Attachment K 

PCWRL EQL-0510-191 SOP 
SOP 5.16.4 EQL 0510-191 

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SOP 5.16.4 EQL 0510-191 

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TABLE OF CONTENTS

1. CHANGES AND REVISIONS ......................................................................................3

2. SCOPE AND APPLICATION.......................................................................................3

3. MATRIX........................................................................................................................3

4. SAMPLE COLLECTION, PRESERVATION, SHIPPING AND STORAGE..................3

5. SUMMARY OF METHOD.............................................................................................3

6. DETECTION LIMIT ......................................................................................................4

7. INTERFERENCES .......................................................................................................4

8. DEVIATIONS FROM METHOD....................................................................................4

9. SAFETY .......................................................................................................................4

10. DEFINITIONS...............................................................................................................4

11. EQUIPMENT AND SUPPLIES.....................................................................................5

12. REAGENTS AND STANDARDS .................................................................................5

13. CALIBRATION AND STANDARDIZATION.................................................................6

14. PROCEDURE...............................................................................................................6

15. QUALITY CONTROL...................................................................................................7

16. DATA ANALYSIS AND CALCULATION.....................................................................8

17. DATA ASSESSMENT AND QC ACCEPTANCE CRITERIA .......................................9

18. CORRECTIVE ACTION FOR OUT-OF-CONTROL .....................................................9

19. HANDLING OUT-OF-CONTROL OR UNACCEPTABLE DATA .................................9

20. POLLUTION PREVENTION.........................................................................................9

21. WASTE MANAGEMENT..............................................................................................9

22. METHOD PERFORMANCE.........................................................................................9

23. REFERENCES.............................................................................................................9

24. TABLES, DIAGRAMS, FLOWCHARTS, AND VALIDATION DATA.........................10
SOP 5.16.4 EQL 0510-191 

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1. Changes and Revisions

1.1 MDL and PQL values in Sec. 6.2 and 6.3 are updated.

1.2 Section 13.8 has been added.

1.3 Section 15.4 states the concentration of the internal standard.

1.4 Section 15.5, 15.6, and 15.7 have been added.

1.5 Section 16.3 and 16.4 have been updated with the number of strips and updated 

mdl values entered into the calculation.

1.6 Table 1 has been added to Section 24.1

2. Scope and Application

2.1 This method provides a procedure for the determination of lead content of ambient 

particulate lead in TSP filters. Lead in the particulate matter is solubilized by 

extraction with nitric and hydrochloric acids facilitated by ultrasonic heating and 

subsequently determined by ICP-MS.

3. Matrix

3.1 This procedure is applicable to TSP filters.

4. Sample Collection, Preservation, Shipping and Storage

4.1 Sample collection is performed by the Pima County Department of Environmental 

Quality or other entity in accordance with 40 CFR part 58. The filters are cut into 

strips, sealed in labeled envelopes and brought to the laboratory. Samples are 

relinquished to the Quality Assurance Department along with the chain of custody. 

Each strip is assigned a laboratory identification number and logged into the 

Sapphire Data Management System before being relinquished to the analyst.

5. Summary of Method

5.1 The method describes extraction and the determination of lead in ambient 

particulate matter by ICP-MS. Sample material once solubilized and in solution is 

introduced by pneumatic nebulization into a radio frequency plasma where energy 

transfer processes cause desolvation, atomization, and ionization. The ions are 

extracted from the plasma through a differentially pumped vacuum interface and 

separated on the basis of their mass-to-charge ratio by a quadrupole mass 

spectrometer having a minimum resolution capability of 1 amu peak width, at 5% 

peak height. The PQ Excel has a resolution of 0.75 amu peak width at 10% peak 

height. The ions transmitted through the quadrupole are registered by a 

continuous dynode electron multiplier and the ion information processed by a data 

handling system. Interferences relating to the technique must be recognized and 

corrected. Such corrections must include compensations for isobaric elemental 
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interferences and interferences from Polyatomic ions derived from the plasma gas, 

reagents, or sample matrix. Instrument drift as well suppressions or 

enhancements of instrument response caused by sample matrix must be 

corrected for by the use of internal standardization.

6. Detection Limit

6.1 Method Detection Limit (MDL) is calculated in accordance with the procedure in 40 

CFR Appendix B, Part 136, Revision 1.11. 

6.2 The mdl for lead in TSP filters is 0.00006 ug/ m3.

6.3 The pql for lead in TSP filters is 0.00018 ug/ m3.

7. Interferences

7.1 Several interference sources may cause inaccuracies in the determination of trace 

elements by ICP-MS. Table 1 lists equations currently being used for interference 

corrections.

7.2 Isobaric elemental interferences – Are caused by isotopes of different elements 

which form singly or doubly charged ions of the same nominal mass-to-charge 

ratio and which cannot be resolved by the mass spectrometer. All elements 

determined by this method have a minimum of one isotope free of isobaric 

elemental interference. These interferences can be corrected in the software by 

applying an interference correction equation. The analytes used in the correction 

equations must first have been defined in the analyte database. There are no 

isobaric interferences with lead isotopes found in ambient air samples.

7.3 Physical interferences are compensated through matrix matching and the use of 

internal standards.

8. Deviations from Method

8.1 Not applicable.

9. Safety

9.1 Required laboratory personal protective equipment must be worn at all times. The 

PPE consists of safety glasses, hand gloves, and lab coat.

9.2 Analyst must be familiar with the MSDS associated with the reagents used in the 

preparation of the audit strips, in particular lead and nitric acid.

9.3 While working with the ultrasonic bath, the analyst should exercise care because 

the temperatures used can cause burns.

10. Definitions

10.1 Definitions of terms used in this SOP are included in the Glossary that is in the 

Quality Assurance Manual, Appendix C.

10.2 NAAQS - acronym for National Ambient Air Quality Standard.

10.3 TSP – acronym for Total Suspended Particles
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10.4 SRM – Standard Reference Material

10.5 NIST - National Institute of Standards and Technology

11. Equipment and Supplies

11.1 A VG PQ ExCell Inductively Coupled Plasma Mass Spectrometer with a stated 

resolution of 0.75 amu at 10% peak height. Use of the collision cell is not required 

for this application.

11.2 S60H Elma Ultrasonic unit with heating capability of 80o C.

11.3 Spinette Laboratory centrifuge.

11.4 NUNC disposable 15ml conical capped centrifuge tubes.

11.5 Digestion tube “DigiTUBE” with threaded caps.

11.6 Assorted Eppendorf pipettes.

11.7 Assorted Class A Volumetric flasks.

11.8 Whatman EMP2000 glass fiber filters.

11.9 Plastic rack to hold DigiTUBEs.

11.10 An immersion heater to facilitate heating of Ultrasonic bath.

12. Reagents and Standards

12.1 Nitric Acid, trace metal grade.

12.2 Hydrochloric acid, trace metal grade.

12.3 ASTM type 1 water is used for all dilutions.

12.4 Extraction solution: In a one liter Class A volumetric flask containing 500 ml of DI, 

add 64 ml concentrated nitric acid and 182 ml of concentrated hydrochloric acid. 

Allow to cool, the dilute to volume with DI. Mix well before using. Extraction 

solution has a shelf life of one week.

12.5 Lead standards with NIST traceability such as High Purity Standards 100028-1.

12.6 Second source lead standard with NIST traceability such as Inorganic Ventures 

CGPB-1.

12.7 Plasma grade bismuth standard for internal standard use such as High Purity 

Standards 100006-1 or equivalent.

12.8 Calibration standard contains the internal standard and is the same matrix as the 

extraction solution.

12.9 A LRB that contains all the reagents used in the extraction process is carried 

through the extraction procedures at the same time the samples are extracted. 

