EFGS-SOP-129 02 Speciated Metals by LC-ICPMS Truncated KET …newtowncreek.info/docs2/2 Remedial...

Document Title: Determination of As, Se, V and Cr in

Sediments, Soils, Tissues and Waters by LC-ICPMS

Eurofins Document Reference: EFGS-SOP-129-R02

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Revision: 2 Effective Date: 1/21/2013 of 28

COMPANY CONFIDENTIAL. All Eurofins Frontier Global Sciences standard operating procedures contain proprietary information and are protected by Washington State Law. Proprietary information must be maintained with the strictest of confidence and must not be used or appropriated to benefit any party without prior written consent from Eurofins Frontier Global Sciences.

Eurofins Document Reference EFGS-SOP-129-R02 Revision 2

Effective Date 1/21/2013 Status Final

Historical/Local Document Number FGS-SOP-129.02

Local Document Level Level 3

Local Document Type SOP

Local Document Category NA

Prepared by Monica Garcia-Strickland

Reviewed and Approved by

Dave Wunderlich and Patrick Garcia-Strickland




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Table of Contents

1 Revision Log: ......................................................................................................................... 4 2 Reference: ............................................................................................................................. 4 3 Cross Reference: ................................................................................................................... 4 4 Purpose: ................................................................................................................................ 4 5 Scope: ................................................................................................................................. 4 6 Basic Principles: .................................................................................................................... 5 7 Reference Modifications: ....................................................................................................... 5 8 Definitions: ............................................................................................................................. 5 9 Interferences: ......................................................................................................................... 6 10 Safety Precautions, Pollution Prevention and Waste Handling: ............................................ 6 11 Personnel Training and Qualifications: .................................................................................. 7 12 Sample Collection, Preservation, and Handling: ................................................................... 8 13 Apparatus and Equipment: .................................................................................................... 8 14 Reagents and Standards: ...................................................................................................... 9 15 Calibration: ............................................................................................................................. 9 16 Procedure: ........................................................................................................................... 10 17 Calculations: ........................................................................................................................ 14 18 Statistical Information/Method Performance: ....................................................................... 16 19 Quality Assurance/Quality Control: ...................................................................................... 16 20 Corrective Action ................................................................................................................. 17 21 List of Attachments .............................................................................................................. 18




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Approvals:

Prepared by: Date:

Approved by: Date:

Approved by: Date:




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1 Revision Log: Revision: 2 Effective Date: This version Section Justification ChangesCover Required change Changed company name from Frontier Global Sciences to Eurofins

Frontier Global Sciences. All Formatting per

LOM SOP-LAB-201 Reformatted document to new corporate specifications.

5.3 Required change Updated SOP reference 6.1 Required change Added 0.45-µm filter 8.2, 8.8 Required change Updated definition 12.2.1 Required change Added comment about storage conditions 15 Required change Expanded calibration options 16.7 Required change Added sample prep section 17.2.4 Required change Added algorithm for final result calculation of solid matrix 19.1 & 20.4 Required change Corrected ICV acceptance criteria App A, B, C & D Required change Updated App E and F Required change Updated and expanded Transport and Field Spike Making Sheets

2 Reference:

2.1 US EPA Method 8000B, “Determinative Chromatographic Separations”, SW-846, Rev. 2, 1996.

2.2 Chemical Hygiene Plan, Eurofins Frontier Global Sciences, current version.

2.3 Chromera Software guide

2.4 Total Chrom Software Guide.

3 Cross Reference: Document Document Title SOP FGS-094, App F Standard Operating Procedure Training Record SOP FGS-099 Waste Disposal Procedure for Client Sample Waste SOP FGS-144 Manual Integration SOP FGS-152 Analysis of Heavy Metals Contaminants in Dietary Supplements, Raw Materials,

and Pharmaceutical Products Using Inductively Coupled Plasma Mass Spectrometry

4 Purpose:

4.1 This purpose of this Standard Operating Procedure (SOP) is to describe the analytical technique used for the analysis of Arsenic, Chromium, Selenium and Vanadium speciation analysis at Eurofins Frontier Global Sciences.

5 Scope:

5.1 This method describes the determination of dissolved selenium species (selenite, selenate and selenocyanate), dissolved arsenic species (arsenate, arsenite and monomethylarsonic acid), dissolved vanadium species (vandyl, vanadate), and dissolved hexavalent chromium in waters using Liquid Chromatography followed by




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Inductively Coupled Plasma - Mass Spectrometry (LC-ICP-MS). This technique can be used for other species with further method development.

5.2 This method is designed for the determination of As, Cr, Se, and V in the range of 0.15–50 µg/L. This range may be extended to higher concentration levels by diluting the samples.

