Attachment K

PCWRL EQL-0510-191 SOPSOP 5.16.4 EQL 0510

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Page 1 of 10SOP 5.16.4 EQL 0510

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Page 2 of 10 **TABLE OF CONTENTS**

**1. CHANGES AND REVISION**  **S**

**................................ ................................**  **...................... 3** 

**2. SCOPE AND APPLICATIO**  **N**

**................................ ................................**  **....................... 3** 

**3. MATRIX** 

**................................ ................................**  **................................ ........................**  **3**

**4. SAMPLE COLLECTION, P**  **RESERVATION, SHIPPIN G AND STORAGE** 

**.................. 3** 

**5. SUMMARY OF METHOD** 

**................................ ................................**  **............................. 3** 

**6. DETECTION LIMIT** 

**................................ ................................**  **................................ ......**  **4**

**7. INTERFERENCES** 

**................................ ................................**  **................................ .......**  **4**

**8. DEVIATIONS FROM METH**  **OD**

**................................ ................................**  **.................... 4** 

**9. SAFETY** 

**................................ ................................**  **................................ .......................**  **4**

**10. DEFINITIONS** 

**................................ ................................**  **................................ ...............**  **4**

**11. EQUIPMENT AND SUPPLI**  **ES**

**................................ ................................**  **..................... 5** 

**12. REAGENTS AND STANDAR**  **DS**

**................................ ................................**  **................. 5** 

**13. CALIBRATION AND STAN**  **DARDIZATION**

**................................ ................................**  **. 6** 

**14. PROCEDURE** 

**................................ ................................**  **................................ ...............**  **6**

**15. QUALITY CONTROL** 

**................................ ................................**  **................................ ...**  **7**

**16. DATA ANALYSIS AND CA**  **LCULATION**

**................................ ................................**  **..... 8** 

**17. DATA ASS**  **ESSMENT AND QC ACCEP TANCE CRITERIA** 

**................................ .......**  **9**

**18. CORRECTIVE ACTION FO**  **R OUT**

**- OF** 

**- CONTROL** 

**................................ .....................**  **9**

**19. HANDLING OUT** 

**- OF** 

**- CONTROL OR UNACCEPTA**  **BLE DA TA** 

**................................ .**  **9**

**20. POLLUTION PREVENTION** 

**................................ ................................**  **......................... 9** 

**21. WASTE MANAGEMENT** 

**................................ ................................**  **.............................. 9** 

**22. ME**  **THOD PERFORMANCE**

**................................ ................................**  **......................... 9** 

**23. REFERENCES** 

**................................ ................................**  **................................ .............**  **9**

**24. TABLES, DIAGRAMS, FL**  **OWCHARTS, AND VALIDA TION DATA** 

**......................... 10** SOP 5.16.4 EQL 0510

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Page 3 of 10 **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 upd ated 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 filt ers. 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, Preservat**  **ion, 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 r esolution 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 inform ation processed by a data handling system. Interferences relating to the technique must be recognized and corrected. Such corrections must include compensations for isobaric elementalSOP 5.16.4 EQL 0510

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Page 4 of 10

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 cal culated 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 u g/ m 3

. 6.3 The pql for lead in TSP filters is 0.00018 u g/ m 3

.

**7. Interferences** 

7.1 Several interference sources may cause inaccurac ies 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 th e 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 interference s 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 Particl esSOP 5.16.4 EQL 0510

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Page 5 of 10 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 ce ll is not required for this application.

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

11.3 Spinette Laboratory centrifuge.

11.4 NUNC disposable 15ml conical capped centrifuge tubes.

11.5 Digestion tube “ Digi TUBE” with threaded caps.

11.6 Assorted Eppendorf pipe ttes.

11.7 Assorted Class A Volumetric flasks.

11.8 Whatman EMP2000 glass fiber filters.

11.9 Plastic rack to hold Digi TUBEs.

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 me tal 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 vol ume 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 Plasm a 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) fro m 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,SOP 5.16.4 EQL 0510

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beryllium, magnesium, cobalt, nickel, indium , lead, barium, bismuth and uranium
stock solutions in 2% HNO 3 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 pre

analysis 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 r 2 = 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 cal ibration, 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 b e 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 pro cedure should be leached in 1%
HNO 3 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 plas tic tweezers. The strips are curled into a coil and placed into a 50 ml
numbered Digi

TUBE. 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 placemen t of the filter allows the entire sample to be covered with

the extraction solution.

