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Eight years of gaseous elemental mercury (GEM) concentration measurements from Alert, Nunavut, Canada (between 1995 and 2002) is presented. The annual time series shows a distinct repeating seasonal pattern with an overall annual median concentration for this time period of 1.58 (S.D.=0.04 ng m(-3)). Strong seasonal variation was observed throughout the years with springtime displaying strong variability in the GEM and overall lower median concentrations due to the so-called mercury depletion events (MDEs). Summer concentrations are higher than the annual average and show a decrease in variability. Fall and winter concentrations are distributed around the annual median concentrations and show little variability. The relationship between the springtime depression and the summer increase shows a change in the behaviour of mercury between 1995 and 2002. Preliminary results suggest that during this period an increasing amount of the mercury lost from the atmosphere in the spring is not returned to atmosphere in summer. A comparison of GEM concentration data from three sites--Alert (Canada), Amderma (Russia) and Kuujjuarapik (Canada)--demonstrated similar monthly distribution of GEM between Alert and Amderma, with the latter not showing as high summer concentrations. Monthly distribution of GEM at Kuujjuarapik varied considerably from the other two sites. MDEs were found to occur at each site in the spring yet displayed different characteristics. MDEs appear to start at Alert shortly after polar sunrise but in Amderma their initiation is delayed approximately 2 months following polar sunrise. MDEs occur in Kuujjuarapik in the springtime despite an incomplete development of the polar day-night cycle. In spring, as soon as air temperature attained temperatures consistently above 0 degrees C, MDEs ended immediately at all three sites. Continued studies into MDEs are warranted, but clearly an important component of future studies must focus on the origins of the variation of GEM behaviour at different sites.

In an effort to investigate both large-scale (spatial) and short/long-term (temporal) distribution characteristics of atmospheric mercury, we have combined and analyzed the Hg concentration data sets collected continuously by four different scientific groups for the areas and periods covering (1) America (three sites near the Canadian Great Lakes (CGL): 1997–2000), (2) Asia (Seoul, Korea (SEL): 1997–2002), (3) Arctic (Alert, Canada (ALT): 1995–2001), and (4) Europe (Mace Head, Ireland (MH): 1996–2002). The mean concentrations of Hg data from those widely dispersed monitoring stations were computed to be (1) 1.58 ± 0.23, 1.69 ± 0.32, and 1.93 ± 0.44 (three sites in CGL), (2) 5.06 ± 2.46 ng m−3 (SEL), (3) 1.55 ± 0.41 (ALT), and (4) 1.76 ± 0.31 (MH). Intersite relationships were investigated among all different stations using the data groups divided into different temporal intervals. The analysis of diurnal variation patterns of Hg indicated differences in regional source/sink characteristics, with increasing amplitudes of variability toward areas under the strong influence of anthropogenic sources. When the analysis was made over different seasons, the patterns contrasted greatly between the Arctic and the other areas. It was found that the relative enhancement of Hg concentrations was dominant during winter/spring in most areas due to direct or indirect influences of anthropogenic emissions. However, the pattern for the Arctic area was distinguished pronouncedly from others with the spring minimum and summer maximum both of which reflect the potent effects of mercury depletion phenomenon (MDP). By contrast, no long-term trend, either being an increase or decrease, was evident from any of the stations during each respective study period. Although our initial attempts to examine the distribution characteristics of Hg analyzed by different scientific groups were successful, we feel that these efforts should be continued further to extend the compatibility of the global database of Hg.

Mercury depletion events (MDEs) are now a well-known phenomenon occurring in Polar Regions during the springtime. During these MDEs gaseous elemental mercury (GEM) is chemically transformed to less volatile mercury species (operationally defined as reactive gaseous mercury (RGM) and mercury associated with particles (PM)). Various measurement techniques have been employed to measure these different mercury species. However, it is still to be established what species of mercury are being measured in the Arctic air during depletion events. A study was undertaken in the spring of 2002 at Alert, Canada to investigate several techniques for the measurement of these reactive mercury species under Arctic conditions during polar sunrise. This study compared automated GEM, manual and automated RGM and PM measurement techniques as well as a method for total atmospheric mercury. Results showed that manual and automated sampling techniques compared reasonably well. Relative differences in RGM and PM concentrations over land and over the ocean were investigated. PM concentrations were consistently higher than RGM, with the same relative abundance at both sample sites. Additionally, flux measurements were undertaken, including chamber and micrometeorological methods.