5.3 Total and Total dissolved As, Cr, Se and V can be determined by ICP-MS (Frontier SOP FGS-152, “Analysis of Heavy Metals Contaminants in Dietary Supplements, Raw Materials, and Pharmaceutical Products Using Inductively Coupled Plasma Mass Spectrometry”).”

6 Basic Principles:

6.1 An aqueous sample is filtered through a 0.22-µm or a 0.45-µm filter.

6.2 A 50µL aliquot of the sample is injected onto an Anion Exchange column.

6.3 After the column, the sample and eluents pass through a self-regenerating suppression system that removes the cations before being aspirated into the plasma.

6.4 The mass-to-charge ratio (m/z) of AsO at mass 91, Chromium at mass 52 and 53, Se at mass 77, 78 and 82, and VO at mass 67, are used for identification of species in the chromatograms.

7 Reference Modifications: None

8 Definitions:

8.1 LIMS – Laboratory Information Management System.

8.2 Batch – No more than 20 client samples grouped for preparation. 1 MBLKs, 1 LCS and 1 MS/MSD pair are prepared per every 10 samples.

8.3 Method Detection Limit (MDL) – the limit derived from an exercise as described in 40 CFR, Part 136, Appendix B. The exercise produces a defined value that is the minimum concentration that can be measured and reported with 99% confidence that the analyte concentration is greater than zero from a given matrix.

8.4 Certified Reference Material (CRM) – a standard of known composition that is certified by a recognized authority and representing a sample matrix. It is used to verify the accuracy of a method.

8.5 Liquid Control Sample (LCS) and Liquid Control Sample Duplicate (LCSD), is a sample containing known concentrations of the analytes of interest that is taken through the entire preparation and analysis process in the same manner as the samples to monitor complete method performance. A Certified Reference Material (CRM) is preferred as the LCS, but a blank spiked sample also meets the requirement.




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8.6 Preparation Blank (BLK) – Reagents used for the digestion and is treated as a sample throughout the preparation and analysis processes, and is a control for system cleanliness. Teflon boiling chips are added to the preparation blanks.

8.7 Matrix Duplicate (MD) – a representative sample is selected and digested in the same manner. This QC sample will indicate sample homogeneity on the analytes of interest.

8.8 Matrix Spike (MS) and Matrix Spike Duplicate (MSD) – a representative sample is selected and spiked with a secondary source at one to five times the ambient concentration or mid curve, whichever is greater. These QC samples will indicate sample matrix effects on the analytes of interest.

8.9 May: This action, activity, or procedural step is optional.

8.10 May Not: This action, activity, or procedural step is prohibited.

8.11 Shall: This action, activity, or procedure is required.

8.12 Should: This action, activity, or procedure is suggested, but not required.

9 Interferences:

9.1 Samples containing high levels of chlorides, sulfides, sulfates and bromides cause polyatomic formations that may cause spectral overlaps.

9.2 The presence of oxidizing acids will cause oxidation/reduction of species.

9.3 Samples containing high levels of anionic species such as but not limited to sulfate and chloride may cause the column to become overloaded, resulting in inconsistent retention times for species. Also samples containing high levels of transitional metals can cause a decrease in column interaction and decrease column life.

9.4 ICP-MS is prone to spectral interferences. These types of interferences result from the formation of polyatomic species in the plasma interface that have the same mass-to-charge ratio as the analyte of interest. Formation of 40Ar+12C- ,40Ar+35Cl-, 81Br-1H+ and 79Br-1H+ species in the presence of carbon, bromide and chloride-containing samples (such as FGD waters) interfere with the determination of 52Cr, 75As, 77Se and 82Se.Therefore, identification of the inorganic arsenic, selenium, vanadium and chromium peak(s) should be performed by utilizing a reaction gas in the dynamic reaction cell.

10 Safety Precautions, Pollution Prevention and Waste Handling:

10.1 Personnel will don appropriate laboratory attire according to the Chemical Hygiene Plan. This includes, but is not limited to, laboratory coat, safety goggles, and nitrile gloves (often worn under clean gloves).

10.2 The toxicity or carcinogenicity of the selenium standards used in this method have 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. All laboratory personnel should refer to the MSDS for each chemical they are working with.




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10.3 Methanol (CH3OH, MeOH): May be fatal or cause blindness if swallowed. Vapor harmful. Flammable liquid and vapor. Harmful if swallowed, inhaled, or absorbed through the skin. Causes eye, skin, and respiratory tract irritation. May cause central nervous system depression. Cannot be made non-poisonous. See MSDS for more details.

10.4 45% w/w Potassium Hydroxide (KOH) – corrosive, liquid and mist cause severe burns to all body tissue. Wear protective clothing, goggles, and gloves. See MSDS for more details.

