LSB APPROVED Page 1 of 40 JUNE 17, 2013 HEXCR
Contents
1. Methc RunName pri M CrSpeciation METH SAcqMetht DI H20 Blank 13 Unknown J CrSpeciation METH SAcqMethe 2 Calib Std 1 13 112 1 200 Standard Clear old points 155 M CrSpeciation METH SAcgMethc 3 Calib Std 2 13 13 1 200 Standard 7 Add 251 M CrSpeciation METH SAcgMethc 4 Calib Std 3 13 14 1 200 Standard 7 Add 3 1 v CrSpeciationn METH SAcgMethc 5 Calib Std 4 E 13 115 1 200 Standard 7 Add 4555 M CrSpeciation METH SAcqMethe 6 QC E3510 13 16 1 200 Unknown v CrSpeciationn METH SAcqMethe 7 TapWaterUnspiked E3510 13 17 1 200 Unknown v CrSpeciation METH SAcgMethrc 8 TapWaterSpiked E3510 13 18 1 200 Unknown v CrSpeciationn METH SAcgMethc 9 ERA CRM E3510 13 1 9 1 200 Unknown 7 v CrSpeciation METH SAcgMethc 10 C000001 13 1 10 1 200 Unknown 7 v CrSpeciationn METH SAcgMethc 11 C000002 13 111 1 200 Unknown v CrSpeciation METH SAcgMethc 12 C000003 13 1 12 1 200 Unknown 7 v CrSpeciation METH SAcgMethc 13 C000004 13 1 13 1 200 Unknown v CrSpeciation METH SAcgMethc 14 C000005 13 114 1 200 Unknown V CrSpeciationn METH SAcgMethc 15 C000006 13 1 15 1 200 Unknown 7 v Cr Speciation METH SAcgMethc 16 C000007 13 116 1 200 Unknown V CrSpeciation METH SAcgMethc 17 C000008 13 117 1 200 Unknown2. 1 7 4 ProStar 210 410 HPLC Operation Manuals 1 7 5 Galaxie Manuals electronic on the Control PC Start All Programs Galaxie Galaxie Manuals 1 7 6 Ministry of Environment 2009 Practices for the Collection and Handling of Drinking Water Samples Version 2 0 Laboratory Services Branch Etobicoke Ontario 1 7 7 Ministry of the Environment Laboratory Services Branch Procedures Manual LSBSOP 026 The Determination of W T and MDL 1 7 8 Ministry of the Environment Laboratory Services Branch Procedures Manual LSBSOP 031 Drinking Water Exceedance Reporting Protocol 1 7 9 Ministry of the Environment Laboratory Services Branch Procedures Manual LSBSOP 039 Laboratory Services Branch Procedures for Processing and Reporting Drinking Water Samples 1 7 10 Ministry of the Environment Laboratory Services Branch SPECSOPOI Procedures for Training and Proficiency Testing within the Spectroscopy Section amp Physical Chemistry Section 1 7 11 Ministry of the Environment Laboratory Services Branch LSBSOP 007 Sample Reception and Routing Procedures 1 7 12 SPC Section SOPs CSEMMSOPIa to CSMMSOP6 CSMMSTDSYS 001 1 7 13 United States Environmental Protection Agency Method 218 7 Determination of hexavalent chromium in drinking water by ion chromatography with post column derivatization and U V Visible spectroscopic detection 1 7 14 LaSB SPC Section SOP SPEC ICP MS 003 Standard operating procedure for data r
3. DIH20 0 05 p v Multiple Cr52 DIH20 0 1 pp LSB APPROVED JUNE 17 2013 VERSION 1 0 500r 90 000 85 000 8000 75 00 70 00 66 00 60 00 56 00 ped 50 00 45 0 400 3500 s 0 05 1 15 2 ys ot select Bracketing 45 Oo A 65 f 15 8 95 Cr Specia Ih Cr53 Cr 6 9 t Page 29 of 40 HEXCR E3510 ondo 07 2012 5 21 19 PMT DATA 0 57 peciationZ UI ZU 743 PITI 19 DATA Cr i u m i J m 2 1 RT mil 5 4 105 11 115 12 125 File Display Acquisition Method Data Session Processing Plug ins CAE ESEN ee ee gije v w Spe amp am amp u amp d zie see C Data Fies BB F AY C amp b noem Cr Speciation 26 07 2 b n c jation 26 07 201 V Bracketing IDLE Cr Speciation METH Cr52 Cr 3 te ee O gt As75 iv TES Se77 v Multiple t L se78 v Multiple Se82 v Multiple t gt ICPMass 7 MZ Mutipie t v Multiple gt ICP Mass 8 Vv Multiple ICP Mass 9 Muliplet C IcPMass 10 V Multiple t v Multiple M Multiple t V Muliplet v Multiple v Multiple C 3l v Multiple t Ll v Multiple t d v Multiple IV Multiple V Multiple t IV Multiple t M Mutiple t v Multiple IV Muttiple V Multiple v Multiple t v Multiple M Multiple Vv Multiple v M
4. fill up to 50 mL with DI H2O cap and mix the solution thoroughly TapWaterUnspiked E3510 This is taken daily directly from a bottle labeled Tap Water unspiked E3510 Use a pre cleaned Corning 15 mL tube and take directly from the spigot with a volume sufficient for an analytical session NOTE The original water was taken from the tap in E212 after running for 30 minutes The pH of the original water was 6 and was adjusted to gt 9 with ultra pure 20 NH4OH NOTE Never pipette directly from the inside of the bottle and caution must be exercised to prevent contaminating the sample inside the bottle Tap WaterSpiked E3510 spiked at 0 2 ug L use an adjustable Eppedorf pipette and pipette 9 98 mL of the above Tap WaterUnspiked E3510 into a pre cleaned 15 mL Corning tube pipette 0 02 mL of the secondary Cr VI QC standard 100 ug L into the tube cap and mix thoroughly Daily use of the CRM from ERA This CRM is taken directly from a concentrate that has been diluted as per the instructions given below no further preparation is required Care must be exercised to avoid any cross contamination to the primary solution Pour a small aliquot sufficient for one analytical session into a pre cleaned Corning tube for daily use NEVER PIPETTE DIRECTLY FROM THE DILUTED STOCK SOLUTION NOTE The Primary Cr VI CRM from Environmental Resources Associates ERA ERA CAT 149 is packaged in a 2 mL flame sealed ambe
5. v CrSpeciation METH SAcgMethc 18 C000009 13 118 1 200 Unknown v CrSpeciation METH v SAcqMethc 19 C0000010 13 119 1 200 Unknown 7 v CrSpeciation METH SAcgMethc 20 C0000011 13 120 1 200 Unknown 7 v CrSpeciation METH SAcgMetht 21 C0000012 13 121 1 200 Unknown 7 M CrSpeciation METH SAcgMethc 22 C0000013 13 122 1 200 Unknown 7 v Cr Speciation METH SAcqMethc 23 C0000014 13 1 23 1 200 Unknown 7 v Cr Speciation METH SAcqMethe 24 C0000015 13 124 1 200 Unknown 7 v CrSpeciation METH SAcgMethc 25 C0000016 13 1 25 1 200 Unknown 7 M CrSpeciation METH 7 SAcgMethe 26 C0000017 13 126 1 200 Unknown 7 v CrSpeciation METH SAcqMethc 27 C0000018 13 127 1 200 Unknown v Cr Speciation METH SAcqMethc 28 C0000019 13 128 1 200 Unknown MV CrSpeciation METH AcqgMethe 29 C0000020 13 129 1 200 Unknown v Cr Speciation METH SAcgMetht 30 DI H20 Blank 13 1 30 1 200 Unknown 7 v CrSpeciation METH SAcqMethc 31 QC E3510 13 1 15 1 200 Unknown M CrSpeciation METH SAcgMethe 32 TapWaterUnspiked E3510 13 1 15 1 200 Unknown 7 M CrSpeciationn METH SAcqMethc 33 TapWaterUnspiked E3510 13 1 15 1 200 Unknown 7 v CrSpeciation METH SAcgMetht 34 ERA CRM E3510 13 1 15 1 200 Unknown V CrSpeciationn METH AcgMethe 35 Calib Std 1 1
6. The spike recovery is calculated using the TapWaterUnspiked E3510 and the TapWaterSpiked E3510 analyzed immediately after 6 2 5 ERA UCMR3 E3510 Within each analytical session the results for the CRM must be within the certified accepted range of 0 319 0 479 ug L NOTE If any of the QC standards in sections 6 2 2 to 6 2 5 do not fall within the acceptance criteria listed the samples within that run must be reanalyzed after recalibration of the instrument Please see SOP SPEC ICP MS 001 Varian 820 ICP MS Routine Operation and Optimization for a detailed description of instrument maintenance and performance 6 3 Calculations Interpretations The chromatography data acquisition software Galaxie calculates quantifies and reports the final results in ug L There is no additional data calculation and interpretation required The chromatographic peak of Cr VI in each sample however needs to be checked by opening the chromatogram and verify the correct Cr VI peak by the retention time RT With the chromagraphy conditions shown in 4 5 8 the Cr VI retention time is 9 5 minutes Refer to refer to Galaxie Manuals for chromatogram reprocessing and recalculations Following is a typical chromatogram with Cr VI retention time LSB APPROVED Page 35 of 40 JUNE 17 2013 HEXCR E3510 VERSION 1 0 n 0 000 crszicr 6 6 4 Reporting The final results are exported automatically by Galaxie as Cr Speciation csv