Mycorrhizae are symbiotic associations between soil fungi and plant roots, which enhance mineral nutrition for the plant, and might play an important role in metals acquisition and accumulation. The processes allowing metals mobilization in the soil, absorption by the root and/or the fungus, transfer or bioaccumulation are still poorly understood. However, the properties of mycorrhizal fungi could be used for phytoremediation, a soft technique using plants for the clean-up of metal polluted soils. In this work, mycorrhized roots of tomato plants grown in a Zn-contaminated soil were investigated. The distribution of metals and the speciation of Zn were studied at the micron scale using micro synchrotron-based X-ray fluorescence (pSXRF) and micro X-ray absorption spectroscopy (μEXAFS). Zn associated to the root was Zn malate and/or Zn citrate, and Zn associated to the fungus was Zn phyllosilicate. This study illustrates the great potential of X-ray microbeams for the study of biological samples containing various amounts of metals.

This paper presents new data and reviews literature results from six field intercomparison studies to further evaluate and validate the AESminiSamplR [Anal. Chem., 70 (1998) 2403] technique for sampling and analysis of total particulate mercury in ambient air. The intercomparison studies were carried out at: two remote sites in the Arctic [Alert, Nunavut, Canada (82 degrees 28'N, 62 degrees 18'W) and Ny-Alesund, Svalbard (78 degrees 54'N, 11 degrees 53'E)], one site in Ann Arbor, MI, and three sites in Europe (one in Italy and two in Sweden). The AESminiSamplR was compared with five other methods using different materials, different flow rates, different sample treatment procedures, and/or different detection techniques. Four of the five methods compared were operated by different laboratories. When the compared methods were operated by different laboratories, a difference

Emissions of volatile mercury species from natural soils are believed to be a significant contributor to the atmospheric burden of mercury, but only order-of-magnitude estimates of emissions from these sources are available. The scaling-up of mercury flux measurements to regional or global scales is confounded by a limited understanding of the physical, chemical and biochemical processes that occur in the soil, a complex environmental matrix. This study is a first step toward the development of an air-surface exchange model for mercury (known as the mercury emission model (MEM)). The objective of the study is to model the partitioning and movement of inorganic Hg(II) and Hg(0) in open field soils, and to use MEM to interpret published data on mercury emissions to the atmosphere. MEM is a multi-layered, dynamic finite-element soil and atmospheric surface-layer model that simulates the exchange of heat, moisture and mercury between soils and the atmosphere. The model includes a simple formulation of the reduction of inorganic Hg(II) to Hg(0). Good agreement was found between the meteorological dependence of observed mercury emission fluxes, and hourly modelled fluxes, and it is concluded that MEM is able to simulate well the soil and atmospheric processes influencing the emission of Hg(0) to the atmosphere. The heretofore unexplained close correlation between soil temperature and mercury emission flux is fully modelled by MEM and is attributed to the temperature dependence of the Hg(0) Henry's Law coefficient and the control of the volumetric soil-air fraction on the diffusion of Hg(0) near the surface. The observed correlation between solar radiation intensity and mercury flux, appears in part to be due to the surface-energy balance between radiation, and sensible and latent heat fluxes which determines the soil temperature. The modelled results imply that empirical correlations that are based only on flux chamber data, may not extend to the open atmosphere for all weather scenarios.

The role of formaldehyde in the atmospheric chemistry of the Arctic marine boundary layer has been studied during both polar day and night at Alert, Nunavut, Canada. Formaldehyde concentrations were determined during two separate field campaigns (PSE 1998 and ALERT2000) from polar night to the light period. The large differences in the predominant chemistry and transport issues in the dark and light periods are examined here. Formaldehyde concentrations during the dark period were found to be dependent on the transport of air masses to the Alert site. Three regimes were identified during the dark period, including background (free-tropospheric) air, transported polluted air from Eurasia, and halogen-processed air transported across the dark Arctic Ocean. In the light period, background formaldehyde levels were compared to a calculation of the steady-state formaldehyde concentrations under background and low-ozone conditions. We found that, for sunlit conditions, the ambient formaldehyde concentrations cannot be reproduced by known gas-phase chemistry. We suggest that snowpack photochemistry contributes to production and emission of formaldehyde in the light period, which could account for the high concentrations observed at Alert.

