cable(s) of the NO/NOX/NO2 analyzer to the input terminals of the strip chart recorder(s). All adjustments to the analyzer should be performed based on the appropriate strip chart readings. References to analyzer responses in the procedures given below refer to recorder responses.

1.5.6 Determine the GPT flow conditions required to meet the dynamic parameter specification as indicated in 1.4.

1.5.7 Adjust the diluent air and O3 generator air flows to obtain the flows determined in section 1.4.2. The total air flow must exceed the total demand of the analyzer(s) connected to the output manifold to insure that no ambient air is pulled into the manifold vent. Allow the analyzer to sample zero air until stable NO, NOX, and NO2 responses are obtained. After the responses have stabilized, adjust the analyzer zero control(s).

Offsetting the analyzer zero adjustments to + 5 percent of scale is recommended to facilitate observing negative zero drift. Record the stable zero air responses as ZNO, Znox, and Zno2.

1.5.8 Preparation of NO and NOX calibration curves.

1.5.8.1 Adjustment of NO span control. Adjust the NO flow from the standard NO cylinder to generate an NO concentration of approximately 80 percent of the upper range limit (URL) of the NO range. This exact NO concentration is calculated from:

1.5.8.2 Adjustment of NOX span control. When adjusting the analyzer’s NOX span control, the presence of any NO2 impurity in the standard NO cylinder must be taken into account. Procedures for determining the amount of NO2 impurity in the standard NO cylinder are given in reference 13. The exact NOX concentration is calculated from:

1.5.8.3 Generate several additional concentrations (at least five evenly spaced points across the remaining scale are suggested to verify linearity) by decreasing FNO or increasing FD. For each concentration generated, calculate the exact NO and NOX concentrations using equations (9) and (11) respectively. Record the analyzer’s NO and NOX responses for each concentration. Plot the analyzer responses versus the respective calculated NO and NOX concentrations and draw or calculate the NO and NOX calibration curves. For subsequent calibrations where linearity can be assumed, these curves may be checked with a two-point calibration consisting of a zero air point and NO and NOX concentrations of approximately 80% of the URL.

1.5.9 Preparation of NO2 calibration curve.

1.5.9.1 Assuming the NO2 zero has been properly adjusted while sampling zero air in step 1.5.7, adjust FO and FD as determined in section 1.4.2. Adjust FNO to generate an NO concentration near 90% of the URL of the NO range. Sample this NO concentration until the NO and NOX responses have stabilized. Using the NO calibration curve obtained in section 1.5.8, measure and record the NO concentration as [NO]orig. Using the NOX calibration curve obtained in section 1.5.8, measure and record the NOX concentration as [NOX]orig.

1.5.9.2 Adjust the O3 generator to generate sufficient O3 to produce a decrease in the NO concentration equivalent to approximately 80% of the URL of the NO2 range. The decrease must not exceed 90% of the NO concentration determined in step 1.5.9.1. After the analyzer responses have stabilized, record the resultant NO and NOX concentrations as [NO]rem and [NOX]rem.

1.5.9.3 Calculate the resulting NO2 concentration from:

1.5.9.4 Maintaining the same FNO, FO, and FD as in section 1.5.9.1, adjust the ozone generator to obtain several other concentrations of NO2 over the NO2 range (at least five evenly spaced points across the remaining scale are suggested). Calculate each NO2 concentration using equation (13) and record the corresponding analyzer NO2 and NOX responses. Plot the analyzer’s NO2 responses versus the corresponding calculated NO2 concentrations and draw or calculate the NO2 calibration curve.

1.5.10 Determination of converter efficiency.

1.5.10.1 For each NO2 concentration generated during the preparation of the NO2 calibration curve (see section 1.5.9) calculate the concentration of NO2 converted from:

2. Alternative B—NO2 permeation device.

Major equipment required:

Stable O3 generator.

Chemiluminescence NO/NOX/NO2 analyzer with strip chart recorder(s).

NO concentration standard.

NO2 concentration standard.

2.1 Principle. Atmospheres containing accurately known concentrations of nitrogen dioxide are generated by means of a permeation device. (10) The permeation device emits NO2 at a known 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 NO2 emitted from the device is diluted with zero air to produce NO2 concentrations suitable for calibration of the NO2 channel of the NO/NOX/NO2 analyzer. An NO concentration standard is used for calibration of the NO and NOX channels of the analyzer.

2.2 Apparatus. A typical system suitable for generating the required NO and NO2 concentrations is shown in Figure 2. All connections between components downstream from the permeation device should be of glass, Teflon ®, or other non-reactive material.

2.2.1 Air flow controllers. Devices capable of maintaining constant air flows within ±2% of the required flowrate.

2.2.2 NO flow controller. A device capable of maintaining constant NO flows within ±2% of the required flowrate. Component parts in contact with the NO must be of a non-reactive material.

2.2.3 Air flowmeters. Calibrated flowmeters capable of measuring and monitoring air flowrates with an accuracy of ±2% of the measured flowrate.

2.2.4 NO flowmeter. A calibrated flowmeter capable of measuring and monitoring NO flowrates with an accuracy of ±2% of the measured flowrate. (Rotameters have been reported to operate unreliably when measuring low NO flows and are not recommended.)

2.2.5 Pressure regulator for standard NO cylinder. This regulator must have a non-reactive diaphragm and internal parts and a suitable delivery pressure.

2.2.6 Drier. Scrubber to remove moisture from the permeation device air system. The use of the drier is optional with NO2 permeation devices not sensitive to moisture. (Refer to the supplier’s instructions for use of the permeation device.)

2.2.7 Constant temperature chamber. Chamber capable of housing the NO2 permeation device and maintaining its temperature to within ±0.1 °C.

2.2.8 Temperature measuring device. Device capable of measuring and monitoring the temperature of the NO2 permeation device with an accuracy of ±0.05 °C.

2.2.9 Valves. A valve may be used as shown in Figure 2 to divert the NO2 from the permeation device when zero air or NO is required at the manifold. A second valve may be used to divert the NO flow when zero air or NO2 is required at the manifold.

The valves should be constructed of glass, Teflon ®, or other nonreactive material.

2.2.10 Mixing chamber. A chamber constructed of glass, Teflon ®, or other nonreactive material and designed to provide thorough mixing of pollutant gas streams and diluent air.

2.2.11 Output manifold. The output manifold should be constructed of glass, Teflon ®, or other non-reactive material and should be of sufficient diameter to insure an insignificant pressure drop at the analyzer connection. The system must have a vent designed to insure atmospheric pressure at the manifold and to prevent ambient air from entering the manifold.

2.3 Reagents.

2.3.1 Calibration standards. Calibration standards are required for both NO and NO2. The reference standard for the calibration may be either an NO or NO2 standard, and must be traceable to a National Bureau of Standards (NBS) NO in N2 Standard Reference Material (SRM 1683 or SRM 1684), and NBS NO2 Standard Reference Material (SRM 1629), or an NBS/EPA-approved commercially available Certified Reference Material (CRM). CRM’s are described in Reference 14, and a list of CRM sources is available from the address shown for Reference 14. Reference 15 gives recommended procedures for certifying an NO gas cylinder against an NO SRM or CRM and for certifying an NO2 permeation device against an NO2 SRM. Reference 13 contains procedures for certifying an NO gas cylinder against an NO2 SRM and for certifying an NO2 permeation device against an NO SRM or CRM. A procedure for determining the amount of NO2 impurity in an NO cylinder is also contained in Reference 13. The NO or NO2 standard selected as the reference standard must be used to certify the other standard to ensure consistency between the two standards.

2.3.1.1 NO2 Concentration standard. A permeation device suitable for generating NO2 concentrations at the required flow-rates over the required concentration range. If the permeation device is used as the reference standard, it must be traceable to an SRM or CRM as specified in 2.3.1. If an NO cylinder is used as the reference standard, the NO2 permeation device must be certified against the NO standard according to the procedure given in Reference 13. The use of the permeation device should be in strict accordance with the instructions supplied with the device. Additional information regarding the use of permeation devices is given by Scaringelli et al. (11) and Rook et al. (12).

2.3.1.2 NO Concentration standard. Gas cylinder containing 50 to 100 ppm NO in N2 with less than 1 ppm NO2. If this cylinder is used as the reference standard, the cylinder must be traceable to an SRM or CRM as specified in 2.3.1. If an NO2 permeation device is used as the reference standard, the NO cylinder must be certified against the NO2 standard according to the procedure given in Reference 13. The cylinder should be recertified on a regular basis as determined by the local quality control program.

2.3.3 Zero air. Air, free of contaminants which might react with NO or NO2 or cause a detectable response on the NO/NOX/NO2 analyzer. When using permeation devices that are sensitive to moisture, the zero air passing across the permeation device must be dry to avoid surface reactions on the device. (Refer to the supplier’s instructions for use of the permeation device.) A procedure for generating zero air is given in reference 13.

2.4 Procedure.

2.4.1 Assemble the calibration apparatus such as the typical one shown in Figure 2.

2.4.2 Insure that all flowmeters are calibrated under the conditions of use against a reliable standard such as a soap bubble meter or wet-test meter. All volumetric flowrates should be corrected to 25 °C and 760 mm Hg. A discussion on the calibration of flowmeters is given in reference 13.

2.4.3 Install the permeation device in the constant temperature chamber. Provide a small fixed air flow (200–400 scm
3/min) across the device. The permeation device should always have a continuous air flow across it to prevent large buildup of NO2 in the system and a consequent restabilization period. Record the flowrate as FP. Allow the device to stabilize at the calibration temperature for at least 24 hours. The temperature must be adjusted and controlled to within ±0.1 °C or less of the calibration temperature as monitored with the temperature measuring device.

2.4.4 Precautions must be taken to remove O2 and other contaminants from the NO pressure regulator and delivery system prior to the start of calibration to avoid any conversion of the standard NO to NO2. Failure to do so can cause significant errors in calibration. This problem may be minimized by

(1) Carefully evacuating the regulator, when possible, after the regulator has been connected to the cylinder and before opening the cylinder valve;

(2) Thoroughly flushing the regulator and delivery system with NO after opening the cylinder valve;

(3) Not removing the regulator from the cylinder between calibrations unless absolutely necessary. Further discussion of these procedures is given in reference 13.

2.4.5 Select the operating range of the NO/NOX NO2 analyzer to be calibrated. In order to obtain maximum precision and accuracy for NO2 calibration, all three channels of the analyzer should be set to the same range. If operation of the NO and NOX channels on higher ranges is desired, subsequent recalibration of the NO and NOX channels on the higher ranges is recommended.

