Gaseous Elemental Mercury Concentrations Research Articles

パッシブサンプラー法によるガス状元素状水銀濃度の測定

パッシブサンプラー法によるガス状元素状水銀濃度の測定

A new approach for the measurement of gaseous elemental mercury (GEM) and H2S in air from anthropogenic and natural sources: Examples from Mt. Amiata (Siena, Central Italy) and Solfatara Crater (Campi Flegrei, Southern Italy)

Real-time measurements of GEM and H2S discharged from natural and anthropogenic sources are a valuable tool to investigate the dispersion dynamics of these contaminants in air. In this study, a new approach to measure GEM and H2S concentrations in air, carried out by coupling a portable Zeeman atomic absorption spectrometer with high frequency modulation of light polarization (Lumex RA-915M) and a pulsed fluorescence gas analyzer (Thermo Scientific Model 450i), was applied to two distinct areas: (i) in the surroundings of Piancastagnaio (Siena, Central Italy), located in the eastern flanks of Mt. Amiata (a 200,000years old volcano), where three geothermal plants are operating and whose exhaust gases are dispersed in the atmosphere after passing through the turbines and an abatement system to mitigate the environmental impact on air, and (ii) at Solfatara Crater (Campi Flegrei, Southern Italy), a volcanic apparatus characterized by intense hydrothermal activity.In 2014, seven GEM and H2S surveys were carried out in the two areas along pre-defined pathways performed by car at both the study sites. The lowest and highest recorded GEM and H2S concentrations at Piancastagnaio were up to 194 and 77ng/m3, respectively, whilst at Solfatara Crater were up to 690 and 3392μg/m3, respectively. Although the GEM concentrations at Piancastagnaio were lower than the limit value recommended by local regulations for outdoor environment (300ng/m3), they were almost one order of magnitude higher than the GEM background both in Tuscany (~3.5ng/m3) and Mt. Amiata (3–5ng/m3), suggesting that the main source of GEM was likely related to the geothermal plants. At Solfatara Crater, the highest GEM values were recognized in proximity of the main fumarolic gas discharges. As far as the H2S concentrations are concerned, the guideline value of 150μg/m3, recommended by WHO (2000), was frequently overcome in the study areas.Dot (in the surroundings of Piancastagnaio) and contour (at Solfatara Crater) maps for GEM and H2S concentrations built for each survey highlighted the important effects played by the meteorological parameters, the latter being measured by a Davis® Vantage Vue weather station. In particular, the GEM and H2S plumes were strongly affected by the wind speed and direction that were able to modify the dispersion of the two parameters in air in a matter of hours, indicating that the proposed analytical approach is able to produce a more realistic picture of the distribution of these air pollutants than that provided by using passive traps.Finally, the H2S/GEM ratio, calculated by normalizing the measured GEM and H2S concentrations to their highest values (nH2S/GEM), was used as a good proxy for the chemical-physical processes that these two gas species can suffer once emitted in the air. In particular, H2S resulted to be more affected by secondary processes than GEM, possibly related to photochemical oxidation reactions.

Atmospheric mercury speciation in Shanghai, China

GEM (Gaseous elemental mercury), fine fraction (<2.5μm) PBM (Particle-bound mercury) and GOM (Gaseous oxidized mercury) were continuously monitored from Jun 1 to Dec 31 2014 at a suburban site in Shanghai. The average concentrations of GEM, PBM and GOM were 4.19±9.13ng·m−3, 197±877pg·m−3, 21±100pg·m−3, respectively, which were all much higher than those at urban sites in Europe and North America and rural areas of China, but lower than those at urban sites of China. The concentrations of the three mercury species were all found with the highest concentration in December than those in summer. Overall, GEM varied little and PBM exhibited higher level during the night, while GOM typically peaked in the noon and afternoon which is consistent with that of ozone, indicating that GOM may depend on the stronger photochemical reactions during the daytime. Despite of the weak correlations of GEM with SO2 (r=0.14, p<0.0001) and NOX (r=0.17, p<0.0001), GEM, PBM, SO2 and NOx exhibited similar diurnal trend, suggesting that coal combustion might be the important sources of mercury in Shanghai because there is no mercury mining companies and few mercuric manufacturers in Shanghai. The strong correlation of PBM with GEM and GOM showed that directly anthropogenic emission was an important source of GEM and PBM, but the gas-particle partitioning of GOM and GEM might be also another source of PBM. The lower GEM/CO ratio of 3.9 (ng·m−3·ppmv−1) in Shanghai than that for mainland China and non-ferrous smelting factories were related to the few non-ferrous smelting factories around Shanghai. The results from the potential source contribution function (PSCF) model furtherly illustrated that in Shanghai the concentration of GEM in summer and autumn might be highly impacted by the local and regional source but wasn't heavily affected by long-range transport.