10.5 All personnel handling environmental samples known to contain or to have been in contact with human waste should be immunized against known disease-causative agents. Eurofins Frontier will reimburse the expense of Hepatitis A and B immunizations for any laboratory staff member who desires this protection.

10.6 See Eurofins Frontier Global Sciences Chemical Hygiene Plan (CHP) for general information regarding employee safety, waste management, and pollution prevention.

10.7 All laboratory waste is accumulated, managed, and disposed of in accordance with all federal, state, and local laws and regulations. Any waste generated by this procedure should be disposed of according to SOP FGS-099 “Waste Disposal Procedure for Client Sample Waste,” which provides instruction on dealing with laboratory and client waste.

10.8 Pollution prevention information can be found in the current Eurofins Frontier Global Sciences Chemical Hygiene Plan (CHP), which details and tracks various waste streams and disposal procedures.

11 Personnel Training and Qualifications:

11.1 An analyst must perform an initial demonstration of capability (IDOC) that includes four replicates of a secondary source before being qualified to analyze samples without supervision. Continuing DOC will be maintained and monitored via performance on CRMs and other QC samples, as well as obtaining acceptable results on proficiency testing exercises.

11.2 The analyst/laboratory technician must have read this SOP and other relevant SOPs and have the training documented on the applicable form(s). The analysis may be questioned on SOP by supervisor(s) and/or trainers.

11.3 Training is documented by the employee and supervisor, and is kept on file in the QA Office. The employee must read, understand, and by signing the training document, agree to perform the procedures as stated in all Standard Operating Procedures (SOPs) related to this method.

11.4 Reading of the SOP must be documented on the correct form, such as “Standard Operating Procedure Training Record,” Appendix F in SOP FGS-094, or the last page of this SOP Appendix A “Standard Operating Procedure Training Record” or a similar document.

11.5 All employees must also, on a yearly basis, read the Quality Manual (QM), and complete the yearly Ethics training.




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11.6 All training documents including initial demonstration of capability (IDOC), continuing demonstration of capability (CDOC), SOP reading, initial QA orientation, and Ethics training are stored by the Quality manager in the employee’s training file for ten years after the employee is no longer working for Eurofins Frontier Global Sciences.

11.7 Chemical Safety Training, Compressed Gas Training, Chemical Hygiene Plan documentation, and Shipping of Hazardous Goods Training are stored by the Health and Safety Officer for ten years after the employee is no longer working for Eurofins Frontier Global Sciences.

12 Sample Collection, Preservation, and Handling:

12.1 The sample (200-1000 mL) is collected directly into new high-density polyethylene (HDPE) bottle using sample handling techniques specially designed for collection of metals at trace levels (FGS-008, “Ultra Clean Aqueous Sample Collection”).

12.2 It is very difficult to preserve the native species, depending on the nature of the water; there can be a spontaneous reduction of species.

12.2.1 The suggested storage scheme for Arsenic and Selenium is to store at –80 °C or less (on dry ice or in a Cryogenic freezer) until analysis. Chromium shall be preserved with KOH with a pH >9.3-9.7 and Vanadium shall be refrigerated at 4 deg. °C. This is a suggested scheme. Samples containing high levels of salts requesting As & Se should be refrigerated only to decrease the chance of precipitation during the thawing process.

12.3 It is recommended that all speciation samples be collected with a transport spike and field spike. Preparation for these spikes can be found in Appendices E & F.

13 Apparatus and Equipment:

13.1 An inductively coupled plasma-mass spectrometer (ICP-MS), such as a Perkin Elmer ELAN 6100DRC with software ELAN 3.3, Cyclonic Spray Chamber and a Burgener Teflon Mira Mist nebulizer.

13.2 Liquid Chromatograph system consisting of the following components.

13.2.1 Binary/Quaternary Pump

13.2.2 Autosampler

13.2.3 Automatic injector

13.2.3.1 200µL PEEK sample loop

13.2.4 External Rheodyne Switching Valve, 6 port <--Optional

13.2.5 Eluent organizer

13.2.6 Vacuum Degasser

13.2.7 Anion self-regenerating suppressor




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13.2.8 Column Oven

13.2.9 Chromatographic software (such as Chromera from Perkin Elmer) used for data acquisition.

13.3 Computer equipped with TotalChrom software version 6.3.1 and printer.

13.4 Chromatographic guard and analytical columns; See Appendices for specifics.

13.5 LIMS – Element, version 5.85 or higher

13.6 Water container for self regenerating system.

13.7 Waste container, 5 gallons.

13.8 A peristaltic pump.

13.9 15-mL and 50-mL plastic centrifuge tubes

13.10 Vacuum Filtration system with 0.2µm or 0.45µm filters (nylon or PTFE support).

14 Reagents and Standards:

14.1 Reagent water – 18 MΩ ultra pure de-ionized water (e.g. Millipore®) starting from a pre-purified (distilled, R.O., etc.) source.

