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Environmental contextMercury, in its methylated form, is a neurotoxin that biomagnifies in marine and terrestrial foodwebs leading to elevated levels in fish and fish-eating mammals worldwide, including at numerous Arctic locations. Elevated mercury concentrations in Arctic country foods present a significant exposure risk to Arctic people. We present a detailed review of the fate of mercury in Arctic terrestrial and marine ecosystems, taking into account the extreme seasonality of Arctic ecosystems and the unique processes associated with sea ice and Arctic hydrology. AbstractThis review is the result of a series of multidisciplinary meetings organised by the Arctic Monitoring and Assessment Programme as part of their 2011 Assessment ‘Mercury in the Arctic’. This paper presents the state-of-the-art knowledge on the environmental fate of mercury following its entry into the Arctic by oceanic, atmospheric and terrestrial pathways. Our focus is on the movement, transformation and bioaccumulation of Hg in aquatic (marine and fresh water) and terrestrial ecosystems. The processes most relevant to biological Hg uptake and the potential risk associated with Hg exposure in wildlife are emphasised. We present discussions of the chemical transformations of newly deposited or transported Hg in marine, fresh water and terrestrial environments and of the movement of Hg from air, soil and water environmental compartments into food webs. Methylation, a key process controlling the fate of Hg in most ecosystems, and the role of trophic processes in controlling Hg in higher order animals are also included. Case studies on Eastern Beaufort Sea beluga (Delphinapterus leucas) and landlocked Arctic char (Salvelinus alpinus) are presented as examples of the relationship between ecosystem trophic processes and biologic Hg levels. We examine whether atmospheric mercury depletion events (AMDEs) contribute to increased Hg levels in Arctic biota and provide information on the links between organic carbon and Hg speciation, dynamics and bioavailability. Long-term sequestration of Hg into non-biological archives is also addressed. The review concludes by identifying major knowledge gaps in our understanding, including: (1) the rates of Hg entry into marine and terrestrial ecosystems and the rates of inorganic and MeHg uptake by Arctic microbial and algal communities; (2) the bioavailable fraction of AMDE-related Hg and its rate of accumulation by biota and (3) the fresh water and marine MeHg cycle in the Arctic, especially the marine MeHg cycle.

Tundra ecosystems store vast amounts of soil organic carbon, which may be sensitive to climatic change. Net ecosystem production, NEP, is the net exchange of carbon dioxide (CO(2)) between landscapes and the atmosphere, and represents the balance between CO(2) uptake by photosynthesis and release by decomposition and autotrophic respiration. Here we examine CO(2) exchange across seven sites in the Canadian low and high Arctic during the peak growing season (July) in summer 2008. All sites were net sinks for atmospheric CO(2) (NEP ranged from 5 to 67 g C m(-2)), with low Arctic sites being substantially larger CO(2) sinks. The spatial difference in NEP between low and high Arctic sites was determined more by CO(2) uptake via gross ecosystem production than by CO(2) release via ecosystem respiration. Maximum gross ecosystem production at the low Arctic sites (average 8.6 μmol m(-2) s(-1)) was about 4 times larger than for high Arctic sites (average 2.4 μmol m(-2) s(-1)). NEP decreased with increasing temperature at all low Arctic sites, driven largely by the ecosystem respiration response. No consistent temperature response was found for the high Arctic sites. The results of this study clearly indicate there are large differences in tundra CO(2) exchange between high and low Arctic environments and this difference should be a central consideration in studies of Arctic carbon balance and climate change.

This paper gives a practical demonstration that the receptor models based on the absolute PCA techniques, to apportion atmospheric contaminants to sources, might bias results. The demonstration is done with two simple examples. Results show in both cases that the mean of ζ j (APCS jk ∗ ) is in fact closer to the absolute PC 0 ∗ than the source distribution ( S j ). These three terms being not, as previously stated, always equal. In this circumstance, elements concentrated in the sources are not accurately reproduced.

A rainwater quality model based on a scavenging coefficient parameterized with rainfall intensity and calibrated on sequential sampling data has been developed. The model can predict ratio to maximum concentration for different species during events at each rainfall amount step. Once calibrated, this model needs as input simple hydrological data, namely instantaneous rainfall intensity and cumulative rainfall depth. These limited and easily available data make it particularly suitable for stormwater control purposes.

