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To assess the role of salt-marsh plants on the vegetation-atmospheric Hg0 fluxes, three salt marsh plant species, Halimione portulacoides, Sarcocornia fruticosa and Spartina maritima were selected from a moderately contaminated site in the Tagus estuary during May 2012. Total mercury in stems and leaves for each plant as well as total gaseous mercury and vegetation-air Hg0 fluxes were measured over two continuous days. Mercury fluxes were estimated with a dynamic flux Tedlar® bag coupled to a high-resolution automated mercury analyzer (Tekran 2537A). Other environmental parameters such as air temperature, relative humidity and net solar radiation were also measured aside. H. portulacoides showed the highest total mercury concentrations in stems and leaves and the highest average vegetation-air Hg0 flux (0.48 ± 0.40 ng Hg m−2 h−1). The continuous measurements converged to a daily pattern for all plants, with enhanced fluxes during daylight and lower flux during the night. It is noteworthy that throughout the measurements a negative flux (air-vegetation) was never observed, suggesting the absence of net Hg0 deposition. Based on the above fluxes and the total area occupied by each species we have estimated the total amount of Hg0 emitted from this salt-marsh plants. A daily emission of 1.19 mg Hg d−1 was predicted for the Alcochete marsh and 175 mg Hg d−1 for the entire salt marsh area of the Tagus estuary.

Intertidal sediments of Tagus estuary regularly experiences complex redistribution due to tidal forcing, which affects the cycling of mercury (Hg) between sediments and the water column. This study quantifies total mercury (Hg) and methylmercury (MMHg) concentrations and fluxes in a flooded mudflat as well as the effects on water-level fluctuations on the air-surface exchange of mercury. A fast increase in dissolved Hg and MMHg concentrations was observed in overlying water in the first 10min of inundation and corresponded to a decrease in pore waters, suggesting a rapid export of Hg and MMHg from sediments to the water column. Estimations of daily advective transport exceeded the predicted diffusive fluxes by 5 orders of magnitude. A fast increase in dissolved gaseous mercury (DGM) concentration was also observed in the first 20-30min of inundation (maximum of 40pg L-1). Suspended particulate matter (SPM) concentrations were inversely correlated with DGM concentrations. Dissolved Hg variation suggested that biotic DGM production in pore waters is a significant factor in addition to the photochemical reduction of Hg. Mercury volatilization (ranged from 1.1 to 3.3ngm-2h-1; average of 2.1ngm-2h-1) and DGM production exhibited the same pattern with no significant time-lag suggesting a fast release of the produced DGM. These results indicate that Hg sediment/water exchanges in the physical dominated estuaries can be underestimated when the tidal effect is not considered.

International audience; Purpose This paper reports a toxicity survey of Canadian Arctic marine sediments. During the Amundsen scientific cruise, eight sites distributed across the Canadian Arctic and sub-Arctic regions were selected to highlight sensitive areas affected by either atmospheric deposition, ocean current, river drainage, or anthropogenic activities. As part of the Canadian-led ArcticNet research program, this study aims to monitor and to better understand potential changes likely to impact the Arctic.Materials and methods Surface sediments were investigated with bioanalytical tests to assess sediment toxicity. Testing of sediment elutriates was undertaken with the ARTOXKIT M, Microtox liquid phase (MLPA), and ROTOXKIT M toxicity assays, while whole sediment testing was carried out with the Microtox solid phase assay (MSPA) toxicity test procedure. Sediment mercury (Hg) content was also determined in each sample since Hg transport and toxicity is specifically an important issue in the Arctic and is generally a key indicator of the pollution status in many aquatic ecosystems.Results and discussion Based on bioassay results and sediment granulometric criteria, these Arctic sediments must be considered nontoxic. However, based on MSPA half maximal inhibitory concentrations (IC50s) and/or MLPA threshold effect concentration (TEC) values, some degree of toxicity may be measureable particularly in the sediments located in southern and northeast Hudson Bay. The Hudson Bay watershed drains 30% of Canadian rivers and extends to northern USA. Despite the large Hg concern in the Arctic, the input of local or long-range Hg sources does not appear to be a contributing factor to sediment toxicity.Conclusions These initial results are valuable in that they set baseline quality levels for these sediments as of 2005. As such, future comparisons can be made to assess temporal and spatial trends. Human activity and climate change is expected to impact these regions in the future, resulting in further reduction of sea ice extent, access to new Arctic seaways, and drilling associated with the exploitation of natural resources.

Depth variations of total mercury (Hg) and methylmercury (MeHg) concentrations were studied in cores from non-colonized sediments, sediments colonized by Halimione portulacoides, Sarcocornia fruticosa and Spartina maritima and belowground biomass, in a moderately contaminated salt marsh (Tagus Estuary, Portugal). Concentrations in belowground biomass exceeded up to 3 (Hg) and 15 (MeHg) times the levels in sediments, and up to 198 (Hg) and 308 (MeHg) times those found in aboveground parts. Methylmercury in colonized sediments reached 3% of the total Hg, 50 times above the maximum values found in non-colonized sediments. The absence of correlations between total Hg concentrations in sediments and the corresponding MeHg levels suggested that methylation was only dependent on the environmental and microbiological factors. The analysis of belowground biomass at high-depth resolution (2 cm) provided evidence that Hg and MeHg were actively absorbed from sediments, with higher enrichment factors at layers where higher microbial activity was probably occurring. The results obtained in this study indicated that the biotransformation of Hg to the toxic MeHg could increase the toxicity of plant-colonized sediments.

Molecular hydrogen (H 2 ) is an indirect greenhouse gas present at the trace level in the atmosphere. So far, the sum of its sources and sinks is close to equilibrium, but its large-scale utilization as an alternative energy carrier would alter its atmospheric burden. The magnitude of the emissions associated with a future H 2 -based economy is difficult to predict and remains a matter of debate. Previous attempts to predict the impact that a future H 2 -based economy would exert on tropospheric chemistry were realized by considering a steady rate of microbial-mediated soil uptake, which is currently responsible of ~ 80% of the tropospheric H 2 losses. Although soil uptake, also known as dry deposition is the most important sink for tropospheric H 2 , microorganisms involved in the activity remain elusive. Given that microbial-mediated H 2 soil uptake is influenced by several environmental factors, global change should exert a significant effect on the activity and then, assuming a steady H 2 soil uptake rate for the future may be mistaken. Here, we present an overview of tropospheric H 2 sources and sinks with an emphasis on microbial-mediated soil uptake process. Future researches are proposed to investigate the influence that global change would exert on H 2 dry deposition and to identify microorganisms involved H 2 soil uptake activity.

