This study provides a review of 13 oceanographic campaigns between 2000 and 2017 to measure Hg in the Mediterranean, highlighting major findings from measurement and modelling activities during the Med-Oceanor program. The initial campaigns showed that high concentrations of RGM could be found far from industrial source regions and the observed daily variation in concentration, with peaks at midday and lower concentrations during darkness gave the first indications that photochemically mediated oxidation reactions were producing RGM in the MBL. Later atmospheric chemistry modelling studies showed the feasibility of Hg oxidation by bromine containing oxidants, which are released as a result of the acidification of sea salt aerosols in the Marine Boundary Layer (MBL). Spatial and seasonal variations of DGM were observed at different depths in the water column, with average DGM concentrations higher in the West and East Mediterranean deep and intermediate waters, than in overlaying Atlantic waters. DGM in water profiles typically increased with depth, together with nutrients and decreasing oxygen, indicating a possible bacterial and/or geogenic origin. Using measured DGM and meteorological variable values Hg fluxes can be calculated. When these are included in regional and global models they suggest that the net Hg evasion from the Mediterranean is around 30 Mg yr-1. Repetition of these campaigns should be an extremely high priority, both to continue to monitor changes in atmospheric and aquatic Hg species concentrations, but also to perform RGM detection methodology intercomparisons so that the historical data is adequately contextualised and may be used to evaluate temporal trends.

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.

Background: The current speciation methods for mercury (Hg) measurements are fraught with considerable uncertainty, from sample collection to calibration. High reactivity of gaseous oxidized Hg (GOM) species and their ultra-trace level presence makes them difficult to sample and calibrate. Given that improper calibration may lead to measurement biases, reliable and metrologically traceable calibration methods are required for accurately quantifying GOM in air. In the present study, we applied the recently developed calibration method based on non-thermal plasma oxidation of elemental Hg, to a commercially available Hg air speciation system for actual environmental measurements of GOM for the first time. Results: Hg species such as HgO, HgCl2, and HgBr2 were produced with trace amounts of reactant gases (oxygen and electrolytically produced chlorine and bromine) and the production was driven by plasma-assisted oxidation. The plasma oxidation efficiency of elemental Hg with oxygen was 98.5 +/- 7.5 % (k = 2), while that for chlorine and bromine was 96.8 +/- 6.9 % (k = 2) and 97.4 +/- 9.6 % (k = 2), respectively. The calibration method was tested against the internal permeation (Hg-0) source of the Tekran 2537B Hg analyzer on-field by loading HgO to different KCl-coated denuders using the plasma. GOM concentrations were measured using the Tekran speciation system. With internal calibration, concentrations were up to 9.1 % lower than those in plasma calibration, thereby emphasizing the importance of the calibration strategy. Measurement uncertainty (k = 2) further emphasizes this distinction. Internal calibration measurement uncertainty was 36.8 %, while plasma calibration boasted lower uncertainty at 13.8 %. Significance: The non-thermal plasma calibration strategy, as a unique and discrete calibration method traceable to the NIST SRM 3133 for ambient air GOM measurements, provide a higher level of confidence in the accuracy of GOM measurements with several advantages over other methods. Calibrations at extreme low concentrations (<100 pg) are possible with this method relevant to ambient air GOM concentrations.

The number of atmospheric mercury (Hg) monitoring stations is growing globally. However, there are still many regions and locations where Hg monitoring is limited or non-existent. Expansion of the atmospheric Hg monitoring network could be facilitated by the use of cost-effective monitoring methods. As such, biomonitoring and passive monitoring offer a unique alternative to well-established monitoring by active measurements, since they do not require a power supply and require minimal workload to operate. The use of biomonitoring (lichens and mosses) and passive air samplers (PASs) (various designs with synthetic materials) has been reported in the literature, and comparisons with active measurement methods have also been made. However, these studies compared either biomonitoring or PASs (not both) to only one type of active measurement. In our work, we used transplanted (7 sampling sites) and in situ lichens (8 sampling sites) for biomonitoring, two PASs from different producers (3 sampling sites), and two different active measurement types (continuous and discontinuous active measurements, 1 and 8 sampling sites, respectively) to evaluate their effectiveness as monitoring methods. In the 9-month sampling campaign, 3 sampling locations with different characteristics (unpolluted, vicinity of a cement plant, and vicinity of a former Hg mine) were used. The results obtained with lichens and PASs clearly distinguished between sampling locations with different Hg concentrations; using both PASs and lichens together increased the confidence of our observations. The present work shows that biomonitoring and passive sampling can be effectively used to identify areas with elevated atmospheric Hg concentrations. The same can be said for discontinuous active measurements; however, the discrepancy between atmospheric Hg concentrations derived from PASs and discontinuous active measurements should be further investigated in the future.