Using inductively coupled plasma-mass spectrometry (ICP-MS), 24 inorganic elements were analysed for about 65 station-events during the summer of 1989, at Montreal Island (Canada). Enrichment factors indicate that numerous elements are enriched as compared to the Earth's crust, since only six elements (titanium, iron, rubidium, yttrium, zirconium, and cerium) can be considered natural. A comparison with results from a rural area indicates that most elements are affected by urbanization. For the majority of the elements, scavenging below the cloud (wash-out) seems to be a significant atmosphere cleansing mechanism, although one element, lead, appears to be rather governed by long-range transportation and rain-out (in-cloud scavenging). Correlation between elements indicates that some elements have similar behaviour, which can be partly explained by sorption phenomena or chemical bonding in the same compound.

Marine ecosystems are influenced by many factors related with human activity, such as eutrophication, chemical contamination, selective ­overfishing, ­bottom trawling and blast fishing. However, various regions have shown at least some changes that were likely to be attributable to recent climate change. Although various works have pointed to repercussions of climate change on ocean processes at physical and biological levels, a few thoughts were highlighted on contaminant pathways in concert with the predicted and confirmed climate changes. Human activities released during the last century a cocktail of contaminants that are stored in soil, coastal sediments and ice. Predicted alterations under climatic changes raise pertinent questions on this topic. Are hazardous substances stored in those compartments released to cycling within the ecosystem under climate changes? To what extent are quantities injected in the ecosystems toxic to marine organisms? Does it affect ecosystem functioning?

Numerous complex atmospheric phenomena influence rainfall water quality variations in time. In order to achieve a better understanding of these phenomena, an automatic sequential rainfall sampler was developed. This device, controlled by a microprocessor, can be programmed to take samples at rainfall depth intervals ranging from 0.032 to 1.6 mm. It also collects total wet fractions. This method of sampling, based on rainfall depth, offers some advantages over the method based on time (one sample every given number of time units): volume of sample is identical from one sample to the other; there is no risk of flooding sample bottles; and heavy storms as well as long and light rainfalls can be handled. Preliminary results obtained in Montreal with this sampler show the large variations of quality encountered during one event. Recalculation of total loads from sequential data compare very well with total rainfall loads, illustrating the fact that the variations are not due to random analytical errors but represent actual variations.

Contaminated sediments in the St. Lawrence River remain a difficult problem despite decreases in emissions. Here, sediment and pore water phases were analyzed for total mercury (THg) and methyl mercury (MeHg) and diffusion from the sediment to the overlying water was 17.5 + or - 10.6 SE ng cm(-2) yr(-1) for THg and 3.8 + or - 1.7 SE ng cm(-2) yr(-1) for MeHg. These fluxes were very small when compared to the particle-bound mercury flux accumulating in the sediment (183 + or - 30 SE ng cm(-2) yr(-1)). Studies have reported that fish from the westernmost site have higher Hg concentrations than fish collected from the other two sites of the Cornwall Area of Concern, which could not be explained by differences in the Hg flux or THg concentrations in sediments, but the highest concentrations of sediment MeHg, and the greatest proportions of MeHg to THg in both sediment and pore water were observed where fish had highest MeHg concentrations.

This chapter presents a review of atmospheric mercury measurements (as total and as speciated mercury) conducted at terrestrial sites during the last decade. A large number of activities have been carried out in different regions of the world aiming to assess the level of mercury in ambient air and precipitation, and its variation over time and with changing meteorological conditions. Recent studies have highlighted that in fast developing countries (i.e., China, India) mercury emissions are increasing in a dramatic fashion due primarily to a sharp increase in energy production from the combustion of coal (Chapter-2 by Street et al.; Chapter-3 by Feng et al. in this report). The large increase in mercury emissions in China over the last decade are not currently reflected in the long-term measurement of total gaseous mercury at Mace Head, Ireland between 1996 to 2006, nor in the precipitation data of the North American Mercury Deposition Network (MDN). There are documented recent increases in the oxidation potential of the atmosphere which might account, at least in part, for the discrepancy between observed gaseous mercury concentrations (steady or decreasing) and global mercury emission inventories (increasing). This chapter provides a detailed overview of atmospheric measurements performed at industrial, remote and rural sites during the last decade with reference to the monitoring techniques and location of monitoring sites in most of the continents.