12.10 Prepare the Initial Calibration Verification (ICV), Lower Level Calibration 

Verification (LLCV), and Continuing Calibration Verification (CCV) from a source 

other than that used to make the calibration standards. The concentrations can be 

at or below the midpoint of the calibration curve and are prepared using the acid 

matrix as the calibration standards. The ICV and CCV may be the same solution. 

All three solutions should be prepared fresh daily.

12.11 TUNING SOLUTION – This solution is used for instrument tuning and detector 

plateau calibration prior to analysis. The solution is prepared by mixing lithium, 
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beryllium, magnesium, cobalt, nickel, indium, lead, barium, bismuth and uranium 

stock solutions in 2% HNO3 to produce a concentration of 10 ug/L of each 

element. Internal standards are not added to this solution.

13. Calibration and Standardization

13.1 The plasma must be on for a minimum of one half hour before starting the preanalysis step.

13.2 Tune the instrument following the protocol provided in SOP 5.11.

13.3 Perform a stability check following the protocol provided in SOP 5.11.

13.4 Calibrate the instrument using a blank and standards of 1, 5, 25, 50, 75 and 100 

ppb. The acceptance criteria for the r2 = 0.998 or greater. The lowest standard 

must recover ± 15 % of the expected value and the remaining must recover ± 10 

% of the expected values to be acceptable. See Section 24 .1 for Table 1.

13.5 Immediately after calibration, analyze an ICV and an ICB. The ICV which is made 

from a second source must have a recovery ± 10 % for the for the analysis to 

continue. The ICB must be less than the reporting level. If either fails, the run is 

terminated and the problem must be identified and corrected before the analysis 

can be restarted.

13.6 A LLCV, CCV, and CCB must be run after the ICV and ICB. A CCV and CCB are 

run every ten extracted samples. As stated before the CCV and ICV may be the 

same solution. The CCV recovery must be within ± 10 % of the expected value to 

continue. The CCB must be less than the reporting level. Failure of any of these 

three solutions to satisfy these conditions will result in the termination of the run. 

The problem must identified, corrected and the analysis restarted at the point 

where the last set of LLCV/CCV/CCB passed.

13.7 A LLCV, CCV, and CCB set must be run at the end of each run. The LLCV 

acceptance criteria are ± 30% of the expected value. Failure to meet this will 

result in the termination of the run until the problem is identified and corrected. 

The analysis may be restarted at the last passing set of the LLCV/CCV/CCB.

13.8 The calibration model used is linear with equal weighting.

14. Procedure

14.1 All the glassware and plastic ware used in this procedure should be leached in 1% 

HNO3 for at least 24 hrs. The items are rinsed with DI prior to use.

14.2 Micropipettes should be calibrated per Laboratory Policy prior to use.

14.3 Filter samples arrive precut by the client. Strips are handled with care using 

plastic tweezers. The strips are curled into a coil and placed into a 50 ml 

numbered DigiTUBE. The filter is pushed down to the bottom of the tube and 15 

ml of the extraction solution is added. The addition is done in a fume hood. 

Ensure that the placement of the filter allows the entire sample to be covered with 

the extraction solution. 

14.4 Cap the DigiTUBE loosely and place upright in a plastic rack. After preparing all 
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the samples, the rack is placed in an uncovered ultrasonic bath that has been preheated to 80oC ± 5 oC. The level of the bath solution must be above the level of 

the extraction solution in the tube but well below the top of the digestion tube. 

Start the ultrasonic unit and allow to run 1 hour ± 5 minutes at 80oC ± 5 oC.

14.5 Remove rack and tubes from bath and allow to cool.

14.6 Add Di to the tubes to the forty ml mark. Cap and shake vigorously.

14.7 Sample is decanted into identified centrifuge tubes and capped. The samples are 

centrifuged for 20 minutes at 2500 rpm.

14.8 After centrifuging, an aliquot is poured into sample vials and placed into the auto 

sampler racks of the ICP-MS for analysis. Extracts may be saved for six months.

14.9 Calibrate the instrument per Section 13 of this SOP.

14.10 Analyze an ICV and ICB per Section 13.5 of this SOP.

14.11 Analyze a LLCV, CCV, and CCB per Section 13.6 of this SOP.

14.12 Sample that exceed the highest calibration standard must be diluted to fall within 

the calibration range.

15. Quality Control

15.1 MDL’s must be determined using seven replicates of a known low-level spike 

added to a filter strip and carried through the extraction process. Use SOP 5.1.4 

guidelines.

15.2 Each batch of sample requires a LRB and a LFB that is spiked at the same level 

as the sample spikes. The LRB must be less than the reporting level. The LFB 

must have a recovery of ± 20% of the expected value. If the result of the LRB is 

greater than the reporting level, then the source of contamination must be 

identified and corrected.

15.3 Any sample exceeding the highest calibration standard must be diluted at a 

minimum of 1 to 5 with the same sample matrix and reanalyzed.

15.4 The internal standard must be monitored throughout the process and must meet a 

recovery of between 70% and 120%. If matrix effects are suspected the sample 

must be diluted and reanalyzed. Dilution is continued until the internal standard 

falls within the specified range. The level of the internal standard is 50.0 μg/l.

15.5 The internal standard ratios the signal obtained from the blank with that of the 

standards and samples and obtains a factor that is displayed on the screen. The 

ratio must fall within the range of 0.833 – 1.42 to pass the quality control 

requirements. Analysts should be aware that the summary page shows all three 

ratios for the individual readings but doesn’t average them. 

15.6 Internal standards are added to the LLCV and ICV/CCV in the following manner: 

ten (10) ml are dispensed into a test tube and 0.1 ml of the 5 ppm stock solution is 

added resulting in a final concentration of 50 ppb.

15.7 Five ml of sample are dispensed into test tubes and 0.05 ml of 5.0 ppb internal 

standard is added resulting in a 50 ppb concentration of the internal standard. 

15.8 Each batch of samples will have a spike and a duplicate. The spike added is 
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normally at a level of the midpoint of the calibration curve. The RPD for the 

duplicates must be ≤ 20%. The spike must be within ± 20%.

15.9 Each batch of samples shall have a serial dilution of a sample that has a 

concentration of 10x the lowest standard. The sample is diluted five fold and the 

result must be within 10% of the undiluted result. If the serial dilution fails, 

physical or chemical interferences should be suspected.

15.10 Any samples which fail to be bracketed by acceptable QC as defined below shall 

be reanalyzed:

ICB prior to the first sample and below the reporting level

ICV prior to the first sample and within 10% of the expected value

LLCV made daily, run before first and after last sample and ± 30% EV

CCB after every 10 extracted samples and less than reporting level

CCV after every 10th extracted sample and within 10% of expected value

15.11 Each batch of sample requires a blank filter strip to be spiked with a NIST 

traceable standard and must recover with ± 20% of the expected value.

15.12 An LLCV must be analyzed with each batch. The LLCV is at a concentration of 

not more than three times the lowest calibration standard and at a level not used in 

the calibration curve. The LLCV assess the performance at the low end of the 

calibration curve. Failure to meet these criteria results in the termination of the 

run. The problem must be corrected and the instrument re-calibrated and the 

analysis repeated.

15.13 Micropipettes that are used must be calibrated prior to use. The criteria is ±1% 

accuracy and precision ≤ 1% RSD.

16. Data Analysis and Calculation

16.1 Sample results are entered into Sapphire as μg/l and are documented in the audit 

tab. Calculation macros in Sapphire convert the entered data to display the result 

in μg/M3 to three significant figures.

