Title 40

Appendix A-1 to Part 50 - Reference Measurement Principle and Calibration Procedure for the Measurement of Sulfur Dioxide in the Atmosphere (Ultraviolet Fluorescence Method)

40:2.0.1.1.1.0.1.20.1 : Appendix A

Appendix A-1 to Part 50 - Reference Measurement Principle and Calibration Procedure for the Measurement of Sulfur Dioxide in the Atmosphere (Ultraviolet Fluorescence Method) 1.0 Applicability

1.1 This ultraviolet fluorescence (UVF) method provides a measurement of the concentration of sulfur dioxide (SO2) in ambient air for determining compliance with the national primary and secondary ambient air quality standards for sulfur oxides (sulfur dioxide) as specified in § 50.4, § 50.5, and § 50.17 of this chapter. The method is applicable to the measurement of ambient SO2 concentrations using continuous (real-time) sampling. Additional quality assurance procedures and guidance are provided in part 58, appendix A, of this chapter and in Reference 3.

2.0 Principle

2.1 This reference method is based on automated measurement of the intensity of the characteristic fluorescence released by SO2 in an ambient air sample contained in a measurement cell of an analyzer when the air sample is irradiated by ultraviolet (UV) light passed through the cell. The fluorescent light released by the SO2 is also in the ultraviolet region, but at longer wavelengths than the excitation light. Typically, optimum instrumental measurement of SO2 concentrations is obtained with an excitation wavelength in a band between approximately 190 to 230 nm, and measurement of the SO2 fluorescence in a broad band around 320 nm, but these wavelengths are not necessarily constraints of this reference method. Generally, the measurement system (analyzer) also requires means to reduce the effects of aromatic hydrocarbon species, and possibly other compounds, in the air sample to control measurement interferences from these compounds, which may be present in the ambient air. References 1 and 2 describe UVF method.

2.2 The measurement system is calibrated by referencing the instrumental fluorescence measurements to SO2 standard concentrations traceable to a National Institute of Standards and Technology (NIST) primary standard for SO2 (see Calibration Procedure below).

2.3 An analyzer implementing this measurement principle is shown schematically in Figure 1. Designs should include a measurement cell, a UV light source of appropriate wavelength, a UV detector system with appropriate wave length sensitivity, a pump and flow control system for sampling the ambient air and moving it into the measurement cell, sample air conditioning components as necessary to minimize measurement interferences, suitable control and measurement processing capability, and other apparatus as may be necessary. The analyzer must be designed to provide accurate, repeatable, and continuous measurements of SO2 concentrations in ambient air, with measurement performance as specified in Subpart B of Part 53 of this chapter.

2.4 Sampling considerations: The use of a particle filter on the sample inlet line of a UVF SO2 analyzer is required to prevent interference, malfunction, or damage due to particles in the sampled air.

3.0 Interferences

3.1 The effects of the principal potential interferences may need to be mitigated to meet the interference equivalent requirements of part 53 of this chapter. Aromatic hydrocarbons such as xylene and naphthalene can fluoresce and act as strong positive interferences. These gases can be removed by using a permeation type scrubber (hydrocarbon “kicker”). Nitrogen oxide (NO) in high concentrations can also fluoresce and cause positive interference. Optical filtering can be employed to improve the rejection of interference from high NO. Ozone can absorb UV light given off by the SO2 molecule and cause a measurement offset. This effect can be reduced by minimizing the measurement path length between the area where SO2 fluorescence occurs and the photomultiplier tube detector (e.g., <5 cm). A hydrocarbon scrubber, optical filter and appropriate distancing of the measurement path length may be required method components to reduce interference.

4.0 Calibration Procedure

Atmospheres containing accurately known concentrations of sulfur dioxide are prepared using a compressed gas transfer standard diluted with accurately metered clean air flow rates.

4.1 Apparatus: Figure 2 shows a typical generic system suitable for diluting a SO2 gas cylinder concentration standard with clean air through a mixing chamber to produce the desired calibration concentration standards. A valve may be used to conveniently divert the SO2 from the sampling manifold to provide clean zero air at the output manifold for zero adjustment. The system may be made up using common laboratory components, or it may be a commercially manufactured system. In either case, the principle components are as follows:

4.1.1 SO2 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, properly calibrated to a NIST-traceable standard.

4.1.2 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, properly calibrated to a NIST-traceable standard.