Distribution of total mercury (THg), gaseous elemental Hg(0) (GEM), monomethyl Hg (MMHg), and dimethyl Hg (DMHg) was examined in marine waters of the Canadian Arctic Archipelago (CAA), Hudson Strait, and Hudson Bay. Concentrations of THg were low throughout the water column in all regions sampled (mean +/- standard deviation; 0.40 +/- 0.47 ng L(-1)). Concentrations of MMHg were also generally low atthe surface (23.8 +/- 9.9 pg L(-1)); however at mid- and bottom depths, MMHg was present at concentrations sufficient to initiate bioaccumulation of MMHg through Arctic marine foodwebs (maximum 178 pg L(-1); 70.3 +/- 37.3 pg L(-1)). In addition, at mid- and bottom depths, the % of THg that was MMHg was high (maximum 66%; 28 +/- 16%), suggesting that active methylation of inorganic Hg(II) occurs in deep Arctic marine waters. Interestingly, there was a constant, near 1:1, ratio between concentrations of MMHg and DMHg at all sites and depths, suggesting that methylated Hg species are in equilibrium with each other and/or are produced by similar processes throughout the water column. Our results also demonstrate that oceanographic processes, such as water regeneration and vertical mixing, affect Hg distribution in marine waters. Vertical mixing, for example, likely transported MMHg and DMHg upward from production zones at some sites, resulting in elevated concentrations of these species in surface waters (up to 68.0 pg L(-1)) where primary production and thus uptake of MMHg by biota is potentially highest. Finally, calculated instantaneous ocean-atmosphere fluxes of gaseous Hg species demonstrated that Arctic marine waters are a substantial source of DMHg and GEM to the atmosphere (27.3 +/- 47.8 and 130 +/- 138 ng m(-2) day(-1), respectively) during the ice-free season.

The Canadian Atmospheric Network for Currently Used Pesticides (CANCUP) was the first comprehensive, nationwide air surveillance study of pesticides in Canada. This paper presentsthe atmospheric occurrence and distribution of pesticides including organochlorine pesticides (OCPs), organophosphate pesticides (OPPs), acid herbicides (AHs), and neutral herbicides (NHs) during the spring to summer of 2004 and 2005 across agricultural regions in Canada. Atmospheric concentrations of pesticides varied within years and time periods, and regional characteristics were observed including the following: (i) highest air concentrations of several herbicides (e.g., mecoprop, triallate, and ethalfluralin) were found at Bratt's Lake, SK, a site in the Canadian Prairies; (ii) the west-coast site at Abbotsford, BC, had the maximum concentrations of diazinon; (iii) the fruit and vegetable growing region in Vineland, ON, showed highest levels for several insecticides including chlorpyrifos, endosulfan, and azinphos-methyl; (iv) high concentrations of atrazine and metolachlor were measured at St. Anicet, QC, a corn-growing region; (v) the Kensington site in PEI, Canada's largest potato-producing province, exhibited highest level of dimethoate. Analysis of particle- and gas-phase fractions of air samples revealed that most pesticides including OCPs, OPPs, and NHs exist mainly in the gas phase, while AHs exhibit more diversity in particle-gas partitioning behavior. This study also demonstrated that stirred up soil dust does not account for pesticides that are detected in the particle phase. The estimated dry and wet deposition fluxes indicate considerable atmospheric inputs for some current-use pesticides (CUPs). This data set represents the first measurements for many pesticides in the atmosphere, precipitation, and soil for given agricultural regions across Canada.

An open-bottom and a closed-bottom mesocosm were developed to investigate the release of mercury from sediments to the water column in a frozen freshwater lake. The mesoscosms were deployed in a hole in the ice and particulate mercury (Hg(P)) and total dissolved mercury (TDHg) were measured in sediments and in water column vertical profiles. In addition, dissolved gaseous mercury (DGM) in water and mercury water/airflux were quantified. Concentrations of TDHg, DGM, and mercury flux were all higher in the open-bottom mesocosm than in the closed-bottom mesocosm. In this paper we focus on the molecular diffusion of mercury from the sediment in comparison with the TDHg accumulation in the water column. We conclude that the molecular diffusion and sediment resuspension play a minor role in mercury release from sediments suggesting that solute release during ebullition is an important transport process for mercury in the lake.

[1] This paper presents mercury (Hg) concentrations and foliage/atmosphere fluxes in a maple forest ecosystem in southern Quebec, Canada. The average total gaseous mercury (TGM) concentration measured at an open field site was significantly (p < 0.001) higher than that measured at an adjacent maple forest site, some 300 m away (1.40 ng m−3 versus 1.03 ng m−3, respectively). Foliage/atmosphere flux of TGM, measured with a dynamic flux bag device, indicated an average deposition flux of 0.39 ± 0.38 ng m−2 h−1 in the maple tree foliage. Although, bi-directional Hg fluxes were observed, the compensation point in the maple forest was low (∼0.6 ng m−3) explaining a net Hg deposition process at TGM background levels. Foliage mercury concentrations increased from 8.7 ± 1.5 ng g−1 to 30.8 ± 3.0 ng g−1 during the leaf-growing season. The average Hg deposition flux was in a similar range to the Hg accumulation rate in the maple tree foliage assuming a foliage productivity rate of 220 g m−2 a−1 (i.e., 0.39 versus 0.55 ng m−2 h−1). Although significant Hg accumulated in foliage, its transport to non-organic surface topsoil was not significant. When the uptake of mercury measured in this experiment was extrapolated to include all of the maple forest in North America (12.5 million ha), it amounted potentially to more than 600 kg of mercury per year. This represents approximately 0.5% of mercury emissions in Canada and the United States (approximately 120 metric tons).