2.4.6 Connect the recorder output cable(s) of the NO/NOX/NO2 analyzer to the input terminals of the strip chart recorder(s). All adjustments to the analyzer should be performed based on the appropriate strip chart readings. References to analyzer responses in the procedures given below refer to recorder responses.

2.4.7 Switch the valve to vent the flow from the permeation device and adjust the diluent air flowrate, FD, to provide zero air at the output manifold. The total air flow must exceed the total demand of the analyzer(s) connected to the output manifold to insure that no ambient air is pulled into the manifold vent. Allow the analyzer to sample zero air until stable NO, NOX, and NO2 responses are obtained. After the responses have stabilized, adjust the analyzer zero control(s).

2.4.8 Preparation of NO and NOX calibration curves.

2.4.8.1 Adjustment of NO span control. Adjust the NO flow from the standard NO cylinder to generate an NO concentration of approximately 80% of the upper range limit (URL) of the NO range. The exact NO concentration is calculated from:

2.4.8.2 Adjustment of NOX span control. When adjusting the analyzer’s NOX span control, the presence of any NO2 impurity in the standard NO cylinder must be taken into account. Procedures for determining the amount of NO2 impurity in the standard NO cylinder are given in reference 13. The exact NOX concentration is calculated from:

2.4.8.3 Generate several additional concentrations (at least five evenly spaced points across the remaining scale are suggested to verify linearity) by decreasing FNO or increasing FD. For each concentration generated, calculate the exact NO and NOX concentrations using equations (16) and (18) respectively. Record the analyzer’s NO and NOX responses for each concentration. Plot the analyzer responses versus the respective calculated NO and NOX concentrations and draw or calculate the NO and NOX calibration curves. For subsequent calibrations where linearity can be assumed, these curves may be checked with a two-point calibration consisting of a zero point and NO and NOX concentrations of approximately 80 percent of the URL.

2.4.9 Preparation of NO2 calibration curve.

2.4.9.1 Remove the NO flow. Assuming the NO2 zero has been properly adjusted while sampling zero air in step 2.4.7, switch the valve to provide NO2 at the output manifold.

2.4.9.2 Adjust FD to generate an NO2 concentration of approximately 80 percent of the URL of the NO2 range. The total air flow must exceed the demand of the analyzer(s) under calibration. The actual concentration of NO2 is calculated from:

2.4.9.3 Adjust FD to obtain several other concentrations of NO2 over the NO2 range (at least five evenly spaced points across the remaining scale are suggested). Calculate each NO2 concentration using equation (20) and record the corresponding analyzer NO2 and NOX responses. Plot the analyzer’s NO2 responses versus the corresponding calculated NO2 concentrations and draw or calculate the NO2 calibration curve.

2.4.10 Determination of converter efficiency.

2.4.10.1 Plot [NOX]M (y-axis) versus [NO2]OUT (x-axis) and draw or calculate the converter efficiency curve. The slope of the curve times 100 is the average converter efficiency, EC. The average converter efficiency must be greater than 96 percent; if it is less than 96 percent, replace or service the converter.

3. Frequency of calibration. The frequency of calibration, as well as the number of points necessary to establish the calibration curve and the frequency of other performance checks, will vary from one analyzer to another. The user’s quality control program should provide guidelines for initial establishment of these variables and for subsequent alteration as operational experience is accumulated. Manufacturers of analyzers should include in their instruction/operation manuals information and guidance as to these variables and on other matters of operation, calibration, and quality control.

1. A. Fontijn, A. J. Sabadell, and R. J. Ronco, “Homogeneous Chemiluminescent Measurement of Nitric Oxide with Ozone,” Anal. Chem., 42, 575 (1970).

2. D. H. Stedman, E. E. Daby, F. Stuhl, and H. Niki, “Analysis of Ozone and Nitric Oxide by a Chemiluminiscent Method in Laboratory and Atmospheric Studies of Photochemical Smog,” J. Air Poll. Control Assoc., 22, 260 (1972).

3. B. E. Martin, J. A. Hodgeson, and R. K. Stevens, “Detection of Nitric Oxide Chemiluminescence at Atmospheric Pressure,” Presented at 164th National ACS Meeting, New York City, August 1972.

4. J. A. Hodgeson, K. A. Rehme, B. E. Martin, and R. K. Stevens, “Measurements for Atmospheric Oxides of Nitrogen and Ammonia by Chemiluminescence,” Presented at 1972 APCA Meeting, Miami, FL, June 1972.

5. R. K. Stevens and J. A. Hodgeson, “Applications of Chemiluminescence Reactions to the Measurement of Air Pollutants,” Anal. Chem., 45, 443A (1973).

6. L. P. Breitenbach and M. Shelef, “Development of a Method for the Analysis of NO2 and NH3 by NO-Measuring Instruments,” J. Air Poll. Control Assoc., 23, 128 (1973).

7. A. M. Winer, J. W. Peters, J. P. Smith, and J. N. Pitts, Jr., “Response of Commercial Chemiluminescent NO-NO2 Analyzers to Other Nitrogen-Containing Compounds,” Environ. Sci. Technol., 8, 1118 (1974).

8. K. A. Rehme, B. E. Martin, and J. A. Hodgeson, Tentative Method for the Calibration of Nitric Oxide, Nitrogen Dioxide, and Ozone Analyzers by Gas Phase Titration,” EPA-R2-73-246, March 1974.

9. J. A. Hodgeson, R. K. Stevens, and B. E. Martin, “A Stable Ozone Source Applicable as a Secondary Standard for Calibration of Atmospheric Monitors,” ISA Transactions, 11, 161 (1972).

10. A. E. O’Keeffe and G. C. Ortman, “Primary Standards for Trace Gas Analysis,” Anal. Chem., 38, 760 (1966).

11. F. P. Scaringelli, 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).

12. H. L. Rook, E. E. Hughes, R. S. Fuerst, and J. H. Margeson, “Operation Characteristics of NO2 Permeation Devices,” Presented at 167th National ACS Meeting, Los Angeles, CA, April 1974.

13. E. C. Ellis, “Technical Assistance Document for the Chemiluminescence Measurement of Nitrogen Dioxide,” EPA-E600/4-75-003 (Available in draft form from the United States Environmental Protection Agency, Department E (MD–76), Environmental Monitoring and Support Laboratory, Research Triangle Park, NC 27711).

14. A Procedure for Establishing Traceability of Gas Mixtures to Certain National Bureau of Standards Standard Reference Materials. EPA–600/7–81–010, Joint publication by NBS and EPA. Available from the U.S. Environmental Protection Agency, Environmental Monitoring Systems Laboratory (MD–77), Research Triangle Park, NC 27711, May 1981.

15. Quality Assurance Handbook for Air Pollution Measurement Systems, Volume II, Ambient Air Specific Methods. The U.S. Environmental Protection Agency, Environmental Monitoring Systems Laboratory, Research Triangle Park, NC 27711. Publication No. EAP–600/4–77–027a.

Appendix G to Part 50—Reference Method for the Determination of Lead in Total Suspended Particulate Matter

1.0 Scope and Applicability

Based on review of the air quality criteria and national ambient air quality standard (NAAQS) for lead (Pb) completed in 2008, the EPA made revisions to the primary and secondary NAAQS for Pb to protect public health and welfare. The EPA revised the level from 1.5 µg/m
3 to 0.15 µg/m
3 while retaining the current indicator of Pb in total suspended particulate matter (Pb-TSP).

Pb-TSP is collected for 24 hours on a TSP filter as described in Appendix B of part 50, the Reference Method for the Determination of Suspended Particulate Matter in the Atmosphere (High-Volume Method). This method is for the analysis of Pb from TSP filters by Inductively Coupled Plasma Mass Spectrometry (ICP–MS) using a heated ultrasonic bath with nitric acid (HNO3) and hydrochloric acid (HCl) or a heated block (hot block) digester with HNO3 for filter extraction.

This method is based on the EPA’s Office of Solid Waste (SW–846) Method 6020A—Inductively Coupled Plasma Mass Spectrometry (U.S. EPA, 2007). Wording in certain sections of this method is paraphrased or taken directly from Method 6020A.

1.1 ICP–MS is applicable for the sub-µg/mL (ppb) determination of Pb in a wide variety of matrices. Results reported for monitoring or compliance purposes are calculated in µg/m
3 at local conditions (LC). This procedure describes a method for the acid extraction of Pb in particulate matter collected on glass fiber, quartz, or PTFE filters and measurement of the extracted Pb using ICP–MS.

1.2 Due to variations in the isotopic abundance of Pb, the value for total Pb must be based on the sum of the signal intensities for isotopic masses, 206, 207, and 208. Most instrument software packages are able to sum the primary isotope signal intensities automatically.

1.3 ICP–MS requires the use of an internal standard.
115In (Indium),
165Ho (Holmium), and
209Bi (Bismuth) are recommended internal standards for the determination of Pb.

1.4 Use of this method is restricted to use by, or under supervision of, properly trained and experienced laboratory personnel. Requirements include training and experience in inorganic sample preparation, including acid extraction, and also knowledge in the recognition and in the correction of spectral, chemical and physical interference in ICP–MS.

2.1 This method describes the acid extraction of Pb in particulate matter collected on glass fiber, quartz, or PTFE ambient air filters with subsequent measurement of Pb by ICP–MS. Estimates of the Method Detection Limit (MDL) or sensitivity of the method are provided in Tables 1, 3 and 5 and determined using Pb-spiked filters or filter strips analyzed in accordance with the guidance provided in 40 CFR 136, Appendix B—Determination and procedures for the Determination of the Method Detection Limit—Revision 1.1. The analytical range of the method is 0.00024 µg/m
3 to 0.60 µg/m
3, and based on the low and high calibration curve standards and a nominal filter sample volume of 2000 m
3.

2.2 This method includes two extraction methods. In the first method, a solution of HNO3 and HCl is added to the filters or filter strips in plastic digestion tubes and the tubes are placed in a heated ultrasonic bath for one hour to facilitate the extraction of Pb. Following ultrasonication, the samples are brought to a final volume of 40 mL (50 mL for PTFE filters), vortex mixed or shaken vigorously, and centrifuged prior to aliquots being taken for ICP–MS analysis. In the second method, a solution of dilute HNO3 is added to the filter strips in plastic digestion tubes and the tubes placed into the hot block digester. The filter strip is completely covered by the solution. The tubes are covered with polypropylene watch glasses and refluxed. After reflux, the samples are diluted to a final volume of 50 mL with reagent water and mixed before analysis.