16.2 If standard 8” X 10” TSP filters are used the following equation applies:

μg/M3 = (μg Pb/ml X 40 ml/strip X A)

Vs

Where:

μg Pb/ml = lead concentration in solution

40.0 ml/strip = extraction solution volume

A = Area correction ( number of strips per filter)

Vs = actual volume of air sampled

16.3 Calculation of mdl in μg/m3 with and ICPMS mdl of 0.365 for lead in TSP media:

(0.361 μg/l Pb) converted to 0.000361 mg/l Pb

(0.000361 mg/l)(1 liter/1000 ml)(40ml digestate/strip)(1000μg/mg)(9 strips/filter)=0.12996 μg/filter

μg/m3 = (μg/l Pb/ml) x (40 ml/strip) x (9 strips/filter)/ 2000 m3

 mdl (μg/m3) = (0.12996 μg/filter) x (1 Filter/nominal 2000 m3)

mdl (μg/m3) = 0.00006 μg/m3 
SOP 5.16.4 EQL 0510-191 

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16.4 Calculation of pql in μg/m3 with a reporting level of 1.0 ppb using the ICPMS:

μg Pb/filter=(0.001 mg/l) x (1 liter/1000ml) x (40 ml digestate/strip) x (1000 μg/mg) x (9 strips/filter)

μg Pb/filter = 0.36 μg Pb/filter

μg Pb/m3 = (0.36 μg Pb/filter)/ (nominal 2000 m3 volume)

μg Pb/m3 = 0.00018 μg Pb/m3

17. Data Assessment and QC Acceptance Criteria

17.1 As stated in Section 15.

18. Corrective Action for Out-of-Control

18.1 Refer to SOP 5.11 for out of control procedures.

19. Handling Out-of-Control or Unacceptable Data

19.1 Out-of-Control or unacceptable data are not reported except for very unusual 

circumstances, with authorization from the Laboratory Director. In such a case the 

appropriate Arizona State Data Qualifier is attached to the data, along with any 

necessary case narratives. As a rule, out-of-control or unacceptable sample 

results are re-run after troubleshooting the system.

20. Pollution Prevention

20.1 Chemicals are ordered in quantities such that they will be used in a timely manner.

20.2 Reagents are made in quantities such that they will be consumed before they 

expire or expire.

21. Waste Management

21.1 It is the laboratory’s responsibility to comply with all federal, state, and local 

regulations governing waste management, particularly the hazardous waste 

identification rules and land disposal restrictions, and to protect the air, water, and 

land by minimizing and controlling all releases from fume hoods and bench 

operations. Compliance with all sewage discharge permits and regulations is also 

required.

22. Method Performance

22.1 Method performance is monitored through the evaluation of the Method Blank 

results, Laboratory Control Sample recoveries, and sample duplicate precision.

23. References

23.1 EPA-Methods for Chemical Analysis of Water and Wastes-600/4-79-020, Issued 

1971, Editorial revision 1978 and 1982.

23.2 NELAC Standards, 2003 Edition

23.3 Methods for Determination of Metals in Environmental Samples, Supplement I, 

Revision 5.4, May 1994, 600/R-94/111, Method 200.8

23.4 Thermo Elemental, VG PQ ExCell Getting Started Guide, Issue 1.01, Dec. 2000
SOP 5.16.4 EQL 0510-191 

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23.5 Thermo Elemental, VG PlasmaLab Reference Guide, Issue 1.06, December 2000

23.6 PlasmaQuad Software Manual, Issue 3, 1992.

23.6 Determination of Lead in TSP by Inductively Coupled Plasma Mass Spectrometry 

(ICP-MS) with Heated Ultrasonic Nitric and Hydrochloric Acid Filter Extraction, F. 

Weber, W. Gutknecht, E. Poitras, C. Salmons, and J. Flanagan, RTI, EQL 0510-

191

24. Tables, Diagrams, Flowcharts, and Validation Data

24.1 TABLE 1

Diluent*

HCl 

Conc.

Diluent* 

HNO3

Conc.

ml of 

1.0 mg/l 

Lead 

Std.

ml of 100 ug/l 

Lead Std.

Final 

Conc. Pb

ug/L

Bi 

Internal

Standard 

ml**

Bi 

Internal

Standard 

Conc. 

μg/l

Final

Volume

Blank 2.23 M 1.03 M -- -- -- 1.00 50.0 100 ml

Std 1 2.23 M 1.03 M -- 1.0 1.0 1.00 50.0 100 ml

Std 2 2.23 M 1.03 M -- 5.0 5.0 1.00 50.0 100 ml

Std 3 2.23 M 1.03 M 2.5 -- 25.0 1.00 50.0 100 ml

Std 4 2.23 M 1.03 M 5.0 -- 50.0 1.00 50.0 100 ml

Std 5 2.23 M 1.03 M 7.5 -- 75.0 1.00 50.0 100 ml

Std 6 2.23 M 1.03 M 10.0 -- 100.0 1.00 50.0 100 ml

*Diluent solution composition =182 ml HCL and 64 ml HNO3 diluted to one liter.

**Internal Standard Stock Standard Conc. is 5.0 mg/l.
Attachment L 

PCWRL Lead Audit Strip SOP 





Attachment M 

EPA EQL-0710-192 SOP 
USEPA REGION 9 LABORATORY 

RICHMOND, CALIFORNIA

HEATED NITRIC ACID HOT BLOCK DIGESTION AND ICP/MS ANALYSIS FOR 

LEAD (Pb) ON TSP HIGH-VOLUME FILTERS 

Revision 0 

July 2010 

This method was prepared by ICF International for the United States Environmental Protection 

Agency under the Region 9 Environmental Services Assistance Team (ESAT) contract (USEPA 

contract no. EP-W-06-041). ESAT Document Control Number: 00801004-11710 
Lead in Suspended Particulate Matter July 2010 

 Page 2 of 22 

R9 FEM TSP July 2010.docx 

TABLE OF CONTENTS 

1 Scope and Applicability ......................................................................................................... 3 

2 Summary of Method .............................................................................................................. 3 

3 Definitions.............................................................................................................................. 3 

4 Health & Safety Warnings ..................................................................................................... 5 

5 Interferences ........................................................................................................................... 6 

6 Personnel Qualifications/Responsibilities ............................................................................. 7 

7 Equipment and Supplies ........................................................................................................ 7 

8 Procedure ............................................................................................................................. 10 

9 Data and Records Management ........................................................................................... 16 

10 Quality Control and Quality Assurance Section .................................................................. 17 

11 References ............................................................................................................................ 21 

 
Lead in Suspended Particulate Matter July 2010 

 Page 3 of 22 

R9 FEM TSP July 2010.docx 

1 Scope and Applicability 

Ambient air suspended particulate matter is collected for 24 hours on a TSP filter as 

described in Appendix B of Part 50, Reference Method for the Determination of Suspended

Particulate Matter in the Atmosphere (High-Volume Method). The lead in the particulate 

matter is solubilized in a heated dilute nitric acid solution and quantitated using inductively 

coupled plasma – mass spectrometry (ICP-MS). 

The method sensitivity is adequate for determining lead at concentrations equal to, or less 

than, 5% of the level of the lead NAAQS (0.15μg/m3

) for Pb-TSP. Results reported for 

monitoring or compliance purposes are calculated in μg/m3at local temperature and pressure 

conditions. 

2 Summary of Method 

Particulate matter is collected on filters over a 24-hour period. Lead on a strip from the TSP 

filter is solubilized by immersion in a dilute nitric acid (approximately 3.5%) solution, 

covering the solution with a watch glass, and refluxing at 95 oC for an hour in a hot block. 

After extraction, the solubilized lead is diluted to a specified volume with reagent water and 

mixed before analysis. 

