Atmospheric Elemental Mercury Research Articles

Deposition and Re-Emission of Atmospheric Elemental Mercury over the Tropical Forest Floor.

Significant knowledge gaps exist regarding the emission of elemental mercury (Hg0) from the tropical forest floor, which limit our understanding of the Hg mass budget in forest ecosystems. In this study, biogeochemical processes of Hg0 deposition to and evasion from soil in a Chinese tropical rainforest were investigated using Hg stable isotopic techniques. Our results showed a mean air-soil flux as deposition of -4.5 ± 2.1 ng m-2 h-1 in the dry season and as emission of +7.4 ± 1.2 ng m-2 h-1 in the rainy season. Hg re-emission, i.e., soil legacy Hg evasion, induces negative transitions of Δ199Hg and δ202Hg in the evaded Hg0 vapor, while direct atmospheric Hg0 deposition does not exhibit isotopic fractionation. Using an isotopic mass balance model, direct atmospheric Hg0 deposition to soil was estimated to be 48.6 ± 13.0 μg m-2 year-1. Soil Hg0 re-emission was estimated to be 69.5 ± 10.6 μg m-2 year-1, of which 63.0 ± 9.3 μg m-2 year-1 is from surface soil evasion and 6.5 ± 5.0 μg m-2 year-1 from soil pore gas diffusion. Combined with litterfall Hg deposition (∼34 μg m-2 year-1), we estimated a ∼12.6 μg m-2 year-1 net Hg0 sink in the tropical forest. The fast nutrient cycles in the tropical rainforests lead to a strong Hg0 re-emission and therefore a relatively weaker atmospheric Hg0 sink.

Buffering effect of global vegetation on the air-land exchange of mercury: Insights from a novel terrestrial mercury model based on CESM2-CLM5

The vegetation uptake of atmospheric elemental mercury [Hg(0)] and its subsequent littering are critical processes of the terrestrial Hg cycles. There is a large uncertainty in the estimated global fluxes of these processes due to the knowledge gap in the underlying mechanisms and their relationship with environmental factors. Here, we develop a new global model based on the Community Land Model Version 5 (CLM5-Hg) as an independent component of the Community Earth System Model 2 (CESM2). We explore the global pattern of gaseous elemental Hg [Hg(0)] uptake by vegetation and the spatial distribution of litter Hg concentration constrained by observed datasets as well as its driving mechanism. The annual vegetation uptake of Hg(0) is estimated as 3132 Mg yr−1, which is considerably higher than previous global models. The scheme of dynamic plant growth including stomatal activities substantially improves the estimation for global terrestrial distribution of Hg, compared to the leaf area index (LAI) based scheme that is often used by previous models. We find the global distribution of litter Hg concentrations driven by vegetation uptake of atmospheric Hg(0), which are simulated to be higher in East Asia (87 ng/g) than in the Amazon region (63 ng/g). Meanwhile, as a significant source for litter Hg, the formation of structural litter (cellulose litter + lignin litter) results in a lagging effect between Hg(0) deposition and litter Hg concentration, implying the buffering effect of vegetation on the air-land exchange of Hg. This work highlights the importance of vegetation physiology and environmental factors in understanding the vegetation sequestration of atmospheric Hg globally, and calls for greater efforts to protect forests and afforestation.

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.

Mercury isotope evidence for Arctic summertime re-emission of mercury from the cryosphere

During Arctic springtime, halogen radicals oxidize atmospheric elemental mercury (Hg0), which deposits to the cryosphere. This is followed by a summertime atmospheric Hg0 peak that is thought to result mostly from terrestrial Hg inputs to the Arctic Ocean, followed by photoreduction and emission to air. The large terrestrial Hg contribution to the Arctic Ocean and global atmosphere has raised concern over the potential release of permafrost Hg, via rivers and coastal erosion, with Arctic warming. Here we investigate Hg isotope variability of Arctic atmospheric, marine, and terrestrial Hg. We observe highly characteristic Hg isotope signatures during the summertime peak that reflect re-emission of Hg deposited to the cryosphere during spring. Air mass back trajectories support a cryospheric Hg emission source but no major terrestrial source. This implies that terrestrial Hg inputs to the Arctic Ocean remain in the marine ecosystem, without substantial loss to the global atmosphere, but with possible effects on food webs.