Sampling was conducted at seven sites on, and at varying distances adjacent to, the Island of Montreal (Quebec, Canada), and as far as 1,100 km away in Northern Quebec, to explore the hazard potential of snowpacks in remote, rural, and urban environments. Ecotoxic effects of melted snow were ascertained with a suite of small-scale bioassays representing several aquatic taxonomic groups (bacteria, micro-algae, micro-invertebrates, fish liver cells) as well as with biomarker measurements determined with a rainbow trout primary hepatocyte (RTPH) assay. Bioassays undertaken with the cnidarian Hydra attenuata and RTPH cell assays, and to a lesser extent with the micro-alga Pseudokirchneriella subcapitata, proved particularly sensitive to infer the presence of bio-available pollutants in snow samples collected from all sites, thereby suggesting their contamination (at least) via atmospheric sources. Furthermore, biomarker responses indicated that snow samples presumably included metals (free Zn biomarker), organics (CYP 1A1 biomarker), estrogens (alkali-labile phosphate biomarker) as well as chemicals capable of causing oxidative stress (LPO biomarker), depending on the site being considered. Overall, effects data acquired during this preliminary investigation on the ecotoxicity of snowpacks submit that adverse impact toward aquatic biota is conceivable at some sites during spring meltdown. Because snow has a recognized affinity for sequestering solids and contaminants of atmospheric origin, future studies aimed at identifying sources and chemicals implicated in observed effects are legitimate endeavors.

Mercury (Hg) contamination in tundra region has raised substantial concerns, especially since the first report of atmospheric mercury depletion events (AMDEs) in the Polar Regions. During the past decade, steady progress has been made in the research of Hg cycling in the Polar Regions. This has generated a unique opportunity to survey the whole Arctic in respect to Hg issue and to find out new discoveries. However, there are still considerable knowledge gaps and debates on the fate of Hg in the Arctic and Antarctica, especially regarding the importance and significance of AMDEs vs. net Hg loadings and other processes that burden Hg in the Arctic. Some studies argued that climate warming since the last century has exerted profound effects on the limnology of High Arctic lakes, including substantial increases in autochthonous primary productivity which increased in sedimentary Hg, whereas some others pointed out the importance of the formation and postdeposition crystallographic history of the snow and ice crystals in determining the fate and concentration of mercury in the cryosphere in addition to AMDEs. Is mercury re-emitted back to the atmosphere after AMDEs? Is Hg methylation effective in the Arctic tundra? Where the sources of MeHg are? What is its fate? Is this stimulated by human made? This paper presents a critical review about the fate of Hg in the Arctic tundra, such as pathways and process of Hg delivery into the Arctic ecosystem; Hg concentrations in freshwater and marine ecosystems; Hg concentrations in terrestrial biota; trophic transfer of Hg and bioaccumulation of Hg through food chain. This critical review of mercury fates and contamination in the Arctic tundra ecosystem is assessing the impacts and potential risks of Hg contamination on the health of Arctic people and the global northern environment by highlighting and "perspectiving" the various mercury processes and concentrations found in the Arctic tundra.

Microbial-mediated soil uptake accounts for approximately 80% of the global tropospheric dihydrogen (H(2)) sinks. Studies conducted over the last three decades provide indirect evidences that H(2) soil uptake is mediated by free soil hydrogenases or by unknown microorganisms that have a high affinity for H(2). The exact nature of these hypothetical free soil enzymes or of H(2)-consuming microorganisms remains elusive because the activity has never been observed in pure culture. Here, we present the first aerobic microorganism able to consume tropospheric H(2) at ambient levels. A dynamic microcosm chamber was developed to enrich a microbial consortium with a high affinity for H(2), from which selected bacterial and fungal strains were isolated and tested for H(2) uptake. Strain PCB7 had a H(2) consumption activity that followed a Michaelis-Menten kinetics, with an apparent K(m) of 11 p.p.m.v. and a H(2) threshold concentration0.100 p.p.m.v., corresponding to the high-affinity uptake of tropospheric H(2) observed in soil. 16S ribosomal RNA gene sequences showed that strain PCB7 is highly related to several Streptomyces species. H(2) consumption occurred during the sporulation period of the bacterium. Addition of nickel increased the activity, suggesting that the enzymes involved in H(2) consumption belong to the NiFe uptake class of hydrogenases. Because this is the first microorganism showing a high-affinity uptake of tropospheric H(2), we anticipate that Streptomyces sp. PCB7 will become a model organism for the understanding of the environmental factors influencing H(2) soil uptake.

The industrialization and the demographic expansion have both influenced the biogeochemical cycle of hydrogen (H 2 ), carbon monoxide (CO) and carbon dioxide (CO 2 ). In the actual context, knowledge about the spatial distribution of the natural sources and sinks of these trace gases is then crucial to infer possible effects of climate and land use changes on their global budget. This article reports the H 2 , CO and CO 2 concentrations and micrometeorological fluxes measured during 1 year in a rural area of the mixed wood ecozone of Canada. Land use represents a critical issue in the control of trace gas natural sources or sinks of that region, which is the most densely habited in Canada. On average, the site emitted CO 2 at a rate of 7.7 g m −2 d −1 and consumed H 2 and CO at 0.34 and 5.1 mg m −2 d −1 , respectively. Temperature was the most important factor affecting the H 2 and CO surface to air exchanges. The strength of the soil sink was maximal at the end of the summer, while H 2 and CO emissions were observed at the snow-melting period. In winter, H 2 and CO depositions were attributed to their oxidation by photochemically active compounds within the snow cover. When soil temperature was above 10 °C, trace gas fluxes followed a well-defined diurnal cycle. H 2 and CO 2 deposition rates were positively correlated with H 2 O fluxes, while CO followed the inverse trend. CO 2 diurnal variations resulted from a balance between photosynthesis and soil respiration, while some biotic and abiotic factors were proposed to explain the trend observed for H 2 . In the case of CO, emissions originating from heat- and photo-induced reactions were involved in the attenuation in the strength of the soil sink during daytime. Measured fluxes were compared with the literature to show the relative importance of the rural areas in the studied trace gases budget.

Air and precipitation samples were collected and analyzed for 91 pesticides or metabolites from May to September 2004 at St. Damase, an agricultural site located in Yamaska basin in Québec, Canada. A broad range of pesticides was detected during this experiment where 40 different compounds were measured. Most of the samples showed more than 10 simultaneous pesticide detections and sometimes reaching 19 simultaneous detections. The most detected pesticides in air were trifluralin, metolachlor and captan, which were found in all the samples during the 5 months of measurements. For the detected compounds, the average concentrations ranged from 4 pg/m3 to 8 ng/m3. Some of the pesticides detected in air were found in precipitation samples as well showing that wet deposition can occur and have an impact on aquatic ecosystems. The most important pesticides detected were related to corn and soya cultivations, the two main cultures in this region highlighting that the major sources come from local applications. On the other hand, the detection of some pesticides in precipitation which were undetectable in air implies that some compounds may have a long range transport origin.

