Gaseous Hg Concentrations Research Articles

Concurrent measurements of atmospheric Hg in outdoor and indoor at a megacity in Southeast Asia: First insights from the region

Atmospheric mercury (Hg) is a critical indoor (ID) air pollutant and necessitates stringent monitoring. However, studies have primarily focused on Hg outdoors (OD) compared to ID, with no investigations conducted within the Southeast Asia (SEA) region. In this study, total gaseous Hg (TGM) concentrations and human exposure levels were investigated across various site characteristics in Ho Chi Minh City (HCMC), a megacity in SEA. The measured TGM concentrations for OD and ID were 5.12 ± 6.87 ng m−3 (1.20–48.7 ng m−3) and 34.5 ± 60.3 ng m−3 (1.26–271.9 ng m−3). The overall ID/OD ratio was 5.01 (0.77–9.3), signifying markedly elevated ID TGM concentrations. This ratio increases in the following order: shopping malls (1.50) < hospitals (3.21) < chemical laboratories (5.76) < households (11.7). Notably, sites associated with Hg incidents and the utilization of Hg-contained chemicals demonstrate notably high ID/OD levels, ranging from 8.0 to 40.1. The use of Hg-containing chemicals within the chemical laboratory serves as a significant contributor to heightened ID TGM levels. Non-combustion Hg sources, therefore, play an important role in inducing the ID TGM level. The hazard index (HQ) values observed for ID and OD were 0.1 and 0.01, respectively, indicating a negligible risk of exposure to TGM within the study area. However, HQ values recorded within laboratory environments employing Hg-associated chemicals and dental hospitals were 1–17 times greater compared to other sites. The present work provides new insight into the non-combustion ID source of TGM and was helpful for upcoming studies in exploring potential sources of TGM in megacities.

Exceptionally low mercury concentrations and fluxes from the 2021 and 2022 eruptions of Fagradalsfjall volcano, Iceland

Mercury (Hg) is naturally released by volcanoes and geothermal systems, but the global flux from these natural sources is highly uncertain due to a lack of direct measurements and uncertainties with upscaling Hg/SO2 mass ratios to estimate Hg fluxes. The 2021 and 2022 eruptions of Fagradalsfjall volcano, southwest Iceland, provided an opportunity to measure Hg concentrations and fluxes from a hotspot/rift system using modern analytical techniques. We measured gaseous Hg and SO2 concentrations in the volcanic plume by near-source drone-based sampling and simultaneous downwind ground-based sampling. Mean Hg/SO2 was an order of magnitude higher at the downwind locations relative to near-source data. This was attributed to the elevated local background Hg at ground level (4.0 ng m−3) likely due to emissions from outgassing lava fields. The background-corrected plume Hg/SO2 mass ratio (5.6 × 10−8) therefore appeared conservative from the near-source to several hundred meters distant, which has important implications for the upscaling of volcanic Hg fluxes based on SO2 measurements. Using this ratio and the total SO2 flux from both eruptions, we estimate the total mass of gaseous Hg released from the 2021 and 2022 Fagradalsfjall eruptions was 46 ± 33 kg, equivalent to a flux of 0.23 ± 0.17 kg d−1. This is the lowest Hg flux estimate in the literature for active open-conduit volcanoes, which range from 0.6 to 12 kg d−1 for other hotspot/rift volcanoes, and 0.5–110 kg d−1 for arc volcanoes. Our results suggest that Icelandic volcanic systems are fed from an especially Hg-poor mantle. Furthermore, we demonstrate that the aerial near-source plume Hg measurement is feasible with a drone-based active sampling configuration that captures all gaseous and particulate Hg species, and recommend this as the preferred method for quantifying volcanic Hg emissions going forward.

Nano-mineral assemblages in mercury- and silver-contaminated soils: records of sequestration, transformation, and release of mercury- and silver-bearing nanoparticles.

