TRACE ELEMENTS IN SERUM

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1 TRACE ELEMENTS IN SERUM Proficiency Test Report Event #, 0 November 6 th, 0

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3 Event #, 0 Serum Aluminum Serum materials were obtained from the Dutch EQA (External Quality Assessment) scheme SKML (Stichting Kwaliteitsbewaking Medische Laboratoria) as part of a global collaborative exercise to harmonize international measurements of Al, Cu, Se and Zn in serum. Additionally, serum pools were spiked with a suite of trace elements (Co, Cr, Li, Mg, Mn, Tl, and V), including aluminum as AlCl at various concentrations. The serum has been tested and found to be negative for BSE (Bovine Spongiform Encephalopathy), and free of pathogens. The Certificate of Analysis provided by SKML is available upon request. The Target Value assigned for each PT material is the robust mean of the results reported by all participants in this event. The robust statistics were obtained utilizing algorithms based on those presented in ISO 58:005E Statistical methods for use in proficiency testing by interlaboratory comparisons. Values for serum aluminum range from µg/l (0.4 µmol/l) to 80 µg/l (6.67 µmol/l). Acceptable ranges for serum aluminum are based on fixed criteria of ±0%, or ±5 µg/l below 5 µg/l. These criteria are based on consensus recommendations from several EQAS organizers (). Discussion. Based on the above criteria, 87.8% of test results reported were judged as satisfactory, with four out of participant laboratories (7.4%) reporting or more of the 5 results outside the acceptable ranges.. Taylor, A., Angerer, J., Claeys, F., Kristiansen, J., Mazarrasa, O., Menditto, A., Patriarca, M., Pineau, A., Schoeters, I., Sykes, C., Valkonen, S. and Weykamp, C. Comparison of procedures for evaluating laboratory performance in external quality assessment schemes for lead in blood and aluminum in serum demonstrates the need for common quality specifications. Clinical Chemistry Trace Elements PT Program

4 Serum Aluminum Test Results, 0 Event # ROBUST STATISTICAL SUMMARY TARGET VALUE ASSIGNMENT AND STATISTICS Results (µg/l serum) SE- SE- SE- SE-4 SE-5 Robust Mean Robust Standard Deviation Standard Uncertainty 0.4 RSD (%) Number of Sample Measurements 0 Acceptable Range: Upper Limit Lower Limit notes: Results reported as less than the method detection limit are excluded from statistical calculations.

5 Serum Aluminum Test Results, 0 Event # PERFORMANCE OF PARTICIPATING LABORATORIES Lab Code Method SE- Results (µg/l serum) SE- SE- SE-4 SE-5 Info Only Target Values: ETAAS-Z ICP-MS FAAS Info 56 ICP-MS < 60 ICP-MS ICP-MS DRC/CC-ICP-MS ICP-MS < DRC/CC-ICP-MS Info 06 DRC/CC-ICP-MS >00 77 >00 >00 87 ETAAS-Z ICP-MS Info 05 ICP-MS ICP-MS Info 5 ETAAS-Z Info 55 ICP-MS ICP-MS ICP-MS ICP-MS ICP-MS ETAAS-Z Info 40 ICP-AES/OES < Info 458 ETAAS Other Percent satisfactory results for all participants: 87.8 % notes: reported outside upper limit Info only: results included for informational purposes only. reported outside lower limit notes: Results reported as less than the method detection limit are excluded from statistical calculations.

6 DRC/CC-ICP-MS New York State Department of Health Serum Aluminum Test Results, 0 Event # STATISTICAL SUMMARY BY METHOD ETAAS Other ETAAS-Z FAAS ICP-AES/OES ICP-MS All Laboratories Results (µg/l serum) SE- SE- SE- SE-4 SE notes: Insufficient data for calculation.

