Sources and deposition of reactive gaseous mercury in the marine atmosphere

Observations of reactive gaseous mercury (RGM) in marine air show a consistent diurnal cycle with minimum at night, rapid increase at sunrise, maximum at midday, and rapid decline in afternoon. We use a box model for the marine boundary layer (MBL) to interpret these observations in terms of RGM sources and sinks. The morning rise and midday maximum are consistent with oxidation of elemental mercury (Hg⁰) by Br atoms, requiring <2 ppt BrO in most conditions. Oxidation of Hg⁰ by Br accounts for 35–60% of the RGM source in our model MBL, with most of the remainder contributed by oxidation of Hg⁰ by ozone (5–20%) and entrainment of RGM-rich air from the free troposphere (25–40%). Oxidation of Hg⁰ by Cl is minor (3–7%), and oxidation by OH cannot reproduce the observed RGM diurnal cycle, suggesting that it is unimportant. Fitting the RGM observations could be achieved in the model without oxidation of Hg⁰ by ozone (leaving Br as the only significant oxidant) by increasing the entrainment flux from the free troposphere. The large relative diurnal amplitude of RGM concentrations implies rapid loss with a lifetime of only a few hours. We show that this can be quantitatively explained by rapid, mass-transfer-limited uptake of RGM into sea-salt aerosols as HgCl₃^? and HgCl₄^2?. Our results suggest that 80–95% of Hg^II in the MBL should be present in sea-salt aerosol rather than gas-phase, and that deposition of sea-salt aerosols is the major pathway delivering Hg^II to the ocean.     

Validation of the integrated RAMS-Hg modelling system using wet deposition observations for eastern North America

Using the well-known Regional Atmospheric Modelling System (RAMS) version 4.3 an integrated system able to simulate the atmospheric mercury cycle has been developed. Basic processes of the mercury atmospheric cycle have been incorporated into the atmospheric model. The model deals with elemental Hg (Hg⁰), divalent gaseous Hg (Hg²) and particulate Hg (Hg^P). Wet deposition mechanisms used to describe the removal of Hg² and Hg^P are merged with the detailed cloud microphysical scheme in order to provide better representation of the wet deposition processes. The advantages of this approach have been examined through results intercomparison with simulated Hg wet deposition using CMAQ-Hg from previous work for two evaluation periods: 4 April–2 May 1995, and 20 June–18 July 1995. An attempt to clarify the main parameters that affect wet deposition mechanism of mercury is also made.     

Aqueous phase methylation as a potential source of methylmercury in wet deposition

The source of monomethylmercury (MMHg) in wet deposition is unknown. Volatilization of gaseous MMHg, evasion and demethylation of dimethylmercury, and methylation of Hg⁰ have been either proposed or tested unsuccessfully as potential sources. Here, we show that MMHg in precipitation, sampled across a wide geographical range in North America, is related positively to an operationally defined and measured reactive Hg species (Hg_R), but connected weakly to total Hg. The mean molar ratio of MMHg:Hg_R measured in continental precipitation (0.025±0.006) is comparable to the MMHg:Hg(II) ratio estimated from first-order rate constants for acetate-mediated Hg methylation and MMHg photolysis (0.025±0.002). This suggests MMHg may be formed in the atmosphere through a reaction between labile Hg(II) complexes and an unknown methylating agent(s), potentially acetate or similar molecules. Availability of Hg(II) appears to limit the reaction, and accordingly, increased atmospheric loadings of Hg could lead to enhanced MMHg in precipitation.     

