Sources Of Atmospheric Mercury Research Articles

Stone coal as a potential atmospheric mercury source in Da-Ba-Shan mountain areas, China

Abstract Mercury (Hg) emissions from stone coal that formed from marine lower organisms in the late Proterozoic and early Paleozoic have not been paid much attention in China. In this research, Hg concentrations in different fueled coals (stone coal, humic coal) and charcoal that derived from wood and paired slags, atmospheric Hg emissions and atmospheric Hg levels were studied in Shaanxi province, China. The average Hg concentration in stone coal produced in Da-Ba-Shan mountain areas in Southern Shaanxi was 539.4 μg·kg−1, about 15 and 38 times higher than that of humic coal (36.0 μg·kg−1) and charcoal (14.2 μg·kg−1), respectively. Atmospheric Hg emission usually lasted for 2–3 h after fueling stone coal, with the majority of Hg emitted during the first 1 h. 95.5–99.4% of Hg in the fuel would be lost into the atmosphere for three types of fuels. Mercury emission factor (MEF) of stone coal was 40–120 times higher than those of humic coal and charcoal based on heat value. Average atmospheric Hg concentration at 0.5 m above the stove could reach 1600–2000 ng·m−3 if burning stone coal, which exceeded the standards for residential ambient air (200–300 ng·m−3) by 5–10 times and also was nearly two orders of magnitude higher than that of burning humic coal (20–60 ng·m−3). Health risk would be a concern for local residents who depend on stone coal for cooking and heating but without any control measures of flue gas. In Shaanxi province alone, Hg emission through domestic combustion of stone coal was estimated to be 1.34 Mg in 2011. Higher mercury emission amounts are possible in southern China where stone coal has been intensively used. Total mercury emissions from this source category need to be further investigated on the national scale.

Characterization and Quantification of Atmospheric Mercury Sources Using Passive Air Samplers

AbstractThe Minamata Convention on Mercury (Hg) requires improved atmospheric Hg monitoring and characterization of Hg sources. Here we demonstrate how a network of passive air samplers (PASs) can be used cost effectively to determine the spatial distribution of gaseous Hg and estimate atmospheric Hg emissions at contaminated sites. Gaseous Hg concentrations were mapped around a former Hg mine in the Monte Amiata district in Italy using simultaneous deployments of PASs across local and regional spatial scale grids. The concentration maps help visualize with great detail and precision the dispersal of gaseous Hg from a contaminated site, revealing even subtle effects of wind, season, and minor sources. Emissions estimated from the empirical data (80 ± 40 and 150 ± 75 kg/year for October and July, respectively) were robust to changes in the most uncertain parameters (excess Hg in the air above the mine and advection rate) and compared well to previous estimates for this and other closed Hg mines. This PAS‐based approach has a number of advantages: (i) concurrent deployments of multiple samplers constrain concentration changes to spatial variability only, (ii) time‐averaged data over longer periods negate biases related to short‐term, infrequent measurements, (iii) more spatially representative estimates of Hg distributions and emissions can be made at a fraction of the cost, and (iv) use is easy, especially in difficult terrain. Time‐averaged data across a broad area are also most pertinent for assessing chronic human exposure, especially in terms of the inhalation of Hg by workers and residents living close to contaminated sites.

Atmospheric mercury emissions from two pre-calciner cement plants in Southwest China

