Ensure adequate baseline separation of the analyses.

4.4.3 Between injections of the appropriate series of calibration standards, inject in duplicate the reagent blanks, quality control sample. and the field samples. Measure the areas or heights of the Cl-, Br- and F- peaks. Use the mean response of the duplicate injections to determine the concentrations of the field samples and reagent blanks using the linear calibration curve. The values from duplicate injections should agree within 5 percent of their mean for the analysis to be valid. Dilute any sample and the blank with equal volumes of water if the concentration exceeds that of the highest standard. 4.5 Audit Analysis. An audit sample must be analyzed, subject to availability. Environmental Protection Agency, EPA at least four calibration standards for each absorbing reagent containing the appropriate stock solutions such that they are within the linear range of the field samples. Using one of the standards in each series, ensure adequate baseline separation for the peaks of interest. Inject the appropriate series of calibration standards. starting with the lowest concentration standard first both before and after Injection of the quality control check sample, reagent blanks, and field samples. This allows compensation for any instrument drift occurring during sample analysis. Determine the peak areas, or heights. for the standards and plot individual values versus halide ion concentrations in µg/ml. Draw a smooth curve through the points. Use linear regression to calculate a formula describing the resulting linear curve. EC01JN92.267 5. Calibration 6. Quality Assurance 5.1 Dry Gas Metering System. Thermometers, Rate Meter. and Barometer. Same as in Method 6, sections 5.1. 5.2, 5.3, and 5.4. 5.2 Ion Chromatograph. To prepare the calibration standards, dilute given amounts (1.0 ml or greater) of the stock standard solutions to convenient volumes, using 0.1 N H₂SO₂ or 0.1 N NaOH, as appropriate. Prepare 6.1 Applicability. When the method is used to analyze samples to demonstrate compliance with a source emission regulation, a set of two audit samples must be analyzed. 6.2 Audit Procedure. The audit sample are chloride solutions. Concurrently analyze the two audit samples and a set of compliance samples in the same manner to evaluate the technique of the analyst and the standards preparation. The same analyst, analytical reagents, and analytical system shall be used both for compliance samples and the EPA audit samples. If this condition is met. auditing the subsequent compliance analyses for the same enforcement agency within 30 days is not required. An audit sample set may not be used to validate different sets of compliance samples under the jurisdiction of different enforcement agencies. unless prior arrangements are made with both enforcement agencies. 6.3 Audit Sample Availability. The audit samples may be obtained by writing or call- Ing the EPA Regional Office or the appropriate enforcement agency. The request for the audit samples must be made at least 30 days prior to the scheduled compliance sample analyses. 6.4 Audit Results. 6.4.1 Calculate the concentrations in mg/ dscm using the specified sample volume in the audit instructions. NOTE: Indication of acceptable results may be obtained immediately by reporting the audit results in mg/dscm and compliance results in total µg HCl/sample to the responsible enforcement agency. Include the results of both audit samples, their Identification numbers, and the analyst's name with the results of the compliance determination samples in appropriate reports to the EPA Regional Office or the appropriate enforcement agency. Include this information with subsequent analyses for the same enforcement agency during the 30-day period. Pt. 60, App. A, Meth. 26A 6.4.2 The concentrations of the audit samples obtained by the analyst shall agree within 10 percent of the actual concentrations. If the 10 percent specification is not met. reanalyze the compliance samples and audit samples, and include initial and reanalysis values in the test report. 