Atmospheric mercury concentrations and speciation measured from 2004 to 2007 in Reno, Nevada, USA

Atmospheric elemental, reactive and particulate mercury (Hg) concentrations were measured north of downtown Reno, Nevada, USA from November 2004 to November 2007. Three-year mean and median concentrations for gaseous elemental Hg (Hg⁰) were 1.6 and 1.5 ng m⁻³ (respectively), similar to global mean Hg⁰ concentrations. The three-year mean reactive gaseous Hg (RGM) concentration (26 pg m⁻³) was higher than values reported for rural sites across the western United States. Well defined seasonal and daily patterns in Hg⁰ and RGM concentrations were observed, with the highest Hg⁰ concentrations measured in winter and early morning, and RGM concentrations being greatest in the summer and mid-afternoon. Elevated Hg⁰ concentrations in winter were associated with periods of cold, stagnant air; while a regularly observed early morning increase in concentration was due to local source and surface emissions. The observed afternoon increase and high summer values of RGM can be explained by in situ oxidation of gaseous Hg⁰ or mixing of RGM derived from the free troposphere to the surface. Because both of these processes are correlated with the same environmental conditions it is difficult to assess their overall contribution to the observed trends.     

Estimating contribution of precipitation scavenging of atmospheric particulate mercury to mercury wet deposition in Japan

Mercury wet deposition is dependent on both the scavenging of divalent reactive gaseous mercury (RGM) and atmospheric particulate mercury (Hg(p)) by precipitation. Estimating the contribution of precipitation scavenging of RGM and Hg(p) is important for better understanding the causes of the regional and seasonal variations in mercury wet deposition. In this study, the contribution of Hg(p) scavenging was estimated on the basis of the scavenging ratios of other trace elements (i.e., Cd, Cu, Mn, Ni, Pb and V) existing entirely in particulate form. Their wet deposition fluxes and concentrations in air, which were measured concurrently from April 2004 to March 2005 at 10 sites in Japan, were used in this estimation. The monthly wet deposition flux of mercury at each site correlated with the amount of monthly precipitation, whereas the Hg(p) concentrations in air tended to decrease during summer. There was a significant correlation (P<0.001) among the calculated monthly average scavenging ratios of trace elements, and the values in each month at each site were similar. Therefore, it is assumed the monthly scavenging ratio of Hg(p) is equivalent to the mean value of other trace elements. Using this scavenging ratio (W), the wet deposition flux (F) due to Hg(p) scavenging in each month was calculated by F=WKP, where K and P are the Hg(p) concentration and amount of precipitation, respectively. Relatively large fluxes due to Hg(p) scavenging were observed at a highly industrial site and at sites on the Japan Sea coast, which are strongly affected by the local sources and the long-range transport from the Asian continent, respectively. However, on average, at the 10 sites, the contribution of Hg(p) scavenging to the annual mercury deposition flux was 26%, suggesting that mercury wet deposition in Japan is dominated by RGM scavenging. This RGM should originate mainly from the in situ oxidation of Hg⁰ in the atmosphere.     

Snow-to-air exchanges of mercury in an Arctic seasonal snow pack in Ny-Ålesund,Svalbard

The study of mercury (Hg) cycle in Arctic regions is a major subject of concern due to the dramatic increases of Hg concentrations in ecosystem in the last few decades. The causes of such increases are still in debate, and an important way to improve our knowledge on the subject is to study the exchanges of Hg between atmosphere and snow during springtime. We organized an international study from 10 April to 10 May 2003 in Ny-Ålesund, Svalbard, in order to assess these fluxes through measurements and derived calculations.Snow-to-air emission fluxes of Hg were measured using the flux chamber technique between ∼0 and 50 ng m⁻² h⁻¹. A peak in Gaseous Elemental Mercury (GEM) emission flux from the snow to the atmosphere has been measured just few hours after an Atmospheric Mercury Depletion Event (AMDE) recorded on 22 April 2004. Surprisingly, this peak in GEM emitted after this AMDE did not correspond to any increase in Hg concentration in snow surface. A peak in GEM flux after an AMDE was observed only for this single event but not for the four other AMDEs recorded during this spring period.In the snow pack which is seasonal and about 40 cm depth above permafrost, Hg is involved in both production and incorporation processes. The incorporation was evaluated to ∼5–40 pg m² h. Outside of AMDE periods, Hg flux from the snow surface to the atmosphere was the consequence of GEM production in the air of snow and was about ∼15–50 ng m⁻² h⁻¹, with a contribution of deeper snow layers evaluated to ∼0.3–6.5 ng m⁻² h⁻¹. The major part of GEM production is then mainly a surface phenomenon. The internal production of GEM was largely increasing when snow temperatures were close to melting, indicating a chemical process occurring in the quasi-liquid layer at the surface of snow grains.     