7 Event #, 0 Serum Copper Serum materials were obtained from the Dutch EQA (External Quality Assessment) scheme SKML (Stichting Kwaliteitsbewaking Medische Laboratoria) as part of a global collaborative exercise to harmonize international measurements of Al, Cu, Se and Zn in serum. Additionally, serum pools were spiked with a suite of trace elements (Co, Cr, Li, Mg, Mn, Tl, and V), including copper as CuCl at various concentrations. The serum has been tested and found to be negative for BSE (Bovine Spongiform Encephalopathy), and!free of pathogens. The Certificate of Analysis provided by SKML is available upon request. The Target Value assigned for each PT material is the robust mean of the results reported by all participants in this event. The robust statistics were obtained utilizing algorithms based on those presented in ISO 58:005E Statistical methods for use in proficiency testing by interlaboratory comparisons. Values for serum copper range from 675 µg/l (0.6 µmol/l) to 869 µg/l (45.5 µmol/l). Acceptable ranges for serum copper are based on fixed criteria of ±5%, or ±95 µg/l below 65 µg/l. These criteria are consistent with those proposed by the OELM Network of EQAS organizers (, ) for trace elements in serum, and are slightly less stringent than those previously suggested for NYS (±0%). Discussion. Based on the above criteria, 95.0% of test results reported were judged as satisfactory, with two out of 0 participant laboratories (0.0%) reporting or more of the 5 results outside the acceptable ranges.. A. Taylor, J. Angerer, J. Arnaud, F. Claeys, R.L. Jones, O. Mazarrasa, E. Mairiaux, A. Menditto, P.J. Parsons, M. Patriarca, A. Pineau, S. Valkonen, J.-P. Weber and C. Weykamp Accreditation and Quality Assurance J. Arnaud, J.-P. Weber, C.W. Weykamp, P.J. Parsons, J. Angerer, E. Mairiaux, O. Mazarrasa, S. Valkonen, A. Menditto, M. Patriarca, and A. Taylor Clinical Chemistry Trace Elements PT Program

8 Serum Copper Test Results, 0 Event # ROBUST STATISTICAL SUMMARY TARGET VALUE ASSIGNMENT AND STATISTICS Results (µg/l serum) SE- SE- SE- SE-4 SE-5 Robust Mean Robust Standard Deviation Standard Uncertainty RSD (%) Number of Sample Measurements Acceptable Range: Upper Limit Lower Limit notes: Results reported as less than the method detection limit are excluded from statistical calculations.

9 Serum Copper Test Results, 0 Event # PERFORMANCE OF PARTICIPATING LABORATORIES Lab Code Method SE- Results (µg/l serum) SE- SE- SE-4 SE-5 Info Only Target Values: DRC/CC-ICP-MS Info 0 ICP-MS ICP-MS ICP-MS Info 56 ICP-AES/OES ICP-MS ICP-MS DRC/CC-ICP-MS ICP-MS ICP-MS Info 06 ICP-MS ICP-MS Info 05 ICP-MS ICP-MS Info 5 ICP-MS Info 59 ICP-MS ETAAS-Z Info 40 DRC/CC-ICP-MS Info 457 ICP-AES/OES Info 48 ICP-MS Percent satisfactory results for all participants: 95.0 % notes: reported outside upper limit Info only: results included for informational purposes only. reported outside lower limit notes: Results reported as less than the method detection limit are excluded from statistical calculations.

10 DRC/CC-ICP-MS New York State Department of Health Serum Copper Test Results, 0 Event # STATISTICAL SUMMARY BY METHOD ETAAS-Z ICP-AES/OES ICP-MS All Laboratories Results (µg/l serum) SE- SE- SE- SE-4 SE notes: Insufficient data for calculation.

