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...

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Main Authors: Teodor D. Andron, Warren T. Corns, Matthew A. Dexter, Igor Živković, Jože Kotnik, Milena Horvat
Format: Article
Language:English
Published: MDPI AG 2025-04-01
Series:Atmosphere
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Online Access:https://www.mdpi.com/2073-4433/16/4/421
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author Teodor D. Andron
Warren T. Corns
Matthew A. Dexter
Igor Živković
Jože Kotnik
Milena Horvat
author_facet Teodor D. Andron
Warren T. Corns
Matthew A. Dexter
Igor Živković
Jože Kotnik
Milena Horvat
author_sort Teodor D. Andron
collection DOAJ
description 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 Hg<sup>II</sup> in NIST 3133 was reduced to Hg<sup>0</sup> and captured on gold traps. Across 10–24 °C, the Hg<sup>0</sup> 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.
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spelling doaj-art-1f0be10077e9444ca50e47ad5bbccfbd2025-08-20T03:14:16ZengMDPI AGAtmosphere2073-44332025-04-0116442110.3390/atmos16040421A Traceable Calibration for Gaseous Elemental Mercury Measurements in Air and WaterTeodor D. Andron0Warren T. Corns1Matthew A. Dexter2Igor Živković3Jože Kotnik4Milena Horvat5Jožef Stefan International Postgraduate School, Jamova cesta 39, 1000 Ljubljana, SloveniaP S Analytical, Arthur House, Crayfields Industrial Estate, Main Road, Orpington, Kent BR5 3HP, UKP S Analytical, Arthur House, Crayfields Industrial Estate, Main Road, Orpington, Kent BR5 3HP, UKJožef Stefan International Postgraduate School, Jamova cesta 39, 1000 Ljubljana, SloveniaJožef Stefan International Postgraduate School, Jamova cesta 39, 1000 Ljubljana, SloveniaJožef Stefan International Postgraduate School, Jamova cesta 39, 1000 Ljubljana, SloveniaCalibration 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 Hg<sup>II</sup> in NIST 3133 was reduced to Hg<sup>0</sup> and captured on gold traps. Across 10–24 °C, the Hg<sup>0</sup> 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.https://www.mdpi.com/2073-4433/16/4/421mercurymetrologyuncertainty
spellingShingle Teodor D. Andron
Warren T. Corns
Matthew A. Dexter
Igor Živković
Jože Kotnik
Milena Horvat
A Traceable Calibration for Gaseous Elemental Mercury Measurements in Air and Water
Atmosphere
mercury
metrology
uncertainty
title A Traceable Calibration for Gaseous Elemental Mercury Measurements in Air and Water
title_full A Traceable Calibration for Gaseous Elemental Mercury Measurements in Air and Water
title_fullStr A Traceable Calibration for Gaseous Elemental Mercury Measurements in Air and Water
title_full_unstemmed A Traceable Calibration for Gaseous Elemental Mercury Measurements in Air and Water
title_short A Traceable Calibration for Gaseous Elemental Mercury Measurements in Air and Water
title_sort traceable calibration for gaseous elemental mercury measurements in air and water
topic mercury
metrology
uncertainty
url https://www.mdpi.com/2073-4433/16/4/421
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