Traceable Calibration of Atmospheric Oxidized Mercury Measurements

Most previous measurements of oxidized mercury were collected using a method now known to be biased low. In this study, a dual-channel system with an oxidized mercury detection limit of 6-12 pg m^-3 was deployed alongside a permeation tube-based automated calibrator at a mountain top site in Steamboat Springs Colorado, USA, in 2021 and 2022. Permeation tubes containing elemental mercury and mercury halides were characterized via an International System of Units (SI)-traceable gravimetric method and gas chromatography/mass spectrometry before deployment in the calibrator. The dual-channel system recovered 97 ± 4 and 100 ± 8% (±standard deviation) of injected elemental mercury and HgBr₂, respectively. Total Hg permeation rates and Hg speciation from the gravimetric method, the chromatography system, the dual-channel system, and an independent SI-traceable measurement method performed at the Jožef Stefan Institute laboratory were all comparable within the respective uncertainties of each method. These are the first measurements of oxidized mercury at low environmental concentrations that have been verified against an SI-traceable calibration system in field conditions while sampling ambient air, and they show that accurate, routinely calibrated oxidized mercury measurements are achievable.