Mercury contamination in the Great Lakes continues to have important public health and wildlife ecotoxicology impacts, and atmospheric deposition is a significant ongoing loading pathway. The objective of this study was to estimate the amount and source-attribution for atmospheric mercury deposition to each lake, information needed to prioritize amelioration efforts. A new global, Eulerian version of the HYSPLIT-Hg model was used to simulate the 2005 global atmospheric transport and deposition of mercury to the Great Lakes. In addition to the base case, 10 alternative model configurations were used to examine sensitivity to uncertainties in atmospheric mercury chemistry and surface exchange. A novel atmospheric lifetime analysis was used to characterize fate and transport processes within the model. Model-estimated wet deposition and atmospheric concentrations of gaseous elemental mercury (Hg(0)) were generally within ∼10% of measurements in the Great Lakes region. The model overestimated non-Hg(0) concentrations by a factor of 2–3, similar to other modeling studies. Potential reasons for this disagreement include model inaccuracies, differences in atmospheric Hg fractions being compared, and the measurements being biased low. Lake Erie, downwind of significant local/regional emissions sources, was estimated by the model to be the most impacted by direct anthropogenic emissions (58% of the base case total deposition), while Lake Superior, with the fewest upwind local/regional sources, was the least impacted (27%). The U.S. was the largest national contributor, followed by China, contributing 25% and 6%, respectively, on average, for the Great Lakes. The contribution of U.S. direct anthropogenic emissions to total mercury deposition varied between 46% for the base case (with a range of 24–51% over all model configurations) for Lake Erie and 11% (range 6–13%) for Lake Superior. These results illustrate the importance of atmospheric chemistry, as well as emissions strength, speciation, and proximity, to the amount and source-attribution of mercury deposition.

An intensive survey of mercury speciation was performed at a site on the Upper St. Lawrence River near Cornwall, Ontario, Canada with a history mercury contamination in sediments. Surface sediments were collected every 1.50 h. Total mercury (Hgtotal), methylmercury (MeHg), organic carbon, inorganic and organic sulphur were determined in the solid fraction. Dissolved Hgtotal, MeHg and dissolved organic carbon (DOC) were measured in pore waters. Concentrations of Hgtotal in the upper layers (first 5 cm) were high, ranging from 1.42 to 25.8 nmol g−1 in solids and from 125 to 449 pM in pore waters. MeHg levels were also high, ranging from 4.34 to 34.1 pmol g−1 in solids and from 40 to 96 pM in pore waters. This amounts to up to 1.4% of Hgtotal present as MeHg in solids and 64% in pore waters. A daily pattern for Hgtotal was observed in the solid fraction. The MeHg distribution in solids and pore waters was not correlated with Hgtotal or DOC, suggesting that the concentrations of MeHg are probably more influenced by the relative rates of methylation/demethylation reactions in the sediment–water interface. Acid volatile sulphide levels and DOC were inversely correlated with organic sulphur (Sorg) levels suggesting that both parameters are involved in the rapid production of Sorg. A positive correlation was also observed between Hgtotal and Sorg in solids (R = 0.87, p < 0.01) illustrating the importance of organic sulphur in the retention and distribution of Hg in the solid fraction of the sediments. The results suggest that variations of Hgtotal concentrations in Upper St. Lawrence River surface sediments were strongly influenced by the formation/deposition/retention of organic sulphur compounds in the sediment–water interface.

This paper reports the first ebullitive fluxes of hydrogen (H2), carbon monoxide (CO), methane (CH4), carbon dioxide (CO2) and total gaseous mercury (TGM) from the Cornwall Area of Concern (CAC). Although sediments were contaminated with mercury, bubbling was a negligible source of mercury for the global atmosphere. Indeed, the average emission of TGM through ebullition was 0.04 pg m(-2) h(-1). Measurements of H2, CO, CH4 and CO2 trapped gas concentrations and fluxes were used as indicators of diagenesis processes. The CAC represented a significant regional source of CH4 since the estimated ebullitive fluxes (3.5 mg m(-2) h(-1)) were similar to the CH4 emissions measured above typical flooded freshwater wetlands. As molecular diffusion is known as the main pathway of CO2 transport from water to the atmosphere, CO2 ebullitive fluxes were weak (0.39 mg m(-2) h(-1)). Bubbling of CO (1.6 microg m(-2) h(-1)) was 10 folds less important than CO fluxes measured over flooded freshwater wetlands. Finally, H2 emissions (0.001 microg m(-2) h(-1)) were negligible since the level of this trace gas is tightly regulated by microorganisms in anaerobic environments.

Long-term monitoring data of total gaseous mercury (TGM) concentrations from the Canadian Atmospheric Mercury Measurement Network (CAMNet) were analysed for temporal trends, seasonality and comparability within the network and compared to other network and model results. Data collected from 11 Canadian measurement sites between 1995 and 2005 were analysed. Sites within CAMNet were characterized by principle component analysis (PCA) into four main categories. For the first time since automated TGM measurements have been made within CAMNet, this paper reveals statistically significant decreasing TGM concentrations from rural locations in Canada during this time period. The largest declines were observed close to the urban areas of Toronto and Montreal, where levels fell by 17% at Point Petre, and 13% at St. Anicet, respectively. Many of the TGM changes are comparable with the overall trends observed in total mercury concentrations in precipitation, for similar time periods, at co-located or nearby National Atmospheric Deposition programme's Mercury Deposition Network (NADP-MDN) sites. The results show that these changes are mostly driven by local or regional changes in mercury emissions. Other sites within CAMNet reflect reported changes in hemispherical global background concentrations of airborne mercury, where slight decreases or no statistically significant trend in TGM concentrations exist over the same time period.

Porewater samples were obtained on five occasions during spring, summer and fall by in situ dialysis from three sites of a large freshwater wetland situated along the St. Lawrence River. These samples were analysed for total dissolved mercury ([Hg] T ) and methylmercury ([MeHg]) concentrations and for complementary variables including dissolved sulfate, sulfide and elemental sulfur concentrations. Sediment cores were obtained on three occasions from one of these sites for the determination of total mercury ({Hg} T ) and methylmercury ({MeHg}) concentration as well as mercury methyltransferase (HgMT) activity profiles. {MeHg} and HgMT activity varied with time and sediment depth. The porewater [Hg] T and [MeHg] depth profiles varied with time and among sites. Modeling the porewater [MeHg] profiles with a one-dimensional reaction-transport equation allowed identification of the sediment depths where MeHg is produced or consumed, as well as an estimate of the net in situ MeHg production rates in the sediments. The model-predicted depths of MeHg production, as well as the sulfate concentration and the HgMT activity depth distributions are all consistent with the involvement of sulfate reducing bacteria in the production of MeHg.