Speciated atmospheric mercury on haze and non-haze days in an inland city in China

Abstract. Long-term continuous measurements of speciated atmospheric mercury were conducted from July 2013 to June 2014 in Hefei, a midlatitude inland city in eastern central China that experiences frequent haze pollution. The mean concentrations (±standard deviation) of gaseous elemental mercury (GEM), gaseous oxidized mercury (GOM) and particle-bound mercury (PBM) were 3.95 ± 1.93 ng m−3, 2.49 ± 2.41 and 23.3 ± 90.8 pg m−3, respectively, on non-haze days, and 4.74 ± 1.62 ng m−3, 4.32 ± 8.36 and 60.2 ± 131.4 pg m−3, respectively, on haze days. Potential source contribution function (PSCF) analysis suggested that atmospheric mercury pollution on haze days was caused primarily by local emissions, instead of via long-range transport. The poorer mixing conditions on haze days also favored the accumulation of atmospheric mercury. Compared to GEM and GOM, PBM was especially sensitive to haze pollution. The mean PBM concentration on haze days was 2.5 times that on non-haze days due to elevated concentrations of particulate matter. PBM also showed a clear seasonal trend; its concentration was the highest in fall and winter, decreased rapidly in spring and was the lowest in summer, following the same order in the frequency of haze days in different seasons. On both non-haze and haze days, GOM concentrations remained low at night, but increased rapidly just before sunrise, which could be due to diurnal variation in air exchange between the boundary layer and free troposphere. However, non-haze and haze days showed different trends in daytime GEM and GOM concentrations. On non-haze days, GEM and GOM declined synchronously through the afternoon, probably due to the retreat of the free tropospheric air as the height of the atmospheric boundary layer increases. In contrast, on haze days, GOM and GEM showed opposite trends with the highest GOM and lowest GEM observed in the afternoon, suggesting the occurrence of photochemical oxidation. This is supported by simple box-model calculations, which showed that oxidation of GEM to GOM does occur and that the transport of free tropospheric GOM alone is not large enough to account for the observed increase in daytime GOM. Our results further postulate that NO2 aggregation with the HgOH intermediate may be a potential mechanism for the enhanced production of GOM during daytime.

Airborne mercury species at the Råö background monitoring site in Sweden: distribution of mercury as an effect of long-range transport

Abstract. Within the EU-funded project, Global Mercury Observation System (GMOS) airborne mercury has been monitored at the background Råö measurement site on the western coast of Sweden from mid-May 2012 to the beginning of July 2013 and from the beginning of February 2014 to the end of May 2015. The following mercury species/fractions were measured: gaseous elemental mercury (GEM), particulate bound mercury (PBM) and gaseous oxidised mercury (GOM) using the Tekran measurement system. The mercury concentrations measured at the Råö site were found to be low in comparison to other, comparable, European measurement sites. A back-trajectory analysis to study the origin of air masses reaching the Råö site was performed. Due to the remote location of the Råö measurement station it receives background air about 60 % of the time. However, elevated mercury concentrations arriving with air masses coming from the south-east are noticeable. GEM and PBM concentrations show a clear annual variation with the highest values occurring during winter, whereas the highest concentrations of GOM were obtained in spring and summer. An evaluation of the diurnal pattern of GOM, with peak concentrations at midday or in the early afternoon, which often is observed at remote places, shows that it is likely to be driven by local meteorology in a similar way to ozone. Evidence that a significant part of the GOM measured at the Råö site has been formed in free tropospheric air is presented.