Sample solutions are introduced by pneumatic nebulization into a plasma, in which 

desolvation, atomization, and ionization occurs. Ions are extracted from the plasma through 

a differentially pumped vacuum interface and separated on the basis of their mass-to-charge 

ratio by a quadrupole mass spectrometer. The ions transmitted through the quadrupole are 

detected by an electron multiplier or Faraday detector. Ion intensities at each mass are 

recorded and compared to those obtained from external calibration standards to generate 

concentration values for the samples. Results are corrected for instrument drift and matrix 

effects using internal standards. Additional corrections are applied as necessary to correct 

for isobaric and polyatomic elemental interferences. 

3 Definitions 

Calibration Blank (CB) - A volume of reagent grade water acidified with the same acid 

matrix as in the calibration standards. The calibration blank is a zero standard and is used to 

calibrate the ICP instrument. 

Calibration Standard (CAL) - A solution prepared from the dilution of stock standard 

solutions. The CAL solutions are used to calibrate the instrument response with respect to 

analyte concentration. 

Initial Calibration (ICAL) – a multi-point calibration analyzed daily. 
Lead in Suspended Particulate Matter July 2010 

 Page 4 of 22 

R9 FEM TSP July 2010.docx 

Internal Standard - Pure analyte(s) added to a sample, extract, or standard solution in 

known amount(s) and used to measure the relative responses of other method analytes that 

are components of the same sample or solution. The internal standard must be an analyte 

that is not a sample component. 

Laboratory Duplicates (LD1 and LD2) - Two aliquots of the same sample taken in the 

laboratory and extracted and analyzed separately with identical procedures. Analysis of LD1 

and LD2 indicates precision associated with laboratory procedures, but not with sample 

collection, preservation, or storage procedures. 

Laboratory Fortified Blank (LFB) - An aliquot of LRB to which known quantities of the 

method analytes are added in the laboratory. The LFB is extracted and analyzed exactly like 

a sample, and its purpose is to determine whether the methodology is in control and whether 

the laboratory is capable of making accurate and precise measurements. The LFB is also 

referred to as a blank spike (BS) or Laboratory Control Sample (LCS). 

Laboratory Fortified Sample Matrix (LFM) - An aliquot of an environmental sample to 

which known quantities of the method analytes are added in the laboratory. The LFM is 

extracted and analyzed exactly like a sample, and its purpose is to determine whether the 

sample matrix contributes bias to the analytical results. The background concentrations of 

the analytes in the sample matrix must be determined in a separate aliquot and the measured 

values in the LFM corrected for background concentrations. 

Laboratory Reagent Blank (LRB) - An aliquot of blank matrix, a portion of unexposed 

filter in this procedure, that is treated exactly as a sample including exposure to all 

glassware, equipment, solvents, reagents, and internal standards that are used with other 

samples. The LRB is used to determine if method analytes or other interferences are present 

in the laboratory environment, reagents, or apparatus. 

Linear Dynamic Range (LDR) - The concentration range over which the instrument

response to an analyte is linear. 

Method Detection Limit (MDL) - The minimum concentration of an analyte that can be 

identified, measured, and reported with 99% confidence that the analyte concentration is 

greater than zero. 

Quality Control Sample (QCS) - A solution of method analytes of known concentrations 

which is used to fortify an aliquot of LRB. The QCS is obtained from a source external to 

the laboratory and different from the source of calibration standards. 

Quantitation Limit (QL) - The concentration at which confidence in the reported value 

requires no qualifying remarks. A standard is run at the QL to verify acceptable data 

quality. 

Quantitation Limit Standard (QLS) - A standard used to check the accuracy of the 

analysis at the quantitation limit. 
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Stock Standard Solution - A concentrated solution containing one or more method analytes 

prepared in the laboratory using assayed reference materials or purchased from a reputable 

commercial source. 

Tuning Solution - A solution used to determine acceptable instrument performance prior to 

calibration and sample analyses. 

4 Health & Safety Warnings 

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 awareness file of OSHA regulations regarding the safe handling of 

the chemicals specified in this method. A reference file of material data handling sheets 

should also be available to all personnel involved in the chemical analysis. Specifically, 

concentrated nitric acid present 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. 

The acidification of samples containing reactive materials may result in the release of acid 

fumes or toxic gases. Acidification of samples should be done in a fume hood. 

Analytical plasma sources emit radio frequency radiation in addition to intense 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. 

Pollution prevention encompasses any technique that reduces or eliminates the quantity or 

toxicity of waste at the point of generation. Numerous opportunities for pollution 

prevention exist in laboratory operations. Whenever feasible, the laboratory shall use 

pollution prevention techniques to address waste generation. When wastes cannot be 

feasibly reduced, recycling is the next best option. Reduce the toxicity of waste by 

purchasing lower concentration stock standards and lower concentration reagents, to replace 

toxic chemicals whenever possible. 

It is the responsibility of the user of this method to comply with relevant disposal and waste 

regulations. Laboratory waste generated by this procedure includes acidic aqueous waste 

with metals, spent vacuum pump oil, and solid waste (gloves, disposable labware, 

contaminated paper, etc.). 
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5 Interferences 

Isobaric elemental interferences result when isotopes of different elements have the same 

nominal mass-to-charge ratio and cannot be resolved with the instrument’s spectrometer. 

One way to solve this problem is to measure a different isotope for which there is no 

interference. Alternatively, one can monitor another isotope of the interfering element and 

subtract an appropriate amount from the element being analyzed, using known isotope ratio 

information. Corrections for most of the common elemental interferences are programmed 

into the software. 

Abundance sensitivity interference refers to the degree of peak overlap that can occur 

between adjacent peaks. The interference can occur when the shoulder of a large peak 

significantly overlaps the peak of a neighboring minor peak, thereby contributing to its 

intensity. The potential for these interferences should be recognized and the spectrometer 

resolution adjusted to minimize them. 

Isobaric polyatomic interferences result when ions containing more than one atom have the 

same nominal mass-to-charge ratio as an analyte of interest and cannot be resolved by the 

instrument’s spectrometer. When possible, one should choose an interference-free isotope 

to measure. For lead, polyatomic interferences are not typically an issue. 

Physical interferences result from the physical processes associated with the transport of 

sample to the plasma, sample behavior within the plasma, and transmission through the 

interface region between the plasma and the mass spectrometer. Viscosity and surface 

tension differences can affect results, as can deposits on the sample and skimmer cones 

caused by large quantities of dissolved solids in the samples. The interferences can be 

compensated for by the use of internal standards that approximate the analytical behavior of 

the elements being determined. 

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. 

The rinse times necessary for a particular analyte should be estimated prior to analysis. This 

can be achieved by aspirating a standard containing the analyte at a concentration ten times 

the highest calibration standard for the normal sample analysis period, followed by analysis 

of the rinse blank at designated intervals. The length of time required to reduce the analyte 

signal to less than ten times the method detection limit should be noted. The minimum rinse 

time between samples should be set to this time. Memory interferences may also be 

assessed within an analytical run by using three or more replicate integrations for data 

acquisition. If the integrated signal values drop consecutively, the analyst should check for 

the possibility of a memory effect. If the analyte concentration in the previous sample is 
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high enough to suspect analyte carryover, the sample should be re-analyzed after a long 

rinse period. 

During sample preparation, contamination is of prime concern. The work area, including 

bench tops and fume hoods, should be kept scrupulously clean in order to eliminate 

environmental contamination. Samples, extracts, and reagents should be covered at all 

times to prevent airborne contamination. 

6 Personnel Qualifications/Responsibilities 

The analytical procedure in this method should be used by analysts experienced in the use of 

inductively coupled plasma mass spectrometry (ICP-MS), the interpretation of spectral and 

matrix interferences and procedures for their correction. A minimum of six months 

experience with commercial instrumentation is recommended. The sample preparation steps 

may be completed by an analyst unfamiliar with ICP-MS but who has training and 

experience in the extraction of samples for the determination of metals. A minimum of six 

months experience extracting samples (filters, water, soil, etc.) for trace level (μg/L in 

solution) lead is recommended. 