Underground coal extraction at Coal Mine Velenje occasionally gives rise to odour complaints from local residents. This manuscript describes a robust quantification of odorous emissions of mine sources and a model-based analysis aimed to establish a better understanding of the sources, concentrations, dispersion, and possible control of odorous compounds during coal extraction process. Major odour sources during underground mining are released volatile sulphur compounds from coal seam that have characteristic malodours at extremely low concentrations at micrograms per cubic metre (μg/m3) levels. Analysis of 1028 gas samples taken over a 6-year period (2008–2013) reveals that dimethyl sulphide ((CH3)2S) is the major odour active compound present in the mine, being detected on 679 occasions throughout the mine, while hydrogen sulphide (H2S) and sulphur dioxide (SO2) were detected 5 and 26 times. Analysis of gas samples has shown that main DMS sources in the mine are coal extraction locations at longwall faces and development headings and that DMS is releasing during transport from main coal transport system. The dispersion simulations of odour sources in the mine have shown that the concentrations of DMS at median levels can represent relatively modest odour nuisance. While at peak levels, the concentration of DMS remained sufficiently high to create an odour problem both in the mine and on the surface. Overall, dispersion simulations have shown that ventilation regulation on its own is not sufficient as an odour abatement measure.

Atmospheric mercury, specifically oxidized mercury (HgII), is the largest anthropogenic pool of mercury in the atmosphere. This type of mercury can accumulate in the food chain after undergoing methylation and entering ecosystems through wet and dry deposition. It is important to evaluate the level of wet and dry deposition, but measurements of atmospheric mercury have been biased due to insufficient consideration of measurement uncertainty and metrological traceability, especially for low ambient concentrations of gaseous HgII species. To address this issue, a calibration method for HgII species has been presented based on atmospheric pressure non-equilibrium plasma oxidation of Hg0 to HgII. Hg0 is generated by reducing HgII in aqueous solution by SnCl2 and aeration, then oxidized to different HgII species using He plasma with traces of different reactive gases. The non-equilibrium plasma oxidation efficiencies, with corresponding expanded standard uncertainty values, were evaluated using a highly sensitive radiotracer. The efficiencies were found to be 100.5 ± 4.7% (k = 2) for 100 pg of HgO, 96.8 ± 7.3% (k = 2) for 250 pg of HgCl2, and 77.3 ± 9.4% (k = 2) for 250 pg of HgBr2. The presence of HgO, HgCl2, and HgBr2 was confirmed by temperature-programmed desorption quadrupole mass spectrometry (TPD-QMS). The results demonstrate the potential of non-equilibrium plasma oxidation for reliable calibration of ambient air measurement instrumentation, leading to a better understanding of the sources, transport, and fate of this toxic pollutant in the environment. Knowing the chemistry and composition of atmospheric HgII species is crucial for assessing the extent of dry and wet deposition and mitigating the negative impacts of mercury pollution on human health and the environment.

Biomonitoring of mercury (Hg) in the air using transplanted and in-situ lichens were studied at three locations in Slovenia: 1) the former Hg mine Idrija, with known Hg contamination; 2) vicinity of a Hg point source of pollution near the cement production plant in Anhovo, and 3) a noncontaminated reference site at Pokljuka. Total Hg concentrations and Hg isotopic composition were measured. Lichens were transplanted from Pokljuka, exposed at different sites in three locations and sampled four times, once per season. Lichens were exposed under tree branches, on fences and also under cover, allowing them different exposure to natural light. Additionally, the in situ lichens were sampled at the beginning and the end of the one year sampling period. As expected, the trend of concentrations in transplanted lichens increased over time, especially in the area of Idrija, and significantly less in the area of Anhovo, which is consistent with previous research. Significant mass dependent fractionation has been observed in transplanted lichens. δ202Hg changed from winter to summer from -2.5 to -0.5 ‰ and dropped again to -2.5 in autumn/winter of the following year. The most likely mechanism for this is Hg reduction (biotic or abiotic) and / or Hg evaporation in summer due to elevated temperatures, leaving heavier isotopes on the lichen thalli. The in situ lichens that were sampled one year apart show no major changes in isotopic composition. Such a trend has been observed in all of the samples apart from the ones from the most polluted Idrija sampling site directly above the former smelting plant. This is probably due to the new Hg constantly being deposited to the lichen with local isotopic fingerprint. Small mass independent fractionation was observed, likely due to photo-reduction as was concluded in similar foliage studies, but no trends in its change over time were seen.

