Atmospheric Mercury Research Articles

Tracing the transboundary transport of atmospheric Particulate Bound Mercury driven by the East Asian monsoon

Taking Beijing-Tianjin-Hebei (BTH) with severe atmospheric mercury (Hg) and PM2.5 pollution as a typical region, this study clarified the characteristics and transboundary transport of atmospheric Particulate Bound Mercury (PBM2.5) affected by the East Asian monsoon. Five sampling sites were conducted in rural, suburban, urban, industrial, and coastal areas of BTH from northwest to southeast along the East Asian monsoon direction. PBM2.5 showed increasing concentrations from northwest to southeast and negative δ202Hg values, indicating significant contributions from anthropogenic sources. However, the mean Δ199Hg values of PBM2.5 at the five sites were significantly positive, probably triggered by the photoreduction of Hg(II) during long-range transport driven by the East Asian monsoon. Apart from local anthropogenic emissions as the primary sources, the transboundary transport of PBM2.5, driven by west and northwest air masses originating in Central Asia and Russia, contributed significantly to the PBM2.5 pollution of BTH. Moreover, these air masses reaching BTH would carry elevated PBM2.5 concentrations further transported to the ocean by the East Asian monsoon. In contrast, the southeast air masses transported from the ocean by the East Asian monsoon in summer diluted inland PBM2.5 pollution. This study provides insight into the atmospheric Hg circulation affected by the East Asian monsoon.

Long-range transport of atmospheric speciated mercury from the eastern waters of Taiwan Island to northern South China Sea

This study explored the temporospatial distribution, gas-particle partition, and pollution sources of atmospheric speciated mercury (ASM) from the eastern offshore waters of the Taiwan Island (TI) to the northern South China Sea (SCS). Both gaseous and particulate mercury were simultaneously sampled at three remote sites in four seasons. The average concentrations of gaseous elemental mercury (GEM), gaseous oxidized mercury (GOM), and particulate bound mercury (PBM) were 2.05 ± 0.45 ng/m3, 19.17 ± 5.39 pg/m3, and 0.11 ± 0.06 ng/m3, respectively. The concentrations of GEM and PBM in the cold seasons were higher than those in the warm seasons, but those of GOM had an opposite trend. In terms of gas-solid partition, ASM was apportioned as 91.3–97.3% of GEM and 2.7–8.7% of GOM and PBM. The average concentrations of GEM, GOM, and PBM at the Green Island (GI) were 2.21 ± 0.47 ng/m3, 22.31 ± 5.35 pg/m3, and 0.12 ± 0.06 ng/m3; those at the Kenting Peninsula (KT) were 2.11 ± 0.43 ng/m3, 20.57 ± 4.38 pg/m3, and 0.11 ± 0.06 ng/m3; and those at the Dongsha Islands (DS) were 1.84 ± 0.40 ng/m3, 15.19 ± 3.58 pg/m3, and 0.08 ± 0.05 ng/m3, respectively. Overall, the spatial distribution of ASM concentrations showed the order as: GI > KT > DS. Air masses blown mainly from the West Pacific Ocean (WPO) and SCS in summer showed the lowest ASM concentrations. Oppositely, high ASM concentrations were commonly observed in spring and winter when polluted air masses were blown by Asian Northeastern Monsoons (ANMs). The transport routes of polluted air masses were originated mainly from North China, Central China, Northeast China, Korea and Japan, and mostly passed through the urban and industrial regions in the northeastern Asian countries.

Enhanced natural releases of mercury in response to the reduction in anthropogenic emissions during the COVID-19 lockdown by explainable machine learning

Abstract. The wide spread of the coronavirus (COVID-19) has significantly impacted the global human activities. Compared to numerous studies on conventional air pollutants, atmospheric mercury that has matched sources from both anthropogenic and natural emissions is rarely investigated. At a regional site in eastern China, an intensive measurement was performed, showing obvious decreases in gaseous elemental mercury (GEM) during the COVID-19 lockdown, while it was not as significant as most of the other measured air pollutants. Before the lockdown, when anthropogenic emissions dominated, GEM showed no correlation with temperature and negative correlations with wind speed and the height of the boundary layer. In contrast, GEM showed significant correlation with temperature, while the relationship between GEM and the wind speed/boundary layer disappeared during the lockdown, suggesting the enhanced natural emissions of mercury. By applying a machine learning model and the SHAP (SHapley Additive exPlanations) approach, it was found that the mercury pollution episodes before the lockdown were driven by anthropogenic sources, while they were mainly driven by natural sources during and after the lockdown. Source apportionment results showed that the absolute contribution of natural surface emissions to GEM unexpectedly increased (44 %) during the lockdown. Throughout the whole study period, a significant negative correlation was observed between the absolute contribution of natural and anthropogenic sources to GEM. We conclude that the natural release of mercury could be stimulated to compensate for the significantly reduced anthropogenic GEM via the surface–air exchange in the balance of mercury.