7. This file is imported into ONLIMS database for QA QC procedure to review QC results control charting and for final export upload to elab and LaSB LIMS Refer to SOP SPEC ICP MS 003 LIMS USER MANUAL Workgroups and Data Processing August 10 2005 http intra moe gov on ca stdprodconsume groups Ir moe essd lasb docu ments nativedocs stdprod_069297 pdf and elab Traning guide for further details about using these data reporting tools http intra moe gov on ca Divisions EnvironmentalSciencesStandards OurBranc hes LaboratoryServices ToolsResources STDU_055777 html The LIMS reported MDL is 0 05 ug L Results are reported to three significant figures with uncertainty see the uncertainty document for details 6 5 Proficiency Testing Refer to SPECSOP 001 Procedure for training and Proficiency Testing within the Spectroscopy amp Physical Chemistry Section LSB APPROVED JUNE 17 2013 Page 36 of 40 HEXCR E3510 VERSION 1 0 Appendix A Minimum Specifications for Environmental Grade Ammonium Hydroxide concentrated or equivalent Analyte Maximum Specification Actual Value in ppb Aluminum Al 1 ppb 0 5 Antimony Sb 0 5 ppb 0 1 Arsenic As 1 ppb 0 1 Barium Ba 0 1 ppb 0 1 Beryllium Be 0 1 ppb 0 1 Bismuth Bi 0 1 ppb lt 0 1 Cadmium Cd 0 5 ppb lt 0 1 Cal
8. lt 0 01 Gadolinium Gd ppt lt 1 lt 0 01 Gallium Ga ppt lt 10 lt 0 1 Germanium Ge ppt lt 10 lt 0 1 Gold Au ppt lt 20 lt 1 Hafnium Hf ppt 10 0 05 Holmium Ho ppt lt 1 lt 0 01 Indium In ppt lt 1 lt 0 1 Iron Fe ppt 10 10 Lanthanum La ppt 1 0 05 Lead Pb ppt 10 0 5 Lithium Li ppt lt 10 lt 0 5 Lutetium Lu ppt lt 1 lt 0 01 Magnesium Mg ppt lt 10 lt 5 Manganese Mn ppt lt 10 lt 1 Mercury Hg ppt lt 50 lt 10 Molybdenum Mo ppt lt 10 lt 1 Neodymium Nd ppt lt 1 lt 0 05 Nickel Ni ppt lt 20 lt 5 Niobium Nb ppt lt lt 1 Palladium Pd ppt lt 20 lt 5 Platinum Pt ppt lt 20 lt 1 Potassium K ppt lt 10 lt 5 Praseodymium Pr ppt lt 1 lt 0 05 Rhenium Re ppt lt 10 lt 0 1 Rhodium Rh ppt lt 10 lt 1 Rubidium Rb ppt lt 10 lt 1 Ruthenium Ru ppt lt 20 lt 1 Samarium Sm ppt lt 1 lt 0 01 Scandium Sc ppt lt 10 lt 1 LSB APPROVED Page 39 of 40 JUNE 17 2013 HEXCR E3510 VERSION 1 0 Result Name Units Specifications Test Value Typical Selenium Se ppt Information only lt 5 Silver Ag ppt lt 10 20 5 Sodium Na ppt lt 10 lt 5 Strontium Sr ppt lt 10 lt 1 Tantalum Ta ppt Information only lt 10 Tellurium Te ppt lt 1 0 5 Terbium Tb ppt lt 1 lt 0 01 Thallium TI ppt lt 10 0 05 Thorium Th ppt 1 0 05 Thulium Tm
9. 1 Terbium Tb 0 1 ppb 0 1 Thalium TI 0 1 ppb 0 1 Thorium Th 0 1 ppb 0 1 Thulium Tm 0 1 ppb 0 1 Tin Sn 0 5 ppb 0 1 Titanium Ti 0 5 ppb 0 1 Tungsten W 0 1 ppb 0 1 Uranium U 0 1 ppb 0 1 Vanadium V 0 5 ppb 0 1 Ytterbium Yb 0 1 ppb 0 1 Yttrium Y 0 1 ppb 0 1 Zinc Zn 0 5 ppb 0 5 Zirconium Zr 0 1 ppb 0 1 Chloride 0 5 ppm 0 5ppm Phosphate 0 01ppm 0 01 Sulfate 1 ppm 1 NOTE The actual value is dependent on the lot of the ammonium hydroxide purchased It is the Minimum specification which is important to the method LSB APPROVED Page 38 of 40 JUNE 17 2013 HEXCR E3510 VERSION 1 0 Appendix B Minimum Specification of Optima Concentrated HNO or equivalent Result Name Units Specifications Test Value Typical Aluminum Al ppt 20 10 Antimony Sb ppt lt 10 lt 5 Arsenic As ppt lt 20 lt 10 Barium Ba ppt lt 10 lt 1 Beryllium Be ppt lt 10 lt 1 Bismuth Bi ppt lt 10 lt 0 05 Boron B ppt lt 10 lt 10 Cadmium Cd ppt lt 10 lt 0 1 Calcium Ca ppt lt 10 lt 10 Cerium Ce ppt lt 10 lt 0 05 Cesium Cs ppt lt 10 lt 0 05 Chromium Cr ppt lt 10 lt 10 Cobalt Co ppt lt 10 lt 1 Copper Cu ppt lt 10 lt 1 Dysprosium Dy ppt lt 1 lt 0 01 Erbium Er ppt lt 1 lt 0 01 Europium Eu ppt lt 1
10. 12 C000003 13 1 12 1 200 Unknown CrSpeciation METH v SAcgqMethtc 13 C000004 13 1 13 1 200 Unknown 7 Cr Speciation METH SAcgMethe 14 C000005 13 114 1 200 Unknown 7 CrSpeciation METH v SAcgMethc 15 C000006 13 1 15 1 200 Unknown Cr Speciation METH SAcqMethc 16 C000007 13 116 1 200 Unknown CrSpeciation METH 7 SAcqMethc 17 C000008 13 117 1 200 Unknown Cr Speciation METH 7 SAcqMethe 18 C000009 13 1 18 1 200 Unknown 7 CrSpeciation METH SAcqMethc 19 C0000010 13 1 19 1 200 Unknown CrSpeciation METH SAcgqMethc 20 C0000011 E 13 1 20 1 200 Unknown 7 Cr Speciation METH 7 SAcqMethc 21 C0000012 13 121 1 200 Unknown Cr Speciation METH SAcqMethe 22 C0000013 13 122 1 200 Unknown CrSpeciation METH SAcgMethc 23 C0000014 13 1 23 1 200 Unknown Cr Speciation METH SAcgMethe 24 C0000015 13 124 1 200 Unknown 7 CrSpeciation METH v SAcqMethe 25 C0000016 13 1 25 1 200 Unknown 7 Cr Speciation METH SAcqMethe 26 C0000017 13 1 26 1 200 Unknown CrSpeciation METH SAcqMethc 27 C0000018 13 1 27 1 200 Unknown Cr Speciation METH SAcqMethc 28 C0000019 13 1 28 1 200 Unknown CrSpeciation METH v SAcqMethc 29 C0000020 13 129 1 200 Unknown Cr Speciation METH v SAcgMethc 30 DI H20 Blank 13 1 30 1 200 Unknown Cr Speciation METH 7 SAcgMethe 31 QC E
11. 4 2 8 125 mL high density polyethylene HDPE bottles Nalgene or equivalent 4 3 Equipments 4 3 1 Bruker formerly Varian 820MS ICP MS with a CRI skimmer cone and a standard sampler cone LSB APPROVED Page 15 of 40 JUNE 17 2013 HEXCR E3510 VERSION 4 3 2 4 3 3 4 3 4 4 3 5 4 3 6 1 0 Kodiak re circulating water chiller Varian ProStar 210 inert dual pump HPLC and autosampler or equivalent Hamilton PRP X100 anion exchange column with guard column or equivalent Instrument control PC with ICP MS control software and a chromatographic data acquisition system A Microzone class 10 metal free vertical laminate flow bench or equivalent 4 4 Reagents 4 4 1 4 4 2 4 4 3 4 44 4 4 5 DI HO Ultra pure 20 NH4OH VWR or equivalent see Appendix A for the minimum specifications It must be stored in a fume hood or vented storage cabinet Ultra pure concentrated HNO3 Optima grade or equivalent see Appendix B for the specifications It must be stored in a fume hood or vented storage cabinet Primary Cr VI calibration standard 1 ug mL in H20 High Purity or equivalent This standard must be capped and re sealed with para film and stored in the designated fridge in E212 at 8 C Note This standard must be from the different source or lot than the QC Primary Cr VI standard Primary Cr VI QC standard 1 ug mL in H20 Inorganic Venture or equivalent This standard must be capped and re sealed with
12. 9 of 40 JUNE 17 2013 HEXCR E3510 VERSION 1 0 Sample Login Binder HEXCR E3510 NOTE Verification of acid dispensers and pipettes Eppendorfs and VWR are recorded in ONLINE LIMS 1 8 History of Changes Revisions 1 8 1 June 2013 Version 1 0 New method documented with initial development and validation summary data 1 9 Safety Ultraviolet Radiation The plasma must never be viewed with naked eyes The Varian 820 ICP MS provides safety interlocks that shut off the plasma when the torch compartment is open Do not attempt to defeat these interlocks During operation the plasma must be viewed only through the protective tinted window located in the torch compartment WARNING Failure to wear safety glasses of a type prescribed for use with ultraviolet sources or to use the built in viewing glass while observing the lit plasma may cause permanent blindness or permanent impairment of eyesight High Voltage The Radio Frequency RF generator provides up to 1 5 kW RF power to the plasma The resulting plasma may cause extensive burns Under no circumstances should you attempt any physical adjustment of the plasma torch when the plasma is on other than through operation software controls The instrument has an extensive set of interlocks to ensure the safety of operator The RF generator also has numerous safety features which turn off the high voltage power should the plasma be extinguished or a high reflected power occurs WARNI
13. Compass CDS Controls Run is selected under Sampling LSB APPROVED Page 19 of 40 JUNE 17 2013 HEXCR E3510 VERSION 1 0 Element Isotope Ratios Optimization Standards Scan Settings Sampling QC Tests Notes Sample Presentation cis Sampling c s Sample Uptake Delay s IU 2373E7 2 373E 2 2E7 2 2E7 2E7 2E7 v Fast pump during sample delay and rinse 18E 1 8E7 v Spray chamber cooling C 3 1 6E 1 6E7 14E 1 4E7 Devices 1 2E7 1 2E7 Use Autosampler 1E7 1E BEG BEG Use Laser 6E6 6E6 4E6 4E6 v Compass CDS Controls Run Run Application s 2E6 2E6 0 po mer 0 ERRIA ARN ANN 3kn INN IRN INN 1RN 1nn EN 34 979 Time fsect Log Normalize Manual Zoom Time Scan Setup Start Select the End of Run in Autorun Actions is set correctly Reporting Start of Run During Run End of Run Plasma Vacuum O Leave On 8 Leave On Leave On amp close Gate Valve O Tum Off 8 Tum Off Pump Leave On 8 Tum Off Autosampler Probe Miscellaneous 8 Up V Audible warning s 5 Down RinseTime s Save the worksheet as Cr WGXXXXXX dd mm yy msws 4 5 4 Switch the three way valve to the HPLC position so that the eluent from the ProStar HPLC is introduced into the ICP MS 4 5 5 Open Galaxie and ensure that the com