Mercury-bearing nano-mineral assemblages (Hg-NMAs) are chemically and mineralogically heterogeneous, micrometer-sized aggregates of nanoparticles (NPs) found in contaminated soils and sediments. Although these NMAs control sequestration and release of Hg that is a global contaminant, our understanding is limited with respect to the conditions of different types of Hg-NMAs, the diversity of its minerals, the size distribution of its NPs and whether mineral replacement and alteration reactions in these NMAs result in the release of Hg-bearing NPs. For this purpose, Hg-NMAs in four sediment samples from the Guanajuato Mining District (GMD) in Mexico, a region that was polluted by Hg and silver (Ag) due to historical mining involving Hg amalgamation, are characterized at the micro- and nanoscale. Microscale examinations with SEM show that the majority of Hg-NMAs occurs in mineral surface coatings (MSC) and fillings in fractures within quartz grains and are enriched in Hg and sulfur (S) relative to Ag, and in S and selenium (Se) relative to chloride (Cl). Examinations at the nanoscale show that Hg-NMAs contain (a) residuals of the patio process such as amalgam phases and elemental Ag; (b) associations of Hg- and Ag-sulfide NPs with pyrite and marcasite; (c) associations of Hg- and Ag-sulfide NPs with goethite and clay minerals along the rims of the MSC. The latter minerals replaced the Fe-Si-rich matrix at high-water rock ratios most likely due to an increase in porosity during flooding of the Pastita River. Consequently, the rims are depleted in Hg-Ag-sulfide NPs relative to the unaltered Fe-Si-rich matrices indicating that changes in the physiochemical conditions of soils and sediments in the GMD can result in the release of Hg-Ag-bearing NPs. In this context, this study discusses whether release and dissolution of Hg-Ag-bearing NPs contribute to the recently observed elevated gaseous elemental Hg concentrations in the soil, interstitial air and ambient air, and to the fate and effects of Hg in local aquatic environments.

Estimation of mercury uptake and distinction of corn cultivation in China

Corn cultivation potentially plays a vital role in the global mercury (Hg) biogeochemical cycle. Nevertheless, there have been limited studies quantifying the Hg mass flow during corn cultivation. This study focuses on Hg uptake by corn plants in China, integrating data from both sample collection and prior studies, resulting in 400 datasets. The findings reveal that the Hg in corn plants is mainly incorporated in leaves (45.5 %–47.5 %) and husks (14.5 %–15.7 %). Despite a decrease in total gaseous Hg (TGM) concentrations in the atmosphere over time, annual Hg uptake by corn cultivation in China has risen from 72.0 (ranging from 47.6 to 96.3) tons (2009–2014) to 84.3 (ranging from 51.9 to 109.6) tons (2015–2020) due to the increasing in corn kernel production. Spatial analysis demonstrates regional disparities in Hg uptake, primarily influenced by corn kernel production, TGM levels, and soil Hg content. Furthermore, temporal analysis reveals a shift in the fate of Hg in corn plants, which can be attributed to variations in corn straw treatment policy or methods. From 2009 to 2014, a substantial amount of absorbed Hg by corn plants was re-released into the atmosphere (48.9 %) due to corn residues burning, whereas, between 2015 and 2020, a greater proportion of Hg ended up accumulating in the soil (51.1 %) after the imposition of the straw burning ban in China. Prior to the ban (2009–2014), corn cultivation contributed approximately 7.7 tons of Hg input to soil annually, with a range from 1.7 to 13.5. However, following the ban (2015–2020), Hg input into the soil increased by approximately 4.5 times, reaching 34.5 (ranging from 17.5 to 52.6) tons per year. These findings emphasize the significant risks associated with soil Hg pollution caused by corn cultivation due to the straw burning ban.

Determining sources of reactive mercury compounds in Reno, Nevada, United States

There is much uncertainty regarding the sources of reactive mercury (RM) compounds and atmospheric chemistry driving their formation. This work focused on assessing the chemistry and potential sources of reactive mercury measured in Reno, Nevada, United States, using 1 year of data collected using Reactive Mercury Active System. In addition, ancillary meteorology and criteria air pollutant data, Hybrid Single-Particle Lagrangian Integrated Trajectory (HYSPLIT) analyses, and a generalized linear model were applied to better understand reactive mercury observations. During the year of sampling, a fire event impacted the sampling site, and gaseous elemental Hg and particulate-bound mercury concentrations increased, as did HgII-S compounds. Data collected on a peak above Reno showed that reactive mercury concentrations were higher at higher elevation, and compounds found in Reno were the same as those measured on the peak. HYSPLIT results demonstrated RM compounds were generated inside and outside of the basin housing Reno. Compounds were sourced from San Francisco, Sacramento, and Reno in the fall and winter, and from long-range transport and the marine boundary layer during the spring and summer. The generalized linear model produced correlations that could be explained; however, when applying the model to similar data collected at two other locations, the Reno model did not predict the observations, suggesting that sampling location chemistry and concentration cannot be generalized.

