Gaseous Elemental Mercury Emissions Research Articles

Combating air pollution significantly reduced air mercury concentrations in China.

In the past decade, China has motivated proactive emission control measures that have successfully reduced emissions of many air pollutants. For atmospheric mercury, which is a globally transported neurotoxin, much less is known about the long-term changes in its concentrations and anthropogenic emissions in China. In this study, over a decade of continuous observations at four Chinese sites show that gaseous elemental mercury (GEM) concentrations continuously increased until the early 2010s, followed by significant declines at rates of 1.8%-6.1% yr-1 until 2022. The GEM decline from 2013 to 2022 (by 38.6%±12.7%) coincided with the decreasing concentrations of criteria air pollutants in China and were larger than those observed elsewhere in the northern hemisphere (5.7%-14.2%). The co-benefits of emission control measures contributed to the reduced anthropogenic Hg emissions and led to the GEM decline in China. We estimated that anthropogenic GEM emissions in China were reduced by 38%-50% (116-151 tons) from 2013 to 2022 using the machine-learning and relationship models.

Gaseous elemental mercury emissions from informal E-Waste recycling facilities in Pakistan

Detrimental effects of mercury (Hg) on ecosystems and human health have been well-documented. Whereas emissions of gaseous elemental mercury (GEM) from e-waste recycling have been reported in developed countries, much less is known about the situation in the Global South. Using a total of 132 passive air samplers, seasonally resolved concentrations of GEM in air were measured continuously at 32 informal e-waste recycling facilities and background location in Pakistan for a period of one year between September 2020 and December 2021. Annual average GEM concentrations at the studied locations ranged from 1.8 to 92 ng m−3. Among the studied cities, higher concentrations were measured in Karachi (mean ± s.d: 17 ± 22, range: 4.2–92 ng m−3), Lahore (16 ± 4.2, 8.2–22 ng m−3) and Peshawar (15 ± 17, 4.9–80 ng m−3), while lower levels were measured in Hyderabad (6.9 ± 6.2, 3.1–25 ng m−3), consistent with a higher rate of informal recycling activities in metropolitan areas. Seasonally, higher GEM levels occurred during autumn (15 ± 16: 3.3–92 ng m−3) and summer (13 ± 8.7: 1.8–80 ng m−3) than in winter (12 ± 8.4: 2.5–49 ng m−3) and spring (9.2 ± 7.3: 1.8–80 ng m−3), possibly reflecting enhanced volatilization at higher temperatures and/or varying magnitude of recycling operations in different seasons. Policies and strict regulations related to e-waste management should be developed and implemented urgently in the country.

Changes in Atmospheric Gaseous Elemental Mercury Concentrations and Isotopic Compositions at Mt. Changbai During 2015–2021 and Mt. Ailao During 2017–2021 in China

AbstractChina is the largest contributor to the global total anthropogenic mercury (Hg) emissions. However, the trend in anthropogenic Hg emissions in recent years in China has not been effectively evaluated due to the lack of long‐term atmospheric Hg observations. This study documents the changes in atmospheric gaseous elemental mercury (GEM) concentrations and isotopic compositions at Mt. Changbai (MCB) in northeastern China during 2015–2021 and Mt. Ailao (MAL) in southwestern China during 2017–2021, and explores the potential factors controlling these changes. GEM concentrations showed continuous declines from 2015 to 2021 (−2.1 ± 0.6% yr−1) at MCB and from 2017 to 2021 (−4.0 ± 1.4% yr−1) at MAL. Accompanied with these GEM declines are positive shifts in δ202Hg (medians: from 0.42 to 0.46‰ at MCB and from 0.17 to 0.57‰ at MAL), and negative shifts in Δ199Hg (medians: from −0.17‰ to −0.21‰ at MCB and from −0.10‰ to −0.17‰ at MAL) and Δ200Hg values (medians: from −0.07‰ to −0.08‰ at MCB and from −0.03‰ to −0.05‰ at MAL) (at significant levels for Δ199Hg at MCB and δ202Hg and Δ199Hg at MAL). These changes were mainly caused by the decreases in regional anthropogenic emissions in the study areas. Based on a ternary mixing model with Δ199Hg and Δ200Hg as input, we estimate decline rates of 5.8 ± 2.8 and 4.8 ± 3.0% yr−1 for the regional anthropogenic GEM emissions in northeastern and southwestern China, respectively.