14.2 Potassium Hydroxide

14.3 Methanol HPLC Grade, Selenium Mobile Phase

14.4 Reagents, Mobile phases are specific to each analysis please refer to the appropriate Appendix.

14.4.1 Se: Appendix A

14.4.2 As: Appendix B

14.4.3 Cr: Appendix C

14.4.4 V: Appendix D

15 Calibration:

15.1 A calibration curve is determined daily from the analysis of at least five different dilutions of the species (As, Se, Cr and V). For environmental samples, the linear and non-linear (second order polynomial only) calibration models discussed in EPA SW-846 Method 8000B can be employed.

15.2 The calibration blank consists of the analytical diluent and is used to determine the baseline for the instrument.

15.3 Pipette calibration standards, ICV, ICB into the 1.8mL autosampler vials and load the autosampler. In the “Sequence” menu, fill in the sample name and description for the




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calibration standards, ICV, and ICB. Save the batch file with the current date (YYMMDD). See Section 16.4 for creating a sequence.

15.4 For linear calibrations using average calibration factors, the RSD must be less than or equal to 20%. The laboratory won’t use the mean of the RSD of calibration factors for all analytes in order to achieve this acceptance criterion. For linear calibrations using least squares regression, the correlation coefficient (r) must be equal to or greater than 0.995. For non-linear calibration using a quadratic model, the coefficient of determination (r2) must be equal to or greater than 0.990. The recovery of the PQL standard must fall within 50-150%, although deviations may be allowed for special circumstances involving research projects.

16 Procedure:

16.1 HPLC pump: Set flow rate to zero. Refill eluents by carefully opening the eluent container and pouring new eluent in without removing the uptake lines. Close the container after filling up.

16.1.1 Purge all lines (All in Chromera)

16.1.1.1 Prime lines by attaching a luer lock empty syringe onto the prime port and open valve by turning counter clockwise on the port. Go to “Manual Control” and enter 10.0 mL/min under PURGE PUMP; purge all lines used for analysis. (i.e. MQA, KOHB for Cr analysis). Disconnect syringe and discard the contents. Continue to purge until air bubbles are no longer present. Repeat for all eluent(s) used in analysis. When complete close valve by turning clockwise.

16.1.1.2 While purging LC lines flush autosampler. In the Manual Control window, under flush autosampler, type in flush volume and flush.

16.1.2 Equilibrating Pump

16.1.2.1 After all lines have been purged, in the manual control box under “Pump Settings,” type in flow rate and the mobile phase composition according to step 1 for the method of the day. Click Apply.

16.1.2.2 Continue to Step 16.2. Once the pressure has stabilized on the LC, slowly increase the flow rate to the method specific flow rate.

16.2 Immediately after the pump is turned on the suppressor must be turned on as well. Set the suppressor flow rate and amperage according to the method specific values. Refer to the following Appendices A-D for each species and special circumstances. Turn on the argon gas flow (ca. 12 psi) and monitor flow of reagent water through the suppressor. Flow rate should never be less than the analytical flow rate.

16.2.1 Changing flow rate and amperage on the RFC-10 controller:

16.2.1.1 On the Default screen press the up arrow




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16.2.1.2 Press enter: Suppressor Type Highlighted

16.2.1.2.1 Press down for suppressor type: Press enter

16.2.1.3 Press the down arrow 3 times to display flow rate.

16.2.1.4 Press the up arrow to select flow rate for analysis of the day. Press enter

16.2.1.5 Press down to go to suppressor current screen. Press enter

16.2.1.6 Press the up arrow until desired amperage is reached and press enter

16.3 Inductively Coupled Plasma Mass Spectrometer/Chromera.

16.3.1 Follow instructions given in Frontier SOP FGS-152, “Analysis of Heavy Metals Contaminants in Dietary Supplements, Raw Materials, and Pharmaceutical Products Using Inductively Coupled Plasma Mass Spectrometry,” for the optimization of the instrument.

16.3.1.1 Note that all methods used will be specific to the DRC. (X-Y, Single, Daily).

16.3.1.2 The .dac file used will also be dependent on the method of the day.

16.3.1.3 The .tun file will always be the default

16.4 Creating Analytical Sequence:

16.4.1 In the Sequence Window File Open New Sequence. Open method specific template-Name: Date of analysis YYMMDD (090320); Description: Analysis Type; Group: Production. Do not use slashes, underscores or any character as this will create method corruption with Chromera. Save.

16.4.2 The template contains the most current calibration curve and ICV/CCV concentration listed as samples under “Sample Type”.