Abstract China produces the most cement product worldwide, and cement plants (CPs) have been regarded as the largest anthropogenic sources of atmospheric mercury (Hg) emissions in China since 2009. Onsite studies of this source are scarce compare to the huge numbers of CPs in China. Hence, quantifying Hg emissions from more CPs is needed in reducing the large uncertainties existed in the current Hg emission inventories and for assessing subsequent impacts of Hg on human and ecosystem health. In this study, two pre-calciner CPs in Guizhou province of Southwest China were selected for quantifying the emission factor and mass balance of Hg. Results showed that Hg emission levels in the two CPs were obviously different due to the differences in Hg input and circulation in the production system. In cement plant #1 (CP #1), the input and output of Hg reached a dynamic equilibrium condition, the emission factor was 76.1 mg Hg·t−1 clinker, and Hg concentration in the stack flue gas was in the range of 14.46–16.64 μg m−3. In cement plant #2 (CP #2), Hg was in an enriching status because it was a new plant with operation of several months and most input Hg was retained inside the production system, hence with a much lower emission factor of 1.8 mg Hg·t−1 clinker and Hg concentration of 0.15–0.49 μg m−3 in the stack gas. Kiln tail stack was the main output pathway of Hg in the clinker production process. With removal efficiency of 73.06% and 99.95% at kiln tail by ESP in CP #1 and humidifier + ESP-FF in CP #2, respectively, Hg emitted into the atmosphere was mainly in the forms of gaseous oxidized mercury (Hg2+) and gaseous elemental mercury (Hg0). Besides, the operation mode (on or off) of raw mill had great impact on the concentration and speciation of Hg in flue gas and flue gas temperature at kiln tail. In the clinker production system, limestone is the main source of Hg input (41.4–56.4%), followed by the fueled coal (15.3–32.5%). While, in the clinker to cement production process, the additives (mainly gypsum from coal-fired power plants, 83.2–94.4%) was the main source of Hg in the cement because Hg concentration in the clinker was very low.

High-resolution measurements of elemental mercury in surface water for an improved quantitative understanding of the Baltic Sea as a source of atmospheric mercury

Abstract. Marginal seas are directly subjected to anthropogenic and natural influences from land in addition to receiving inputs from the atmosphere and open ocean. Together these lead to pronounced gradients and strong dynamic changes. However, in the case of mercury emissions from these seas, estimates often fail to adequately account for the spatial and temporal variability of the elemental mercury concentration in surface water (Hg0wat). In this study, a method to measure Hg0wat at high resolution was devised and subsequently validated. The better-resolved Hg0wat dataset, consisting of about one measurement per nautical mile, yielded insight into the sea's small-scale variability and thus improved the quantification of the sea's Hg0 emission. This is important because global marine Hg0 emissions constitute a major source of atmospheric mercury. Research campaigns in the Baltic Sea were carried out between 2011 and 2015 during which Hg0 both in surface water and in ambient air were measured. For the former, two types of equilibrators were used. A membrane equilibrator enabled continuous equilibration and a bottle equilibrator assured that equilibrium was reached for validation. The measurements were combined with data obtained in the Baltic Sea in 2006 from a bottle equilibrator only. The Hg0 sea–air flux was newly calculated with the combined dataset based on current knowledge of the Hg0 Schmidt number, Henry's law constant, and a widely used gas exchange transfer velocity parameterization. By using a newly developed pump–CTD with increased pumping capability in the Hg0 equilibrator measurements, Hg0wat could also be characterized in deeper water layers. A process study carried out near the Swedish island Øland in August 2015 showed that the upwelling of Hg0-depleted water contributed to Hg0 emissions of the Baltic Sea. However, a delay of a few days after contact between the upwelled water and light was apparently necessary before the biotic and abiotic transformations of ionic to volatile Hg0 produced a distinct sea–air Hg0 concentration gradient. This study clearly showed spatial, seasonal, and interannual variability in the Hg0 sea–air flux of the Baltic Sea. The average annual Hg0 emission was 0.90 ± 0.18 Mg for the Baltic proper and extrapolated to 1.73 ± 0.32 Mg for the entire Baltic Sea, which is about half the amount entrained by atmospheric deposition. A comparison of our results with the Hg0 sea–air fluxes determined in the Mediterranean Sea and in marginal seas in East Asia were to some extent similar but they partly differed in terms of the deviations in the amount and seasonality of the flux.

Mercury enrichment in Brassica napus in response to elevated atmospheric mercury concentrations

Mercury enrichment in response to elevated atmospheric mercury concentrations in the organs of rape (Brassica napus) was investigated using an open top chamber fumigation experiment and a soil mercury enriched cultivation experiment. Results indicate that the mercury concentration in leaves and stems showed a significant variation under different concentrations of mercury in atmospheric and soil experiments while the concentration of mercury in roots, seeds and seed coats showed no significant variation under different atmospheric mercury concentrations. Using the function relation established by the experiment, results for atmospheric mercury sources in rape field biomass showed that atmospheric sources accounted for at least 81.81%of mercury in rape leaves and 32.29% of mercury in the stems. Therefore, mercury in the aboveground biomass predominantly derives from the absorption of atmospheric mercury.