4.1.3 Mixing chamber, of an inert material such as glass and of proper design to provide thorough mixing of pollutant gas and diluent air streams.

4.1.4 Sampling manifold, constructed of glass, polytetrafluoroethylene (PTFE Teflon TM), or other suitably inert material and of sufficient diameter to insure a minimum pressure drop at the analyzer connection, with a vent designed to insure a minimum over-pressure (relative to ambient air pressure) at the analyzer connection and to prevent ambient air from entering the manifold.

4.1.5 Standard gas pressure regulator, of clean stainless steel with a stainless steel diaphragm, suitable for use with a high pressure SO2 gas cylinder.

4.1.6 Reagents

4.1.6.1 SO2 gas concentration transfer standard having a certified SO2 concentration of not less than 10 ppm, in N2, traceable to a NIST Standard Reference Material (SRM).

4.1.6.2 Clean zero air, free of contaminants that could cause a detectable response or a change in sensitivity of the analyzer. Since ultraviolet fluorescence analyzers may be sensitive to aromatic hydrocarbons and O2-to-N2 ratios, it is important that the clean zero air contains less than 0.1 ppm aromatic hydrocarbons and O2 and N2 percentages approximately the same as in ambient air. A procedure for generating zero air is given in reference 1.

4.2 Procedure

4.2.1 Obtain a suitable calibration apparatus, such as the one shown schematically in Figure 1, and verify that all materials in contact with the pollutant are of glass, Teflon TM, or other suitably inert material and completely clean.

4.2.2 Purge the SO2 standard gas lines and pressure regulator to remove any residual air.

4.2.3 Ensure that there are no leaks in the system and that the flow measuring devices are properly and accurately calibrated under the conditions of use against a reliable volume or flow rate standard such as a soap-bubble meter or a wet-test meter traceable to a NIST standard. All volumetric flow rates should be corrected to the same reference temperature and pressure by using the formula below:

$$ Where: Fc = corrected flow rate (L/min at 25 °C and 760 mm Hg), Fm = measured flow rate, (at temperature, Tm and pressure, Pm), Pm = measured pressure in mm Hg, (absolute), and Tm = measured temperature in degrees Celsius.

4.2.4 Allow the SO2 analyzer under calibration to sample zero air until a stable response is obtained, then make the proper zero adjustment.

4.2.5 Adjust the airflow to provide an SO2 concentration of approximately 80 percent of the upper measurement range limit of the SO2 instrument and verify that the total air flow of the calibration system exceeds the demand of all analyzers sampling from the output manifold (with the excess vented).

4.2.6 Calculate the actual SO2 calibration concentration standard as:

$$ Where: C = the concentration of the SO2 gas standard Fp = the flow rate of SO2 gas standard Ft = the total air flow rate of pollutant and diluent gases

4.2.7 When the analyzer response has stabilized, adjust the SO2 span control to obtain the desired response equivalent to the calculated standard concentration. If substantial adjustment of the span control is needed, it may be necessary to re-check the zero and span adjustments by repeating steps 4.2.4 through 4.2.7 until no further adjustments are needed.

4.2.8 Adjust the flow rate(s) to provide several other SO2 calibration concentrations over the analyzer's measurement range. At least five different concentrations evenly spaced throughout the analyzer's range are suggested.

4.2.9 Plot the analyzer response (vertical or Y-axis) versus SO2 concentration (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.

Note:

Additional information on calibration and pollutant standards is provided in Section 12 of Reference 3.

5.0 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 3, Appendix D: Measurement Quality Objectives and Validation Template for SO2 (page 9 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 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 for SO2 Method 1. H. Okabe, P. L. Splitstone, and J. J. Ball, “Ambient and Source SO2 Detector Based on a Fluorescence Method”, Journal of the Air Control Pollution Association, vol. 23, p. 514-516 (1973). 2. F. P. Schwarz, H. Okabe, and J. K. Whittaker, “Fluorescence Detection of Sulfur Dioxide in Air at the Parts per Billion Level,” Analytical Chemistry, vol. 46, pp. 1024-1028 (1974). 3. QA Handbook for Air Pollution Measurement Systems - Volume II. Ambient Air Quality Monitoring Programs. U.S. [75 FR 35593, June 22, 2010]

Appendix A-2 to Part 50 - Reference Method for the Determination of Sulfur Dioxide in the Atmosphere (Pararosaniline Method)