A survey on pesticides (73 compounds) in the Bay St. Francois wetland and its catchment (part of the wetlands of Lake St. Pierre area [St. Lawrence River, Quebec]) was achieved in 2006. The metabolites as well as the active ingredients of pesticides (11 compounds) were detected in the wetland and its catchment. This wetland ecosystem was active in the degradation of agricultural pesticides (e.g., atrazine). The measured pesticides were individually below the criteria for aquatic species in natural water, except chlorpyrifos. Overall, the pesticides lost from agricultural field towards the streams were

[1] Snow samples were collected in the seasonal snow cover of the low arctic tundra (Whapmagoostui-Kuujjuarapik, Quebec) during episodic atmospheric mercury depletion events (AMDEs) and in the snowmelt period, long after AMDEs had occurred. Total and methyl mercury analyses were done in order to investigate the critical factors influencing the fate of mercury once deposited in the snowpack. Following AMDEs, snow total mercury (THg) concentrations increased and were inversely proportional to the distance from Hudson Bay. The correlations between MeHg, sulfate (SO42−), and chlorine (Cl−) snow concentrations implicated marine aerosols as a significant source of MeHg, independent of AMDEs. However, the newly deposited MeHg was unstable in the snow cover as 15–56% of the MeHg was demethylated or otherwise “lost” during the nighttime period. In contrast, during the snowmelt period, marine aerosols were not a significant source of MeHg. MeHg snow concentrations higher than 200 pg L−1 were observed when snow's heterotrophic plate counts, total suspended volatile solids, and total suspended solids were higher than 5.0 × 105 CFU L−1, 25 mg L−1, and 90 mg L−1, respectively. During the snowmelt, although the THg snow concentrations remained at 8–9 ng L−1, the proportion of MeHg increased from 2.7 to 7.6%. This is the first report suggestive of the presence of mercury methylation activities within the snow cover of the low arctic tundra.

[1] Total gaseous mercury (TGM) air-water flux measurements were taken using a dynamic flux chamber (DFC) coupled with a gaseous mercury (Hg) analyzer at the Bay St. Francois (BSF) wetlands (Quebec, Canada) in summer 2003. The measured TGM fluxes over water exhibited a consistent diurnal pattern, with maximum emissions during daytime and minimum fluxes occurring at night. Pearson correlation analysis showed that solar radiation was the most influential environmental parameter in TGM air-water exchange. Significant correlations were also found between TGM fluxes and 1 hour time-lagged water temperature, indicating the enhancement of fluxes by bacterial activities or chemical reactions. The concentrations of dissolved gaseous mercury (DGM) in water were measured during the 2003 sampling period and indicated that DGM was always supersaturated, which implied that the water body acted primarily as a source of mercury to the atmosphere. Several empirical models of mercury air-water gas exchange were developed and evaluated. Compared to the published models, these proposed models were capable of producing good results, leading to a better agreement between the measured and modeled fluxes (improvements by 48–98%). Among these empirical models, the ones linking TGM fluxes with net radiation were superior because of their strong predictive capability. Two preferred models were selected for air-water TGM flux estimation from Lake St. Pierre's surrounding wetlands. These two models yield a mean emission of 0.19–0.24 kg mercury during May–September each year from 1999 to 2003.

Recent theoretical studies indicate that reactive organic iodocarbons such as CH2I2 would be extremely effective agents for tropospheric Arctic ozone depletion and that iodine compounds added to a Br2/BrCl mixture have a significantly greater ozone (and mercury) depletion effect than additional Br2 and BrCl molecules. Here we report the first observations of CH2I2, CH2IBr, and CH2ICl in Arctic air, as well as other reactive halocarbons including CHBr3, during spring at Kuujjuarapik, Hudson Bay. The organoiodine compounds were present atthe highest levels yet reported in air. The occurrence of the halocarbons was associated with northwesterly winds from the frozen bay, and, in the case of CHBr3, was anticorrelated with ozone and total gaseous mercury (TGM), suggesting a link between inorganic and organic halogens. The absence of local leads coupled with the extremely short atmospheric lifetime of CH2I2 indicates that production occurred in the surface of the sea-ice/overlying snowpack over the bay. We propose an abiotic mechanism for the production of polyhalogenated iodo- and bromocarbons, via reaction of HOI and/or HOBr with organic material on the quasi-liquid layer above sea-ice/snowpack, and report laboratory data to support this mechanism. CH2I2, CH2IBr, and other organic iodine compounds may therefore be a ubiquitous component of air above sea ice where they will increase the efficiency of bromine-initiated ozone and mercury depletion.