14. after ensuring that the valve caps are secured Locate gas cylinders away from heat or ignition sources Cylinders have a high pressure relief device which releases the contents of the cylinder if the temperature exceeds 520 C 1250 F Arrange gas hoses where they will not be damaged or stepped on or where things will not drop on them Always wear approved safety footwear when moving empty or full cylinders Personal protective equipments labcoat safety glasses and gloves Concentrated acids are moderately toxic and extremely irritating to skin and mucus membranes Use these reagents in a fume hood and if skin contact occurs flush with large quantities of water Some type of eye protection must always be worn when working with these reagents Basic safety precautions must be taken such as the use of rubber or plastic gloves when cleaning lab wares Good housekeeping practices should be observed at all times LSB APPROVED Page 11 of 40 JUNE 17 2013 HEXCR E3510 VERSION 1 0 2 2 1 22 2 3 SAMPLE PREPARATION Labware 2 1 1 pH strip 0 to 14 range 2 1 2 4mL LDPE drop bottle Reagents 2 2 1 Ultra pure concentrated NH4OH Anachemia Science or equivalent See Appendix A for minimum specification requirements Procedure Upon receipt of samples in the lab check sample pH using a pH testing strip by transferring a small volume of sample to prevent cross contamination If the pH is gt 9 sample is ready for IC ICP MS analys
15. coefficient 0 9961 a 34291 lum b 1699253898 a 10 000 o a 9 000 8 0004 7 000 6 0004 5 000 4 000 zur Standard Advanced Weighting 2 0004 Point to point Iv Polynomial order 4 T force through 0 0 1 000 These calibration and QC standards must be made daily from the secondary standard listed in Section 4 4 5 4 Preparation of Daily Calibration Standards CalStd 1 0 05 ug L pipette 0 025 mL of the secondary Cr VI calibration standard 100 ug L into a 50 mL Nalgene flask fill up to 50 mL with DI H O cap and mix the solution thoroughly CalStd 2 0 1 ug L pipette 0 05 mL of the secondary Cr VI calibration standard 100 ug L into a 50 mL Nalgene flask fill up to 50 mL with DI H O cap and mix the solution thoroughly CalStd 3 0 5 ug L pipette 0 25 mL of the secondary Cr VT calibration standard 100 ug L into a 50 mL Nalgene flask fill up to 50 mL with DI H O cap and mix the solution thoroughly LSB APPROVED JUNE 17 2013 VERSION 1 0 CalStd 4 1 ug L pipette 0 5 mL of the secondary Cr VJ calibration standard 100 ug L into a 50 mL Nalgene flask fill up to 50 mL with DI H20 cap and mix the solution thoroughly 5 2 Preparation of Daily Quality Control Standards 5 3 5 2 1 5 2 2 5 2 3 Lab QC E3510 0 2 ug L half fill a 50 mL Nalgene flask with DI H2O pipette 0 1 mL of the secondary Cr VI QC standard 100 ug L into the flask
16. para film and stored in the designated fridge in E212 at 8 C Secondary Cr VI standards diluted from the primary standards listed in 4 4 4 and 4 4 5 100 ug L in DI H20 Preparation of the secondary Cr VI standards fill half of a 100 mL flask with DI H2O pipette 10 mL primary Cr VI standard into the flask fill up to the line with DI H2O cap and mix the solution thoroughly transfer it completely to a 125 mL HPDE bottle and label it accordingly The secondary standards must be stored in the designated fridge in E212 at lt 8 C and have the same expiry date as the primary standards used for the preparation LSB APPROVED Page 16 of 40 JUNE 17 2013 HEXCR E3510 VERSION 1 0 4 4 6 1 ug L Cr VI in DI H20 solution for checking instrument signal to noise ratio see 4 4 7 4 4 8 Section 4 5 2 Preparation of 1 ug L Cr VI solution the precise concentration is not necessary pipette 0 5 mL of the secondary Cr VI standard from 4 4 6 into a 50 ml Corning tube fill up to 50 mL mark with DI H2O capand mix the solution thoroughly IC mobile phase A 100 mmol L NH4NO pH 9 NOTE The precise concentration of the mobile phase is not critical An approximate concentration of 100 mmol L is sufficient Preparation of mobile phase A fila2L Teflon bottle with 1 L DI H20 dispense 12 5 mL Optima grade HNO 16 N into the bottle add 39 2 mL ultra pure NH4OH 20 v v using an adjustable pipette fil
17. quantified using the first bracketing calibration curve The subsequent samples will be quantified in the same format If any sample has been manually checked and re integrated for misidentified peaks and the manually integrated chromatogram has been saved click on Method Properties and uncheck all except Calibration Export and Post Processing pur Lu 2 SEQ te av EP Q uno Cr Speciation 26 07 201 Bracketing IDLE v mer c 7 Multiple Spe Cr53 v Whie dass v ee c x TT Unknown Multiple Spe Cr52 White glass v ChromiumiC Cr52 Modified Unknown v Multiple Spe Cr53 White glass y Chromium C Cr53 Modified Unknown M MulipleSpe Cr2 White glass v ChromumiC Cr52 7 Modified Unknown M Multiple Spe Cr53 White glass y Chromium C Cr53 v Modified Unknown M Multiple Spe Cr52 White glass v ChromiumiC Cr52 Modified Unknown M Multiple Spe Cr53 White glass y ChromiumiC Cr53 Modified Unknown 7 Multiple Spe Cr52 White glass ChromiumiC Cr52 Modified Unknown v Multiple Spe Cr53 White glass y Chromium C Cr53 Modified Unknown 7 V Mutiple Spe Cr52 White glass v ChromiumiC Cr52 Modified Unknown 7 Multiple Spe Cr53 White glass y Chromium C Cr53 Modified Unknown v M Multiple Spe Cr52 White glass v ChromiumiC CrS2 Modified Unknown M Multiple Spe C
18. results are stored and exported in the following locations Raw data file in C Galaxie Data Chromium 2013 Cr Speciation26 07 20121 59 13 PMI 1 DATA Sequence file after run is complete C Galaxie Data Chromium 2013 Cr Speciation 26 07 2012 27 07 20129 14 07 AM SEQU LSB APPROVED Page 22 of 40 JUNE 17 2013 HEXCR E3510 VERSION 1 0 The file name is the same as the original sequence file with a time stamp when the last sample in the sequence was analyzed Exported chromatographic data C Galaxie Data Chromium Export Cr52 XLS and Cr53 XLS Quantified results C Galaxie Data Chromium Output Cr Speciation csv This is the file that will be imported into ONLIMS for further processing Calibration files C Galaxie Data Cr52 CALB and Cr53 CALB NOTE Since Cr Speciation csv Cr52 CALB and Cr53 CALB is overwritten each time a sequence is run or reprocessed it must be archived once a sequence is complete by moving these files to an archive directly e g C Galaxie Data Chromium Archived 2012 Calibrations WG X XX XX X dd mm yyyy Cr52 CALB and WG XXXXXX dd mm yyyy Cr53 CALB C Galaxie Data Chromium Archived 2012 Quantified Results WG XXXX X X dd mm yyyy Cr Speciation csv LSB APPROVED Page 23 of 40 JUNE 17 2013 HEXCR E3510 VERSION 1 0 5 CALIBRATION 5 1 Labware 5 1 1 Adjustable volume pipettes Eppendorf or equivalent 5 1 2 50 mL Nalgene flask 5 1 3 Thomson 0 5 mL syringerless filter vials 5 2 Reagents 5 2 1 DIH O
19. 2 20137 11 38 AM65 65 DATA Cr52 16 0004 14000 35 days 12 0004 10 000 8 0004 6 0004 4 000 2 0003 i I A H These chromatograms were obtained using the Tap Water Spiked E3510 The days denote the time lap after the sample spiking These results also demonstrate the Cr VI stability after 30 days The baseline and retention time may change due to changes in mobile phases and instrument parts the overall Cr VI peak position and quantified results remain the same