Temporal variation of speciated atmospheric Hg and characteristics of size-fractioned HgP at a suburban site in Shijiazhuang City, North China

Atmospheric mercury (Hg) species were determined at a suburban site near Shijiazhuang, China from May 2016 to January 2017 to ascertain their seasonal and diurnal patterns, to identify the relationship with other parameters, and furthermore to elucidate their potential sources areas. The gaseous elemental Hg (GEM) concentration (3.66 ± 2.62 ng m−3) was about 2 times higher than the background level in the Northern Hemisphere, and the fine particulate bound Hg (HgP2.5) concentration (92.4 ± 59.6 pg m−3) was comparable to those at urban sites, while the gaseous oxidized Hg (GOM) level was quite low (5.7 ± 5.6 pg m−3). GEM and HgP2.5 concentrations exhibit pronounced seasonal (January > May > October > August) and diurnal (nighttime > daytime) patterns. In contrast, the seasonal and diurnal patterns of GOM were just opposite to those of GEM and HgP2.5. The significant positive relationship among GEM, HgP, CO, SO2, and NO2 reveals that they have similar anthropogenic sources. Interestingly, the size distributions of HgP in PM10 were observed to be unimodal during the four study periods, and peaks were all located in the fine mode (0.7–2.1 μm), and fine HgP contributed ∼70% (38.2–81.5%) of HgP10, indicating that the fine mode was the dominant size. The potential source contribution function (PSCF) result suggests that GEM level at the sampling site was highly impacted by regional sources rather than the long-range transport, and the potential source areas were predominantly located in southern Hebei and western Shandong. The results of wind rose and cluster analyses were consistent with the PSCF results.

Monitoring of Airborne Mercury: Comparison of Different Techniques in the Monte Amiata District, Southern Tuscany, Italy.

In the present study, mercury (Hg) concentrations were investigated in lichens (Flavoparmelia caperata (L.) Hale, Parmelia saxatilis (L.) Ach., and Xanthoria parietina (L.) Th.Fr.) collected in the surrounding of the dismissed Abbadia San Salvatore Hg mine (Monte Amiata district, Italy). Results were integrated with Hg concentrations in tree barks and literature data of gaseous Hg levels determined by passive air samplers (PASs) in the same area. The ultimate goal was to compare results obtained by the three monitoring techniques to evaluate potential mismatches. Lichens displayed 180–3600 ng/g Hg, and Hg concentrations decreased exponentially with distance from the mine. Mercury concentration was lower than in Pinus nigra barks at the same site. There was a moderate correlation between Hg in lichen and Hg in bark, suggesting similar mechanisms of Hg uptake and residence times. However, correlation with published gaseous Hg concentrations (PASs) was moderate at best (Kendall Tau = 0.4–0.5, p > 0.05). The differences occurred because a) PASs collected gaseous Hg, whereas lichens and barks also picked up particulate Hg, and b) lichens and bark had a dynamic exchange with the atmosphere. Lichen, bark, and PAS outline different and complementary aspects of airborne Hg content and efficient monitoring programs in contaminated areas would benefit from the integration of data from different techniques.

Black pine (Pinus nigra) barks: A critical evaluation of some sampling and analysis parameters for mercury biomonitoring purposes