11 Event #, 0 Serum Selenium Serum materials were obtained from the Dutch EQA (External Quality Assessment) scheme SKML (Stichting Kwaliteitsbewaking Medische Laboratoria) as part of a global collaborative exercise to harmonize international measurements of Al, Cu, Se and Zn in serum. Additionally, serum pools were spiked with a suite of trace elements (Co, Cr, Li, Mg, Mn, Tl, and V), including selenium as SeO at various concentrations. The serum has been tested and found to be negative for BSE (Bovine Spongiform Encephalopathy), and free of pathogens. The Certificate of Analysis provided by SKML is available upon request. The Target Value assigned for each PT material is the robust mean of the results reported by all participants in this event. The robust statistics were obtained utilizing algorithms based on those presented in ISO 58:005E Statistical methods for use in proficiency testing by interlaboratory comparisons. Values for serum selenium range from 47 µg/l (0.60 µmol/l) to 68 µg/l (.9 µmol/l). Acceptable ranges for serum selenium are based on fixed criteria of ±0%, or ± µg/l below 0 µg/l. These criteria are a little less stringent than those proposed by the OELM Network of EQAS organizers (±5% or ±8 µg/l below 55 µg/l) (, ) for trace elements in serum. As performance for serum Se improves among NYS-permit laboratories, consideration will be given to adopting the OELM criteria. Discussion. We have become aware of a potential interference on Se in ICP-MS when sera from bovine sources are used for PT sample pools. We are currently investigating this and will report on our findings in due course. Until that time, grading for serum Se is suspended. We ask that participants continue to analyze our serum pools for Se, along with other trace elements, to aid in the investigation. We included human sera for comparison purposes with this PT event (SE- through 5), and we requested participant s cooperation by analyzing these additional materials for Se. We will shortly be circulating a summary of the results, as well as from the questionnaire which asked for more details of the analytical methods used for Se.. A. Taylor, J. Angerer, J. Arnaud, F. Claeys, R.L. Jones, O. Mazarrasa, E. Mairiaux, A. Menditto, P.J. Parsons, M. Patriarca, A. Pineau, S. Valkonen, J.-P. Weber and C. Weykamp Accreditation and Quality Assurance J. Arnaud, J.-P. Weber, C.W. Weykamp, P.J. Parsons, J. Angerer, E. Mairiaux, O. Mazarrasa, S. Valkonen, A. Menditto, M. Patriarca, and A. Taylor Clinical Chemistry Trace Elements PT Program

12 Serum Selenium Test Results, 0 Event # ROBUST STATISTICAL SUMMARY TARGET VALUE ASSIGNMENT AND STATISTICS Results (µg/l serum) SE- SE- SE- SE-4 SE-5 Robust Mean Robust Standard Deviation Standard Uncertainty RSD (%) Number of Sample Measurements Acceptable Range: Upper Limit Lower Limit notes: Results reported as less than the method detection limit are excluded from statistical calculations.

13 Serum Selenium Test Results, 0 Event # PERFORMANCE OF PARTICIPATING LABORATORIES Lab Code Method SE- Results (µg/l serum) SE- SE- SE-4 SE-5 Info Only Target Values: DRC/CC-ICP-MS Info 0 DRC/CC-ICP-MS ICP-MS DRC/CC-ICP-MS Info 56 ICP-MS DRC/CC-ICP-MS DRC/CC-ICP-MS DRC/CC-ICP-MS Info 06 DRC/CC-ICP-MS DRC/CC-ICP-MS Info 05 ICP-MS ICP-MS Info 66 ETAAS-Z Info 67 DRC/CC-ICP-MS Info 40 DRC/CC-ICP-MS Info Percent satisfactory results for all participants: 00.0 % notes: reported outside upper limit Info only: results included for informational purposes only. reported outside lower limit notes: Results reported as less than the method detection limit are excluded from statistical calculations.

14 DRC/CC-ICP-MS New York State Department of Health Serum Selenium Test Results, 0 Event # STATISTICAL SUMMARY BY METHOD ETAAS-Z ICP-MS All Laboratories Results (µg/l serum) SE- SE- SE- SE-4 SE notes: Insufficient data for calculation.