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.

The main purpose of this work was to assess the potential of using temperature-programmed desorption coupled to quadrupole mass spectrometry to study the mercury partitioning in the cement production. This information is of significance to understanding mercury's migration and partitioning in the production process. In conventional raw materials-limestone, mercury is matrix-bound, but with the introduction of other mineral components, this stability is variable. In raw mills, mercury exhibits three distinct fractions that remain until the raw meal is dispatched in the preheater. Mercury collected in dust from fabric filters was desorbed at 200-250 C, indicating the presence of chloro-containing mercury compounds to be the predominant form. Clinker had a low content of mercury primarily present as a very stable fraction. These results add to the current knowledge of mercury behavior in the cement production process and can be used to support the development of control technologies.

Mercury (Hg) in seawater is subject to interconversions via (photo)chemical and (micro)biological processes that determine the extent of dissolved gaseous mercury (DGM) (re)emission and the production of monomethylmercury. We investigated Hg speciation in the South Atlantic Ocean on a GEOTRACES cruise along a 40 degrees S section between December 2011 and January 2012 (354 samples collected at 24 stations from surface to 5250 m maximum depth). Using statistical analysis, concentrations of methylated mercury (MeHg, geometric mean 35.4 fmol L-1) were related to seawater temperature, salinity, and fluorescence. DGM concentrations (geometric mean 0.17 pmol L-1) were related to water column depth, concentrations of macronutrients and dissolved inorganic carbon (DIC). The first-ever observed linear correlation between DGM and DIC obtained from high-resolution data indicates possible DGM production by organic matter remineralization via biological or dark abiotic reactions. DGM concentrations projected from literature DIC data using the newly discovered DGM-DIC relationship agreed with published DGM observations.

Atmospheric mercury measurements carried out in the recent decades have been a subject of bias largely due to insufficient consideration of metrological traceability and associated measurement uncertainty, which are ultimately needed for the demonstration of comparability of the measurement results. This is particularly challenging for gaseous HgII species, which are reactive and their ambient concentrations are very low, causing difficulties in proper sampling and calibration. Calibration for atmospheric HgII exists, but barriers to reliable calibration are most evident at ambient HgII concentration levels. We present a calibration of HgII species based on nonthermal plasma oxidation of Hg0 to HgII. Hg0 was produced by quantitative reduction of HgII in aqueous solution by SnCl2 and aeration. The generated Hg0 in a stream of He and traces of reaction gas (O2, Cl2, or Br2) was then oxidized to different HgII species by nonthermal plasma. A highly sensitive 197Hg radiotracer was used to evaluate the oxidation efficiency. Nonthermal plasma oxidation efficiencies with corresponding expanded standard uncertainty values were 100.5 ± 4.7% (k = 2) for 100 pg of HgO, 96.8 ± 7.3% (k = 2) for 250 pg of HgCl2, and 77.3 ± 9.4% (k = 2) for 250 pg of HgBr2. The presence of HgO, HgCl2, and HgBr2 was confirmed by temperature-programmed desorption quadrupole mass spectrometry (TPD-QMS). This work demonstrates the potential for nonthermal plasma oxidation to generate reliable and repeatable amounts of HgII compounds for routine calibration of ambient air measurement instrumentation.

