21 Sep 2023
 | 21 Sep 2023
Status: a revised version of this preprint was accepted for the journal AMT.

Traceable and continuous flow calibration method for gaseous elemental mercury at low ambient concentrations

Teodor D. Andron, Warren T. Corns, Igor Živković, Saeed W. Ali, Sreekanth Vijayakumaran Nair, and Milena Horvat

Abstract. The monitoring of low gaseous elemental mercury (GEM) concentrations in the atmosphere requires continuous high-resolution measurements and corresponding calibration capabilities. Currently, continuous calibration for GEM is still an issue at ambient concentrations (1–2 ng m−3). This paper presents a continuous flow calibration for GEM, traceable to NIST 3133 Standard Reference Material (SRM). This calibration approach was tested using a direct mercury analyser based on atomic absorption spectrometry with Zeeman background correction (Zeeman AAS). The produced continuous flow of GEM standard was obtained through reduction of Hg2+ from liquid SRM NIST 3133 and used for traceable calibration of Zeeman AAS. Measurements of atmospheric GEM using the calibrated Zeeman AAS were compared with two methods: manual gold amalgamation atomic fluorescence spectrometry (AFS) calibrated with the chemical reduction of NIST 3133 and automated gold amalgamation AFS calibrated using the mercury bell-jar syringe technique. The comparisons showed that factory-calibrated Zeeman AAS underestimates concentrations under 10 ng m−3 by up to 35 % relative to the two other methods of determination. However, when a calibration based on SRM NIST 3133 was used to perform a traceable calibration of Zeeman AAS, the results were more comparable with other methods. The expanded relative combined uncertainty for Zeeman AAS ranged from 8 % for measurements at the 40 ng m−3 level to 91.6 % for concentrations under 5 ng m−3 using the newly developed calibration system. High uncertainty for measurements performed under 5 ng m−3 was due mainly to instrument noise and concentration variation in the samples.

Teodor D. Andron et al.

Status: final response (author comments only)

Comment types: AC – author | RC – referee | CC – community | EC – editor | CEC – chief editor | : Report abuse
  • RC1: 'Comment on amt-2023-169', Anonymous Referee #2, 11 Oct 2023
    • AC1: 'Reply on RC1', Teodor Andron, 18 Oct 2023
  • RC2: 'Comment on amt-2023-169', Anonymous Referee #2, 11 Oct 2023
    • AC2: 'Reply on RC2', Teodor Andron, 18 Oct 2023
  • RC3: 'Comment on amt-2023-169', Anonymous Referee #1, 12 Oct 2023
    • AC3: 'Reply on RC3', Teodor Andron, 23 Oct 2023

Teodor D. Andron et al.

Teodor D. Andron et al.


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Short summary
Atmospheric mercury monitoring is an important activity in order to model the global trajectory of this toxic element and to assess if certain areas are polluted or not in accordance to global guidelines. One of the analysers tested in this work is globally used in this regards due to its practicality compared to other devices. Because it is only calibrated at the manufacturer at very high concentrations, we wanted to see how it performs at ambient mercury concentrations.