Lake St. Pierre (LSP), constituted of a 120 km² stretching of the St. Lawrence River (Southern Québec), hosts the largest freshwater fishery industry in Canada. The lake drains, through its main tributaries, an important area of agrarian land and was subjected to intense industrial activities in the past century. In this paper, we present (1) an estimation of the seasonal aquatic mercury (Hg) inputs to LSP from the St-Lawrence River and two major tributaries; (2) a reconstruction, by the analysis of sediment cores, of the historic inputs of Hg into LSP and in a large riparian wetland, Bay St. François. Our results indicate that the aquatic Hg inputs to LSP (290 kg Hg between April 2003 and April 2004) are moderately elevated with most of the inputs occurring from the St. Lawrence River, either in spring or early winter, during high flow episodes. The sediment profiles suggest a recent decrease in Hg inputs, likely attributable to improvements of industrial practices. The observed perturbation of the surface sediments give evidence of an active hydrodynamic regime, suggesting that LSP could only act as a transitory system for suspended sediment and Hg, with seasonal accumulation and recurrent re-suspension resulting from changes in the hydrodynamic regime. Finally, we observed positive MeHg fluxes from the sediment to the water at different seasons in Bay St. François. However, Hg levels in fish like walleyes of LSP are reported to be low, which could be explained by faster fish growth rates following in part intense fishing pressure in LSP.

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.

Communities of aquatic macroinvertebrates, fish density and biomass, and environmental variables were investigated in three Patagonian mountain rivers affected by urbanization. The rivers Las Minas, Esquel and Carbón that flow through the towns of Cholila, Esquel and Corcovado, respectively (northwest Chubut, Argentina) were selected to assess the degree of impairment. A reference site and an urban site were established on each river. Water quality variables including conductivity, major nutrients, total suspended solids (TSS) and dissolved oxygen, habitat conditions and quality of riparian ecosystems were investigated in autumn, winter, spring and summer 2005–2006. Macroinvertebrates were sampled concurrently in three riffles and three pools at each site. Invertebrate species richness, EPT richness, the Shannon–Weaver diversity index, % EPT density, and the BMPS index were lower at urban sites, whereas % collectors increased. The most impaired site was below Esquel, the largest town. Senzilloides panguipulli (Plecoptera), Polypedilum and Rheotanytarsus species (Diptera: Chironomidae), Nais communis (Oligochaeta) and Meridialaris chiloeensis (Ephemeroptera) dominated assemblages at reference and moderately impaired sites in summer, whereas the strongly polluted reach below Esquel had low flow in summer and a community dominated by Limnodrilus spp. (Oligochaeta), Helobdella spp. (Hirudinea), and two Hyallela species (Amphipoda). Canonical correspondence analysis indicated that ammonia, conductivity and TSS were important variables structuring invertebrate assemblages. In contrast, fish density and biomass varied in a non-systematic manner among sites. Overall, urbanization resulted in varying degrees of habitat degradation, sedimentation and nutrient enrichment that were reflected by the macroinvertebrate assemblages, which can be used effectively to monitor the effects of urban communities on Patagonian mountain streams.

The arsenic bioavailability in the bed sediments from the Anllóns River (NW Spain) has been assessed by using several analytical approaches. A six-step sequential fractionation was compared to three general availability tests: the Toxicity Characteristic Leaching Procedure (TCLP) extraction, which estimates the leaching potential of As and its effect on the survival of microorganisms (Vibrio fischeri), an extraction with 1 M HCl extraction, which estimates the bioavailability to higher plants, and a physiologically based extraction test (PBET), which estimates the bioavailability to superior animals. Arsenic was found to be mainly associated to the least mobile fractions: bound to Fe-Al oxides and in the residual phase. Among the three single extractants considered, the PBET extracted the highest As concentrations (1-11% of the total As). The TCLP extracts showed toxicity to Vibrio fischeri whereas for the plants evaluated, aqueous extracts did not show adverse effects.