7 Equipment and Supplies 

The mention of trade names or commercial products in this method is for illustrative 

purposes only, and does not constitute an EPA endorsement or exclusive recommendation 

for use. The products and instrument settings cited the method represent those products and 

settings used during method development by the EPA Region 9 Laboratory. Glassware, 

reagents, supplies, equipment, and settings other than those listed in this method may be 

employed provided that method performance appropriate for the intended application has 

been demonstrated and documented. 

7.1 Inductively coupled plasma mass spectrometer (ICP-MS) 

 Instrument capable of scanning the mass range 5-250 amu with a minimum 

resolution capability of 1 amu peak width at 5% peak height. Instrument may be 

fitted with a conventional or extended dynamic range detection system. 

 Radio-frequency generator compliant with FCC regulations. 

 A variable-speed peristaltic pump is required for solution delivery to the nebulizer. 

 A mass-flow controller on the nebulizer gas supply is required. A water-cooled 

spray chamber may be of benefit in reducing some types of interferences (e.g., from 

polyatomic oxide species). 

 If an electron multiplier detector is being used, precautions should be taken, where 

necessary, to prevent exposure to high ion flux. Otherwise changes in instrument 

response or damage to the multiplier may result. Samples having high 

concentrations of elements beyond the linear range of the instrument and with 

isotopes falling within scanning windows should be diluted prior to analysis. 
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EPA Region 9 Laboratory uses a Perkin Elmer Elan DRC Plus Inductively Coupled 

Plasma Mass Spectrometer. 

7.2 Environmental Express Hot Block Digestion System or equivalent capable of 

maintaining a temperature of 95°C. 

7.3 Air displacement pipette(s) capable of delivering volumes ranging from 100-2500 μL 

with a tolerance of 2% and an assortment of high quality disposable pipet tips. Tips 

must be lead-free. 

7.4 Glassware, Class A - volumetric flasks, pipettes, and graduated cylinders. 

7.5 Polypropylene Digestion Vessels, Environmental Express P/N SC475 or equivalent 

(50-mL, graduated and certified to within 0.5% by volume), polypropylene screw caps, 

and polypropylene ribbed watch glasses to cover digestion vessels. 

7.6 Paper cutter, pizza cutter, scissors, or other suitable cutting tool capable of making 

straight cuts to make accurately measured strips. 

7.7 Plastic or Teflon wash bottles 

7.8 Tweezers – plastic, Teflon or stainless steel 

7.9 Filter - QMA, High Purity Quartz, Microfiber Filters, 8 x 10 in, Whatman or 

equivalent.

7.10 Disposable plastic syringes, 5-mL Luerlock, with 25 mm, 0.45 micron PTFE filters. 

Materials must be lead-free. 

7.11 Reagents 

Reagents may contain elemental impurities that might affect the integrity of analytical 

data. Owing to the high sensitivity of ICP-MS, high-purity reagents should be used 

whenever possible. 

7.11.1 Nitric acid, concentrated (specific gravity 1.41). 

7.11.2 Nitric acid, dilute (1+19, v/v) - Add 50 mL conc. nitric acid to 400 mL of reagent 

grade water and dilute to 1 L. 

7.11.3 Argon gas supply - high purity grade (99.99%). When analyses are conducted 

frequently, liquid argon is more economical and requires less frequent replacement of 

tanks than compressed argon in conventional cylinders. 
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7.11.4 Reagent water 

All references to reagent grade water in this method refer to ASTM Type I water 

(ASTM D1193). Suitable water may be prepared by passing distilled water through a 

mixed bed of anion and cation exchange resins. 

7.11.5 Standard Solutions 

The following instructions for solution preparation are provided as guidance for 

instrument operation and calibration. The analyst must refer to the instrument 

manufacturer’s recommendations regarding instrument setup and calibration to assure 

that appropriate solutions and concentrations are employed. Solutions must be 

diluted in Class A volumetric glassware using air-displacement or Class A pipettes to 

measure standard solutions. 

Standard Stock Solutions - Stock standards may be purchased from a reputable 

commercial source or prepared from ultra high-purity grade chemicals or metals 

(99.99-99.999% pure). Stock solutions should be stored in FEP bottles. Multielement solutions containing lead are acceptable. 

 Lead solution, stock 1 mL = 1000 μg Pb: Dry lead nitrate (PbNO3) for one 

hour at 105°C; dissolve 0.1599 g PbNO3 in 5 mL (1+1) nitric acid. Dilute to 

100 mL with reagent grade water. 

CAL Standards - Prepare initial calibration standards at a minimum of three levels. 

Use a stock standard solution as the source and dilute to the appropriate volume with 

1% (v/v) nitric acid. CAL standards containing 10 μg/L, 20 μg/L, and 100 μg/L of 

Pb are generally acceptable. Prepare fresh every two weeks or as needed. 

ICV / CCV - The ICV standard and CCV standard are identical and only 

differentiated by their place within the analytical sequence. A solution with 50 μg/L 

of lead is appropriate with the above CAL standard concentrations. Prepare the 

solution as needed from the same source as the CAL solutions in 1% (v/v) nitric acid. 

Prepare fresh every two weeks or as needed. 

QLS - Prepare the QLS standard to contain 3.6 μg/L of lead. Prepare the solution 

from the same source as the CAL standards in 1% (v/v) nitric acid. Prepare fresh 

every two weeks or as needed. 

CB - Dilute concentrated nitric acid with reagent water to obtain a 1% (v/v) nitric 

acid solution. 

QCS - Prepare the QCS to contain 50 μg/L of lead. Prepare the solution from a 

source different from the CAL standards in 1% (v/v) nitric acid. Prepare fresh every 

two weeks or as needed. 
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Internal Standard Solution 

 Obtain or prepare holmium and terbium as single-element stock standards. 

 Prepare internal standard solution to contain 100 μg/L each of, holmium, 

and terbium in 1% (v/v) nitric acid. (Note: this solution may contain 

additional elements used as internal standards for other ICP-MS methods.) 

Tuning Solution 

 Obtain or prepare barium, beryllium, cerium, cobalt, indium, lead, 

magnesium, thorium, and uranium single-element stock standards. 

 If necessary, prepare an intermediate standard to contain 1,000 μg/L of 

barium, beryllium, cerium, cobalt, indium, lead, magnesium, thorium, and 

uranium from the single-element stock standards. 

 Prepare a working solution from the intermediate standard at 1.0 μg/L in 1% 

(v/v) nitric acid. 

Rinse solution - Dilute concentrated nitric acid with reagent water to obtain a 2% 

(v/v) nitric acid solution. 

8 Procedure 

8.1 Sample Collection 

Sampling procedures are detailed in Appendix B of Part 50, Reference Method for the 

Determination of Suspended Particulate Matter in the Atmosphere (High-Volume 

Method). Sampling organizations may also send unexposed filters to the laboratory for 

analysis for quality control purposes (i.e. filter lot, trip, equipment blanks). Unexposed 

filters can have positive values for lead (Pb). Each manufacturer lot of filters may need 

to be investigated to ensure that filters will meet the data quality objectives of a given 

project. It is recommended that the sampling organization consult 40 CFR Appendix G 

to part 50, section 6.1 for guidance. 

8.2 Sample Handling and Preservation 

A representative strip from a TSP filter (high-volume filter, 8 by 10 inch, glass fiber or 

quartz) is required. Filters should be received in the laboratory in separate holders 

under chain-of-custody. Cold storage is not required for filters to be analyzed for lead; 

however, if filters were stored cold, they must be allowed to reach room temperature 

prior to analysis. 

