Methylmercury in tuna

Demonstrating measurement capabilities and evaluating comparability of results worldwide from the CCQM P-39 comparison

C. R. Quétel, J. P. Snell, Y. Aregbe, L. Abrankó, Zs Jókai, C. Brunori, R. Morabito, W. Hagan, S. Azemard, E. Wyse, V. Fajon, M. Horvat, M. Logar, O. F X Donard, E. Krupp, J. Entwisle, R. Hearn, M. Schantz, K. Inagaki, A. Takatsu & 10 others P. Grinberg, S. Willie, B. Dimock, H. Hintelmann, J. Zhu, E. Blanco Gonzalez, G. Centineo, J. Ignacio Garcia Alonso, A. Sanz-Medel, E. Björn

Research output: Contribution to journalArticle

12 Citations (Scopus)

Abstract

Six metrology institutes (NMIs) representing at the Comité International des Poids et Mesures (CIPM) 4 Member States of the Metre Convention and 2 international organisations, and 8 "expert" laboratories selected outside CIPM have compared their capabilities to quantitatively measure methylmercury (MeHg) in a prepared tuna material containing approximately 4.3 mg kg-1 Hg. This comparison was the object of the CIPM-Comité Consultatif pour la Quantité de Matière (CCQM) Pilot Study 39, organised by the Institute for Reference Materials and Measurements (IRMM), from the European Commission - Joint Research Centre. Beside the test material itself, a bottle of the BCR-464 tuna Certified Reference Material (CRM) and an ampoule of IRMM-670, a 202Hg isotope enriched MeHg candidate isotopic CRM, were distributed to all participants, who were free to apply the measurement strategy of their choice. Four, including 1 NMI, relied on external calibration or the method of standard additions, whereas the other 10 implemented an isotope dilution mass spectrometry (IDMS) approach and chose to use the IRMM-670 for their measurements. Alkaline digestion at room temperature (with manual shaking) or high temperature (under sonication, oven or hot plate conditions) was employed by most participants, with hydrochloric acid leaching the second most popular choice. Alkylation (4 phenylations, 4 ethylations and 3 propylations) in the aqueous phase was preferred by a large majority over butylation by the Grignard reaction. All participants were requested to estimate the uncertainty associated with their results and 9 out of 14 stated relative combined uncertainties below 6% (k = 2). Despite this apparent consensus, the perception of which factor caused the largest contribution to this estimation differed among participants because of the differences in the analytical methodologies deployed but also because of wide differences of the concepts of uncertainty estimation. The 'mixture mode' (MM) median, calculated also from the measurement uncertainties stated by the participants, was 1.967 ± 0.204 × 10-5 mol kg -1 (95% confidence). Twelve of the results were re-grouped within a range of less than 0.3 × 10-5 mol kg-1 (MM median = 1.967 ± 0.162 × 10-5 mol kg-1, 95% confidence): they nearly all (1 exception) overlapped with each other within k = 2 stated uncertainties. For the other 2 results the uncertainty seemed to have been particularly underestimated as they lay, respectively, at more than 20% above and less than -40% below the overall average. The relative standard deviation of the results of 9 laboratories out of the 10 that applied IDMS was about 2.6%. It can be assumed from the degree of equivalence shown by 12 out of 14 study participants that, at present, laboratories worldwide are potentially able to supply accurate results for MeHg in fish-type matrices (containing about 2 × 10-5 mol kg-1) within ± 10% uncertainty. This encouraging outcome permitted scheduling of a follow-up CCQM-K43 key comparison for a lower MeHg content level in salmon tissues.

Original languageEnglish
Pages (from-to)1058-1066
Number of pages9
JournalJournal of Analytical Atomic Spectrometry
Volume20
Issue number10
DOIs
Publication statusPublished - Oct 2005

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Isotopes
Dilution
Mass spectrometry
Sonication
Hydrochloric Acid
Alkylation
Bottles
Ovens
Uncertainty
Fish
Leaching
Scheduling
Calibration
Tissue
Temperature

ASJC Scopus subject areas

  • Spectroscopy

Cite this

Methylmercury in tuna : Demonstrating measurement capabilities and evaluating comparability of results worldwide from the CCQM P-39 comparison. / Quétel, C. R.; Snell, J. P.; Aregbe, Y.; Abrankó, L.; Jókai, Zs; Brunori, C.; Morabito, R.; Hagan, W.; Azemard, S.; Wyse, E.; Fajon, V.; Horvat, M.; Logar, M.; Donard, O. F X; Krupp, E.; Entwisle, J.; Hearn, R.; Schantz, M.; Inagaki, K.; Takatsu, A.; Grinberg, P.; Willie, S.; Dimock, B.; Hintelmann, H.; Zhu, J.; Gonzalez, E. Blanco; Centineo, G.; Alonso, J. Ignacio Garcia; Sanz-Medel, A.; Björn, E.