15 Event #, 0 Serum Zinc Serum materials were obtained from the Dutch EQA (External Quality Assessment) scheme SKML (Stichting Kwaliteitsbewaking Medische Laboratoria) as part of a global collaborative exercise to harmonize international measurements of Al, Cu, Se and Zn in serum. Additionally, serum pools were spiked with a suite of trace elements (Co, Cr, Li, Mg, Mn, Tl, and V), including zinc as ZnCl at various concentrations. The serum has been tested and found to be negative for BSE (Bovine Spongiform Encephalopathy), and free of pathogens. The Certificate of Analysis provided by SKML is available upon request. The Target Value assigned for each PT material is the robust mean of the results reported by all participants in this event. The robust statistics were obtained utilizing algorithms based on those presented in ISO 58:005E Statistical methods for use in proficiency testing by interlaboratory comparisons. Values for serum zinc range from 89 µg/l (9.7 µmol/l) to 975 µg/l (45.50 µmol/l). Acceptable ranges for serum zinc are based on fixed criteria of ±5%, or ±5 µg/l below 00 µg/l. These criteria are consistent with those proposed by the OELM network of EQAS organizers () for trace elements in serum. Discussion. Based on the above criteria, 86.7% of test results reported were judged as satisfactory, with four out of 7 participant laboratories (4.8 %) reporting or more of the 5 results outside the acceptable ranges.. A. Taylor, J. Angerer, J. Arnaud, F. Claeys, R.L. Jones, O. Mazarrasa, E. Mairiaux, A. Menditto, P.J. Parsons, M. Patriarca, A. Pineau, S. Valkonen, J.-P. Weber and C. Weykamp Accreditation and Quality Assurance J. Arnaud, J.-P. Weber, C.W. Weykamp, P.J. Parsons, J. Angerer, E. Mairiaux, O. Mazarrasa, S. Valkonen, A. Menditto, M. Patriarca, and A. Taylor Clinical Chemistry Trace Elements PT Program

16 Serum Zinc Test Results, 0 Event # ROBUST STATISTICAL SUMMARY TARGET VALUE ASSIGNMENT AND STATISTICS Results (µg/l serum) SE- SE- SE- SE-4 SE-5 Robust Mean Robust Standard Deviation Standard Uncertainty RSD (%) Number of Sample Measurements Acceptable Range: Upper Limit Lower Limit notes: Results reported as less than the method detection limit are excluded from statistical calculations.

17 Serum Zinc Test Results, 0 Event # PERFORMANCE OF PARTICIPATING LABORATORIES Lab Code Method SE- Results (µg/l serum) SE- SE- SE-4 SE-5 Info Only Target Values: DRC/CC-ICP-MS Info 0 ICP-MS ICP-MS ICP-MS Info 56 ICP-AES/OES ICP-MS ICP-MS DRC/CC-ICP-MS ICP-MS ICP-MS Info 06 ICP-MS FAAS ICP-MS Info 05 ICP-MS ICP-MS Info 5 ICP-MS Info 55 ICP-MS ICP-MS ICP-MS ICP-MS ICP-MS ICP-MS ETAAS-Z Info 40 DRC/CC-ICP-MS Info 457 ICP-AES/OES Info 458 FAAS ICP-MS Percent satisfactory results for all participants: 86.7 % notes: reported outside upper limit Info only: results included for informational purposes only. reported outside lower limit notes: Results reported as less than the method detection limit are excluded from statistical calculations.

18 DRC/CC-ICP-MS New York State Department of Health Serum Zinc Test Results, 0 Event # STATISTICAL SUMMARY BY METHOD ETAAS-Z FAAS ICP-AES/OES ICP-MS All Laboratories Results (µg/l serum) SE- SE- SE- SE-4 SE notes: Insufficient data for calculation.

