Hg Compound-Specific Isotope Analysis at Ultratrace Levels Using an on Line Gas Chromatographic Preconcentration and Separation Strategy Coupled to Multicollector-Inductively Coupled Plasma Mass Spectrometry

Stable Hg isotope analyses are nowadays widely employed to discriminate Hg sources and understand its biogeochemical cycle. Until now, total Hg isotopic compositions have been mainly used but Hg compound-specific isotopic analysis (CSIA) methodologies are emerging. Online Hg-CSIA were limited to samples containing high concentrations, but in this work we overcome this limitation for the measurement of inorganic (IHg) and monomethylmercury (MMHg) by gas chromatography hyphenated to multicollector-inductively coupled plasma mass spectrometry (GC/MC-ICPMS) through the use of an automated online preconcentration strategy, allowing injection volumes up to 100 times larger than usual. The preconcentration of Hg species and subsequent transfer to the column were achieved by a programmed temperature vaporization (PTV) injector fitted with a packed liner. The PTV parameters were first optimized using a quadrupole ICPMS, and then its suitability for Hg-CSIA was evaluated with long-term replicate analysis of various standards and reference materials (RMs). The large preconcentration capability enables analyses with Hg concentrations in the organic solvent 2 orders of magnitude lower than the previous conventional GC/MC-ICPMS method, but a compound specific standard bracketing procedure was required for MMHg in order to correct for the differential behavior of Hg species in the liner. The external reproducibility of the method ranged from 0.19 to 0.39 ‰ for Δ¹⁹⁹Hg and δ²⁰²Hg (as 2 SD, n = 143–167) depending on the species. The analysis of various RMs demonstrated the applicability to environmental samples with species concentrations down to about 150 ng g^–1. This new methodology opens the way for a much wider range of online Hg-CSIA measurements that will improve our understanding of the Hg biogeochemical cycle.