Whereas many ecosystem characteristics and processes influence mercury accumulation in higher trophic-level organisms, the mercury flux from the atmosphere to a lake and its watershed is a likely factor in potential risk to biota. Atmospheric deposition clearly affects mercury accumulation in soils and lake sediments. Thus, knowledge of spatial patterns in atmospheric deposition may provide information for assessing the relative risk for ecosystems to exhibit excessive biotic mercury contamination. Atmospheric mercury concentrations in aerosol, vapor, and liquid phases from four observation networks were used to estimate regional surface concentration fields. Statistical models were developed to relate sparsely measured mercury vapor and aerosol concentrations to the more commonly measured mercury concentration in precipitation. High spatial resolution deposition velocities for different phases (precipitation, cloud droplets, aerosols, and reactive gaseous mercury (RGM)) were computed using inferential models. An empirical model was developed to estimate gaseous elemental mercury (GEM) deposition. Spatial patterns of estimated total mercury deposition were complex. Generally, deposition was higher in the southwest and lower in the northeast. Elevation, land cover, and proximity to urban areas modified the general pattern. The estimated net GEM and RGM fluxes were each greater than or equal to wet deposition in many areas. Mercury assimilation by plant foliage may provide a substantial input of methyl-mercury (MeHg) to ecosystems.

[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.

[1] Atmospheric mercury speciation and deposition are critical to understanding the fate of mercury in the environment. The importance of atmospheric mercury speciation and deposition was investigated during an intensive field campaign in the Bay St. Francois wetlands in late summer 2002. Measured gaseous elemental mercury (GEM), reactive gaseous mercury (RGM), and particulate mercury (PM: 0.1–2.5 μm) concentrations were 0.85–2.16 ng/m3 (average 1.38 ng/m3), 0–22 pg/m3 (average 3.63 pg/m3), and 0.5–18 pg/m3 (average 6.44 pg/m3), respectively. PM and RGM represented

High-volume air samples were collected from 1993 to 1996 in rural areas of Quebec to investigate on the levels and the vapor-particle partitioning of polycyclic aromatic hydrocarbons (PAHs). Ranges for the mean concentrations of total PAHs (ng m -3 ) were as follows: Villeroy, 3.31-18.92; St. Anicet, 7.57-22.84; and Mingan, 0.50-0.53. Lower molecular weight PAHs predominated at all locations. Particle-gas partition coefficients (Kp) were in good correlation with their vapor pressures (r 2 = 0.79-0.97) with slopes deviating from the expected value of -1. The curve of the fractions of PAHs on particles in St. Anicet in 1995 fell on that of Lake Superior. In St. Anicet, fractions of phenanthrene, fluoranthene, pyrene, and chrysene on particles were close to those calculated from the soot-air partition coefficient (K SA ). At all sites the mean ratios of particulate PAH of the same molecular weight but of very different reactivities were similar during the same sampling days, suggesting that particle-bearing PAHs in Villeroy and Mingan were of the same nature as those found in St. Anicet where adsorption onto soot particles was the major mechanism. Furthermore, the enthalpies of desorption for the predominant PAHs were close at all sites.

An extensive mercury study was conducted in April 2002 prior to and during the annual melting of a snowpack in a sub-arctic site along the Hudson Bay (Canada). Gas-phase measurements show that the snowmelt coincides with an elemental mercury (Hg°) pulse in the snowpack air far above ambient levels. Additional measurements of inorganic mercury (Hg2+) and methylmercury (MeHg+) in snow pits, in surface snow and in a meltwater sample clearly reveal that most of Hg is removed from the snow during the first days of snowmelt. We estimate that gas-phase exchanges contribute poorly to remove Hg from the snowpack; consequently during a snowmelt day more than 90% of Hg present in the snow surface is likely released with the meltwater. In arctic areas, where Hg accumulates at an accelerated rate in the snow surfaces [Lu et al., 2001] during mercury depletion events (MDE), the discharge of this toxic and bio-accumulating pollutant in water systems could be a threat to ecosystems and local indigenous populations.