Passive air sampling of gaseous elemental mercury: a critical review

Abstract. Because gaseous elemental mercury (GEM) is distributed globally through the atmosphere, reliable means of measuring its concentrations in air are important. Passive air samplers (PASs), designed to be cheap, simple to operate, and to work without electricity, could provide an alternative to established active sampling techniques in applications such as (1) long-term monitoring of atmospheric GEM levels in remote regions and in developing countries, (2) atmospheric mercury source identification and characterization through finely resolved spatial mapping, and (3) the recording of personal exposure to GEM. An effective GEM PAS requires a tightly constrained sampling rate, a large and stable uptake capacity, and a sensitive analytical technique. None of the GEM PASs developed to date achieve levels of accuracy and precision sufficient for the reliable determination of background concentrations over extended deployments. This is due to (1) sampling rates that vary due to meteorological factors and manufacturing inconsistencies, and/or (2) an often low, irreproducible and/or unstable uptake capacity of the employed sorbents. While we identify shortcomings of existing GEM PAS, we also reveal potential routes to overcome those difficulties. Activated carbon and nanostructured metal surfaces hold promise as effective sorbents. Sampler designs incorporating diffusive barriers should be able to notably reduce the influence of wind on sampling rates.

Transboundary transport and deposition of Hg emission from springtime biomass burning in the Indo‐China Peninsula

AbstractBiomass burning from the Indo‐China Peninsula region is an important source of atmospheric mercury (Hg). We isolated 18 unique transport events over 2 years using observations of Hg and CO at a high‐altitude background site in southwestern China (Mount Ailao Observatory Station) to assess the transport and impact of Hg emissions from biomass burning. The quantity of Hg emission and the source regions were determined using ΔTGM/ΔCO slopes coupled with backward trajectory analysis and CO emission inventories. The slopes of ΔTGM/ΔCO appeared to be a useful chemical indicator for source identification. Industrial emission sources exhibited slopes in the range of 5.1–61.0 × 10−7 (parts per trillion by volume, pptv/pptv), in contrast to a slope of 2.0–6.0 × 10−7 for typical biomass burning. Transboundary transport of Hg from biomass burning led to episodically elevated atmospheric Hg concentrations during springtime. Hg emissions from biomass burning in the Indo‐China Peninsula region from 2001 to 2008 were estimated to be 11.4 ± 2.1 Mg yr−1, equivalent to 40% of annual anthropogenic emissions in the region. In addition, Hg emissions from biomass burning contained a substantial fraction of particulate bound Hg (PBM). Assuming that PBM readily deposits locally (within 50 km), the local Hg deposition caused by the PBM was estimated to be 2.2 ± 0.4 Mg yr−1, up to 1 order of magnitude higher than the PBM deposition caused by anthropogenic emissions during springtime in the region. The strong springtime emissions potentially pose a threat to the ecosystems of the Indo‐China Peninsula and southwest China.

Characteristics and potential sources of atmospheric mercury at a subtropical near‐coastal site in East China

AbstractTo evaluate the impact of regional mercury (Hg) emissions and understand possible source regions of atmospheric Hg in Eastern China, 2 year observation for speciated atmospheric Hg was conducted at the Dameishan Atmospheric Observatory, a mountain site near the east coast of China. The observed concentration of total gaseous Hg (TGM) was 3.3 ± 1.4 ng m−3. During the sampling period, gaseous oxidized Hg and particulate bound Hg were 6.7 ± 4.3 pg m−3 and 180 ± 110 pg m−3 in winter and 5.9 ± 3.4 pg m−3 and 130 ± 100 pg m−3 in spring, respectively. The relatively high mean concentration of TGM was mainly caused by regional anthropogenic emissions and occasional long‐range transport from domestic source regions. Seasonal variation in the TGM concentration was observed with lower values in the wet monsoon season (from May to September) and higher values in the dry monsoon season (from October to April). Backward trajectories and potential source contribution function analysis suggested that anthropogenic Hg emission from coal combustion in the Yangtze River Delta region was the most likely cause for the elevated TGM concentrations. Relatively clean air originating from the East China Sea was the most possible cause for the observed low TGM concentrations. Positive correlation between TGM concentration and air quality index suggests that emissions that influenced regional air quality contributed to the elevated TGM concentrations.

