Extending the application range of hg isotopic analysis to sub-μg l−1 levels using cold vapor generation multi-collector inductively coupled plasma-mass spectrometry with 1013 ohm faraday cup amplifiers
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High-precision determination of the isotopic composition of mercury (Hg) is of paramount importance for unraveling its biogeochemical cycle and for identifying the origin of Hg in environmental compartments. Cold vapor generation multi-collector inductively coupled plasma-mass spectrometry (CVG-MC-ICPMS) is the standard approach for such application. Cold vapor generation provides a high Hg introduction efficiency into the ICP, while chromatographic Hg isolation is not required as a result of the selective reaction between Hg2+ and SnCl2. For environmental or biota samples with low Hg concentrations, however, this approach still presents challenges and reliable measurements typically require a Hg concentration $1 mg L−1 in the solution analyzed. Recent improvements of MC-ICP-MS instrumentation, including the introduction of the so-called Jet interface and 1013 U Faraday cup amplifiers, enhance the signal-to-noise ratio. In this study, it was investigated to what extent this allows Hg isotopic analysis at lower concentration. Performance in Hg isotopic analysis was compared using two different sets of cones (standard vs. Jet), two plasma conditions (wet vs. dry) and two amplifier types (1011 U vs. 1013 U). Satisfactory accuracy and precision were achieved at a Hg concentration down to 0.1 mg L−1 in the solution measured when using Jet cones, dry plasma conditions, and the four available 1013 U amplifiers. The uncertainty expressed as 2SD for the d202Hg values measured for the in-house standard solution was ±0.2& at 0.25 mg Hg L−1 and ± 0.3& at 0.1 mg Hg L−1 . The method was subsequently applied to the analysis of real surface water samples contaminated with toxic metals.
High-precision determination of the isotopic composition of mercury (Hg) is of paramount importance for unraveling its biogeochemical cycle and for identifying the origin of Hg in environmental compartments. Cold vapor generation multi-collector inductively coupled plasma-mass spectrometry (CVG-MC-ICPMS) is the standard approach for such application. Cold vapor generation provides a high Hg introduction efficiency into the ICP, while chromatographic Hg isolation is not required as a result of the selective reaction between Hg2+ and SnCl2. For environmental or biota samples with low Hg concentrations, however, this approach still presents challenges and reliable measurements typically require a Hg concentration $1 mg L−1 in the solution analyzed. Recent improvements of MC-ICP-MS instrumentation, including the introduction of the so-called Jet interface and 1013 U Faraday cup amplifiers, enhance the signal-to-noise ratio. In this study, it was investigated to what extent this allows Hg isotopic analysis at lower concentration. Performance in Hg isotopic analysis was compared using two different sets of cones (standard vs. Jet), two plasma conditions (wet vs. dry) and two amplifier types (1011 U vs. 1013 U). Satisfactory accuracy and precision were achieved at a Hg concentration down to 0.1 mg L−1 in the solution measured when using Jet cones, dry plasma conditions, and the four available 1013 U amplifiers. The uncertainty expressed as 2SD for the d202Hg values measured for the in-house standard solution was ±0.2& at 0.25 mg Hg L−1 and ± 0.3& at 0.1 mg Hg L−1 . The method was subsequently applied to the analysis of real surface water samples contaminated with toxic metals.
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Laura Suárez-Criado acknowledges the Principality of Asturias, Spain, for their financial support through the Severo Ochoa scholarship ref. BP19-131 and the Banco Santander for the financial support through “Ayudas de movilidad de excelencia para docentes e investigadores”. The Spanish Ministry of Science and Innovation is acknowledged for the funding through Project MCIU-22-PID2021-125795NB-I00. The authors would also like to thank José Ignacio Calvelo Chouza (Empresa Municipal de Aguas de Gijón S. A.) for the assistance provided during sample collection. E. B.-F. acknowledges financial support from the Ramón y Cajal programme (RYC2021-031093-I) funded by MCIN/AEI/10.13039/501100011033 and the European Union (NextGenerationEU/PRTR), the grant PID2021-122455NB-I00, funded by MCIN/AEI/10.13039/501100011033 and by “ERDF A way of making Europe”, and also the Aragón Government (DGA, Construyendo Europa desde Aragón, Grupo E43_20R). The Research Foundation FWO-Vlaanderen is acknowledged for providing the funding for the acquisition of the MC-ICP-MS instrumentation and its installation at the A&MS research group at Ghent University (ZW15-02 – G0H6216N).
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