16.4.3 Begin by adding all Blanks, BS/BSDs and samples from the batch. Please note a SEQ-CCV/SEQ-CCB to be added per 10 samples.

16.4.4 Verify method and dilution factors for all samples. Please note that the dilution factor found on Chromera must match LIMS Data Entry/Review Diln column. (i.e. Chromera DF 10x, LIMS Data Entry/Review Diln: Initial Volume 10).

16.4.4.1 If no dilution is necessary, then pipette the filtered sample(s) into the autosampler vials. If a dilution is required, depending on the dilution factor, add the appropriate sample into a 15mL centrifuge tube and bring it up to a final volume of 10mL.

16.4.5 Once all of the samples are added after the last SEQ-CCBX the last entry will be as follows-click on sample type and scroll down to WASH; Sample name:




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SHTDN method: KOHSHTDNDRC, if analyzing Cr6 or V speciation this step is not required.

16.5 Condition Column (All in Chromera).

16.5.1 Highlight the sequence window. Click file open click on Group and highlight “ColumnCare” and highlight “Column Begin”. Click ok.

16.5.2 Load 2 high standards from the previous analysis onto the autosampler. Note the autosampler positions.

16.5.3 In the Sequence, Sample Type: Sample; Name: type in concentration of 2 high standards; Add autosampler positions; Method: Select method for the day; Injections: 5 each. Refer to the following Appendices A-D for each species and special circumstances.

16.5.4 Start Sequence.

16.6 Calibration – see Section 15.

16.7 Sample Preparation at the analytical level

16.7.1 Prior to analysis, all aqueous or digested samples are filtered via 0.22µm or 0.45µm filter.

16.8 Data Export From the Instrument Hard Drive

16.8.1 Once all of the data has been analyzed, open the TCNavigator menu and the Chromera data manager.

16.8.2 In Data Manager Results Data Export to TotalChrom raw file (raw)

16.8.3 Highlight the batch of interest and click ok

16.8.4 The data can be located:

16.8.4.1 \\Icpms5\Export

16.8.4.2 The data can now be copied to the analyst local hard drive for further processing.

16.8.5 Once complete all processed data and method will be moved to the network under the following path:

16.8.5.1 \\al_group\Mercury & Trace Metals\Speciation Data

16.9 Data Processing

16.9.1 Log on to TCNavigator

16.9.2 Once data is found on the local hard drive, create a new folder, YYMMDD Species.




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16.9.2.1 Create subfolders for each isotope, primer and one folder for all interferences.

16.9.2.2 Move each file to its designated folder.

16.9.3 Click on “Build Method” and Clear MRU List. Click on “Load method stored on disk”. In TC Method click on the method specific to the species.

16.9.3.1 Save As: YYMMDD (Isotope).

16.9.3.2 In the Method Editor window click “Components” scroll down to “Edit Component”.

16.9.3.3 Under the calibration tab verify that all areas are set to 0. If not, delete all lines by highlighting and clicking delete and reentering the level and amount columns.

16.9.3.4 Calibration Type: As, Se, V, Cr-Use Curve, Curve Fit type-1st order, Curve Fit type-2nd order or Avg. calibration factor, Origin Treatment-Non selected.

16.9.3.5 Response: Area for all

16.9.3.6 File save and exit

16.9.4 Click on “Graphic Edit” and open a mid level calibration point as a .raw file.

16.9.4.1 Click on File Open Method of the day

16.9.4.2 Click on Calibration Edit Components

16.9.4.3 Identify each peak and reset each retention time

16.9.4.4 Once complete click return

16.9.4.5 File Save

16.9.5 Click on “Batch”.

16.9.5.1 File Open Data File Open each calibration standard one by one starting with the calibration blank.

16.9.5.2 Method File-Method of the day

16.9.5.3 Report format file - Can be found in the TC method folder

16.9.5.4 Unclick Enable optional report(s) in method

16.9.5.5 Click on Overwrite existing result files

16.9.5.6 All other parameters are to be left as default

16.9.5.7 Click ok




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16.9.5.8 Reprocess start

16.9.5.9 Once processed, click on “Results” and visually inspect and integrate according to SOP FGS-144, “Manual Integration” and print each individual chromatogram.

16.9.6 Click on “Build Method” and Clear MRU List. Click on “Load method stored on disk’.

16.9.6.1 In the Method Editor window click “Components” scroll down to “Calibrate”.

16.9.6.2 Unclick “Identify peaks before calibrating”.

16.9.6.3 Click on Replace

16.9.6.4 Select the calibration files making sure that the standard matches the level under calibration parameters

16.9.6.5 Once complete click ok. Verify that calibration is within control before continuing. Calibration criteria can be found in Section 15.4

16.9.7 Once the calibration is determined to be in control, process SEQ-ICV to the last SEQ-CCB by repeating section 16.9.5.