The Canadian Pesticide Air Sampling Campaign was initiated in 2003 to assess atmospheric levels of pesticides, especially currently used pesticides (CUPs) in agricultural regions across Canada. In the first campaign during the spring to summer of 2003, over 40 pesticides were detected. The spatial and temporal distribution of pesticides in the Canadian atmosphere was shown to reflect the pesticide usage in each region. Several herbicides including triallate, bromoxynil, MCPA, 2,4-D, dicamba, trifluralin and ethalfluralin were detected at highest levels at Bratt's Lake, SK in the prairie region. Strong relationships between air concentrations and dry depositions were observed at this site. Although no application occurred in the Canadian Prairies in 2003, high air concentrations of lindane (γ-hexachlorocyclohexane) were still observed at Bratt's Lake and Hafford, SK. Two fungicides (chlorothalonil and metalaxyl) and two insecticides (endosulfan and carbofuran) were measured at highest levels at Kensington, PEI. Maximum concentrations of chlorpyrifos and metolachlor were found at St. Anicet, QC. The southern Ontario site, Egbert showed highest concentration of alachlor. Malathion was detected at the highest level at the west coast site, Abbotsford, BC. In case of legacy chlorinated insecticides, high concentrations of DDT, DDE and dieldrin were detected in British Columbia while α-HCH and HCB were found to be fairly uniform across the country. Chlordane was detected in Ontario, Quebec and Prince Edward Island. This study demonstrates that the sources for the observed atmospheric occurrence of pesticides include local current pesticide application, volatilization of pesticide residues from soil and atmospheric transport. In many instances, these data represent the first measurements for certain pesticides in a given part of Canada.

This paper, and its companion (that dealt with lindane and endosulfan) review available data on the presence of currently used pesticides (CUPs) in air and precipitation in Canada, since the late 1980s. Pesticides usage/sales are also given when available. Data from local studies/initiatives, region-wide monitoring networks and remote locations are compiled to summarize atmospheric levels of different CUP classes (e.g. acid herbicides, organophosphates, “new” organochlorines, triazines, etc.) and how this varies among regions and with time. Based on this information, and other parameters not specific to Canada, knowledge gaps are identified and ideas for further research work are proposed.

This paper, and its companion, review available data on the presence of currently used pesticides (CUPs) in air and precipitation of Canada, since the late 1980s. Pesticides usage/sales are also given when available. Two older CUPs—lindane, which shows a wealth of data, and endosulfan, one of the most abundant and ubiquitous organochlorine pesticides in the North American atmosphere today—are the focus of this first part. Data from local process studies, monitoring work in source and receptor regions, and modelling efforts are compiled to give an overall picture of the atmospheric levels and deposition and how this varies between regions and with time.

One fate of gaseous elemental mercury (GEM) in the Arctic has been identified as gas phase oxidation by halogen-containing radicals, leading to abrupt atmospheric mercury depletion concurrent with ozone depletion. Rapid deposition of oxidized mercury leads to snow enrichment in mercury. In this report, we describe experiments that demonstrate the ability of snow to directly scavenge atmospheric mercury. The study was conducted at Kuujjuarapik, Québec, Canada (latitude 55 degrees 17'N). A mercury depletion event (MDE) caused the mercury concentration in the surface snow of the coastal snowpack to double, from (9.4+/-2.0) to (19.2+/-1.7) ng/L. Independent of the MDE, mercury concentrations increased five-fold, from (10.0+/-0.1) to (51.4+/-6.0) ng/L, upon spiking the snow with 500 microM hydrogen peroxide under solar irradiation. Total organic carbon in the spiked irradiated snow samples also decreased, consistent with the formation of strongly oxidizing species. The role of the snowpack in releasing GEM to the atmosphere has been reported; these findings suggest that snow may also play a role in enhancing deposition of mercury.

An intensive field study quantifying total gaseous mercury (TGM) and mercury speciation fluxes in a wetland ecosystem (Bay St. Franc - ois wetlands, Quebec, Canada) was conducted in summer 2003. This study is one of the first attempts to design and develop an innovative approach—dynamic flux bag (DFB) technique to measure in situ mercury air-vegetation exchange with a monoculture of river bulrush (Scirpus fluviatilis). Air-vegetation flux measurements were conducted under dry condition at site 1 and flood condition at site 2. TGM fluxes fluctuated from � 0.91 to 0.64 ng/m 2 (leaf area)/h with an average value of -0.2670.28 ng/m 2 (leaf area)/h at site 1 and ranged from � 0.98 to 0.08 ng/m 2 (leaf area)/h with a mean flux of � 0.3370.24 ng/m 2 (leaf area)/h at site 2 (positive sign means volatilization, and negative sign indicates deposition). The data indicated that TGM air-vegetation exchange is bidirectional. However, the net flux is primarily featured by dry deposition of TGM from atmosphere to the vegetation. In mercury speciation study using the DFB approach, particulate mercury (PM) and reactive gaseous mercury (RGM) represented less than 1% of total mercury. Ambient ozone concentrations had significant influences on RGM concentrations (r ¼ 0.54, po0.05), implicating oxidation of gaseous elemental mercury (GEM) by ozone to form RGM. A discussion about the similarities and discrepancies between the DFB and other approaches (dynamic flux chamber and modified Bowen ratio) is presented. During the course of this study, some operational effects associated with the bag design, mainly the emergence of condensation within the bag, were encountered. Several improvements relating to the DFB design were recommended. Upon improvement, the DFB method could be one of the most promising techniques to study the role of a single plant in air-vegetation exchange of mercury. r 2005 Elsevier Ltd. All rights reserved.

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.

Air and precipitation samples were collected in three stations located in Quebec between January 1993 and March 1996 to determine spatial and seasonal variations of several organochlorine pesticides and metabolites (alpha-HCH, gamma-HCH, HCB, gamma-chlordane, DDT, DDE, Mirex). alpha-HCH, gamma-HCH, and HCB were more or less measured in large amounts at all sites, whereas gamma-chlordane, DDT, and DDE concentrations were lower and Mirex was undetectable. Higher concentrations levels were observed in air during hot spring/summer periods except for HCB, indicating a probable temperature dependence. Ln concentrations vs reciprocal temperature plots and Henry's law determinations helped to highlight the contribution of soil and/or water volatilization of those compounds. Itwas observed that alpha-HCH came mainly from Atlantic Ocean volatilization at Mingan, whereas sources of gamma-chlordane and DDE were mostly due to volatilization from soils in southern Quebec. DDT may be present in the atmosphere by the way of transport from remote regions. Lindane sources were multiple: it may be found in the atmosphere bythe processes of transport and volatilization coming from soil or water. Finally, a negative correlation between HCB and air temperature implies that processes other than volatilization are involved in transport of this compound.

