A new approach was demonstrated for the isotope ratio measurement in different elemental species of Hg using transient signal obtained by chromatography coupled with multicollector-inductively coupled plasma mass spectrometry (MC-ICPMS). The method based on the slope of linear regression by transient intensities of different isotopes shows improved accuracy and reproducibility (0.2-0.5 parts per thousand as 2 standard deviation (SD)). Internal precision (RSD) of the method is very close to the theoretical value given by the counting statistic and is better by a factor of 6 in comparison with previous conventional methods of calculation. We demonstrated that internal RSD (uncertainty) depends on regression coefficients of the linear function (R-2). The typical internal precision of isotopic ratio measurements (0.003-0.02%) was achieved for delta Hg-202 when injecting as low as 90 pg of Hg species. With the new methodology, it is possible to (i) measure the isotopic composition when a sample and a bracketing standard have significantly different concentrations, (ii) measure the isotopic composition of different species in samples versus single species in a bracketing standard, and (iii) measure the isotopic ratios for low abundant isotopes. We demonstrated application of this method for different environmental samples and processes.
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