16.9.8 Manually enter all instrumental concentrations into LIMS.

17 Calculations:

17.1 The sample concentrations are printed on the chromatograms for the ICV/CCV, ICB/CCB and samples only. These values are transcribed into LIMS. Dilution factors must be entered in LIMS under “Data Entry Review” for waters and soils, sediments and tissues. The dilution factor must match that of the Chromera Run Log.

17.2 Recovery:

17.2.1 Recoveries for ICV and CCV standards are calculated as follows:

Recovery (%) = CS / S *100 Where: CS = sample concentration S = true value of spike or CRM.

17.2.2 Relative percent difference (RPD) for sample and matrix duplicate (MD) are calculated as follows:

RPD (%) = abs((CS – CMD) * 200/(CS + CMD))




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Where: abs = absolute value CS = sample concentration CMD = sample concentration of matrix duplicate

17.2.3 Matrix spike recovery for matrix spike (MS) and matrix spike duplicate (MSD) are calculated as follows:

Recovery (%) = (CMS - CS ) /S *100 Where: CMS = concentration of matrix spike CS = sample concentration S = true value of spike




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17.2.4 Calculation for the concentration of a solid material:

Final Concentration (µg/g) = (I.R.* F.V.* D.F.) / Mass Where: I.R. = Instrument Result, µg/L F.V. = Final Volume, Liters D.F. = Dilution Factor Mass = Mass of solid material, grams

18 Statistical Information/Method Performance:

18.1 Method Detection Limit (MDL) and Practical Quantitation Limit (PQL) studies are based on 40 CFR 136, Appendix B. The MDL and PQL must be performed for each analyte/matrix/preparation combination.

18.2 The PQL is determined by 10 replicates of an applicable matrix spike with a concentration that must fall within the control limits for the lowest calibration standard, which is between 70-130%.

18.3 The method detection limit (MDL) for Cr(VI) in reagent water has been determined to be less than 0.5 µg/L with a Practical Quantitation Level (PQL) at 1.0 µg/L.

18.4 Current MDLs and PQLs are stored at: \Gen_Admin\Quality Assurance\MDLs PQLs & RLs\Complete Reports of MDL Studies by Analyte and Matrix\Current\.

19 Quality Assurance/Quality Control:

19.1 Initial Calibration Verification (ICV) - Immediately after calibration, initial calibration verification should be performed through the analysis of an ICV standard. A second source standard near the mid-point of the calibration range is analyzed and the recovery calculated. If the acceptance criterion of 75-125% recovery is not met, the calibration curve and the ICV must be remade and reanalyzed along with the samples.

19.2 Initial Calibration Blank (ICB) - Immediately after the ICV, an initial calibration blank should be performed through the analysis of an ICB. If the acceptance criterion of <PQL is not met, the calibration curve and the ICV must be remade and reanalyzed along with the samples. ICBs >PQL can be reported only if the bracketing samples are below the PQL or 10 times greater than the level of contamination.

19.3 Continuing Calibration Verification (CCV) - Calibration should be verified every ten samples by analyzing a mid-point calibration standard. If the recovery does not meet the acceptance criteria of 75-125% recovery, analysis must be halted, the problem corrected, and the instrument re-calibrated. All samples after the last acceptable calibration verification must be reanalyzed. CCVs >125% can be reported only if the bracketing samples are below the PQL.




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19.4 Continuing Calibration Blank (CCB) – Instrument cleanliness and carryover should be verified every ten samples by analyzing a blank. If the recovery does not meet the acceptance criteria of <PQL, analysis must be halted, the problem corrected, and the instrument re-calibrated. All samples after the last acceptable continuing calibration blank must be reanalyzed. CCBs >PQL can be reported only if the bracketing samples are below the PQL or 10 times greater than the level of contamination.

19.5 Laboratory Control Sample and Duplicates (LCS, LCSD) - For every 10 or fewer samples prepare one LCS, spiked at approximately the midpoint of the calibration, and process in the same manner as the samples. Recoveries should be in the range 75-125%. RPD values should be less than 25%.

19.6 Preparation Blanks (PBs) - For every batch of 10 samples, analyze at least one reagent aliquot in the same manner as a sample to detect contamination and variability. The concentration of the PB should be less than the detection limit.

19.7 Duplicates – For every batch of 20 or less samples a duplicate sample can be prepared at the request of the client from a randomly selected sample, and process it in the same manner as the samples. Sample and duplicate must have an RPD of less than 25%.

19.8 Matrix spikes and matrix spike duplicates (MS, MSD) - For every 10 or fewer samples prepare two additional aliquots from a randomly selected sample, spike them at approximately the midpoint of the calibration, and process in the same manner as the samples. Recoveries should be in the range 75-125%. RPD values should be less than 25%.