Health risk assessment of gaseous elemental mercury (GEM) in Mexico City.

Emissions of gaseous elemental mercury (GEM or Hg0) from different sources in urban areas are important subjects for environmental investigations. In this study, atmospheric Hg measurements were conducted to investigate air pollution in the urban environment by carrying out several mobile surveys in Mexico City. This work presents atmospheric concentrations of GEM in terms of diurnal variation trends and comparisons with criteria for pollutant concentrations such as CO, SO2, NO2, PM2.5, and PM10. The concentration of GEM was measured during the pre-rainy period by using a high-resolution active air sampler, the Lumex RA 915 M mercury analyzer. In comparison with those for other cities worldwide, the GEM concentrations were similar or slightly elevated, and they ranged from 0.20 to 30.23 ng m−3. However, the GEM concentration was significantly lower than those in contaminated areas, such as fluorescent lamp factory locations and gold mining zones. The GEM concentrations recorded in Mexico City did not exceed the WHO atmospheric limit of 200 ng m−3. We performed statistical correlation analysis which suggests equivalent sources between Hg and other atmospheric pollutants, mainly NO2 and SO2, emitted from urban combustion and industrial plants. The atmospheric Hg emissions are basically controlled by sunlight radiation, as well as having a direct relationship with meteorological parameters. The area of the city studied herein is characterized by high traffic density, cement production, and municipal solid waste (MSW) treatment, which constantly release GEM into the atmosphere. In this study, we included the simulation with the HYSPLIT dispersion model from three potential areas of GEM release. Emissions from industrial corridors and volcanic plumes localized outside the urban area contribute to the pollution of Mexico City and mainly affect the northern area during specific periods and climate conditions. Using the USEPA model, we assessed the human health risk resulting from exposure to inhaled GEM among residents of Mexico City. The results of the health risk assessment indicated no significant noncarcinogenic risk (hazard quotient (HQ) < 1) or consequent adverse effects for children and adults living in the sampling area over the study period. GEM emissions inventory data is necessary to improve our knowledge about the Hg contribution and effect in urban megacity areas with the objective to develop public safe policy and implementing the Minamata Convention.Supplementary informationThe online version contains supplementary material available at 10.1007/s10661-022-10107-7.

Temporal and spatial assessment of gaseous elemental mercury concentrations and emissions at contaminated sites using active and passive measurements

Gaseous elemental mercury (GEM) concentrations and emissions at legacy contaminated sites represent poorly characterised components of global mercury (Hg) inventories. Here we apply both active (Tekran 2537A) and passive (MerPAS) sampling methods to comprehensively assess GEM concentrations and emissions across four dimensions (three spatial, one temporal) at a legacy contaminated site with elevated soil Hg. Concentrations are measured up to 37.4 (active) and 10.8 (passive) ng m−3, which represents enhancements of 23× and 7× above background (1.62 ng m−3), respectively. Temporal resolution of the sampling methods defines this difference (active: 5-min; passive: 44 days). Diurnal (active) GEM concentration patterns were highest in contaminated areas at night when low wind speeds compress the boundary layer. Passive sampling substantially improves the spatial characterisation of GEM concentrations both horizontally (highest GEM concentration in areas with elevated soil Hg) and vertically (improved vertical concentration gradient using telescopic sampling towers). Passive sampler deployments were used to generate a GEM emissions estimate (landfill-to-atmosphere) of 1.2 ± 0.6 kg yr−1 (or 310 ± 150 ng m−2 h−1). This study demonstrates how combining active (strength: temporal assessment) and passive (strength: spatial assessments) sampling improves the evaluation of GEM concentrations and emissions to the atmosphere at Hg contaminated sites across four dimensions.

First simultaneous mercury and major volatiles characterization of atmospheric hydrothermal emissions at the Pisciarelli's fumarolic system (Campi Flegrei, Italy)