Abstract Tree barks are increasingly used as biomonitors of airborne pollutants. However, many authors stress the poor comparability of the results achieved in different studies. This drawback is mainly caused by a poor understanding of the critical sampling parameters to be considered. To minimize the biases that could be introduced during sampling, in this study the barks of Pinus nigra J.F. Arnold from thirteen sites were investigated in the abandoned Mt. Amiata mercury (Hg) mining district (Southern Tuscany, Italy) and surroundings. The influence of some sampling and analyzing parameters on Hg content was critically assessed. At each site, a total of eight bark samples were taken from a single tree at two heights (70 cm and 150 cm from soil) and at four different sides of the trunk, corresponding to the four cardinal directions; a composite soil sample was also collected. Mercury contents in barks range from 0.1 to 28.8 mg/kg, and are correlated with soil Hg contents (1–480 mg/kg), indicating that barks record both gaseous Hg concentrations in air, and wind-transported Hg-bearing particulate. For each tree, samples at 70 cm and 150 cm show Hg contents of the same order of magnitude, even if values for 150 cm are slightly less dispersed, possibly because barks at 70 cm are more influenced by random soil particles. There is no statistically significant dependence of Hg content on direction and tree age. Simulated rain events cause a negligible loss of Hg from barks. Results suggest that a convenient sampling practice for Pinus nigra is to collect a bark slice (typically 1–2 mm) within the outermost 1.5 cm layer.

Experimental Tests of Natural Gas Samplers Prior to Mercury Concentration Analysis

Mercury (Hg) is a natural, trace component of natural gas. Corrosion of aluminum heat exchangers by liquid metallic Hg can lead to dramatic issues. The quantification of gaseous Hg concentration in natural gas streams is therefore crucial prior to the implementation of Hg removal units for preventing the formation of liquid Hg. Different methodologies exist for the determination of Hg concentration in natural gas, one of which relies on the sampling of natural gas at high pressure using stainless-steel cylinders prior to off-site Hg measurement. An inert internal coating is supposed to hamper Hg adsorption, presumably making the Hg analysis reliable. Here, we challenge this statement by showing that even silicon-coated cylinders are inefficient for preventing Hg adsorption on internal walls. Different cylinders were tested for gaseous Hg concentration stability over time in a clean Argon matrix. We find that gaseous Hg concentration sharply declines in almost all tested cylinders (uncoated, PTFE-coated an...

Application of the Passive Sampler Developed for Atmospheric Mercury and Its Limitation

In this study, a passive sampler for gaseous elemental mercury (GEM) was developed and applied to field monitoring. Three Radiello® diffusive bodies with gold-coated beads as Hg adsorbent were installed in an acrylic external shield. Hg uptake mass linearly increased as the deployment time increased until 8 weeks with an average gaseous Hg concentration of 2 ng m−3. The average of the experimental sampling rate (SR) was 0.083 m3 day−1 and showed a good correlation with theoretical SRs, indicating that a major adsorption mechanism was molecular diffusion. Nonetheless, the experimental SR was approximately 33% lower than the modeled SR, which could be associated with inefficient uptake of GEM in the sampler or uncertainty in constraining model parameters. It was shown that the experimental SR was statistically affected by temperature and wind speed but the calibration equation for the SR by meteorological variables should be obtained with a wider range of variables in further investigation. When the uptake rates were compared to the active Hg measurements, the correlation was not significant because the passive sampler was not sufficiently adept at detecting a small difference in the GEM concentration of from 1.8 to 2.0 ng m−3. However, the results for spatial Hg concentrations measured near cement plants in Korea suggest a possible application in field monitoring. Future research is needed to fully employ the developed passive sampler in quantitative assessment of Hg concentrations.

Mercury emission from underground coal fires in the mining goaf of the Wuda Coalfield, China

The Wuda Coalfield, Inner Mongolia suffers from serious coal fires for more than half a century. Fire-extinguishing projects have been carried out to suppress the coal fires since the last decade, but sporadic surface fires still occur and underground fires are more prevailing. Here, we used a real-time RA-915M Mercury Analyzer with modified inlet to monitor gaseous Hg concentrations in fumes emitted from boreholes that were designed to detect and control the underground coal fires. Meanwhile, offline methods were used to collect the fumes and analyze the contents of the gases including CO, CO2, CH4, C2H6, C2H4 and C2H2. The results showed that gaseous Hg concentrations in fumes from boreholes ranged from 6.42 ± 0.73 to 123.53 ± 34.66 ng m−3, with an average value of 49 ± 44 ng m−3. We suggest that the amounts of coal left for burning or smoldering mainly accounted for the large variation in fume Hg concentrations of underground coal fires. The gaseous Hg concentrations in near-surface air surrounding boreholes varied from 2.38 ± 0.28 to 13.10 ± 0.97 ng m−3, with a mean value of 6.68 ± 3.09 ng m−3. They were higher than the ambient air Hg concentrations measured at a background site near the Yellow River (<2 ng m−3), suggesting underground coal fires were one significant Hg pollution source. Importantly, we found that gaseous Hg concentrations in the boreholes had significantly positive correlations with temperatures and CO (a traditional coal-fire index gas) contents, implying that Hg has the potential to serve as an index gas to monitor the occurrences of underground coal fires in mining goafs.