In this paper a three-step procedure is proposed to deal with ecological data, usually very complex in their treatment. The three steps – exploratory, confirmatory, and modelling phases – reflect the different methodological approaches necessary in each phase of the study. To illustrate the methodology, a case study is proposed, concerning the suitability of plants as pollution bioindicators. Samples of differently aged Pinus pinea L. needles were collected throughout 1 year in three different locations, whose human disturbance was known to be different. In the samples some morphological and functional parameters were measured, whose relation with the stress was already known. The exploratory analysis suggested pollution with human origin, the needle’s age, and the environmental conditions as the main factors of influence of damage. The confirmatory analysis confirmed both site and age as main factors and occasionally the sampling date. On this basis, some models were estimated separately for each site: models that best described the damage as function of age resulted non-linear and some of them with seasonal fluctuations. As a result, whereas the models described well enough the pollution temporal variation, the difference of pollution in the sites was best described by the different values of the models parameters in the different sites. In short, different pollution conditions are described better by the damage trend than by the individual measures. The three-step procedure resulted of high utility in outlining the most interesting relations to investigate through the modelling, the opportunity to model the indicators variation along time separately for each site, and to introduce the seasonal variation in some models.

This work describes recent research carried out in an extremely acidic (pH 0.61–0.82) and hypersaline (e.g., 134 g/L SO₄ ²⁻, 74 g/L Fe, 7.5 g/L Al, 3 g/L Mg, 2 g/L Cu, 1 g/L Zn) leachate which seeps from a pyrite pile in San Telmo mine (Huelva, SW Spain) and forms evaporative pools of ultra-concentrated water in which attractive crystals of Zn-rich melanterite (FeᴵᴵSO₄ 7H₂O) are formed. Geochemical modeling with the Pitzer method indicates that the acidic brine was near saturation with respect to melanterite (SIMₑₗ = 0 ± 0.2). The microbiological investigation has revealed a surprisingly high biomass (1.4 × 10⁶ cells mL⁻¹) and an exotic ecosystem composed of acidophilic, Fe-oxidizing archaea (mainly Ferroplasma spp., representing 52% of the microbial population), and minor numbers of acidophilic bacteria (including Leptospirillum spp. (3.2%), Acidithiobacillus spp. (1.6%), and Alphaproteobacteria (2.8%)). The microbial production of Feᴵᴵᴵ allows the oxidative dissolution of pyrite and other sulphides, which results in additional inputs of Feᴵᴵ, SO₄ ²⁻ and acidity to the system. The surfaces of the pyrite crystals show a typical etch-pitted texture, as well as blobs of elemental sulphur, which are both compatible with this indirect, microbially mediated oxidation mechanism. The composition of the acidic leachate seems to result from the combination of several processes which include: (1) formation of melanterite within the pile during relatively dry seasons, (2) subsequent dissolution of melanterite during rainy episodes, (3) microbial oxidation of Feᴵᴵ, (4) sulphide oxidation mediated by Feᴵᴵᴵ, (5) dissolution of chlorite and other aluminosilicates present in the pile, and (6) cooling and/or evaporation of seepage from the pile and consequent melanterite precipitation.

Salvinia minima has been reported as a cadmium and lead hyperaccumulator being the adsorption and intracellular accumulation the main uptake mechanisms. However, its physicochemical properties, the effect of metal concentration and the presence of organic and inorganic compounds on its hyperaccumulating capacity are still unknown. Furthermore, the specific adsorption and accumulation mechanisms occurring in the plant are not clear yet. Thus, based on a compartmentalization analysis, a bioadsorption (BAF) and an intracellular accumulation factor (IAF) were calculated in order to differentiate and quantify these two mechanisms. The use of kinetic models allowed predicting the specific type of uptake mechanisms involved. Healthy plants were exposed to five lead concentrations ranging from 0.80 ± 0.0 to 28.40 ± 0.22 mg Pb²⁺l⁻¹ in batch systems. A synthetic wastewater, amended with propionic acid and magnesium sulfate, and deionized water were used as media. The BAF and IAF contributed to gain an in-depth insight into the hyperaccumulating lead capacity of S. minima. It is clear that such capacity is mainly due to adsorption (BAF 780–1980) most likely due to its exceptional physico-chemical characteristics such as a very high surface area (264 m² g⁻¹) and a high content of carboxylic groups (0.95 mmol H⁺g⁻¹ dw). Chemisorption was predicted as the responsible mechanism according to the pseudo-second order adsorption model. Surprisingly, the ability of S. minima to accumulate the metal into the cells (IAF 57–1007) was not inhibited at concentrations as high as 28.40±0.22 mg Pb²⁺l⁻¹.