Overview of receptor-based source apportionment studies for speciated atmospheric mercury

Abstract. Receptor-based source apportionment studies of speciated atmospheric mercury are not only concerned with source contributions but also with the influence of transport, transformation, and deposition processes on speciated atmospheric mercury concentrations at receptor locations. Previous studies applied multivariate receptor models including principal components analysis and positive matrix factorization, and back trajectory receptor models including potential source contribution function, gridded frequency distributions, and concentration–back trajectory models. Combustion sources (e.g., coal combustion, biomass burning, and vehicular, industrial and waste incineration emissions), crustal/soil dust, and chemical and physical processes, such as gaseous elemental mercury (GEM) oxidation reactions, boundary layer mixing, and GEM flux from surfaces were inferred from the multivariate studies, which were predominantly conducted at receptor sites in Canada and the US. Back trajectory receptor models revealed potential impacts of large industrial areas such as the Ohio River valley in the US and throughout China, metal smelters, mercury evasion from the ocean and the Great Lakes, and free troposphere transport on receptor measurements. Input data and model parameters specific to atmospheric mercury receptor models are summarized and model strengths and weaknesses are also discussed. Multivariate models are suitable for receptor locations with intensive air monitoring because they require long-term collocated and simultaneous measurements of speciated atmospheric Hg and ancillary pollutants. The multivariate models provide more insight about the types of Hg emission sources and Hg processes that could affect speciated atmospheric Hg at a receptor location, whereas back trajectory receptor models are mainly ideal for identifying potential regional Hg source locations impacting elevated Hg concentrations. Interpretation of the multivariate model output to sources can be subjective and challenging when speciated atmospheric Hg is not correlated with ancillary pollutants and when source emissions profiles and knowledge of Hg chemistry are incomplete. The majority of back trajectory receptor models have not accounted for Hg transformation and deposition processes and could not distinguish between upwind and downwind sources effectively. Ensemble trajectories should be generated to take into account the trajectory uncertainties where possible. One area of improvement that applies to all the receptor models reviewed in this study is the greater focus on evaluating the accuracy of the models at identifying potential speciated atmospheric mercury sources, source locations, and chemical and physical processes in the atmosphere. In addition to receptor model improvements, the data quality of speciated atmospheric Hg plays an equally important part in producing accurate receptor model results.

Arctic Ocean: Is It a Sink or a Source of Atmospheric Mercury?

High levels of mercury in marine mammals threaten the health of Arctic inhabitants. Whether the Arctic Ocean (AO) is a sink or a source of atmospheric mercury is unknown. Given the paucity of observations in the Arctic, models are useful in addressing this question. GEOS-Chem and GRAHM, two complex numerical mercury models, present contrasting pictures of atmospheric mercury input to AO at 45 and 108 Mg yr(-1), respectively, and ocean evasion at 90 and 33 Mg yr(-1), respectively. We provide a comprehensive evaluation of GRAHM simulated atmospheric mercury input to AO using mercury observations in air, precipitation and snowpacks, and an analysis of the discrepancy between the two modeling estimates using observations. We discover two peaks in high-latitude summertime concentrations of atmospheric mercury. We show that the first is caused mainly by snowmelt revolatilization and the second by AO evasion of mercury. Riverine mercury export to AO is estimated at 50 Mg yr(-1) based on measured DOC export and at 15.5-31 Mg yr(-1) based on simulated mercury in meltwater. The range of simulated mercury fluxes to and from AO reflects uncertainties in modeling mercury in the Arctic; comprehensive observations in all compartments of the Arctic ecosystem are needed to close the gap.

Assessing the emission sources of atmospheric mercury in wet deposition across Illinois

