Seasonal variability of denitrification efficiency in northern salt marshes: an example from the St. Lawrence Estuary

In coastal ecosystems, denitrification is a key process in removing excess dissolved nitrogen oxides and participating in the control of eutrophication process. Little is known about the role of salt marshes on nitrogen budgets in cold weather coastal areas. Although coastal salt marshes are important sites for organic matter degradation and nutrient regeneration, bacterial-mediated nitrogen cycling processes, such as denitrification, remain unknown in northern and sub-arctic regions, especially under winter conditions. Using labelled nitrogen (15N), denitrification rates were measured in an eastern Canadian salt marsh in August, October and December 2005. Freshly sampled undisturbed sediment cores were incubated over 8h and maintained at their sampling temperatures to evaluate the influence of low temperatures on the denitrification rate. From 2 to 12 degrees C, average denitrification rate and dissolved oxygen consumption increased from 9.6 to 25.5 micromol N2 m-2 h-1 and from 1.3 to 1.8 mmol O2 m-2 h-1, respectively, with no statistical dependence of temperature (p>0.05). Nitrification has been identified as the major nitrate source for denitrification, supplying more than 80% of the nitrate demand. Because no more than 31% of the nitrate removed by sediment is estimated to be denitrified, the presence of a major nitrate sink in sediment is suspected. Among possible nitrate consumption mechanisms, dissimilatory reduction of nitrate to ammonium, metal and organic matter oxidation processes are discussed. Providing the first measurements of denitrification rate in a St. Lawrence Estuary salt marsh, this study evidences the necessity of preserving and restoring marshes. They constitute an efficient geochemical filter against an excess of nitrate dispersion to coastal waters even under cold northern conditions.     

On the petrology of brittle precursors of shear zones – An expression of concomitant brittle deformation and fluid–rock interactions in the ‘ductile’ continental crust?

The inherited localization model for shear zone development suggests that ductile deformation in the middle and lower continental crust is localized on mechanical anisotropies, like fractures, referred to as shear zone brittle precursors. In the Neves area (Western Tauern Window, Eastern Alps), although the structural control of these brittle precursors on ductile strain localization is well established, the relative timing of the brittle deformation and associated localized fluid flow with respect to ductile deformation remains in most cases a matter of debate. The present petrological study, carried out on a brittle precursor of a shear zone affecting the Neves metagranodiorite, aims to determine whether brittle and ductile deformations are concomitant and therefore relate to the same tectonic event. The brittle precursor consists of a 100–500 µm wide recrystallized zone with a host mineral‐controlled stable mineral assemblage composed of plagioclase–garnet–quartz–biotite–zoisite±white mica±pyrite. Plagioclase and garnet preserve an internal compositional zoning interpreted as the fingerprint of Alpine metamorphism and fluid–rock interactions concomitant with the brittle deformation. Phase equilibrium modelling of this garnet‐bearing brittle precursor shows that metamorphic garnet and plagioclase both nucleated at 0.6 ± 0.05 GPa, 500 ± 20°C and then grew along a prograde path to 0.75 ± 0.05 GPa, 530 ± 20°C. These amphibolite facies conditions are similar to those inferred from ductile shear zones from the same area, suggesting that both brittle and ductile deformation were active in the ductile realm above 500°C for a depth range between 17 and 21 km. We speculate that the Neves area fulfils most of the required conditions to have hosted slow earthquakes during Alpine continental collision, that is, coupled frictional and viscous deformation under high‐fluid pressure conditions ~450°C. Further investigation of this potential geological record is required to demonstrate that slow earthquakes may not be restricted to subduction zones but are also very likely to occur in modern continental collision settings.     

Colloidal complexed silver and silver nanoparticles in extrapallial fluid of Mytilus edulis

Metal transport in mollusk extrapallial fluid (EPF) that acts as a "bridge" between soft tissues and shell has surprisingly received little attention until now. Using ultrafiltration and radiotracer techniques we determined silver concentrations and speciation in the EPF of the blue mussel Mytilus edulis after short-term uptake and depuration laboratory experiments. Radiolabelled silver ((11?m)Ag) was used in dissolved or nanoparticulate phases (AgNPs < 40 nm), with a similar low Ag concentration (total radioactive and cold Ag ~0.7 μg/L) in a way that mussels could uptake radiotracers only from seawater. Our results indicated that silver nanoparticles were transported to the EPF of blue mussels at a level similar to the Ag ionic form. Bulk activity of radiolabelled silver in the EPF represented only up to 7% of the bulk activity measured in the whole mussels. The EPF extracted from mussels exposed to both treatments exhibited an Ag colloidal complexed form based on EPF ultrafiltration through a 3 kDa filter. This original study brings new insights to internal circulation of nanoparticles in living organisms and contributes to the international effort in studying the potential impacts of engineered nanomaterials on marine bivalves which play an essential role in coastal ecosystems, and are important contributors to human food supply from the sea.     