Store filters in the original holder and extracts in the extraction vessel (with the filter 

strip in the solution) under ambient conditions. 
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8.3 Sample Preparation 

The hot block should be located in a fume hood and previously adjusted to provide 

evaporation at a temperature of approximately, but no higher than, 90-95 oC in a 

extraction vessel covered with a ribbed watch glass. Preheat the hot block for 30 

minutes. 

8.3.1 Filter Handling Procedure 

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 subsampling. Document 

any deformities and qualify the data appropriately.

Care must be taken to protect filters from contamination. Filters must be kept 

covered prior to sample preparation. 

With the whole TSP filter still in its container, using clean tweezers carefully remove 

the filter from its holder and transfer to a clean paper cutter (or use a cutting tool and 

straightedge as described in Appendix G of Part 50). Cut a suitable strip (1 by 8 

inches or 3⁄4 by 8 inches). Make certain that no particulates fall off before or after 

cutting the strip. Using the tweezers, roll the filter strip and transfer to the 

corresponding labeled extraction vessel. 

The cutting tools and tweezers must be cleaned after contact with each filter because 

particulates may transfer to the blades or surfaces that contact the exposed filter. 

Gently wipe the blades with a paper towel dampened with deionized water. If the 

paper towel is visibly dirty, wipe the blade with another dampened paper towel until 

no further particulates transfer to the paper towel. Allow the tools to air dry or blot 

dry with a lint-free tissue. Do not use wet or damp tools to cut or handle filters 

because the moisture will attract particulates from the filters. 

8.3.2 QC Sample Preparation: 

8.3.2.1 LRB - Transfer a strip of blank filter of the same dimensions as selected for 

exposed filters to a labeled 50-mL extraction vessel. 

8.3.2.2 LFB - Transfer a strip of blank filter of the same dimensions as selected for 

exposed filters to a labeled 50-mL digestion vessel. Spike the filter with the lead 

stock standard solution (or a multi-element solution containing lead) or 

preferably, a solid certified reference material. Use an amount that will result in a 

concentration of 500 μg/L in the solution. 

8.3.2.3 LD - Transfer an exposed filter strip of the designated QC sample of the same 

dimensions as selected for exposed filters to a 50-mL extraction vessel. 
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8.3.2.4 LFM - Transfer an exposed filter strip of the designated QC sample of the same 

dimensions as selected for exposed filters to a 50-mL extraction vessel. Using an 

air displacement pipette, spike the filter with the lead stock standard solution (or a 

multi-element solution containing lead). Use an amount that will result in a 

concentration of 500 μg/L in the solution. 

8.4 Extraction Procedure 

Transfer a 20-mL aliquot of dilute nitric acid (1:19, v/v) to each extraction vessel, 

ensuring that the filter strip is covered with acid. Place the vessel on the hot block. 

Cover with a ribbed watch glass. 

Heat at 95 oC for 60 to 70 minutes. Do not let the sample evaporate to dryness. 

Remove the vessels from the hot block and allow to cool. In the graduated extraction 

vessel, bring the extract to a final volume of 50 mL by diluting to the 50-mL mark on 

the vessel with reagent grade water. Cap the vessel and shake vigorously for 5 seconds. 

Set aside the extract (with the filter strip in the extraction vessel) for at least 30 minutes 

to allow the nitric acid trapped in the filter to diffuse into the extract. 

Shake the extract vigorously for 5 seconds (with the filter strip in the extraction vessel) 

and let settle for at least an hour. The sample is now ready for analysis. 

8.5 Instrument or Method Calibration and Standardization 

The analyst is advised to follow the recommended operating conditions provided by the 

instrument manufacturer. The following guidance is intended to be general; instrument 

specifics or technological developments may dictate modified procedures or criteria. It 

is the responsibility of the analyst to verify that the instrument configuration and 

operating conditions satisfy the analytical requirements and to maintain quality control 

data verifying instrument performance and analytical results. 

8.5.1 Precalibration routine 

The following precalibration routine must be completed prior to calibrating the 

instrument until such time it can be documented with periodic performance data that 

the instrument meets the criteria listed below without daily tuning. 

Initiate operating configuration of instrument and data system. Allow a period of not 

less than 30 minutes for the instrument to warm up. During this process align the 

torch and conduct mass calibration and resolution checks using the tuning solution. 

Resolution at isotopes 206, 207, and 208 is critical for quantitation of lead. For good 

performance adjust spectrometer resolution to produce a peak width of approximately 

0.75 amu at 5% peak height. Adjust mass calibration if it has shifted by more than 0.1 

amu from unit mass. 
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Instrument stability must be demonstrated by running the tuning solution a minimum 

of five times with resulting relative standard deviations of absolute signals for all 

analytes of less than 5%. 

8.5.2 Internal Standardization 

Internal standardization must be used in all analyses to correct for instrument drift 

and physical interferences. For lead analysis, a minimum of one internal standard 

must be used, and an alternate is recommended. Procedures described in this method 

detail the use of two internal standards; terbium and holmium. Internal standards must 

be present in all samples, standards and blanks at identical levels. This may be 

achieved by directly adding an aliquot of the internal standards to the CAL standard, 

blank or sample solution or alternatively by mixing with the solution prior to 

nebulization using a second channel of the peristaltic pump and a mixing coil. The 

concentration of the internal standard should be sufficiently high that good precision 

is obtained in the measurement of the isotope used for data correction and to 

minimize the possibility of correction errors if the internal standard is naturally 

present in the sample. Depending on the sensitivity of the instrument, a concentration 

range of 10-100 μg/L of each internal standard is recommended. Internal standards 

should be added to blanks, samples and standards in a like manner, so that dilution 

effects resulting from the addition may be disregarded. 

8.5.3 Calibration 

Prior to initial calibration, set up instrument software routines for quantitative 

analysis. The instrument must be calibrated using one of the internal standards. At a 

minimum, masses 206, 207 and 208 must be monitored for lead and the sum of the 

isotopes used for quantitation. A minimum of three replicate integrations are required 

for data acquisition. Use the average of the integrations for instrument calibration and 

data reporting. 

8.5.3.1 Perform a multi-point calibration (ICAL) daily. Analyze a minimum of three 

CAL standards and a CB. A linear or linear-through-zero calibration equation is 

required and the correlation coefficient (r2

) for the curve must be 0.995 or greater. 

Forcing the curve through zero will result in more consistent recovery of the QLS 

but is not required if adequate recovery is obtained using a linear curve. 

8.5.3.2 An ICV is analyzed immediately following initial calibration and the CCV at a 

frequency of one per 10 analytical samples and at the end of the analytical run. 

The recovery of the analyte in the ICV and CCV is calculated as follows: 

% 





  100
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Where 

%R = percent recovery 

M = measured concentration at the instrument, μg/L 

T = true concentration of the analyte in the ICV/CCV, μg/L 

The ICV and CCV recoveries must fall within 95 to 105 percent. If the %R for 

lead in the ICV falls outside of the QC criteria, the instrument must be recalibrated. Samples cannot be analyzed until an acceptable ICV is analyzed. If 

the %R for lead in the CCV falls outside of the QC criteria, the instrument must 

be re-calibrated. Once an acceptable calibration is obtained, the samples 

preceding the out-of-control CCV must be re-analyzed. 

8.5.3.3 The stability of the baseline must be monitored by analyzing a CB immediately 

after every ICV/CCV standard. If the value of the CB result is less than 1⁄2 the 

QL, the result is acceptable. If the value of the CB result equals or exceeds onehalf the QL, the analysis may not continue. The cause of the high CB result must 

be determined and the problem corrected. The instrument must be re-calibrated 

and all samples not bracketed by acceptable CB results must be re-analyzed. 

8.5.3.4 Analyze a QCS daily to verify the calibration standards and acceptable instrument 

performance. If the measured concentration is not within + 10% of the true value, 

the method performance is unacceptable. The source of the problem must be 

identified and corrected before proceeding with analyses. 