14.4 Cap the Digi

TUBE loosely and place upright in a plastic rack. After preparing allSOP 5.16.4 EQL 0510

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the samples, the rack is placed in an uncovered ultrasonic bath that has been pre

heat ed to 80 o C ± 5 o C. 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 80 o C ± 5 o C.

14.5 Remove rack and t ubes 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 i s 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, C CV, 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 filte r 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 recover y 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 o n 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 a re 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 isSOP 5.16.4 EQL 0510

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normally at a level of the midpoint of the calibration curve. The RPD for th e 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 fi rst 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 E ach 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 lowe st 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 μ g/l and are documented in the audit tab. Calculation macros in Sapphire convert the entered data to display the result

in μ g/M 3 to three significant figures.

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

μ g/M 3 = ( μ g Pb/ml X 40 ml/strip X A)

V s Where:

μ g Pb/ml = lead concentration in solution 40.0 ml/strip = extraction solution volume A = Area correction ( number of strips per filter)

V s = actual volume of air sampled

16.3 Calculation of mdl in μg/m 3 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/m 3 = (μg/l Pb/ml) x (40 ml/strip) x (9 strips/filter)/ 2000 m 3
mdl (μg/m 3 ) = (0.12996 μg/f ilter) x (1 Filter/nominal 2000 m 3 ) mdl (μg/m 3 ) = 0.00006 μg/m 3SOP 5.16.4 EQL 0510

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Page 9 of 10 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/fi lter) μg P b/filter = 0.36 μg Pb/filter μg Pb/m 3 = (0.36 μg Pb/filter)/ (nominal 2000 m 3 volume) μg Pb/m 3 = 0.00018 μg Pb/m 3

**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 contro l 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 Qual ifier 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 managem ent, 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 o f 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, V G PQ ExCell Getting Started Guide, Issue 1.01, Dec. 2000SOP 5.16.4 EQL 0510

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Page 10 of 10 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 Spectrometr y (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. D iluent*

HNO 3 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
*Di luent solution composition =182 ml HCL and 64 ml HNO 3 diluted to one liter. **Internal Standard Stock Standard Conc. is 5.0 mg/l.Attachment L

PCWRL Lead Audit Strip SOPAttachment M

EPA EQL-0710-192 SOPUSEPA REGION 9 LABORATORY RICHMOND, CALIFORNIA

HEATED NITRIC ACID HOT BLOCK DIGESTION AND ICP/MS A NALYSIS FOR

LEAD (Pb) ON TSP HIGH-VOLUME FILTERS

Revision 0 July 2010

This method was prepared by ICF International for t he United States Environmental Protection Agency under the Region 9 Environmental Services As sistance Team (ESAT) contract (USEPA contract no. EP-W-06-041). ESAT Document Control N umber: 00801004-11710Lead 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 .....................................

................................................... .................................... 21Lead 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 collect ed 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 M ethod) . The lead in the particulate

matter is solubilized in a heated dilute nitric aci d 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 (0.15 μ g/m 3 ) for Pb-TSP. Results reported for monitoring or compliance purposes are calculated in μ g/m 3 at local temperature and pressure

conditions.

2 Summary of Method

Particulate matter is collected on filters over a 2 4-hour period. Lead on a strip from the TSP filter is solubilized by immersion in a dilute nitr ic acid (approximately 3.5%) solution, covering the solution with a watch glass, and reflu xing at 95 oC for an hour in a hot block. After extraction, the solubilized lead is diluted t o a specified volume with reagent water and mixed before analysis.