The Marais Vernier is the largest freshwater wetland in the Seine Estuary in northern France. It is in a heavily urbanized and industrialized region and could be affected by atmospheric deposition and by fluvial input of contaminants in water diverted from the Seine River. To evaluate contaminant histories in the wetland and the region, sediment cores were collected from two open-water ponds in the Marais Vernier: the Grand-Mare, which was connected to the Seine by a canal from 1950 to 1996, and the Petite Mare, which has a small rural watershed. Diversions from the Seine to the Grand-Mare increased sedimentation rates but mostly resulted in low contaminant concentrations and loading rates, indicating that the sediment from the Seine was predominantly brought upstream by tidal currents from the estuary and was not from the watershed. Atmospheric sources of metals dominate inputs to the Petite Mare; however, runoff of metals from vehicle-related sources in the watershed might contribute to the upward trends in concentrations of Cr, Cu, and Zn. Estimates of atmospheric deposition using the Petite Mare core are consistent with measured deposition in the region and are mixed (similar for Hg and Pb; larger for Cd, Cu, and Zn) compared with deposition estimated from sediment cores in the northeastern United States. A local source of PAHs in the watershed of the Petite Mare is indicated by higher concentrations, higher accumulation rates, and a different, more petrogenic, PAH assemblage than in the Grand-Mare. The study illustrates how diverse sources and transport pathways can affect wetlands in industrial regions and can be evaluated using sediment cores from the wetland ponds.

The direct spectrophotometric analysis of aqueous nitrates is a simple analytical procedure but prone to interferences. A twelve-month study of the Preakness Brook in Wayne Township, New Jersey demonstrated that two wavelength, three wavelength, and second derivative calculation methods provide very different results from the same ultraviolet absorption spectrum. On average, the two wavelength and second derivative methods yielded the same concentration at each sample point over the entire study period. These methods provided concentration results closest to those obtained by ion chromatography and significantly lower than the three wavelength computation method. The degree of variation between the different computation methods was not consistent as it rose with increasing absorbances at wavelengths associated with interfering compounds. This variation was especially pronounced between May and August.

Measurements of nitrogen dioxide, nitrous and nitric acids as well as ozone were made using newly developed instrumentation onboard the research vessel Aegeon in the Aegean Sea between 25th-29th July 2000. Typical nitrogen dioxide concentrations observed aboard the boat were 4-6 ppb (v/v) with a broad maximum of 20-30 ppb (v/v). Ozone concentrations typically ranged between 40 and 80 ppb (v/v). Mixing ratios of both nitric and nitrous acids in the ambient air of the Aegean Sea were mainly below 50 ppt (v/v). The data also showed a number of short pollution episodes with rapid changes in the concentration of reactive nitrogen compounds [nitrogen dioxide maximum up to 164 ppb (v/v), nitric acid maximum up to 12 ppb (v/v), nitrous acid maximum up to 2.7 ppb (v/v)] and ozone [maximum up to 88 ppb (v/v)]. These episodes were correlated with pollution plumes originating from boats upwind, at short distance, from the R/V Aegeon. The measurements revealed the importance of nitrous and nitric acids for the transport of nitrogen to marine biota in busy ship lanes.