Hydrothermal systems with active surface expressions are important natural source of atmospheric mercury. Here we report on the first simultaneous assessment of gaseous elemental mercury (GEM) and major volatiles (H2S and CO2) fluxes from the fumarolic system of Pisciarelli, currently the most active at the Campi Flegrei caldera (CFc), Naples (Italy). This was achieved via a GPS-synchronized Lumex and MultiGAS survey which extends similar investigations reported elsewhere. GEM concentrations measured in the fumarolic emissions were consistently above background air level close to the degassing area (mean ~ 8 ± 3 ng m−3 on average) and ranged up to 12,000 ng m−3. Our data evidenced pulsed sequences of GEM increases in the fumarole plume, closely matched by temporally consistent increases in CO2 and H2S (r2 = 0.9), supporting the idea that major volatiles, such as CO2 acts as potential carrier in transporting GEM within the magmatic/hydrothermal systems. The slope of the best fit calculated for the dispersion of our data provides a GEM/CO2 molar ratio of 1.1 × 10−8 and a GEM/H2S of 5 × 10−6, respectively. These ratios are comparable to those reported for both low (~ 100 °C) and high-T (~ 250 °C) fumaroles from non-explosive volcanic/hydrothermal degassing systems elsewhere. We adopted an ad-hoc method that combines video footages and gas measurements to obtain high precision concentration maps of gas emissions used to estimate the total atmospheric GEM, CO2 and H2S flux of about 0.0113, 225059 and 511 t y−1, respectively. The human health risk assessment related to the GEM emissions at Pisciarelli, confirms that, except for the degassing fumarolic area, all the main sites affected by the plume dispersion, always remain well below the safe threshold recommended by the health authorities.

Gaseous mercury capture by coir fibre coated with a metal-halide

ABSTRACT Toxic gaseous elemental mercury (GEM) is emitted to the atmosphere through a variety of routes at rates estimated at over 5000 tonnes per annum, a large fraction of which is Anthropogenic. It is then widely disbursed atmospherically and eventually deposited, where it is subject to further biogeochemical cycling, including re-emission. Research into capture of point source mercury emissions revolves almost exclusively around the use of activated carbons, various catalytic oxidation substrates, or as a by-product of acidic treatments of flue gas during SOx and NOx reduction methods. GEM is very non-reactive in its native state, but capture rates are greatly enhanced if GEM is first oxidized, or at least where oxidation states play a role at the substrate GEM interface. Little research has been devoted to capture of GEM directly. However, presented here is a novel adaption of coir fibers for use as a substrate in capturing GEM emissions directly. Various coir modifications were investigated, with the most effective being fibers coated with CuI crystals dispersed in a non-crosslinked poly-siloxane matrix. Scanning electron microscopy was used to view surface morphologies, and sorption characteristics were measured using atomic absorption spectroscopy (AAS). These results indicate that coir fibers modified by CuI-[SiO2] n show great promise in their ability to efficiently sorb GEM, and could potentially be utilized in a variety of configurations and settings where GEM emissions need to be captured. Implications Highly toxic gaseous elemental mercury (GEM) has proved very difficult to capture, requiring complex catalytic oxidation or expensive gas scrubbing technologies. The modified coir fiber described in this work can effectively capture GEM without prior catalytic oxidation or any other physicochemical treatment of the gas. The solution provided here is made from renewable resources, is low cost, and the raw materials are readily available in bulk. Further, the mercury is bound in a stable and insoluble form that can be readily isolated from the substrate. This filtration device can be adapted to suit a variety of settings for GEM capture.

Mercury emission from industrially contaminated soils in relation to chemical, microbial, and meteorological factors

The Minamata Convention entered into force in 2017 with the aim to phase-out the use of mercury (Hg) in manufacturing processes such as the chlor-alkali or vinyl chloride monomer production. However, past industrial use of Hg had already resulted in extensive soil pollution, which poses a potential environmental threat. We investigated the emission of gaseous elemental mercury (Hg0) from Hg polluted soils in settlement areas in the canton of Valais, Switzerland, and its impact on local air Hg concentrations. Most soil Hg was found as soil matrix-bound divalent Hg (HgII). Elemental mercury (Hg0) was undetectable in soils, yet we observed substantial Hg0 emission (20–1392 ng m−2 h−1) from 27 soil plots contaminated with Hg (0.2–390 mg Hg kg−1). The emissions of Hg0 were calculated for 1274 parcels covering an area of 8.6 km2 of which 12% exceeded the Swiss soil remediation threshold of 2 mg Hg kg−1. The annual Hg0 emission from this area was approximately 6 kg a−1, which is almost 1% of the total atmospheric Hg emissions in Switzerland based on emission inventory estimates. Our results show a higher abundance of Hg resistance genes (merA) in soil microbial communities with increasing soil Hg concentrations, indicating that biotic reduction of HgII is likely an important pathway to form volatile Hg0 in these soils. The total soil Hg pool in the top 20 cm of the investigated area was 4288 kg; hence, if not remediated, these contaminated soils remain a long-term source of atmospheric Hg, which is prone to long-range atmospheric transport.

