Understanding atmospheric mercury chemistry is the key for explaining the biogeochemical cycle of mercury and for improving the predictive capability of computational models. Increased efforts are being made to ensure comparable Hg speciation measurements in the air through establishing metrological traceability. While traceability for elemental mercury has been recently set, this is by no means the case for gaseous oxidized mercury (GOM). Since a calibration unit suitable for traceable GOM calibrations based on evaporation of HgCl₂ solution was recently developed, the purpose of our work was to extensively evaluate its performance. A highly specific and sensitive ¹⁹⁷Hg radiotracer was used for validation over a wide range of concentrations. By comparing experimental and calculated values, we obtained recoveries for the calibration unit. The average recoveries ranged from 88.5% for 1178 ng m⁻³ HgCl₂ gas concentration to 39.4% for 5.90 ng m⁻³ HgCl₂ gas concentration. The losses were due to the adsorption of oxidized Hg on the inner walls of the calibrator and tubing. An adsorption isotherm was applied to estimate adsorption enthalpy (ΔH_ads); a ΔH_ads value of −12.33 kJ mol⁻¹ was obtained, suggesting exothermal adsorption. The results of the calibrator performance evaluation suggest that a newly developed calibration unit is only suitable for concentrations of HgCl₂ higher than 1 µg m⁻³. The concentration dependence of recoveries prevents the system from being used for calibration of instruments for ambient GOM measurements. Moreover, the previously assessed uncertainty of this unit at µg m⁻³ level (2.0%, k = 2) was re-evaluated by including uncertainty related to recovery and was found to be 4.1%, k = 2. Calibrator performance was also evaluated for HgBr₂ gas calibration; the recoveries were much lower for HgBr₂ gas than for HgCl₂ gas even at a high HgBr₂ gas concentration (>1 µg m⁻³). As HgBr₂ is often used as a proxy for various atmospheric HgBr species, the suitability of the unit for such calibration must be further developed.

Traceable determination of atmospheric mercury (Hg) represents a major analytical problem due to low environmental concentrations. Although Hg pre-concentration on activated carbon (AC) traps is a simple method for sample collection, Hg determination is difficult due to a complex matrix that cannot be easily digested using wet chemistry. Two approaches for Hg loading on iodinated AC, the purging of elemental mercury (Hg⁰) and the spiking a solution of standard reference material (SRM), were used to test whether spiking SRM solution on AC can be used for the traceable determination of atmospheric mercury collected as Hg⁰. Mercury on AC was determined using atomic absorption spectrometry after sample combustion. The detector’s response for both loading methods was identical in a wide concentration range, indicating that the spiking of SRM on AC can, indeed, be used for the calibration of analytical systems used for the determination of atmospheric mercury. This was confirmed by the determination of Hg in a real atmospheric sample collected on an iodinated AC trap and using an SRM spiking calibration. Different ACs were compared regarding their ability to quantitatively capture Hg while having the lowest breakthrough. Use of a specific impregnating solution probably converted Hg on AC to Millon’s iodide, as estimated from the fractionation thermogram.

Continuous dissolved gaseous mercury (DGM) measurements were performed during the summer months (May to September 2019) in the Gulf of Trieste (northern Adriatic Sea), a well-studied contaminated site due to releases of mercury from the former mercury mine Idrija in Slovenia. Continuous DGM data were regularly checked by the discrete manual method to assure traceability and comparability of the results and used for the calculation of the upward flux of Hg(0) between the water and the air compartment, using the gas exchange model applied in previous studies in the Mediterranean Sea. DGM concentrations measured by continuous and discrete methods showed good agreement, 68.7 and 73.5 ng·m⁻³, respectively. The diurnal DGM variability examined by sorting the DGM concentrations in 24 1-h intervals was extremely low (68.3–69.2 ng·m⁻³). Various environmental parameters measured at oceanographic buoy Vida, and the nearby stations were used to determine the relationship between DGM and the individual environmental parameters. The correlation with the oxygen saturation was pronounced during the July high DGM event (R² = 0.70, p < 0.05), and the gradient between the bottom and surface temperature was correlated with both DGM peaks in June and July (R² = 0.42 and R² = 0.43, p < 0.05). Transport from the more polluted northern part of the Gulf was determined as the most probable source of both high DGM events. The computed average annual Hg(0) flux across the water–air interface (5.13 ng·m⁻²·h⁻¹) was lower than those reported in recent studies. We assume that for an appropriate assessment of the Hg evasion flux and of the temporal DGM variability in such heterogeneously polluted coastal areas, both spatial and temporal coverage are required.