In: Journal of Analytical Atomic Spectrometry, Vol. 20, No. 10, 10.2005, p. 1058-1066.

Research output: Contribution to journalArticle

Quétel, CR, Snell, JP, Aregbe, Y, Abrankó, L, Jókai, Z, Brunori, C, Morabito, R, Hagan, W, Azemard, S, Wyse, E, Fajon, V, Horvat, M, Logar, M, Donard, OFX, Krupp, E, Entwisle, J, Hearn, R, Schantz, M, Inagaki, K, Takatsu, A, Grinberg, P, Willie, S, Dimock, B, Hintelmann, H, Zhu, J, Gonzalez, EB, Centineo, G, Alonso, JIG, Sanz-Medel, A & Björn, E 2005, 'Methylmercury in tuna: Demonstrating measurement capabilities and evaluating comparability of results worldwide from the CCQM P-39 comparison', Journal of Analytical Atomic Spectrometry, vol. 20, no. 10, pp. 1058-1066. https://doi.org/10.1039/b505368d
Quétel, C. R. ; Snell, J. P. ; Aregbe, Y. ; Abrankó, L. ; Jókai, Zs ; Brunori, C. ; Morabito, R. ; Hagan, W. ; Azemard, S. ; Wyse, E. ; Fajon, V. ; Horvat, M. ; Logar, M. ; Donard, O. F X ; Krupp, E. ; Entwisle, J. ; Hearn, R. ; Schantz, M. ; Inagaki, K. ; Takatsu, A. ; Grinberg, P. ; Willie, S. ; Dimock, B. ; Hintelmann, H. ; Zhu, J. ; Gonzalez, E. Blanco ; Centineo, G. ; Alonso, J. Ignacio Garcia ; Sanz-Medel, A. ; Björn, E. / Methylmercury in tuna : Demonstrating measurement capabilities and evaluating comparability of results worldwide from the CCQM P-39 comparison. In: Journal of Analytical Atomic Spectrometry. 2005 ; Vol. 20, No. 10. pp. 1058-1066.
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abstract = "Six metrology institutes (NMIs) representing at the Comit{\'e} International des Poids et Mesures (CIPM) 4 Member States of the Metre Convention and 2 international organisations, and 8 {"}expert{"} laboratories selected outside CIPM have compared their capabilities to quantitatively measure methylmercury (MeHg) in a prepared tuna material containing approximately 4.3 mg kg-1 Hg. This comparison was the object of the CIPM-Comit{\'e} Consultatif pour la Quantit{\'e} de Mati{\`e}re (CCQM) Pilot Study 39, organised by the Institute for Reference Materials and Measurements (IRMM), from the European Commission - Joint Research Centre. Beside the test material itself, a bottle of the BCR-464 tuna Certified Reference Material (CRM) and an ampoule of IRMM-670, a 202Hg isotope enriched MeHg candidate isotopic CRM, were distributed to all participants, who were free to apply the measurement strategy of their choice. Four, including 1 NMI, relied on external calibration or the method of standard additions, whereas the other 10 implemented an isotope dilution mass spectrometry (IDMS) approach and chose to use the IRMM-670 for their measurements. Alkaline digestion at room temperature (with manual shaking) or high temperature (under sonication, oven or hot plate conditions) was employed by most participants, with hydrochloric acid leaching the second most popular choice. Alkylation (4 phenylations, 4 ethylations and 3 propylations) in the aqueous phase was preferred by a large majority over butylation by the Grignard reaction. All participants were requested to estimate the uncertainty associated with their results and 9 out of 14 stated relative combined uncertainties below 6{\%} (k = 2). Despite this apparent consensus, the perception of which factor caused the largest contribution to this estimation differed among participants because of the differences in the analytical methodologies deployed but also because of wide differences of the concepts of uncertainty estimation. The 'mixture mode' (MM) median, calculated also from the measurement uncertainties stated by the participants, was 1.967 ± 0.204 × 10-5 mol kg -1 (95{\%} confidence). Twelve of the results were re-grouped within a range of less than 0.3 × 10-5 mol kg-1 (MM median = 1.967 ± 0.162 × 10-5 mol kg-1, 95{\%} confidence): they nearly all (1 exception) overlapped with each other within k = 2 stated uncertainties. For the other 2 results the uncertainty seemed to have been particularly underestimated as they lay, respectively, at more than 20{\%} above and less than -40{\%} below the overall average. The relative standard deviation of the results of 9 laboratories out of the 10 that applied IDMS was about 2.6{\%}. It can be assumed from the degree of equivalence shown by 12 out of 14 study participants that, at present, laboratories worldwide are potentially able to supply accurate results for MeHg in fish-type matrices (containing about 2 × 10-5 mol kg-1) within ± 10{\%} uncertainty. This encouraging outcome permitted scheduling of a follow-up CCQM-K43 key comparison for a lower MeHg content level in salmon tissues.",
author = "Qu{\'e}tel, {C. R.} and Snell, {J. P.} and Y. Aregbe and L. Abrank{\'o} and Zs J{\'o}kai and C. Brunori and R. Morabito and W. Hagan and S. Azemard and E. Wyse and V. Fajon and M. Horvat and M. Logar and Donard, {O. F X} and E. Krupp and J. Entwisle and R. Hearn and M. Schantz and K. Inagaki and A. Takatsu and P. Grinberg and S. Willie and B. Dimock and H. Hintelmann and J. Zhu and Gonzalez, {E. Blanco} and G. Centineo and Alonso, {J. Ignacio Garcia} and A. Sanz-Medel and E. Bj{\"o}rn",
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T1 - Methylmercury in tuna