Temporal changes in atmospheric mercury concentrations at a background mountain site downwind of the East Asia continent in 2006–2016

Atmospheric mercury (Hg) has been monitored at the Lulin Atmospheric Background Station (LABS) in Taiwan since April 2006 and is still continuing. Here we reported the trend in gaseous elemental Hg (GEM) concentrations at LABS between April 2006 and December 2016, before the Minamata Convention on Mercury entered into force in 2017. Previous research indicated nighttime (0–8 am) data collected at LABS are better representative of regional influence. Therefore, only nighttime GEM data were used for trend analysis. A significant decreasing trend in GEM at a rate of −1.5% yr−1 (−0.022 ng m−3 yr−1, p < 0.01) was found, comparable to the decreasing trends observed in Europe, North America, South Africa, and over the North Atlantic Ocean. Five major GEM source regions to the LABS were identified, including northern Indochina Peninsula, China, Northeast Asia, the Pacific Ocean, and South China Sea. Significant decreasing trends in GEM were found for air masses coming from northern Indochina Peninsula (−0.042 ng m−3 yr−1, −2.6% yr−1, p < 0.01), China (−0.041 ng m−3 yr−1, −2.4% yr−1, p < 0.01), Northeast Asia (−0.031 ng m−3 yr−1, −2.0% yr−1, p < 0.05), and the Pacific Ocean (−0.022 ng m−3 yr−1, −1.7% yr−1, p < 0.05). Decreasing GEM trend (−0.020 ng m−3 yr−1, −1.5% yr−1), but insignificant (p > 0.05), was also found for air masses coming from South China Sea. The decreasing trends observed with air from the Pacific Ocean and South China Sea indicated declining background GEM concentrations in Northern Hemisphere. Decrease in GEM concentrations at the LABS was in agreement with the reduction in atmospheric Hg export from the East Asia continent caused by changes in Hg emission quantity and speciation, and temporal and spatial distribution in emission sources that have been suggested by recent research. Additionally, changes in the frequency distribution of air mass origins and transport paths may also contribute to the changes in GEM concentrations at LABS.

Characterization and Quantification of Atmospheric Mercury Sources Using Passive Air Samplers

AbstractThe Minamata Convention on Mercury (Hg) requires improved atmospheric Hg monitoring and characterization of Hg sources. Here we demonstrate how a network of passive air samplers (PASs) can be used cost effectively to determine the spatial distribution of gaseous Hg and estimate atmospheric Hg emissions at contaminated sites. Gaseous Hg concentrations were mapped around a former Hg mine in the Monte Amiata district in Italy using simultaneous deployments of PASs across local and regional spatial scale grids. The concentration maps help visualize with great detail and precision the dispersal of gaseous Hg from a contaminated site, revealing even subtle effects of wind, season, and minor sources. Emissions estimated from the empirical data (80 ± 40 and 150 ± 75 kg/year for October and July, respectively) were robust to changes in the most uncertain parameters (excess Hg in the air above the mine and advection rate) and compared well to previous estimates for this and other closed Hg mines. This PAS‐based approach has a number of advantages: (i) concurrent deployments of multiple samplers constrain concentration changes to spatial variability only, (ii) time‐averaged data over longer periods negate biases related to short‐term, infrequent measurements, (iii) more spatially representative estimates of Hg distributions and emissions can be made at a fraction of the cost, and (iv) use is easy, especially in difficult terrain. Time‐averaged data across a broad area are also most pertinent for assessing chronic human exposure, especially in terms of the inhalation of Hg by workers and residents living close to contaminated sites.