The recovery of the analyte in the QCS is calculated as: 

% 





  100

Where 

%R = percent recovery 

M = measured concentration at the instrument, μg/L 

T = true concentration in the QCS, μg/L 

8.5.3.5 To verify the ability to detect target analytes near the QL, a QLS must be 

analyzed at the beginning of the analytical run and after each 40 analytical 

samples. The recovery of lead in the QLS is calculated as: 

% 





  100

Where 

%R = percent recovery 

M = measured concentration at the instrument, μg/L 

T = true concentration in the QLS, μg/L 
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If the QLS recovery does not meet the recovery criteria of 60 to 140 percent, 

determine the cause, take corrective action, and re-analyze the QLS. 

8.5.3.6 The system must be flushed with the rinse solution between blanks, standards and 

samples. Allow sufficient time to remove traces of the previous sample. The 

required time is instrument dependent and must be determined by aspirating a 

high level standard and observing the instrument response return to background 

when the rinse solution is introduced. Solutions to be measured should be 

aspirated for 30 seconds prior to the acquisition of data to allow equilibrium to be 

established. 

8.6 Typical Analytical Sequence 

The following table shows a typical analytical sequence. Samples are indicated as S1, 

S2, S3...S20. All sample extracts are analyzed at a 10 times dilution with 1% v/v nitric 

acid. The analyst must make appropriate additional dilutions using 1% v/v nitric acid 

as the diluent on the basis of screening data, sample history, or other information. All 

results must be less than the highest calibration standard or further dilution is required. 

Extracts that contain particulates should be allowed to settle for a longer period of time. 

If particulates do not settle after 24 hours, filter an aliquot of the extract using a 

disposable plastic syringe equipped with a 0.45 micron PFTE filter prior to analysis to 

prevent damage to the instrument. Filtration must be reported to the client with the 

analytical result. 

Seq. Description Seq. Description Seq. Description 

1 CB 15 S2 29 S14 

2 Cal Std 1 16 S3 30 CCV 

3 Cal Std 2 17 S4 31 CB 

4 Cal Std 3 18 CCV 32 S15 

5 Cal Std 4 19 CB 33 S16 

6 ICV 20 S5 34 S17 

7 CB 21 S6 35 S18 

8 QCS 22 S7 36 S19 

9 QLS 23 S8 37 S20 

10 LRB 24 S9 38 CCV 

11 LFB 25 S10 39 CB 

12 S1 26 S11 40 

13 S1-LD 27 S12 41 

14 S1-LFM 28 S13 42 

8.7 Analyte Identification and Quantitation 

Lead is quantitated from the sum of three isotopes, masses 206, 207, and 208. A linear 

or linear-forced-through zero calibration must be constructed. Only results between the 
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QLS concentration and the highest calibration standard may be reported without 

qualification (i.e. results between 3.6 and 100 μg/L, adjusted for sample preparation 

and dilutions). 

9 Data and Records Management 

After set-up and calibration, most ICP-MS instrument data systems report results for the 

analyzed solution in units of μg/L. The instrument calculations include elemental correction 

calculations, internal standard calculations, and calibration factors. 

Report results for all filters delivered to the laboratory along with the associated batch quality 

control (LRB, LFB, LD, and LFM). Reporting units will vary depending upon the sampling 

organizations requirements but will usually be μg Pb/filter or μg Pb/m3 (when the sampling 

organization provides total volume, in m3). Sample results that exceed the calibration range 

must be reanalyzed at a higher dilution. Results below the QL should be reported as “not 

detected” or “ND” at the QL expressed as μg Pb/filter or μg Pb/m3

. Results should not be 

corrected for the concentration of lead in the LRB or the field, trip, or filter lot blanks 

provided by sampling organizations. 

To report results in μg/filter using the following equation and report three significant 

figures: 



   






    9     12    

Where: 



 = concentration, in μg/filter 

M = measured concentration at the instrument, in μg/L


 = volume of sample solution after sample extraction, in L 

D = dilution factor, performed after sample extraction 

To report results as μg/m3, use the following equation and provide results to three decimal 

places for ACS reporting as required in 40 CFR Part 50 Appendix R: 


 
  





!"

Where 


 
 = Concentration, μg Pb/m3

VAir = volume of air sampled, in m3 

The number of strips/filter is based on the exposed area of the 8“ x 10” filter and assumes a 

1⁄2” unexposed border. This leaves 7“ x 9” as the exposed area of the filter or 63 square 

inches. One strip is 1” x 8” but the exposed area is 1” x 7”or 7 square inches which 
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represents one ninth of the exposed area. A similar calculation for 3⁄4” x 8” strips yields 12 

strips per filter. 

10 Quality Control and Quality Assurance 

Each laboratory using this method is required to operate a formal quality control (QC) 

program. The minimum requirements of this program consist of an initial demonstration of 

laboratory capability, and the periodic analysis of laboratory reagent blanks, fortified blanks 

and calibration solutions as a continuing check on performance. Table 10.1 summarizes the 

routine requirements for ongoing quality control. The laboratory is required to maintain 

performance records that define the quality of the data thus generated. 

10.1 Initial Demonstration of Performance (mandatory) 

The initial demonstration of performance is used to characterize instrument 

performance (determination of linear calibration ranges and analysis of quality control 

samples) and laboratory performance (determination of method detection limits) prior 

to analyses conducted by this method. 

10.1.1 Linear Calibration Ranges 

Linear calibration ranges are primarily detector limited. The upper limit of the linear 

calibration range should be established for lead by determining the signal responses 

from a minimum of three different concentration standards, one of which is close to 

the upper limit of the linear range. Care should be taken to avoid potential damage to 

the detector during this process. The linear calibration range which may be used for 

the analysis of samples should be judged by the analyst from the resulting data. The 

upper LDR limit should be an observed signal no more than 10% below the level 

extrapolated from lower standards. Determined sample analyte concentrations that are 

greater than 90% of the determined upper LDR limit must be diluted and reanalyzed. 

The LDRs should be verified whenever, in the judgment of the analyst, a change in 

analytical performance caused by either a change in instrument hardware or operating 

conditions would dictate they be redetermined. 

10.1.2 Quality control sample (QCS) 

When beginning the use of this method, verify the calibration standards and 

acceptable instrument performance with the preparation and analyses of a QCS. To 

verify the calibration standards the determined mean concentration from a minimum 

of three analyses of the QCS; the result must be within ±10% of the stated QCS 

value. If the calibration standards and/or acceptable instrument performance cannot 

be verified, the source of the problem must be identified and corrected before either 

proceeding on with the initial determination of method detection limits or continuing 

with on-going analyses. 
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10.1.3 Method detection limits (MDL) should be established using at least seven (7) filter 

strips from an unexposed TSP filter fortified at a concentration of two to five times 

the estimated quantitation limit. The size of the filter strip must be the same as the 

laboratory selects in Section 8.3.1 to process filters from sampling organizations. 

Process the fortified filter strips through the entire analytical method. Perform all 

calculations defined in the method and report the concentration values in the 

appropriate units. Compute the MDL as follows: 

#  $%&','&!)*.,,-$.-

where: 

MDL = method detection limit 

n = number of replicates analyzed 

t(n-1,1-α=.99) = students’ t value appropriate for a 99% confidence level 

and a standard deviation estimate with n-1 degrees of 

freedom. 

S = standard deviation of the replicate analyses

Refer to 40 CFR Part 136, Appendix B for complete requirements for MDLs. MDLs 

must be determined prior to the analysis of any field samples by the laboratory and 

annually thereafter, when a new operator begins work, or whenever, in the judgment 

of the analyst, a change in analytical performance caused by either a change in 

instrument hardware or operating conditions would dictate they be redetermined. 