20 Corrective Action

20.1 Should the instrument performance fail to meet expected standards, the analyst must determine the cause of the failure and attempt to rectify it prior to analysis. (i.e., Daily Performance, refer to SOP FGS-152, “Analysis of Heavy Metals Contaminants in Dietary Supplements, Raw Materials, and Pharmaceutical Products Using Inductively Coupled Plasma Mass Spectrometry”).

20.2 Quality Control (QC) samples must all be within specified guidelines. The reason for a QC set not achieving the desired potential must be determined as soon as possible. The cause and method of determining the set's failure must be documented.

20.3 For any Blank (preparation and/or calibration) that appears high, it is suggested that the blank be re-analyzed to confirm, to determine the possible reason for the elevated levels. If a reason is determined, this finding must be documented on the bench sheet as well as in the MMO. Any sample greater than 10 times the contamination or less than the PQL does not require reprep.

20.4 If the recoveries for the ICV/CCV standards are not within 75 and 125%, bracketing samples must be reanalyzed.




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20.5 If matrix spike recoveries outside acceptable limits are observed check the recoveries from the LCS/LCSD spike. If recoveries from LCS/LCSD spike are within specifications, the low/high recoveries from spikes are probably due to matrix effects.

20.6 Possible causes of non-achievement are; instrument failure, incorrect pipette calibration, incorrect pipetting of samples, incorrect initial pH, low spike to sample ratio or matrix interference. Once the cause is determined, the samples are re-prepped and re-analyzed, if applicable.

20.7 If a carryover interference is suspected (usually due to column overload), the sample should be reanalyzed after a long rinse period or after the analysis of an acceptable blank (less than the PQL).

21 List of Attachments Appendix A: Se Speciation Analysis for Se IV, Se VI,SeCN, SeMe and SeMeCyst

Appendix B: As Speciation Analysis for AsIII, MMA, AsV, AsB and DMA

Appendix C: Cr Speciation analysis for Cr (VI)

Appendix D: Vanadium Speciation

Appendix E: Spike Making Cheat Sheet for As, Cr, V & Se Speciation: LC-ICP-DRC-MS

Appendix F: Spike Making Cheat Sheet for As (Cryo) & Se (AFS) Speciation

Appendix G: Example - Standard Operating Procedure Training Record




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Appendix A: Se Speciation Analysis for Se IV, Se VI,SeCN, SeMe and SeMeCyst




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Appendix B: As Speciation Analysis for AsIII, MMA, AsV, AsB and DMA




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21.1.1.1.1




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Appendix C: Cr Speciation analysis for Cr (VI)




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Appendix D: Vanadium Speciation




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Appendix E: Spike Making Cheat Sheet for As, Cr, V & Se Speciation: LC-ICP-DRC-MS Materials: (No Acid)

1. 2 – 15mL centrifuge tubes (non-soaked). 2. 2 – 250ml HDPE bottles for Arsenic and Selenium Speciation. 3. 3 – 500mL HDPE bottles for Vanadium and Chromium Speciation. 4. 10µL pipette. 5. 5mL pipette. 6. 1000 ppm of PM requested species: found in LC fridge (used to prep 1000ppb), stored

in 15mL centrifuge tubes. **allow time for standards to come to room temperature**

7. MQ/RO for pipette rinse. 8. MQ/RO for filling. 9. 45% w/w KOH to be used as a preservative for Cr6 only.

Process for mid level spiking: 1. Please document the pipettes used. 2. Label one 250mL bottle as Transport Spike, initial and date.

i. Note: Cr(IV) and V must be prepped in 500mL bottles. 3. Label another 250mL bottle as Field Spike A and set aside (leave empty).

i. For Cr(IV) and V a 500mL bottle would be labeled. 4. Label one 15mL tube Field Spike Stock, initial and date. 5. From the materials section select appropriate bottle and label as “Transport Spike”.

i. For Selenium and Arsenic weigh MQ or RO ii. For Hexavalent Chromium add 45% w/w KOH and bring to a final mass with MQ

or RO. iii. For Vanadium weigh MQ or RO.

6. Rinse the 5mL pipette with MQ. 7. Pipette 10mL of MQ/RO into both 15mL centrifuge tubes. 8. Rinse 10µL pipette with MQ. 9. Remove 10µL for each species-Transport and Field Spike Stock containers (ex for

Selenium Speciation - 30uL total for 3 species: Se4, Se6 and SeCN). 10. Shake room temperature standards. 11. Add 10µL of the PM requested species to the Transport and Field Spike Stocks: Make

sure to change pipette tip for each standard. 12. Cap both vials and homogenize. 13. Field spike Stock is finished and can be double bagged. 14. Pour unlabeled vial into the Transport Spike bottle. 15. Cap bottle and homogenize. 16. Pour some of the spike back into the vial (about half way). 17. Cap vial and homogenize. 18. Pour vial back into the bottle, cap and homogenize. 19. Repeat steps 13-15, 2 times (total of 3). 20. The Transport Spike and Field Spike Stocks are done.