A Review of Dry Deposition Schemes for Speciated Atmospheric Mercury

This study reviewed the existing framework of dry deposition schemes for speciated atmospheric mercury. As the most commonly used methods for mercury dry deposition estimation, the big-leaf resistance scheme for gaseous oxidized mercury (GOM), the size distribution regarded resistance scheme for particulate bound mercury (PBM), and the bidirectional air-surface exchange scheme for gaseous elemental mercury (GEM) were introduced in detail. Sensitivity analysis were conducted to quantitatively identify the key parameters for the estimation of speciated mercury dry deposition velocities. The dry deposition velocity of GOM was found to be sensitive to the wind speed and some land use related parameters. The chemical forms of GOM could have a significant impact on the dry deposition velocity. The dry deposition velocity of PBM is sensitive to the mass fraction of PBM in coarse particles, while that of GEM is most sensitive to air temperature. Future research needs were proposed accordingly.

Human exposure to mercury in the atmosphere and soils in Konongo: an age-old mining centre in the Ashanti Region of Ghana.

The dramatic upsurge of artisanal and small-scale gold mining (ASGM) activities in Ghana has resulted in environmental degradation, water pollution and human exposure to mercury-the main hazardous element used in gold extraction. This study evaluated the degree of human exposure to mercury based on the concentrations found in the air and soil samples taken at a resolution of 1 km2 across Konongo, a historic mining town in Ghana's Ashanti Region. The highest atmospheric mercury concentration was 193ng/m3, which is much higher than the levels the European Union and Japan allowed, which are 10ng/m3 and 40ng/m3, respectively. The concentration in the soil was 3.6mg Hg/kg, which is around ten times higher than the background concentration in nature. Additionally, the soil concentrations were higher above the worrisome levels of soil contamination in agricultural land (4mg/kg) and industrial areas (16mg/kg), respectively. Soils are extremely contaminated with mercury at sites artisanal mining activities take place. The concentrations of mercury in the air and soils were significantly higher (p < 0.5) at locations of prominent mining activities compared to areas not close to mining sites. The inhabitants of the Konongo community are therefore exposed to mercury, most likely emitted from artisanal mining activities. A non-carcinogenic risk is posed to the people by inhaling mercury vapour through the air and vapourisation from the soil. Children are exposed to a higher risk than adults as they receive higher daily doses of mercury than adults.

Root uptake dominates mercury accumulation in permafrost plants of Qinghai-Tibet Plateau

Uptake of atmospheric elemental mercury via foliage is thought to be the dominant pathway of mercury accumulation in terrestrial ecosystems, including those in the Arctic permafrost regions. Whether a similar process operates in alpine permafrost regions remains unknown. Here we report mercury concentrations and stable isotopic signatures in a large cluster alpine permafrost regions of mid-latitude Qinghai-Tibet Plateau. We find a transition from foliage to root uptake of mercury as elevation increases. In alpine permafrost regions, we find that root uptake of mercury from the surrounding soil is the dominant accumulation pathway. We estimate that root uptake accounts for 70 ± 19% of plant mercury in permafrost regions of the Qinghai-Tibet Plateau and propose that this may be related to the harsh climate conditions suppressing foliage growth and promoting lateral root growth.

