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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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.