20. 3 131 1 200 Standard 7 Add 1 v CrSpeciation METH SAcgMetht 36 Calib Std 2 13 132 1 200 Standard Add 263 v CrSpeciationn METH SAcgMethc 37 Calib Std 3 13 1 33 1 200 Standard 7 Add 3 v CrSpeciation METH SAcqMetht 38 13 1 34 1 200 Standard Add 45 6 2 Run Control and Quality Assurance The quality assurance procedure involves evaluation of laboratory QC standards these are DI H20 Blank E3510 QC E3510 TapWaterUnspiked E3510 TapWaterSpiked E3510 ERA CRM E3510 These QC standards are prepared freshly at the beginning of each analytical session as outlined in Section 5 The run control limits and data acceptance criteria are outlined below 6 2 1 DI H20 Blank E3510 Within each analytical session the results for DI H20 blanks must be less than the the average blanks 3 x standard deviations listed in Table 1 6 1 Otherwise contamination from the DI H5O or sample containers is suspected LSB APPROVED Page 34 of 40 JUNE 17 2013 HEXCR E3510 VERSION 1 0 6 2 2 QC E3510 Within each analytical session the results for QC E3510 must be within 15 of the expected value 0 2 ug L 6 2 3 TapWaterUnspiked E3510 Within each analytical session the results for this QC standard must be within 20 of the long term average currently 0 14 ug L see Table 1 6 3 6 2 4 TapWaterSpiked E3510 Within each analytical session the spike recovery for the QC must be between 80 and 120
21. 3 7 White glass Chromium C Cr53 v Modified Unknown v M MulipleSpe Cr52 Whiteglass ChromiumiC Cr52 7 Modified Unknown M Multiple Spe C3 7 White glass y ChromiumC Cr53 7 Modified Unknown v v Multiple Spe Cr52 Amber glass Chromium C Cr52 Modified Unknown 7 LSB APPROVED Page 31 of 40 JUNE 17 2013 HEXCR E3510 VERSION 1 0 Method Options c2 External method parts to apply x canc i Pre Processing DAE s X Cancel Integration Suitability Tests _ Help Identification l Clear chromatogram manual operations Additional options Ai v Export Export e Print Report Summary Rep Add Delete In this way all manually integrated chromatographic information is retained except that sample is quantified using the bracketing calibrations The results are automatically exported as a csv file in C Galaxie Data Chromium Output Cr Speciation csv Rename the file to WGxxxxxx dd mm yyyy bracketing csv Rename the calibration file to WGXXXXXX dd mm yyyy Cr52 bracketing CALB Move both files to the archived directory C Galaxie Data Chromium Archived 2012 Quantified Results WG XXXXXX dd mm yyyy non bracketing csv C Galaxie Data Chromium Archived 2012 Quantified Results WG XXXXXX dd mm yyyy Cr52 CALB This is an example of bracketing calibration and can be found in the Galaxie Help in the chromatography data software LSB
22. 31 0 125 B water pH 9 46 0 3231 0 v Compressibility compensation 9 00 l 8000 20 000 Equilibration Time min 0 00 Hold Time min 0 00 Pumps gradient chart 0 2 3 4 5 6 ri 8 9 WD EAC WAB hA Flow Solvent A on top LSB APPROVED Page 21 of 40 JUNE 17 2013 HEXCR E3510 VERSION 1 0 A typical run sequence 4 5 9 WII XIX I I XI I I I XIX XI I XI I I I XI I X I XI I I I XI I I X Cr Speciation METH SAcqMethe 1 DI H20 Blank 13 111 1 200 Unknown Cr Speciation METH SAcqMethe 2 Calib Std 1 3 13 112 1 200 Standard Clear old points 7 1 CrSpeciation METH SAcqMethe 3 Calib Std 2 13 1 3 1 200 Standard 7 Add 2c Cr Speciation METH SAcqMethe 4 Calib Std 3 13 14 1 200 Standard 7 Add 3rz Cr Speciation METH 7 SAcqMethc 5 Calib Std 4 13 15 1 200 Standard 7 Add 4c Cr Speciation METH v7 SAcqMethe 6 QC E3510 13 16 1 200 Unknown CrSpeciation METH SAcgqMethc 7 TapWaterUnspiked E3510 13 117 1 200 Unknown CrSpeciation METH v SAcgMethc 8 TapWaterSpiked E3510 13 18 1 200 Unknown Cr Speciation METH SAcqMethc 9 ERA CRM E3510 13 19 1 200 Unknown Cr Speciation METH SAcqMethe 10 C000001 13 1 10 1 200 Unknown CrSpeciation METH 7 SAcqMethe 11 C000002 13 111 1 200 Unknown Cr Speciation METH v SAcgMethe
23. 3510 13 1 15 1 200 Unknown Cr Speciation METH 7 SAcqMethe 32 TapWaterUnspiked E3510 13 1 15 1 200 Unknown Cr Speciation METH SAcqMethc 33 TapWaterUnspiked E3510 13 1 15 1 200 Unknown 7 Cr Speciation METH SAcqMetht 34 ERA CRM E3510 13 1 15 1 200 Unknown Cr Speciation METH 7 SAcqMethe 35 Calib Std 1 13 1 31 1 200 Standard 7 Add 13 Cr Speciation METH SAcqMethe 36 Calib Std 2 ES 13 132 1 200 Standard 7 Add 7 25 CrSpeciation METH 7 SAcqMethe 37 Calib Std 3 13 1 33 1 200 Standard 7 Add 7 3te3 CrSpeciation METH SAcqMethc 38 13 1 34 1 200 Standard 7 Add gt 4H NOTE A sequence must include a set of the calibration standards QC standards DI H20 blanks QC E3510 TapWaterUnspiked E3510 TapWaterSpiked E3510 CRM from ERA ERA CRM E3510 for every 20 samples and one sample duplicate Always bracket samples with standards 1 e start with standards sample 1 to 20 and then standards and so on NOTE Ensure that the number of the lines in both Quantum and Galaxie sequence agree with each other NOTE The autosampler has a total of 84 positions The analytical time for each vial is 9 minutes A full autosampler load takes 15 hours However one can continue replacing the completed sample vials during the run to have a longer run sequence when needed Once the analysis is complete the raw data file chromatographic data and quantified
24. 5 2 2 Secondary Cr VI standard 100 ug L prepared in 4 4 6 5 3 Procedures There are four calibration standards in this method at 0 05 0 1 0 5 and 1 ug L respectively see 5 4 for preparation This is specified in the calibration part of the Galaxie method Cr Speciation METH as shown below Type Options Unknown compounds C Response Factors Identical Groups C Normalization Cuve sts External Standard mi 100 000 x C Intemal Standard 7 Mone Standard Response unit Reference Component DE iee Calibration Curve n2c 6 vj meje d Response C Height C 2 Height C sqrt Height Area C Z rea C sqtt Area m 2 on Initialize from ID tables Use references Level number fa Average Levels Levels format Pd Select Component D 1 RF T Define Qty intervals Model 0 0 Add 0 0 mm 2 Linear Bd Cr52 C4 3 EDTA Linear E 0 0500 0 1000 0 5000 1 0000 Other parts of calibration such as model through zero and weighing is also specified here LSB APPROVED Page 24 of 40 JUNE 17 2013 HEXCR E3510 VERSION 1 0 A typical calibration curve is shown below The regression coefficient must be gt 0 995 S C152 Calibration curve CrS2 Cr52 Cr 6 sies Component Cr52 Cr 6 eo Date 07 Mar 13 4 09 16 PM 17 000 46 000 Model Display 15 000 Results 14 000 X ppb Y Area 13 000 Polynom ys b x a 12 000 Regression
25. APPROVED Page 32 of 40 JUNE 17 2013 HEXCR E3510 VERSION 1 0 Run Suffix n ID Standard Level Run 1 Standard 1 B1 Run 2 Standard 2 B1 Run 3 Unknown B1 Run 4 Unknown B1 Run 5 Standard 1 B1 B2 Run 6 Standard 2 B1 B2 Run 7 Unknown B2 Run 8 Unknown B2 Run 9 Standard 1 B2 Run 10 Standard 2 B2 The processing of the chromatograms acquired in sequence with is made after the acquisition of the whole sequence In the previous example the 10 injections are performed then the calibration curve of the first is created with the four standard chromatograms Run Run2 Run5 and Run6 Then the first two unknown chromatograms Run3 and Rund are processed with this calibration curve This calibration curve is then archived and deleted and a second calibration curve is created with the four standard chromatograms Run5 Run6 Run9 and Run10 The last two unknown chromatograms Run and Run8 are processed with this calibration curve LSB APPROVED Page 33 of 40 JUNE 17 2013 HEXCR E3510 VERSION 1 0 6 RUN PROCESSING AND QUALITY ASSURANCE 6 1 Run Format Following is a typical run sequence It is located under Cr Speciation E3510 Template SEQU There must be a set of calibration standards QC standards and CRM for every 20 samples and one sample duplicate and samples must always be bracketed with standards in order to perform bracketing calibration as described in previous section
26. Cr VI solution see 4 4 7 and DI H20 introduced via peristaltic pump the signal noise ratio 1 ug L DI H20 at mass 52 must be between 5 and 10 If not re optimize the instrument as outlined in the SOP SPEC ICP MS 001 Print the tuning window which shows 1 ug L Cr VI solution and DI H5O signals and attach it to the daily performance report Typical signal noise ratio Optimization oa EOS 406333404 z m e 35144 595914 400 5400 f R 1 b C VI BeS 1000000E4C1 50000 49007 PP T iens 130009 of 46000 cs 7 ves 4200 C4 44m 44000 eno A pA M MAA or LU 300 p pamo 3600 suxp now 30000 29000 260001 297 220 xu 18000 16000 14007 14000 12000 sil 120 m enn pod ANIM AN mg LYING 10006 nose DI H O ENNEN 8000 led ORIN III ET Nn Ps m F400 ne f k eM E E Y 135 140 145 157 155120 165 120178 190 185 180 186 008 21 4 5 3 Create worksheet in Quantum ICP MS software Create a new worksheet from a template Cr Speciation E3510 msws The template contains all information for ICP MS operation Copy the optimized ICP MS parameters to the newly created worksheet A typical set of ICP MS parameters is shown below LSB APPROVED JUNE 17 2013 VERSION 1 0 Parameter value gt Flow Parameters L min Plasma Flow 18 0 Auxiliar Flow 2 10 Sheath Gas 0 20 Nebulizer Flow 0 94 gt Torch Alignment mm Sampling Depth 5 5 Other RF Power k 1 40 Pump Rate