2.3 Calibration standards and check standards are prepared to matrix match the acid composition of the samples. ICP–MS analysis is then performed. With this method, the samples are first aspirated and the aerosol thus created is transported by a flow of argon gas into the plasma torch. The ions produced (e.g., Pb+ 1) in the plasma are extracted via a differentially-pumped vacuum interface and are separated on the basis of their mass-to-charge ratio. The ions are quantified by a channel electron multiplier or a Faraday detector and the signal collected is processed by the instrument’s software. Interferences must be assessed and corrected for, if present.

4.1 Reagents, glassware, plasticware, and other sample processing hardware may yield artifacts and/or interferences to sample analysis. If reagent blanks, filter blanks, or quality control blanks yield results above the detection limit, the source of contamination must be identified. All containers and reagents used in the processing of the samples must be checked for contamination prior to sample extraction and analysis. Reagents shall be diluted to match the final concentration of the extracts and analyzed for Pb. Labware shall be rinsed with dilute acid solution and the solution analyzed. Once a reagent or labware article (such as extraction tubes) from a manufacturer has been successfully screened, additional screening is not required unless contamination is suspected.

4.2 Isobaric elemental interferences in ICP–MS are caused by isotopes of different elements forming atomic ions with the same nominal mass-to-charge ratio (m/z) as the species of interest. There are no species found in ambient air that will result in isobaric interference with the three Pb isotopes (206, 207, and 208) being measured. Polyatomic interferences occur when two or more elements combine to form an ion with the same mass-to-charge ratio as the isotope being measured. Pb is not subject to interference from common polyatomic ions and no correction is required.

4.3 The distribution of Pb isotopes is not constant. The analysis of total Pb should be based on the summation of signal intensities for the isotopic masses 206, 207, and 208. In most cases, the instrument software can perform the summation automatically.

4.4 Physical interferences are associated with the sample nebulization and transport processes as well as with ion-transmission efficiencies. Dissolved solids can deposit on the nebulizer tip of a pneumatic nebulizer and on the interface skimmers of the ICP–MS. Nebulization and transport processes can be affected if a matrix component causes a change in surface tension or viscosity. Changes in matrix composition can cause significant signal suppression or enhancement. These interferences are compensated for by use of internal standards. Sample dilution will reduce the effects of high levels of dissolved salts, but calibration standards must be prepared in the extraction medium and diluted accordingly.

4.5 Memory interferences are related to sample transport and result when there is carryover from one sample to the next. Sample carryover can result from sample deposition on the sample and skimmer cones and from incomplete rinsing of the sample solution from the plasma torch and the spray chamber between samples. These memory effects are dependent upon both the analyte being measured and sample matrix and can be minimized through the use of suitable rinse times.

5.1 The toxicity or carcinogenicity of reagents used in this method has not been fully established. Each chemical should be regarded as a potential health hazard and exposure to these compounds should be as low as reasonably achievable. Each laboratory is responsible for maintaining a current file of OSHA regulations regarding the safe handling of the chemicals specified in this method. A reference file of material safety data sheets (MSDSs) should be available to all personnel involved in the chemical analysis. Specifically, concentrated HNO3 presents various hazards and is moderately toxic and extremely irritating to skin and mucus membranes. Use this reagent in a fume hood whenever possible and if eye or skin contact occurs, flush with large volumes of water. Always wear safety glasses or a shield for eye protection, protective clothing, and observe proper mixing when working with these reagents.

5.2 Concentrated HNO3 and HCl are moderately toxic and extremely irritating to the skin. Use these reagents in a fume hood, and if eye and skin contact occurs, flush with large volumes of water. Always wear safety glasses or a shield for eye protection when working with these reagents. The component of this procedure requiring the greatest care is HNO3. HNO3 is a strong, corrosive, oxidizing agent that requires protection of the eyes, skin, and clothing. Items to be worn during use of this reagent include:

1. Safety goggles (or safety glasses with side shields),

2. Acid resistant rubber gloves, and

3. A protective garment such as a laboratory apron. HNO3 spilled on clothing will destroy the fabric; contact with the skin underneath will result in a burn.

It is also essential that an eye wash fountain or eye wash bottle be available during performance of this method. An eye wash bottle has a spout that covers the eye. If acid or any other corrosive gets into the eye, the water in this bottle is squirted onto the eye to wash out the harmful material. Eye washing should be performed with large amounts of water immediately after exposure. Medical help should be sought immediately after washing. If either acid, but especially HNO3, is spilled onto the skin, wash immediately with large amounts of water. Medical attention is not required unless the burn appears to be significant. Even after washing and drying, HNO3 may leave the skin slightly brown in color; this will heal and fade with time.

5.3 Pb salts and Pb solutions are toxic. Great care must be taken to ensure that samples and standards are handled properly; wash hands thoroughly after handling.

5.4 Care must be taken when using the ultrasonic bath and hot block digester as they are capable of causing mild burns. Users should refer to the safety guidance provided by the manufacturer of their specific equipment.

5.5 Analytical plasma sources emit radio frequency radiation in addition to intense ultra violet (UV) radiation. Suitable precautions should be taken to protect personnel from such hazards. The inductively coupled plasma should only be viewed with proper eye protection from UV emissions.

6.1 Thermo Scientific X-Series ICP–MS or equivalent. The system must be capable of providing resolution better or equal to 1.0 atomic mass unit (amu) at 10 percent peak height. The system must have a mass range from at least 7 to 240 amu that allows for the application of the internal standard technique. For the measurement of Pb, an instrument with a collision or reaction cell is not required.

6.2.1 Heated ultrasonic bath capable of maintaining a temperature of 80 °C; VWR Model 750HT, 240W, or equivalent. Ultrasonic bath must meet the following performance criteria:

1. Cut a strip of aluminum foil almost the width of the tank and double the depth.

2. Turn the ultrasonic bath on and lower the foil into the bath vertically until almost touching the bottom of the tank and hold for 10 seconds.

3. Remove the foil from the tank and observe the distribution of perforations and small pin prick holes. The indentations should be fine and evenly distributed. The even distribution of indentations indicates the ultrasonic bath is acceptable for use.

6.2.2 Laboratory centrifuge, Beckman GS–6, or equivalent.

6.2.3 Vortex mixer, VWR Signature Digital Vortex Mixer, VWR Catalog No. 14005–824, or equivalent.

6.3 Hot block extraction equipment

6.3.1 Hot block digester, SCP Science DigiPrep Model MS, No. 010–500–205 block digester capable of maintaining a temperature of 95 °C, or equivalent.

6.4 Materials and Supplies

• Argon gas supply, 99.99 percent purity or better. National Welders Microbulk, or equivalent.

• Plastic digestion tubes with threaded caps for extraction and storage, SCP Science DigiTUBE® Item No. 010–500–063, or equivalent.

• Disposable polypropylene ribbed watch glasses (for heated block extraction), SCP Science Item No. 010–500–081, or equivalent.

• Pipette, Rainin EDP2, 100 µL, ±1 percent accuracy, ≤1 percent RSD (precision), with disposable tips, or equivalent.

• Pipette, Rainin EDP2, 1000 µL, ±1 percent accuracy, ≤1 percent RSD (precision), with disposable tips, or equivalent.

• Pipette, Rainin EDP2, 1–10 mL, ±1 percent accuracy, ≤1 percent RSD (precision), with disposable tips, or equivalent.

• Pipette, Thermo Lab Systems, 5 mL, ±1 percent accuracy, ≤1 percent RSD (precision), with disposable tips, or equivalent.

• Plastic tweezer, VWR Catalog No. 89026–420, or equivalent.

• Laboratory marker.

• Ceramic knife, Kyocera LK–25, and non-metal ruler or other suitable cutting tools for making straight cuts for accurately measured strips.

• Blank labels or labeling tape, VWR Catalog No. 36425–045, or equivalent.

• Graduated cylinder, 1 L, VWR 89000–260, or equivalent.

• Volumetric flask, Class A, 1 L, VWR Catalog No. 89025–778, or equivalent.

• Millipore Element deionized water system, or equivalent, capable of generating water with a resistivity of ≥17.9 MΩ-cm).

• Disposable syringes, 10-mL, with 0.45 micron filters (must be Pb-free).

• Plastic or PTFE wash bottles.

• Glassware, Class A—volumetric flasks, pipettes, and graduated cylinders.

• Glass fiber, quartz, or PTFE filters from the same filter manufacturer and lot used for sample collection for use in the determination of the MDL and for laboratory blanks.

7.1 Reagent—or trace metals-grade chemicals must be used in all tests. Unless otherwise indicated, it is intended that all reagents conform to the specifications of the Committee on Analytical Reagents of the American Chemical Society, where such specifications are available.

7.2 Concentrated nitric acid, 67–70 percent, SCP Science Catalog No. 250–037–177, or equivalent.

7.3 Concentrated hydrochloric acid (for the ultrasonic extraction method), 33–36 percent, SCP Science Catalog No. 250–037–175, or equivalent.

7.4 Deionized water—All references to deionized water in the method refer to deionized water with a resistivity ≥17.9 MΩ-cm.

7.5 Standard stock solutions may be commercially purchased for each element or as a multi-element mix. Internal standards may be purchased as a mixed multi-element solution. The manufacturer’s expiration date and storage conditions must be adhered to.

7.5.1 Lead standard, 1000 µg/mL, NIST traceable, commercially available with certificate of analysis. High Purity Standards Catalog No. 100028–1, or equivalent.

7.5.2 Indium (In) standard, 1000 µg/mL, NIST traceable, commercially available with certificate of analysis. High Purity Standards Catalog No. 100024–1, or equivalent.

7.5.3 Bismuth (Bi) standard, 1000 µg/mL, NIST traceable, commercially available with certificate of analysis. High Purity Standards Catalog No. 100006–1, or equivalent.

7.5.4 Holmium (Ho) standard, 1000 µg/mL, NIST traceable, commercially available with certificate of analysis. High Purity Standards Catalog No. 100023–1, or equivalent.

7.5.5 Second source lead standard, 1000 µg/mL, NIST traceable, commercially available with certificate of analysis. Must be from a different vendor or lot than the standard described in 7.5.1. Inorganic Ventures Catalog No. CGPB–1, or equivalent.

7.5.6 Standard Reference Materials, NIST SRM 2583, 2586, 2587 or 1648, or equivalent.
5

Note: The In, Bi, and Ho internal standards may also be purchased as 10 µg/mL standards. Calibration standards are prepared by diluting stock standards to the appropriate levels in the same acid concentrations as in the final sample volume. The typical range for calibration standards is 0.001 to 2.00 µg/mL. At a minimum, the curve must contain a blank and five Pb containing calibration standards. The calibration standards are stored at ambient laboratory temperature. Calibration standards must be prepared weekly and verified against a freshly prepared ICV using a NIST-traceable source different from the calibration standards.