The objective of this paper is to give an overview of the findings of the Canadian chapter of the Northeast States and Eastern Canadian Provinces Mercury Study, which was conducted between 1995 and 1998. The Canadian chapter provided information on mercury emissions, sources and levels in air, water, biota and humans. Industry, governments and universities provided information for the Canadian chapter. The study showed that the Northeast States and Eastern Canadian Provinces (NES/ECP) is a region impacted by airborne mercury. Annual mercury emissions for the NES/ECP region are estimated to be approximately 19 t (12%) of the combined Canadian and US national anthropogenic mercury emissions of 155 t/year. 210 Pb-dated lake sediment cores from Atlantic Canada showed a mercury enrichment factor of 2.5 for coastal sites with mercury increases starting in 1860. Regional mercury wet deposition for the NES/ECP region was 7–11 μg/m 2 /year. Provincial and federal fish health advisories have been updated in the ECP for children and women of child-bearing age limiting the consumption of freshwater fish, as well as fresh or frozen shark, tuna or swordfish.

Le mercure est l'un des metaux les plus toxiques de l'environnement Meme en faible concentration, il peut avoir des effets importants sur les ecosystemes. La methode de mesure utilisee lors de celte etude permet des mesures en continu automatique a une frequence quart horaire (aux 15 minutes) avec une limite de detection de 0,2 ng/m3. Le train analytique de la mesure automatique du mercure est base sur l'amalgame de celui-ci sur une trappe garnie d'or suivie d'une desorption thermique et d'une analyse par fluorescence a froid (γ=253,7 nm). Des mesures effectuees en milieu rural (Saint-Anicet, Quebec, Canada) entre le 13 septembre et 30 novembre 1994, nous indiquent que des episodes de sources locales ou regionales s'ajoutent au bruit de fond estime ici a environ 1,4ng/m3. Des apports locaux et regionaux en provenance des secteurs des vents N-E et S-E s'ajoutent par episode au bruit de fond pour atteindre des pointes de concentrations maximales de 5,50 ng/m3. La grande region de Montreal pourrait enrichir d'environ 20 % les valeurs moyennes seuil de base. Un leger cycle diurne est mesure avec des maxima observes lors de la periode de jour, illustrant une certaine concomitance avec l'activite economique. Une relation entre le logarithme de la concentration de la vapeur mercurielle et la reciproque de la temperature mesuree au sol (Log Hg = A/T + K) est significative pour le secteur des vents S-O (R = - 0,37). Cette observation indiquerait que des phenomenes de volatilisation/condensation ou absorption/desorption du mercure a l'interieur de ce secteur de vent sont possibles entre les surfaces (particules, sol, eau, vegetation, etc.) et l'atmosphere. En contrepartie, la relation pour le secteur N-O est moins evidente laissant presumer que les concentrations mercurielles atmospheriques seraient plutot representatives du bruit de fond atmospherique et moins influence par des phenomenes locaux.

Recent mercury depletion events observed in the Arctic have opened the horizon to numerous new aspects on mercury fate and cycling in the environment. Total Gaseous Mercury and other Atmospheric Mercury speciations are measured in Kuujjuarapik/Whapmagoostui (Lat.: 55.30°N; Long.: 77.73°O) along the Hudson Bay (Quebec) with Tekran 2537A, 1130 and 1135 units. The former is measured since August 1999 whereas the latter are measured during springtime periods over the last three years. Mercury Depletion Events are observed at this low latitude region. MDEs are observed between February and April and are occurring during both the day and nighttime periods. Typically, MDE in Kuujjuarapik are related to air temperature. During MDEs, a significant speciation conversion from Hg 0 to RGM and TPM is operating. However, ratios of TPM to RGM conversion are variable in time.

Diffuse anthropogenic and naturally mercury-enriched areas represent long- lived sources of elemental mercury to the atmosphere. The Nevada Study and Tests of the Release of Mercury From Soils (STORMS) project focused on the measurement of mercury emissions from anaturally enriched area. During the project, concurrent measurements of mercury fluxes from naturally mercury-enriched substrate were made September 1-4, 1997, using four micrometeorological methods and seven field flux chambers. Ambient air mercury concentrations ranged from 2 to nearly 200 ng m- 3 indicating that the field site is a source of atmospheric mercury. The mean day time mercury fluxes, durin p conditions of no precipitation, measured with field chambers were 50 to 360 ng m -2 h - , and with the micrometeorological methods we re 230 to 600 ng m- 2 h -1. This wide range in mercury emission rates reflects differences in method experimental designs and local source strengths. Mercury fluxes measured by many field chambers were significantly different (p < 0.05) but linearly correlated. This indicates that field chambers responded similarly to environmental conditions, but differences in experimental design and site heterogeneity had a significant influence on the magnitude of mercury fluxes. Data developed during the field study demonstrated that field flux chambers are ideal for assessment of the physicochemical processes driving mercury flux and development of an understanding of the magnitude of the influence of individual factors on flux. In general, mean mercury fluxes measured with micrometeorological methods during day time periods were nearly 3 times higher than me an fluxes measured with field flux chambers. Micrometeorological methods allow for derivation of a representative mercury flux occurring from an unconstrained system and provide an assessment of the actual magnitude and variability of fluxes occurring from an area.