Investigation of the biochemical controls on mercury uptake and mobility in trees

Atmospheric elemental mercury (Hg(0)) enters plant stomata, becomes oxidized, and is then transferred to annual growth rings providing an archive of air Hg(0) concentrations. To better understand the processes of Hg accumulation and translocation, the foliage of quaking aspen and Austrian pine were exposed to Hg(0), and methylmercury (MeHg) or Me198Hg via roots, in controlled exposures during the summer. Isotopic measurements demonstrated, in a laboratory setting, that the natural mass-dependent fractionation observed was the same as that measured in field studies, with the lighter isotopes being preferentially taken up by the leaves. Hg was measured in plant tissues across seasons. Aspen trees moved Hg into new growth immediately after exposure, resorbed Hg in the fall, and then distributed Hg to new growth tissues in the spring. Austrian pine did not reallocate Hg. Mercury measured in aspen leaf fractions of trees exposed to Hg(0) demonstrated that 85 % of Hg was in the cell wall. It was also found that redox-active molecules, such as H2O2, could potentiate the release of cell wall-bound Hg from aspen leaves, providing a potential mechanism for remobilization. Regardless of the mechanism, the ability of aspen to reallocate Hg to new tissues indicates that Hg distribution in tree rings from aspen do not provide a reliable record of yearly changes in atmospheric Hg(0).

Evaluating atmospheric mercury (Hg) uptake by vegetation in a chemistry-transport model.

Mercury (Hg), a neurotoxic heavy metal, is transferred to marine and terrestrial ecosystems through atmospheric transport. Recent studies have highlighted the role of vegetation uptake as a sink for atmospheric elemental mercury (Hg0) and a source of Hg to soils. However, the global magnitude of the Hg0 vegetation uptake flux is highly uncertain, with estimates ranging 1000-4000 Mg per year. To constrain this sink, we compare simulations in the chemical transport model GEOS-Chem with a compiled database of litterfall, throughfall, and flux tower measurements from 93 forested sites. The prior version of GEOS-Chem predicts median Hg0 dry deposition velocities similar to litterfall measurements from Northern hemisphere temperate and boreal forests (∼0.03 cm s-1), yet it underestimates measurements from a flux tower study (0.04 cm s-1vs. 0.07 cm s-1) and Amazon litterfall (0.05 cm s-1vs. 0.17 cm s-1). After revising the Hg0 reactivity within the dry deposition parametrization to match flux tower and Amazon measurements, GEOS-Chem displays improved agreement with the seasonality of atmospheric Hg0 observations in the Northern midlatitudes. Additionally, the modelled bias in Hg0 concentrations in South America decreases from +0.21 ng m-3 to +0.05 ng m-3. We calculate a global flux of Hg0 dry deposition to land of 2276 Mg per year, approximately double previous model estimates. The Amazon rainforest contributes 29% of the total Hg0 land sink, yet continued deforestation and climate change threatens the rainforest's stability and thus its role as an important Hg sink. In an illustrative worst-case scenario where the Amazon is completely converted to savannah, GEOS-Chem predicts that an additional 283 Mg Hg per year would deposit to the ocean, where it can bioaccumulate in the marine food chain. Biosphere-atmosphere interactions thus play a crucial role in global Hg cycling and should be considered in assessments of future Hg pollution.

Pan-Arctic surface ozone: modelling vs. measurements

Abstract. Within the framework of the International Arctic Systems for Observing the Atmosphere (IASOA), we report a modelling-based study on surface ozone across the Arctic. We use surface ozone from six sites – Summit (Greenland), Pallas (Finland), Barrow (USA), Alert (Canada), Tiksi (Russia), and Villum Research Station (VRS) at Station Nord (North Greenland, Danish realm) – and ozone-sonde data from three Canadian sites: Resolute, Eureka, and Alert. Two global chemistry models – a global chemistry transport model (parallelised-Tropospheric Offline Model of Chemistry and Transport, p-TOMCAT) and a global chemistry climate model (United Kingdom Chemistry and Aerosol, UKCA) – are used for model data comparisons. Remotely sensed data of BrO from the GOME-2 satellite instrument and ground-based multi-axis differential optical absorption spectroscopy (MAX-DOAS) at Eureka, Canada, are used for model validation. The observed climatology data show that spring surface ozone at coastal sites is heavily depleted, making ozone seasonality at Arctic coastal sites distinctly different from that at inland sites. Model simulations show that surface ozone can be greatly reduced by bromine chemistry. In April, bromine chemistry can cause a net ozone loss (monthly mean) of 10–20 ppbv, with almost half attributable to open-ocean-sourced bromine and the rest to sea-ice-sourced bromine. However, the open-ocean-sourced bromine, via sea spray bromide depletion, cannot by itself produce ozone depletion events (ODEs; defined as ozone volume mixing ratios, VMRs, < 10 ppbv). In contrast, sea-ice-sourced bromine, via sea salt aerosol (SSA) production from blowing snow, can produce ODEs even without bromine from sea spray, highlighting the importance of sea ice surface in polar boundary layer chemistry. Modelled total inorganic bromine (BrY) over the Arctic sea ice is sensitive to model configuration; e.g. under the same bromine loading, BrY in the Arctic spring boundary layer in the p-TOMCAT control run (i.e. with all bromine emissions) can be 2 times that in the UKCA control run. Despite the model differences, both model control runs can successfully reproduce large bromine explosion events (BEEs) and ODEs in polar spring. Model-integrated tropospheric-column BrO generally matches GOME-2 tropospheric columns within ∼ 50 % in UKCA and a factor of 2 in p-TOMCAT. The success of the models in reproducing both ODEs and BEEs in the Arctic indicates that the relevant parameterizations implemented in the models work reasonably well, which supports the proposed mechanism of SSA production and bromide release on sea ice. Given that sea ice is a large source of SSA and halogens, changes in sea ice type and extent in a warming climate will influence Arctic boundary layer chemistry, including the oxidation of atmospheric elemental mercury. Note that this work dose not necessary rule out other possibilities that may act as a source of reactive bromine from the sea ice zone.