From August 4, 2007 to August 31, 2009, we collected event-based precipitation samples for mercury (Hg) and trace element analyses at four sites in Illinois (IL), USA. The objectives of these measurements were to quantify Hg wet deposition across the state, and to assess the contributions to Hg in precipitation from major local and regional emission sources. Monitoring sites were located, from north to south, in Chicago, Peoria, Nilwood, and Carbondale, IL. Measurements from these four sites demonstrated that a clear spatial gradient in Hg wet deposition was not evident across the state. Each site received>10μgm(-2) of Hg wet deposition annually, and these observed values were comparable to annual Hg wet deposition measurements from other event-based precipitation monitoring sites in source-impacted areas of the Midwestern U.S. We applied the multivariate statistical receptor model, Positive Matrix Factorization (EPA PMF v3.0), to the measured Hg and trace element wet deposition amounts at the four sites. Results suggested that 50% to 74% of total Hg wet deposition at each site could be attributed to coal combustion emissions. The other source signatures identified in the precipitation compositions included cement manufacturing, mixed metal smelting/waste incineration, iron-steel production, and a phosphorus source. We also applied a hybrid receptor model, Quantitative Transport Bias Analysis (QTBA), to the Hg wet deposition datasets to identify the major source regions associated with the measured values. The calculated QTBA probability fields suggested that transport from urban/industrial areas, such as Chicago/Gary, St. Louis, and the Ohio River Valley, resulted in some of the highest estimated event-based Hg wet deposition amounts at the four sites (potential mass transfer of up to 0.32μgm(-2)). The combined application of PMF and QTBA supported the hypothesis that local and regional coal combustion was the largest source of Hg wet deposition in Illinois.

Mercury release flux and its influencing factors at the air-water interface in paddy field in Chongqing, China

The exchange of mercury (Hg) across the air-water interface is an important part of Hg biogeochemical cycle. Mercury fluxes across the air-water interface in paddy fields were measured by a Dynamic Flux Chamber (DFC) coupled with a Lumex® multifunctional mercury analyzer RA-915+ at two sites (Chengjiang (CJ) and Caoshang (CS)) in Beibei, Chongqing, China in 2008. The results showed that mercury emission followed a power-law relationship with solar radiation and air temperature, and it increased exponentially with water temperature at both sites. Mercury emission was mainly influenced by the solubility of gaseous elemental Hg, photo-thermal effect, electron activity (Eh) and air Hg concentrations. Solar radiation made the greatest direct contribution to mercury emission during the daytime (0.80), with an 83.60% contribution, whereas at nighttime the water temperature (0.72) contributed to 71.65% of emissions. The temperature gradient between water and air might also influenced mercury emission across the air/water interface at nighttime. These findings suggest that paddy fields could act as a significant source of atmospheric mercury, and it can contribute significantly to the atmospheric mercury in a local region.

Sources of atmospheric mercury in the tropics: continuous observations at a coastal site in Suriname

Abstract. Mercury measurements at a coastal site in Nieuw Nickerie (5°56' N, 56°59' W), Suriname, provide the only continuous records of atmospheric mercury in the tropics. Here we evaluate observations of total gaseous mercury (TGM) during 2007. Nieuw Nickerie typically samples marine air from the Atlantic Ocean, with occasional influence from continental South America. Over the year, average concentrations are 1.40 ng m−3. As the intertropical convergence zone passes over Suriname twice each year, the site samples both northern and southern hemispheric air masses. We use back trajectories to classify each measurement by hemisphere, as well as continental or ocean. For air passing over ocean before sampling, TGM concentrations are 10% higher in air coming from the Northern Hemisphere (1.45 ng m−3) than from the Southern Hemisphere (1.32 ng m−3). Air from the South American continent also carries higher TGM (1.43 ng m−3) than air from the South Atlantic Ocean, with most of these trajectories occurring in August and September. Biomass burning in Brazil peaks in the same months and likely contributes significantly to elevated concentrations seen in Nickerie. We also compare the observed seasonal cycle to two atmospheric mercury chemistry and transport models (GRAHM and GEOS-Chem). Both models simulate transition between northern and southern hemispheric air, thus capturing the seasonal cycle; however the models overestimate the TGM concentrations during months when Nickerie samples Northern Hemisphere air. It is difficult to determine whether the models' sources or sinks in the Northern Hemisphere tropics are responsible.

Spatial distribution of mercury deposition fluxes in Wanshan Hg mining area, Guizhou province, China