Sample solutions are introduced by pneumatic nebuli zation into a plasma, in which desolvation, atomization, and ionization occurs. I ons are extracted from the plasma through a differentially pumped vacuum interface and separa ted 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 detec tor. Ion intensities at each mass are recorded and compared to those obtained from extern al calibration standards to generate concentration values for the samples. Results are corrected for instrument drift and matrix effects using internal standards. Additional corre ctions 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 th e same acid

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

calibrate the ICP instrument.

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

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 st andard solution in known amount(s) and used to measure the relative re sponses 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 wi th identical procedures. Analysis of LD1 and LD2 indicates precision associated with laborat ory procedures, but not with sample collection, preservation, or storage procedures.

Laboratory Fortified Blank (LFB) - An aliquot of LRB to which known quantities of th e method analytes are added in the laboratory. The LF B is extracted and analyzed exactly like a sample, and its purpose is to determine whether t he methodology is in control and whether the laboratory is capable of making accurate and pr ecise measurements. The LFB is also referred to as a blank spike (BS) or Laboratory Con trol Sample (LCS).

Laboratory Fortified Sample Matrix (LFM) - An aliquot of an environmental sample to which known quantities of the method analytes are a dded in the laboratory. The LFM is extracted and analyzed exactly like a sample, and i ts purpose is to determine whether the sample matrix contributes bias to the analytical re sults. The background concentrations of the analytes in the sample matrix must be determine d in a separate aliquot and the measured values in the LFM corrected for background concentr ations.

Laboratory Reagent Blank (LRB) - An aliquot of blank matrix, a portion of unexpose d filter in this procedure, that is treated exactly a s a sample including exposure to all glassware, equipment, solvents, reagents, and inter nal standards that are used with other samples. The LRB is used to determine if method ana lytes or other interferences are present in the laboratory environment, reagents, or apparat us.

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% confide nce that the analyte concentration is greater than zero.

Quality Control Sample (QCS) - A solution of method analytes of known concentrat ions 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 cal ibration standards.

Quantitation Limit (QL) - The concentration at which confidence in the rep orted 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.Lead in Suspended Particulate Matter July 2010 Page 5 of 22

R9 FEM TSP July 2010.docx Stock Standard Solution - A concentrated solution containing one or more me thod analytes prepared in the laboratory using assayed reference materials or purchased from a reputable

commercial source.

Tuning Solution - A solution used to determine acceptable instrumen t 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 achi evable. Each laboratory is responsible for maintaining a current awareness file of OSHA re gulations regarding the safe handling of the chemicals specified in this method. A referenc e 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 an d is moderately toxic and extremely irritating to skin and mucus membranes. Use this re agent 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 ma terials may result in the release of acid fumes or toxic gases. Acidification of samples shou ld be done in a fume hood.

Analytical plasma sources emit radio frequency radi ation 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 wi th 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. Nume rous opportunities for pollution prevention exist in laboratory operations. Wheneve r feasible, the laboratory shall use pollution prevention techniques to address waste ge neration. 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 pr ocedure includes acidic aqueous waste with metals, spent vacuum pump oil, and solid waste (gloves, disposable labware, contaminated paper, etc.).Lead in Suspended Particulate Matter July 2010 Page 6 of 22

R9 FEM TSP July 2010.docx 5 Interferences

Isobaric elemental interferences result when isotop es 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 diffe rent isotope for which there is no interference. Alternatively, one can monitor anoth er isotope of the interfering element and subtract an appropriate amount from the element bei ng analyzed, using known isotope ratio

information. Corrections for most of the common el emental interferences are programmed

into the software.

Abundance sensitivity interference refers to the de gree 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 mi nor peak, thereby contributing to its intensity. The potential for these interferences s hould 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 shou ld choose an interference-free isotope to measure. For lead, polyatomic interferences are not typically an issue.