40:2.0.1.1.1.0.1.20.2 : Appendix A

Appendix A-2 to Part 50 - Reference Method for the Determination of Sulfur Dioxide in the Atmosphere (Pararosaniline Method)

1.0 Applicability.

1.1 This method provides a measurement of the concentration of sulfur dioxide (SO2) in ambient air for determining compliance with the primary and secondary national ambient air quality standards for sulfur oxides (sulfur dioxide) as specified in § 50.4 and § 50.5 of this chapter. The method is applicable to the measurement of ambient SO2 concentrations using sampling periods ranging from 30 minutes to 24 hours. Additional 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 A measured volume of air is bubbled through a solution of 0.04 M potassium tetrachloromercurate (TCM). The SO2 present in the air stream reacts with the TCM solution to form a stable monochlorosulfonatomercurate(3) complex. Once formed, this complex resists air oxidation(4, 5) and is stable in the presence of strong oxidants such as ozone and oxides of nitrogen. During subsequent analysis, the complex is reacted with acid-bleached pararosaniline dye and formaldehyde to form an intensely colored pararosaniline methyl sulfonic acid.

(6) The optical density of this species is determined spectrophotometrically at 548 nm and is directly related to the amount of SO2 collected. The total volume of air sampled, corrected to EPA reference conditions (25 °C, 760 mm Hg [101 kPa]), is determined from the measured flow rate and the sampling time. The concentration of SO2 in the ambient air is computed and expressed in micrograms per standard cubic meter (µg/std m 3).

3.0 Range.

3.1 The lower limit of detection of SO2 in 10 mL of TCM is 0.75 µg (based on collaborative test results).(7) This represents a concentration of 25 µg SO2/m 3 (0.01 ppm) in an air sample of 30 standard liters (short-term sampling) and a concentration of 13 µg SO2/m 3 (0.005 ppm) in an air sample of 288 standard liters (long-term sampling). Concentrations less than 25 µg SO2/m 3 can be measured by sampling larger volumes of ambient air; however, the collection efficiency falls off rapidly at low concentrations.(8, 9) Beer's law is adhered to up to 34 µg of SO2 in 25 mL of final solution. This upper limit of the analysis range represents a concentration of 1,130 µg SO2/m 3 (0.43 ppm) in an air sample of 30 standard liters and a concentration of 590 µg SO2/m 3 (0.23 ppm) in an air sample of 288 standard liters. Higher concentrations can be measured by collecting a smaller volume of air, by increasing the volume of absorbing solution, or by diluting a suitable portion of the collected sample with absorbing solution prior to analysis.

4.0 Interferences.

4.1 The effects of the principal potential interferences have been minimized or eliminated in the following manner: Nitrogen oxides by the addition of sulfamic acid,(10, 11) heavy metals by the addition of ethylenediamine tetracetic acid disodium salt (EDTA) and phosphoric acid,(10, 12) and ozone by time delay.(10) Up to 60 µg Fe (III), 22 µg V (V), 10 µg Cu (II), 10 µg Mn (II), and 10 µg Cr (III) in 10 mL absorbing reagent can be tolerated in the procedure.(10) No significant interference has been encountered with 2.3 µg NH3.(13)

5.0 Precision and Accuracy.

5.1 The precision of the analysis is 4.6 percent (at the 95 percent confidence level) based on the analysis of standard sulfite samples.(10)

5.2 Collaborative test results (14) based on the analysis of synthetic test atmospheres (SO2 in scrubbed air) using the 24-hour sampling procedure and the sulfite-TCM calibration procedure show that:

• The replication error varies linearly with concentration from ±2.5 µg/m 3 at concentrations of 100 µg/m 3 to ±7 µg/m 3 at concentrations of 400 µg/m 3. • The day-to-day variability within an individual laboratory (repeatability) varies linearly with concentration from ±18.1 µg/m 3 at levels of 100 µg/m 3 to ±50.9 µg/m 3 at levels of 400 µg/m 3. • The day-to-day variability between two or more laboratories (reproducibility) varies linearly with concentration from ±36.9 µg/m 3 at levels of 100 µg/m 3 to ±103.5 µ g/m 3 at levels of 400 µg/m 3. • The method has a concentration-dependent bias, which becomes significant at the 95 percent confidence level at the high concentration level. Observed values tend to be lower than the expected SO2 concentration level.