Global and regional trends in mercury emissions and concentrations, 2010–2015

Mercury (Hg) is a naturally occurring element in the Earth's crust. It can be harmful to human health when released in large quantities and/or converted to the neurotoxicant methyl mercury in aquatic ecosystems. This study analyzes global and regional trends in anthropogenic Hg releases to the atmosphere between 2010 and 2015, as well as the associated trends in modeled and measured Hg concentrations at sites around the world. In general, we find that global Hg emissions and concentrations have grown slightly in this period, as declines from the phase-out of commercial Hg use in the developed world have been more than matched by increases in Hg-related activities in the industrializing countries of the world. We estimate that global Hg emissions between 2010 and 2015 have grown at a rate of 1.8%/yr, from 2188 Mg (+44%/-20%, 80% C.I.) in 2010 to 2390 Mg (+42%/-19%, 80% C.I.) in 2015. Regionally, emissions declined over this period in the U.S. (−10%), OECD Europe (−5.8%), and Canada (−3.2%), while they increased in Central America (+5.4%), South Asia (+4.6%), and Eastern Africa (+4.0%). East Asia remained the largest emitting region at 1012 Mg in 2015, though growth there has slowed significantly in recent years. The production of Hg (+7.9%), caustic soda (+6.3%), and cement (+6.3%) showed the highest increases by source type, though artisanal and small-scale gold mining (ASGM) was the single largest source of emissions in 2015 (775 Mg). The commercial use of Hg in dental applications (−5.6%) and electrical equipment (−5.2%) continued to decline. These emission trends show a continuation of the regional and sectoral shifts that began in the 1970s, but with a resulting reversal in global trends, because the benefits from Hg phase-out in North America and Europe have been largely realized and industrial growth in developing countries has begun to dominate. The emission trends are in agreement with trends in modeled and measured concentrations, which show small declines in surface air total gaseous Hg concentrations in eastern North America and Western Europe between 2010 and 2015, but slight increases for much of the rest of the world, driven by the continued increases in emissions from Asia and from ASGM. Our results suggest that reductions of Hg in the North Atlantic region have been largely successful, and focus now needs to shift to Asia and to the continued practice of ASGM worldwide.

Identifying and evaluating urban mercury emission sources through passive sampler-based mapping of atmospheric concentrations

Beyond emissions from coal-fired power generation, urban sources of mercury (Hg) to the atmosphere, especially minor fugitive sources, are relatively poorly characterized. To identify urban sources of fugitive Hg emissions, passive air samplers (PASs) were deployed for periods of 4–6 weeks in the summer of 2016 at 145 sites across the Greater Toronto Area (GTA). PASs were also deployed along transects of increasing distance from five sites listed as Hg sources in the National Pollution Release Inventory (NPRI) within or near the GTA. Mean gaseous Hg concentrations in downtown Toronto (1.77 ± 0.28 ng m−3) are slightly, but significantly elevated relative to other parts of the GTA (1.42 ± 0.20 ng m−3). Similarly, concentrations at sites close to waste/recycling (1.61 ± 0.22 ng m−3) and hospitals/dental facilities (1.63 ± 0.21 ng m−3) are significantly higher than at sites presumably distant from potential sources (1.37 ± 0.20 ng m−3). Gaseous Hg concentrations are elevated near four of five NPRI source sites, but not near a wastewater treatment plant. Measured or predicted concentrations (using extrapolated transect relationships) close to known Hg sources do not correlate with reported NPRI emissions. For example, the Hg disposal company Aevitas Inc. has the lowest reported NPRI emissions (0.11 kg yr−1) among the five sources, but measured (12.3 ng m−3) and predicted (60.0 ng m−3) concentrations outside the facility are the highest. The PAS’s ability to precisely and accurately discriminate small differences in gaseous Hg concentration (<0.2 ng m−3) at and near global background concentrations enables the mapping of the spatial concentration variability and the identification of fugitive Hg emission sources.