Depletion of atmospheric gaseous elemental mercury by plant uptake at Mt. Changbai, Northeast China

Abstract. There exists observational evidence that gaseous elemental mercury (GEM) can be readily removed from the atmosphere via chemical oxidation followed by deposition in the polar and sub-polar regions, free troposphere, lower stratosphere, and marine boundary layer under specific environmental conditions. Here we report GEM depletions in a temperate mixed forest at Mt. Changbai, Northeast China. The strong depletions occurred predominantly at night during the leaf-growing season and in the absence of gaseous oxidized mercury (GOM) enrichment (GOM &lt; 3 pg m−3). Vertical gradients of decreasing GEM concentrations from layers above to under forest canopy suggest in situ loss of GEM to forest canopy at Mt. Changbai. Foliar GEM flux measurements showed that the foliage of two predominant tree species is a net sink of GEM at night, with a mean flux of −1.8 ± 0.3 ng m2 h−1 over Fraxinus mandshurica (deciduous tree species) and −0.1 ± 0.2 ng m2 h−1 over Pinus Koraiensis (evergreen tree species). Daily integrated GEM δ202Hg, Δ199Hg, and Δ200Hg at Mt. Changbai during 8–18 July 2013 ranged from −0.34 to 0.91 ‰, from −0.11 to −0.04 ‰ and from −0.06 to 0.01 ‰, respectively. A large positive shift in GEM δ202Hg occurred during the strong GEM depletion events, whereas Δ199Hg and Δ200Hg remained essentially unchanged. The observational findings and box model results show that uptake of GEM by forest canopy plays a predominant role in the GEM depletion at Mt. Changbai forest. Such depletion events of GEM are likely to be a widespread phenomenon, suggesting that the forest ecosystem represents one of the largest sinks ( ∼ 1930 Mg) of atmospheric Hg on a global scale.

Is Mercury in a Remote Forested Watershed of the Adirondack Mountains Responding to Recent Decreases in Emissions?

Although there has been a decline in U.S. mercury emissions, the effects of this change on remote ecosystems are not well understood. We examine decadal (2004-2015) responses of atmospheric mercury deposition, along with total mercury (THg) and methylmercury (MeHg) concentrations and fluxes, to decrease in mercury emissions at Arbutus Lake-watershed in the remote forested Adirondack region of New York, a biological mercury hotspot. Although wet mercury deposition remains constant, THg deposition has decreased through decreases in litter mercury inputs (17.9 to 10.8 μg/m2-yr) apparently driven by decreases in atmospheric concentrations of gaseous elemental mercury (Hgo). While the lake is a net sink for THg and MeHg, concentrations and fluxes of THg and MeHg have decreased in the inlet stream and lake water apparently in response to decreases in Hgo deposition. Decreases in surface water mercury have occurred despite decadal increases in concentrations of dissolved organic carbon. Moreover, the fraction of THg as MeHg at the inlet has not changed despite decadal decreases in atmospheric sulfate deposition and surface water concentrations of sulfate. Our results indicate that recent decreases in U.S. mercury emissions have resulted in decreases in litter mercury deposition, and stream and lake THg and MeHg concentrations and fluxes, suggesting the first steps toward ecosystem recovery.

Characteristics of Speciated Atmospheric Mercury in Chongming Island, Shanghai

Continuous monitoring of gaseous elemental mercury (GEM), reactive gaseous mercury (RGM) and particulate mercury (PBM) was conducted in the Dongtan wetland park in Chongming Island, Shanghai from March 2014 to February 2015. The average concentrations of GEM, RGM, and PBM were (2.75±1.13) ng·m-3, (13.39±15.95) pg·m-3, and (21.89±40.42) pg·m-3, respectively, higher than the background concentrations of Northern Hemisphere. The atmospheric mercury showed obvious seasonal variations, with the highest seasonal average GEM concentration in summer (3.65 ng·m-3), which was mainly influenced by natural sources, while lower GEM concentrations appeared in autumn and winter influenced mainly by anthropogenic sources. The concentration of RGM was highest in spring and lowest in winter, mainly influenced by the wind direction, while PBM showed higher concentrations in autumn and winter, when heavy fine particulate pollution episodes occurred frequently. The concentrations of GEM and PBM were generally elevated in nighttime and lower in daytime caused by the mixing condition of the air masses. Most of the high RGM concentration values occurred in the afternoon of all seasons due to the higher atmospheric oxidation. The concentrations of GEM and PBM were higher in the west wind due to the emission from anthropogenic sources in Shanghai, Jiangsu, etc. The RGM concentration in southeast wind was obviously higher than those in other wind directions. The RGM was mainly from the anthropogenic sources, and the smaller wind in the southeast direction was against the dispersion of RGM.