An intensive field campaign was conducted from 1 January to 31 December 2003 in St. Anicet (Quebec, Canada) using a set of Automatic Atmospheric Mercury Speciation Analyzers (Tekran 2537A with 1130 and 1135 units) for the measurements of gaseous elemental mercury (GEM), reactive gaseous mercury (RGM) and particulate mercury (Hg p ). This study is one of the first attempts to present the most extensive data sets of a year of continuous measurements of atmospheric mercury species. Average concentrations of GEM, RGM and Hg p in 2003 were 1.65±0.42 ng m −3 , 3±11 and 26±54 pg m −3 (mean±SD), respectively. On an average, the atmospheric mercury apportioned as follows: GEM (98.4%)>Hg p (1.4%)>RGM (0.2%). Regional atmospheric mercury sources contributed to the Southern Quebec atmospheric mercury contamination. The results showed large seasonality of GEM, RGM and Hg p (GEM: 0.37–10.4 ng m −3 ; RGM: 0–386 pg m −3 and Hg p : 0–1528 pg m −3 ). As a whole, mercury speciation concentrations are larger in wintertime than in summertime. RGM and Hg p concentrations showed the sharpest seasonal variations. Hourly variations were observed for the mercury species. Maximum RGM and Hg p concentrations were measured normally during mid-day with a Gaussian shape whereas GEM showed a bimodal shape with minimum values early in the morning. The backward trajectory model showed that atmospheric mercury speciation might be transported from local or regional sources. Also, it was observed that atmospheric mercury transformation times converting GEM to Hg p were short (∼4 h). However, atmospheric kinetics involving O 3 and OH radicals do not support such fast oxidation processes with normal concentrations.

Data from 13 National Atmospheric Deposition Program Mercury Monitor Network (NADP/ MDN) monitoring stations (1996-2002) and the Underhill (VT) event-based monitoring site (1993-2002) were evaluated for spatial and temporal trends. More precipitation and mercury deposition occurred in the southern and coastal MDN sites, except for the Underhill site, which received more mercury deposition than surrounding sites. Precipitation patterns varied. Regionally, higher concentrations of mercury were recorded during the late spring and summer months. Several sub-regional clusters of MDN sites were evident, based on mercury deposition patterns. In general, more mercury was deposited during the summer months. "Enhanced" weekly deposition (250 ng/m2) and distinct seasonal deposition patterns were evident at all MDN sites. Regionally, high depositional periods contributed significantly to annual loads (20%- approximately 60%). Southern and coastal sites measured more frequent periods of high deposition than inland sites. Spring and summer "enhanced" deposition may be important contributing factors to mercury bioaccumulation during the growing season. Recent regional reductions of mercury emissions were not reflected in the regional mercury concentration or deposition data. Few sites showed linear relations between the concentration of mercury in precipitation and acid rain co-contaminants (sulfates and nitrates).

In order to evaluate and understand the mercury gas exchange processes in fluvial wetlands, related researches were initiated in a St. Lawrence River wetland (Bay St. Francois, Que., Canada). Mercury fluxes were measured using dynamic flux chamber methods, coupled with an automatic mercury vapor analyzer (namely, Tekran, Model 2537A). Mercury air–surface gas exchanges as well as meteorological conditions were measured during two intensive field campaigns from August to September, 1999 and May, 2000, respectively. The field studies in 1999 were performed under bare soil (unvegetated portions) dry wetland conditions whereas the studies in 2000 were conducted under flooded conditions. Both field measurements were performed at the same location in the aim to study the impact of the water levels on the mercury fluxes. The water-level effect was simply to provide either a dry or a flooded site. Water-level fluctuations in fluvial wetland can result in a conversion between a standing water environment and an environment in which sediments are exposed to air. Mercury flux dynamics and processes would alter accordingly to changing environmental conditions. The average concentration of total Hg in the soil and water were ∼0.06 ng mg−1 (dry weight basis) and ∼1 ng l−1, respectively. The predominant flux of Hg° over both bare soil and water was emission. Median Hg flux under dry conditions was 0.83 ng m−2 h−1 in comparison with 0.50 ng m−2 h−1 under flooded conditions. Correlations between Hg flux, net radiation and temperature (bare soil or water) indicated that the main process involved in air–soil gas exchange under dry conditions is the enthalpy of volatilization; whereas photoreduction predominates under flooded conditions. This paper discusses the Hg flux results under both conditions in the perspective of water-level fluctuations and their impacts on the air–surface exchange of mercury.

Atmospheric concentrations of α - and γ -hexachlorocyclohexane (HCH) were measured during 1993–1995 along the St. Lawrence River in Quebec, Canada. Average α - and γ -HCH concentrations (pg/m 3 ) were St. Anicet: 93–101; Villeroy: 92–42; Mingan: 96–20, respectively. α -HCH mean concentrations were similar in all sites and appeared to be more influenced by long-range transport than local sources. γ -HCH mean levels in St. Anicet were 2 and 5 times higher than in Villeroy and Mingan, respectively. The time-series of γ -HCH air concentrations at St. Anicet and Villeroy were characterised by highly elevated springtime episodes, which are in agreement with the γ -HCH usage in Quebec as corn seed dressing pesticide. No temporal trend was observed for the α -HCH in air. Clausius–Clapeyron plots (log conc. vs. 1/ T ) showed a stronger correlation between temperature and measured γ -HCH concentrations at St. Anicet and Villeroy than Mingan. On a regional scale, the influence of the local sources of γ -HCH implied a seasonal variability in air concentrations due to its short transport, while at the background site (Mingan), the observed α - and γ -HCH concentrations in air were the result of its long-range transport and/or water/air gas exchanges.

In order to better understand MDE chemistry, which are thought to happen in the presence of halogenated (chloride and bromide) species, we have led several kinetic experiments with gaseous mercury, ozone and chlorine in Teflon bags under polar atmospheric conditions. The chlorine was expected to produce, with natural solar radiation, the reactive chloride species assumed to play a role in the MDE mechanism. The aim of the first experiment was to study the reactivity between ozone and gaseous mercury: we obtained a rate constant of (13±6)x10 -20 cm 3 /molec/s, which is roughly comparable to constants given in the literature. Concerning the second experiment, for which chlorine has been introduced, a rate constant of (6.2 ±2.2))x10 -17 cm 3 /molec/s for the reactivity of gaseous mercury was obtained. This constant is too weak to recover the atmospheric lifetime of gaseous mercury during MDE. This difference is in discussion in this paper.