Gaseous elemental mercury (GEM) concentration measurements were made during the Alert 2000 campaign in Alert, Nunavut, Canada, between February and May 2000. GEM exhibits dramatic mercury depletion events (MDE) concurrently with ozone in the troposphere during the Arctic springtime. Using a cold regions pyrolysis unit, it was confirmed that GEM is converted to more reactive mercury species during the MDEs. It was determined that on average 48% of this converted GEM was recovered through pyrolysis suggesting that the remaining converted GEM is deposited on the snow surfaces. Samples collected during this campaign showed an approximate 20 fold increase in mercury concentrations in the snow from the dark to light periods. Vertical gradient air profiling experiments were conducted. In the non-depletion periods GEM was found to be invariant in the air column between surface and 1–2 m heights. During a depletion period, GEM was found to be invariant in the air column except at the surface where a noticeable increase in the GEM concentration was observed. Concurrent ozone concentration profiles showed a small gradient in the air column but a sharp decrease in ozone concentration at the surface. Other profile studies showed a 41% average GEM concentration difference between the interstitial air in the snow pack and ∼2 m above the surface suggesting that GEM is emitted from the snow pack. Further profile studies showed that during MDEs surface level GEM exhibits spikes of mercury concentrations that were over double the ambient GEM concentrations. It is thought that the solar radiation may reduce reactive mercury that is deposited on the snow surface during a MDE back to its elemental form which is then increasingly released from the snow pack as the temperature increases during the day. This is observed when wind speeds are very low.

Unlike other heavy metals that are inherently associated with atmospheric aerosols, mercury in ambient air exists predominantly in the gaseous elemental form. Because of its prolonged atmospheric residence time, elemental mercury vapor is distributed on a global scale. Recently, Canadian researchers have discovered that total gaseous mercury levels in the lower tropospheric boundary layer in the Canadian Arctic are often significantly depleted during the months after polar sunrise. A possible explanation may involve oxidation of elemental mercury, followed by adsorption and deposition of the oxidized form, leading to an increased input of atmospheric mercury into the Arctic ecosystem. Here we present the first continuous high-time-resolution measurements of total gaseous mercury in the Antarctic covering a 12-month period between January 2000 and January 2001 at the German Antarctic research station Neumayer (70 degrees 39' S, 8 degrees 15' W). We report that mercury depletion events also occur in the Antarctic after polar sunrise and compare our measurements with a data setfrom Alert, Nunavut, Canada. We also present indications that BrO radicals and ozone play a key role in the boundary-layer chemistry during springtime mercury depletion events in the Antarctic troposphere.

Mercury—in the chemical/physical forms present in the biosphere—is a persistent, toxic, bioaccumulative pollutant that is dispersed throughout the environment on a global scale, mainly via the atmosphere. It is among the “heavy metals” for which the natural biogeochemical cycle has been perturbed by a wide range of human activities, including fossil-fuel combustion and waste incineration. Results of our recent measurements of gaseous elemental mercury (GEM), as well as total particulate-phase mercury (TPM) concentrations in Arctic air, ‘total Hg’ concentrations in Arctic snow, and tropospheric BrO concentrations from an earth-orbiting-satellite platform are presented and discussed. Findings of our research, and the conclusions derived therefrom, are important for environmental protection as well as the health and well-being of aboriginal people in Arctic circumpolar nations.

