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LEAD by Flame AAS

7082

Pb

MW:

207.19 (Pb) CAS: 7439-92-1 (Pb) RTECS: 223.19 (PbO) 1317-36-8 (PbO)
EVALUATION: FULL

OF7525000 (Pb) OG1750000 (PbO)
Issue 1: 15 February 1984 Issue 2: 15 August 1994

METHOD: 7082, Issue 2

OSHA : 0.05 mg/m3 NIOSH: <0.1 mg/m3; blood Pb 60 µg/100 g ACGIH: 0.05 mg/m3

PROPERTIES: soft metal; d 11.3 g/cm3; MP 327.5 C valences +2, +4 in salts

SYNONYMS: elemental lead and lead compounds except alkyl lead

SAMPLING SAMPLER: FILTER (0.8-µm cellulose ester membrane) 1 to 4 L/min 200 L @ 0.05 mg/m3 1500 L routine TECHNIQUE:

MEASUREMENT ATOMIC ABSORPTION SPECTROPHOTOMETER, FLAME lead conc. HNO3, 6 mL + 30% H2O2, 1 mL; 140 C 10% HNO3, 10 mL air-acetylene, oxidizing 283.3 nm

FLOW RATE: VOL-MIN: -MAX: SHIPMENT: SAMPLE STABILITY: BLANKS:

ANALYTE: ASHING:

FINAL SOLUTION: FLAME:

stable WAVELENGTH: 2 to 10 field blanks per set ACCURACY BACKGROUND CORRECTION: CALIBRATION: RANGE ESTIMATED LOD: PRECISION ( r): D2 or H2 lamp, or Zeeman Pb2+ in 10% HNO3 10 to 200 µg per sample [2,3] 2.6 µg per sample [4] 0.03 [1]

RANGE STUDIED:

0.13 to 0.4 mg/m3 [1]; 0.15 to 1.7 mg/m3 (fume) [2] 3.1%
rT): 0.072 [1]; 0.068 (fume) [2]

BIAS: OVERALL PRECISION(

ACCURACY:

± 17.6%

APPLICABILITY: The working range is 0.05 to >1 mg/m3 for a 200-L air sample. The method is applicable to elemental lead, including Pb fume, and all other aerosols containing lead. This is an elemental analysis, not compound specific. Aliquots of the samples can be analyzed separately for additional elements.

INTERFERENCES: Use D2 or H2 continuum or Zeeman background correction to control flame or molecular absorption. High concentrations of calcium, sulfate, carbonate, phosphate, iodide, fluoride, or acetate can be corrected.

OTHER METHODS: This method combines and replaces P&CAM 173 [3] and S341 [4,5] for lead. Method 7300 (ICP-AES) and 7105 (AAS/GF) are alternate analytical methods. Method 7505 is specific for lead sulfide. The following have not been revised: the dithizone method, which appears in P&CAM 102 [5] and the lead criteria document [6]; and P&CAM 191 (ASV) [7].