Mercury chemistry in the MBL: Mediterranean case and sensitivity studies using the AMCOTS (Atmospheric Mercury Chemistry over the Sea) model

The atmospheric oxidation of mercury in the Mediterranean marine boundary layer (MBL) has been studied using the Atmospheric Mercury Chemistry over the Sea (AMCOTS) model. The model results have been compared to measured data obtained during an oceanographic research campaign in 2000, with more success than previous modelling attempts. In light of the often high concentrations of ozone present in the Mediterranean boundary layer, seasonal case studies using typical meteorological conditions and average ozone concentrations have been performed to identify the main oxidants of elemental mercury. The sensitivity of the modelled reactive gaseous mercury (RGM) concentrations to the Hg+O₃ rate constant has been assessed using the two most recent rate determinations. The results using the higher of the two literature values gives results inconsistent with measured values of RGM when the reaction between Hg and O₃ is assumed to give a gas phase product. This does not necessarily indicate that the rate constant is incorrect but possibly that other rate constants in the model are overestimated or indeed that there may be reduction reactions occurring in the atmosphere which have yet to be identified. Alternatively, when the reaction product of Hg and O₃ is assumed to be a solid and therefore not contribute to RGM the modelled and measured results are comparable. The deposition rates calculated by the model when compared with calculated and measured sea surface emission fluxes available in the literature indicate that dry deposition flux of RGM is comparable to the sea surface emission flux. The calculated lifetime of Hg⁰ in the Mediterranean MBL is between one and two weeks.     

Airborne Emissions of Mercury from Municipal Solid Waste. II: Potential Losses of Airborne Mercury before Landfill

Abstract

Waste distribution and compaction at the working face of municipal waste landfills releases mercury vapor (Hg⁰) to the atmosphere, as does the flaring of landfill gas. Waste storage and processing before its addition to the landfill also has the potential to release Hg⁰ to the air if it is initially present or formed by chemical reduction of Hg^II to Hg⁰ within collected waste. We measured the release of Hg vapor to the atmosphere during dumpster and transfer station activities and waste storage before landfilling at a municipal landfill operation in central Florida. We also quantified the potential contribution of specific Hg-bearing wastes, including mercury (Hg) thermometers and fluorescent bulbs, and searched for primary Hg sources in sorted wastes at three different landfills. Surprisingly large fluxes were estimated for Hg losses at transfer facilities (～100 mg/hr) and from dumpsters in the field (～30 mg/hr for 1,000 dumpsters), suggesting that Hg emissions occurring before landfilling may constitute a significant fraction of the total emission from the disposal/landfill cycle and a need for more measurements on these sources. Reducing conditions of landfill burial were obviously not needed to generate strong Hg⁰ signals, indicating that much of the Hg was already present in a metallic (Hg⁰) form. Attempts to identify specific Hg sources in excavated and sorted waste indicated few readily identifiable sources; because of effective mixing and diffusion of Hg⁰, the entire waste mass acts as a source. Broken fluorescent bulbs and thermometers in dumpsters emitted Hg⁰ at 10 to >100 μg/hr and continued to act as near constant sources for several days.     