7.6 Internal standards may be added to the test solution or by on-line addition. The nominal concentration for an internal standard is 0.010 µg/mL (10 ppb). Bismuth (Bi) or holmium (Ho) are the preferred internal standards for Pb, but indium (In) may be used in the event the sample contains Bi and high recoveries are observed.

7.7 Three laboratory blank solutions are required for analysis: (1) The calibration blank is used in the construction of the calibration curve and as a periodic check of system cleanliness (ICB and CCB); (2) the reagent blank (RB) is carried through the extraction process to assess possible contamination; and (3) the rinse blank is run between samples to clean the sample introduction system. If RBs or laboratory blanks yield results above the detection limit, the source of contamination must be identified. Screening of labware and reagents is addressed in Section 4.1.

7.7.1 The calibration blank is prepared in the same acid matrix as the calibration standards and samples and contains all internal standards used in the analysis.

7.7.2 The RB contains all reagents used in the extraction and is carried through the extraction procedure at the same time as the samples.

7.7.3 The rinse blank is a solution of 1 to 2 percent HNO3 (v/v) in reagent grade water. A sufficient volume should be prepared to flush the system between all standards and samples analyzed.

7.7.4 The EPA currently provides glass fiber, quartz, and PTFE filters to air monitoring agencies as requested annually. As part of the procurement process, these filters are tested for acceptance by the EPA. The current acceptance criteria for glass fiber and quartz filters is 15 µg per filter or 0.0075 µg/m
3 using a nominal sample volume of 2000 m
3 and 4.8 ng/cm
2 or 0.0024 µg/m
3 for PTFE filters using a nominal sample volume of 24 m
3. Acceptance test results for filters obtained by the EPA are typically well below the criterion specified and also below the recently revised Pb method performance detection limit of 0.0075 µg/m
3; therefore, blank subtraction should not be performed.

7.7.5 If filters are not provided by the EPA for sample collection and analysis, filter lot blanks should be analyzed for Pb content. For large filter lots (>500 filters), randomly select 20 to 30 filters from the lot and analyze the filter or filter strips for Pb. For smaller filter lots, a lesser number of filters can be analyzed. Glass, quartz and PTFE filters must not have levels of Pb above the criteria specified in section 7.7.4 and, therefore, blank correction should not be performed. If acceptance testing shows levels of Pb above the criteria in Section 7.7.4, corrective action must be taken to reduce the levels before proceeding.

7.8 The Initial Calibration Verification (ICV), Lower Level Calibration Verification (LLCV), and Continuing Calibration Verification (CCV) solutions are prepared from a different Pb source than the calibration curve standards and at a concentration that is either at or below the midpoint on the calibration curve, but within the calibration range. Both are prepared in the same acid matrix as the calibration standards. Note that the same solution may be used for both the ICV and CCV. The ICV/CCV and LLCV solutions must be prepared fresh daily.

7.9 Tuning Solution. Prepare a tuning solution according to the instrument manufacturer’s recommendations. This solution will be used to verify the mass calibration and resolution of the instrument.

8.1 Standard QC practices shall be employed to assess the validity of the data generated, including: MDL, RB, duplicate samples, spiked samples, serial dilutions, ICV, CCV, LLCV, ICB, CCB, and SRMs/CRMs.

8.2 MDLs must be calculated in accordance with 40 CFR part 136, Appendix B. RBs with low-level standard spikes are used to estimate the MDL. The low-level standard spike is added to at least 7 individual filter strips and then carried through the entire extraction procedure. This will result in at least 7 individual samples to be used for the MDL. The recommended range for spiking the strips is 1 to 5 times the estimated MDL.

8.3 For each batch of samples, one RB and one reagent blank spike (RBS) that is spiked at the same level as the sample spike (see Section 8.6) must be prepared and carried throughout the entire process. The results of the RB must be below 0.001 µg/mL. The recovery for the RBS must be within ±20 percent of the expected value. If the RB yields a result above 0.001 µg/mL, the source of contamination must be identified and the extraction and analysis repeated. Reagents and labware must be suspected as sources of contamination. Screening of reagents and labware is addressed in Section 4.1.

8.4 Any samples that exceed the highest calibration standard must be diluted and rerun so that the concentration falls within the curve. The minimum dilution will be 1 to 5 with matrix matched acid solution.

8.5 The internal standard response must be monitored during the analysis. If the internal standard response falls below 70 percent or rises above 120 percent of expected due to possible matrix effects, the sample must be diluted and reanalyzed. The minimum dilution will be 1 to 5 with matrix matched acid solution. If the first dilution does not correct the problem, additional dilutions must be run until the internal standard falls within the specified range.

8.6 For every batch of samples prepared, there must be one duplicate and one spike sample prepared. The spike added is to be at a level that falls within the calibration curve, normally the midpoint of the curve. The initial plus duplicate sample must yield a relative percent difference ≤20 percent. The spike must be within ±20 percent of the expected value.

8.7 For each batch of samples, one extract must be diluted five-fold and analyzed. The corrected dilution result must be within ±10 percent of the undiluted result. The sample chosen for the serial dilution shall have a concentration at or above 10X the lowest standard in the curve to ensure the diluted value falls within the curve. If the serial dilution fails, chemical or physical interference should be suspected.

8.8 ICB, ICV, LLCV, CCB and CCV samples are to be run as shown in the following table.

If any of these QC samples fails to meet specifications, the source of the unacceptable performance must be determined, the problem corrected, and any samples not bracketed by passing QC samples must be reanalyzed.

8.9 For each batch of samples, one certified reference material (CRM) must be combined with a blank filter strip and carried through the entire extraction procedure. The result must be within ±10 percent of the expected value.

8.10 For each run, a LLCV must be analyzed. The LLCV must be prepared at a concentration not more than three times the lowest calibration standard and at a concentration not used in the calibration curve. The LLCV is used to assess performance at the low end of the curve. If the LLCV fails (±10 percent of the expected value) the run must be terminated, the problem corrected, the instrument recalibrated, and the analysis repeated.

8.11 Pipettes used for volumetric transfer must have the calibration checked at least once every 6 months and pass ±1 percent accuracy and ≤1 percent RSD (precision) based on five replicate readings. The pipettes must be checked weekly for accuracy with a single replicate. Any pipette that does not meet ±1 percent accuracy on the weekly check must be removed from service, repaired, and pass a full calibration check before use.

8.12 Samples with physical deformities are not quantitatively analyzable. The analyst should visually check filters prior to proceeding with preparation for holes, tears, or non-uniform deposit which would prevent representative sampling. Document any deformities and qualify the data with flags appropriately. Care must be taken to protect filters from contamination. Filters must be kept covered prior to sample preparation.

9.0 ICP MS Calibration

Follow the instrument manufacturer’s instructions for the routine maintenance, cleaning, and ignition procedures for the specific ICP–MS instrument being used.

9.1 Ignite the plasma and wait for at least one half hour for the instrument to warm up before beginning any pre-analysis steps.

9.2 For the Thermo X-Series with Xt cones, aspirate a 10 ng/mL tuning solution containing In, Bi, and Ce (Cerium). Monitor the intensities of In, Bi, Ce, and CeO (Cerium oxide) and adjust the instrument settings to achieve the highest In and Bi counts while minimizing the CeO/Ce oxide ratio. For other instruments, follow the manufacturer’s recommended practice. Tune to meet the instrument manufacturer’s specifications. After tuning, place the sample aspiration probe into a 2 percent HNO3 rinse solution for at least 5 minutes to flush the system.

9.3 Aspirate a 5 ng/mL solution containing Co, In, and Bi to perform a daily instrument stability check. Run 10 replicates of the solution. The percent RSD for the replicates must be less than 3 percent at all masses. If the percent RSD is greater than 3 percent, the sample introduction system, pump tubing, and tune should be examined, and the analysis repeated. Place the sample aspiration probe into a 2 percent HNO3 rinse solution for at least 5 minutes to flush the system.

9.4 Load the calibration standards in the autosampler and analyze using the same method parameters that will be used to analyze samples. The curve must include one blank and at least 5 Pb-containing calibration standards. The correlation coefficient must be at least 0.998 for the curve to be accepted. The lowest standard must recover ±15 percent of the expected value and the remaining standards must recover ±10 percent of the expected value to be accepted.

9.5 Immediately after the calibration curve is completed, analyze an ICV and an ICB. The ICV must be prepared from a different source of Pb than the calibration standards. The ICV must recover 90–110 percent of the expected value for the run to continue. The ICB must be less than 0.001 µg/mL. If either the ICV or the ICB fails, the run must be terminated, the problem identified and corrected, and the analysis re-started.

9.6 A LLCV, CCV and a CCB must be run after the ICV and ICB. A CCV and CCB must be run at a frequency of not less than every 10 extracted samples. A typical analytical run sequence would be: Calibration blank, Calibration standards, ICV, ICB, LLCV, CCV, CCB, Extracts 1–10, CCV, CCB, Extracts 11–20, CCV, CCB, Extracts 21–30, CCV, CCB, LLCV, CCV, CCB. Extracts are any field sample or QC samples that have been carried through the extraction process. The CCV solution is prepared from a different source than the calibration standards and may be the same as the ICV solution. The LLCV must be within ±10 percent of expected value. The CCV value must be within ±10 percent of expected for the run to continue. The CCB must be less than 0.001 µg/mL. If either the CCV, LLCV, or CCB fails, the run must be terminated, the problem identified and corrected, and the analysis re-started from the last passing CCV/LLCV/CCB set.

9.7 A LLCV, CCV, and CCB set must be run at the end of the analysis. The LLCV must be within ±30 percent of expected value. If either the CCV, LLCV, or CCB fails, the run must be terminated, the problem identified and corrected, and the analysis re-started from the last passing CCV/LLCV/CCB set.

All plasticware (e.g., Nalgene) and glassware used in the extraction procedures is soaked in 1 percent HNO3 (v/v) for at least 24 hours and rinsed with reagent water prior to use. All mechanical pipettes used must be calibrated to ±1 percent accuracy and ≤1 percent RSD at a minimum of once every 6 months.

10.1 Sample Preparation—Heated Ultrasonic Bath

10.1.1 Extraction solution (1.03M HNO3 + 2.23M HCl). Prepare by adding 500 mL of deionized water to a 1000 mL flask, adding 64.4 mL of concentrated HNO3 and 182 mL of concentrated HCl, shaking to mix, allowing solution to cool, diluting to volume with reagent water, and inverting several times to mix. Extraction solution must be prepared at least weekly.