NIOSH Manual of Analytical Methods (NMAM), Fourth Edition

filtered. Issue 2. 8. and 1 mL 30% H2O2 and cover with a watchglass.* flexible connecting tubing.* 1. surface temperature 140 C. Hotplate. dilute to 1 L with 1% (v/v) HCl. 5. 1000 µg/mL Pb. 0. Open the cassette filter holders and transfer the samples and blanks to clean beakers. and corrosive to the skin.8. 10. Air. 10% (v/v). When sample is dry. Personal sampling pump.00 g Pb an air-acetylene burner head and metal in minimum volume of (1+1) HCl and background correction. for air and 6. 100-mL. 0. 125-mL. Fourth Edition . 50-mL with watchglass covers. Store in a 4. Sample at an accurately known flow rate between 1 and 4 L/min for up to 8 h for a total sample size of 200 to 1500 L for TWA measurements. 1 to 4 L/min. 9. Steps 4 through 9 of Method 7300 or other quantitative ashing techniques may be substituted. 10. Repeat two more times using 2 mL conc. 5. 4. Calibration stock solution. dilute to 1 L. Distilled or deionized water. with 2 reagent grade. 3 2 7. 30% H O2 (w/w). 2. Add 3 mL conc. or Griffin. ** Clean all glassware with conc. Wear gloves and eye protection.Page 2 of 7 : REAGENTS: EQUIPMENT: 1.LEAD by Flame AAS Method 7082. Nitric acid. NOTE 2: The Appendix gives a microwave digestion procedure which may be necessary for complete recovery of lead from some matrices. Bottles. HNO . a strong irritant. 7.** * See SPECIAL PRECAUTIONS. SAMPLING: 1. Heat on 140 C hotplate until volume is reduced to about 0. compressed. Transfer the solution quantitatively to a 10-mL volumetric flask and dilute to volume with distilled water. 3. pore size. the solution to evaporate to dryness. dated 15 August 1994 .** 8. in cassette HNO3 to 500 mL water. 6. Nitric acid. polyethylene. Sampler: Cellulose ester filter. 9. NOTE 1: NIOSH Manual of Analytical Methods (NMAM). Regulators. Perform all acid digestions in a fume hood. Beakers. Do not exceed a filter loading of ca. Hydrogen peroxide. 2. 3. NOTE: If PbO2 is not present in the sample. 6.5 mL liquid remains. Add 100 mL conc.** 7. Stable one year. HNO 3.and 100-mL. two-stage. dischargeless lamp. Phillips. 37-mm diameter.5 mL. rinse the watchglass and walls of the beaker with 3 to 5 mL 10% HNO Allow 3. 2 5. especially if several metals are to be determined on a single filter. 10. Calibrate each personal sampling pump with a representative sampler in line. Assorted volumetric pipets as needed. Lead hollow cathode lamp or electrode polyethylene bottle. SPECIAL PRECAUTIONS: Concentrated nitric acid is an irritant and may burn skin. Acetylene acetylene. Heat on 140 C hotplate until ca. 2 mg total dust. conc. Start reagent blanks at 3 this step. Volumetric flasks. 3. especially epoxy-based paint. HNO and 1 mL 30% H O2 each time. Cool each beaker and dissolve the residues in 1 mL conc. 4.4]. Hydrogen peroxide is a strong oxidizing agent. Atomic Absorption Spectrophotometer with Commercial standard or dissolve 1. SAMPLE PREPARATION: The following sample preparation gave quantitative recovery (see EVALUATION OF METHOD) [4]. filter holder.m 2. nitric acid and rinse thoroughly with distilled or deionized water before use. the 30% HO2 need not be added [2.

I . reanalyze.0 nm [8]. dated 15 August 1994 . C (mg/m ).8-m mixed cellulose ester filters (Millipore Type AA) was 100% for the aerosols. If Ca2+ or SO2 are present in 3 4 4 2+ 10-fold or greater excess. MEASUREMENT: 14. and average media blank. Set spectrophotometer as specified by the manufacturer and to conditions on page 7082-1. Use method of standard additions occasionally to check for interferences. NOTE: µg/mL mg/m EVALUATION OF METHOD: 3 Method S341 [9] was issued on October 24. c. Using the solution volumes (mL) of the sample. Store the working standards in polyethylene bottles and prepare fresh weekly. Using the measured absorbances. Recovery in the range 18 to 72 µg Pb per sample was 98%. samples.4]: NIOSH Manual of Analytical Methods (NMAM). Aspirate a standard for every 10 samples to check for instrument drift. mg/m 3. 15. V (L): C CsVs V CbVb . making the use of Dor H2 continuum. from the calibration graph. and collection efficiency of 0. 1975. add 1 mL 1 M NaEDTA to each flask before 2 2 dilution to volume: CO . using generated atmospheres of lead nitrate [1]. Subsequent studies on analytical recovery of 200 µg Pb per sample gave the following results [2. CH3COO . Aspirate standards.0 nm have slightly greater sensitivity. dilute with 10% HNO3. b. 13. C. but poorer signal-to-noise ratio compared to 283. V. Cs.13 to 0. and validated over the range 0.LEAD by Flame AAS Method 7082. CALIBRATION AND QUALITY CONTROL: 11.3 nm. a. Check recoveries with at least one spiked media blank per 10 samples.5 to 200 µg Pb per sample). and blanks. NOTE: If the absorbance values for the samples are above the linear range of the standards. and apply the appropriate dilution factor in the calculations. b 17. Analyses at 217. and media blanks. F .25 to 20 µg/mL Pb (2. or 2 Zeeman background correction mandatory at that wavelength. solution concentration (µg/mL). Record absorbance readings. Prepare a series of working standards covering the range 0. Issue 2. 12. CALCULATIONS: 16. Analyze the working standards together with the blanks and samples (steps 14 and 15). of lead in the air volume sampled. V . calculate the s b 3 concentration. Fourth Edition . PO3 . non-atomic absorption is significantly greater at 217. calculate the corresponding concentrations (µg/mL) of lead in the sample. Prepare a calibration graph of absorbance vs. Dilute to volume with 10% HNO3.0 nm. make all standards and samples 1% (w/w) in La [3].Page 3 of 7 : NOTE: If the concentration (M) of any of the following is expected to exceed the lead concentration (M) by 10-fold or more. Add aliquots of calibration stock solution to 100-mL volumetric flasks. Also. NOTE: An alternate wavelength is 217.4 mg/m a for 180-L air sample.