Automated Stable Isotope Sampling of Gaseous Elemental Mercury (ISO-GEM): Insights into GEM Emissions from Building Surfaces.

Atmospheric monitoring networks quantify gaseous elemental mercury (GEM) concentrations, but not isotopic compositions. Here, we present a new method for automated and quantitative stable isotope sampling of GEM (ISO-GEM) at the outlet of a commercial Hg analyzer. A programmable multivalve manifold selects Hg at the analyzer inlet and outlet based on specific criteria (location, time, GEM concentration, auxiliary threshold). Outlet Hg recovery was tested for gold traps, oxidizing acidic solution traps, and activated carbon traps. We illustrate the ISO-GEM method in an exploratory study on the effect of building walls on local GEM. We find that GEM concentrations directly at the building surface (wall inlet) are significantly enhanced (mean 3.8 ± 1.8 ng/m3) compared to 3 m from the building wall (free inlet) (mean 1.5 ± 0.4 ng/m3). GEM δ202Hg (-1.26‰ ± 0.41‰, 1 SD, n = 16) and Δ199Hg (-0.05‰ ± 0.10‰, 1 SD, n = 16) at the wall inlet were different from ambient GEM δ202Hg (0.76‰ ± 0.09‰, 1 SD, n = 16) and Δ199Hg (-0.21‰ ± 0.05‰, 1 SD, n = 16) at the free inlet. The isotopic fingerprint of GEM at the wall inlet suggests that GEM emission from the aluminum building surface affected local GEM concentration measurements. These results illustrate the versatility of the automated Hg isotope sampling.

Isotopic Composition of Gaseous Elemental Mercury in the Marine Boundary Layer of East China Sea

AbstractCharacterizing the speciation and isotope signatures of atmospheric mercury (Hg) downwind of mainland China is critical to understanding the outflow of Hg emission and the contributing sources. In this study, we measured the concentrations of gaseous elemental mercury (GEM), particulate bound mercury, gaseous oxidized mercury, and the GEM isotopic composition in the marine boundary layer of East China Sea from October 2013 to January 2014. Mean (±1σ) GEM, particulate bound mercury, and gaseous oxidized mercury concentrations were 2.25 ± 1.03 ng/m3, 26 ± 38 pg/m3, and 8 ± 10 pg/m3, respectively. Most events of elevated GEM are associated with the outflow of Hg emissions in mainland China. The 24‐ and 48‐hr integrated GEM samples showed large variations in both δ202Hg (−1.63‰ to 0.34‰) and Δ199Hg (−0.26‰ to −0.02‰). GEM δ202Hg and Δ199Hg were negatively and positively correlated to its atmospheric concentrations, respectively, suggesting a binary physical mixing of regional background GEM and Hg emissions in mainland China. Using a binary mixing model, highly negative δ202Hg (−1.79 ± 0.24‰, 1σ) and near‐zero Δ199Hg (0.02 ± 0.04‰, 1σ) signatures for China GEM emissions are predicted. Such isotopic signatures are significantly different from those found in North America and Europe and the background global/regional atmospheric GEM pool. It is likely that emissions from industrial and residential coal combustion (lacking conventional air pollutant control devices), cement and mercury production, biomass burning, and soil emissions contributed significantly to the estimated isotope signatures of GEM emissions in China.

Fluxes of gaseous elemental mercury (GEM) in the High Arctic during atmospheric mercury depletion events (AMDEs)

Abstract. Measurements of gaseous elemental mercury (GEM) fluxes over snow surfaces using a relaxed eddy accumulation (REA) system are carried out at the High Arctic site at the Villum Research Station, Station Nord, in North Greenland. Simultaneously, CO2 fluxes are determined using the eddy covariance (EC) technique. The REA system with dual inlets and dual analyzers is used to measure fluxes directly over the snow. The measurements were carried out from 23 April to 12 May during spring 2016, where atmospheric mercury depletion events (AMDEs) took place. The measurements showed a net emission of 8.9 ng m−2 min−1, with only a few minor episodes of net depositional fluxes, from a maximum deposition of 8.1 ng m−2 min−1 to a maximum emission of 179.2 ng m−2 min−1. The data support the theory that gaseous oxidized mercury (GOM) is deposited during AMDEs followed by formation of GEM on surface snow and is re-emitted as GEM shortly after the AMDEs. Furthermore, observation of the relation between GEM fluxes and atmospheric temperature suggests that GEM emission partly could be affected by surface heating. However, it is also clear that the GEM emissions are affected by many parameters.