Abstract. The legacy of long-term mining activities in Wanshan mercury (Hg) mining area (WMMA), Guizhou, China including a series of environmental issues related to Hg pollution. The spatial distribution of gaseous elemental mercury (Hg0) concentrations in ambient air were monitored using a mobile RA-915+ Zeeman Mercury Analyzer during daytime and night time in May 2010. The data imply that calcines and mine wastes piles located at Dashuixi and on-going artisanal Hg mining activities at Supeng were major sources of atmospheric mercury in WMMA. For a full year (May 2010 to May 2011), sampling of precipitation and throughfall were conducted on a weekly basis at three sites (Shenchong, Dashuixi, and Supeng) within WMMA. Hg in deposition was characterized by analysis of total Hg (THg) and dissolved Hg (DHg) concentrations. The corresponding data exhibit a high degree of variability, both temporarily and spatially. The volume-weighted mean THg concentrations in precipitation and throughfall samples were 502.6 ng l−1 and 977.8 ng l−1 at Shenchong, 814.1 ng l−1and 3392.1 ng l−1 at Dashuixi, 7490.1 ng l−1and 9641.5 ng l−1 at Supeng, respectively. THg was enhanced in throughfall compared to wet deposition samples by up to a factor of 7. The annual wet Hg deposition fluxes were 29.1, 68.8 and 593.1 μg m−2 yr−1 at Shenchong, Dashuixi and Supeng, respectively, while the annual dry Hg deposition fluxes were estimated to be 378.9, 2613.6 and 6178 μg m−2 yr−1 at these sites, respectively. Dry deposition played a dominant role in total atmospheric Hg deposition in WMMA since the dry deposition fluxes were 10.4–37.9 times higher than the wet deposition fluxes during the whole sample period. Our data showed that air deposition was still an important pathway of Hg contamination to the local environment in WMMA.

Mercury in the Southern Ocean

We present here the first mercury speciation study in the water column of the Southern Ocean, using a high-resolution south-to-north section (27 stations from 65.50!S to 44.00!S) with up to 15 depths (0–4440 m) between Antarctica and Tasmania (Australia) along the 140!E meridian. In addition, in order to explore the role of sea ice in Hg cycling, a study of mercury speciation in the snow–sea ice–seawater continuum was conducted at a coastal site, near the Australian Casey station (66.40!S; 101.14!E). In the open ocean waters, total Hg (HgT) concentrations varied from 0.63 to 2.76 pmol L!1 with transient-type vertical profiles and a latitudinal distribution suggesting an atmospheric mercury source south of the Southern Polar Front (SPF) and a surface removal north of the Subantartic Front (SAF). Slightly higher mean HgT concentrations (1.35 ± 0.39 pmol L!1) were measured in Antarctic Bottom Water (AABW) compared to Antarctic Intermediate water (AAIW) (1.15 ± 0.22 pmol L!1). Labile Hg (HgR) concentrations varied from 0.01 to 2.28 pmol L!1, with a distribution showing that the HgT enrichment south of the SPF consisted mainly of HgR (67 ± 23%), whereas, in contrast, the percentage was half that in surface waters north of PFZ (33 ± 23%). Methylated mercury species (MeHgT) concentrations ranged from 0.02 to 0.86 pmol L!1. All vertical MeHgT profiles exhibited roughly the same pattern, with low concentrations observed in the surface layer and increasing concentrations with depth up to an intermediate depth maximum. As for HgT, low mean MeHgT concentrations were associated with AAIW, and higher ones with AABW. The maximum of MeHgT concentration at each station was systematically observed within the oxygen minimum zone, with a statistically significant MeHgT vs Apparent Oxygen Utilization (AOU) relationship (p < 0.001). The proportion of HgT as methylated species was lower than 5% in the surface waters, around 50% in deep waters below 1000 m, reaching a maximum of 78% south of the SPF. At Casey coastal station HgT and HgR concentrations found in the snow–sea ice–seawater continuum were one order of magnitude higher than those measured in open ocean waters. The distribution of HgT there suggests an atmospheric Hg deposition with snow and a fractionation process during sea ice formation, which excludes Hg from the ice with a parallel Hg enrichment of brine, probably concurring with the Hg enrichment of AABW observed in the open ocean waters. Contrastingly, MeHgT concentrations in the sea ice environment were in the same range as in the open ocean waters, remaining below 0.45 pmol L!1. The MeHgT vertical profile through the continuum suggests different sources, including atmosphere, seawater and methylation in basal ice. Whereas HgT concentrations in the water samples collected between the Antarctic continent and Tasmania are comparable to recent measurements made in the other parts of the World Ocean (e.g., Soerensen et al., 2010), the Hg species distribution suggests distinct features in the Southern Ocean Hg cycle: (i) a net atmospheric Hg deposition on surface water near the ice edge, (ii) the Hg enrichment in brine during sea ice formation, and (iii) a net methylation of Hg south of the SPF.