10.2 Assessing Laboratory Performance (mandatory) 

10.2.1 Laboratory reagent blank (LRB) - The laboratory must analyze at least one LRB with 

each batch of 20 or fewer filters. LRB data are used to assess contamination from the 

laboratory environment and to characterize spectral background from the reagents 

used in sample processing. LRB values > 1⁄2 the QL indicate potential laboratory or 

reagent contamination but may also be the result of background levels of lead in the 

filter extracted as the LRB and therefore unrelated to the exposed filters in the batch. 

When LRB values constitute 10% or more of the analyte level determined for a 

sample or are > 1⁄2 the QL whichever is greater, re-extraction may be required for TSP 

filters; consult the laboratory supervisor for direction. The result (in μg/filter) for the 

LRB must be reported to the sampling organization. 

10.2.2 Laboratory fortified blank (LFB) - The laboratory must analyze at least one LFB with 

each batch of 20 or fewer filter strips. Calculate accuracy as percent recovery using 

the following equation: 

% 





    100
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Where 

%R = percent recovery 

M = measured concentration at the instrument, μg/L 

T = true concentration in the LFB, μg/L 

D = dilution factor, performed after sample extraction 

If the recovery falls outside the required control limits of 80-120%, the method is 

judged out of control, and the source of the problem must be identified and resolved 

before continuing analyses. The result (in percent recovery) for the LFB must be 

reported to the sampling organization. 

10.2.3 The laboratory must use LFB analyses data to assess laboratory performance against 

the required control limits of 80-120%. When sufficient internal performance data 

become available (usually a minimum of 20-30 analyses), optional control limits can 

be developed from the mean percent recovery (x) and the standard deviation (S) of 

the mean percent recovery. These data can be used to establish the upper and lower 

control limits as follows: 

UPPER CONTROL LIMIT = x + 3S 

LOWER CONTROL LIMIT = x - 3S 

The optional control limits must be equal to or better than the required control limits 

of 80-120%. After each five to ten new recovery measurements, new control limits 

can be calculated using only the most recent 20-30 data points. Also, the standard 

deviation (S) data should be used to establish an on-going precision statement for the 

level of concentrations included in the LFB. These data must be kept on file and be 

available for review. 

10.2.4 Instrument performance - For all determinations the laboratory must check instrument 

performance and verify that the instrument is properly calibrated on a continuing 

basis. To verify calibration run the CB and CCV immediately following each 

calibration routine, after every ten analyses and at the end of the sample run. The 

results of the analyses of the standards will indicate whether the calibration remains 

valid. The lead recovery within the standard solutions must be within ±5% of 

calibration. If the calibration cannot be verified within the specified limits, the 

instrument must be recalibrated. If the sample matrix is responsible for the calibration 

drift, it is recommended that the previous 10 samples are reanalyzed in groups of five 

between calibration checks to prevent a similar drift situation from occurring. 

10.3 Assessing Analyte Recovery and Data Quality 

Sample homogeneity and the chemical nature of the sample matrix can affect analyte 

recovery and the quality of the data. Taking separate strips from a filter for replicate 

and fortified analyses can in some cases assess the effect. Unless otherwise specified by 

the data user, laboratory or program, the following laboratory fortified matrix (LFM) 

procedure is required. 
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10.3.1 The laboratory must add a known amount of analyte to a minimum of 5% of the 

routine samples. In each case the LFM strip must be a duplicate of the strip used for 

lead analysis and the spike added prior to sample preparation steps. The added 

analyte concentration must be the same as that used in the LFB. 

Calculate the percent recovery for lead, corrected for background concentrations 

measured in the unfortified sample, and compare these values to the designated LFM 

recovery range of 70-130%. Recovery calculations are not required if the 

concentration of the analyte added is less than 30% of the sample background 

concentration. Percent recovery may be calculated using the following equation: 

% 


/01 2 
!34



  100

Where 

%R = percent recovery 


/01 = measured concentration in the LFM, in μg/filter. 


!34 = measured concentration in the routine sample, in μg/filter 

s = spiked concentration added to the LFM, in μg/filter 

If recovery falls outside the designated range and laboratory performance is shown to 

be in control, the recovery problem encountered with the fortified filter is judged to 

be matrix related, not system related. The data user must be informed that the result 

for that analyte in the unfortified sample is suspect due to either the heterogeneous 

nature of the sample or an uncorrected matrix effect. 

10.3.2 Laboratory duplicate 

One laboratory duplicate must be analyzed for every 20 or fewer field samples in a 

batch. Treat the laboratory duplicate as a routine sample. In each case the strip must 

be a duplicate of the strip used for lead analysis and taken through the preparation 

steps separately. 

To assess precision, the relative percent difference (RPD) of the LD1 and LD2 is 

compared to the acceptance criterion of ≤20 percent. Calculate the RPD between the 

routine sample (LD1) and the laboratory duplicate (LD2) using the following 

equation: 

5 

6
/7 2 

6

8
/7 9 

:/2 < 100

Where 

RPD = relative percent difference 

CLD = measured concentration in LD, in μg/filter 



 = measured concentration in sample filter, in μg/filter 
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Apply precision criteria for samples with analyte levels > QL. If control limits are 

exceeded, re-analyze the sample and duplicate once. If the control limits are 

exceeded again, flag the associated sample result indicating that the particulate matter 

may not be homogenous across the TSP filter. 

10.4 Internal Standard Response 

Monitor the signal intensity for the internal standard masses throughout the analytical 

run. This information is useful in detecting instrument drift, sensitivity shift; dissolved 

solids content, and inherent internal standard (i.e., a natural constituent in a sample). 

The absolute intensity of the internal standard must not deviate more than 60 - 125% 

from its original intensity in the calibration blank. If deviations greater than these are 

observed, flush the instrument with the rinse blank and monitor the responses in the 

calibration blank. If the responses of the internal standards are now within the limit, 

take a fresh aliquot of the sample, dilute by a further factor of two, add the internal 

standards and reanalyze. If after flushing the response of the internal standards in the 

calibration blank is out of limits, terminate the analysis and determine the cause of the 

drift. Possible causes of drift may be a partially blocked sampling cone or a change in 

the tuning condition of the instrument. 

Table 10.1 Quality Control Measures and Acceptance Criteria 

Parameter Frequency Criteria 

Correlation Coefficient Each ICAL > 0.995 

ICV After ICAL 95 - 105% 

CCV Every 10 Samples 95 - 105% 

CB After each ICV/CCV < 1⁄2 QL 

QCS After ICAL 90 - 110% 

QLS After ICAL & after every 40 

analytical samples 

60 - 140% 

LRB Each Batch < 1⁄2 QL 

LFB Each Batch 80 - 120% 

MD, Precision Every 20 samples < 20 RPD 

LFM, Accuracy Every 20 samples 70 - 130% 

Internal Standard Every analysis 60 - 125% of initial CB 

11 References 

40 CFR Part 136, Appendix B. Definition and Procedure for the Determination of the 

Method Detection Limit – Revision 1.11. 

40 CFR Part 50, Appendix B. Reference Method for the Determination of Suspended

Particulate Matter in the Atmosphere (High-Volume Method) 
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40 CFR Part 50, Appendix G. Reference Method for the Determination of Lead in 

Suspended Particulate Matter Collected from Ambient Air. 

U.S. Environmental Protection Agency Method 200.8, Determination of Trace Elements in 

Waters and Wastes by Inductively Coupled Plasma - Mass Spectrometry, Revision 5.4, 

EMMC Version, May 1994. 

U.S. Environmental Protection Agency SW846 Method 6020A, Inductively Coupled 

Plasma-Mass Spectrometry, Revision 1, February 2007.