Sea-to-air flux of contaminants via bubbles bursting. An experimental approach for tributyltin

Although seawater concentration of tributyltin (TBT) should decrease when the direct inputs from ship hulls will cease after the incoming world ban of organotin-based antifouling paints in 2003 or later, the TBT environmental issue will still be present for decades as contaminated sediments in shallow waters will be acting as a long-lasting reservoir for TBT and its degradation products. The lost of TBT to the atmosphere by volatilization has already been proposed as a part of its molecular motion through the aquatic environment but most recent calculated values of water-to-air rate of exchange of TBT (from 20 to 510 nmol m⁻² year⁻¹) do not take into account the potential contribution of aerosols ejection to the atmosphere upon bubbles bursting, an important process for pollutants transport in the marine environment. In this work, an experimental approach to measure the seawater-to-air flux of TBT mediated by bubbles bursting is described, and the influence of phytoplankton cells and dissolved organic matter from exudates and culture weathering on flux rates was assessed. The results demonstrate that TBT can be transferred from water to air via the ejection of droplets from bubbles bursting and that cell density strongly affected the transfer. Under a bubbling regime, the water-to-air flux (pmol TBT cm⁻² min⁻¹ level) is estimated up to 1000-fold the flux measured for the molecular diffusion and volatilization under static quiescent conditions. The surface microlayer acted as a transient boundary between the water column and the atmosphere where the dynamic of TBT accumulation has the same trend as the dynamic of TBT ejection. This physical transfer mechanism might be of high significance in nearshore environments, harbors, and shallow channels where clouds of bubbles generated in the wake of large ships play an important role for the atmosphere/seawater chemical exchanges.     

Potential link between exposure to fungicides chlorothalonil and mancozeb and haemic neoplasia development in the soft-shell clam Mya arenaria: A laboratory experiment

The aetiology of haemic neoplasia (HN) is unknown, so far but many causative factors are suggested such as viral, pollution and genetics. The aim of this study was to determine if, under chronic exposure, two major pesticides (chlorothalonil and mancozeb) which are used in potato production could induce HN in soft-shell clams (Mya arenaria). Short-term experiments with acute exposure were also performed. Clams were collected from an epizootic site (North River, PEI) and from a site free of the disease (Magdalen Islands, Quebec). The tetraploid level of haemocytes was assessed by flow cytometry for each clam to determine the HN status. The bioaccumulation of pesticides in tissues was quantified by gas chromatography/mass spectrometry (GC/MS) for chlorothalonil while mancozeb and manganese were quantified by inductively coupled plasma-mass spectrometer (ICP/MS). Long term exposure to fungicide Bravo 500^® did not induce high tetraploid levels on negative calm from North River and the analysis of the digestive gland and the mantle did not reveal any detectable level of chlorothalonil. In the Manzate 200 DF^®, some clams revealed high level of tetraploid cells but no difference were observed between the treatments and the control. The analysis of the digestive gland and the mantle for manganese did not highlight any significant difference in tissue concentration (p = 0.05). For the acute exposure, chlorothalonil analysis showed that the active ingredient is distributed between four chlorinated compounds: 99.5% for chlorothalonil isomers, 0.4% for pentachlorothalonil and 0.1% for trichlorothalonil isomers. For a 72 h experiment, the accumulation was within 4 h; the higher tissue concentration of chlorothalonil was 59.2 μg g⁻¹ in the mantle after 48 h, following by a decrease to an undetectable level at the end. For the manganese, the accumulation was detected after 4 h; the higher tissue concentration was 48.8 μg g⁻¹ in the mantle after 24 h and, over the following 48 h, the accumulation decreased until the end of the trial. Based on the data, the accumulation of these fungicides seems to be transitory. Chlorothalonil and mancozeb are both oxidative-stress promoters and could have induced cell dysfunction while in the tissue. Study on the effect of these fungicides on the p53 protein system is an example of strategy that would provide information on cellular events promoting neoplasia.