The role of halogen species in the troposphere

While the role of reactive halogen species (e.g. Cl, Br) in the destruction of the stratospheric ozone layer is well known, their role in the troposphere was investigated only since their destructive effect on boundary layer ozone after polar sunrise became obvious. During these 'Polar Tropospheric Ozone Hole' events O(3) is completely destroyed in the lowest approximately 1000 m of the atmosphere on areas of several million square kilometres. Up to now it was assumed that these events were confined to the polar regions during springtime. However, during the last few years significant amounts of BrO and Cl-atoms were also found outside the Arctic and Antarctic boundary layer. Recently even higher BrO mixing ratios (up to 176 ppt) were detected by optical absorption spectroscopy (DOAS) in the Dead Sea basin during summer. In addition, evidence is accumulating that BrO (at levels around 1-2 ppt) is also occurring in the free troposphere at all latitudes.In contrast to the stratosphere, where halogens are released from species, which are very long lived in the troposphere, likely sources of boundary layer Br and Cl are autocatalytic oxidation of sea salt halides (the 'Bromine Explosion'), while precursors of free tropospheric BrO and coastal IO probably are short-lived organo-halogen species. At the levels suggested by the available measurements reactive halogen species have a profound effect on tropospheric chemistry: In the polar boundary layer during 'halogen events' ozone is usually completely lost within hours or days. In the free troposphere the effective O(3)-losses due to halogens could be comparable to the known photochemical O(3) destruction. Further interesting consequences include the increase of OH levels and (at low NO(X)) the decrease of the HO(2)/OH ratio in the free troposphere.     

A reactive transport model for mercury fate in soil—application to different anthropogenic pollution sources

Soil systems are a common receptor of anthropogenic mercury (Hg) contamination. Soils play an important role in the containment or dispersion of pollution to surface water, groundwater or the atmosphere. A one-dimensional model for simulating Hg fate and transport for variably saturated and transient flow conditions is presented. The model is developed using the HP1 code, which couples HYDRUS-1D for the water flow and solute transport to PHREEQC for geochemical reactions. The main processes included are Hg aqueous speciation and complexation, sorption to soil organic matter, dissolution of cinnabar and liquid Hg, and Hg reduction and volatilization. Processes such as atmospheric wet and dry deposition, vegetation litter fall and uptake are neglected because they are less relevant in the case of high Hg concentrations resulting from anthropogenic activities. A test case is presented, assuming a hypothetical sandy soil profile and a simulation time frame of 50 years of daily atmospheric inputs. Mercury fate and transport are simulated for three different sources of Hg (cinnabar, residual liquid mercury or aqueous mercuric chloride), as well as for combinations of these sources. Results are presented and discussed with focus on Hg volatilization to the atmosphere, Hg leaching at the bottom of the soil profile and the remaining Hg in or below the initially contaminated soil layer. In the test case, Hg volatilization was negligible because the reduction of Hg²⁺ to Hg⁰ was inhibited by the low concentration of dissolved Hg. Hg leaching was mainly caused by complexation of Hg²⁺ with thiol groups of dissolved organic matter, because in the geochemical model used, this reaction only had a higher equilibrium constant than the sorption reactions. Immobilization of Hg in the initially polluted horizon was enhanced by Hg²⁺ sorption onto humic and fulvic acids (which are more abundant than thiols). Potential benefits of the model for risk management and remediation of contaminated sites are discussed.     

The influence of ozone on atmospheric emissions of gaseous elemental mercury and reactive gaseous mercury from substrates

Experiments were performed to investigate the effect of ozone (O₃) on mercury (Hg) emission from a variety of Hg-bearing substrates. Substrates with Hg(II) as the dominant Hg phase exhibited a 1.7 to 51-fold increase in elemental Hg (Hg^o) flux and a 1.3 to 8.6-fold increase in reactive gaseous mercury (RGM) flux in the presence of O₃-enriched clean (50 ppb O₃; 8 substrates) and ambient air (up to ∼70 ppb O₃; 6 substrates), relative to clean air (oxidant and Hg free air). In contrast, Hg^o fluxes from two artificially Hg^o-amended substrates decreased by more than 75% during exposure to O₃-enriched clean air relative to clean air. Reactive gaseous mercury emissions from Hg^o-amended substrates increased immediately after exposure to O₃ but then decreased rapidly. These experimental results demonstrate that O₃ is very important in controlling Hg emissions from substrates. The chemical mechanisms that produced these trends are not known but potentially involve heterogenous reactions between O₃, the substrate, and Hg. Our experiments suggest they are not homogenous gas-phase reactions. Comparison of the influence of O₃ versus light on increasing Hg^o emissions from dry Hg(II)-bearing substrates demonstrated that they have a similar amount of influence although O₃ appeared to be slightly more dominant. Experiments using water-saturated substrates showed that the presence of high-substrate moisture content minimizes reactions between atmospheric O₃ and substrate-bound Hg. Using conservative calculations developed in this paper, we conclude that because O₃ concentrations have roughly doubled in the last 100 years, this could have increased Hg^o emissions from terrestrial substrates by 65–72%.     