An international intercomparison of micrometerological techniques and dynamic flux chamber methods applied to measure mercury fluxes was conducted from September 1 to 4, 1997, during the Nevada Study and Tests of the Release of Mercury From Soils (STORMS) in Reno, Nevada. Nine research groups from four countries met in the Steamboat Springs, Nevada Geothermal Area, to participate in the first international flux intercomparison ever attempted for mercury. The highly heterogeneous soil Hg concentrations and complex landscape within the study area (4 ha) were unfavorable for spatial intercomparison of Hg fluxes between the research groups. However, reliable and correlated Hg fluxes were measured between our micrometerological technique and a dynamic flux chamber method (r2 = 0.29), run side by side (5 m). Hg fluxes and their relationships with environmental factors were complex. After ∼90 days of dry condition, a series of storm events impacted the site and increased the soil moisture from

Le but de la présente étude était d'étudier l'impact de la variation des niveaux d'eau d'un marais d'eau douce (Baie Saint-François, Québec) sur l'évolution des concentrations et des flux d'hydrogène, monoxyde de carbone, méthane et dioxyde de carbone. Une approche originale impliquant l'association d'un gradient de concentration de ces composés sur un profil vertical de 1,5 m au transfert de flux turbulent micrométéorologique fut utilisée pour la détermination des flux. L'étude démontre qu'une hausse du niveau d'eau d'un bassin versant alimentant une zone humide influence les flux de méthane, de monoxyde de carbone d'hydrogène et de dioxyde de carbone. En conditions submergées, le marais émettait du méthane et du monoxyde de carbone et consommait moins d'hydrogène troposphérique. Ainsi, cette étude démontre que des mesures in situ peuvent servir à inférer des scénarios d'impacts possibles des changements climatiques et des variations des niveaux d'eau sur les émissions des gaz à effets de serre dans l'écosystème du fleuve Saint-Laurent., Wetlands are known for their great biodiversity and the important carbon reservoir that they represent. Moreover, in the global warming context, these ecosystems represent net sources or sinks for different greenhouse gases depending of their conditions. For instance, flooded conditions favour methane production whereas they prevent hydrogen and carbon monoxide soil consumption. Baie Saint-François is a freshwater wetland that opens onto Lake Saint-Pierre (St. Lawrence River) where water levels are subject to important fluctuations due to natural processes and human activities (hydroelectricity and navigation). This study was done in order to assess the impact of the Lake Saint-Pierre water level variations on the tropospheric methane, carbon monoxide, hydrogen and carbon dioxide dynamics over the wetland. Knowledge of these dynamics should provide indications about the possible effects of the decreasing or increasing water level associated with the global warming on the production or consumption of these trace gases.Studies were carried out between June and August 2003 in Baie Saint-François where soil was subjected to successions of flooded and dry conditions. Water and carbon dioxide fluxes were obtained with a Bowen ratio micrometeorological station including a high frequency single infrared gas analyser. Hydrogen, carbon monoxide and methane fluxes were estimated with the modified Bowen method, their vertical concentration gradients (1.5 m) were measured over the plant canopy. The Bowen Ratio station was equipped with different probes to measure parameters such as net radiations, soil heat fluxes and vertical temperature gradients. The turbulent transfer coefficient (k) obtained every 20 min was assumed equal for heat, water vapour and trace gases. Hence, fluxes calculations were done by the multiplication of the turbulent transfer coefficients with the vertical concentration gradients of hydrogen, carbon monoxide and methane.The instrument used to detect hydrogen, carbon monoxide and methane was a RGA5. This analyser has two detectors: the reductive gas detector (RGD) for hydrogen and carbon monoxide and a flame ionisation detector (FID) for methane. The RGD contains an HgO bed wherein oxygen reacts with reductive gases resulting in Hg° releases detectable by differential UV absorbance. Chemicals were detected continuously in 10 min cycles with an analytical reproducibility of ±0.2, 0.3 and 2% for hydrogen, carbon monoxide and methane. Generally, vertical concentration gradients measured were greater than these limits. A calibration gas containing hydrogen, carbon monoxide and methane at 4940, 1000 and 1000 ppbv respectively in nitrogen was analysed daily to verify calibration. To ensure data integrity, linearity of the instrument was assayed by several dilutions of the standard gas and the integration of the curves gave