Mercury wet deposition and speciated mercury air concentrations at rural and urban sites across New York state: Temporal patterns, sources and scavenging coefficients

Measurements of ambient speciated mercury (Hg) concentrations and Hg wet deposition were made at two urban sites (Bronx, NY and Rochester, NY) and one rural site (Potsdam, NY) in New York State in 2013 and 2014 to: 1) determine the factors influencing Hg wet deposition concentrations, 2) identify the contribution of gaseous oxidized Hg (GOM) and particulate bound Hg (PBM) scavenging to Hg wet deposition concentrations, and 3) identify potential source areas associated with high concentration events. The Bronx had the highest mean gaseous elemental Hg (GEM) and GOM concentrations, Rochester had the highest mean PBM and the lowest GOM concentrations, and Potsdam had the lowest mean GEM and PBM concentrations. The annual volume weighted mean (VWM) Hg concentrations and Hg wet deposition fluxes in the Bronx, Rochester, and Potsdam were significantly different with mean values of 10.3 ± 8.16, 10.2 ± 9.06, and 5.07 ± 1.79 ngL−1 and 8.45 ± 0.64, 6.65 ± 0.21, and 5.25 ± 0.49 μg/m2 year−1, respectively. Hg wet deposition flux and precipitation depth were positively correlated at all three sites as were Hg concentration in precipitation and weekly GOM concentrations at the Bronx and Potsdam sites. Scavenging coefficients (SC) of 680, 630, 850 for GOM and 410, 320, and 410 for PBM at Bronx, Rochester, and Potsdam, respectively, suggest GOM is responsible for most of the scavenged Hg. Measured GOM and PBM concentrations were relatively constant before precipitation events and Hg concentrations in precipitation did not vary significantly during precipitation events implying the scavenging process mainly occurred in clouds. VWM Hg concentrations, monthly accumulated Hg flux, and SCs for GOM and PBM were higher at the urban sites and significantly different for non-snow and snow events. Local sources appeared more important at the rural site while regional sources affected high urban concentrations.

Global evaluation and calibration of a passive air sampler for gaseous mercury

Abstract. Passive air samplers (PASs) for gaseous mercury (Hg) were deployed for time periods between 1 month and 1 year at 20 sites across the globe with continuous atmospheric Hg monitoring using active Tekran instruments. The purpose was to evaluate the accuracy of the PAS vis-à-vis the industry standard active instruments and to determine a sampling rate (SR; the volume of air stripped of gaseous Hg per unit of time) that is applicable across a wide range of conditions. The sites spanned a wide range of latitudes, altitudes, meteorological conditions, and gaseous Hg concentrations. Precision, based on 378 replicated deployments performed by numerous personnel at multiple sites, is 3.6 ± 3.0 %1, confirming the PAS's excellent reproducibility and ease of use. Using a SR previously determined at a single site, gaseous Hg concentrations derived from the globally distributed PASs deviate from Tekran-based concentrations by 14.2 ± 10 %. A recalibration using the entire new data set yields a slightly higher SR of 0.1354 ± 0.016 m3 day−1. When concentrations are derived from the PAS using this revised SR the difference between concentrations from active and passive sampling is reduced to 8.8 ± 7.5 %. At the mean gaseous Hg concentration across the study sites of 1.54 ng m−3, this represents an ability to resolve concentrations to within 0.13 ng m−3. Adjusting the sampling rate to deployment specific temperatures and wind speeds does not decrease the difference in active–passive concentration further (8.7 ± 5.7 %), but reduces its variability by leading to better agreement in Hg concentrations measured at sites with very high and very low temperatures and very high wind speeds. This value (8.7 ± 5.7 %) represents a conservative assessment of the overall uncertainty of the PAS due to inherent uncertainties of the Tekran instruments. Going forward, the recalibrated SR adjusted for temperature and wind speed should be used, especially if conditions are highly variable or deviate considerably from the average of the deployments in this study (9.89 ∘C, 3.41 m s−1). Overall, the study demonstrates that the sampler is capable of recording background gaseous Hg concentrations across a wide range of environmental conditions with accuracy similar to that of industry standard active sampling instruments. Results at sites with active speciation units were inconclusive on whether the PASs take up total gaseous Hg or solely gaseous elemental Hg primarily because gaseous oxidized Hg concentrations were in a similar range as the uncertainty of the PAS.

Biogenesis of Mercury-Sulfur Nanoparticles in Plant Leaves from Atmospheric Gaseous Mercury.