Together, Not Separately, OH and O3 Oxidize Hg(0) to Hg(II) in the Atmosphere

Mercury, a highly toxic metal, is emitted to the atmosphere mostly as gaseous Hg(0). Atmospheric Hg(0) enters ecosystems largely through uptake by vegetation, while Hg(II) largely enters ecosystems in oceans and in rainfall. Consequently, the redox chemistry of atmospheric mercury strongly influences its fate and its global biogeochemical cycling. Here we report on the oxidation and reduction of Hg(I) (BrHg and HOHg radicals) in reactions with ozone and how the electronic structure of these Hg(I) species affects the kinetics of these reactions. The oxidation reactions lead to YHgO· + O2 (Y = Br and OH), while the reduction reactions produce Hg(0), OY, and O2. According to our calculations with CCSD(T), NEVPT2, and CAM-B3LYP-D3BJ, the kinetics of both oxidation reactions are very similar and much faster than their reduction counterparts. Past modeling of field data has supported the idea that OH and/or O3 (rather than Br) dominates Hg(II) production in the continental boundary layer. Almost all models invoking OH- and ozone-initiated oxidation of Hg(0) assume that these reactions produce Hg(II) in one step, despite the lack of plausible mechanisms. The two-step mechanism of formation of HOHg followed by its reaction with ozone helps reconcile modeling results with mechanistic insights.

Assessment of tree-ring mercury radial translocation and age effect in Masson pine: Implications for historical atmospheric mercury reconstruction

The tree ring has been regarded as an emerging archive to reconstruct historical atmospheric mercury (Hg) trends, but with the large knowledge gaps in the reliability. In this study, we comprehensively evaluated the Hg source, radial translocation and age effect of Masson pine (Pinus massoniana) tree ring at Mt. Jinyun in Chongqing, to assess the suitability of such tree ring as the archive of atmospheric Hg. Results showed that distinct variabilities among Masson pine tree-ring Hg concentration profiles. The Hg concentration significantly increased along with stem height (P < 0.05), indicating the Hg in tree rings mainly derived from foliage uptake atmospheric Hg. We found a distinct age effect that the tree ring of young trees had the higher Hg concentration. Besides, we used the advection-diffusion model to demonstrate how Hg concentration shifted by the advection or/and diffusion in tree rings. The modeling results showed that the advection induced radial translocation during the young growth period of tree was a plausible mechanism to result in the tree-ring Hg record largely different from the trend of anthropogenic Hg emissions in Chongqing. We finally suggest that in further Hg dendrochemistry, better discarding the tree-ring Hg profile of the young growth period to reduce impacts of the radial translocation and age effect.

Gaseous elemental mercury and its evasion fluxes in the marine boundary layer of the marginal seas of the northwestern Pacific: Results from two cruises in September–December 2019

There are many questions regarding the behavior of mercury in the sea-atmosphere system of the northwestern Pacific. Continuous underway measurements of atmospheric gaseous elemental mercury (GEM) and measurements of sea-air GEM evasion fluxes were carried out in the marginal seas of northwestern Pacific from the South China Sea to the Sea of Okhotsk in fall-winter 2019. The median GEM concentration (1.1 ng/m3) was lower than both the background value and the averages previously observed in these areas. A latitudinal gradient of atmospheric GEM and GEM evasion fluxes with maximum values at southern latitudes was found. The following areas have been identified as potential source areas: the Kurill area of the Pacific Ocean Northeast China, Korean Peninsula, and the territory from the southwest coast of the Yellow Sea to the south of Indochina. Seasonal variations were observed in the Sea of Japan and East China Sea with higher GEM concentrations in winter than in fall. Our data and analysis of published data showed significant relationships between GEM evasion fluxes, latitude and sea surface temperature (SST). It seems that on a global scale, along with the GEM gradient between water and atmosphere, SST is the most significant parameter for sea-air GEM evasion fluxes.

The dynamics of mercury around an artisanal and small-scale gold mining area, Camarines Norte, Philippines.