Atomistic View of Mercury Cycling in Polar Snowpacks: Probing the Role of Hg2+ Adsorption Using Ab Initio Calculations

Photochemical oxidation of atmospheric elemental mercury (Hg0) promotes reactive oxidized Hg (HgII) adsorption on particles and deposition to the polar snowpack. The deposited Hg either returns to the atmosphere via photochemical reduction or remains in the snowpack depending on the strength of adsorption. In this study, we performed ab initio calculations to understand the atomic-level cause of the fate of adsorbed Hg by determining the adsorption affinity for Hg2+, the simplest form of HgII, of barite, halite, muscovite, illite, and ice-Ih as potential adsorbents. The adsorption affinity was estimated by calculating the energy required to dissociate adsorbed Hg2+ from the adsorbents. The results reveal that Hg2+ is stable on the surfaces of the selected adsorbents, except barite, but is prone to photodissociation under solar ultraviolet radiation. This mild adsorption is expected to contribute to the bidirectional exchange of Hg between the atmosphere and the polar snowpack. Thus, this theoretical approach can provide complementary perspectives on polar Hg dynamics beyond the limitations of field and laboratory experiments. Further studies on more complicated and realistic adsorption models with different HgII species and adsorbent surfaces having diverse defective structures are required to better comprehend air–snow Hg cycling in the polar regions.

Fiber optic based evanescent wave sensor for the detection of elemental mercury utilizing gold nanorods

We developed a fiber optic based sensor using gold nanorods as the sensing medium for the detection of atmospheric elemental mercury. Mercury readily adsorbs on the nanoparticles causing a measurable shift in the longitudinal localized surface plasmon resonance. Depositing the nanorods on the surface of a bare, bent fiber optic cable provides a means to excite the resonance and determine the absorbance through the evanescent wave at the surface. The response of the system is linear with concentration, and we have been able to directly measure concentrations down to 1.0μg/m3.

Quantification of Total Mercury in Antarctic Surface Snow using ICP-SF-MS: Spatial Variation from the Coast to Dome Fuji

The total mercury concentration () of surface snow samples collected along a ~1500 km transect in east Queen Maud Land was determined using inductively coupled plasma sector field mass spectrometry to address the behavior of Hg on the Antarctic Plateau. Due to the volatile nature of mercury, measures were taken against Hg loss from standard solutions by choosing appropriate container material and stabilizing agents. Glass bottles with Teflon-lined caps were superior to Teflon and polyethylene containers in protecting against Hg loss, but addition of gold chloride () or bromine chloride (BrCl) was necessary to ensure preservation of Hg. As Hg loss was also observed in snowmelt samples, our analysis may underestimate the actual amount of HgT in the snow. Even so, the measured HgT was still very low (, n = 44) without a signal of depositional enhancement accompanying photo-oxidation of atmospheric elemental mercury in austral midsummer. Moreover, the dynamic variation along the traverse implies spatial and temporal heterogeneity in its source processes.

A cold plasma dielectric barrier discharge atomic emission detector for atmospheric mercury

An automated atmospheric elemental mercury analyzer based on the dielectric barrier discharge (DBD) atomic emission technique was developed. The instrument is based on a gold-on tungsten coiled filament preconcentrator fashioned from commercial quartz-halogen lamps, a DBD excitation source and a radiation detector. An in-house program provided system control and data collection. Several types of radiation detectors, e.g., charge coupled device (CCD) array spectrometers, photomultiplier tubes (PMTs) and phototube (PT) are investigated. An argon plasma provided better performance than a nitrogen plasma. With approximately 0.88 standard liters per min sampling rate and preconcentration for 2min, the estimated (S/N=3) detection limit was 0.12ng/L (Hg(0)), the linear range extended at least to 6.6ngHg/L. Typical RSD values for determination at the single digit ng/L level ranged from 2.8 to 4.9%. In 19 separate calibrations conducted over 7 days, the calibration slope had a standard error of 1%. The system was applied to the determination of atmospheric mercury in two different locations.