Recent studies of contaminants under the Canadian Northern Contaminants Program (NCP) have substantially enhanced our understanding of the pathways by which contaminants enter Canada’s Arctic and move through terrestrial and marine ecosystems there. Building on a previous review (Barrie et al., Arctic contaminants: sources, occurrence and pathways. Sci Total Environ 1992:1–74), we highlight new knowledge developed under the NCP on the sources, occurrence and pathways of contaminants (organochlorines, Hg, Pb and Cd, PAHs, artificial radionuclides). Starting from the global scale, we examine emission histories and sources for selected contaminants focussing especially on the organochlorines. Physical and chemical properties, transport processes in the environment (e.g. winds, currents, partitioning), and models are then used to identify, understand and illustrate the connection between the contaminant sources in industrial and agricultural regions to the south and the eventual arrival of contaminants in remote regions of the Arctic. Within the Arctic, we examine how contaminants impinge on marine and terrestrial pathways and how they are subsequently either removed to sinks or remain where they can enter the biosphere. As a way to focus this synthesis on key concerns of northern residents, a number of special topics are examined including: a mass balance for HCH and toxaphene (CHBs) in the Arctic Ocean; a comparison of PCB sources within Canada’s Arctic (Dew Line Sites) with PCBs imported through long-range transport; an evaluation of concerns posed by three priority metals — Hg, Pb and Cd; an evaluation of the risks from artificial radionuclides in the ocean; a review of what is known about new-generation pesticides that are replacing the organochlorines; and a comparison of natural vs. anthropogenic sources of PAH in the Arctic. The reseArch and syntheses provide compelling evidence for close connectivity between the global emission of contaminants from industrial and agricultural activities and the Arctic. For semi-volatile compounds that partition strongly into cold water (e.g. HCH) we have seen an inevitable loading of Arctic aquatic reservoirs. Drastic HCH emission reductions have been rapidly followed by reduced atmospheric burdens with the result that the major reservoir and transport agent has become the ocean. In the Arctic, it will take decades for the upper ocean to clear itself of HCH. For compounds that partition strongly onto particles, and for which the soil reservoir is most important (e.g. PCBs), we have seen a delay in their arrival in the Arctic and some fractionation toward more volatile compounds (e.g. lower-chlorinated PCBs). Despite banning the production of PCB in the 1970s, and despite decreases of PCBs in environmental compartments in temperate regions, the Arctic presently shows little evidence of reduced PCB loadings. We anticipate a delay in PCB reductions in the Arctic and environmental lifetimes measured in decades. Although artificial radionuclides have caused great concern due to their direct disposal on Russian Shelves, they are found to pose little threat to Canadian waters and, indeed, much of the radionuclide inventory can be explained as remnant global fallout, which was sharply curtailed in the 1960s, and waste emissions released under license by the European reprocessing plants. Although Cd poses a human dietary concern both for terrestrial and marine mammals, we find little evidence that Cd in marine systems has been impacted by human activities. There is evidence of contaminant Pb in the Arctic, but loadings appear presently to be decreasing due to source controls (e.g. removal of Pb from gasoline) in Europe and North America. Of the metals, Hg provokes the greatest concern; loadings appear to be increasing in the Arctic due to global human activities, but such loadings are not evenly distributed nor are the pathways by which they enter and move within the Arctic well understood.

Over a distance of approximately 800 km simultaneous measurements of total gaseous mercury (TGM) were performed at four sampling sites between Stockholm and Berlin. The time resolution of mercury concentration measurements was 5 min. During the sampling period from 26 June to 7 July 1995, event sampling for precipitation was carried out using bulk samplers. In addition to the mercury data, the most common meteorological and air-quality parameters were determined. Comparing the TGM background concentrations at the four sites, a weak but statistically significant south-to-north declining TGM gradient was found. From the most southern sampling site to the northern most site median values of 1.93, 1.78, 1.53 and 1.54 ng m-3 TGM were detected. Compared with the median TGM concentration observed at the two Swedish sites, the regional background concentration near Berlin was elevated by about 25%. Whereas the 0.5 h average TGM concentration varies at the Swedish sampling sites in a very narrow range of only 0.69 ng m-3, a much broader range of 3.28 ng m-3 was observed at the southern sites. The increased TGM variability near Berlin was characterised by a diurnal cycle with a distinct maximum in the early morning hours (about 4:00 a.m.) before sun rise. The short time variability of the TGM concentration measured at the four sites on the south-to-north transect shows regional differences. A decreasing variability from the most southern to the most northern site became evident.