To elucidate the dynamics of mercury emitted and released by artisanal and small-scale gold mining (ASGM) activity and to estimate its impact on the ecosystems of the bay, the distribution of mercury in the atmosphere, soil, water, and sediment around Mambulao Bay, Camarines Norte, Philippines, was investigated. The ASGM operations use mercury to extract gold from ore and are located on the east shore side of the bay. Samplings were conducted in August 2017 and September 2018. The samples were used for determination of total mercury (T-Hg) and organic mercury (org-Hg) concentrations, total organic carbon (TOC) content, and chemical composition. The atmospheric mercury concentration on the east shore side, 6.1-25.8ngm-3, was significantly higher than the value of 1.4-9.9ngm-3 observed on the west shore side. The average concentrations of T-Hg in the forest soils of the west shore side and those of the east shore side were 0.081 ± 0.028mgkg-1 and 0.496 ± 0.439mgkg-1, respectively. In the vertical distribution of T-Hg in the soil of the east shore side, a higher concentration was observed near the surface. For the vertical variations in T-Hg in the marine sediment, higher values were observed near the estuary, and the vertical variations in core samples showed an increase in mercury concentration toward the surface. The highest concentration of T-Hg in sediment, 9.5mgkg-1, which was 2 orders of magnitude higher than the background levels of this area, was found near the river mouth. The T-Hg, org-Hg, and TOC levels showed a positive correlation, suggesting that the rivers are the main sources of T-Hg and org-Hg in the bay. Although the fish sample containing a mercury content higher than the regulatory level for fish and shellfish of 0.4mgkg-1 in Japan was only one of 42 samples, the percentage of org-Hg in fish samples was 91 ± 18%. Mercury released into the surroundings by the ASGM activities can be converted into methylmercury and affect the bay's ecosystem.

Meteorological Drivers of Atmospheric Mercury Seasonality in the Temperate Northern Hemisphere

AbstractMercury (Hg) is a neurotoxic pollutant that can be transported globally by atmospheric circulation and poses risks to wildlife and humans. Strong atmospheric Hg seasonality has been observed in the temperate Northern Hemisphere and explained by several hypothetical mechanisms. Here, we found that meteorological conditions were important drivers of the seasonality across diverse temperate regions particularly Asia through various indirect effects. Meteorological conditions can explain approximately 47%, 43%, and 67% of the seasonal amplitudes at the North American (NA) remote sites, European remote sites, and Asian monsoon sites, respectively. Surface air temperature, solar radiation, and surface wind collectively contributed significantly to the seasonality at the NA and European sites through vegetation resistance and oceanic evasion, while monsoon wind and precipitation promoted the summertime removal of Hg at the Asian sites through atmospheric transport and wet deposition, respectively. The findings predicted further changes in atmospheric Hg seasonality under future global warming.

Atmospheric Mercury Concentrations in Guangzhou City, Measured by Spectroscopic Techniques

Atmospheric levels of atomic mercury pollution were measured using spectroscopic techniques in the city of Guangzhou, Guangdong Province, China. Assessments were mainly performed at ground level using a portable (vehicle mounted or hand carried) Zeeman modulation correlation spectrometer (Lumex RA-915M), and the results are given in easily comprehensible diagrams. Measurements were made with continuous recording in car traverses along major roads which cross the city, but also at selected spots, such as at a university campus with laboratory buildings. Further, pollution levels at different locations were recorded when walking through a major and a small hospital. While concentrations in the city in the range 3–10 ng/m3 were typical, and strongly dependent on the traffic situation, very high concentrations (up to 1300 ng/m3) were found at certain indoor hospital locations, again drawing attention to the fact that high mercury levels due to inadequate handling routines can remain undetected but could readily be eliminated by adequate measurements and subsequent sanitation.

A high spatial resolution dataset for anthropogenic atmospheric mercury emissions in China during 1998–2014

China is the largest atmospheric mercury (Hg) emitter globally, which has been substantially investigated. However, the estimation of national or regional Hg emissions in China is insufficient in supporting emission control, as the location of the sources may have significant impacts on the effects of Hg emissions. In this concern, high-spatial-resolution datasets of China’s Hg emissions are necessary for in-depth and accurate Hg-related studies and policymaking. Existing gridded datasets are constructed using population distribution as the proxy, which is limited as Hg emissions are closely related to energy consumption and economic processes. This study constructs a dataset of anthropogenic atmospheric Hg emissions in China gridded to a 1 km resolution during 1998–2014. This dataset is produced based on data of land uses, individual enterprises, roadmaps, and population, uncovering Hg emissions in agriculture, industries, services, and residents. This dataset can promote the reliability of Hg-related studies at a high spatial resolution. Moreover, this dataset can support spatially explicit Hg reduction of economic sectors.