Mercury flux over West Antarctic Seas during winter, spring and summer

For the first time elemental mercury in air and surface seawater was measured continuously in the remote seas of western Antarctica. A major contributor to atmospheric emissions of the toxic and globally dispersed pollutant mercury is the re-evasion from water surfaces, due to a supersaturation of dissolved gaseous mercury (DGM) in surface water. In this study the degree of saturation and mercury flux at the air-sea surface interface have been estimated from continuous measurements of gaseous elemental mercury (GEM) or total gaseous mercury (TGM) in air, DGM in surface water and meteorological parameters. The measurements were performed during winter and spring (2013) in the Weddell Sea and during summer (2010/2011) in the Bellingshausen, Amundsen and Ross Seas, and show spatial and seasonal variations. The average DGM concentration in surface water in open sea was highest during spring (12 +/- 7pg L-1) and lowest during summer (7 +/- 6.8 pg L-1), resulting in a net evasion of mercury during spring (1.1 +/- 1.6 ng m(-2)h(-1)) and a net deposition during summer (-0.2 +/- 1.3 ng m(-2)h(-1)). In open sea, higher average concentrations of GEM (or TGM) and DGM were found close to the Drake Passage compared to in the Bellingshausen and Weddell Seas. Emission sources from the South American continent, identified with back trajectories, were suggested to explain the observed variations. The yearly mercury evasion from open sea surfaces in the Southern Ocean was estimated to 30 ( -450-1700) tons, using the average (and min and max) flux rates obtained in this study. Higher DGM was measured under sea ice (19-62 pg L-1 compared to in open sea due to a capsuling effect, resulting in a theoretical prevented evasion of 520 (0-3400) tons per year. Diminishing sea ice and higher water temperatures in polar regions could result in increased mercury evasion to the atmosphere. However, the contribution of the Southern Ocean to the global modeled annual emissions of mercury from sea surfaces would probably only be a few percent.

Monsoon-driven transport of atmospheric mercury to the South China Sea from the Chinese mainland and Southeast Asia-Observation of gaseous elemental mercury at a background station in South China.

Concentrations of gaseous elemental mercury (GEM) were continuously monitored from May 2011 to May 2012 at the Wuzhishan State Atmosphere Background Monitoring Station (109°29'30.2″ E, 18°50'11.0″ N) located in Hainan Island. This station is an ideal site for monitoring long-range transport of atmospheric pollutants from mainland China and Southeast Asia to South China Sea. Annual average GEM concentration was 1.58±0.71ngm-3 during the monitoring period, which was close to background values in the Northern Hemisphere. GEM concentrations showed a clear seasonal variation with relatively higher levels in autumn (1.86±0.55ngm-3) and winter (1.80±0.62ngm-3) and lower levels in spring (1.16±0.45ngm-3) and summer (1.43±0.46ngm-3). Long-range atmospheric transport dominated by monsoons was a dominant factor influencing the seasonal variations of GEM. The GEM diel trends were related to the wind speed and long-range atmospheric mercury transport. We observed 30 pollution episodes throughout the monitoring period. The analysis of wind direction and backward trajectory suggested that elevated GEM concentrations at the monitoring site were primarily related to the outflows of atmospheric Hg from mainland China and the Indochina peninsula. The △GEM/△CO values also suggested that GEM was significantly affected by the long-range transport from the anthropogenic sources and biomass burning in Asia and Indochina peninsula.

Pattern of atmospheric mercury speciation during episodes of elevated PM2.5 levels in a coastal city in the Yangtze River Delta, China

Measurement of atmospheric mercury speciation was conducted in a coastal city of the Yangtze River Delta, China from July 2013 to January 2014, in conjunction with air pollutants and meteorological parameters. The mean concentrations of gaseous elemental mercury (GEM), particulate bound mercury (HgP) and reactive gaseous mercury (RGM) were 3.26 ± 1.63 ng m−3, 659 ± 931 pg m−3, and 197 ± 246 pg m−3, respectively. High percentages of HgP during haze days were found, due to the increase in direct emissions and gas-particle partitioning of RGM. The average gas-particle partitioning coefficients (Kp) during moderate or severe haze days (PM2.5 > 150 μg m−3) were obviously decreased. GEM and HgP were positively correlated with PM2.5, SO2, NO2 and CO, suggesting a significant contribution of anthropogenic sources. Elevated HgP concentrations in cold seasons and in the morning were observed while RGM exhibited different seasonal and diurnal pattern. The ratio of HgP/SO2 and Pearson correlation analysis suggested that coal combustion was the main cause of increasing atmospheric Hg concentrations. The monitoring site was affected by local, regional and interregional sources. The back trajectory analysis suggested that air mass from northwest China and Huabei Plain contributed to elevated atmospheric Hg in winter and autumn, while southeast China with clean air masses were the major contributor in summer.