Gaseous elemental mercury (GEM) fluxes over canopy of two typical subtropical forests in south China

Abstract. Mercury (Hg) exchange between forests and the atmosphere plays an important role in global Hg cycling. The present estimate of global emission of Hg from natural source has large uncertainty, partly due to the lack of chronical and valid field data, particularly for terrestrial surfaces in China, the most important contributor to global atmospheric Hg. In this study, the micrometeorological method (MM) was used to continuously observe gaseous elemental mercury (GEM) fluxes over forest canopy at a mildly polluted site (Qianyanzhou, QYZ) and a moderately polluted site (Huitong, HT, near a large Hg mine) in subtropical south China for a full year from January to December in 2014. The GEM flux measurements over forest canopy in QYZ and HT showed net emission with annual average values of 6.67 and 0.30 ngm-2h-1, respectively. Daily variations of GEM fluxes showed an increasing emission with the increasing air temperature and solar radiation in the daytime to a peak at 13:00, and decreasing emission thereafter, even as a GEM sink or balance at night. High temperature and low air Hg concentration resulted in the high Hg emission in summer. Low temperature in winter and Hg absorption by plant in spring resulted in low Hg emission, or even adsorption in the two seasons. GEM fluxes were positively correlated with air temperature, soil temperature, wind speed, and solar radiation, while it is negatively correlated with air humidity and atmospheric GEM concentration. The lower emission fluxes of GEM at the moderately polluted site (HT) when compared with that in the mildly polluted site (QYZ) may result from a much higher adsorption fluxes at night in spite of a similar or higher emission fluxes during daytime. This shows that the higher atmospheric GEM concentration at HT restricted the forest GEM emission. Great attention should be paid to forests as a crucial increasing Hg emission source with the decreasing atmospheric GEM concentration in polluted areas because of Hg emission abatement in the future.

Mercury fluxes over an Australian alpine grassland and observation of nocturnal atmospheric mercury depletion events

Abstract. Aerodynamic gradient measurements of the air–surface exchange of gaseous elemental mercury (GEM) were undertaken over a 40 ha alpine grassland in Australia's Snowy Mountains region across a 3-week period during the late austral summer. Bi-directional GEM fluxes were observed throughout the study, with overall mean value of 0.2 ± 14.5 ng m−2 h−1 and mean nocturnal fluxes of −1.5 ± 7.8 ng m−2 h−1 compared to diurnal fluxes of 1.8 ± 18.6 ng m−2 h−1. Deposition velocities ranged from −2.2 to 2.9 cm s−1, whilst ambient GEM concentrations throughout the study were 0.59 ± 0.10 ng m−3. Cumulative GEM fluxes correlated well with 24 h running mean soil temperatures, and one precipitation event was shown to have a positive impact on diurnal emission fluxes. The underlying vegetation had largely senesced and showed little stomatal control on fluxes. Nocturnal atmospheric mercury depletion events (NAMDEs) were observed concomitant with O3 depletion and dew formation under shallow, stable nocturnal boundary layers. A mass balance box model was able to reproduce ambient GEM concentration patterns during NAMDE and non-NAMDE nights without invoking chemical oxidation of GEM throughout the column, indicating a significant role of surface processes controlling deposition in these events. Surface deposition was enhanced under NAMDE nights, though uptake to dew likely represents less than one-fifth of this enhanced deposition. Instead, enhancement of the surface GEM gradient as a result of oxidation at the surface in the presence of dew is hypothesised to be responsible for a large portion of GEM depletion during these particular events. GEM emission pulses following nights with significant deposition provide evidence for the prompt recycling of 17 % of deposited mercury, with the remaining portion retained in surface sinks. The long-term impacts of any sinks are however likely to be minimal, as cumulative GEM flux across the study period was close to zero.