International audience; Mercury in different environmental compartments has been measured at Ny-Ålesund (78°54? N, 11°53? E) during an intensive campaign, 17 April to 14 May 2002. Time-resolved speciated determination of mercury in the atmosphere and snow was conducted at the Norwegian research station at the Zeppelin mountain, 474 m above the sea level, and at the Italian research facility Dirigibile Italia, 12 m above the sea level. Total Gaseous Mercury (TGM) was present in the range ?3 during the campaign. Three mercury depletion events, identified as periods with decreased TGM concentrations, were observed. At the lower altitude, TGM concentrations following such events were found to exhibit both higher magnitude and larger variability in comparison to results from the Zeppelin station. Oxidised mercury species in air and fall-out with snow as well as mercury attached to particles were also measured and their concentrations were found to be anti-correlated with TGM in air. The strongest modulation was observed for total mercury concentration (Hg-tot) in snow (range 1.5?76.5 ng L?1). Solid evidence for photo-stimulated emissions of Hg0(g) from the snow pack in conjunction to depletion events were obtained from gradient measurements as well as from flux chamber measurements. Steep diurnal concentration variations of Hg0(aq) in surface seawater were also found to concur with changing solar radiation. The concentration of Hg0(aq) in seawater was found to be in the range 12.2?70.4 pg L?1, which corresponds to supersaturation. Hence, the seawater surface constituted a source emitting elemental mercury. The concentrations of the transient mercury forms RGM (Reactive Gaseous Mercury) and PM (Particulate Mercury) respectively and BrO column densities detected using a zenith and off-axis sky viewing DOAS instrument were very low except for a few individual samples during the major depletion event. An evaluation of trajectories for selected events and comparisons with BrO vertical column densities obtained by the GOME (Global Ozone Monitoring Experiment) instrument aboard the earth remote sensing satellite ESR-2 indicates that the air masses exhibiting low Hg0 concentrations originated from areas with high BrO densities. It was concluded that the observed depletion events at Ny-Ålesund were a results of transport from areas with high photochemical activity around the polar region.

[1] Field measurements of mercury air-surface exchange from natural settings were made in various Canadian landscapes. Soil and water samples were analyzed for mercury concentrations, and air-surface exchange fluxes from these substrates were determined using dynamic chamber, micrometeorological, or modeling methods. Environmental variables, including air and soil/water temperature, solar radiation, humidity, and wind speed, were monitored concurrently with the air-surface exchange to better understand the processes affecting the environmental cycling of mercury. Average mercury fluxes from aquatic landscapes ranged from 0.0 to 5.0 ng m−2 h−1 with total mercury concentration in water ranging from 0.3 to 6.5 ng L−1. A significant correlation (R2 = 0.47) was found between gaseous Hg fluxes and total Hg concentration in water. Mean gaseous Hg fluxes from forest soils varied from −0.4 to 2.2 ng m−2 h−1, while those from agricultural fields ranged from 1.1 to 2.9 ng m−2 h−1. Non-mineralized bedrock, sand, and till sites yielded fluxes ranging from −0.03 to 5.9 ng m−2 h−1. Mean fluxes from mercuriferous geological substrates at various locations were large compared to non-mercuriferous sites, ranging from 9.1 to 1760 ng m−2 h−1, and represent natural emissions. The corresponding total mercury substrate concentrations ranged from 0.360 to 180 ppm. A significant correlation (R2 = 0.66) was found between Hg fluxes and total Hg concentrations in mineralized and non-mineralized substrates. These gaseous Hg flux measurements represent a significant contribution to understanding natural mercury cycling, but there are still insufficient data and knowledge of processes to properly scale up fluxes from natural sources in Canada.

This paper describes a method for speciation of Hg associated with airborne particulate matter. This method uses a mini-sampler for sample collection and analysis, thermal desorption for separating Hg species, and inductively coupled plasma mass spectrometry (ICP-MS) for identification and quantification of Hg. Coal fly ash spiked with different Hg compounds (e.g. Hg0, HgCl2, HgO, and HgS) was used for qualitative calibration. A standard reference material with a certified value for Hg concentration was used to evaluate the method. When the temperature of the furnace was programmed at a linear rate of increase of 50 degrees min(-1), different Hg compounds could clearly be separated. Three airborne particulate matter samples were collected in parallel in Toronto, ON, Canada and analyzed using this method. Reproducible results were obtained and Hg0, HgCl2, HgO, and HgS species from these samples were detected.