Atmospheric mercury speciation dynamics at the high-altitude Pic du Midi Observatory, southern France

Abstract. Continuous measurements of atmospheric gaseous elemental mercury (GEM), particulate bound mercury (PBM) and gaseous oxidized mercury (GOM) at the high-altitude Pic du Midi Observatory (PDM Observatory, 2877 m a.s.l.) in southern France were made from November 2011 to November 2012. The mean GEM, PBM and GOM concentrations were 1.86 ng m−3, 14 pg m−3 and 27 pg m−3, respectively and we observed 44 high PBM (peak PBM values of 33–98 pg m−3) and 61 high GOM (peak GOM values of 91–295 pg m−3) events. The high PBM events occurred mainly in cold seasons (winter and spring) whereas high GOM events were mainly observed in the warm seasons (summer and autumn). In cold seasons the maximum air mass residence times (ARTs) associated with high PBM events were observed in the upper troposphere over North America. The ratios of high PBM ARTs to total ARTs over North America, Europe, the Arctic region and Atlantic Ocean were all elevated in the cold season compared to the warm season, indicating that the middle and upper free troposphere of the Northern Hemisphere may be more enriched in PBM in cold seasons. PBM concentrations and PBM ∕ GOM ratios during the high PBM events were significantly anti-correlated with atmospheric aerosol concentrations, air temperature and solar radiation, suggesting in situ formation of PBM in the middle and upper troposphere. We identified two distinct types of high GOM events with the GOM concentrations positively and negatively correlated with atmospheric ozone concentrations, respectively. High GOM events positively correlated with ozone were mainly related to air masses from the upper troposphere over the Arctic region and middle troposphere over the temperate North Atlantic Ocean, whereas high GOM events anti-correlated with ozone were mainly related to air masses from the lower free troposphere over the subtropical North Atlantic Ocean. The ARTs analysis demonstrates that the lower and middle free troposphere over the North Atlantic Ocean was the largest source region of atmospheric GOM at the PDM Observatory. The ratios of high GOM ARTs to total ARTs over the subtropical North Atlantic Ocean in summer were significantly higher than those over the temperate and sub-arctic North Atlantic Ocean as well as that over the North Atlantic Ocean in other seasons, indicating abundant in situ oxidation of GEM to GOM in the lower free troposphere over the subtropical North Atlantic Ocean in summer.

A new reconstruction of atmospheric gaseous elemental mercury trend over the last 60 years from Greenland firn records

This study presents measurements of gaseous elemental mercury (GEM) concentrations in the 80 m of firn air at the international drilling site of NEEM in Greenland (2452 m, 77°25.8 N, 51°06.4 W). Using inverse modeling, we were able to reconstruct the atmospheric GEM trend at this Arctic site over the last 60 years. We show discrepancies between this record and the previous firn record of Summit. This could be attributed to experimental biases and/or differences in air mass transport. A multisite inverse model was used to derive an atmospheric scenario reconciling the two firn records. We show that GEM seasonal variations are very limited at these high altitude sites and thus probably unaffected by spring/summer photochemistry. The firn reconstructions suggest an increase of GEM concentrations since the 1950s peaking in the late 1960s and early 1970s. A decrease is then observed with minimum GEM concentrations around 1995–2000. The reconstruction compares well with historical mercury (Hg) releases and recent simulations of atmospheric Hg. Our optimal GEM scenario does not allow to categorically conclude on recent trends for GEM concentrations over the 2000–2010 decade.