T2 - Demonstrating measurement capabilities and evaluating comparability of results worldwide from the CCQM P-39 comparison

AU - Quétel, C. R.

AU - Snell, J. P.

AU - Aregbe, Y.

AU - Abrankó, L.

AU - Jókai, Zs

AU - Brunori, C.

AU - Morabito, R.

AU - Hagan, W.

AU - Azemard, S.

AU - Wyse, E.

AU - Fajon, V.

AU - Horvat, M.

AU - Logar, M.

AU - Donard, O. F X

AU - Krupp, E.

AU - Entwisle, J.

AU - Hearn, R.

AU - Schantz, M.

AU - Inagaki, K.

AU - Takatsu, A.

AU - Grinberg, P.

AU - Willie, S.

AU - Dimock, B.

AU - Hintelmann, H.

AU - Zhu, J.

AU - Gonzalez, E. Blanco

AU - Centineo, G.

AU - Alonso, J. Ignacio Garcia

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AU - Björn, E.

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AB - Six metrology institutes (NMIs) representing at the Comité International des Poids et Mesures (CIPM) 4 Member States of the Metre Convention and 2 international organisations, and 8 "expert" laboratories selected outside CIPM have compared their capabilities to quantitatively measure methylmercury (MeHg) in a prepared tuna material containing approximately 4.3 mg kg-1 Hg. This comparison was the object of the CIPM-Comité Consultatif pour la Quantité de Matière (CCQM) Pilot Study 39, organised by the Institute for Reference Materials and Measurements (IRMM), from the European Commission - Joint Research Centre. Beside the test material itself, a bottle of the BCR-464 tuna Certified Reference Material (CRM) and an ampoule of IRMM-670, a 202Hg isotope enriched MeHg candidate isotopic CRM, were distributed to all participants, who were free to apply the measurement strategy of their choice. Four, including 1 NMI, relied on external calibration or the method of standard additions, whereas the other 10 implemented an isotope dilution mass spectrometry (IDMS) approach and chose to use the IRMM-670 for their measurements. Alkaline digestion at room temperature (with manual shaking) or high temperature (under sonication, oven or hot plate conditions) was employed by most participants, with hydrochloric acid leaching the second most popular choice. Alkylation (4 phenylations, 4 ethylations and 3 propylations) in the aqueous phase was preferred by a large majority over butylation by the Grignard reaction. All participants were requested to estimate the uncertainty associated with their results and 9 out of 14 stated relative combined uncertainties below 6% (k = 2). Despite this apparent consensus, the perception of which factor caused the largest contribution to this estimation differed among participants because of the differences in the analytical methodologies deployed but also because of wide differences of the concepts of uncertainty estimation. The 'mixture mode' (MM) median, calculated also from the measurement uncertainties stated by the participants, was 1.967 ± 0.204 × 10-5 mol kg -1 (95% confidence). Twelve of the results were re-grouped within a range of less than 0.3 × 10-5 mol kg-1 (MM median = 1.967 ± 0.162 × 10-5 mol kg-1, 95% confidence): they nearly all (1 exception) overlapped with each other within k = 2 stated uncertainties. For the other 2 results the uncertainty seemed to have been particularly underestimated as they lay, respectively, at more than 20% above and less than -40% below the overall average. The relative standard deviation of the results of 9 laboratories out of the 10 that applied IDMS was about 2.6%. It can be assumed from the degree of equivalence shown by 12 out of 14 study participants that, at present, laboratories worldwide are potentially able to supply accurate results for MeHg in fish-type matrices (containing about 2 × 10-5 mol kg-1) within ± 10% uncertainty. This encouraging outcome permitted scheduling of a follow-up CCQM-K43 key comparison for a lower MeHg content level in salmon tissues.

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