Physical interferences result from the physical pro cesses associated with the transport of sample to the plasma, sample behavior within the pl asma, and transmission through the interface region between the plasma and the mass sp ectrometer. Viscosity and surface tension differences can affect results, as can depo sits on the sample and skimmer cones caused by large quantities of dissolved solids in t he samples. The interferences can be compensated for by the use of internal standards th at approximate the analytical behavior of the elements being determined.

Memory interferences are related to sample transpor t 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 rinsin g 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 mat rix 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 sam ple analysis period, followed by analysis of the rinse blank at designated intervals. The le ngth 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. M emory 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 isLead in Suspended Particulate Matter July 2010 Page 7 of 22

R9 FEM TSP July 2010.docx high enough to suspect analyte carryover, the sampl e should be re-analyzed after a long rinse period.

During sample preparation, contamination is of prim e concern. The work area, including bench tops and fume hoods, should be kept scrupulou sly clean in order to eliminate environmental contamination. Samples, extracts, an d reagents should be covered at all times to prevent airborne contamination.

6 Personnel Qualifications/Responsibilities

The analytical procedure in this method should be u sed by analysts experienced in the use of inductively coupled plasma mass spectrometry (ICP-M S), the interpretation of spectral and matrix interferences and procedures for their corre ction. A minimum of six months experience with commercial instrumentation is recom mended. 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 det ermination of metals. A minimum of six months experience extracting samples (filters, wate r, soil, etc.) for trace level (μg/L in solution) lead is recommended.

7 Equipment and Supplies

The mention of trade names or commercial products i n this method is for illustrative purposes only, and does not constitute an EPA endor sement 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 t han those listed in this method may be employed provided that method performance appropria te for the intended application has

been demonstrated and documented.

7.1 Inductively coupled plasma mass spectrometer (ICP-M S)

 Instrument capable of scanning the mass range 5-250 amu with a minimum resolution capability of 1 amu peak width at 5% pea k height. Instrument may be fitted with a conventional or extended dynamic rang e detection system.

 Radio-frequency generator compliant with FCC regula tions.

 A variable-speed peristaltic pump is required for s olution 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 ty pes of interferences (e.g., from polyatomic oxide species).

 If an electron multiplier detector is being used, p recautions should be taken, where necessary, to prevent exposure to high ion flux. Ot herwise changes in instrument response or damage to the multiplier may result. Sa mples 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.Lead in Suspended Particulate Matter July 2010 Page 8 of 22

R9 FEM TSP July 2010.docx

EPA Region 9 Laboratory uses a Perkin Elmer Elan DR C 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 v olumes ranging from 100-2500 μ L with a tolerance of 2% and an assortment of high qu ality disposable pipet tips. Tips

must be lead-free.

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

7.5 Polypropylene Digestion Vessels, Environmental Expr ess P/N SC475 or equivalent (50-mL, graduated and certified to within 0.5% by v olume), polypropylene screw caps, and polypropylene ribbed watch glasses to cover dig estion vessels.

7.6 Paper cutter, pizza cutter, scissors, or other suit able 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 Filter s, 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 migh t 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. n itric 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 req uires less frequent replacement of tanks than compressed argon in conventional cylinde rs.Lead in Suspended Particulate Matter July 2010 Page 9 of 22

R9 FEM TSP July 2010.docx 7.11.4 Reagent water

All references to reagent grade water in this metho d refer to ASTM Type I water (ASTM D1193). Suitable water may be prepared by pas sing 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 e mployed. Solutions must be diluted in Class A volumetric glassware using air-d isplacement or Class A pipettes to

measure standard solutions.

Standard Stock Solutions - Stock standards may be p urchased from a reputable commercial source or prepared from ultra high-purit y grade chemicals or metals (99.99-99.999% pure). Stock solutions should be sto red in FEP bottles. Multielement solutions containing lead are acceptable.

 Lead solution, stock 1 mL = 1000 μ g Pb: Dry lead nitrate (PbNO 3 ) for one hour at 105°C; dissolve 0.1599 g PbNO 3 in 5 mL (1+1) nitric acid. Dilute to 100 mL with reagent grade water.