10.1.2 Use a ceramic knife and non-metal ruler, or other cutting device that will not contaminate the filter with Pb. Cut a
3/4 inch × 8 inch strip from the glass fiber or quartz filter by cutting a strip from the edge of the filter where it has been folded along the 10 inch side at least 1 inch from the right or left side to avoid the un-sampled area covered by the filter holder. The filters must be carefully handled to avoid dislodging deposits.

10.1.3 Using plastic tweezers, roll the filter strip up in a coil and place the rolled strip in the bottom of a labeled 50 mL extraction tube. In a fume hood, add 15.00 ±0.15 mL of the extraction solution (see Section 10.1.1) using a calibrated mechanical pipette. Ensure that the extraction solution completely covers the filter strip.

10.1.4 Loosely cap the 50 mL extraction tube and place it upright in a plastic rack. When all samples have been prepared, place the racks in an uncovered heated ultrasonic water bath that has been preheated to 80 ±5 °C and ensure that the water level in the ultrasonic is above the level of the extraction solution in the tubes but well below the level of the extraction tube caps to avoid contamination. Start the ultrasonic bath and allow the unit to run for 1 hour ±5 minutes at 80 ±5 °C.

10.1.5 Remove the rack(s) from the ultrasonic bath and allow the racks to cool.

10.1.6 Add 25.00 ±0.25 mL of D.I. water with a calibrated mechanical pipette to bring the sample to a final volume of 40.0 ±0.4 mL. Tightly cap the tubes, and vortex mix or shake vigorously. Place the extraction tubes in an appropriate holder and centrifuge for 20 minutes at 2500 revolutions per minute (RPM).

CAUTION—Make sure that the centrifuge holder has a flat bottom to support the flat bottomed extraction tubes.

10.1.7 Pour an aliquot of the solution into an autosampler vial for ICP–MS analysis to avoid the potential for contamination. Do not pipette an aliquot of solution into the autosampler vial.

10.1.8 Decant the extract to a clean tube, cap tightly, and store the sample extract at ambient laboratory temperature. Extracts may be stored for up to 6 months from the date of extraction.

10.2 47 mm PTFE Filter Extraction—Heated Ultrasonic Bath

10.2.1 Extraction solution (1.03M HNO3 + 2.23M HCl). Prepare by adding 500 mL of D.I. water to a 1000mL flask, adding 64.4 mL of concentrated HNO3 and 182 mL of concentrated HCl, shaking to mix, allowing solution to cool, diluting to volume with reagent water, and inverting several times to mix. Extraction solution must be prepared at least weekly.

10.2.2 Using plastic tweezers, bend the PTFE filter into a U-shape and insert the filter into a labeled 50 mL extraction tube with the particle loaded side facing the center of the tube. Gently push the filter to the bottom of the extraction tube. In a fume hood, add 25.00 ±0.15 mL of the extraction solution (see Section 10.2.1) using a calibrated mechanical pipette. Ensure that the extraction solution completely covers the filter.

10.2.3 Loosely cap the 50 mL extraction tube and place it upright in a plastic rack. When all samples have been prepared, place the racks in an uncovered heated ultrasonic water bath that has been preheated to 80 ±5 °C and ensure that the water level in the ultrasonic is above the level of the extraction solution in the tubes, but well below the level of the extraction tube caps to avoid contamination. Start the ultrasonic bath and allow the unit to run for 1 hour ±5 minutes at 80 ±5 °C.

10.2.4 Remove the rack(s) from the ultrasonic bath and allow the racks to cool.

10.2.5 Add 25.00 ±0.25 mL of D.I. water with a calibrated mechanical pipette to bring the sample to a final volume of 50.0 ±0.4 mL. Tightly cap the tubes, and vortex mix or shake vigorously. Allow samples to stand for one hour to allow complete diffusion of the extracted Pb. The sample is now ready for analysis.

Note: Although PTFE filters have only been extracted using the ultrasonic extraction procedure in the development of this FRM, PTFE filters are inert and have very low Pb content. No issues are expected with the extraction of PTFE filters using the heated block digestion method. However, prior to using PTFE filters in the heated block extraction method, extraction method performance test using CRMs must be done to confirm performance (see Section 8.9).

All plasticware (e.g., Nalgene) and glassware used in the extraction procedures is soaked in 1 percent HNO3 for at least 24 hours and rinsed with reagent water prior to use. All mechanical pipettes used must be calibrated to ±1 percent accuracy and ≤1 percent RSD at a minimum of once every 6 months.

11.1 Sample Preparation—Hot Block Digestion

11.1.1 Extraction solution (1:19, v/v HNO3). Prepare by adding 500 mL of D.I. water to a 1000 mL flask, adding 50 mL of concentrated HNO3, shaking to mix, allowing solution to cool, diluting to volume with reagent water, and inverting several times to mix. The extraction solution must be prepared at least weekly.

11.1.2 Use a ceramic knife and non-metal ruler, or other cutting device that will not contaminate the filter with Pb. Cut a 1-inch × 8-inch strip from the glass fiber or quartz filter. Cut a strip from the edge of the filter where it has been folded along the 10-inch side at least 1 inch from the right or left side to avoid the un-sampled area covered by the filter holder. The filters must be carefully handled to avoid dislodging particle deposits.

11.1.3 Using plastic tweezers, roll the filter strip up in a coil and place the rolled strip in the bottom of a labeled 50 mL extraction tube. In a fume hood, add 20.0 ±0.15 mL of the extraction solution (see Section 11.1.1) using a calibrated mechanical pipette. Ensure that the extraction solution completely covers the filter strip.

11.1.4 Place the extraction tube in the heated block digester and cover with a disposable polyethylene ribbed watch glass. Heat at 95 ±5 °C for 1 hour and ensure that the sample does not evaporate to dryness. For proper heating, adjust the temperature control of the hot block such that an uncovered vessel containing 50 mL of water placed in the center of the hot block can be maintained at a temperature approximately, but no higher than 85C. Once the vessel is covered with a ribbed watch glass, the temperature of the water will increase to approximately 95 °C.

11.1.5 Remove the rack(s) from the heated block digester and allow the samples to cool.

11.1.6 Bring the samples to a final volume of 50 mL with D.I. water. Tightly cap the tubes, and vortex mix or shake vigorously for at least 5 seconds. Set aside (with the filter strip in the tube) for at least 30 minutes to allow the HNO3 trapped in the filter to diffuse into the extraction solution.

11.1.7 Shake thoroughly (with the filter strip in the digestion tube) and let settle for at least one hour. The sample is now ready for analysis.

12.1 Follow the instrument manufacturer’s startup procedures for the ICP–MS.

12.2 Set instrument parameters to the appropriate operating conditions as presented in the instrument manufacturer’s operating manual and allow the instrument to warm up for at least 30 minutes.

12.3 Calibrate the instrument per Section 9.0 of this method.

12.4 Verify the instrument is suitable for analysis as defined in Sections 9.2 and 9.3.

12.5 As directed in Section 8.0 of this method, analyze an ICV and ICB immediately after the calibration curve followed by a LLCV, then CCV and CCB. The acceptance requirements for these parameters are presented in Section 8.8.

12.6 Analyze a CCV and a CCB after every 10 extracted samples.

12.7 Analyze a LLCV, CCV and CCB at the end of the analysis.

12.8 A typical sample run will include field samples, field sample duplicates, spiked field sample extracts, serially diluted samples, the set of QC samples listed in Section 8.8 above, and one or more CRMs or SRMs.

12.9 Any samples that exceed the highest standard in the calibration curve must be diluted and reanalyzed so that the diluted concentration falls within the calibration curve.

13.0 Results

13.1 The filter results must be initially reported in µg/mL as analyzed. Any additional dilutions must be accounted for. The internal standard recoveries must be included in the result calculation; this is done by the ICP–MS software for most commercially-available instruments. Final results should be reported in µg Pb/m
3 to three significant figures as follows:

The calculation assumes the use of a standard 8-inch × 10-inch TSP filter which has a sampled area of 9-inch × 7-inch (63.0 in
2) due to the
1/2-inch filter holder border around the outer edge. The
3/4-inch × 8-inch strip has a sampled area of
3/4-inch × 7-inch (5.25 in
2). The 1-inch × 8-inch strip has a sampled area of 1-inch × 7-inch (7.0 in
2). If filter lot blanks are provided for analysis, refer to Section 7.7.5 of this method for guidance on testing.

Information in this section is an example of typical performance results achieved by this method. Actual performance must be demonstrated by each individual laboratory and instrument.

14.1 Performance data have been collected to estimate MDLs for this method. MDLs were determined in accordance with 40 CFR 136, Appendix B. MDLs were estimated for glass fiber, quartz, and PTFE filters using seven reagent/filter blank solutions spiked with low level Pb at three times the estimated MDL of 0.001 µg/mL. Tables 1, 3, and 5 shows the MDLs estimated using both the ultrasonic and hot block extraction methods for glass fiber and quartz filters and the ultrasonic method for PTFE filters. The MDLs are well below the EPA requirement of five percent of the current Pb NAAQS or 0.0075 µg/m
3. These MDLs are provided to demonstrate the adequacy of the method’s performance for Pb in TSP. Each laboratory using this method should determine MDLs in their laboratory and verify them annually. It is recommended that laboratories also perform the optional iterative procedure in 40 CFR 136, Appendix B to verify the reasonableness of the estimated MDL and subsequent MDL determinations.

14.2 Extraction method recovery tests with glass fiber and quartz filter strips, and PTFE filters spiked with NIST SRMs were performed using the ultrasonic/HNO3 and HCl filter extraction methods and measurement of the dissolved Pb with ICP–MS. Tables 2, 4, and 6 show recoveries obtained with these SRM. The recoveries for all SRMs were ≥90 percent at the 95 percent confidence level.

15.1 Pollution prevention encompasses any technique that reduces or eliminates the quantity and/or toxicity of waste at the point of generation. Numerous opportunities for pollution prevention exist in laboratory operations. Whenever feasible, laboratory personnel should use pollution prevention techniques to address their waste generation. The sources of pollution generated with this procedure are waste acid extracts and Pb-containing solutions.

15.2 For information about pollution prevention that may be applicable to laboratories and research institutions, consult Less is Better: Laboratory Chemical Management for Waste Reduction, available from the American Chemical Society’s Department of Government Relations and Science Policy, 1155 16th St. NW., Washington, DC 20036, www.acs.org.