19 Event #, 0 Additional Trace Elements Reported in Serum Participant laboratories reported their analytical results for any additional trace elements (other than Al, Cu, Se and Zn) that are routinely reported so that a more complete characterization can be recorded for these PT materials. Results for additional trace elements are reported here, but no target value is implied nor are any acceptable ranges provided. These data are provided solely for educational and informational purposes. Serum materials were obtained from the Dutch EQA (External Quality Assessment) scheme SKML (Stichting Kwaliteitsbewaking Medische Laboratoria) as part of a global collaborative exercise to harmonize international measurements of Al, Cu, Se and Zn in serum. Additionally, serum pools were spiked with a suite of trace elements at various concentrations including cobalt as CoCl, chromium as CrCl, lithium as LiCl, magnesium as MgCl, manganese as MnCl, thallium as TlNO, and vanadium as VOSO 4. The serum has been tested and found to be negative for BSE (Bovine Spongiform Encephalopathy), and free of pathogens. The Certificate of Analysis provided by SKML is available upon request. Additional Elements Co, Cr, Li, Mg, Mn, Tl, V Trace Elements PT Program

20 Serum Additional Elements, 0 Event # Page Serum Antimony (µg/l) Lab Code Method SE- SE- SE- SE-4 SE-5 0 ICP-MS ICP-MS Serum Arsenic (µg/l) Lab Code Method SE- SE- SE- SE-4 SE-5 97 DRC/CC-ICP-MS <0.0 <0.0 <0.0 <0.0 <0.0 Serum Barium (µg/l) Lab Code Method SE- SE- SE- SE-4 SE-5 47 ICP-MS ICP-MS ICP-MS Arithmetic mean SD n Serum Beryllium (µg/l) Lab Code Method SE- SE- SE- SE-4 SE-5 47 ICP-MS <0.45 <0.45 <0.45 <0.45 < ICP-MS 0. <0. <0. <0. <0. Serum Bismuth (µg/l) Lab Code Method SE- SE- SE- SE-4 SE-5 97 ICP-MS <.0 <.0 <.0 <.0 <.0 Serum Cadmium (µg/l) Lab Code Method SE- SE- SE- SE-4 SE-5 0 ICP-MS ICP-MS DRC/CC-ICP-MS <0.5 <0.5 <0.5 <0.5 <0.5 4 ICP-MS Arithmetic mean SD n Serum Chromium (µg/l) Lab Code Method SE- SE- SE- SE-4 SE-5 47 DRC/CC-ICP-MS DRC/CC-ICP-MS < DRC/CC-ICP-MS DRC/CC-ICP-MS DRC/CC-ICP-MS < DRC/CC-ICP-MS < ICP-MS * ETAAS-Z *Omitted Arithmetic mean SD n

21 Serum Additional Elements, 0 Event # Page Serum Cobalt (µg/l) Lab Code Method SE- SE- SE- SE-4 SE-5 0 ICP-MS ICP-MS ICP-MS DRC/CC-ICP-MS < ICP-MS DRC/CC-ICP-MS ICP-MS ICP-MS ICP-MS Arithmetic mean SD n Serum Iodine (µg/l) Lab Code Method SE- SE- SE- SE-4 SE-5 4 ICP-MS ICP-MS DRC/CC-ICP-MS ICP-MS ICP-MS ICP-MS Arithmetic mean SD n Serum Iron (µg/l) Lab Code Method SE- SE- SE- SE-4 SE ICP-AES/OES Serum Lead (µg/l) Lab Code Method SE- SE- SE- SE-4 SE-5 47 ICP-MS DRC/CC-ICP-MS Serum Lithium (µg/l) Lab Code Method SE- SE- SE- SE-4 SE-5 47 ICP-MS Serum Manganese (µg/l) Lab Code Method SE- SE- SE- SE-4 SE-5 0 ICP-MS ICP-MS ICP-MS DRC/CC-ICP-MS DRC/CC-ICP-MS * ICP-MS ICP-MS ICP-MS *Omitted Arithmetic mean SD n