Air-sea exchange of gaseous mercury in the East China Sea

Two oceanographic cruises were carried out in the East China Sea (ECS) during the summer and fall of 2013. The main objectives of this study are to identify the spatial-temporal distributions of gaseous elemental mercury (GEM) in air and dissolved gaseous mercury (DGM) in surface seawater, and then to estimate the Hg0 flux. The GEM concentration was lower in summer (1.61 ± 0.32 ng m−3) than in fall (2.20 ± 0.58 ng m−3). The back-trajectory analysis revealed that the air masses with high GEM levels during fall largely originated from the land, while the air masses with low GEM levels during summer primarily originated from ocean. The spatial distribution patterns of total Hg (THg), fluorescence, and turbidity were consistent with the pattern of DGM with high levels in the nearshore area and low levels in the open sea. Additionally, the levels of percentage of DGM to THg (%DGM) were higher in the open sea than in the nearshore area, which was consistent with the previous studies. The THg concentration in fall was higher (1.47 ± 0.51 ng l−1) than those of other open oceans. The DGM concentration (60.1 ± 17.6 pg l−1) and Hg0 flux (4.6 ± 3.6 ng m−2 h−1) in summer were higher than those in fall (DGM: 49.6 ± 12.5 pg l−1 and Hg0 flux: 3.6 ± 2.8 ng m−2 h−1). The emission flux of Hg0 from the ECS was estimated to be 27.6 tons yr−1, accounting for ∼0.98% of the global Hg oceanic evasion though the ECS only accounts for ∼0.21% of global ocean area, indicating that the ECS plays an important role in the oceanic Hg cycle.

Atmospheric Mercury Transfer to Peat Bogs Dominated by Gaseous Elemental Mercury Dry Deposition.

Gaseous elemental mercury (GEM) is the dominant form of mercury in the atmosphere. Its conversion into oxidized gaseous and particulate forms is thought to drive atmospheric mercury wet deposition to terrestrial and aquatic ecosystems, where it can be subsequently transformed into toxic methylmercury. The contribution of mercury dry deposition is however largely unconstrained. Here we examine mercury mass balance and mercury stable isotope composition in a peat bog ecosystem. We find that isotope signatures of living sphagnum moss (Δ(199)Hg = -0.11 ± 0.09‰, Δ(200)Hg = 0.03 ± 0.02‰, 1σ) and recently accumulated peat (Δ(199)Hg = -0.22 ± 0.06‰, Δ(200)Hg = 0.00 ± 0.04‰, 1σ) are characteristic of GEM (Δ(199)Hg = -0.17 ± 0.07‰, Δ(200)Hg = -0.05 ± 0.02‰, 1σ), and differs from wet deposition (Δ(199)Hg = 0.73 ± 0.15‰, Δ(200)Hg = 0.21 ± 0.04‰, 1σ). Sphagnum covered during three years by transparent and opaque surfaces, which eliminate wet deposition, continue to accumulate Hg. Sphagnum Hg isotope signatures indicate accumulation to take place by GEM dry deposition, and indicate little photochemical re-emission. We estimate that atmospheric mercury deposition to the peat bog surface is dominated by GEM dry deposition (79%) rather than wet deposition (21%). Consequently, peat deposits are potential records of past atmospheric GEM concentrations and isotopic composition.

Speciated atmospheric mercury in the marine boundary layer of the Bohai Sea and Yellow Sea

The objectives of this study are to identify the spatial and temporal distributions of gaseous elemental mercury (GEM), reactive gaseous mercury (RGM), and fine particulate mercury (HgP2.5) in the marine boundary layer (MBL) of the Bohai Sea (BS) and Yellow Sea (YS), and to investigate the relationships between mercury species and meteorological parameters. The mean concentrations of GEM, RGM, and HgP2.5 were 2.03 ng m−3, 2.5 pg m−3, and 8.2 pg m−3 in spring, and 2.09 ng m−3, 4.3 pg m−3, and 8.3 pg m−3 in fall. Reactive mercury (RGM + HgP2.5) represented < 1% of total atmospheric mercury (GEM + RGM + HgP2.5), which indicated that most mercury export in the MBL was GEM and the direct outflow of reactive mercury was very small. Moreover, GEM concentrations over the BS were generally higher than those over the YS both in spring and fall. Although RGM showed a homogeneous distribution over the BS and YS both in spring and fall, the mean RGM concentration in fall was significantly higher than that in spring. In contrast, the spatial distribution of HgP2.5 generally reflected a gradient with high levels near the coast of China and low levels in the open sea, suggesting the significant atmospheric mercury outflow from China. Interestingly, the mean RGM concentrations during daytime were significantly higher than those during nighttime both in spring and fall, while the opposite results were observed for HgP2.5. Additionally, RGM positively correlates with air temperature while negatively correlates with relative humidity. In conclusion, the elevated atmospheric mercury levels in the BS and YS compared to other open seas suggested that the human activities had a significant influence on the oceanic mercury cycle downwind of China.

