Page images

Pb/ml; concentration S 10 ME Pb/ml. If either standard deviates by more than 5 per. cent from the value predicted by the call. bration curve, recallbrate and repeat the previous 10 analyses.

10. Calculation

10.1 Measured air volume. Calculate the measured air volume at Standard Tempera

ture and Pressure as described in Reference 10.

10.2 Lead concentration. Calculate lead concentration in the air sample.

(ug Pb/ml x 100 ml/strip 12 strips/filter) - Fo

C =


where: C=Concentration, ug Pb/sm'. ug Pb/ml=Lead concentration determined

from section 8. 100 ml/strip=Total sample volume. 12 strips=Total useable filter area, 8" x 9".

Exposed area of one strip, 4" x 7". Filter=Total area of one strip, 44" X 8". Fo=Lead concentration of blank filter, ug,

from section Vstp=Air volume from section 10.2.

11. Quality control

44" x 8" glass fiber filter strips containing 80 to 2000 ug Pb/strip (as lead salts) and blank strips with zero Pb content should be used to determine if the method-as being used-has any bias. Quality control charts should be established to monitor differences between measured and true values. The frequency of such checks will depend on the local quality control program.

To minimize the possibility of generating unreliable data, the user should follow practices established for assuring the quality of air pollution data, (13) and take part in EPA's semiannual audit program for lead analyses.

12. Trouble shooting.

1. During extraction of lead by the hot extraction procedure, it is important to keep the sample covered so that corrosion products-formed on fume hood surfaces which may contain lead-are not deposited in the extract.

2. The sample acid concentration should minimize corrosion of the nebulizer. However, different nebulizers may require lower acid concentrations. Lower concentrations can be used provided samples and standards have the same acid concentration.

3. Ashing of particulate samples has been found, by EPA and contractor laboratories, to be unnecessary in lead analyses by atomic absorption. Therefore, this step was omitted from the method.

4. Filtration of extracted samples, to remove particulate matter, was specifically excluded from sample preparation, because

some analysts have observed losses of lead due to filtration.

5. If suspended solids should clog the nebulizer during analysis of samples, centrifuge the sample to remove the solids.

13. Authority.

(Secs. 109 and 301(a), Clean Air Act, as amended (42 U.S.C. 7409, 7601(a)))

14. References.

1. Scott, D. R. et al. “Atomic Absorption and Optical Emission Analysis of NASN Atmospheric Particulate Samples for Lead." Envir. Sci. and Tech., 10, 877-880 (1976).

2. Skogerboe, R. K. et al. "Monitoring for Lead in the Environment." pp. 57-66, Department of Chemistry, Colorado State University, Fort Collins, Colo. 80523. Submitted to National Science Foundation for publications, 1976.

3. Zdrojewski, A. et al. “The Accurate Measurement of Lead in Airborne Particulates." Inter. J. Environ. Anah Chem., 2, 6377 (1972).

4. Slavin, W., "Atomic Absorption Spectroscopy.” Published by Interscience Company, New York, N.Y. (1968).

5. Kirkbright, G. F., and Sargent, M., “Atomic Absorption and Fluorescence Spectroscopy." Published by Academic Press, New York, N.Y. 1974.

6. Burnham, C. D. et al., "Determination of Lead in Airborne Particulates in Chicago and Cook County, II. by Atomic Absorption Spectroscopy." Envir. Sci. and Tech., 3, 472475 (1969).

7. "Proposed Recommended Practices for Atomic Absorption Spectrometry." ASTM Book of Standards, part 30, pp. 1596-1608 (July 1973).

8. Koirttyohann, S. R. and Wen, J. W., "Critical Study of the APCD-MIBK Extraction System for Atomic Absorption." Anal Chem., 45, 1986-1989 (1973).

9. Collaborative Study of Reference Method for the Determination of Suspended Particulates in the Atmosphere (High Volume Method). Obtainable from National Technical Information Service, Department

[merged small][merged small][graphic][subsumed][subsumed][subsumed][merged small][subsumed][ocr errors][subsumed][subsumed][merged small][subsumed][subsumed][subsumed][subsumed][subsumed][subsumed][subsumed][merged small]
[graphic][subsumed][subsumed][merged small][merged small][merged small]

(Secs. 109, 301(a) of the Clean Air Act, as amended (42 U.S.C. 7409, 7601(a)); secs. 110, 301(a) and 319 of the Clean Air Act (42 U.S.C. 7410, 7601(a), 7619)) [43 FR 46258, Oct. 5, 1978; 44 FR 37915, June 29, 1979, as amended at 46 FR 44163, Sept. 3, 1981; 52 FR 24664, July 1, 1987)

This appendix explains how to determine when the expected number of days per cal. endar year with maximum hourly average concentrations above 0.12 ppm (235 ug/m') 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 & 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 aver



1. General

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 likel 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:

[blocks in formation]

age 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. 2. Interpretation of Expected Exceedances

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. 3. Estimating the Number of Exceedances for a Year

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

(*Indicates multiplication.) where: e=the estimated number of exceedances

for the year, N=the number of required monitoring

days in the year, n=the number of valid daily maxima, V=the number of daily values above the

level of the standard, and Z=the number of days assumed to be less

than the standard level. 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 2, 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.

(44 FR 8220, Feb. 8, 1979)




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 (PM10) in ambient air over a 24hour 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 PM10 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 di. vided by the volume of air sampled, and is expressed in micrograms per standard cubic meter (ug/std m%). 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. Al. though 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 filterchanging 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 ug/std ms while maintaining the operating flow rate within the specified limits.

4.0 Precision.

4.1 The precision of PM10 samplers must be 5 ug/m3 for PM10 concentrations below 80 ug/ms and 7 percent for PM10 concentrations above 80 ug/m3, 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 condi. tions. 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 effectivensss 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

« PreviousContinue »