Impacts of Material Input and Production Process on the Isotopic Fingerprint of Atmospheric Mercury Emissions from Cement Clinker Production

Impacts of Material Input and Production Process on the Isotopic Fingerprint of Atmospheric Mercury Emissions from Cement Clinker Production

Comparison and calibration of methods for ambient reactive mercury quantification

Gaseous oxidized mercury (GOM) is the dominant form of atmospheric mercury (Hg) deposited and sequestered within ecosystems. Thus, accurate, calibrated measurements of GOM are needed. Here, two active membrane-based collection systems (RMAS) were used to determine GOM and particulate-bound Hg (PBM), as well as reactive Hg (RM = GOM + PBM), and compared with two dual-channel systems (DCS) and a Tekran 2537/1130 speciation system. The DCS measured operationally defined GOM by difference, using concentrations of gaseous elemental Hg (GEM) and total gaseous Hg. One DCS was linked to a custom-built, automated calibration system that permeated GEM, HgBr2, or HgCl2. The five systems were co-located for one-year to develop a dataset that would allow for understanding limitations of each system, and assessing measurement accuracy and long-term precision of the calibrator. The Tekran system measured ~14.5 % of the GOM measured by the other systems. The USU and UNR DCS and RMAS were significantly correlated, but the DCS was 50 and 30 % higher, respectively, than the RMAS. The calibrator performed consistently in the field and lab, and the DCS fully recovered GOM injected by the calibrator. Since the uncalibrated DCS measured the same concentrations as the calibrated DCS, they are both accurate methods for measuring RM and/or GOM. Some loss occurred from the RMAS membranes. SynopsisAccurate and calibrated measurements of atmospheric reactive mercury using membranes and two dual-channel systems.

Mercury in soil, sediment, and lake water in upland headwater catchments in Ireland

Mercury concentrations in the atmosphere, surface waters, and soils have increased beyond natural levels as a result of human activities, which poses a risk to human and environmental health. Ireland is situated on the western periphery of Europe, and it is generally assumed that environmental mercury is low but there is limited information on mercury within natural environments. In this study, the interlinkages in the concentration of mercury in soils, lake sediment, and lake water were investigated in remote upland acid-sensitive catchments influenced by low deposition of atmospheric mercury. Thirty-one upland lake catchments were sampled for topsoil, lake sediment, and lake water during 2017–2018. Total mercury (THg) concentrations in water (median 5.4 ng/L) and sediment (median 30 ng/g) were low, owing to the remote location of the lakes. In contrast, THg in catchment soil was relatively high for a background region (median: 240 ng/g), which was attributed to the high organic matter content of the soil (median 87%). The results suggest catchment soils are the dominant driver of variation in THg in lake water and sediment in upland regions in Ireland. Further, given that highly organic soils can obscure interlinkages within catchments, this study demonstrated the value of exploring mercury independent of the influence of organic matter, i.e., THg normalized by organic carbon. As global action (such as the Minamata Convention) decreases mercury emissions, legacy soil mercury may become a more important input to aquatic systems than atmospheric deposition, which makes the relationships between terrestrial catchments and their water bodies vital for our understanding of mercury cycling.

Heterogeneous Variations on Historical and Future Trends of CO2 and Multiple Air Pollutants from the Cement Production Process in China: Emission Inventory, Spatial-Temporal Characteristics, and Scenario Projections.

Cement production is a major contributor to carbon dioxide (CO2) and multiple hazardous air pollutant (HAP) emissions, threatening climate mitigation and urban/regional air quality improvement. In this study, we established a comprehensive emission inventory by coupling the unit-based bottom-up and mass balance methods, revealing that emissions of most HAPs have been remarkably controlled. However, an increasing 6.0% of atmospheric mercury emissions, as well as 14.1 and 23.7% of fuel-related and process-related CO2 emission growth were witnessed unexpectedly. Industrial adjustment policies have imposed a great impact on the spatiotemporal changes in emission characteristics. Monthly emissions of CO2 and multiple HAPs decreased from December to February due to the "staggered peak production," especially in northern China after implementing the intensified action plan for air pollution control in winter. Upgrading environmental technologies and adjusting capacity structures are identified as dominant driving forces for reducing HAP emissions. Besides, energy intensity improvement can help offset some of the impact caused by the increase in clinker/cement production. Furthermore, scenario analysis results show that ultra-low emission and low-carbon technology transformation constitute the keys to achieve the synergic reduction of CO2 and multiple HAP emissions in the future.