Investigation of Selective Catalytic Reduction Impact on Mercury Speciation under Simulated NOx Emission Control Conditions

Abstract

Selective catalytic reduction (SCR) technology increasingly is being applied for controlling emissions of nitrogen oxides (NO_x) from coal-fired boilers. Some recent field and pilot studies suggest that the operation of SCR could affect the chemical form of mercury (Hg) in coal combustion flue gases. The speciation of Hg is an important factor influencing the control and environmental fate of Hg emissions from coal combustion. The vanadium and titanium oxides, used commonly in the vanadia-titania SCR catalyst for catalytic NO_x reduction, promote the formation of oxidized mercury (Hg²⁺).

The work reported in this paper focuses on the impact of SCR on elemental mercury (Hg⁰) oxidation. Bench-scale experiments were conducted to investigate Hg⁰ oxidation in the presence of simulated coal combustion flue gases and under SCR reaction conditions. Flue gas mixtures with different concentrations of hydrogen chloride (HCl) and sulfur dioxide (SO₂) for simulating the combustion of bituminous coals and subbituminous coals were tested in these experiments. The effects of HCl and SO₂ in the flue gases on Hg⁰ oxidation under SCR reaction conditions were studied. It was observed that HCl is the most critical flue gas component that causes conversion of Hg⁰ to Hg²⁺ under SCR reaction conditions. The importance of HCl for Hg⁰ oxidation found in the present study provides the scientific basis for the apparent coal-type dependence observed for Hg⁰ oxidation occurring across the SCR reactors in the field.     

A review of current knowledge concerning dry deposition of atmospheric mercury

The status of the current knowledge concerning the dry deposition of atmospheric mercury, including elemental gaseous mercury (Hg⁰), reactive gaseous mercury (RGM), and particulate mercury (Hg_p), is reviewed. The air–surface exchange of Hg⁰ is commonly bi-directional, with daytime emission and nighttime deposition over non-vegetated surfaces and vegetated surfaces with small leaf area indices under low ambient Hg⁰ conditions. However, daytime deposition has also been observed, especially when the ambient Hg⁰ is high. Typical dry deposition velocities (V_d) for Hg⁰ are in the range of 0.1–0.4 cm s^?1 over vegetated surfaces and wetlands, but substantially smaller over non-vegetated surfaces and soils below canopies. Meteorological, biological, and soil conditions, as well as the ambient Hg⁰ concentrations all play important roles in the diurnal and seasonal variations of Hg⁰ air–surface exchange processes. Measurements of RGM deposition are limited and are known to have large uncertainties. Nevertheless, all of the measurements suggest that RGM can deposit very quickly onto any type of surface, with its V_d ranging from 0.5 to 6 cm s^?1. The very limited data for Hg_p suggest that its V_d values are in the range of 0.02–2 cm s^?1.A resistance approach is commonly used in mercury transport models to estimate V_d for RGM and Hg_p; however, there is a wide range of complexities in the dry deposition scheme of Hg⁰. Although resistance-approach based dry deposition schemes seem to be able to produce the typical V_d values for RGM and Hg⁰ over different surface types, more sophisticated air–surface exchange models have been developed to handle the bi-directional exchange processes. Both existing and newly developed dry deposition schemes need further evaluation using field measurements and intercomparisons within different modelling frameworks.     