During a field experiment at Kuujjuarapik/Whapmagoustui (55°31N, 77°75W), Quebec, we have pointed out modifications in the size distribution of particles during a Mercury Depletion Event (MDE). We observed an increase of atmospheric particles concentrations in the ambient air, correlated with depletions of ozone and atmospheric mercury. These increases were followed by a change in the size particles distribution. Assuming that the divalent mercury species formed during the MDE could be adsorbed onto particles, this is likely to contribute to higher deposition fluxes of oxidised mercury on the snow pack.

This study reported the first synchronized automated high-time resolution mercury species fluxes over plant canopy. It is suggested that plants can uptake reactive gaseous mercury and release elemental gaseous mercury during daytime. This can be environmentally significant due to the bio-transfer (conversion) from a short transported mercury species (Hg (II)) to a long transport mercury species (Hg°).

The snowpack is a medium that greatly interacts with a variety of atmospheric gases. Its role in the mercury depletion events in arctic and sub-arctic regions seems to be crucial though it is poorly understood. We studied an environmental component of mercury that is interstitial gaseous mercury (IGM) present in the air of the snowpack at Kuujjuarapik (55°N, 77°W), Quebec in April 2002. Our data demonstrate that the snow-pack plays a major role in the global mercury cycle. Indeed, IGM concentrations exhibit a well-marked diurnal cycle with uninterrupted events of Hg° depletion and production within the snowpack. During snowmelt episode, high IGM concentrations (∼20 ng/m 3 at a depth of 37 cm) have been recorded. This study gives us the confirmation that Hg° is involved in oxidation processes occurring in the snowpack. Additionally, we assume that the impressive production of Hg° during the daytime may be the results of photoreduction and photo-initiated reduction of Hg(II) complexes.

The combined effect of light and hydrogen peroxide on the ability of surface snow to scavenge atmospheric mercury was investigated in Kuujjuarapik, Nunavik, Canada (latitude 55°N). Mercury concentrations in the snowpack increased five-fold upon spiking with hydrogen peroxide under solar irradiation. Anion analysis of the snow revealed the presence of chloride, which may stabilize Hg(II). Measurements of total inorganic and organic carbon showed that both kinds of carbon content decreased in the spiked irradiated snow samples.

An efficient linear Kalman filter has been combined with a coupled atmospheric transport and soil–air exchange model to determine organochlorine pesticides emissions on the regional scale. In this study, results of γ-HCH emissions from the Great Lakes–St. Lawrence ecosystem, estimated from the coupled model, are presented and discussed. A source receptor technique is used to identify a priori the locations of emission sources of γ-HCH, the emissions are then updated through a Kalman filtering procedure which minimizes the weighted difference between the predicted mixing ratios from the coupled model and the measured concentrations over the Great Lakes–St. Lawrence river region. Two experiments using the inverse algorithm are carried out. In the first experiment, the coupled atmospheric transport and soil–air exchange model is implemented to predict γ-HCH air and soil concentrations. Emissions are then updated every 12 days using the updated soil concentrations and emission factors. However, the updated emissions are not input into the coupled atmospheric transport and soil–air exchange model. On the other hand, in the second experiment the updated emissions are fed back to the coupled model, so that the model is reinitialized in each 12 days. The results from the inverse technique for the year 1995 have been compared with grided γ-HCH emission inventory in Canada, generated by emission factors. It is shown that the estimated emissions of γ-HCH are consistent with the measured emissions. It is found that the St. Lawrence valley has larger emissions of γ-HCH than the Great Lakes region, indicating an opposite distribution to the emission usage inventory, but in agreement with the measured γ-HCH concentration.

Mercury may be one of the best-documented hazardous substances utilised by man. Still the uncovering of the global human impacts on the environment through the use and mobilisation of mercury cannot be considered complete. Recent mercury depletion events observed in the Arctic have opened the horizon to numerous new aspects on mercury fate and cycling in the environment. This chapter browses various aspects of the extremely complex cycling and fate of mercury in the perspective of mercury as a global pollutant and discusses some new emerging research fields in mercury.

Volatilization of elemental Hg represents an important Hg flux for many aquatic systems. In order to model this flux accurately, it is necessary to measure elemental Hg concentrations in air and water, as well as meteorological variables. Up to now, temporal resolution of elemental Hg analysis has been low (0.5–1 h between data points) compared to other variables used in models (5 min between data points). Here we present an analytical system that allows for the near-real time measurement (every 5 min) of dissolved gaseous mercury (DGM). This system is automated and has a detection limit of 8.5 pg l−1. By using solar radiation as a predictor of DGM concentrations in aquatic systems, we demonstrate the fast response time of the analytical system to fluctuations in ambient DGM in the St. Lawrence river, at sunrise. Complete covering of the purge apparatus and tubing resulted in a 2.6-fold decrease in the slope of the DGM versus light relationship, revealing the importance of light shielding the instrumentation to obtain realistic values.

The main objectives of this paper were to report total gaseous mercury (TGM) concentrations at four stations along the St. Lawrence River in 1998 and to give some insights regarding their fate. The TGM network stretches from latitudes 45 degrees N to 50 degrees N. TGM and ozone concentrations (used as complementary pollutant) were presented. The median TGM concentrations throughout the network varied from 1.62 to 1.79 ng/m3. Sites close to Montreal had larger TGM concentrations. Montreal surroundings appeared to be a source of TGM. The TGM concentrations were maximum in wintertime and minimum in summertime throughout the sites. However, the diurnal variations were site specific. St. Anicet and L'Assomption were more variable in terms of large concentrations, whereas Mingan and Villeroy were more variable in terms of low concentrations. Ozone and TGM concentrations were positively correlated at some sites (Villeroy, Mingan and St. Anicet) whereas they were not at L'Assomption (closest site to Montreal). Local TGM and ozone precursor sources would affect the correlation.

The paper presents an analysis of a set of data that includes both Hg profiles and modeled fluxes over water surface (using the two-layer model) and develops some insights regarding mercury water−air exchanges in Lake Ontario and the Upper St. Lawrence River (USLR). This paper presents the first in situ estimation of the water−air Hg gas exchange in Lake Ontario. It shows that water−air exchange fluxes over Lake Ontario and the Upper St. Lawrence River contributed to atmospheric mercury built-up over water bodies. TGM concentrations over Lake Ontario were significantly higher on the South shore than on the North shore, whereas the degree of saturation was higher on the North shore. Moreover TGM concentrations over water bodies were significantly higher than the reference station located on the ground surface (St. Anicet) indicated. TGM gradient measurements suggested that the South shore of Lake Ontario was mostly in evasion mode, whereas on the North shore and the Upper St. Lawrence River, both evasion a...