Mercury concentration and speciation in the coastal and open ocean boundary layer

Atmospheric elemental mercury and reactive gaseous mercury (RGHg) concentrations, as well as ancillary parameters and meteorological data, were collected during a cruise in the North Atlantic Ocean between Bermuda and Barbados and at two land‐based sites: the Chesapeake Biological Laboratory (CBL), a semirural, coastal site, and a site within the city of Baltimore, Maryland. There were two deployments at CBL, including a 6‐month deployment in 2003/2004. Wet deposition samples were collected and analyzed for mercury where possible. A diurnal change in RGHg concentration was found at both CBL and over the North Atlantic Ocean, with maxima in the afternoon that coincided with maximum UV radiation, demonstrating the importance of in situ formation of RGHg. The maxima in RGHg concentration did not coincide with elevated Hg0 but were often found under conditions of low wind speed, and over the ocean, under low ozone conditions. In contrast, at the urban site there was more evidence of local sources. The data collected at the sites are contrasted and compared and used to examine the factors controlling the formation of RGHg in open ocean and nearshore locales and to estimate the importance of the dry deposition of RGHg to surface waters. Finally, the data collected at CBL in 2002–2004 were compared to earlier data collected in 1997–2000 to examine trends in concentration with time and to contrast these with the open ocean data sets to examine changes in Hg0 at the hemispheric scale.

Mercury accumulation in grass and forb species as a function of atmospheric carbon dioxide concentrations and mercury exposures in air and soil

The goal of this study was to investigate the potential for atmospheric Hg° uptake by grassland species as a function of different air and soil Hg exposures, and to specifically test how increasing atmospheric CO 2 concentrations may influence foliar Hg concentrations. Four common tallgrass prairie species were germinated and grown for 7 months in environmentally controlled chambers using two different atmospheric elemental mercury (Hg°; 3.7 ± 2.0 and 10.2 ± 3.5 ng m −3), soil Hg (<0.01 and 0.15 ± 0.08 μg g −1), and atmospheric carbon dioxide (CO 2) (390 ± 18, 598 ± 22 μmol mol −1) exposures. Species used included two C4 grasses and two C3 forbs. Elevated CO 2 concentrations led to lower foliar Hg concentrations in plants exposed to low (i.e., ambient) air Hg° concentrations, but no CO 2 effect was apparent at higher air Hg° exposure. The observed CO 2 effect suggests that leaf Hg uptake might be controlled by leaf physiological processes such as stomatal conductance which is typically reduced under elevated CO 2. Foliar tissue exposed to elevated air Hg° concentrations had higher concentrations than those exposed to low air Hg°, but only when also exposed to elevated CO 2. The relationships for foliar Hg concentrations at different atmospheric CO 2 and Hg° exposures indicate that these species may have a limited capacity for Hg storage; at ambient CO 2 concentrations all Hg absorption sites in leaves may have been saturated while at elevated CO 2 when stomatal conductance was reduced saturation may have been reached only at higher concentrations of atmospheric Hg°. Foliar Hg concentrations were not correlated to soil Hg exposures, except for one of the four species (Rudbeckia hirta). Higher soil Hg concentrations resulted in high root Hg concentrations and considerably increased the percentage of total plant Hg allocated to roots. The large shifts in Hg allocation patterns—notably under soil conditions only slightly above natural background levels—indicate a potentially strong role of plants in belowground Hg transformation and cycling processes.

Reactive gaseous mercury formation in the North Pacific Ocean's marine boundary layer: A potential role of halogen chemistry

Reactive gaseous mercury (RGHg), atmospheric elemental mercury (Hg0), and ozone (O3) along with other ancillary parameters have been measured simultaneously in the marine boundary layer (MBL) over the North Pacific Ocean during the 2002‐IOC cruise between Osaka, Japan, and Honolulu, Hawaii. Atmospheric Hg0 concentrations varied from 1.6 to 4.7 ng m−3 with an average of 2.5 ng m−3 and did show significant variations along the cruise track with a slight diel cycle in Hg0 concentrations. RGHg concentrations varied from 0.15 to 92.4 pg m−3 with an average of 9.5 pg m−3. The data strongly suggest photochemical in situ formation of RGHg with increasing concentrations in the tropical regions concomitant to a dramatic decrease in O3 (from over 50 to less than 5 ppbv). A distinct diurnal variation in RGHg concentrations with maxima at midday suggests a photochemically driven oxidation of marine boundary layer Hg0. In the tropical area, enhanced RGHg formation and daily variation in O3 could both be related to reactive halogen chemistry. Flux calculations also emphasize the role of the tropical marine boundary layer in mercury cycling over the North Pacific Ocean.