27. LSB APPROVED Page 1 of 40 JUNE 17 2013 HEXCR E3510 VERSION 1 0 MINISTRY OF ENVIRONMENT LABORATORY SERVICES BRANCH METHOD TITLE The Determination of Hexavalent Chromium in Waters by lon Exchange Chromatography Inductively Coupled Plasma Mass Spectrometry IC ICP MS METHOD CATALOGUE CODE HEXCR E3510 Version 1 0 DATE OF LAST REVISION New NEXT REVIEW DATE JUNE 17 2015 SECTION SPECTROSCOPY AND PHYSICAL CHEMISTRY SECTION METHOD OWNER S Qianli Xie QMS REVIEWED BY ESA MISTRY APPLICABLE REGULATIONS GUIDELINES NONE MANAGER APPROVAL CONTACT TERESA SWITZER AUTHORIZATION DATE JUNE 17 2013 This method is deemed fit for purpose as of the date shown in the header of this cover page by the data provided in section 1 6 Analytical Performance Summary The approval of this document is valid for two years at which time it will be subject to review to determine if any updates or modifications are warranted NOTE Equivalent suppliers to those stated in the method are acceptable Reference to a particular brand does not constitute an endorsement by the Ontario Ministry of the Environment LSB APPROVED Page 2 of 40 JUNE 17 2013 HEXCR E3510 VERSION 1 0 The Determination of Hexavalent Chromium in Waters by lon Exchange Chromatography Inductively Coupled Plasma Mass Spectrometry IC ICP MS 1 SUMMARY Hexavalent chromium Cr VT is a known toxic metal in the environment and a known carcinogen to humans even at re
28. NG The equipment contains high voltages which may be lethal Observe all cautions in this method and those posted on the equipment No instrument operator must attempt to access or adjust high voltages Radio Frequency Radiation Exposure of personnel to Radio Frequency RF Radiation should be minimized Personnel should not be permitted in the vicinity of open energized RF generating circuits RF transmission systems cables connectors etc or energized antennae It is generally accepted that exposure LSB APPROVED Page 10 of 40 JUNE 17 2013 HEXCR E3510 VERSION 1 0 to high levels of RF radiation can result in severe bodily harm including blindness NOTE Cardiac pacemakers may be affected Toxic Chemicals It is essential that the toxic effects of compounds being analyzed are understood and that adequate ventilation is provided If the ventilation system is not working do NOT operate the plasma torch WARNING Some of the products of combustion of the plasma torch can be highly toxic Operation of the equipment without a torch exhaust vent may constitute a serious health hazard NOTE Ozone is hazardous and always produced when the ICP is in operation High pressure and flammable gases Argon gas is used in this method and a suffocation hazard exists Hydrogen gas is used in this method and a flammable hazard exists High pressure gas cylinders can be dangerous if mishandled Move gas cylinders with an approved handcart
29. Ontario Safe Drinking Water Act for total Cr is also 50 ug L The United States Environmental Protection Agency USEPA and California Office of Environmental Health Hazard Assessment OEHHA however have recently proposed a guideline specific for Cr VI with a Maximum Contaminant Level MCL of 0 02 ug L In Canada federal provincial territorial environmental agencies are planning to reassess current Canadian drinking water guidelines and may consider a separate Cr VI drinking water standard This method is developed in anticipation of a possible Cr VI specific drinking water standard which will require a much lower detection limit than existing methods at the Laboratory Service Branch LaSB of the Ontario Ministry of the Environment MOE 11 Principle of Method This method utilizes a hyphenated technique i e ion exchange chromatography IC coupled to an inductively couple plasma mass spectrometry ICP MS to determine Cr VI in treated drinking water surface water and ground water Samples are collected and preserved at a pH gt 9 condition and then injected directly into an anion exchange column Cr VI is separated from other possible Cr species and other metals by the anion exchange functioning group inside the column The column eluent is introduced directly into the sample introduction LSB APPROVED Page 3 of 40 JUNE 17 2013 VERSION 1 0 1 2 1 3 1 4 HEXCR E3510 interface and the ionization source of the ICP M
30. S Chromium chromatographic peak is identified and quantified by the mass spectrometry with external calibration 1 1 1 Relationship to Other Methods This method is developed and validated in house The method is complimentary to LaSB HEXCR E3056 The Determination of Hexavalent Chromium in Waters Landfill leachates and Effluents by Colourimetry Parameters Measured Hexavalent chromium Cr VI is measured using this method The LaSB LIMS product codes are Department 6410 Analysis and Reporting Product Code CHROM3510 Element Parameter CAS Number Cr VI as CroO Hexavalent Chromium 13907 45 4 Sample Matrices Treated drinking water preserved in pH gt 9 can be analyzed for Cr VI using this method Surface and ground water may be analyzed for Cr VI using this method provided that it has been established that sample is highly oxygenated free of dissolved organic carbon and preserved in pH gt 9 Surface and ground water that are anoxic and high in dissolved organic carbon may contain significant amount of Cr II When such surface and ground water samples are analyzed using this method the Cr VT result may be biased high Matrix Code WD Drinking Water WS Surface Water WG Ground Water Refer to 1 5 3 for further details for WS and WG matrices Sample Requirements 1 4 A Sample Preservatives Sample must be preserved to achieve pH gt 9 with ultra pure concentrated NH4OH see Appendix A for Certificate of A
31. acid bath allow tubes and caps to soak inside acid bath for at least 24 hours transfer tubes and caps into a DI H20 bath allow tubes and caps to soak in DI H20 bath for at least 24 hours remove tubes and caps rinse with DI H20 at least three times remove water as much as possible place them inside a Class 10 vertical lamina flow metal free bench and let them dry log the date and initials on the labware pre cleaning log book It is absolutely critical to pre clean and dry labwares in a clean flow bench in order to minimize contamination 3 4 Procedure 3 4 1 Labela ial according the sequence number 3 4 2 Use an adjustable volume pipette and pipette 0 5 mL sample solution into the vial LSB APPROVED Page 13 of 40 JUNE 17 2013 HEXCR E3510 VERSION 1 0 3 4 3 Insert the filter top into the vial and place them on the vial pressor the pressor holds 5 vials each time and press the filter top into place 3 4 4 Load vials on to the Varian ProStar 410 autosampler in sequence 3 5 Run Sequence A typical run sequence must include two DI H20 blanks a set of calibration standards a set of QC standard 20 samples a sample duplicate a second set of QC standards a second set of calibration standards another 20 samples a sample duplicate QC standards two DI H20 blanks calibration standards and so on see section 6 1 LSB APPROVED Page 14 of 40 JUNE 17 2013 HEXCR E3510 VERSION 1 0 4 4 1 4 2 DETECTION SYSTEM Safe
32. cium Ca 1 ppb lt 0 5 Cerium Ce 0 1 ppb lt 0 1 Cesium Cs 0 1 ppb lt 0 1 Chromium Cr 0 5 ppb lt 0 1 Cobalt Co 0 5 ppb lt 0 1 Copper Cu 0 5 ppb lt 0 5 Dysprosium Dy 0 1 ppb lt 0 1 Erbium Er 0 1 ppb lt 0 1 Europium Eu 0 1 ppb lt 0 1 Gadolinium Gd 0 1 ppb lt 0 1 Gallium Ga 0 1 ppb lt 0 1 Germanium Ge 0 1 ppb lt 0 1 Gold Au 0 5 ppb 0 1 Hafnium Hi Information only 0 5 Holmium Ho 0 1 ppb 0 1 Indium In 0 1 ppb 0 1 Iron Fe 1 ppb 0 5 Lanthanum La 0 1 ppb 0 1 Lead Pb 0 1 ppb 0 1 Lithium Li 0 1 ppb 0 1 Lutetium Lu 0 1 ppb 0 1 Magnesium Mg 1 ppb 0 2 Manganese Mn 0 5 ppb 0 2 Mercury Hg 0 2 ppb 0 2 Molybdenum Mo 0 5 ppb 0 1 Neodymium Nd 0 1 ppb 0 1 Nickel Ni 0 5 ppb 0 2 Niobium Nb 0 1 ppb 0 1 Palladium Pd Information only 1 Platinum Pt Information only 1 Potassium K 1 ppb 0 2 Praseodymium Pr 0 1 ppb 0 1 Rhenium Re Information only lt 1 Rhodium Rh 0 5 ppb lt 0 1 Rubidium Rb 0 1 ppb lt 0 1 Ruthenium Ru Information only lt 1 Samarium Sm 0 1 ppb lt 0 1 LSB APPROVED Page 37 of 40 JUNE 17 2013 HEXCR E3510 VERSION 1 0 Analyte Maximum Specification Actual Value in ppb Scandium Sc 0 1 ppb 0 1 Selenium Se 1 ppb 0 1 Silver Ag 0 5 ppb 0 1 Sodium Na 1 ppb 1 Strontium Sr 0 1 ppb 0 1 Tellurium Te 0 1 ppb 0