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The above are guidelines for the preparation of the mid level standard. Masses and volumes can be adjusted pending client request. If an analyst or technician has questions they are asked to speak with the Senior analyst or the Manager from the Trace Metals Ceutical & Emerging Markets Department.

LC-ICPMS Table for all species: The concentrations can be adjusted as per client request

Low Level Spiking Table:

Mid Level Spiking Table (Standard Spiking level):

High Level Spiking Table:

Spike Name

Initial Concentration

(ppm)

Initial Volume

(µL)

Final Volume (mL)

Final Species Concentration (ppb)

Field Spike Stock *Note only 2.5mL of the above standard will be sent to the client. Transport Spike Stock

Transport Spike

Spike Name


(ppm)

Initial Volume

(µL)

Final Volume (mL)


Field Spike Stock *Note all 10mL of the above standard will be sent to the client. Transport Spike Stock

Transport Spike

Spike Name


(ppm)

Initial Volume

(µL)

Final Volume (mL)


Field Spike Stock *Note all 10mL of the above standard will be sent to the client. Transport Spike Stock

Transport Spike




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Appendix F: Spike Making Cheat Sheet for As (Cryo) & Se (AFS) Speciation Materials: (No Acid)

1. 1 – 15mL centrifuge tubes (non-soaked). 2. 1 – 100mL HDPE bottle (designated as ”Field/Transport Spike Stock”)

1. Note: Bottle can be re-used as long as bottle & cap are rinsed 3x’s after use and stored in MQ/RO and bagged.

3. 2 – 250ml HDPE bottles. 4. 10µL pipette. 5. 5mL pipette. 6. PM requested element(s): found in LC fridge stored in 15mL centrifuge tubes. **allow

time for standards to come to room temperature** 7. MQ/RO for pipette rinse. 8. MQ/RO for filling. 9. HCl solution for Cryo spikes only.

Process:

1. Please document the pipettes used. 2. Label one 250ml bottle as Transport Spike, initial and date. 3. Label another 250ml bottle as Field Spike A and set aside (leave empty). 4. In the 250ml labeled “Transport Spike”, weigh MQ or RO water,

i. For Arsenic speciation use an HCl solution in place of water. 5. Label one 15mL centrifuge tube Field Spike Stock, initial and date. 6. In Field/Transport Spike Stock bottle weigh MQ or RO water.

i. For Arsenic speciation use an HCl solution in place of water. 7. Rinse the 5mL pipette with MQ. 8. Rinse 10µL pipette with MQ. 9. Remove 10µL for each species-Field/Transport Spike Stock container (ex. 20uL total for

2 species: As3 and As5). 10. Shake standards. 11. Add 10µL of the PM requested species to the Field/Transport Spike Stocks: Make sure to

change pipette tip for each standard. 12. Cap Stock and homogenize. 13. Pipette 10mL from the 100mL Field/Transport spike Stock bottle into the 15mL

centrifuge tube labeled from line 6. Field Spike Stock is finished, initial and date and double bag.

14. Pipette 10mL from the 100mL Field/Transport Spike Stock bottle into the labeled 250mL Transport Spike bottle.

15. Cap bottle and homogenize. 16. The Transport Spike and Field Spike Stocks are done.




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AFS/Cryo Table for all species:

Spike Name


(ppm)

Initial Volume

(µL)

Final Volume (mL)

Final Species Concentration

(ppb)

Field/Transport Spike Stock *Note only 10mL of the above standard will be sent to the client.

Transport Spike




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Appendix G: Example - Standard Operating Procedure Training Record

By signing this document, I the employee, certifies to have read, understood and agreed to follow the test method and quality procedure as described in this procedure.

Reading of SOP FGS-129.02: Determination of As, Se, V and Cr in Sediments, Soils, Tissues and Waters by Liquid Chromatography – Inductively Coupled Plasma Mass Spectrometry.

SOP name and Revision number

Employee name (print)

Employee name (sign) Date:

Supervisor name (sign) Date:

Initial SOP Training (leave blank if not applicable)

Initial reading of method and training Initials Date Supervisor 1. Read method 2. Observe the method 3. Detailed review of method and associated literature 4. Supervised practice of method with trainer 5. Unsupervised practice of the method with trainer 6. Review of work with trainer and/or peer-review 7. IDOC to determine precision and accuracy 8. Determination of blanks

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