Diffuse soil gas emissions of gaseous elemental mercury (GEM) from hydrothermal-volcanic systems: An innovative approach by using the static closed-chamber method

This study was aimed to test a new methodological approach to carry out measurements of gaseous elemental mercury (GEM) diffusively emitted from soils in hydrothermal-volcanic environments. This method was based on the use of a static closed-chamber (SCC) in combination with a Lumex® RA-915M analyzer that provides GEM measurements in a wide range of concentrations (from 2 to 50,000 ng m−3). Gas samples were collected at fixed time intervals from the SCC positioned on the ground (time-series samples). The Lumex® inlet port was equipped with a three-way Teflon valve allowing the free entrance of air through a carbon trap, in order to: (i) prevent disturbance to the Lumex® operative flow rate (10 L min−1) during the injection of the gas samples from the SCC and (ii) minimize the instability of the baseline signal induced by possible variations of GEM concentrations in air. In the lab, known amounts of GEM, pipetted from a vessel containing an Hg-saturated air in equilibrium with liquid mercury at 27 °C, were injected in the Lumex® via the modified inlet port to construct a calibration curve. The latter was used to calculate the amount of GEM in the SCC (KSCC) from the corresponding GEM concentrations measured by the Lumex® analyzer. The KSCC values of the time-series samples were proportionally increasing with the GEM fluxes (ϕGEM), thus ϕGEM values were computed according to the following equation: ϕGEM=(dKSCC/dt)/A, where A is the basal area of the SCC and dt is the time interval of the time-series sampling. Up to 214 ϕGEM measurements were carried out at Solfatara crater (Campi Flegrei, southern Italy), a hydrothermally altered tuff cone characterized by an anomalous diffuse soil emission of GEM-rich geogenic gases. The measured ϕGEM values varied up to 4 orders of magnitude, from 1,296, corresponding to the sensitivity of the method at the selected sampling time interval (1 min), to 1,957,500 ng m−2 day−1, and were consistent with those recently measured in this crater using a different method. In the field, 10 replicates were carried out in 5 selected sites, allowing to demonstrate that the proposed method has a high reproducibility (RDS < 4%). The ϕGEM and ϕCO2 values, the latter being measured in the same 214 sites by using the accumulation chamber method, showed a low correlation, although both gases were originated from the same deep source. This suggests that GEM and CO2 soil fluxes are differently affected by environmental parameters, such as soil humidity and temperature, which have a strong effect on the release of GEM from the soil, whereas they do not play a significant role in the diffuse degassing of CO2. The measured fluxes were used to compute the CO2 and GEM total outputs (402 and 5.41 × 10−6 t day−1, respectively) from the study area (92,000 m2) and to construct contour maps showing the spatial distribution of the ϕCO2 and ϕGEM values. By modifying the geometry of SCC and the time interval of the sampling series, the proposed method can be applied to the measurements of GEM soil fluxes in other geological systems and man-made environments.

Modeling the global atmospheric transport and deposition of mercury to the Great Lakes

Abstract Mercury contamination in the Great Lakes continues to have important public health and wildlife ecotoxicology impacts, and atmospheric deposition is a significant ongoing loading pathway. The objective of this study was to estimate the amount and source-attribution for atmospheric mercury deposition to each lake, information needed to prioritize amelioration efforts. A new global, Eulerian version of the HYSPLIT-Hg model was used to simulate the 2005 global atmospheric transport and deposition of mercury to the Great Lakes. In addition to the base case, 10 alternative model configurations were used to examine sensitivity to uncertainties in atmospheric mercury chemistry and surface exchange. A novel atmospheric lifetime analysis was used to characterize fate and transport processes within the model. Model-estimated wet deposition and atmospheric concentrations of gaseous elemental mercury (Hg(0)) were generally within ∼10% of measurements in the Great Lakes region. The model overestimated non-Hg(0) concentrations by a factor of 2–3, similar to other modeling studies. Potential reasons for this disagreement include model inaccuracies, differences in atmospheric Hg fractions being compared, and the measurements being biased low. Lake Erie, downwind of significant local/regional emissions sources, was estimated by the model to be the most impacted by direct anthropogenic emissions (58% of the base case total deposition), while Lake Superior, with the fewest upwind local/regional sources, was the least impacted (27%). The U.S. was the largest national contributor, followed by China, contributing 25% and 6%, respectively, on average, for the Great Lakes. The contribution of U.S. direct anthropogenic emissions to total mercury deposition varied between 46% for the base case (with a range of 24–51% over all model configurations) for Lake Erie and 11% (range 6–13%) for Lake Superior. These results illustrate the importance of atmospheric chemistry, as well as emissions strength, speciation, and proximity, to the amount and source-attribution of mercury deposition.