Plant leaves serve both as a sink for gaseous elemental mercury (Hg) from the atmosphere and a source of toxic mercury to terrestrial ecosystems. Litterfall is the primary deposition pathway of atmospheric Hg to vegetated soils, yet the chemical form of this major Hg input remains elusive. We report the first observation of in vivo formation of mercury sulfur nanoparticles in intact leaves of 22 native plants from six different species across two sampling areas from China. The plants grew naturally in soils from a mercury sulfide mining and retorting region at ambient-air gaseous-Hg concentrations ranging from 131 ± 19 to 636 ± 186 ng m-3 and had foliar Hg concentration between 1.9 and 31.1 ng Hg mg-1 dry weight (ppm). High energy resolution X-ray absorption near-edge structure (HR-XANES) spectroscopy shows that up to 57% of the acquired Hg is nanoparticulate, and the remainder speciated as a bis-thiolate complex (Hg(SR)2). The fractional amount of nanoparticulate Hg is not correlated with Hg concentration. Variation likely depends on leaf age, plant physiology, and natural variability. Nanoparticulate Hg atoms are bonded to four sulfide or thiolate sulfur atoms arranged in a metacinnabar-type (β-HgS) coordination environment. The nanometer dimension of the mercury-sulfur clusters outmatches the known binding capacity of plant metalloproteins. These findings give rise to challenging questions on their exact nature, how they form, and their biogeochemical reactivity and fate in litterfall, whether this mercury pool is recycled or stored in soils. This study provides new evidence that metacinnabar-type nanoparticles are widespread in oxygenated environments.

Evidence for Nonstomatal Uptake of Hg by Aspen and Translocation of Hg from Foliage to Tree Rings in Austrian Pine.

To determine whether trees are reliable biomonitors of air mercury (Hg) pollution concentrations were measured in bark, foliage, and tree rings. Data were developed using 4-year old Pinus and Populus trees grown from common genetic stock in Oregon and subsequently transferred to four air treatments differing in gaseous oxidized mercury (GOM) chemistry and total gaseous Hg (TGM) concentrations. Soil of a subset of trees was spiked with HgBr2 in solution to test for root uptake. Results indicate no significant effect of the soil spike or GOM compounds on tree tissue Hg concentrations. TGM treatment had a significant effect on Pinus and Populus foliage, and Pinus year 5 growth ring concentrations. Populus foliar Hg concentrations were highest in the exposure where 24 h TGM concentrations were highest, indicating the importance of the nonstomatal pathway for uptake. Pinus tree ring concentrations were correlated to day time TGM concentrations suggesting Hg accumulation into tree rings is by way of the stomata and subsequent translocation by way of phloem. Populus leaves and Pinus rings can be used as biomonitors for TGM concentrations over space. However, the use of trees as temporal proxies requires further investigation due to radial translocation observed in active sapwood tree rings.

Distribution of gaseous and particle-bound Hg concentrations at the sites representative for urban and non-urban zones of Silesia Province

The basic features of the distribution of total gaseous (TGM) and particle-bound mercury (PBM) concentrations were determined for a five locations representative for urban (Bielsko-Biała, Lubliniec, Zabrze) and rural areas (Godów, Złoty Potok) of Silesia Province. Gaseous mercury concentrations were measured (1) continuously - the automatic 1h TGM measurements in Zloty Potok and Zabrze and (2) non-continuously manual 24h TGM measurements with a pre-concentration of the Hg on gold traps (Bielsko-Biała, Lubliniec, Godów). The PBM concentrations were measured non-continuously by taking PM2.5 samples. The Hg content was determined by using a CVAAS method. The highest average concentration of TGM was recorded in Zabrze (2.8ng/m3), significantly lower (2.0ng/m3) in Bielsko-Biała and in the non-urban station in Godów, the lowest concentration (&lt;2.0 ng/m3) was observed in Lubliniec and at the regional background station in Zloty Potok. The results obtained for TGM concentrations exceeded the European average level of 1.5 ng/m3 (AirBase, 2014). The highest average PBM concentration, associated with PM2.5, was obtained in Zabrze (70pg/m3), more than 20% lower results were obtained in Bielsko-Biała and Godów, finally, the lowest one (lower by about 40% in comparison with Zabrze) were obtained in Lubliniec and Złoty Potok. Moreover, an enrichment of Hg concentration in PM was observed with the increasing of the PM content, during the heating season.