A Traceable Calibration for Gaseous Elemental Mercury Measurements in Air and Water

Calibration is crucial in quantitative analysis, ensuring the traceability of standards for an accurate comparison of results. In mercury determinations, a gas calibrator unit containing liquid mercury is used for calibration by injecting headspace volumes via syringe. The Dumarey equation has been used for over 35 years to calculate mercury headspace concentration, aligning closely with saturated vapor pressure equations. However, the 2006 Huber equation yields different values, creating discrepancies. This paper compares calibrations using the Dumarey equations against NIST 3133 certified reference material, with detection by a cold vapor atomic fluorescence spectrophotometer (CV-AFS). The gas standard was injected directly, while HgII in NIST 3133 was reduced to Hg0 and captured on gold traps. Across 10–24 °C, the Hg0 concentration was determined, with uncertainties ranging from 2.9% to 8.4% for a coverage factor of two. No significant differences were found between calibrations using NIST 3133 and the Dumarey equation. These findings provide crucial insights into the traceability and accuracy of mercury calibration methods, ensuring the reliability of measurements used for environmental monitoring and regulatory compliance.