6.4.3 Failure to meet the 10 percent specification may require retests until the audit problems are resolved. However, if the audit results do not affect the compliance or noncompliance status of the affected facility, the Administrator may waive the reanalysis requirement, further audits. or retests and accept the results of the compliance test. While steps are being taken to resolve audit analysis problems, the Administrator may also choose to use the data to determine the compliance or noncompliance status of the affected facility. 7. Calculations Retain at least one extra decimal figure beyond those contained in the available data in intermediate calculations, and round off only the final answer appropriately. 7.1 Sample Volume, Dry Basis, Corrected to Standard Conditions. Calculate the sample volume using Eq. 6-1 of Method 6. 7.2 Total µg HCI, HBr. or HF Per Sample. max=K V. (Sx Eq. 26-4 where: Bx =Mass concentration of applicable absorbing solution blank, µg halide ion (CI-, Br-, F-)/ml, not to exceed 1 µg/ml which is 10 times the published analytical detection limit of 0.1 µg/ml. mHx=Mass of HCI, HBr, or HF in sample, µg. Sx-=Analysis of sample, µg halide ion (CI-, Br-, F-)/ml. V,=Volume of filtered and diluted sample, ml. KHCI=1.028 (ug HCl/ug-mole)/(ug C1-/ µg-mole). KHBr=1.013 (ug HBr/ug-mole)/(ug Br-/ µg-mole). KHF=1.053 (µg HF/ug-mole)/(ug F-/ µg-mole). 7.3 Total µg C1₂ or Br₂ Per Sample. mx2=V, (Sx⁻-Bx⁻) Eq. 26-5 where: mx2=Mass of Cl₂ or Br₂ in sample, µg. 7.4 Concentration of Hydrogen Halide or Halogen in Flue Gas. C=K mHx,x2/Vm(etd) Eq. 26-6 where: C=Concentration of hydrogen halide (HX) or halogen (X2). dry basis. mg/dscm. V=(std)= Dry gas volume measured by the dry gas meter, corrected to standard conditions, dscm. K=10- mg/ug. 40 CFR Ch. I (7-1-99 Edition) 8. Bibliography 1. Steinsberger, S.C. and J.H. Margeson, "Laboratory-and Field Evaluation of a Methodology for Determination of Hydrogen Chloride Emissions form Municipal and Hazardous Waste Incinerators." U.S. Environmental Protection Agency, Office of Research and Development, Report No. 600/3-89/ 064, April 1989. Available from the National Technical Information Service, Springfield. VA 22161 as PB89220586/AS. 2. State of California, Air Resources Board. Method 421. "Determination of Hydrochloric Acid Emissions from Stationary Sources." March 18, 1987. 3. Cheney, J.L. and C.R. Fortune. Improvements in the Methodology for Measuring Hydrochloric Acid in Combustion Source Emissions. J. Environ. Sci. Health. A19(3): 337-350. 1984. 4. Stern, D. A., B. M. Myatt, J. F. Lachowski, and K. T. McGregor. Speciation of Halogen and Hydrogen Halide Compounds in Gaseous Emissions. In: Incineration and Treatment of Hazardous Waste: Proceedings of the 9th Annual Research Symposium. Cincinnati, Ohio, May 2-4, 1983. Publication No. 600/9-84-015. July 1984. Available from National Technical Information Service, Springfield. VA 22161 as PB84-234525. 5. Holm. R. D. and S. A. Barksdale. Analysis of Anions in Combustion Products. In: Ion Chromatographic Analysis of Environmental Pollutants. E. Sawicki, J. D. Mulik, and E. Wittgenstein (eds.). Ann Arbor, Michigan. Ann Arbor Science Publishers. 