Application of isotopically labeled methylmercury for isotope dilution analysis of biological samples using gas chromatography/ICPMS

R C R Martin-Doimeadios, Eva Maria Krupp, D Amouroux, O F X Donard

Research output: Contribution to journalArticle

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Abstract

An isotope dilution (ID) procedure for the determination of methylmercury (MMHg) in biological samples using an inductively coupled plasma mass spectrometer as detector after the capillary gas chromatographic separation (CGC/ICPMS) has been developed. For the first time, open-focused-microwave pretreatment has been used in conjunction with ID. Optimum conditions for the measurement of isotope ratios on the fast transient chromatographic peaks have been established. Mass bias was found to be about 1.5%/mass unit and was corrected by using the simultaneously measured thallium signals at Tl-203 and Tl-205. After mass-bias correction, deviation of the theoretical mercury ratio values was found to be as low as 0.2%. Isotope ratio precisions based on the peak areas measurements were 0.3% RSD for 20 pg injected (as Hg absolute). The absolute detection limits were in the range of 20-30 fg for Hg-202 and Hg-201. Methylmercury enriched in Hg-201 has been synthesized by direct reaction with methylcobalamine. The concentration of the MMHg spike has been measured by reverse isotope dilution with a natural MMHg standard. The capabilities of CGC/ICPMS to measure isotope ratios were used to optimize sample derivatization by aqueous ethylation with NaBEt4 with respect to MMHg degradation pathways and quantitative recovery. The accuracy of the method developed has been validated with biological certified reference materials (CRM-463, DORM-1).

Original languageEnglish
Pages (from-to)2505-2512
Number of pages8
JournalAnalytical Chemistry
Volume74
Issue number11
DOIs
Publication statusPublished - 1 Jun 2002

Keywords

  • INDUCTIVELY-COUPLED PLASMA
  • ATOMIC FLUORESCENCE SPECTROMETRY
  • ICP-MS DETECTION
  • MASS-SPECTROMETRY
  • HYDRIDE GENERATION
  • MERCURY SPECIATION
  • MONOMETHYLMERCURY CH3HG+
  • ABSORPTION SPECTROMETRY
  • ENVIRONMENTAL-SAMPLES
  • RATIO MEASUREMENTS

Cite this

Application of isotopically labeled methylmercury for isotope dilution analysis of biological samples using gas chromatography/ICPMS. / Martin-Doimeadios, R C R ; Krupp, Eva Maria; Amouroux, D ; Donard, O F X .

In: Analytical Chemistry, Vol. 74, No. 11, 01.06.2002, p. 2505-2512.

Research output: Contribution to journalArticle

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abstract = "An isotope dilution (ID) procedure for the determination of methylmercury (MMHg) in biological samples using an inductively coupled plasma mass spectrometer as detector after the capillary gas chromatographic separation (CGC/ICPMS) has been developed. For the first time, open-focused-microwave pretreatment has been used in conjunction with ID. Optimum conditions for the measurement of isotope ratios on the fast transient chromatographic peaks have been established. Mass bias was found to be about 1.5{\%}/mass unit and was corrected by using the simultaneously measured thallium signals at Tl-203 and Tl-205. After mass-bias correction, deviation of the theoretical mercury ratio values was found to be as low as 0.2{\%}. Isotope ratio precisions based on the peak areas measurements were 0.3{\%} RSD for 20 pg injected (as Hg absolute). The absolute detection limits were in the range of 20-30 fg for Hg-202 and Hg-201. Methylmercury enriched in Hg-201 has been synthesized by direct reaction with methylcobalamine. The concentration of the MMHg spike has been measured by reverse isotope dilution with a natural MMHg standard. The capabilities of CGC/ICPMS to measure isotope ratios were used to optimize sample derivatization by aqueous ethylation with NaBEt4 with respect to MMHg degradation pathways and quantitative recovery. The accuracy of the method developed has been validated with biological certified reference materials (CRM-463, DORM-1).",
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N2 - An isotope dilution (ID) procedure for the determination of methylmercury (MMHg) in biological samples using an inductively coupled plasma mass spectrometer as detector after the capillary gas chromatographic separation (CGC/ICPMS) has been developed. For the first time, open-focused-microwave pretreatment has been used in conjunction with ID. Optimum conditions for the measurement of isotope ratios on the fast transient chromatographic peaks have been established. Mass bias was found to be about 1.5%/mass unit and was corrected by using the simultaneously measured thallium signals at Tl-203 and Tl-205. After mass-bias correction, deviation of the theoretical mercury ratio values was found to be as low as 0.2%. Isotope ratio precisions based on the peak areas measurements were 0.3% RSD for 20 pg injected (as Hg absolute). The absolute detection limits were in the range of 20-30 fg for Hg-202 and Hg-201. Methylmercury enriched in Hg-201 has been synthesized by direct reaction with methylcobalamine. The concentration of the MMHg spike has been measured by reverse isotope dilution with a natural MMHg standard. The capabilities of CGC/ICPMS to measure isotope ratios were used to optimize sample derivatization by aqueous ethylation with NaBEt4 with respect to MMHg degradation pathways and quantitative recovery. The accuracy of the method developed has been validated with biological certified reference materials (CRM-463, DORM-1).

AB - An isotope dilution (ID) procedure for the determination of methylmercury (MMHg) in biological samples using an inductively coupled plasma mass spectrometer as detector after the capillary gas chromatographic separation (CGC/ICPMS) has been developed. For the first time, open-focused-microwave pretreatment has been used in conjunction with ID. Optimum conditions for the measurement of isotope ratios on the fast transient chromatographic peaks have been established. Mass bias was found to be about 1.5%/mass unit and was corrected by using the simultaneously measured thallium signals at Tl-203 and Tl-205. After mass-bias correction, deviation of the theoretical mercury ratio values was found to be as low as 0.2%. Isotope ratio precisions based on the peak areas measurements were 0.3% RSD for 20 pg injected (as Hg absolute). The absolute detection limits were in the range of 20-30 fg for Hg-202 and Hg-201. Methylmercury enriched in Hg-201 has been synthesized by direct reaction with methylcobalamine. The concentration of the MMHg spike has been measured by reverse isotope dilution with a natural MMHg standard. The capabilities of CGC/ICPMS to measure isotope ratios were used to optimize sample derivatization by aqueous ethylation with NaBEt4 with respect to MMHg degradation pathways and quantitative recovery. The accuracy of the method developed has been validated with biological certified reference materials (CRM-463, DORM-1).

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KW - MASS-SPECTROMETRY

KW - HYDRIDE GENERATION

KW - MERCURY SPECIATION

KW - MONOMETHYLMERCURY CH3HG+

KW - ABSORPTION SPECTROMETRY

KW - ENVIRONMENTAL-SAMPLES

KW - RATIO MEASUREMENTS

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