Mercury contamination in vicinity of secondary copper smelters in Fuyang, Zhejiang Province, China: Levels and contamination in topsoils

In the present study, we aim to investigate the extent of soil contamination by Hg, particularly by anthropogenic Hg, and tentatively estimate the total Hg (Hg_T) accumulation in topsoils (0-15 cm) in Fuyang, Zhejiang Province—a secondary Cu smelter of China. The results show that the levels of soil Hg in the vicinity of the smelters have been substantially elevated following local smelting activities. The spatial distribution of soil Hg in this area reveals a rapid decrease as the distance from the smelter reaches 1.5 km, which is probably due to the quick deposition process of particulate Hg and reactive gaseous Hg emitted from the smelters. The total accumulation of Hg_T in the topsoils of the study area of 10.9 km² is approximately 365-561 kg and of which 346-543 kg might be contributed by anthropogenic emission alone with an annual emission of 17.3-27.2 kg Hg to the topsoils.     

Long-term mercury dynamics in UK soils

A model assuming first-order losses by evasion and leaching was used to evaluate Hg dynamics in UK soils since 1850. Temporal deposition patterns of Hg were constructed from literature information. Inverse modelling indicated that 30% of 898 rural sites receive Hg only from the global circulation, while in 51% of cases local deposition exceeds global. Average estimated deposition is 16 μg Hg m⁻² a⁻¹ to rural soils, 19 μg Hg m⁻² a⁻¹ to rural and non-rural soils combined. UK soils currently hold 2490 tonnes of reactive Hg, of which 2140 tonnes are due to anthropogenic deposition, mostly local in origin. Topsoil currently releases 5.1 tonnes of Hg⁰ per annum to the atmosphere, about 50% more than the anthropogenic flux. Sorptive retention of Hg in the lower soil exerts a strong control on surface water Hg concentrations. Following decreases in inputs, soil Hg concentrations are predicted to decline over hundreds of years.     

Mercury speciation and mobility in mine wastes from mercury mines in China

Mercury (Hg) speciation and mobility were determined in calcines and waste rocks collected from 9 Hg mines in China. Total Hg (THg) concentrations in the mine wastes varied widely in different Hg mines (with a range of 0.369 to 2,620 mg kg^?1). Cinnabar is the dominant form of Hg in the mine wastes. However, Hg²⁺ and Hg⁰ concentrations in the calcines were significantly higher than these in the waste rocks, which suggested the retorting can produce large amounts of by-product Hg compounds. The THg and Hg⁰ concentrations in certain mine wastes exceeded soil guidelines recommended by US Environmental Protection Agency; while total soluble Hg concentrations of leachates in certain mine wastes exceeded National Surface Water Quality Standard of China. Mine wastes are important Hg pollution sources to the aquatic ecosystem and atmosphere.     

Characteristics of mercury exchange flux between soil and air in the heavily air-polluted area,eastern Guizhou,China

To investigate the characteristics of mercury exchange between soil and air in the heavily air-polluted area, total gaseous mercury (TGM) concentration in air and Hg exchange flux were measured in Wanshan Hg mining area (WMMA) in November, 2002 and July–August, 2004. The results showed that the average TGM concentrations in the ambient air (17.8–1101.8 ng m⁻³), average Hg emission flux (162–27827 ng m⁻² h⁻¹) and average Hg dry deposition flux (0–9434 ng m⁻² h⁻¹) in WMMA were 1–4 orders of magnitude higher than those in the background area. It is said that mercury-enriched soil is a significant Hg source of the atmosphere in WMMA. It was also found that widely distributed roasted cinnabar banks are net Hg sources of the atmosphere in WMMA. Relationships between mercury exchange flux and environmental parameters were investigated. The results indicated that the rate of mercury emission from soil could be accelerated by high total soil mercury concentration and solar irradiation. Whereas, highly elevated TGM concentrations in the ambient air can restrain Hg emission from soil and even lead to strongly atmospheric Hg deposition to soil surface. A great amount of gaseous mercury in the heavily polluted atmosphere may cycle between soil and air quickly and locally. Vegetation can inhibit mercury emission from soil and are important sinks of atmospheric mercury in heavily air-polluted area.     