a correction factor for hydrogen (18%) and carbon monoxide (13%). An intercomparison with NOAA (National Oceanic and Atmospheric Administration) was done to corroborate these correction factors.Background carbon monoxide, methane and carbon dioxide levels were in agreement with literature values. However, hydrogen was low, as observed by other investigators in summertime, since this season is related to minimal concentrations. Methane followed a diurnal cycle where maximum levels were observed during nighttime. In wet conditions, these nocturnal peaks reached occasionally 4000 ppbv and could be explained by specific production mechanisms and diurnal changes of vertical mixing in the boundary layer. Sensitivity of the processes responsible for methane and carbon monoxide cycling was seen between July 21st and 26th where a rain episode (total precipitation of 33.2 mm) increased their background concentrations. It seems that this precipitation was enough to favour methanogenesis and inhibit tropospheric CO and CH4 consumptions by a reduction of the diffusion of these chemicals into the soil.Our results demonstrated that four to eleven days following a variation of the Lake Saint-Pierre water level, a change in the tropospheric hydrogen, carbon monoxide and methane concentrations was observed. This lag might be explained by the distance between the lake and the research station (about 1.5 km) and the required time for the adaptation of soil microorganisms to the disruption of their environment. The concentration variations of these chemicals resulted from the inhibition of the processes responsible for their consumption or the activation of the processes accountable for their production.In June, the wetland was flooded and the CO2 median flux was -56.5 g m-2 d-1. Fluxes increased significantly (Mann-Whitney, α=0.01) in July to 5.30 g m-2 d-1, possibly due to dry conditions. Indeed, absence of water favours the activity of soil aerobic microorganisms which might produce more carbon dioxide than the quantity used by plants during photosynthesis.Methane was produced in June where the median flux was 54 mg m-2 d-1. These emissions were caused by the presence of water which maintained anaerobic conditions in the sediments, a suitable environment for methanogenic microorganisms. July was characterised by dry conditions, which generated aerobic environments in soils, an unfavourable microniche for methanogens. Therefore, methane median fluxes decreased significantly (Mann-Whitney, α=0.05) to 0.011 mg m-2 d-1 in July. In August, before the end of the investigation period, water levels had increased but methane fluxes were not significantly higher than in July. Moreover, in this period, methane concentrations tended to increase, showing that after an augmentation of the Lake Saint-Pierre water level, Baie Saint-François flooding area could represent a methane source.During summer 2003, Baie Saint-François acted as a net source of carbon monoxide. In June, the median flux was 21 µg m-2 d-1 due to presence of water which inhibited consumption by soil. Emissions were significantly (Mann-Whitney, α=0.05) lower in July (15 µg m-2 d-1) due to the absence of water, which represented a suitable environment for microorganisms consuming tropospheric carbon monoxide. In August, the median carbon monoxide flux attained 65 µg m-2 d-1 due to an increase of the Lake Saint-Pierre water level. Net carbon monoxide emissions observed in wet and dry conditions might be due to the high organic content in soil and water in addition to the presence of plants since all of these are subjected to photooxidation, generating this pollutant. Therefore, an increase of the Lake Saint-Pierre water level is associated with an augmentation of tropospheric carbon monoxide due to the inhibition of the processes responsible of its consumption.A decline in the water level might result in the activation of the soil microorganisms (or abiotic hydrogenases) able to consume tropospheric hydrogen. At the beginning of the campaign (June), the median hydrogen flux was weak (-1.37 g m-2 d-1) due to the presence of water. However, a net soil consumption was seen in July, where the median hydrogen flux decreased to -125 g m-2 d-1. The Lake Saint-Pierre water level increase observed in August was associated with a significant (Mann-Whitney, α=0.05) augmentation of the hydrogen median flux to 299 g m-2 d-1. Consequently, a rise in the Lake Saint-Pierre water levels induced an inhibition of the processes responsible of the tropospheric hydrogen consumption.This study illustrated that the water level fluctuations of the Lake Saint-Pierre have an impact on the H2, CO, CH4 and CO2 dynamics over the surrounding wetlands. When the Lake Saint-Pierre water level decreased, the wetlands acted as a carbon monoxide and carbon dioxide source, but as a consumer of tropospheric hydrogen and a minor source of methane.