Gaseous elemental mercury in the marine boundary layer and air-sea flux in the Southern Ocean in austral summer

Gaseous elemental mercury (GEM) in the marine boundary layer (MBL), and dissolved gaseous mercury (DGM) in surface seawater of the Southern Ocean were measured in the austral summer from December 13, 2014 to February 1, 2015. GEM concentrations in the MBL ranged from 0.4 to 1.9ngm−3 (mean±standard deviation: 0.9±0.2ngm−3), whereas DGM concentrations in surface seawater ranged from 7.0 to 75.9pgL−1 (mean±standard deviation: 23.7±13.2pgL−1). The occasionally observed low GEM in the MBL suggested either the occurrence of atmospheric mercury depletion in summer, or the transport of GEM-depleted air from the Antarctic Plateau. Elevated GEM concentrations in the MBL and DGM concentrations in surface seawater were consistently observed in the ice-covered region of the Ross Sea implying the influence of the sea ice environment. Diminishing sea ice could cause more mercury evasion from the ocean to the air. Using the thin film gas exchange model, the air-sea fluxes of gaseous mercury in non-ice-covered area during the study period were estimated to range from 0.0 to 6.5ngm−2h−1 with a mean value of 1.5±1.8ngm−2h−1, revealing GEM (re-)emission from the East Southern Ocean in summer.

Erratum to: Gaseous Elemental Mercury Level and Distribution in a Heavily Contaminated Site: the Ex-chlor Alkali Plant in Torviscosa (Northern Italy)

Mercury (Hg) poses environmental and health risks due to its global distribution and high toxicity exhibited in some of its chemical forms. Although Hg is naturally present in the environment, human activities have increased its cycling among the land, atmosphere and ocean by a factor of three to five comparing the pre-industrial period to the present day. The Torviscosa chlor-alkali plant (CAP), which operated since the beginning of twentieth century, was one of the most important Cl2 production capacity in the Northern Italy and was responsible for an uncontrolled discharge of Hg in the surrounding area. Previous studies reported the high degree of Hg pollution in soils, river sediments and surface waters of the area, but the Hg level in the atmospheric media was never taken into consideration. In this work, an integrated approach was applied with the aim to assess the level, distribution and dispersion of gaseous elemental mercury (GEM) close to the CAP area. GEM levels were monitored by means of four surveys conducted from September 2014 to July 2015, at fixed locations and covering an area of about 10 km2 (including CAP area, Torviscosa village and reclaimed land), accomplished to Hg bioaccumulation measurements in selected lichens. The results indicate that the CAP area currently represents the main source of GEM in the Friuli Venezia Giulia region. The highest levels were found close to the old factory’s buildings (more than 5000 ng m−3), whereas other sites are less impacted. The emission of GEM is not clearly related to the intensity of solar radiation (temperature) at the soil level; however, this latter influences the release from the old buildings employed in the past for the production activities. The most important factor driving the GEM dispersion is the wind, as confirmed by the map of lichens bioaccumulation. In this context, the GEM plume partially affects the nearby village of Torviscosa (about 1 km), but the values found were always well below the international thresholds for residential areas, thus excluding the risk of inhalation for local inhabitants.

Observations of atmospheric mercury in China: a critical review

Abstract. China presently contributes the largest amount of anthropogenic mercury (Hg) emission into the atmosphere in the world. Over the past decade, numerous studies have been conducted to characterize the concentration and forms of atmospheric Hg in China, which provide insights into the spatial and temporal distributions of atmospheric Hg through ground-based measurements at widely diverse geographical locations and during cruise and flight campaigns. In this paper, we present a comprehensive review of the state of understanding in atmospheric Hg in China. Gaseous elemental mercury (GEM) and particulate-bound mercury (PBM) measured at the remote sites in China are substantially elevated compared to the background values in the Northern Hemisphere. In Chinese urban areas, the highly elevated GEM, PBM and gaseous oxidized mercury (GOM) were mainly derived from local anthropogenic Hg emissions, whereas regional anthropogenic emissions and long-range transport from domestic source regions are the primary causes of the elevated GEM and PBM concentrations at remote sites. Using 7–9 years of continuous observations at a remote site and an urban site, a slight increase in atmospheric GEM (2.4–2.5 % yr−1) was identified (paired samples test: p &lt; 0.01), which is in agreement with the increasing domestic anthropogenic emissions. Anthropogenic GEM emission quantity in China estimated through the observed GEM / CO concentration ratios ranged from 632 to 1138 t annually over the past decade, 2–3 times larger than published values using emission activity data. Modeling results and filed measurements show dry deposition is the predominant process for removing Hg from the atmosphere, 2.5–9.0 times larger than wet deposition, due to the elevated atmospheric GEM and PBM concentrations that facilitate dry deposition to terrestrial landscapes. Further studies to reconcile the observed and simulated Hg concentrations, to understand the impact of domestic emission reduction on Hg concentration and deposition and to delineate the role of Hg emission and deposition of China in the global Hg biogeochemical cycle, are needed.