Pilot-Scale Study of the Effect of Selective Catalytic Reduction Catalyst on Mercury Speciation in Illinois and Powder River Basin Coal Combustion Flue Gases

Abstract

A study was conducted to investigate the effect of selective catalytic reduction (SCR) catalyst on mercury (Hg) speciation in bituminous and subbituminous coal combustion flue gases. Three different Illinois Basin bituminous coals (from high to low sulfur [S] and chlorine [Cl]) and one Powder River Basin (PRB) subbituminous coal with very low S and very low Cl were tested in a pilot-scale combustor equipped with an SCR reactor for controlling nitrogen oxides (NO_x) emissions. The SCR catalyst induced high oxidation of elemental Hg (Hg⁰), decreasing the percentage of Hg⁰ at the outlet of the SCR to values <12% for the three Illinois coal tests. The PRB coal test indicated a low oxidation of Hg⁰ by the SCR catalyst, with the percentage of Hg⁰ decreasing from ～96% at the inlet of the reactor to ～80% at the outlet. The low Cl content of the PRB coal and corresponding low level of available flue gas Cl species were believed to be responsible for low SCR Hg oxidation for this coal type. The test results indicated a strong effect of coal type on the extent of Hg oxidation.     

Dry deposition and foliar leaching of mercury and selected trace elements in deciduous forest throughfall

The estimated annual throughfall deposition flux of Hg in a northern mixed-hardwood forest in the Lake Huron Watershed was 10.5±1.0 μg m⁻² compared to an annual precipitation Hg flux of 8.7±0.5 μg m⁻² (June 1996–June 1997). The source of this additional Hg in throughfall is often attributed to wash-off of dry deposition, but foliar leaching of Hg may also be important. To determine the influence of both dry deposition and foliar leaching of Hg and other elements in throughfall, we measured a suite of trace elements (Hg, Al, Mg, V, Mn, Cu, Zn, As, Rb, Sr, Cd, Ba, La, Ce, and Pb) in throughfall, precipitation, and ambient air samples from a northern mixed-hardwood forest. Based on a multiple linear regression model, dry deposition had the most important influence on Hg, Al, La, Ce, V, As, Cu, Zn, Cd, and Pb fluxes while foliar leaching strongly influenced Mg, Mn, Rb, Sr, and Ba fluxes in net throughfall. The Hg dry deposition flux was estimated using gaseous and aerosol Hg measurements and modeled deposition velocities. The calculated dry deposition flux (∼12–14 μg m⁻²) of Hg to the canopy indicated that atmospheric deposition of Hg could easily account for all of the Hg deposited in net throughfall (1.9±0.1 μg m⁻²). Although there is a large uncertainty associated with these techniques, the modeling estimates indicate that atmospheric Hg may account for all of the Hg deposited in litterfall (11.4±2.8 μg m⁻²).     

Formation of chlorinated species through reaction of SO2 with NaClO2 powder and their role in the oxidation of NO and Hg0

This study examines gaseous chlorinated species generated from the reaction of sulfur dioxide (SO₂) with sodium chlorite powder (NaClO_2(s)) to obtain insight into the propensity of this process to enhance NO and Hg⁰ oxidation. A packed bed reactor containing NaClO_2(s) was used and the reaction temperature was set to 130 °C. Initially, we determined that the presence of SO₂ enhances the oxidation of NO and Hg⁰ by reaction with NaClO_2(s). We then introduced NO₂ into the gas mixture as a radical scavenger and determined that the chlorinated species generated by the reaction of SO₂ with NaClO_2(s) are OClO, Cl, ClO, and Cl₂. Based on these results, we suggest that such gaseous chlorinated ones are responsible for the enhancement of NO and Hg⁰ oxidation.