Isotope Tracing of Atmospheric Mercury Sources in an Urban Area of Northeastern France

Mercury (Hg) isotope composition was investigated in lichens over a territory of 900 km(2) in the northeast of France over a period of nine years (2001-2009). The studied area was divided into four geographical areas: a rural area, a suburban area, an urban area, and an industrial area. In addition, lichens were sampled directly at the bottom of chimneys, within the industrial area. While mercury concentrations in lichens did not correlate with the sampling area, mercury isotope compositions revealed both mass dependent and mass independent fractionation globally characteristic of each geographical area. Odd isotope deficits measured in lichens were smallest in samples close to industries, with Delta(199)Hg of -0.15 +/- 0.03 per thousand, where Hg is thought to originate mainly from direct anthropogenic inputs. Samples from the rural area displayed the largest anomalies with Delta(199)Hg of -0.50 +/- 0.03 per thousand. Samples from the two other areas had intermediate Delta(199)Hg values. Mercury isotopic anomalies in lichens were interpreted to result from mixing between the atmospheric reservoir and direct anthropogenic sources. Furthermore, the combination of mass-dependent and mass independent fractionation was used to characterize the different geographical areas and discriminate the end-members (industrial, urban, and local/regional atmospheric pool) involved in the mixing of mercury sources.

Atmospheric wet deposition of mercury and other trace elements in Pensacola, Florida

Abstract. In an effort to understand and quantify the impact of local, regional, and far-distant atmospheric mercury sources to rainfall mercury deposition in the Pensacola, Florida watershed, a program of event-based rainfall sampling was started in late 2004. Modified Aerochem-Metrics wet/dry rainfall samplers were deployed at three sites in the region around the Crist coal-fired power plant and event-based samples were collected continuously for three years. Samples were analyzed for total Hg and a suite of trace elements including Al, As, Ba, Bi, Cd, Ce, Co, Cr, Cs, Cu, Fe, Ga, La, Li, Mg, Mn, Na, Nb, Ni, P, Pb, Sb, Se, Si, Sn, Sr, Th, U, V, and Zn. Nutrients (ammonia and nitrate) and major anions (chloride and sulfate) were also measured on each sample. Multivariate statistical methods were used to sort these tracers into factors that represent potential source categories contributing to the rainfall chemistry. As, Hg, Sb, Se, Sn, and non sea-salt sulfate were all significantly correlated (R&gt;0.6) with one factor which we interpret as an anthropogenic source term reflecting input from coal combustion throughout the southeastern US. Using ratios of total Hg to volatile elements, we estimate that 22–33% of the rainfall Hg results from coal combustion in the southeastern US with the majority coming from the global background.

Temporal distribution and potential sources of atmospheric mercury measured at a high-elevation background station in Taiwan

Abstract Measurements of gaseous elemental mercury (GEM), reactive gaseous mercury (RGM), and particulate mercury (PHg) have been conducted at Lulin Atmospheric Background Station (LABS) in Taiwan since April 2006. This was the first long-term free tropospheric atmospheric Hg monitoring program in the downwind region of East Asia, which is a major Hg emission source region. Between April 13, 2006 and December 31, 2007, the mean concentrations of GEM, RGM, and PHg were 1.73 ng m −3 , 12.1 pg m −3 , and 2.3 pg m −3 , respectively. A diurnal pattern was observed for GEM with afternoon peaks and nighttime lows, whereas the diurnal pattern of RGM was opposite to that of GEM. Spikes of RGM were frequently observed between midnight and early morning with concurrent decreases in GEM and relative humidity and increases in O 3 , suggesting the oxidation of GEM and formation of RGM in free troposphere (FT). Upslope movement of boundary layer (BL) air in daytime and subsidence of FT air at night resulted in these diurnal patterns. Considering only the nighttime data, which were more representative of FT air, the composite monthly mean GEM concentrations ranged between 1.06 and 2.06 ng m −3 . Seasonal variation in nighttime GEM was evident, with lower concentrations usually occurring in summer when clean marine air masses prevailed. Between fall and spring, air masses passed the East Asian continent prior to reaching LABS, contributing to the elevated GEM concentrations. Analysis of GEM/CO correlation tends to support the argument. Good GEM/CO correlations were observed in fall, winter, and spring, suggesting influence of anthropogenic emission sources. Our results demonstrate the significance of East Asian Hg emissions, including both anthropogenic and biomass burning emissions, and their long-range transport in the FT. Because of the pronounced seasonal monsoon activity and the seasonal variation in regional wind field, export of the Asian Hg emissions to Taiwan occurs mainly during fall, winter, and spring.