Eddy covariance flux measurements of gaseous elemental mercury using cavity ring-down spectroscopy.

A newly developed pulsed cavity ring-down spectroscopy (CRDS) system for measuring atmospheric gaseous elemental mercury (GEM) concentrations at high temporal resolution (25 Hz) was used to successfully conduct the first eddy covariance (EC) flux measurements of GEM. GEM is the main gaseous atmospheric form, and quantification of bidirectional exchange between the Earth's surface and the atmosphere is important because gas exchange is important on a global scale. For example, surface GEM emissions from natural sources, legacy emissions, and re-emission of previously deposited anthropogenic pollution may exceed direct primary anthropogenic emissions. Using the EC technique for flux measurements requires subsecond measurements, which so far has not been feasible because of the slow time response of available instrumentation. The CRDS system measured GEM fluxes, which were compared to fluxes measured with the modified Bowen ratio (MBR) and a dynamic flux chamber (DFC). Measurements took place near Reno, NV, in September and October 2012 encompassing natural, low-mercury (Hg) background soils and Hg-enriched soils. During nine days of measurements with deployment of Hg-enriched soil in boxes within 60 m upwind of the EC tower, the covariance of GEM concentration and vertical wind speed was measured, showing that EC fluxes over an Hg-enriched area were detectable. During three separate days of flux measurements over background soils (without Hg-enriched soils), no covariance was detected, indicating fluxes below the detection limit. When fluxes were measurable, they strongly correlated with wind direction; the highest fluxes occurred when winds originated from the Hg-enriched area. Comparisons among the three methods showed good agreement in direction (e.g., emission or deposition) and magnitude, especially when measured fluxes originated within the Hg-enriched soil area. EC fluxes averaged 849 ng m(-2) h(-1), compared to DFC fluxes of 1105 ng m(-2) h(-1) and MBR fluxes of 1309 ng m(-2) h(-1). This study demonstrated that a CRDS system can be used to measure GEM fluxes over Hg-enriched areas, with a conservative detection limit estimate of 32 ng m(-2) h(-1).

An approach estimating bidirectional air‐surface exchange for gaseous elemental mercury at AMNet sites

AbstractThe bidirectional air‐surface exchange for gaseous elemental mercury (GEM) and existing measurements of the compensation points over a variety of canopy types are reviewed. Deposition and emission of GEM are dependent on several factors such as the type of canopy, temperature, season, atmospheric GEM concentrations, and meteorological conditions, with compensation points varying between 0.5 and 33 ng m−3. Emissions tend to increase from the spring to summer seasons, as the GEM accumulates in the foliage of the vegetation. A strong dependence on solar radiation has been observed, with higher emissions under light conditions. A bidirectional air‐surface exchange flux model is proposed for estimating GEM fluxes at a two‐hourly time resolution for the National Atmospheric Deposition Program's, Atmospheric Mercury Network (AMNet) sites. Compared to the unidirectional dry deposition model used in Zhang et al. (2012), two additional parameters, stomatal and soil emission potential, were needed in the bidirectional model and were chosen based on knowledge gained in the literature review and model sensitivity test results. Application of this bidirectional model to AMNet sites have produced annual net deposition fluxes comparable to those estimated in Zhang et al. (2012) at the majority of the sites. In this study, the net GEM dry deposition has been estimated separately for each dominant land use type surrounding each site, and this approach is also recommended for future calculations for easy application of the results to assessments of the mercury effects on various ecosystems.