16.1 Laboratory waste management practices must be conducted consistent with all applicable rules and regulations. Laboratories are urged to protect air, water, and land by minimizing all releases from hood and bench operations, complying with the letter and spirit of any sewer and discharge permits and regulations, and by complying with all solid and hazardous waste regulation. For further information on waste management, consult The Waste Management Manual for Laboratory Personnel available from the American Chemical Society listed in Section 15.2 of this method.

16.2 Waste HNO3, HCl, and solutions containing these reagents and/or Pb must be placed in labeled bottles and delivered to a commercial firm that specializes in removal of hazardous waste.

Appendix H to Part 50—Interpretation of the 1-Hour Primary and Secondary National Ambient Air Quality Standards for Ozone

1. General

This appendix explains how to determine when the expected number of days per calendar year with maximum hourly average concentrations above 0.12 ppm (235 µg/m
3) is equal to or less than 1. An expanded discussion of these procedures and associated examples are contained in the “Guideline for Interpretation of Ozone Air Quality Standards.” For purposes of clarity in the following discussion, it is convenient to use the term “exceedance” to describe a daily maximum hourly average ozone measurement that is greater than the level of the standard. Therefore, the phrase “expected number of days with maximum hourly average ozone concentrations above the level of the standard” may be simply stated as the “expected number of exceedances.”

The basic principle in making this determination is relatively straightforward. Most of the complications that arise in determining the expected number of annual exceedances relate to accounting for incomplete sampling. In general, the average number of exceedances per calendar year must be less than or equal to 1. In its simplest form, the number of exceedances at a monitoring site would be recorded for each calendar year and then averaged over the past 3 calendar years to determine if this average is less than or equal to 1.

The ozone standard states that the expected number of exceedances per year must be less than or equal to 1. The statistical term “expected number” is basically an arithmetic average. The following example explains what it would mean for an area to be in compliance with this type of standard. Suppose a monitoring station records a valid daily maximum hourly average ozone value for every day of the year during the past 3 years. At the end of each year, the number of days with maximum hourly concentrations above 0.12 ppm is determined and this number is averaged with the results of previous years. As long as this average remains “less than or equal to 1,” the area is in compliance.

In general, a valid daily maximum hourly average value may not be available for each day of the year, and it will be necessary to account for these missing values when estimating the number of exceedances for a particular calendar year. The purpose of these computations is to determine if the expected number of exceedances per year is less than or equal to 1. Thus, if a site has two or more observed exceedances each year, the standard is not met and it is not necessary to use the procedures of this section to account for incomplete sampling.

The term “missing value” is used here in the general sense to describe all days that do not have an associated ozone measurement. In some cases, a measurement might actually have been missed but in other cases no measurement may have been scheduled for that day. A daily maximum ozone value is defined to be the highest hourly ozone value recorded for the day. This daily maximum value is considered to be valid if 75 percent of the hours from 9:01 a.m. to 9:00 p.m. (LST) were measured or if the highest hour is greater than the level of the standard.

In some areas, the seasonal pattern of ozone is so pronounced that entire months need not be sampled because it is extremely unlikely that the standard would be exceeded. Any such waiver of the ozone monitoring requirement would be handled under provisions of 40 CFR, part 58. Some allowance should also be made for days for which valid daily maximum hourly values were not obtained but which would quite likely have been below the standard. Such an allowance introduces a complication in that it becomes necessary to define under what conditions a missing value may be assumed to have been less than the level of the standard. The following criterion may be used for ozone:

A missing daily maximum ozone value may be assumed to be less than the level of the standard if the valid daily maxima on both the preceding day and the following day do not exceed 75 percent of the level of the standard.

Let z denote the number of missing daily maximum values that may be assumed to be less than the standard. Then the following formula shall be used to estimate the expected number of exceedances for the year:

(*Indicates multiplication.)

This estimated number of exceedances shall be rounded to one decimal place (fractional parts equal to 0.05 round up).

It should be noted that N will be the total number of days in the year unless the appropriate Regional Administrator has granted a waiver under the provisions of 40 CFR part 58.

The above equation may be interpreted intuitively in the following manner. The estimated number of exceedances is equal to the observed number of exceedances (v) plus an increment that accounts for incomplete sampling. There were (N-n) missing values for the year but a certain number of these, namely z, were assumed to be less than the standard. Therefore, (N-n-z) missing values are considered to include possible exceedances. The fraction of measured values that are above the level of the standard is v/n. It is assumed that this same fraction applies to the (N-n-z) missing values and that (v/n)*(N-n-z) of these values would also have exceeded the level of the standard.

Appendix I to Part 50—Interpretation of the 8-Hour Primary and Secondary National Ambient Air Quality Standards for Ozone

1. General.

This appendix explains the data handling conventions and computations necessary for determining whether the national 8-hour primary and secondary ambient air quality standards for ozone specified in § 50.10 are met at an ambient ozone air quality monitoring site. Ozone is measured in the ambient air by a reference method based on appendix D of this part. Data reporting, data handling, and computation procedures to be used in making comparisons between reported ozone concentrations and the level of the ozone standard are specified in the following sections. Whether to exclude, retain, or make adjustments to the data affected by stratospheric ozone intrusion or other natural events is subject to the approval of the appropriate Regional Administrator.

2. Primary and Secondary Ambient Air Quality Standards for Ozone.

2.1 Data Reporting and Handling Conventions.

2.1.1 Computing 8-hour averages. Hourly average concentrations shall be reported in parts per million (ppm) to the third decimal place, with additional digits to the right being truncated. Running 8-hour averages shall be computed from the hourly ozone concentration data for each hour of the year and the result shall be stored in the first, or start, hour of the 8-hour period. An 8-hour average shall be considered valid if at least 75% of the hourly averages for the 8-hour period are available. In the event that only 6 (or 7) hourly averages are available, the 8-hour average shall be computed on the basis of the hours available using 6 (or 7) as the divisor. (8-hour periods with three or more missing hours shall not be ignored if, after substituting one-half the minimum detectable limit for the missing hourly concentrations, the 8-hour average concentration is greater than the level of the standard.) The computed 8-hour average ozone concentrations shall be reported to three decimal places (the insignificant digits to the right of the third decimal place are truncated, consistent with the data handling procedures for the reported data.)

2.1.2 Daily maximum 8-hour average concentrations. (a) There are 24 possible running 8-hour average ozone concentrations for each calendar day during the ozone monitoring season. (Ozone monitoring seasons vary by geographic location as designated in part 58, appendix D to this chapter.) The daily maximum 8-hour concentration for a given calendar day is the highest of the 24 possible 8-hour average concentrations computed for that day. This process is repeated, yielding a daily maximum 8-hour average ozone concentration for each calendar day with ambient ozone monitoring data. Because the 8-hour averages are recorded in the start hour, the daily maximum 8-hour concentrations from two consecutive days may have some hourly concentrations in common. Generally, overlapping daily maximum 8-hour averages are not likely, except in those non-urban monitoring locations with less pronounced diurnal variation in hourly concentrations.

(b) An ozone monitoring day shall be counted as a valid day if valid 8-hour averages are available for at least 75% of possible hours in the day (i.e., at least 18 of the 24 averages). In the event that less than 75% of the 8-hour averages are available, a day shall also be counted as a valid day if the daily maximum 8-hour average concentration for that day is greater than the level of the ambient standard.

2.2 Primary and Secondary Standard-related Summary Statistic. The standard-related summary statistic is the annual fourth-highest daily maximum 8-hour ozone concentration, expressed in parts per million, averaged over three years. The 3-year average shall be computed using the three most recent, consecutive calendar years of monitoring data meeting the data completeness requirements described in this appendix. The computed 3-year average of the annual fourth-highest daily maximum 8-hour average ozone concentrations shall be expressed to three decimal places (the remaining digits to the right are truncated.)

2.3 Comparisons with the Primary and Secondary Ozone Standards. (a) The primary and secondary ozone ambient air quality standards are met at an ambient air quality monitoring site when the 3-year average of the annual fourth-highest daily maximum 8-hour average ozone concentration is less than or equal to 0.08 ppm. The number of significant figures in the level of the standard dictates the rounding convention for comparing the computed 3-year average annual fourth-highest daily maximum 8-hour average ozone concentration with the level of the standard. The third decimal place of the computed value is rounded, with values equal to or greater than 5 rounding up. Thus, a computed 3-year average ozone concentration of 0.085 ppm is the smallest value that is greater than 0.08 ppm.

(b) This comparison shall be based on three consecutive, complete calendar years of air quality monitoring data. This requirement is met for the three year period at a monitoring site if daily maximum 8-hour average concentrations are available for at least 90%, on average, of the days during the designated ozone monitoring season, with a minimum data completeness in any one year of at least 75% of the designated sampling days. When computing whether the minimum data completeness requirements have been met, meteorological or ambient data may be sufficient to demonstrate that meteorological conditions on missing days were not conducive to concentrations above the level of the standard. Missing days assumed less than the level of the standard are counted for the purpose of meeting the data completeness requirement, subject to the approval of the appropriate Regional Administrator.

(c) Years with concentrations greater than the level of the standard shall not be ignored on the ground that they have less than complete data. Thus, in computing the 3-year average fourth maximum concentration, calendar years with less than 75% data completeness shall be included in the computation if the average annual fourth maximum 8-hour concentration is greater than the level of the standard.

(d) Comparisons with the primary and secondary ozone standards are demonstrated by examples 1 and 2 in paragraphs (d)(1) and (d) (2) respectively as follows:

(1) As shown in example 1, the primary and secondary standards are met at this monitoring site because the 3-year average of the annual fourth-highest daily maximum 8-hour average ozone concentrations (i.e., 0.084 ppm) is less than or equal to 0.08 ppm. The data completeness requirement is also met because the average percent of days with valid ambient monitoring data is greater than 90%, and no single year has less than 75% data completeness.

(2) As shown in example 2, the primary and secondary standards are not met at this monitoring site because the 3-year average of the fourth-highest daily maximum 8-hour average ozone concentrations (i.e., 0.093 ppm) is greater than 0.08 ppm. Note that the ozone concentration data for 1994 is used in these computations, even though the data capture is less than 75%, because the average fourth-highest daily maximum 8-hour average concentration is greater than 0.08 ppm.

3. Design Values for Primary and Secondary Ambient Air Quality Standards for Ozone. The air quality design value at a monitoring site is defined as that concentration that when reduced to the level of the standard ensures that the site meets the standard. For a concentration-based standard, the air quality design value is simply the standard-related test statistic. Thus, for the primary and secondary ozone standards, the 3-year average annual fourth-highest daily maximum 8-hour average ozone concentration is also the air quality design value for the site.