S. 2nd ed. rT. Additional collection efficiency studies were also done using Gelman GN-4 filters for the collection of Pb fume. Office of Solid Waste and Emergency Response. 1. P&CAM 191. P&CAM 173. Washington. Validation of a Method for Determining Elements in Solid Waste by Microwave Digestion. Grohse. P..15 and 4. (NIOSH) 77-157-C (1977). Department of Health.072 for lead nitrate > aerosol [1. Department of Health. NIOSH Manual of Analytical Methods. U. Final Report of NIOSH Contract 210-79-0058. Grohse. Yeager.S.LEAD by Flame AAS Method 7082. U. 5.M. Introduction to Microwave Sample Preparation: Theory and Practice. P. L. Quarterly Report. NIOSH Manual of Analytical Methods. Test Methods for Evaluating Solid Waste. Government Printing Office: Washington. 1989). Publ. H. U. H. Analytical Methods for Atomic Absorption Spectrophotometry. W. dated 15 August 1994 . Heavy Metal Aerosols: Collection and Dissolution Efficiencies. A. (1988). ACS Professional Reference Book Series.. and D. Vol. Eds. Kingston.Occupational Exposure to Inorganic Lead (Revised Criteria). D1193 – 77 (1985). Publ.B. Gutknecht.. DC. [3] [4] [5] [6] [7] [8] [9] [10] [11] [12] [13] [14] [15] [16] METHOD REVISED BY: NIOSH Manual of Analytical Methods (NMAM). L. U. M.S. A.M.S..Page 4 of 7 : Species Pb metal Pb metal PbO PbS PbO2 PbO2 Pb in paint* Pb in paint* Digestion Method HNO3 only HNO3 + H2O2 HNO3 only HNO3 only HNO3 only HNO3 + H2O2 HNO3 only HNO3 + H2O2 Analytical Recovery. M. Philadelphia. Department of Health.S. U. Springfield.B... NIOSH Manual of Analytical Methods. Kingston. U. (NIOSH) 77-157-A (1979). (NIOSH) 77-185 (1977).01. and Jassie. DC.M.. PA. SW-846 (1986). D.S. Overall precision.4]. S341 (revised 3/25/81). "Standard Specification for Reagent Water. Publ. 2nd ed. F. Education. Research Triangle Institute.S. ASTM." Introduction to Microwave Acid Decomposition: Theory and Practice. Environmental Protection Agency. S341. Kingston. 7. U.S.B. which had geometric mean diameter of 0. Department of Health. V. RTI Project Number 321U-3579-24. Damle. ed. Publ. and Welfare. 2nd ed. Ranade. 1988.M.. and Welfare. Education. O'Neal. REFERENCES: [1] [2] Documentation of the NIOSH Validation Tests. Jassie. VA 22161 (1981).0 L/min was 97 ± 2%. W. Perkin-Elmer (1976). PB 83-106740 from NTIS.A. (NIOSH) 82-100 (1982). Environmental Protection Agency.. and L. H. U. was 0. available as Order No. NIOSH Manual of Analytical Methods. Department of Health.M. "Safety Guidelines for Microwave Systems in the Analytical Laboratory. and Welfare. and Welfare. Education. Eds. Criteria for a Recommended Standard.068 for Pb fume [2. % 92 ± 4 103 ± 3 93 ± 4 93 ± 5 82 ± 3 100 ± 1 95 ± 6 95 ± 6 *Standard Reference Material #1579. 2nd ed. V. (NIOSH) 78-158 (1978). 3rd Ed. Mean collection efficiency for 24 sampling runs at flow rates between 0. 11. Binstock. Publ.. Department of Health and Human Services.S.. EPA IAG #DW1-393254-01-0 January 1 – March 31. Education. V. 2nd. prepared for the Office of Solid Waste.. V. H. (NIOSH) 77-157-A (1977). 1985 Annual Book of ASTM Standards. U. Issue 2. H. Research Triangle Institute Technical Report Draft.S. NIOSH Manual of Analytical Methods. DC 20460 (November. U. DataChem Laboratories in-house procedure for microwave sample digestion. and Welfare..M. 3. Education. P&CAM 102.1 µm [2]. ACS Professional Reference Book Series. American Chemical Society: Washington. National Institute of Standards and Technology. Physical/Chemical Methods. American Chemical Society: Washington DC (1988). and Gaskill. Publ. Kingston. and Jassie.9] and 0. Fourth Edition .