Abundances of heavy metals and Pb and Sr isotope ratios have been determined in precipitation collected between December 1997 and June 1999 at St. Anicet and L'Assomption, near Montreal, Canada. Median enrichment factors for the heavy metals, relative to upper crustal abundances, are all »10 indicative of an anthropogenic origin. The 206Pb/207Pb values exhibit a large variation at both stations, with values of 1.170–1.190 and 1.130–1.150 recorded during the winter and summer seasons, respectively. The Pb isotope systematics defined by most of the samples from both stations may be explained by mixing of anthropogenic emissions from U.S. and Canadian sources. Comparison of Pb isotope ratios and heavy metal abundances between the same, individual precipitation events from both stations, however, do not systematically yield similar values and may be attributable to significant, local anthropogenic sources. The 87Sr/86Sr values for precipitations also exhibit a seasonal variation at both stations with the least radiogenic values being recorded, in general, during the winter months (

Elemental Hg (Hg0) is a volatile species that is responsible for water-to-air transfer of Hg in Lake Ontario and the St. Lawrence River. We conducted two cruises in 1998 to identify spatial and temporal patterns in Hg0 levels in these systems and performed field and laboratory experiments on redox transformations of Hg. Elemental Hg concentrations were higher in Lake Ontario than in the St. Lawrence River. At stations in Lake Ontario, Hg0 levels were higher at the bottom of the water column than at the surface, whereas they were homogeneous throughout the water column of the river. Elemental Hg concentrations were generally higher in July than in September and, in contrast with experiments on inland lakes, were relatively constant during the day except for a narrow peak at sunrise. Field and laboratory experiments showed that photoreduction of Hg(II) in St. Lawrence River water was substrate limited and was influenced by visible and ultraviolet radiation. Pseudo first-order kinetics best described photoreduction, with k values between 1 and 2·h-1.

The potential source contribution function (PSCF) has been used to study the source–receptor relationships for total gaseous mercury (TGM) found in air collected at two sites along the St. Lawrence River valley, namely at St. Anicet and Mingan. TGM concentrations have been measured with high time-resolution analysers (Tekran instrument). The source–receptor analyses have been applied with regards to the seasonality of TGM. Median TGM concentrations are significantly less (χ2: α=0.01) during the summertime than other periods at both sites. A total of 12 225 trajectory end-points for St. Anicet and 4480 trajectory end points for Mingan have been used to create potential source area maps. This study identifies preferred potential sources of TGM at St. Anicet during wintertime with strongest probability stretching from the Gulf of Mexico to the southern tip of Greenland. This pattern mimics, the North American anthropogenic Hg emission inventory. Furthermore, some Eurasian mercury air mass intrusions are suggested at Mingan during wintertime. The summertime period at Mingan points out some potential sources stretching from the american mid-west to the St. Lawrence River valley as well as areas around the southern tip of the Hudson Bay.

The paper presents one year of results (1995–1996) of an on-going research study in southern Quebec with regard to mercury in precipitation. A modified rain water collector (MIC-B1) coupled to a data logger is used, in order to be able to select individual events from a remote site. A peristaltic pump coupled with an enclosed Teflon system train separates `in situ' the particulate and the dissolved phases of mercury. QA/QC sampling protocol including memory effect, percentage of recovery as well as field blanks are applied to maintain the high standards of quality. Total mercury concentrations in both phases are measured by Cold Vapour Atomic Fluorescence Spectrophotometry (CVAFS). The volume-weighted mean of total Hg concentration is 6.98 ng.l−1 (the median concentration is 6.58 ng.l−1 and the arithmetic mean is 8.26 ng.l−1). The annual total mercury deposition is about 7.6 μg.m−2. The particulate fraction accounts for a median of 26% of the total mercury concentration. According to Henry's Law, the truly dissolved mercury accounts for less than 0.5% whereas most of the dissolved fraction is expected to be in molecular complexes or colloidal form (

In order to evaluate and understand the processes of water-air and soil-air exchanges involved at background sites, an intensive field measurement campaign has been achieved during the summer of 1995 using high-time resolution techniques (10 min) at two sites (land and water) in southern Quebec (Canada). Mercury flux was measured using a dynamic flux chamber technique coupled with an automatic mercury vapour-phase analyser (namely, Tekran®). The flux chamber shows that the rural grassy site acted primarily as a source of atmospheric mercury, its flux mimicked the solar radiation, with a maximum daytime value of ∼ 8.3 ng m−2 h−1 of TGM. The water surface location (St. Lawrence River site located about 3 km from the land site) shows deposition and evasion fluxes almost in the same order of magnitude (−0.5 vs 1.0 ng m−2 h−1).The latter is influenced to some extent by solar radiation but primarily by the formation of a layer of stable air over the water surface in which some redox reactions might promote evasion processes over the water surface. This process does not appear over the soil surface. As a whole, soil-air exchange rate is about 6–8 fold greater than the water-air exchange.

Total Gaseous Mercury (TGM) data (n = 5125) measured from September 9 to November 30, 1994 in Southern Quebec with an automatic TGM analyser (Tekran®) are used to study the behaviour of TGM with ozone and the water vapour mixing ratio. Results show, as a whole, no straight-forward correlation between TGM and ozone concentrations. A significant correlation between TGM and water vapour mixing ratio was measured. Some back reduction of Hg(II) to Hgo in the aqueous phase and subsequent evaporation of Hg0 according to Henry's Law is expected. The latter correlation seems to be partly ozone dependent since under ‘clean conditions’ (ozone > 30 ppbv) the slope of TGM vs the water vapour mixing ratio is twice that during ‘polluted conditions’ (ozone > 30 ppbv) which suggests some compensation effects under polluted conditions (counteracting the back-reduction of Hg(II) to Hgo in the aqueous phase). Oxidation of TGM by ozone during high moisture conditions (water vapour mixing ratio ∼14g/kg) seems to appear at the threshold ozone concentration ⩾ 30 ppbv.

A fugacity-based model to explain the partitioning of contaminants in the environment is evaluated. Using emission inventories, air and water concentrations predicted by the model for the southwestern Quebec region generally agree with field data for phenanthrene, α-HCH, lindane, and DDT. For pyrene, air concentrations are in agreement but water concentrations were in error by a factor of nearly 20. There is also a possibility for using the model to predict emissions from known air and water concentrations. The model was run over 120 times each for phenanthrene, HCB, and lindane while randomly varying the input parameters each time. A Principal Components Analysis and a partial correlation analysis indicate that certain input parameters are more important for some compounds than for others and that log Kow is the physical-chemical property of greatest importance.