1978. pp. 99-110. Method 26A-Determination of Hydrogen Halide and Halogen Emissions from Stationary Sources-Isokinetic Method 1. Applicability, Principle, Interferences, Precision. Bias, and Stability 1.1 Applicability. This method is applicable for determining emissions of hydrogen halides (HX) [hydrogen chloride (HCI), hydrogen bromide (HBr), and hydrogen fluoride (HF)] and halogens (X2) [chlorine (CI 2) and bromine (Br2)] from stationary sources. This method collects the emission sample isokinetically and is therefore particularly suited for sampling at sources, such as those controlled by wet scrubbers, emitting acid particulate matter (e.g., hydrogen halides dissolved in water droplets). [Note: Mention of trade names or specific products does not constitute endorsement by the Environmental Protection Agency.] 1.2 Principle. Gaseous and particulate pollutants are withdrawn isokinetically from the source and collected in an optional cyclone, on a filter, and in absorbing solutions. The cyclone collects any liquid droplets and is not necessary if the source emissions do not contain them; however, it is preferable METHOD 29 40 CFR PART 60 APPENDIXA Environmental Protection Agency, EPA EC16NO91.235 6.4 Air to Fuel Ratio. Use Equation 28a-3 to calculate the air to fuel ratio on a dry mass basis. EC16NO91.236 6.5 Burn Rate. Calculate the fuel burn rate as in Method 28, Section 8.3. 7. Bibliography Same as Method 3, Section 7, and Method 5H, Section 7. METHOD 29-DETERMINATION OF METALS EMISSIONS FROM STATIONARY SOURCES 1. Applicability and Principle 1.1 Applicability. This method is applicable to the determination of antimony (Sb), arsenic (As), barlum (Ba), beryllium (Be), cadmium (Cd), chromium (Cr). cobalt (Co). copper (Cu), lead (Pb). manganese (Mn), mercury (Hg). nickel (NI), phosphorus (P), selenium (Se), silver (Ag), thallium (T1), and zinc (Zn) emissions from stationary sources. This method may be used to determine particulate emissions in addition to the metals emissions if the prescribed procedures and precautions are followed. 1.1.1 Hg emissions can be measured, alternatively. using EPA Method 101A of Appendix B. 40 CFR Part 61. Method 101-A measures only Hg but it can be of special interest to sources which need to measure both Hg and Mn emissions. 1.2 Principle. A stack sample is withdrawn isokinetically from the source, particulate emissions are collected in the probe and on a heated filter. and gaseous emissions are then collected in an aqueous acidic solution of hydrogen peroxide (analyzed for all metals including Hg) and an aqueous acidic solution of potassium permanganate (analyzed only for Hg). The recovered samples are digested. and appropriate fractions are analyzed for Hg by cold vapor atomic absorption spectroscopy (CVAAS) and for Sb, As, Ba, Be, Cd, Cr. Co, Cu, Pb, Mn. NI, P. Se, Ag, T1, and Zn by inductively coupled argon plasma emission spectroscopy (ICAP) or atomic absorption spectroscopy (AAS). Graphite furnace atomic absorption spectroscopy (GFAAS) is used for analysis of Sb, As, Cd, Co. Pb. Se. and TI if these elements require greater analytical sensitivity than can be obtained by ICAP. If one so chooses. AAS may be used for analysis of all listed metals if the resulting in-stack method detection limits meet the goal of the testing program. Similarly, inductively coupled plasma-mass spectroscopy (ICP-MS) may be used for analysis of Sb, As, Ba, Be, Cd, Cr. Co, Cu, Pb, Mn, Ni, As, TI and Zn. 2. Range, Detection Limits, Precision, and Interferences 2.1 Range. For the analysis described and for similar analyses, the ICAP response is linear over several orders of magnitude. Samples containing metal concentrations in the nanograms per ml (ng/ml) to micrograms per ml (µg/ml) range in the final analytical solution can be analyzed using this method. Samples containing greater than approximately 50 µg/ml As, Cr, or Pb should be diluted to that level or lower for final analysis. Samples containing greater than approximately 20 µg/ml of Cd should be diluted to that level before analysis. 