Appendix J to Part 50—Reference Method for the Determination of Particulate Matter as PM10 in the Atmosphere

1.0 Applicability.

1.1 This method provides for the measurement of the mass concentration of particulate matter with an aerodynamic diameter less than or equal to a nominal 10 micrometers (PM1O) in ambient air over a 24-hour period for purposes of determining attainment and maintenance of the primary and secondary national ambient air quality standards for particulate matter specified in § 50.6 of this chapter. The measurement process is nondestructive, and the PM10 sample can be subjected to subsequent physical or chemical analyses. Quality assurance procedures and guidance are provided in part 58, appendices A and B, of this chapter and in References 1 and 2.

2.0 Principle.

2.1 An air sampler draws ambient air at a constant flow rate into a specially shaped inlet where the suspended particulate matter is inertially separated into one or more size fractions within the PM10 size range. Each size fraction in the PM1O size range is then collected on a separate filter over the specified sampling period. The particle size discrimination characteristics (sampling effectiveness and 50 percent cutpoint) of the sampler inlet are prescribed as performance specifications in part 53 of this chapter.

2.2 Each filter is weighed (after moisture equilibration) before and after use to determine the net weight (mass) gain due to collected PM10. The total volume of air sampled, corrected to EPA reference conditions (25 C, 101.3 kPa), is determined from the measured flow rate and the sampling time. The mass concentration of PM10 in the ambient air is computed as the total mass of collected particles in the PM10 size range divided by the volume of air sampled, and is expressed in micrograms per standard cubic meter (µg/std m
3). For PM10 samples collected at temperatures and pressures significantly different from EPA reference conditions, these corrected concentrations sometimes differ substantially from actual concentrations (in micrograms per actual cubic meter), particularly at high elevations. Although not required, the actual PM10 concentration can be calculated from the corrected concentration, using the average ambient temperature and barometric pressure during the sampling period.

2.3 A method based on this principle will be considered a reference method only if (a) the associated sampler meets the requirements specified in this appendix and the requirements in part 53 of this chapter, and (b) the method has been designated as a reference method in accordance with part 53 of this chapter.

3.0 Range.

3.1 The lower limit of the mass concentration range is determined by the repeatability of filter tare weights, assuming the nominal air sample volume for the sampler. For samplers having an automatic filter-changing mechanism, there may be no upper limit. For samplers that do not have an automatic filter-changing mechanism, the upper limit is determined by the filter mass loading beyond which the sampler no longer maintains the operating flow rate within specified limits due to increased pressure drop across the loaded filter. This upper limit cannot be specified precisely because it is a complex function of the ambient particle size distribution and type, humidity, filter type, and perhaps other factors. Nevertheless, all samplers should be capable of measuring 24-hour PM10 mass concentrations of at least 300 µg/std m
3 while maintaining the operating flow rate within the specified limits.

4.0 Precision.

4.1 The precision of PM10 samplers must be 5 µg/m
3 for PM10 concentrations below 80 µg/m
3 and 7 percent for PM10 concentrations above 80 µg/m
3, as required by part 53 of this chapter, which prescribes a test procedure that determines the variation in the PM10 concentration measurements of identical samplers under typical sampling conditions. Continual assessment of precision via collocated samplers is required by part 58 of this chapter for PM10 samplers used in certain monitoring networks.

5.0 Accuracy.

5.1 Because the size of the particles making up ambient particulate matter varies over a wide range and the concentration of particles varies with particle size, it is difficult to define the absolute accuracy of PM10 samplers. Part 53 of this chapter provides a specification for the sampling effectiveness of PM10 samplers. This specification requires that the expected mass concentration calculated for a candidate PM10 sampler, when sampling a specified particle size distribution, be within ±10 percent of that calculated for an ideal sampler whose sampling effectiveness is explicitly specified. Also, the particle size for 50 percent sampling effectiveness is required to be 10 ±0.5 micrometers. Other specifications related to accuracy apply to flow measurement and calibration, filter media, analytical (weighing) procedures, and artifact. The flow rate accuracy of PM10 samplers used in certain monitoring networks is required by part 58 of this chapter to be assessed periodically via flow rate audits.

6.0 Potential Sources of Error.

6.1 Volatile Particles. Volatile particles collected on filters are often lost during shipment and/or storage of the filters prior to the post-sampling weighing
3. Although shipment or storage of loaded filters is sometimes unavoidable, filters should be reweighed as soon as practical to minimize these losses.

6.2 Artifacts. Positive errors in PM10 concentration measurements may result from retention of gaseous species on filters.
4 5 Such errors include the retention of sulfur dioxide and nitric acid. Retention of sulfur dioxide on filters, followed by oxidation to sulfate, is referred to as artifact sulfate formation, a phenomenon which increases with increasing filter alkalinity.
6 Little or no artifact sulfate formation should occur using filters that meet the alkalinity specification in section 7.2.4. Artifact nitrate formation, resulting primarily from retention of nitric acid, occurs to varying degrees on many filter types, including glass fiber, cellulose ester, and many quartz fiber filters.
5 7 8 9 10 Loss of true atmospheric particulate nitrate during or following sampling may also occur due to dissociation or chemical reaction. This phenomenon has been observed on Teflon ® filters
8 and inferred for quartz fiber filters.
11 12 The magnitude of nitrate artifact errors in PM10 mass concentration measurements will vary with location and ambient temperature; however, for most sampling locations, these errors are expected to be small.

6.3 Humidity. The effects of ambient humidity on the sample are unavoidable. The filter equilibration procedure in section 9.0 is designed to minimize the effects of moisture on the filter medium.

6.4 Filter Handling. Careful handling of filters between presampling and postsampling weighings is necessary to avoid errors due to damaged filters or loss of collected particles from the filters. Use of a filter cartridge or cassette may reduce the magnitude of these errors. Filters must also meet the integrity specification in section 7.2.3.

6.5 Flow Rate Variation. Variations in the sampler’s operating flow rate may alter the particle size discrimination characteristics of the sampler inlet. The magnitude of this error will depend on the sensitivity of the inlet to variations in flow rate and on the particle distribution in the atmosphere during the sampling period. The use of a flow control device (section 7.1.3) is required to minimize this error.

6.6 Air Volume Determination. Errors in the air volume determination may result from errors in the flow rate and/or sampling time measurements. The flow control device serves to minimize errors in the flow rate determination, and an elapsed time meter (section 7.1.5) is required to minimize the error in the sampling time measurement.

7.0 Apparatus.

7.1 PM10 Sampler.

7.1.1 The sampler shall be designed to:

a. Draw the air sample into the sampler inlet and through the particle collection filter at a uniform face velocity.

b. Hold and seal the filter in a horizontal position so that sample air is drawn downward through the filter.

c. Allow the filter to be installed and removed conveniently.

d. Protect the filter and sampler from precipitation and prevent insects and other debris from being sampled.

e. Minimize air leaks that would cause error in the measurement of the air volume passing through the filter.

f. Discharge exhaust air at a sufficient distance from the sampler inlet to minimize the sampling of exhaust air.

g. Minimize the collection of dust from the supporting surface.

7.1.2 The sampler shall have a sample air inlet system that, when operated within a specified flow rate range, provides particle size discrimination characteristics meeting all of the applicable performance specifications prescribed in part 53 of this chapter. The sampler inlet shall show no significant wind direction dependence. The latter requirement can generally be satisfied by an inlet shape that is circularly symmetrical about a vertical axis.

7.1.3 The sampler shall have a flow control device capable of maintaining the sampler’s operating flow rate within the flow rate limits specified for the sampler inlet over normal variations in line voltage and filter pressure drop.

7.1.4 The sampler shall provide a means to measure the total flow rate during the sampling period. A continuous flow recorder is recommended but not required. The flow measurement device shall be accurate to ±2 percent.

7.1.5 A timing/control device capable of starting and stopping the sampler shall be used to obtain a sample collection period of 24 ±1 hr (1,440 ±60 min). An elapsed time meter, accurate to within ±15 minutes, shall be used to measure sampling time. This meter is optional for samplers with continuous flow recorders if the sampling time measurement obtained by means of the recorder meets the ±15 minute accuracy specification.

7.1.6 The sampler shall have an associated operation or instruction manual as required by part 53 of this chapter which includes detailed instructions on the calibration, operation, and maintenance of the sampler.

7.2 Filters.

7.2.1 Filter Medium. No commercially available filter medium is ideal in all respects for all samplers. The user’s goals in sampling determine the relative importance of various filter characteristics (e.g., cost, ease of handling, physical and chemical characteristics, etc.) and, consequently, determine the choice among acceptable filters. Furthermore, certain types of filters may not be suitable for use with some samplers, particularly under heavy loading conditions (high mass concentrations), because of high or rapid increase in the filter flow resistance that would exceed the capability of the sampler’s flow control device. However, samplers equipped with automatic filter-changing mechanisms may allow use of these types of filters. The specifications given below are minimum requirements to ensure acceptability of the filter medium for measurement of PM10 mass concentrations. Other filter evaluation criteria should be considered to meet individual sampling and analysis objectives.

7.2.2 Collection Efficiency. ≥99 percent, as measured by the DOP test (ASTM–2986) with 0.3 µm particles at the sampler’s operating face velocity.

7.2.3 Integrity. ±5 µg/m
3 (assuming sampler’s nominal 24-hour air sample volume). Integrity is measured as the PM10 concentration equivalent corresponding to the average difference between the initial and the final weights of a random sample of test filters that are weighed and handled under actual or simulated sampling conditions, but have no air sample passed through them (i.e., filter blanks). As a minimum, the test procedure must include initial equilibration and weighing, installation on an inoperative sampler, removal from the sampler, and final equilibration and weighing.

7.2.4 Alkalinity.

7.3 Flow Rate Transfer Standard. The flow rate transfer standard must be suitable for the sampler’s operating flow rate and must be calibrated against a primary flow or volume standard that is traceable to the National Bureau of Standards (NBS). The flow rate transfer standard must be capable of measuring the sampler’s operating flow rate with an accuracy of ±2 percent.

7.4 Filter Conditioning Environment.

7.4.1 Temperature range: 15 to 30 C.

7.4.2 Temperature control: ±3 C.

7.4.3 Humidity range: 20% to 45% RH.

7.4.4 Humidity control: ±5% RH.

7.5 Analytical Balance. The analytical balance must be suitable for weighing the type and size of filters required by the sampler. The range and sensitivity required will depend on the filter tare weights and mass loadings. Typically, an analytical balance with a sensitivity of 0.1 mg is required for high volume samplers (flow rates >0.5 m
3/min). Lower volume samplers (flow rates 3/min) will require a more sensitive balance.