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

Use a stock standard solution as the source and dil ute 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 t wo weeks or as needed.

ICV / CCV - The ICV standard and CCV standard are i dentical 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 w ater 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.Lead in Suspended Particulate Matter July 2010 Page 10 of 22

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Internal Standard Solution

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

 Prepare internal standard solution to contain 100 μ g/L each of, holmium, and terbium in 1% (v/v) nitric acid. (Note: this s olution 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 stoc k standards.

 If necessary, prepare an intermediate standard to c ontain 1,000 μg/L of barium, beryllium, cerium, cobalt, indium, lead, ma gnesium, thorium, and uranium from the single-element stock standards.

 Prepare a working solution from the intermediate st andard at 1.0 μg/L in 1% (v/v) nitric acid.

Rinse solution - Dilute concentrated nitric acid wi th 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 P art 50, Reference Method for the Determination of Suspended Particulate Matter in th e Atmosphere (High-Volume Method). Sampling organizations may also send unex posed 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). Ea ch 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 organ ization 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-volu me 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 require d 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 i n the extraction vessel (with the filter strip in the solution) under ambient conditions.Lead in Suspended Particulate Matter July 2010 Page 11 of 22

R9 FEM TSP July 2010.docx 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 quantitat ively analyzable. The analyst should visually check filters prior to proceeding w ith preparation for holes, tears, or non-uniform deposit which would prevent representat ive subsampling. Document any deformities and qualify the data appropriately.

Care must be taken to protect filters from contamin ation. Filters must be kept covered prior to sample preparation.

With the whole TSP filter still in its container, u sing 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 par ticulates fall off before or after cutting the strip. Using the tweezers, roll the fi lter strip and transfer to the corresponding labeled extraction vessel.

The cutting tools and tweezers must be cleaned afte r 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 a nother 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 dam p 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 vesse l.

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 solutio n containing lead) or preferably, a solid certified reference material. U se 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 design ated QC sample of the same dimensions as selected for exposed filters to a 50- mL extraction vessel.Lead in Suspended Particulate Matter July 2010 Page 12 of 22

R9 FEM TSP July 2010.docx 8.3.2.4 LFM - Transfer an exposed filter strip of the desig nated 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 am ount 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 (1:1 9, 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 m L by diluting to the 50-mL mark on the vessel with reagent grade water. Cap the vesse l 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 d iffuse into the extract.

Shake the extract vigorously for 5 seconds (with th e 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 Standardizatio n

The analyst is advised to follow the recommended op erating 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 require ments and to maintain quality control data verifying instrument performance and analytica l results.

8.5.1 Precalibration routine

The following precalibration routine must be comple ted prior to calibrating the

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

the instrument meets the criteria listed below with out 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 c hecks using the tuning solution. Resolution at isotopes 206, 207, and 208 is critica l for quantitation of lead. For good performance adjust spectrometer resolution to produ ce 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.Lead in Suspended Particulate Matter July 2010 Page 13 of 22

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Instrument stability must be demonstrated by runnin g the tuning solution a minimum of five times with resulting relative standard devi ations of absolute signals for all analytes of less than 5%.

8.5.2 Internal Standardization

Internal standardization must be used in all analys es to correct for instrument drift and physical interferences. For lead analysis, a mi nimum of one internal standard must be used, and an alternate is recommended. Proc edures described in this method detail the use of two internal standards; terbium a nd 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 inter nal 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 peristal tic pump and a mixing coil. The

concentration of the internal standard should be su fficiently 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 th e internal standard is naturally present in the sample. Depending on the sensitivity of the instrument, a concentration range of 10-100 μ g/L of each internal standard is recommended. Inter nal standards should be added to blanks, samples and standards in a like manner, so that dilution effects resulting from the addition may be disregar ded.

8.5.3 Calibration

Prior to initial calibration, set up instrument sof tware routines for quantitative analysis. The instrument must be calibrated using o ne 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 integr ations for instrument calibration and data reporting.