Different aspects and techniques of time series analysis were used to investigate long-term data sets of atmospheric mercury in the Northern Hemisphere. Two perennial time series from different latitudes with different seasonal behaviour were chosen: first, Mace Head on the west coast of Ireland (53 degrees 20'N, 9 degrees 54'W), representing Northern Hemispherical background conditions in Europe with no indications for so-called atmospheric mercury depletion events (AMDEs); and second, Alert, Canada (82 degrees 28'N, 62 degrees 30'W), showing strong AMDEs during Arctic springtime. Possible trends were extracted and forecasts were performed by using seasonal decomposition procedures, autoregressive integrated moving average (ARIMA) methods and exponential smoothing (ES) techniques. The application of time series analysis to environmental data is shown in respect of atmospheric long-term data sets, and selected advantages are discussed. Both time series have not shown any statistically significant temporal trend in the gaseous elemental mercury (GEM) concentrations since 1995, representing low Northern Hemispherical background concentrations of 1.72+/-0.09 ng m(-3) (Mace Head) and 1.55+/-0.18 ng m(-3) (Alert), respectively. The annual forecasts for the GEM concentrations in 2001 at Alert by two different techniques were in good agreement with the measured concentrations for this year.

[1] The inventories of global anthropogenic emissions of mercury for years from 1979/1980 to 1995 suggest a substantial reduction in the 1980s and almost constant emissions afterwards. In contrast to emission inventories, measurements of atmospheric mercury suggest a concentration increase in the 1980s and a decrease in the 1990s. Here we present a first attempt to reconstruct the worldwide trend of atmospheric mercury concentrations from direct measurements since the late 1970s. In combination, long term measurements at 6 sites in the northern, 2 sites in the southern hemispheres, during 8 ship cruises over the Atlantic Ocean (1977–2000) provide a consistent picture, suggesting that atmospheric mercury concentrations increased in the late 1970s to a peak in the 1980s, then decreased to a minimum at about 1996, and have been nearly constant since. The observed trend is not consistent with the published inventories of anthropogenic emissions and the assumed ratios of anthropogenic/natural emissions, and suggests the need to improve the mercury emission inventories and to re-evaluate the contribution of natural sources.

[1] Measurements of gaseous elemental mercury (GEM) were made in three locations in Canada at altitudes from 0.1 to 7 km. In the summer in southeastern Canada, northwesterly winds bring air with a constant mixing ratio of GEM at altitudes up to 7 km, with a concentration near 1.5 nanograms per standard cubic meter of air (ng sm−3). In the winter in southern and central Ontario the mixing ratio is still approximately constant with altitude, but the concentration is 1.7 ng sm−3. In the spring in the Arctic the concentration of gaseous elemental mercury at altitudes above 1 km is near 1.7 ng sm−3; however, there is evidence of episodic depletion of elemental mercury near the surface with mixing of depleted air to altitudes of 1 km. Measurements of GEM in cloud interstitial air and of mercury in cloud water indicate that the influence of a single cycling of air through cloud has little effect on the concentration of GEM. The GEM in air masses transported over the relatively unpopulated terrain of northern Canada during the summer indicates a lower limit of 5000 ng m−2 for an atmospheric column from the surface to 5 km. This gives a global burden of at least 2500 t for that altitude range. These data demonstrate the existence of a vast pool of mercury aloft, provide evidence for a long atmospheric lifetime, and illustrate the potential for long-range atmospheric transport of this metal at altitudes up to at least 7 km.