8.0 Calibration.

8.1 General Requirements.

8.1.1 Calibration of the sampler’s flow measurement device is required to establish traceability of subsequent flow measurements to a primary standard. A flow rate transfer standard calibrated against a primary flow or volume standard shall be used to calibrate or verify the accuracy of the sampler’s flow measurement device.

8.1.2 Particle size discrimination by inertial separation requires that specific air velocities be maintained in the sampler’s air inlet system. Therefore, the flow rate through the sampler’s inlet must be maintained throughout the sampling period within the design flow rate range specified by the manufacturer. Design flow rates are specified as actual volumetric flow rates, measured at existing conditions of temperature and pressure (Qa). In contrast, mass concentrations of PM10 are computed using flow rates corrected to EPA reference conditions of temperature and pressure (Qstd).

8.2 Flow Rate Calibration Procedure.

8.2.1 PM10 samplers employ various types of flow control and flow measurement devices. The specific procedure used for flow rate calibration or verification will vary depending on the type of flow controller and flow indicator employed. Calibration in terms of actual volumetric flow rates (Qa) is generally recommended, but other measures of flow rate (e.g., Qstd) may be used provided the requirements of section 8.1 are met. The general procedure given here is based on actual volumetric flow units (Qa) and serves to illustrate the steps involved in the calibration of a PM10 sampler. Consult the sampler manufacturer’s instruction manual and Reference 2 for specific guidance on calibration. Reference 14 provides additional information on the use of the commonly used measures of flow rate and their interrelationships.

8.2.2 Calibrate the flow rate transfer standard against a primary flow or volume standard traceable to NBS. Establish a calibration relationship (e.g., an equation or family of curves) such that traceability to the primary standard is accurate to within 2 percent over the expected range of ambient conditions (i.e., temperatures and pressures) under which the transfer standard will be used. Recalibrate the transfer standard periodically.

8.2.3 Following the sampler manufacturer’s instruction manual, remove the sampler inlet and connect the flow rate transfer standard to the sampler such that the transfer standard accurately measures the sampler’s flow rate. Make sure there are no leaks between the transfer standard and the sampler.

8.2.4 Choose a minimum of three flow rates (actual m
3/min), spaced over the acceptable flow rate range specified for the inlet (see 7.1.2) that can be obtained by suitable adjustment of the sampler flow rate. In accordance with the sampler manufacturer’s instruction manual, obtain or verify the calibration relationship between the flow rate (actual m
3/min) as indicated by the transfer standard and the sampler’s flow indicator response. Record the ambient temperature and barometric pressure. Temperature and pressure corrections to subsequent flow indicator readings may be required for certain types of flow measurement devices. When such corrections are necessary, correction on an individual or daily basis is preferable. However, seasonal average temperature and average barometric pressure for the sampling site may be incorporated into the sampler calibration to avoid daily corrections. Consult the sampler manufacturer’s instruction manual and Reference 2 for additional guidance.

8.2.5 Following calibration, verify that the sampler is operating at its design flow rate (actual m
3/min) with a clean filter in place.

8.2.6 Replace the sampler inlet.

9.0 Procedure.

9.1 The sampler shall be operated in accordance with the specific guidance provided in the sampler manufacturer’s instruction manual and in Reference 2. The general procedure given here assumes that the sampler’s flow rate calibration is based on flow rates at ambient conditions (Qa) and serves to illustrate the steps involved in the operation of a PM10 sampler.

9.2 Inspect each filter for pinholes, particles, and other imperfections. Establish a filter information record and assign an identification number to each filter.

9.3 Equilibrate each filter in the conditioning environment (see 7.4) for at least 24 hours.

9.4 Following equilibration, weigh each filter and record the presampling weight with the filter identification number.

9.5 Install a preweighed filter in the sampler following the instructions provided in the sampler manufacturer’s instruction manual.

9.6 Turn on the sampler and allow it to establish run-temperature conditions. Record the flow indicator reading and, if needed, the ambient temperature and barometric pressure. Determine the sampler flow rate (actual m
3/min) in accordance with the instructions provided in the sampler manufacturer’s instruction manual. NOTE.—No onsite temperature or pressure measurements are necessary if the sampler’s flow indicator does not require temperature or pressure corrections or if seasonal average temperature and average barometric pressure for the sampling site are incorporated into the sampler calibration (see step 8.2.4). If individual or daily temperature and pressure corrections are required, ambient temperature and barometric pressure can be obtained by on-site 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 sampling site and the airport.

9.7 If the flow rate is outside the acceptable range specified by the manufacturer, check for leaks, and if necessary, adjust the flow rate to the specified setpoint. Stop the sampler.

9.8 Set the timer to start and stop the sampler at appropriate times. Set the elapsed time meter to zero or record the initial meter reading.

9.9 Record the sample information (site location or identification number, sample date, filter identification number, and sampler model and serial number).

9.10 Sample for 24 ±1 hours.

9.11 Determine and record the average flow rate (Q
a) in actual m
3/min for the sampling period in accordance with the instructions provided in the sampler manufacturer’s instruction manual. Record the elapsed time meter final reading and, if needed, the average ambient temperature and barometric pressure for the sampling period (see note following step 9.6).

9.12 Carefully remove the filter from the sampler, following the sampler manufacturer’s instruction manual. Touch only the outer edges of the filter.

9.13 Place the filter in a protective holder or container (e.g., petri dish, glassine envelope, or manila folder).

9.14 Record any factors such as meteorological conditions, construction activity, fires or dust storms, etc., that might be pertinent to the measurement on the filter information record.

9.15 Transport the exposed sample filter to the filter conditioning environment as soon as possible for equilibration and subsequent weighing.

9.16 Equilibrate the exposed filter in the conditioning environment for at least 24 hours under the same temperature and humidity conditions used for presampling filter equilibration (see 9.3).

9.17 Immediately after equilibration, reweigh the filter and record the postsampling weight with the filter identification number.

10.0 Sampler Maintenance.

10.1 The PM10 sampler shall be maintained in strict accordance with the maintenance procedures specified in the sampler manufacturer’s instruction manual.

11.0 Calculations.

11.1 Calculate the average flow rate over the sampling period corrected to EPA reference conditions as Q
std. When the sampler’s flow indicator is calibrated in actual volumetric units (Qa), Q
std is calculated as:

11.2 Calculate the total volume of air sampled as:

11.3 Calculate the PM10 concentration as:

12.0 References.

1. Quality Assurance Handbook for Air Pollution Measurement Systems, Volume I, Principles. EPA–600/9–76–005, March 1976. Available from CERI, ORD Publications, U.S. Environmental Protection Agency, 26 West St. Clair Street, Cincinnati, OH 45268.

2. Quality Assurance Handbook for Air Pollution Measurement Systems, Volume II, Ambient Air Specific Methods. EPA–600/4–77–027a, May 1977. Available from CERI, ORD Publications, U.S. Environmental Protection Agency, 26 West St. Clair Street, Cincinnati, OH 45268.

3. Clement, R.E., and F.W. Karasek. Sample Composition Changes in Sampling and Analysis of Organic Compounds in Aerosols. Int. J. Environ. Analyt. Chem., 7:109, 1979.

4. Lee, R.E., Jr., and J. Wagman. A Sampling Anomaly in the Determination of Atmospheric Sulfate Concentration. Amer. Ind. Hyg. Assoc. J., 27:266, 1966.

5. Appel, B.R., S.M. Wall, Y. Tokiwa, and M. Haik. Interference Effects in Sampling Particulate Nitrate in Ambient Air. Atmos. Environ., 13:319, 1979.

6. Coutant, R.W. Effect of Environmental Variables on Collection of Atmospheric Sulfate. Environ. Sci. Technol., 11:873, 1977.

7. Spicer, C.W., and P. Schumacher. Interference in Sampling Atmospheric Particulate Nitrate. Atmos. Environ., 11:873, 1977.

8. Appel, B.R., Y. Tokiwa, and M. Haik. Sampling of Nitrates in Ambient Air. Atmos. Environ., 15:283, 1981.

9. Spicer, C.W., and P.M. Schumacher. Particulate Nitrate: Laboratory and Field Studies of Major Sampling Interferences. Atmos. Environ., 13:543, 1979.

10. Appel, B.R. Letter to Larry Purdue, U.S. EPA, Environmental Monitoring and Support Laboratory. March 18, 1982, Docket No. A–82–37, II-I-1.

11. Pierson, W.R., W.W. Brachaczek, T.J. Korniski, T.J. Truex, and J.W. Butler. Artifact Formation of Sulfate, Nitrate, and Hydrogen Ion on Backup Filters: Allegheny Mountain Experiment. J. Air Pollut. Control Assoc., 30:30, 1980.

12. Dunwoody, C.L. Rapid Nitrate Loss From PM10 Filters. J. Air Pollut. Control Assoc., 36:817, 1986.

13. Harrell, R.M. Measuring the Alkalinity of Hi-Vol Air Filters. EMSL/RTP-SOP-QAD-534, October 1985. Available from the U.S. Environmental Protection Agency, EMSL/QAD, Research Triangle Park, NC 27711.

14. 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 27711, 1978.

Appendix K to Part 50—Interpretation of the National Ambient Air Quality Standards for Particulate Matter

1.0 General

(a) This appendix explains the computations necessary for analyzing particulate matter data to determine attainment of the 24-hour standards specified in 40 CFR 50.6. For the primary and secondary standards, particulate matter is measured in the ambient air as PM10 (particles with an aerodynamic diameter less than or equal to a nominal 10 micrometers) by a reference method based on appendix J of this part and designated in accordance with part 53 of this chapter, or by an equivalent method designated in accordance with part 53 of this chapter. The required frequency of measurements is specified in part 58 of this chapter.

(b) The terms used in this appendix are defined as follows:

Average refers to the arithmetic mean of the estimated number of exceedances per year, as per Section 3.1.

Daily value for PM10 refers to the 24-hour average concentration of PM10 calculated or measured from midnight to midnight (local time).

Exceedance means a daily value that is above the level of the 24-hour standard after rounding to the nearest 10 µg/m
3 (i.e., values ending in 5 or greater are to be rounded up).

Expected annual value is the number approached when the annual values from an increasing number of years are averaged, in the absence of long-term trends in emissions or meteorological conditions.

Year refers to a calendar year.

(c) Although the discussion in this appendix focuses on monitored data, the same principles apply to modeling data, subject to EPA modeling guidelines.