Impact of marine mercury cycling on coastal atmospheric mercury concentrations in the North- and Baltic Sea region

Abstract The cycling of mercury between ocean and atmosphere is an important part of the global Hg cycle. Here we study the regional contribution of the air-sea exchange in the North- and Baltic Sea region. We use a newly developed coupled regional chemistry transport modeling (CTM) system to determine the flux between atmosphere and ocean based on the meteorological model COSMO-CLM, the ocean-ecosystem model ECOSMO, the atmospheric CTM CMAQ and a newly developed module for mercury partitioning and speciation in the ocean (MECOSMO). The model was evaluated using atmospheric observations of gaseous elemental mercury (GEM), surface concentrations of dissolved gaseous mercury (DGM), and air-sea flux (ASF) calculations based on observations made on seven cruises in the western and central Baltic Sea and three cruises in the North Sea performed between 1991 and 2006. It was shown that the model is in good agreement with observations: DGM (Normalized Mean Bias NMB=-0.27 N=413), ASF (NMB=-0.32, N=413), GEM (NMB=0.07, N=2359). Generally, the model was able to reproduce the seasonal DGM cycle with the best agreement during winter and autumn (NMBWinter=-0.26, NMBSpring=-0.41, NMBSummer=-0.29, NMBAutumn=-0.03). The modelled mercury evasion from the Baltic Sea ranged from 3400 to 4000 kg/a for the simulation period 1994–2007 which is on the lower end of previous estimates. Modelled atmospheric deposition, river inflow and air-sea exchange lead to an annual net Hg accumulation in the Baltic Sea of 500 to 1000 kg/a. For the North Sea the model calculates an annual mercury flux into the atmosphere between 5700 and 6000 kg/a. The mercury flux from the ocean influenced coastal atmospheric mercury concentrations. Running CMAQ coupled with the ocean model lead to better agreement with GEM observations. Directly at the coast GEM concentrations could be increased by up to 10% on annual average and observed peaks could be reproduced much better. At stations 100km downwind the impact was still observable but reduced to 1–3%.

Temporal variations in gaseous elemental mercury concentrations at a contaminated site: Main factors affecting nocturnal maxima in daily cycles

Abstract Mercury is considered to be a global pollutant and it has been globally transported as gaseous elemental mercury (GEM). International networks for the continuous monitoring of mercury, all of which are based on background sites, study the dispersion pattern of this metal and trends in its evolution in time and space. However, information about seasonal and daily cycling of polluted sites is scarce. The aim of the work described here was to cover this gap in knowledge. For this purpose, continuous (GEM) measurements were carried out in Almaden town from November 2011 to September 2013. Meteorological data were also collected during this time. GEM data show an average concentration during the sampling period (2011–2013) of 27.4 ng m−3, with a range of 0.8–686.9 ng m−3. The results highlighted seasonal and daily cycles of GEM in Almaden town, with seasonally higher levels in summer (686.9 ng m−3) and significantly daily higher levels during the night. A multiple linear regression model has established wind speed as the best GEM predictor in all seasons during the night, while the best predictor in winter is relative humidity, temperature in spring, solar radiation in summer and wind speed in autumn during the day. These results provide evidence that, in mining polluted sites like Almaden, photochemical reactions have a negligible impact on GEM levels during the daytime and that meteorological parameters are more relevant. Further studies on diurnal GEM cycling in polluted sites must be carried out to obtain a realistic local risk assessment, taking into account night GEM levels and their importance in each case study.