First combined flux chamber survey of mercury and CO2 emissions from soil diffuse degassing at Solfatara of Pozzuoli crater, Campi Flegrei (Italy): Mapping and quantification of gas release

There have been limited studies to date targeting gaseous elemental mercury (GEM) flux from soil emission in enriched volcanic substrates and its relation with CO2 release and tectonic structures. In order to evaluate and understand the processes of soil–air exchanges involved at Solfatara of Pozzuoli volcano, the most active zone of Campi Flegrei caldera (Italy), an intensive field measurement survey has been achieved in September 2013 by using high-time resolution techniques. Soil–air exchange fluxes of GEM and CO2 have been measured simultaneously at 116 points, widely distributed within the crater. Quantification of gas flux has been assessed by using field accumulation chamber method in conjunction with a Lumex®-RA 915+ portable mercury vapor analyzer and a LICOR for CO2 determination, respectively. The spatial distribution of GEM and CO2 emissions correlated quite closely with the hydrothermal and geological features of the studied area. The highest GEM fluxes (from 4.04 to 5.9×10−5gm−2d−1) were encountered close to the southern part of the crater interested by an intense fumarolic activity and along the SE–SW tectonic fracture (1.26×10−6–6.91×10−5gGEMm−2d−1). Conversely, the lowest values have been detected all along the western rim of the crater, characterized by a weak gas flux and a lush vegetation on a very sealed clay soil, which likely inhibited mercury emission (range: 1.5×10−7–7.18×10−6gGEMm−2d−1). Results indicate that the GEM exchange between soil and air inside the Solfatara crater is about 2–3 orders of magnitude stronger than that in the background areas (10−8–10−7gm−2d−1). CO2 soil diffuse degassing exhibited an analogous spatial pattern to the GEM fluxes, with emission rates ranging from about 15 to ~20,000gCO2m−2d−1, from the outermost western zones to the south-eastern sector of the crater. The observed significant correlation between GEM and CO2 suggested that in volcanic system GEM volatilizes from substrate in a similar manner to the release of CO2. The quantitative estimation of the total amount of CO2 and GEM released from the Solfatara crater gave values of about 304±13 and 3.7±0.2×10−6td−1, respectively. Finally, based on our dataset and previous work, we propose that an average GEM/CO2 molar ratio of ~2×10−8 (n=9) is best representative of hydrothermal degassing. Taking into account the uncertainty in global hydrothermal CO2 emissions from sub-aerial environments (~1012Molyr−1), we infer a global volcanic GEM flux from hydrothermal environments of ~about 8.5tyr−1. Although this value has to be considered as a lower limit for the global emission of GEM from these sources, we suggest that on a local scale hydrothermal activity can be regarded as a significant source of GEM than previously recognized to the atmospheric pool.

Mercury Speciation at a Coastal Site in the Northern Gulf of Mexico: Results from the Grand Bay Intensive Studies in Summer 2010 and Spring 2011

During two intensive studies in summer 2010 and spring 2011, measurements of mercury species including gaseous elemental mercury (GEM), gaseous oxidized mercury (GOM), and particulate-bound mercury (PBM), trace chemical species including O3, SO2, CO, NO, NOY, and black carbon, and meteorological parameters were made at an Atmospheric Mercury Network (AMNet) site at the Grand Bay National Estuarine Research Reserve (NERR) in Moss Point, Mississippi. Surface measurements indicate that the mean mercury concentrations were 1.42 ± 0.12 ng∙m−3 for GEM, 5.4 ± 10.2 pg∙m−3 for GOM, and 3.1 ± 1.9 pg∙m−3 for PBM during the summer 2010 intensive and 1.53 ± 0.11 ng∙m−3 for GEM, 5.3 ± 10.2 pg∙m−3 for GOM, and 5.7 ± 6.2 pg∙m−3 for PBM during the spring 2011 intensive. Elevated daytime GOM levels (&gt;20 pg∙m−3) were observed on a few days in each study and were usually associated with either elevated O3 (&gt;50 ppbv), BrO, and solar radiation or elevated SO2 (&gt;a few ppbv) but lower O3 (~20–40 ppbv). This behavior suggests two potential sources of GOM: photochemical oxidation of GEM and direct emissions of GOM from nearby local sources. Lack of correlation between GOM and Beryllium-7 (7Be) suggests little influence on surface GOM from downward mixing of GOM from the upper troposphere. These data were analyzed using the HYSPLIT back trajectory model and principal component analysis in order to develop source-receptor relationships for mercury species in this coastal environment. Trajectory frequency analysis shows that high GOM events were generally associated with high frequencies of the trajectories passing through the areas with high mercury emissions, while low GOM levels were largely associated the trajectories passing through relatively clean areas. Principal component analysis also reveals two main factors: direct emission and photochemical processes that were clustered with high GOM and PBM. This study indicates that the receptor site, which is located in a coastal environment of the Gulf of Mexico, experienced impacts from mercury sources that are both local and regional in nature.