Mercury in a birch forest in SW Europe: Deposition flux by litterfall and pools in aboveground tree biomass and soils

Atmospheric mercury (Hg) is largely assimilated by vegetation and subsequently transferred to the soil by litterfall, which highlights the role of forests as one of the largest global Hg sinks within terrestrial ecosystems. We assessed the pool of Hg in the aboveground biomass (leaves, wood, bark, branches and twigs), the Hg deposition flux through litterfall over two years (by sorting fallen biomass in leaves, twigs, reproductive structures and miscellaneous) and its accumulation in the soil profile in a deciduous forest dominated by Betula alba from SW Europe. The total Hg pool in the aboveground birch biomass was in the range 532–683 mg ha−1, showing the following distribution by plant tissues: well-developed leaves (171 mg ha−1) > twigs (160 mg ha−1) > bark (159 mg ha−1) > bole wood (145 mg ha−1) > fine branches (25 mg ha−1) > thick branches (24 mg ha−1) > newly sprouted leaves (20 mg ha−1). The total Hg deposition fluxes through litterfall were 15.4 and 11.7 μg m−2 yr−1 for the two years studied, with the greatest contribution coming from birch leaves (73 %). In the soil profile, the pool of Hg in the mineral soil (37.0 mg m−2) was an order of magnitude higher than in the organic horizons (1.0 mg m−2), mostly conditioned by parameters such as soil bulk density and thickness, total C and N contents and the presence of certain Al compounds.

Uptake of Hg0(g) on TiO2, Al2O3, and Fe2O3 Nanoparticles: Importance in Atmospheric Chemical and Physical Processes.

Mineral dust aerosols play an important role in tropospheric chemistry and aerosol-cloud interaction processes. Yet, their interactions with gaseous elemental mercury (Hg0(g)) are not currently well understood. Using a coated-wall flow tube (CWFT) reactor, we measured the uptake of Hg0(g) on some common components of mineral dust aerosols, including TiO2, Al2O3, and Fe2O3, and the effects of irradiation (dark, visible and UV-A) and relative humidity (<2% to 60%) on the uptake kinetics. Under UV-A irradiation (320-400 nm) in dry air, we measured uptake coefficients (γ) equal to >1 × 10-3 and (3 ± 1) × 10-6 on TiO2 and Al2O3, respectively. Under visible light irradiation (380-700 nm), Hg0(g) uptake was only observed on TiO2, with γ = (4 ± 3) × 10-4. Raising the relative humidity inhibited the uptake on both TiO2 and Al2O3, and the uptake coefficient at 60% RH for TiO2 under UV-A irradiation was lower by ca. 3 orders of magnitude than dry conditions. Furthermore, we observed that water vapor induced the desorption of two distinct fractions from Hg-exposed surfaces via the displacement of weakly, physisorbed Hg and the photocatalyzed reduction of chemisorbed Hg. Based on the uptake coefficients from this report, we estimate that heterogeneous interactions with mineral dust may be significant under conditions with low relative humidity (<30%) and high dust loading masses. We herein discuss the implication of this study on understanding the life cycle analysis of atmospheric mercury in nature.

Near-global mapping of TGM based on aircraft measurements from intercontinental flights

Atmospheric mercury sources are numerous and complex. Accessing and understanding the strength of each source is important for understanding mercury cycling between the various environmental compartments as it affects atmospheric loadings.In this regard, this study presents an upper tropospheric near-global source evaluation of total gaseous mercury (TGM) and its impacts on atmospheric loadings are therefore examined using TGM measurements from a container aboard intercontinental passenger flights between 2005 and 2016. The trove of measurements performed on board of IAGOS-CARIBIC was exploited through developed receptor models, assuring a high likelihood of extracting the maximal amount of information from the collected data. We reconstructed atmospheric mercury concentrations and assessed the contribution of the major natural and anthropogenic sources, explaining 98% of the observations with a correlation of 82% and a significance level of 0.001 (p-value).The results show that Asia stands out as the main hotspot of TGM, mainly loaded by factors linked to industrial and SO2-related sources. Contribution and geolocation strength of industrial, volcanic, biogenic, biomass burning, and petrogenic-related sources were quantified, identified and presented.The improved data analysis tools as probability mass factorization methods provide additional insights into the nature of the mercury source that can then guide the development of more effective mercury-related management strategies.