001 g. and inductively coupled plasma spectroscopy (ICP) [10]. allow the reaction to stop before capping the vessel. d. Temperature is the important variable controlling the reaction. Pressure is needed to attain elevated temperatures but must be safely contained [12]. additional studies under NIOSH Contract 210-79-0058. All digestion vessels and volumetric ware must be carefully acid washed and rinsed with reagent water. Ph. Nitric acid. It provides a rapid. The speed of the turntable should be a minimum of 3 rpm. b. All digestion vessels should be cleaned by leaching with hot (1:1) nitric acid for a minimum of fifteen minutes.Page 5 of 7 : Mark Millson.1 g paint chip sample to the nearest 0. If a vigorous reaction occurs. weigh to the nearest 0. The microwave unit provides programmable power with a minimum of 574 W and can be programmed to within ± 10 W of the required power. Tare the Teflon PFA digestion vessel. Calibration of Microwave Equipment Calibrate microwave equipment in accordance with manufacturer's instructions. heated graphite furnace atomic absorption (HGFAA). Apparatus and Material[11-16] 1. 50. NIOSH/DPSE and R. Connect the overflow vessels to the center well of the unit. James B. Fourth Edition . A safety concern relates to the useof sealed containers without pressure relief valves in the unit. Weigh out 0.or 100-mL capacity.MICROWAVE DIGESTION FOR LEAD IN PAINT CHIPS (AND OTHER MATRICES) This procedure is an alternative to the procedure presented in the Sample Preparation section of this method. 2 With large paint chip samples. The sample vessel may be connected to an overflow vessel using Teflon PFA connecting tubes.7 atm (110 ± 10 psi). All references to water in the method refer to reagent water that meets the ASTM Type 2 standard. Microwave apparatus requirements a. prepared the microwave digestion procedure in the Appendix. Reagent Water. Disposable polypropylene filter funnel.. e. DeLon Hull. c. Sample Digestion a. and dried in a clean environment. UT.5 ± 0. Perkins. A rotating turntable is employed to ensure homogeneous distribution of microwave radiation within the unit. Reagents 1. d.7 atm (110 ± 10 psi) and capable of controlled pressure relief at pressures exceeding 7. 3. DataChem Laboratories. David L. APPENDIX .D. NIOSH/DBBS. 2. h. complete acid digestion prior to analysis by flame atomic absorption (FAA).5 ± 0. Analytical balance. The system requires Teflon PFA digestion vessels (120-mL capacity) capable of withstanding pressures up to 7. Salt Lake City. Wheeler. and quantitatively transfer it to the vessel.D.0 ± 0. f.001 g into the tared Teflon PFA sample vessel. spectroscopy grade. If calibration instructions are not available. 300-g capacity. rinsed with reagent water. Place the vessels evenly distributed in the turntable of the microwave unit using groups of two. All electronics are protected against corrosion for safe operation. and minimum ± 0.. six.LEAD by Flame AAS Method 7082. measure out a 2 cm piece. Procedure 1. see EPA Method 3051 [11]. The microwave unit cavity is corrosion resistant as well as ventilated. Polymeric volumetric ware in plastic (Teflon or polyethylene).1 mL concentrated nitric acid to the sample vessel in a fume hood. g. NIOSH Manual of Analytical Methods (NMAM). concentrated. Place the vessels in the microwave carrousel. Ph. and Keith Nicholson. 2.001 g. Reagent water shall be interference free. dated 15 August 1994 . S341 originally validated under NIOSH Contract CDC-94-74-45. b. c. Add 5. Issue 2. Cap the vessel torque and the cap to 12 ft-lb (16 N-m) according to the manufacturer's directions.