6.0 Stability.

6.1 By sampling in a controlled temperature environment of 15° ±10 °C, greater than 98.9 percent of the SO2-TCM complex is retained at the completion of sampling. (15) If kept at 5 °C following the completion of sampling, the collected sample has been found to be stable for up to 30 days. (10) The presence of EDTA enhances the stability of SO2 in the TCM solution and the rate of decay is independent of the concentration of SO2. (16)

7.0 Apparatus.

7.1 Sampling.

7.1.1 Sample probe: A sample probe meeting the requirements of section 7 of 40 CFR part 58, appendix E (Teflon ® or glass with residence time less than 20 sec.) is used to transport ambient air to the sampling train location. The end of the probe should be designed or oriented to preclude the sampling of precipitation, large particles, etc. A suitable probe can be constructed from Teflon ® tubing connected to an inverted funnel.

7.1.2 Absorber - short-term sampling: An all glass midget impinger having a solution capacity of 30 mL and a stem clearance of 4 ±1 mm from the bottom of the vessel is used for sampling periods of 30 minutes and 1 hour (or any period considerably less than 24 hours). Such an impinger is shown in Figure 1. These impingers are commercially available from distributors such as Ace Glass, Incorporated.

7.1.3 Absorber - 24-hour sampling: A polypropylene tube 32 mm in diameter and 164 mm long (available from Bel Art Products, Pequammock, NJ) is used as the absorber. The cap of the absorber must be a polypropylene cap with two ports (rubber stoppers are unacceptable because the absorbing reagent can react with the stopper to yield erroneously high SO2 concentrations). A glass impinger stem, 6 mm in diameter and 158 mm long, is inserted into one port of the absorber cap. The tip of the stem is tapered to a small diameter orifice (0.4 ±0.1 mm) such that a No. 79 jeweler's drill bit will pass through the opening but a No. 78 drill bit will not. Clearance from the bottom of the absorber to the tip of the stem must be 6 ±2 mm. Glass stems can be fabricated by any reputable glass blower or can be obtained from a scientific supply firm. Upon receipt, the orifice test should be performed to verify the orifice size. The 50 mL volume level should be permanently marked on the absorber. The assembled absorber is shown in Figure 2.

7.1.4 Moisture trap: A moisture trap constructed of a glass trap as shown in Figure 1 or a polypropylene tube as shown in Figure 2 is placed between the absorber tube and flow control device to prevent entrained liquid from reaching the flow control device. The tube is packed with indicating silica gel as shown in Figure 2. Glass wool may be substituted for silica gel when collecting short-term samples (1 hour or less) as shown in Figure 1, or for long term (24 hour) samples if flow changes are not routinely encountered.

7.1.5 Cap seals: The absorber and moisture trap caps must seal securely to prevent leaks during use. Heat-shrink material as shown in Figure 2 can be used to retain the cap seals if there is any chance of the caps coming loose during sampling, shipment, or storage.

7.1.6 Flow control device: A calibrated rotameter and needle valve combination capable of maintaining and measuring air flow to within ±2 percent is suitable for short-term sampling but may not be used for long-term sampling. A critical orifice can be used for regulating flow rate for both long-term and short-term sampling. A 22-gauge hypodermic needle 25 mm long may be used as a critical orifice to yield a flow rate of approximately 1 L/min for a 30-minute sampling period. When sampling for 1 hour, a 23-gauge hypodermic needle 16 mm in length will provide a flow rate of approximately 0.5 L/min. Flow control for a 24-hour sample may be provided by a 27-gauge hypodermic needle critical orifice that is 9.5 mm in length. The flow rate should be in the range of 0.18 to 0.22 L/min.

7.1.7 Flow measurement device: Device calibrated as specified in 9.4.1 and used to measure sample flow rate at the monitoring site.

7.1.8 Membrane particle filter: A membrane filter of 0.8 to 2 µm porosity is used to protect the flow controller from particles during long-term sampling. This item is optional for short-term sampling.

7.1.9 Vacuum pump: A vacuum pump equipped with a vacuum gauge and capable of maintaining at least 70 kPa (0.7 atm) vacuum differential across the flow control device at the specified flow rate is required for sampling.