8.5.3.1 Perform a multi-point calibration (ICAL) daily. An alyze a minimum of three CAL standards and a CB. A linear or linear-through -zero calibration equation is required and the correlation coefficient (r 2 ) 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 obtaine d using a linear curve.

8.5.3.2 An ICV is analyzed immediately following initial ca libration and the CCV at a frequency of one per 10 analytical samples and at t he end of the analytical run. The recovery of the analyte in the ICV and CCV is c alculated as follows:



### % 

  100Lead in Suspended Particulate Matter July 2010 Page 14 of 22

R9 FEM TSP July 2010.docx

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 1 05 percent. If the %R for lead in the ICV falls outside of the QC criteria, t he instrument must be recalibrated. Samples cannot be analyzed until an ac ceptable 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 i s obtained, the samples preceding the out-of-control CCV must be re-analyze d.

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 ca use of the high CB result must be determined and the problem corrected. The instr ument must be re-calibrated and all samples not bracketed by acceptable CB resu lts must be re-analyzed.

8.5.3.4 Analyze a QCS daily to verify the calibration stand ards 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 ana lyses.

The recovery of the analyte in the QCS is calculate d 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 nea r 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 calcul ated as:

% 

  100

Where %R = percent recovery

M = measured concentration at the instrument, μg/L

T = true concentration in the QLS, μg/LLead in Suspended Particulate Matter July 2010 Page 15 of 22

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If the QLS recovery does not meet the recovery crit eria 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 d etermined by aspirating a high level standard and observing the instrument re sponse return to background

when the rinse solution is introduced. Solutions t o be measured should be aspirated for 30 seconds prior to the acquisition o f data to allow equilibrium to be

established.

8.6 Typical Analytical Sequence

The following table shows a typical analytical sequ ence. 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, samp le history, or other information. All results must be less than the highest calibration s tandard or further dilution is required. Extracts that contain particulates should be allowe d to settle for a longer period of time. If particulates do not settle after 24 hours, filte r an aliquot of the extract using a disposable plastic syringe equipped with a 0.45 mic ron 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 c onstructed. Only results between theLead in Suspended Particulate Matter July 2010 Page 16 of 22

R9 FEM TSP July 2010.docx QLS concentration and the highest calibration stand ard 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 instrumen t data systems report results for the analyzed solution in units of μg/L. The instrument calculations include elemental correction calculations, internal standard calculations, and c alibration factors.

Report results for all filters delivered to the lab oratory along with the associated batch quality control (LRB, LFB, LD, and LFM). Reporting units w ill vary depending upon the sampling organizations requirements but will usually be μg P b/filter or μg Pb/m 3 (when the sampling organization provides total volume, in m 3 ). Sample results that exceed the calibration rang e must be reanalyzed at a higher dilution. Results b elow the QL should be reported as “not detected” or “ND” at the QL expressed as μg Pb/filt er or μg Pb/m 3 . 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 extractio n

To report results as μg/m 3 , 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/m 3

V Air = volume of air sampled, in m 3

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 ex posed 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 whichLead in Suspended Particulate Matter July 2010 Page 17 of 22

R9 FEM TSP July 2010.docx represents one ninth of the exposed area. A simila r 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 op erate a formal quality control (QC) program. The minimum requirements of this program c onsist 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. T he 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 ra nges 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 li mited. 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 sta ndards, 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 calibr ation range which may be used for the analysis of samples should be judged by the ana lyst from the resulting data. The upper LDR limit should be an observed signal no mor e than 10% below the level extrapolated from lower standards. Determined sampl e 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 judgme nt 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 c alibration standards and acceptable instrument performance with the preparat ion and analyses of a QCS. To verify the calibration standards the determined mea n concentration from a minimum of three analyses of the QCS; the result must be wi thin ±10% of the stated QCS value. If the calibration standards and/or acceptab le instrument performance cannot be verified, the source of the problem must be iden tified and corrected before either proceeding on with the initial determination of met hod detection limits or continuing with on-going analyses.Lead in Suspended Particulate Matter July 2010 Page 18 of 22

R9 FEM TSP July 2010.docx 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 filt ers from sampling organizations. Process the fortified filter strips through the ent ire analytical method. Perform all calculations defined in the method and report the c oncentration 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% confid ence 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 r equirements for MDLs. MDLs must be determined prior to the analysis of any fie ld samples by the laboratory and annually thereafter, when a new operator begins wor k, 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 d ictate they be redetermined.