33. ction interface of the Bruker 820 ICP MS with H as a reaction gas in the skimmer cone significantly reduces any Ar based polyatomic interference refer to SOP SPEC ICP MS 001 Standard Operating Procedure for Varian Bruker 820MS Routine Operation amp optimization Secondly the ion exchange chromatography described in this method can separate other ions in the sample matrix e g C and Cl from Cr due to differences in retention time in the chromatography separation see Appendix C for a typical chromatogram of Cr VT Accordingly the remaining significant polyatomic interference is N Ar Since N comes mainly from the mobile phases NH4NO3 and NH4OH see Section 4 used in the chromatographic separation this results in an elevated baseline in the chromatogram with the Cr VI peak superimposed over the baseline see Appendix C Biases When the method is followed properly there should be no bias in the results of Cr VI measurement Limitations This method analyzes Cr VI in an anion form CrO and is very sensitive to the Eh pH of the sample When the samples are collected and preserved as prescribed in 1 4 the method integrity is not compromised However if the sample is anoxic and highly acidic e g ground water or mine waste the sample collection preservation prescribed in 1 4 may not be adequate to maintain all Cr VI in CrO form and the method performance may be negatively impacted Analytical Perfor
34. eporting using ONLINE LIMS LSB APPROVED Page 8 of 40 JUNE 17 2013 HEXCR E3510 VERSION 1 0 1 7 15 List of forms and logbooks used Current version of forms are posted and available on LaSB desktop NON CONFORMANCE FORM FRM 1925 Varian 820 ICP MS Instrument Log Book Serial No IP0903M009 Varian 820 ICP MS Instrument Service performance Reports binder IP0903M009 Varian 820 ICP MS Instrument Log Book Serial No EL06013871 Varian 820 ICP MS Instrument Service performance binder EL06013871 Millipore Log Book Serial No FSAN28094 Millipore Log Book Serial No F5AN99734A Millipore Log Book Serial No FSAN28094B Balance Log Book Adam Balance Model AEA 250G Serial No AE164121657 Balance Log Book Adam Balance Model AEA 250G Serial No AE164113258 Balance Log Book Satorius Balance Model CPA2202S Serial No 2655310 Balance Log Book Ohaus Balance Model AP250D Serial No 09675 Balance Log Book Mettler Balance Model AE163 Serial No F55873 Log Book Record of labware pre cleaning Certificates of Analysis binder for standards used in E3510 FRM LSB 054 Customer Software Validation Summary Approval Form Laboratory Service Branch Primary amp Intermediate N I S T Spectrometric Standard Solution binder 3 Expired Exhausted Spectroscopy Standards Binder 4 Expired Exhausted Spectroscopy Standards Binder 5 Expired Exhausted Spectroscopy Standards Binder 6 Discarded Sample Binder Stock Standard Logbook LSB APPROVED Page
35. i wage co Mi iP hits IIl f New Reprocessing List Wizard x vil C Create a new reprocessing list l Number af lin Import sequence file nd a select the finished sequence file and click on Open LSB APPROVED Page 28 of 40 JUNE 17 2013 HEXCR E3510 VERSION 1 0 Bl Open File HL AS i File Selection Query Look in ROOT DIRECTORY Number of selected filss _X Cancel Help n 26 07 2012 SEQU 21 Aug 14 Preview not available File name Information DI H20 spiked at various concentration of Cr6 only for determination of LCMRL check that Cr VI peak is identified correctly by opening the chromatogram and examine the peak and retention time RT Galaxie Chromatography Data System File Display Acquisition Method Data Session Processing Plug CA i ob 86m Al he oe N ig amat tiie l Data Files SF Be AY cupere 7 OE cr speciation 26 07 201 P Bra M ates oe Se W gt Cr52 gt Cr53 t O gt As75 C Se7 Se78 L Se 2 Duplicate line C gt ICPMass7 C o ICP Mass 8 Delete TEL n m C gt ICPMass 9 Open chromatogram s DI H20 0 01 p C gt ICPMass 10 ia w WMU mpie Lrsz DIH20 0 01 p v Multiple Cr52 DIH20 0 01 p z Multiple Cr52 DIH20 0 05 p V Multiple Cr52 DIH20 0 05 MV Multiple Cr52
36. is and no further sample preparation is required If pH is lt 9 a LIMS remark code SIP sample improperly preserved will be issued to the customer to qualify the results The sample however can still be analysed provided that the sample container is intact Adjust the pH to gt 9 by adding 1 2 drops of ultra pure concentrated NH4OH and allow the sample to sit in the walk in fridge located in E237 and labeled as Alkaline preserved samples at lt 8 C for 24 hours before analysis LSB APPROVED Page 12 of 40 JUNE 17 2013 VERSION 1 0 HEXCR E3510 3 ANALYTICAL PROCESSING 3 1 This method does not require any further sample processing 3 22 Reagents 3 2 1 Reagent grade HNO see Appendix B for minimum specification requirements 3 2 2 Pure Water that has been further deionized DI H20 by Millipore Milli Q water Note The resistivity of deionized water is maintained at 18 0 megaohms per centimetre or greater Cartridges on the water systems will be changed as soon as the resistivity drops below 18 0 NOTE Throughout this document DI H O is always referred to the water as defined in 3 2 2 3 3 Lab wares 33 1 Thomson 0 45 um PTFE filter vials or equivalent 3 3 2 Pipettes adjustable volumes 3 3 3 Disposable gloves 3 3 4 Pre cleaned 15 mL Corning tube with cap NOTE Cleaning procedure for labwares NOTE remove cap place tubes and caps into 10 HNO made from reagent grade
37. latively low doses Ref 1 7 1 Chromium may occur in the environment either from natural or anthropogenic sources and can exist in various chemical forms most commonly as trivalent Cr III and hexavalent Cr VI The distribution of Cr between Cr II and Cr VI is strongly controlled by Eh pH of the system Typically Cr III is dominant in highly oxygenated and low pH environment whereas Cr VI becomes dominant in high pH environment In aqueous environment Cr III and Ci VI can also exist in various ionic species such as Cr CrOH Cr OH HCrO and CrO depending on the activity of electrons Eh and the activity of hydrogen ions pH In most treated drinking water Cr VI is expected to be dominate due to the presence of strong oxidants such as chlorine Cl and the elimination of dissolved organic carbon after treatment Ref 1 7 1 Because of the human heath risks of Cr VI Cr in drinking water is regulated by various jurisdictions The World Health Organization s WHO Guidelines for Drinking Water Quality states because the heath effects are determined largely by the oxidation state different guideline values for Cr III and Cr VI should be derived However current analytical methods and the variable speciation of Cr in water favor a guideline value for total Cr The WHO and Canadian Federal drinking water guidelines for total Cr is 50 ug L The Ontario Drinking Water Quality Standards Ontario Reg 169 03 under the
38. mC CrS2 ChromiumC Cr53 Chromium C Cr52 Chromium Cr53 Chromium C CrS2 Chromium Cr53 4 4 4 14 14 4 4 4 4 4 4 4 iste pee EX g Standard v 2 x Standard gt 3 51 B1 Standard 4 51 81 z Unknown B1 EJ Unknown v BA Em Unknown B1 ES Unknown v B1 5m Unknown B1 Unknown v B1 Unknown B1 Unknown B1 Unknown B1 Unknown v B1 Unknown BA Unknown B1 Unknown B1 pes Unknown v B1 Unknown gt B1 Unknown 7 B1 Unknown B1 Unknown v B1 Unknown B1 Unknown v B1 Unknown B1 Unknown v B1 i Standard 11B1 B2 Standard 2 3 B1 B2 Standard v 3 5 B1 B2 Standard 4 3 B1 B2_ Standard 4 21 B1 B2 Unknown B2 Unknown Unknown B2 B2 Unknown LSB APPROVED JUNE 17 2013 VERSION 1 0 Page 30 of 40 HEXCR E3510 Bracket building x Overall bracketin OK Every unknown sample is calculated X Cancel Bracket pi Boe Next bracket gt gt Overlapped brackets Second bracke B2 Next bracket gt gt Clear this bracket Bracketing standards can be selected by clicking the drop down button In this example the first bracketing calibration is established using the first and second set of calibration standards and the samples between the two sets of calibration standards will be