7.1.10 Temperature control device: The temperature of the absorbing solution during sampling must be maintained at 15° ±10 °C. As soon as possible following sampling and until analysis, the temperature of the collected sample must be maintained at 5° ±5 °C. Where an extended period of time may elapse before the collected sample can be moved to the lower storage temperature, a collection temperature near the lower limit of the 15 ±10 °C range should be used to minimize losses during this period. Thermoelectric coolers specifically designed for this temperature control are available commercially and normally operate in the range of 5° to 15 °C. Small refrigerators can be modified to provide the required temperature control; however, inlet lines must be insulated from the lower temperatures to prevent condensation when sampling under humid conditions. A small heating pad may be necessary when sampling at low temperatures (<7 °C) to prevent the absorbing solution from freezing.(17)

7.1.11 Sampling train container: The absorbing solution must be shielded from light during and after sampling. Most commercially available sampler trains are enclosed in a light-proof box.

7.1.12 Timer: A timer is recommended to initiate and to stop sampling for the 24-hour period. The timer is not a required piece of equipment; however, without the timer a technician would be required to start and stop the sampling manually. An elapsed time meter is also recommended to determine the duration of the sampling period.

7.2 Shipping.

7.2.1 Shipping container: A shipping container that can maintain a temperature of 5° ±5 °C is used for transporting the sample from the collection site to the analytical laboratory. Ice coolers or refrigerated shipping containers have been found to be satisfactory. The use of eutectic cold packs instead of ice will give a more stable temperature control. Such equipment is available from Cole-Parmer Company, 7425 North Oak Park Avenue, Chicago, IL 60648.

7.3 Analysis.

7.3.1 Spectrophotometer: A spectrophotometer suitable for measurement of absorbances at 548 nm with an effective spectral bandwidth of less than 15 nm is required for analysis. If the spectrophotometer reads out in transmittance, convert to absorbance as follows:

$$ where: A = absorbance, and T = transmittance (0<≥T<1).

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)

• Place 0.20 mL of potassium permanganate solution (0.316 g/L), 500 mL of distilled water, and 1mL of concentrated sulfuric acid in a chemically resistant glass bottle, stopper the bottle, and allow to stand. • If the permanganate color (pink) does not disappear completely after a period of 1 hour at room temperature, the water is suitable for use. • If the permanganate color does disappear, the water can be purified by redistilling with one crystal each of barium hydroxide and potassium permanganate in an all glass still.

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:

$$ where: M = volume of thiosulfate required in mL, and W = weight of potassium iodate in g (recorded weight in Section 8.2.7). $$

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:

$$ where: A = volume of thiosulfate titrant required for the blank, mL; B = volume of thiosulfate titrant required for the sample, mL; NT = normality of the thiosulfate titrant, from equation (3); 32,000 = milliequivalent weight of SO2, µg; 25 = volume of standard sulfite solution, mL; and 0.02 = dilution factor.

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 -

• The dye must have a maximum absorbance at a wavelength of 540 nm when assayed in a buffered solution of 0.1 M sodium acetate-acetic acid; • The absorbance of the reagent blank, which is temperature sensitive (0.015 absorbance unit/ °C), must not exceed 0.170 at 22 °C with a 1-cm optical path length when the blank is prepared according to the specified procedure; • The calibration curve (Section 10.0) must have a slope equal to 0.030 ±0.002 absorbance unit/µg SO2 with a 1-cm optical path length when the dye is pure and the sulfite solution is properly standardized.

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

$$ where: A = measured absorbance of the final mixture (absorbance units); W = weight in grams of the PRA dye used in the assay to prepare 50 mL of stock solution (for example, 0.100 g of dye was used to prepare 50 mL of solution in the purification procedure; when obtained from commercial sources, use the stated concentration to compute W; for 98% PRA, W = .098 g.); and K = 21.3 for spectrophotometers having a spectral bandwidth of less than 15 nm and a path length of 1 cm.

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.

$$ where: Qstd = flow rate at standard conditions, std L/min (25 °C and 760 mm Hg); Qact = flow rate at monitoring site conditions, L/min; Pb = barometric pressure at monitoring site conditions, mm Hg or kPa; RH = fractional relative humidity of the air being measured; PH2O = vapor pressure of water at the temperature of the air in the flow or volume standard, in the same units as Pb, (for wet volume standards only, i.e., bubble flowmeter or wet test meter; for dry standards, i.e., dry test meter, PH2O = 0); Pstd = standard barometric pressure, in the same units as Pb (760 mm Hg or 101 kPa); and Tmeter = temperature of the air in the flow or volume standard, °C (e.g., bubble flowmeter).

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

$$ where: H = sampling site elevation above sea level in meters.

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:

$$ where: A = corrected absorbance, Aobs = uncorrected absorbance, and Ac = cell correction.

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.