Mercury and many of its compounds behave exceptionally in the environment because of their volatility, capability for methylation, and subsequent biomagnification in contrast with most of the other heavy metals. Long-range atmospheric transport of elemental mercury, its transformation to more toxic methylmercury compounds, the ability of some to undergo photochemical reactions, and their bioaccumulation in the aquatic food chain have made it a subject of global research activities, even in polar regions. The first continuous high-time-resolution measurements of total gaseous mercury in the Antarctic covering a 12-month period were carried out at the German Antarctic research station Neumayer (70 degrees 39' S, 8 degrees 15' W) between January 2000 and February 2001. We recently reported that mercury depletion events (MDEs) occur in the Antarctic after polar sunrise, as was previously shown for Arctic sites. These events (MDEs) end suddenly during Antarctic summer. A possible explanation of this phenomenon is presented in this paper, showing that air masses originating from the sea-ice surface were a necessary prerequisite for the observations of depletion of atmospheric mercury at polar spring. Our extensive measurements at Neumayer of atmospheric mercury species during December 2000-February 2001 show that fast oxidation of gaseous elemental mercury leads to variable Hg0 concentrations during Antarctic summer, accompanied by elevated concentrations, up to more than 300 pg/m3, of reactive gaseous mercury. For the first time in the Southern Hemisphere, atmospheric mercury species measurements were also performed onboard of a research vessel, indicating the existence of homogeneous background concentrations over the south Atlantic Ocean. These new findings contain evidence for an enhanced oxidizing potential of the Antarctic atmosphere over the continent that needs to be considered for the interpretation of dynamic transformations of mercury during summertime.

The Arctic ecosystem is showing increasing evidence of contamination by persistent, toxic substances, including metals such as mercury1, that accumulate in organisms. In January 1995, we began continuous surface-level measurements of total gaseous mercury in the air at Alert, Northwest Territories, Canada (82.5° N, 62.5° W). Here we show that, during the spring (April to early June) of 1995, there were frequent episodic depletions in mercury vapour concentrations, strongly resembling depletions of ozone in Arctic surface air, during the three-month period following polar sunrise (which occurs in March)2,3.

Mercury is a persistent, toxic and bio-accumulative pollutant of global interest. Its main mass in the troposphere is in the form of elemental gas-phase mercury. Rapid, near-complete depletion of mercury has been observed during spring in the atmospheric boundary layer of frozen marine areas in Arctic, sub-Arctic and Antarctic locations. It is strongly correlated with ozone depletion. To date, evidence has indicated strongly that chemistry involving halogen gases from surface sea-salt is the mechanism of this destruction. Precisely which halogen gases are the main players has remained unresolved. Our novel kinetic data and multiscale modelling show that Br atoms and BrO radicals are the most effective halogens driving mercury oxidation. The reduction of oxidized mercury deposited in the snow pack back to Hg 0 and subsequent diffusion to the atmosphere is observed. However, it cannot compensate for the total deposition, and a net accumulation occurs. We use a unique global atmospheric mercury model to estimate that halogen-driven mercury depletion events result in a 44% increase in the net deposition of mercury to the Arctic. Over a 1-yr cycle, we estimate an accumulation of 325 tons of mercury in the Arctic. DOI: 10.1111/j.1600-0889.2004.00118.x

Information on mercury and its environmentally significant forms (species) which frequently occur in natural water samples is presented. Compartments of the natural environment considered include surface waters (marine and fresh water systems) as well as hydrometeors. Computational and experimental methods for the physical/chemical speciation of mercury in natural waters are discussed and their limitations for deriving data on mercury speciation under environmental conditions are delineated. The need for considering kinetic aspects of aqueous solution chemistry is emphasized.

A new analytical method has been developed for direct analysis of solid samples of airborne particulate matter by a graphite probe collection technique coupled with graphite furnace atomic absorption spectrometry. A porous graphite probe is used as a filter for air particles. The probe is then subjected to atomization by being inserted into a graphite furnace which has been pre-heated to a constant atomization temperature. Some aspects of the method have been tested by recovery studies using NBS Urban Particulate Matter, SR M No. 1648, and found to give recoveries of 91–107% for Pb, Cd, Ni, Cu and Mn. By combining a highly efficient filtering medium with the extremely high relative sensitivity of solid sampling, this method has the potential of monitoring sources of air particulate emission with sufficient temporal and spatial resolution for unequivocal identification of the pollution source (at least on a local scale).