39. mance Summary July 2012 Jan 2013 The method performance is measured using internal QC s unspiked treated tap water spiked treated tap water and a CRM The method has participated in proficiency testing study PT provided by external jurisdiction All performance data are summarized below LSB APPROVED Page 6 of 40 JUNE 17 2013 HEXCR E3510 VERSION 1 0 Table 1 6 1 Cr VI Data for deionized water blanks July 2012 Jan 2013 Sample N Average ppb std DI H O Blank E3510 52 0 0035 0 0032 Note The data represent an average of within and between run for Millipore deionized water DI H20 integrated over the expected Cr VI retention time and quantified as equivalent concentration Table 1 6 2 Cr VT Data for QC standard July 2012 Jan 2013 Sample N Average ppb std RSD QC E3510 15 0 1989 0 025 12 4 Note QC standard is prepared in DI H20 using a second source Cr VI standard independent of the calibration standards see Section 5 for details Table 1 6 3 Cr VI Data for Tap Water from Room E212 July 2012 Jan 2013 Sample N Average ppb std RSD Tap Water unspiked E3510 45 0 1424 0 023 16 3 Note This is tap water collected from Room E212 in the LaSB lab and the pH is adjusted to gt 9 using ultra pure concentrated NH4OH It is used as a matrix equivalent QC for continuous monitoring of method performance for real matrix samples Table 1 6 4 Cr VI Data for Spiked Tap Water from Room E212 July 2012 Jan 2013 Sam
40. munication between ICP MS software Quantum and chromatographic software Galaxie is established correctly Refer to SOP SPEC ICP MS 001 Varian 820MS Routine Operation amp Optimization for further details LSB APPROVED Page 20 of 40 JUNE 17 2013 HEXCR E3510 VERSION 1 0 4 5 6 For this method the User Identification is MOE the Group is MOE and the Project is Chromium no password in the log in window is required as shown below however entry to lab is restricted by combination locked doors Galaxie Chromatography Data System Connection ak gt Version 1 9 302 530 User Identificetidmoe Group MOE Y Cancel Project Chromium Y 4 Z Password VARIAN 4 5 7 Follow SOP SPEC ICP MS 001 Varian 820MS Routine Operation amp Optimization 4 5 8 to create a run sequence in Galaxie and to establish the communication between ICP MS software Quantum and chromatography software Galaxie The Galaxie method used is named Cr Speciation E3510 METH and can be found under C Galaxie Data Chromium The chromatography conditions and a typical sequence is shown below The chromatogtaphy conditions are specified in the method Cr Speciation E3510 METH These conditions must not be changed unless the method is re validated Solvent Compressibility 1 Mbar Pressure Constant bar Refill Time msec A 100 mmol L NH4NO3 pH 9 Y 46 0 32
41. nalysis The amount of NH4OH required will depend on the original pH of the water For a typical LSB APPROVED JUNE 17 2013 VERSION 1 0 1 5 Page 4 of 40 HEXCR E3510 treated drinking water with a pH between 5 and 8 1 v v of NH4OH sample will be sufficient NOTE NH4OH is toxic to the upper respiratory tract skin and eyes Ensure that all handling of this material is performed inside a fume hood and observe all the applicable safe laboratory practices Refer to the MSDS for further information 1 4 2 1 4 3 1 4 4 Sample Collection Sample is collected in a 15 mL amber high density polyethylene HDPE bottle with a plastic cap For tap water turn on the tap and allow the system to flush for approximately 5 minutes Fill sample bottle with the tap water slowly to approximately 10 to 12 mL Add 1 to 2 drops of the ultra pure concentrated NH4OH preservative from a drop battle Mix thoroughly and check that pH is gt 9 using a pH indicator strip For surface and ground waters fill sample bottle with the tap water slowly to approximately 10 to 12 mL Add 1 to 2 drops of the ultra pure concentrated NH4OH preservative from a drop battle Mix thoroughly and check that pH is gt 9 using a pH indicator strip Sample shipping and Storage It was demonstrated at the initial method development stage that treated drinking water sample can be stored in a fridge at 8 C or below for up to 30 days see Appendix C without the
42. ple N Average ppb std RSD Spike Recovery Tap Water Spiked E3510 51 0 3358 0 021 6 2 96 7 Note This is the same tap water as above but spiked with 0 2 ug L Cr VI using a second source Cr VI standard independent of the calibration standards see Section 5 for details Table 1 6 5 Cr VI Data for ERA UCMR3 E3510 July 2012 Jan 2013 Sample N Average ppb std RSD Accuracy ERA UCMR3 E3510 16 0 3929 0 028 7296 98 5 Note This is a certified reference material CRM supplied by Environmental Resources Associates ERA and was designed specifically for the US EPA 3 unregulated contaminant monitoring rule UCMR3 The certified value is 0 399 ug L with an uncertainty of 3 5 and the accepted range of 0 319 0 479 ug L Table 1 6 6 Estimated MDL Analyte MDL ppb CE 0 049 Note The MDL is estimated using the standard deviation of the spiked tap water data listed in Table 1 6 4 and a student t value of 2 369 following the LSBSOP 026 LSB APPROVED Page 7 of 40 JUNE 17 2013 HEXCR E3510 VERSION 1 0 1 7 Bibliography Note Current versions of Branch and Section SOPs and Forms are posted and available on LaSB desktop 1 7 1 Dana R Lindsay et al 2012 Oxidation of Cr III to Cr VI during chlorination of drinking water Journal of Environmental Monitoring 14 1789 1797 1 7 2 Varian 820 ICP MS Customer Training Manual 1 7 3 Section SOP SPEC ICP MS 001 Standard Procedure for Varian 820MS Routine Operations amp Optimization
43. ppt 1 0 01 Tin Sn ppt 20 5 Titanium Ti ppt 10 lt 5 Tungsten W ppt lt 10 lt 1 Uranium U ppt lt 1 lt 0 01 Vanadium V ppt lt 10 lt 0 5 Ytterbium Yb ppt lt 1 lt 0 01 Yttrium Y ppt lt 1 0 1 Zinc Zn ppt 10 1 Zirconium Zr ppt lt 10 lt 0 5 NOTE The typical test value is dependent on the lot of the acid purchased It is the Minimum specifications which is important to the method LSB APPROVED Page 40 of 40 JUNE 17 2013 HEXCR E3510 VERSION 1 0 Appendix C Typical chromatograms of Cr VI using this method Zero hour 50 0007 cs Cr Speciation24 01 20132 23 41 PM7 7 DATA Cr52 40 0004 48 hours 30 0004 20 0004 iu poer FT niin 0 0 5 1 15 2 25 3 35 4 45 5 55 6 65 7 75 8 85 9 95 10 10 5 1 115 12 125 Mn c s Cr Specialion30 01 20132 52 21 PM7 7 DATA Cr52 30 0004 8 days 25 000 20 0004 15 000 ne mau Yo 5 0004 RT min 0 o5 1 15 a2 2 a as A As 5 ss 78 85 1 T8 8 e 9 95 wq 15 td s 250004 f 20 0004 15 days 15 0004 10 0004 A e a ERN 5 000 AA P MERGE d Ee a ee ea ee a ED ee E EDAD CROP PRX RR VOD CREE RR RT EC ANE PEE cls Cr Speciationi4 02 20131 27 11 PM9 9 DATA Cr52 99 UUU 30 000 AMI 22 days 20 0004 15 000 10 000 5 0007 RT rin 0 05 1 15 2 25 3 35 4 45 5 5 5 6 65 7 75 8 85 9 95 10 10 5 1 115 12 125 2U UUUT 18 0003 o s Cr Speciation27 0
44. r ampoule containing approximately 1 5 mL of concentrate standard The diluted standard contains 0 4 ug L Cr VI refer to the Certificate of Analysis Page 25 of 40 HEXCR E3510 LSB APPROVED Page 26 of 40 JUNE 17 2013 HEXCR E3510 VERSION 1 0 Dilution of the primary CRM add 100 200 mL of DI H20 to a clean 1000 mL volumetric flask carefully snap the top off the UCMR 3 Hexavalent Chromium ampule using a clean dry class A pipette volumetrically pipette 0 5 mL of the concentrate into the 1000 mL volumetric flask dilute the flask to the final volume of 1000 mL with DI H20 cap the flask and mix well transfer the solution into a 2 L Teflon bottle pre cleaned from a re used Optima acid container Store bottle in the designated fridge in E212 at 8 C and use up to expiry date stated on the C of A 5 4 Reprocess the Data with a Bracketing Calibration This method does not employ the internal standardization technique commonly used in ICP MS analysis Instead it relies on bracketing samples between two consecutive calibration curves to correct for any instrumental drift over the sample analytical period Such Bracketing however can only be achieved after the data have already been acquired i e in a re processing The reprocessing procedure is outlined here Users are referred to the Galaxie Manuals for further details NOTE When a sequence is complete an exported csv file is created automaticall