2.2 Analytical Detection Limits. (NOTE See section 2.3 for the description of in-stack detection limits.) 2.2.1 ICAP analytical detection limits for the sample solutions (based on Method 6010 in EPA Publication SW-846, Third Edition (November 1986) including updates I, II. ILA, and HB. as incorporated by reference in $60.17(i)) are approximately as follows: Sb (32 ng/ml), As (53 ng/ml), Ba (2 ng/ml), Be (0.3 ng/ ml), Cd (4 ng/ml), Cr (7 ng/ml), Co (7 ng/ml), Cu (6 ng/ml), Pb (42 ng/ml). Mn (2 ng/ml). Ni (15 ng/ml). P (75 ng/ml). Se (75 ng/ml). Ag (7 ng/ml). T1 (40 ng/ml). and Zn (2 ng/ml). ICP- MS analytical detection limits (based on based on Method 6020 in EPA Publication SW-846, Third Edition (November 1986) as incorporated by reference in $60.17(I)) are lower generally by a factor of ten or more. Be is lower by a factor of three. The actual sample analytical detection limits are sample dependent and may vary due to the sample matrix. 2.2.2 The analytical detection limits for analysis by direct aspiration AAS are approximately as follow: Sb (200 ng/ml). As (2 ng/ml). Ba (100 ng/ml), Be (5 ng/ml). Cd (5 ng/ ml). Cr (50 ng/ml), Co (50 ng/ml). Cu (20 ng/ ml). Pb (100 ng/ml), Mn (10 ng/ml), NI (40 ng/ ml). Se (2 ng/ml). Ag (10 ng/ml), T1 (100 ng/ ml). and Zn (5 ng/ml). 2.2.3 The detection limit for Hg by CVAAS (on the resultant volume of the disgestion of the aliquots taken for Hg analyses) can be approximately 0.02 to 0.2ng/ml. depending upon the type of CVAAS analytical instrument used. 2.2.4 The use of GFAAS can enhance the detection limits compared to direct aspiration AAS as follows: Sb (3 ng/ml). As (1 ng/ ml). Be (0.2 ng/ml). Cd (0.1 ng/ml). Cr (1 ng/ ml). Co (1 ng/ml). Pb (1 ng/ml), Se (2 ng/ml), and T1 (ng/ml). 2.3 In-stack Detection Limits. 2.3.1 For test planning purposes in-stack detection limits can be developed by using the following Information (1) the procedures Pt. 60, App. A, Meth. 29 40 CFR Ch. I (7-1-99 Edition) described in this method, (2) the analytical detection limits described in Section 2.2 and in EPA Publication SW-846, Third Edition (November 1986) including updates I. II, IIA and IIB, as incorporated by reference in $60.17(i). (3) the normal volumes of 300 ml (Analytical Fraction 1) for the front-half and 150 ml (Analytical Fraction 2A) for the backhalf samples, and (4) a stack gas sample volume of 1.25 m³. The resultant in-stack method detection limits for the above set of conditions are presented in Table 29-1 and were calculated by using Eq. 29-1. AxB/C-D Eq. 29-1 Where: A=Analytical detectin limit, µg/ml. B=Liquid volume of digested sample prior to aliquotting for analysis, MI. C=Stack sample gas volume, dsm 3. D=In-stack detection limit, µg/m³ TABLE 29-1.-IN-STACK METHOD DETECTION LIMITS (µG/M³) FOR THE FRONT-HALF, THE BACK- HALF, AND THE TOTAL SAMPLING TRAIN USING ICAP AND AAS Metal Front-halt: Probe and Back-half: Impingers Back-half: Impingers filter 1-3 (4-6)* Total train: Antimony 17.7 (0.7) '3.8 (0.4) 111.5 (1.1) Arsenic 112.7 (0.3) 16.4 (0.1) 119.1 (0.4) Barium 0.5 0.3 0.8 Beryllium 10.07 (0.05) 10.04 (0.03) 10.11 (0.08) Cadmium 11.0 (0.02) '0.5 (0.01) 11.5 (0.03) Chromium 11.7 (0.2) '0.8 (0.1) 12.5 (0.3) Cobalt 11.7 (0.2) '0.8 (0.1) 12.5 (0.3) Copper 1.4 0.7 2.1 Lead 10.1 (0.2) 15.0 (0.1) 115.1 (0.3) Manganese 10.5 (0.2) 10.2 (0.1) 10.7 (0.3) Mercury 20.06 20.3 20.2