. liquid outside liner). the remaining vessels should be filled with 5 mL of nitric acid to achieve the full complement of vessels. If it does not clear.g. i. When fewer than the recommended number of samples are to be digested. At the end of the microwave program. Any vessels containing 5 mL of nitric acid for reagent blank purposes are counted as sample vessels.. This provides an energy balance since the microwave power absorbed is proportional to the total mass in the cavity [14]. loss of vessel seal integrity. psi Run Time.Page 6 of 7 : or 12 sample vessels. min Time @ P. use different values of power as long as they result in the same time and temperature conditions. dilute remaining digestate and note that some sample loss may have occurred. or 12 samples at a time. prepare a new sample beginning at Section 2.e. filter the sample.1 g (1) 90% 50 10:00 05:00 180 C 100% (2) 90% 100 20:00 15:00 180 C 100% (3) 0% 0 05:00 00:00 0 C 100% If the analyst wishes to digest other than two. Add 20 mL reagent water. Irradiate each group of samples to achieve a temperature of 180 °C in five minutes at a pressure of 50 psi. then reseal vessels and shake to mix thoroughly. three samples plus one blank. material in overflow collection vessel. Issue 2. allow the vessels to cool for a minimum of five minutes before removing them from the microwave unit. Filtering: The filtering apparatus must be thoroughly precleaned and rinsed with dilute nitric acid. min Temperature Fan Speed Number of Vessels: Liquid Volume per Vessel: Sample Weight: 12 5 mL 0. Fourth Edition . Continue digestion for five minutes. If the digested sample contains particulates which may clog nebulizers or interfere with injection of the sample into the instrument. dated 15 August 1994 . A sample digestion program for 12 samples is presented in the following table. e. NIOSH Manual of Analytical Methods (NMAM). allow the sample to settle or filter it: Settling: Allow the sample to stand until the supernatant is clear (usually. or improper heating conditions). Uncap and vent each vessel in a fume hood. overnight is sufficient). Filter the sample through quantitative filter paper into a second acid-cleaned container. If insufficient material is available for reanalysis.. The digestate is now ready for analysis for elements of interest using the appropriate method.g. use of a digestion time longer than 30 minutes.LEAD by Flame AAS Method 7082. If a loss of sample is detected (e. six. too large a sample. f. Continue to irradiate to achieve a temperature of 180 °C at 100 psi after 25 minutes. Transfer the sample to an acid-cleaned polyethylene bottle. determine the reason for the loss (e. PROGRAM VARIABLES FOR PAINT CHIPS SAMPLE DIGESTION WITH NITRIC ACID Stage Power Pressure. Once the source of the loss has been corrected.

Fourth Edition . Calculations: Report the concentrations based on the actual weight of the original sample.LEAD by Flame AAS Method 7082. NIOSH Manual of Analytical Methods (NMAM).Page 7 of 7 : 4. dated 15 August 1994 . Issue 2.