This paper presents a year of data on certain persistent organic pollutants and heavy metals in the atmosphere over a St.Lawrence River valley site (Villeroy) in 1992. These results are compared with other sites in North America: most of the concentration levels found here are characteristic of a rural site. The specific behaviours of certain species are presented and discussed with regard to physical and chemical laws as well as with the potential source and transport in the atmospheric compartment of the environment.

The use of sulfonylurea herbicides (SU) has increased greater than 100 times over the past 30 years in both Europe and North America. Applied at low rates, their presence, persistence and potential impacts on aquatic ecosystems remain poorly studied. During late-spring to early fall in 2009-2011, concentrations of 9 SU were assessed in two agricultural streams and their receiving wetland, an enlargement of the St. Lawrence River (Canada). Six SU in concentrations >LOQ (10 ng L(-1)) were detected in 10% or less of surface water samples. Rimsulfuron was detected each year, sulfosulfuron and nicosulfuron in two years and the others in one year only, suggesting that application of specific herbicides varied locally between years. Detection frequency and concentrations of SU were not significantly associated with total precipitation which occurred 1 to 5d before sampling. Concentrations and fate of SU differed among sites due to differences in stream dynamics and water quality characteristics. The persistence of SU in catchment basin streams reflected the dissipation effects associated with stream discharge. Maximum concentrations of some SU (223 and 148 ng L(-1)) were occasionally above the baseline level (100 ng L(-1)) for aquatic plant toxicity, implying potential toxic stress to flora in the streams. Substantially lower concentrations (max 55 ng L(-1)) of SU were noted at the downstream wetland site, likely as a result from dilution and mixing with St. Lawrence River water, and represent less toxicological risk to the wetland flora. Sporadic occurrence of SU at low concentrations in air and rain samples indicated that atmospheric deposition was not an important source of herbicides to the study area.

The southern Ontario oxidant study (SONTOS) is one of the scientific responses to the problem of ozone exceedences in the Windsor/Quebec City corridor, the strip extending from Windsor in the extreme southwest of Ontario, along the north shores of Lake Erie and Lake Ontario and down the St Lawrence valley. This corridor includes the two major metropolitan areas of Toronto and Montreal and experiences more exceedences of the Canadian ozone guideline per year than any other part of the country. The overall objective of SONTOS is to elucidate the factors which lead to these high levels. The study design is based on intensive measurements made at a site to the NNW of Toronto, with supplementary measurements at other sites and on board an aircraft. This paper, and the seven which follow, describe and interpret the measurements made in the summer of 1992. Although this summer was noteworthy for generally very low ozone concentrations, a number of interesting observations have been made which have a bearing on the oxidant phenomenon in southern Ontario. In particular, this paper describes two specific events. In one, which occurred on 6 August 1992, the intensive measurement site experienced the impact of a polluted air mass, which had apparently travelled to the site from Toronto, by way of Lake Ontario. This case has been contrasted with an event in the last week of August, in which large-scale, organised southwesterly flow led to the conditions which more typically give rise to widespread ozone episodes in the province. Events similar to the 6 August episode occurred on several occasions during the study period, and underline the very important role of the Great Lakes in ozone transport and delivery in southern Ontario.

Statistical analysis of observations made between 7 and 31 August 1992 at a rural site in Southern Ontario, Canada, is presented using principal component analysis (PCA), as well as rank and partial correlation analyses. Data for ozone, CO, SO 2 , NO, NO y (NO + NO 2 including NO x , PAN and HNO 3 ), ethane, ethylene, propane, acetylene and isoprene are employed, as well as such meteorological information as temperature, relative humidity, wind speed and direction. The analysis involved several scenarios classifying the data according to daytime, nighttime and wind direction. A normal correlation analysis suggests that isoprene might be important in the build-up of ozone in the S-W sector, whereas it is not important in the N-E wind sector. PCA show that the chemical and the meteorological variables interact differently within the different scenarios. Finally, the relationships between ozone and isoprene for both wind sectors are found to be the same when the data are subjected to a partial correlation analysis including the meteorological parameters and it is concluded that the S-W ozone-isoprene relationship might be biased by temperature.

The atmospheric concentration of lindane and α-HCH measured at Villeroy (Quebec, Canada) are presented. Time−series and source−receptor recognition techniques permit us to point out that agricultural activities, namely, corn seeding, are mainly responsible for the atmospheric release of lindane. About 350 000 ha of land are used for this crop activity in Quebec, and the period of seeding appears to be concomitant with the highest peak of atmospheric lindane. The relationship of lindane with temperature shows that desorption mechanisms are important processes in the atmospheric lindane buildup. This volatilization might come from soil and might involve old as well as fresh lindane.

Global emissions of mercury continue to change at the same time as the Arctic is experiencing ongoing climatic changes. Continuous monitoring of atmospheric mercury provides important information about long-term trends in the balance between transport, chemistry, and deposition of this pollutant in the Arctic atmosphere. Ten-year records of total gaseous mercury (TGM) from 2000 to 2009 were analyzed from two high Arctic sites at Alert (Nunavut, Canada) and Zeppelin Station (Svalbard, Norway); one sub-Arctic site at Kuujjuarapik (Nunavik, Québec, Canada); and three temperate Canadian sites at St. Anicet (Québec), Kejimkujik (Nova Scotia) and Egbert (Ontario). Five of the six sites examined showed a decreasing trend over this time period. Overall trend estimates at high latitude sites were: −0.9% yr−1 (95% confidence limits: −1.4, 0) at Alert and no trend (−0.5, +0.7) at Zeppelin Station. Faster decreases were observed at the remainder of the sites: −2.1% yr−1 (−3.1, −1.1) at Kuujjuarapik, −1.9% yr−1 (−2.1, −1.8) at St. Anicet, −1.6% yr−1 (−2.4, −1.0) at Kejimkujik and −2.2% yr−1 (−2.8, −1.7) at Egbert. Trends at the sub-Arctic and mid-latitude sites agree with reported decreases in background TGM concentration since 1996 at Mace Head, Ireland, and Cape Point, South Africa, but conflict with estimates showing an increase in global anthropogenic emissions over a similar period. Trends in TGM at the two high Arctic sites were not only less negative (or neutral) overall but much more variable by season. Possible reasons for differences in seasonal and overall trends at the Arctic sites compared to those at lower latitudes are discussed, as well as implications for the Arctic mercury cycle. The first calculations of multi-year trends in reactive gaseous mercury (RGM) and total particulate mercury (TPM) at Alert were also performed, indicating increases from 2002 to 2009 in both RGM and TPM in the spring when concentrations are highest.