45. risk of Cr VI being converted into other species provided that sample pH is adjusted to gt 9 refer to method validation documents Samples are stored at 8 C for up to 30 days provided that the sample containers are sealed properly and stored in an acid fume free environment However it is recommended that samples be analyzed as soon as possible upon receipt Contingencies If samples are not preserved and shipped as prescribed in Section 1 4 1 analysis will be carried out and the results will be reported with a LaSB LIMS remark code UNP unreliable sample not preserved properly If samples are collected other than containers specified in section 1 4 2 the analysis will be carried out and the results will be qualified with LIMS remark code UIC Unreliable Improper Container Shortcomings 1 5 1 Interferences LSB APPROVED JUNE 17 2013 VERSION 1 0 1 6 1 5 2 1 5 3 Page 5 of 40 HEXCR E3510 Chromium has four naturally occurring isotopes i e 0Cr Cr Cr and Cr with a relative abundance of 4 35 83 79 9 50 and 2 37 respectively Cr and Cr are measured in this method There are some polyatomic species that will potentially interfere with Cr and Cr measurements The most common ones include C Ar Ar O IN SAr S79 7c1 6O PC Ar 350150 and Ar O H Various techniques employed in this method can minimize or eliminate these polyatomic interferences First the collision rea
46. rpm 20 Stabilization delay s o lon Optics volts First Extraction Lens 1 Second Extraction Lens 130 Third Extraction Lens 236 Corner Lens 230 Mirror Lens Left 46 Mirror Lens Right 26 Mirror Lens Bottom 26 Entrance Lens 2 Fringe Bias 1 5 Entrance Plate 26 Pole bias 0 0 QRI mL min Skimmer Gas Source H2 Sampler Gas Source OFF Skimmer Flow 30 Sampler Flow o Page 18 of 40 HEXCR E3510 NOTE After copying all the parameters from the daily optimization worksheet System Setup Normal Sensitivity msws make sure that these parameters are set as following Pump Rate rpm Stablization delay s Skimmer Gas Source Skimmer Flow 20 0 H2 30 Set the total samples in accordance with the total number of analysis in the chromatographic run sequence in the Galaxie See 4 5 5 l Method 2 Sequence 3 worksheet Showsamples on Show corrected d Sample Label Sample2 Samole3 Samole4 Samples Sample6 Sample7 Samole8 Samole9 Samole10 Sampole11 Samople12 Sample13 ___ Sample14 Samole15 Samoplei6 Samole17 Samole18 Sample19 Sample20 Sample Sample Sample Sample Sample Sample Sample Sample Sample Sample Sample Sample Sample Sample Sample Sample Sample Sample Sample Sample Total samples ig Set 3 Sample Introduction Manual O Autosampler implir EY Sequence Wizard m Back Loading Guide Ensure that
47. ty Refer to Section 1 9 SPEC ICP MS 001 and Varian ProStar 210 410 Operation Manuals for safety in operation of all equipment and in handling of all chemicals listed in this section ONLY PROFICIENT ANALYSTS CAN OPERATE THE INSTRUMENTS USED IN THIS METHOD Labwares NOTE The determination of trace level Cr VI requires a consideration of potential sources of contamination A clean laboratory work area designated for trace element sample handling must be used All reusable labware glass quartz polyethylene Teflon etc must be cleaned prior to use see Reference 1 7 12 NOTE Nalgene volumetric flasks are used for the preparation of calibration and QC standards These volumetric flasks are available only in Class B The volume of each volumetric flask is checked upon initial receipt of the volumetric and once a year following this time Each volumetric flask is independently labeled and the verification data is stored under S ICPMS ICP MS Nalgene Volumetric Flasks 4 2 1 Thomson 0 5 mL syringerless filter vials 4 2 2 50 mL Nalgene volumetric flasks 4 2 3 Adjustable volume pipettes Eppendorf or equivalent 4 2 4 Disposable gloves 4 2 5 Disposable plastic transfer pipettes 3 mL a precise volume is not necessary 4 2 6 2L Teflon bottles these are re used from Optima grade acid containers after being cleaned following the procedure in Ref 1 7 12 4 2 7 Acid dispensers variable volumes Fortuna Optifix or equivalent
48. ultiple V Multiple v Multiple t V Mutiple v Mutiple v Multiple cr52 Cr52 Cr82 CrS2 Cr53 Crs2 Crsa Cr52 Cr53 lela atala eatea ees cipem CLE Std2 17 07 20 Std3 17 07 20 Std4 17 07 20 QC 17 07 201 DI H2 26 07 DI H20 26 07 DI H20 26 07 DI H20 0 01 5 DIH20 0 01 p DI H20 0 01 p DIH20 0 05 DI H20 0 05 p _DIH20 0 05 p DIH20 0 1 py DIH20 0 1 pr DIH20 0 1 pp DIH20 0 5 pp DI H20 0 5 py DIH20 0 5 pr DIH20 1 ppb _DIH20 1 ppb DI H20 1 ppb DIH20 2 ppb _DIH20 2 ppb DI H20 2 ppb Std1 17 07 20 Std2 17 07 20 1 Std3 17 07 20 Std4 17 07 20 Std4 17 07 20 QC 17 07 201 QC 17 07 201 DI H20 26 07 Di H20 26 07 Tor ine Chromium C CrS2 Chromium Cr52 Chromium c Cr52 Chromium c Cr52 Chromium C CrS2 Chromium Chromium C Cr52 crs2 Chromium c CrS2 _Chromium C CrS2 Chromium c Cr52 Chromium C CrS2 Chromium c Cr52 Chromium Cr52 Chromium c Chromium C Chromium Chromium C Chromium C Chromium C Chromium ChromiumC Chromium C ChromiumiC Chromium C Chromium C Chromium c Chromium c Chromium C Chromiu
49. upto2L line with DI HO cap and mix the solution thoroughly check prepared solution to ensure pH gt 9 with a pH strip Note If the pH is not gt 9 then re prepare the mobile phase HPLC mobile phase B DI H20 pH gt 9 Preparation of mobile phase B fila2L Teflon bottle with 1 L DI H2O pipette 5 x 3 mL a precise volume is not necessary plastic disposable transfer pipettes ultra pure NH4OH fill up to 2 L line with DI H2O cap and mix the solution thoroughly check pH gt 9 with a pH strip Note If the pH is not gt 9 then re prepare the mobile phase NOTE Handling of NH4OH and HNO must be carried out inside a fume hood 4 5 Instrument Setup Procedure NOTE Refer to relevant instrument manuals and SOP s listed in Section 1 7 for further details 4 5 1 Switch the three way valve mounted on the side of the ProStar HPLC to by pass position so the solution can be introduced from peristaltic pump LSB APPROVED Page 17 of 40 JUNE 17 2013 HEXCR E3510 VERSION 1 0 4 5 2 Start the plasma on 820MS ICP MS and optimize the instrument according to SOP SPEC ICP MS 001 Print the Daily Performance Check results and keep a copy in the Varian 820 ICP MS Performance Test Reports Binder SN IP0903M009 NOTE The SOP outlines routine optimization For this method besides the routine optimization criteria it is important to check the signal to noise ratio at mass 52 When the instrument is optimized with 1 ug L
50. y in C Galaxie Data Chromium Output Cr Speciation csv This is the quantified results with non bracketing calibration Since this file is created automatically each time a sequence is analyzed or re processed it must be renamed and moved to the achived directory with a file name WGxxxxxx dd mm yyyy non bracketing csv C Galaxie Data Chromium Archived 2012 Quantified Results WG XXXXXX dd mm yyyy non bracketing csv To reprocess the data in a sequence that has been completed Open anew reprocess list by File New New Reprocessing List Select Create a reprocessing list with sequence file LSB APPROVED Page 27 of 40 JUNE 17 2013 HEXCR E3510 VERSION 1 0 Galaxie Chromatography Data System sm Display Acquisition Method Data Session Processing Plug ins Help New Method Ctri ait 2 i iz Open d New Method From Template E save gt New Report Style Ctri Alt W Save As gt i New Sequence Ctri Alt 4 fel Save AI Ctrl S SRNR ee a e NO E ee fi Close gt 3 New Summary Report Ctri Alt 6 L3 zl Close All Shift Ctrl F4 e New Spectral Library Ctri Alt 7 afio E Import C Internal Standard v Subtracti amp TD L amp Print Preview Ctri Alt P Standard Response unit amp Print Ctri P Unit ppb Curve unit Print as PDF Calibration Curve E Quit Alt F4 File Jerse L Response Heigh C Heic C sqrt He S
Download Pdf Manuals
Related Search