The cement industry is the second largest source of anthropogenic mercury (Hg) emissions in Europe, accounting for 11% of global anthropogenic Hg emissions. The main objective of this study was to examine the influence of Hg emissions from the Salonit Anhovo cement plant on Hg levels measured in the ambient air at Vodarna, 1 km downwind from the flue gas chimney. The findings reveal that the plant raw mill operational status plays an important role in Hg concentrations in the flue gas emitted from the plant. Emitted total gaseous mercury was, on average, higher (49.4 μg/m3) when raw mills were in the direct mode (both raw mills-off) and lower (23.4 μg/m3) in the combined mode (both raw mills-on). The average Hg concentrations in Vodarna were 3.14 ng/m3 for gaseous elemental mercury, 53.7 pg/m3 for gaseous oxidised mercury, and 41.9 pg/m3 for particulate bound mercury for the whole measurement period. Atmospheric Hg speciation in Vodarna, coupled with plant emissions and wind data, has revealed that the total gaseous mercury emitted from the cement plant is clearly related to all Hg species measured in Vodarna. Wind blowing from the northeastern quadrant (mostly NE, ENE) is responsible for the elevated Hg levels in Vodarna, where gaseous oxidised mercury levels are highly linked to the cement plant emissions. However, elevated levels of Hg species in the absence of northeastern winds indicate potential inputs from other unknown local sources as well as inputs from regional and global transport mechanisms.

The cement industry is the second largest source of anthropogenic mercury (Hg) emissions in Europe, accounting for 11% of global anthropogenic Hg emissions. The main objective of this study was to examine the influence of Hg emissions from the Salonit Anhovo cement plant on Hg levels measured in the ambient air at Vodarna, 1 km downwind from the flue gas chimney. The findings reveal that the plant raw mill operational status plays an important role in Hg concentrations in the flue gas emitted from the plant. Emitted total gaseous mercury was, on average, higher (49.4 µg/m 3 ) when raw mills were in the direct mode (both raw mills-off) and lower (23.4 µg/m 3 ) in the combined mode (both raw mills-on). The average Hg concentrations in Vodarna were 3.14 ng/m 3 for gaseous elemental mercury, 53.7 pg/m 3 for gaseous oxidised mercury, and 41.9 pg/m 3 for particulate bound mercury for the whole measurement period. Atmospheric Hg speciation in Vodarna, coupled with plant emissions and wind data, has revealed that the total gaseous mercury emitted from the cement plant is clearly related to all Hg species measured in Vodarna. Wind blowing from the northeastern quadrant (mostly NE, ENE) is responsible for the elevated Hg levels in Vodarna, where gaseous oxidised mercury levels are highly linked to the cement plant emissions. However, elevated levels of Hg species in the absence of northeastern winds indicate potential inputs from other unknown local sources as well as inputs from regional and global transport mechanisms.

Wet deposition is the main source of mercury (Hg) from the atmosphere to the Earth’s surface. However, the processes that govern the dispersion of deposited Hg in seawater are currently not well understood. To address this issue, total mercury (THg) concentrations in surface seawaters and precipitation were determined on a monthly basis in the Bay of Kaštela (Central Adriatic Sea). Following the assumption that deposited THg is diluted in the seawater bulk due to mixing processes, an exponential decay-like model was developed and the wet deposition of THg was normalized based on periods between precipitation events and seawater sampling. Normalized wet deposition of THg showed significant correlation with the THg gradient in surface seawater after removal of an outlier. To explain the observed outlier, further data normalization included wind data to account for enhanced seawater mixing due to strong winds. Wind-normalized THg deposition of all datapoints showed significant correlation with the THg gradient in surface seawater. The correlation showed that the THg gradient in surface seawater of 0.378 pg L−1 m−1 corresponds to THg wet deposition of 1 ng m−2 after including the influence of wind speed on seawater mixing.