10.2 Assessing Laboratory Performance (mandatory)

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

each batch of 20 or fewer filters. LRB data are use d 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 analy te level determined for a sample or are > 1⁄2 the QL whichever is greater, re-extraction may b e required for TSP filters; consult the laboratory supervisor for dire ction. The result (in μg/filter) for the LRB must be reported to the sampling organization.

10.2.2 Laboratory fortified blank (LFB) - The laboratory m ust analyze at least one LFB with each batch of 20 or fewer filter strips. Calculate accuracy as percent recovery using the following equation:

% 

    100Lead in Suspended Particulate Matter July 2010 Page 19 of 22

R9 FEM TSP July 2010.docx

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 extractio n

If the recovery falls outside the required control limits of 80-120%, the method is judged out of control, and the source of the proble m 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 suffic ient internal performance data become available (usually a minimum of 20-30 analys es), 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 t o 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 bet ter than the required control limits of 80-120%. After each five to ten new recovery mea surements, 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 o n-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 prope rly calibrated on a continuing basis. To verify calibration run the CB and CCV imm ediately following each calibration routine, after every ten analyses and a t the end of the sample run. The results of the analyses of the standards will indic ate whether the calibration remains valid. The lead recovery within the standard soluti ons must be within ±5% of

calibration. If the calibration cannot be verified within the specified limits, the instrument must be recalibrated. If the sample matr ix is responsible for the calibration drift, it is recommended that the previous 10 sampl es are reanalyzed in groups of five between calibration checks to prevent a similar dri ft situation from occurring.

10.3 Assessing Analyte Recovery and Data Quality

Sample homogeneity and the chemical nature of the s ample matrix can affect analyte recovery and the quality of the data. Taking separa te 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.Lead in Suspended Particulate Matter July 2010 Page 20 of 22

R9 FEM TSP July 2010.docx 10.3.1 The laboratory must add a known amount of analyte t o 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 p reparation 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 the se values to the designated LFM recovery range of 70-130%. Recovery calculations ar e not required if the concentration of the analyte added is less than 30% of the sample background concentration. Percent recovery may be calculated u sing 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/filt er

If recovery falls outside the designated range and laboratory performance is shown to be in control, the recovery problem encountered wit h the fortified filter is judged to be matrix related, not system related. The data use r must be informed that the result for that analyte in the unfortified sample is suspe ct due to either the heterogeneous nature of the sample or an uncorrected matrix effec t.

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 differenc e (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

C LD = measured concentration in LD, in μg/filter

 = measured concentration in sample filter, in μg/fi lterLead in Suspended Particulate Matter July 2010 Page 21 of 22

R9 FEM TSP July 2010.docx

Apply precision criteria for samples with analyte l evels > 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 i ndicating that the particulate matter may not be homogenous across the TSP filter.

10.4 Internal Standard Response

Monitor the signal intensity for the internal stand ard masses throughout the analytical run. This information is useful in detecting instr ument 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 mus t not deviate more than 60 - 125% from its original intensity in the calibration blan k. 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 fur ther factor of two, add the internal standards and reanalyze. If after flushing the resp onse of the internal standards in the calibration blank is out of limits, terminate the a nalysis 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 initi al CB

11 References

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

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 M ethod)Lead in Suspended Particulate Matter July 2010 Page 22 of 22

R9 FEM TSP July 2010.docx 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 - M ass Spectrometry, Revision 5.4, EMMC Version, May 1994.

U.S. Environmental Protection Agency SW846 Method 6 020A , Inductively Coupled Plasma-Mass Spectrometry, Revision 1, February 2007

.