Methylmercury in tuna: demonstrating measurement capabilities and evaluating comparability of results worldwide from the CCQM P-39 comparison

C R Quetel, J P Snell, Y Aregbe, L Abranko, Z Jokai, C Brunori, R Morabito, W Hagan, S Azemard, E Wyse, V Fajon, M Horvat, M Logar, O F X Donard, Eva Maria Krupp, J Entwisle, R Hearn, M Schantz, K Inagaki, A TakatsuP Grinberg, S Willlie, B Dimock, H Hintelmann, J Zhu, E B Gonzalez, G Centineo, J E G Alonso, A Sanz-Medel, E Bjorn

Research output: Contribution to journalArticle

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Abstract

Six metrology institutes (NMIs) representing at the Comite '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 - Comite Consultatif pour la Quantite de Matiere (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 202 Hg 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 x 10(-5) mol kg(-1) (95% confidence). Twelve of the results were re-grouped within a range of less than 0.3 x 10(-5) mol kg(-1) (MM median = 1.967 +/- 0.162 x 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 x 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 - 2005

Keywords

  • plasma-mass spectrometry
  • microextraction gas chromatography
  • level environmental samples
  • methyl mercury compounds
  • GC-ICP-MS
  • sodium tetra(n-propyl)borate
  • inorganic mercury
  • speciation
  • derivatization
  • certification

Cite this

Methylmercury in tuna : demonstrating measurement capabilities and evaluating comparability of results worldwide from the CCQM P-39 comparison. / Quetel, C R ; Snell, J P ; Aregbe, Y ; Abranko, L ; Jokai, Z ; Brunori, C ; Morabito, R ; Hagan, W ; Azemard, S ; Wyse, E ; Fajon, V ; Horvat, M ; Logar, M ; Donard, O F X ; Krupp, Eva Maria; Entwisle, J ; Hearn, R ; Schantz, M ; Inagaki, K ; Takatsu, A ; Grinberg, P ; Willlie, S ; Dimock, B ; Hintelmann, H ; Zhu, J ; Gonzalez, E B ; Centineo, G ; Alonso, J E G ; Sanz-Medel, A ; Bjorn, E .

In: Journal of Analytical Atomic Spectrometry, Vol. 20, No. 10, 2005, p. 1058-1066.

Research output: Contribution to journalArticle

Quetel, CR, Snell, JP, Aregbe, Y, Abranko, L, Jokai, Z, Brunori, C, Morabito, R, Hagan, W, Azemard, S, Wyse, E, Fajon, V, Horvat, M, Logar, M, Donard, OFX, Krupp, EM, Entwisle, J, Hearn, R, Schantz, M, Inagaki, K, Takatsu, A, Grinberg, P, Willlie, S, Dimock, B, Hintelmann, H, Zhu, J, Gonzalez, EB, Centineo, G, Alonso, JEG, Sanz-Medel, A & Bjorn, 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
Quetel, C R ; Snell, J P ; Aregbe, Y ; Abranko, L ; Jokai, Z ; Brunori, C ; Morabito, R ; Hagan, W ; Azemard, S ; Wyse, E ; Fajon, V ; Horvat, M ; Logar, M ; Donard, O F X ; Krupp, Eva Maria ; Entwisle, J ; Hearn, R ; Schantz, M ; Inagaki, K ; Takatsu, A ; Grinberg, P ; Willlie, S ; Dimock, B ; Hintelmann, H ; Zhu, J ; Gonzalez, E B ; Centineo, G ; Alonso, J E G ; Sanz-Medel, A ; Bjorn, 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 Comite '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 - Comite Consultatif pour la Quantite de Matiere (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 202 Hg 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 x 10(-5) mol kg(-1) (95{\%} confidence). Twelve of the results were re-grouped within a range of less than 0.3 x 10(-5) mol kg(-1) (MM median = 1.967 +/- 0.162 x 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 x 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.",
keywords = "plasma-mass spectrometry, microextraction gas chromatography, level environmental samples, methyl mercury compounds, GC-ICP-MS, sodium tetra(n-propyl)borate, inorganic mercury, speciation, derivatization, certification",
author = "Quetel, {C R} and Snell, {J P} and Y Aregbe and L Abranko and Z Jokai 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 Krupp, {Eva Maria} and J Entwisle and R Hearn and M Schantz and K Inagaki and A Takatsu and P Grinberg and S Willlie and B Dimock and H Hintelmann and J Zhu and Gonzalez, {E B} and G Centineo and Alonso, {J E G} and A Sanz-Medel and E Bjorn",
year = "2005",
doi = "10.1039/b505368d",
language = "English",
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journal = "Journal of Analytical Atomic Spectrometry",
issn = "0267-9477",
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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 - Quetel, C R

AU - Snell, J P

AU - Aregbe, Y

AU - Abranko, L

AU - Jokai, Z

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, Eva Maria

AU - Entwisle, J

AU - Hearn, R

AU - Schantz, M

AU - Inagaki, K

AU - Takatsu, A

AU - Grinberg, P

AU - Willlie, S

AU - Dimock, B

AU - Hintelmann, H

AU - Zhu, J

AU - Gonzalez, E B

AU - Centineo, G

AU - Alonso, J E G

AU - Sanz-Medel, A

AU - Bjorn, E

PY - 2005

Y1 - 2005

N2 - Six metrology institutes (NMIs) representing at the Comite '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 - Comite Consultatif pour la Quantite de Matiere (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 202 Hg 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 x 10(-5) mol kg(-1) (95% confidence). Twelve of the results were re-grouped within a range of less than 0.3 x 10(-5) mol kg(-1) (MM median = 1.967 +/- 0.162 x 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 x 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.

AB - Six metrology institutes (NMIs) representing at the Comite '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 - Comite Consultatif pour la Quantite de Matiere (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 202 Hg 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 x 10(-5) mol kg(-1) (95% confidence). Twelve of the results were re-grouped within a range of less than 0.3 x 10(-5) mol kg(-1) (MM median = 1.967 +/- 0.162 x 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 x 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.

KW - plasma-mass spectrometry

KW - microextraction gas chromatography

KW - level environmental samples

KW - methyl mercury compounds

KW - GC-ICP-MS

KW - sodium tetra(n-propyl)borate

KW - inorganic mercury

KW - speciation

KW - derivatization

KW - certification

U2 - 10.1039/b505368d

DO - 10.1039/b505368d

M3 - Article

VL - 20

SP - 1058

EP - 1066

JO - Journal of Analytical Atomic Spectrometry

JF - Journal of Analytical Atomic Spectrometry

SN - 0267-9477

IS - 10

ER -