Bio-monitoring of mercury (Hg) in air using transplanted and in-situ lichens was conducted at three locations in Slovenia: (I) the town of Idrija in the area of the former Hg mine, where Hg contamination is well known; (II) Anhovo, a settlement with a cement production plant, which is a source of Hg contamination, and (III) Pokljuka, a part of a national park. Lichens from Pokljuka were transplanted to different sites and sampled four times-once per season, from January 2020 to February 2021. Lichens were set on tree branches, fences, and under cover, allowing them to be exposed to different environmental conditions (e.g., light and rain). The in-situ lichens were sampled at the beginning and the end of the sampling period. The highest concentrations were in the Idrija area, which was consistent with previous research. Significant mass-dependent fractionation has been observed in transplanted lichens during summer period. The δ202Hg changed from -3.0‰ in winter to -1.0‰ in summer and dropped again to the same value in winter the following year. This trend was observed in all samples, except those from the most polluted Idrija sampling site, which was in the vicinity of the former Hg ore-smelting plant. This was likely due to large amounts of Hg originating from polluted soil close to the former smelting plant with a distinct isotopic fingerprint in this local area. The Δ199Hg in transplanted lichens ranged from -0.5‰ to -0.1‰ and showed no seasonal trends. These findings imply that seasonality, particularly in summer months, may affect the isotopic fractionation of Hg and should be considered in the sampling design and data interpretation. This trend was thus described in lichens for the first time. The mechanism behind such change is not yet fully understood.

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 (ΔHads); a ΔHads 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.

Studies on the influence of CN on Hg methylation rates in aquatic systems draining gold mining (artisanal and small-scale) communities in Africa are rare. The study assessed the influence of CN on Hg methylation in aquatic sediments of two major river systems draining artisanal and small-scale gold mining (ASGM) communities of the Prestea-Huni Valley district, Southwestern Ghana. The miners extract gold (Au) through exclusive amalgam [Hg-Au] formation or cyanidation of Au-rich Hg-contaminated tailings, or a combination of both techniques. Hg water solubility and probable mercuric compounds in sediments of Hg-contaminated CN-loaded (River Aprepre) and Hg-contaminated non-CN (River Ankobra) aquatic systems within the district were investigated. THg was determined by CV-AAS after HF/HNO3/HCl digestion. MeHg in sediments were extracted with H2SO4/KBr/CuSO4-CH2Cl2; followed by aqueous-phase propylation, preconcentration-on-Tenax, and GC-CV-AFS. River Aprepre showed 4.58–14.83 ngMeHg/g as Hg (1.4–3.7% THg as MeHg), with 241–415 ngTHg/g, and 0.05–0.21 mgCN/kg. For River Ankobra, MeHg ranged 0.24–1.21 ngMeHg/g (0.08–0.35% THg as MeHg) with 162–490 ngTHg/g dw and CN < 0.001 mg/kg. There was positive correlation (r2 = 0.5974; p < 0.01) between MeHg and CN in River Aprepre. The water-soluble fraction of Hg in sediment from both rivers was < 1% of THg. Hg in sediments from River Aprepre were generally more soluble than that from River Ankobra, indicating that Hg in sediments from River Aprepre were potentially more bioavailable for methylation. Accordingly, the presence of CN in Hg-dominated river sediments potentially influences and enhances the solubility and mobility of Hg, resulting in increased Hg methylation rates.

Atmospheric mercury speciation is of paramount importance for understanding the behavior of mercury once it is emitted into the atmosphere as gaseous elemental mercury (GEM), gaseous oxidized mercury (GOM) and particulate-bound mercury (PBM). GOM and PBM can also be formed in the atmosphere; their sampling is the most problematic step in the atmospheric mercury speciation. GOM sampling with speciation traps composed of KCl sorbent materials and KCl trapping solutions are commonly used sampling methods, although the research conducted with them at ambient air concentrations is limited. The results of the specificity test demonstrated that the KCl sorbent traps are highly specific when using new traps, while their specificity drops dramatically when they are reused. The results of the stability test indicated that the highest Hg2+ losses (up to 5.5 % of Hg2+ loss) occur when low amounts of Hg2+ (< 1 ng) are loaded, due to a reduction of Hg2+ to Hg0. KCl trapping solutions have also been considered as a selective trapping media for GOM in atmospheric samples. A dimensionless Henry law constant was experimentally derived and was used to calculate the solubility of elemental Hg in KCl solution. The degree of GEM oxidation was established by purging elemental Hg calibration gas into a KCl solution and determining the GOM trapped using aqueous-phase propylation liquid–liquid extraction and gas chromatography–atomic fluorescence spectrometry (GC-AFS) measurement. A positive GOM bias was observed due to the solubility and oxidation of GEM in KCl trapping solutions, strongly suggesting that this approach is unsuitable for atmospheric mercury speciation measurements.