22 Serum Additional Elements, 0 Event # Page Serum Mercury (µg/l) Lab Code Method SE- SE- SE- SE-4 SE-5 47 ICP-MS <0. <0. <0. <0. <0. 97 ICP-MS <5.0 <5.0 <5.0 <5.0 <5.0 Serum Molybdenum (µg/l) Lab Code Method SE- SE- SE- SE-4 SE-5 0 ICP-MS ICP-MS ICP-MS ICP-MS Arithmetic mean SD n Serum Nickel (µg/l) Lab Code Method SE- SE- SE- SE-4 SE-5 4 ICP-MS.4. *..6 *. 47 ICP-MS DRC/CC-ICP-MS ICP-MS <.0 <.0 <.0 <.0 <.0 06 ICP-MS <0.0 <0.0 <0.0 <0.0 <0.0 *Omitted Arithmetic mean SD n - - Serum Platinum (µg/l) Lab Code Method SE- SE- SE- SE-4 SE-5 0 ICP-MS ICP-MS <0.0 <0.0 <0.0 <0.0 <0.0 Serum Silver (µg/l) Lab Code Method SE- SE- SE- SE-4 SE-5 47 ICP-MS ICP-MS <0. <0. <0. <0. <0. 97 ICP-MS <.0 <.0 <.0 <.0 <.0 Serum Tellurium (µg/l) Lab Code Method SE- SE- SE- SE-4 SE-5 47 ICP-MS <0.09 <0.09 <0.09 <0.09 < ICP-MS <.0 <.0 <.0 <.0 <.0 Serum Thallium (µg/l) Lab Code Method SE- SE- SE- SE-4 SE-5 0 ICP-MS ICP-MS ICP-MS < Arithmetic mean SD n -

23 Serum Additional Elements, 0 Event # Page 4 Serum Thorium (µg/l) Lab Code Method SE- SE- SE- SE-4 SE-5 47 ICP-MS <0.0 <0.0 <0.0 <0.0 <0.0 Serum Tin (µg/l) Lab Code Method SE- SE- SE- SE-4 SE-5 0 ICP-MS ICP-MS ICP-MS <5.0 <5.0 <5.0 <5.0 <5.0 Serum Tungsten (µg/l) Lab Code Method SE- SE- SE- SE-4 SE-5 47 ICP-MS <0.68 <0.68 <0.68 < Serum Uranium (µg/l) Lab Code Method SE- SE- SE- SE-4 SE-5 47 ICP-MS Serum Vanadium (µg/l) Lab Code Method SE- SE- SE- SE-4 SE-5 47 DRC/CC-ICP-MS DRC/CC-ICP-MS

24 ATOMIC SPECTROMETRY METHODS New York State Department of Health Trace Elements in Serum METHOD NOTES A- ETAAS-Z (Electrothermal atomic absorption spectrometry with Zeeman background correction) A- ETAAS other (i.e., D, S-H background correction) A- FAAS (Flame atomic absorption spectrometry) A-4 CV-AAS (Cold vapor atomic absorption spectrometry) A-5 HG-AAS (Hydride generation atomic absorption spectrometry) A-6 AFS (Atomic fluorescence spectrometry) A-7 Other INDUCTIVELY COUPLED PLASMA P- ICP-MS (Inductively coupled plasma - mass spectrometry) P- DRC/CC-ICP-MS (ICP-MS used in the Dynamic Reaction Cell or Collision Cell mode) P- ICP-AES/OES (ICP atomic/optical emission spectrometry) P-4 HR-ICP-MS (High resolution ICP-MS) P-5 ETV-ICP-MS (Electrothermal vaporization ICP-MS) P-6 ID-ICP-MS (Isotope dilution ICP-MS) P-7 Other ELECTROCHEMICAL METHODS E- ASV (Anodic stripping voltammetry without digestion) E- ASV-LeadCare (Anodic stripping voltammetry using the ESA LeadCare system) E- Fluoride specific electrode E-4 Other MOLECULAR FLUORIMETRY F- EtOAc (Ethyl acetate-acetic acid extraction method for determination of erythrocyte protoporphyrin) F- Aviv hematofluorometry (for determination of EP at hematocrit 5) F- Helena ZPP (for determination of zinc protoporphyrin in µmol ZPP/mol heme) F-4 Other OTHER METHODS If your method is not listed in the above list, please describe it briefly.

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