Mercury emissions and stable isotopic compositions at Vulcano Island (Italy)

Abstract Sampling and analyses methods for determining the stable isotopic compositions of Hg in an active volcanic system were tested and optimized at the volcanic complex of Vulcano (Aeolian Islands, Italy). Condensed gaseous fumarole Hg(fum)T, plume gaseous elemental Hg(g)0 and plume particulate Hg(p)II were obtained at fumaroles F0, F5, F11, and FA. The average total Hg emissions, based on HgT/SO2 in condensed fumarolic gases and plumes, range from 2.5 to 10.1 kg y− 1, in agreement with published values [Ferrara, R., Mazzolai, B., Lanzillotta, E., Nucaro, E., Pirrone, N., 2000. Volcanoes as emission sources of atmospheric mercury in the Mediterranean Basin. Sci. Total Environ. 259(1–3), 115–121; Aiuppa, A., Bagnato, E., Witt, M.L.I., Mather, T.A., Parello, F., Pyle, D.M., Martin, R.S., 2007. Real-time simultaneous detection of volcanic Hg and SO2 at La Fossa Crater, Vulcano (Aeolian Islands, Sicily). Geophys. Res. Lett. 34(L21307).]. Plume Hg(p)II increases with distance from the fumarole vent, at the expense of Hg(g)0 and indicates significant in-plume oxidation and condensation of fumarole Hg(fum)T. Relative to the NIST SRM 3133 Hg standard, the stable isotopic compositions of Hg are δ202Hg(fum)T = − 0.74‰ ± 0.18 (2SD, n = 4) for condensed gaseous fumarole Hg(fum)T, δ202Hg(g)0 = − 1.74‰ ± 0.36 (2SD, n = 1) for plume gaseous elemental Hg(g)0 at the F0 fumarole, and δ202Hg(p)II = − 0.11‰ ± 0.18 (2SD, n = 4) for plume particulate Hg(p)II. The enrichment of Hg(p)II in the heavy isotopes and Hg(g)0 in the light isotopes relative to the total condensed fumarolic Hg(fum)T gas complements the speciation data and demonstrates a gas-particle fractionation occurring after the gas expulsion in ambient T° atmosphere. A first order Rayleigh equilibrium condensation isotope fractionation model yields a fractionation factor αcond-gas of 1.00135 ± 0.00058.

Particulate-Phase and Gaseous Elemental Mercury Emissions During Biomass Combustion: Controlling Factors and Correlation with Particulate Matter Emissions

Mercury emissions from wildfires are significant natural sources of atmospheric mercury, but little is known about what controls speciation of emissions important to mercury deposition processes. The goal of this study was to quantify gaseous elemental mercury (GEM) and particulate-phase mercury (PHg) emissions from biomass combustion to identify key factors controlling the speciation. Emissions were characterized in an exhaust stack 17 m above fires using a gaseous mercury analyzer and quartz-fiber filters. Fuels included fresh and air-dried leaves, needles, and branches with different fuel moistures (9-95% of dry weight) and combustion properties (e.g., from < 10 to 90% of fire durations characterized by flaming phases). Fuel moisture was the overall driving factor defining emissions, with GEM being the dominant fraction (> or = 95%) in low moisture fuels and substantial PHg contributions--up to 50% of total mercury emissions--in fresh fuels. High PHg emissions were observed during smoldering combustion whereas flaming-dominated fires showed insignificant PHg emissions. PHg mass emissions were correlated with particulate matter (PM; r2 = 0.67), organic carbon (OC; r2 = 0.63) and sulfur (S; r2 = 0.46) mass emissions, but not with elemental carbon (EC) nor with the total mercury emissions. These data suggest that the formation of PHg involves similar processes as the formation of particulate OC, for example condensation of volatile species onto preexisting smoke particles during cooling and dilution. Based on the observed relationship between PM and OC mass concentrations and published emission inventories, we estimate global PHg emissions by wildfires of 4-5 Mg yr(-1).