Mixing behaviour and sources of Ag, Pd, and other trace elements in the Estuary and Gulf of St. Lawrence under winter conditions.

The marine chemistry of platinum group elements is poorly documented despite robust evidence of their widespread emissions and deposition around the globe. Here, we report the concentrations and discuss the geochemical behaviours of Ag, Pd and other trace and ultra-trace elements in the Estuary and Gulf of St. Lawrence (EGSL).

Ocean deoxygenation caused non-linear responses in the structure and functioning of benthic ecosystems.

The O content of the global ocean has been declining progressively over the past decades, mainly because of human activities and global warming. Nevertheless, how long-term deoxygenation affects macrobenthic communities, sediment biogeochemistry and their mutual feedback remains poorly understood. Here, we evaluate the response of the benthic assemblages and biogeochemical functioning to decreasing O concentrations along the persistent bottom-water dissolved O gradient of the Estuary and Gulf of St.

Large-scale control of the retroflection of the Labrador Current.

The Labrador Current transports cold, relatively fresh, and well-oxygenated waters within the subpolar North Atlantic and towards the eastern American continental shelf. The relative contribution of these waters to either region depends on the eastward retroflection of the Labrador Current at the Grand Banks of Newfoundland. Here, we develop a retroflection index based on the pathway of virtual Lagrangian particles and show that strong retroflection generally occurs when a large-scale circulation adjustment, related to the subpolar gyre, accelerates the Labrador Current and shifts the Gulf Stream northward, partly driven by a northward shift of the wind patterns in the western North Atlantic.

Global fjords as transitory reservoirs of labile organic carbon modulated by organo-mineral interactions.

The global carbon cycle is strongly modulated by organic carbon (OC) sequestration and decomposition. Whereas OC sequestration is relatively well constrained, there are few quantitative estimates of its susceptibility to decomposition. Fjords are hot spots of sedimentation and OC sequestration in marine sediments.

Concentrations of reactive Mn(III)-L and MnO in estuarine and marine waters determined using spectrophotometry and the leuco base, leucoberbelin blue.

In terms of its oxidative strength, the MnO/Mn couple is one of the strongest in the aquatic environment. The intermediate oxidation state, manganese(III), is stabilized by a range of organic ligands (Mn(III)-L) and some of these complexes are also strong oxidants or reductants. Here, we present improved methods for quantifying soluble reactive oxidized manganese(III) and particulate reactive oxidized manganese at ultra-low concentrations; the respective detection limits are 6.

Current CaCO dissolution at the seafloor caused by anthropogenic CO.

Oceanic uptake of anthropogenic CO leads to decreased pH, carbonate ion concentration, and saturation state with respect to CaCO minerals, causing increased dissolution of these minerals at the deep seafloor. This additional dissolution will figure prominently in the neutralization of man-made CO However, there has been no concerted assessment of the current extent of anthropogenic CaCO dissolution at the deep seafloor. Here, recent databases of bottom-water chemistry, benthic currents, and CaCO content of deep-sea sediments are combined with a rate model to derive the global distribution of benthic calcite dissolution rates and obtain primary confirmation of an anthropogenic component.

Subsurface seawater methylmercury maximum explains biotic mercury concentrations in the Canadian Arctic.

Mercury (Hg) is a contaminant of major concern in Arctic marine ecosystems. Decades of Hg observations in marine biota from across the Canadian Arctic show generally higher concentrations in the west than in the east. Various hypotheses have attributed this longitudinal biotic Hg gradient to regional differences in atmospheric or terrestrial inputs of inorganic Hg, but it is methylmercury (MeHg) that accumulates and biomagnifies in marine biota.

Disparate acidification and calcium carbonate desaturation of deep and shallow waters of the Arctic Ocean.

The Arctic Ocean is acidifying from absorption of man-made CO. Current predictive models of that acidification focus on surface waters, and their results argue that deep waters will acidify by downward penetration from the surface. Here we show, with an alternative model, the rapid, near simultaneous, acidification of both surface and deep waters, a prediction supported by current, but limited, saturation data.

Abundant porewater Mn(III) is a major component of the sedimentary redox system.

Soluble manganese(III) [Mn(III)] can potentially serve as both oxidant and reductant in one-electron-transfer reactions with other redox species. In near-surface sediment porewater, it is often overlooked as a major component of Mn cycling. Applying a spectrophotometric kinetic method to hemipelagic sediments from the Laurentian Trough (Quebec, Canada), we found that soluble Mn(III), likely stabilized by organic or inorganic ligands, accounts for up to 90% of the total dissolved Mn pool.

Preservation of organic matter in sediments promoted by iron.

The biogeochemical cycles of iron and organic carbon are strongly interlinked. In oceanic waters, organic ligands have been shown to control the concentration of dissolved iron. In soils, solid iron phases shelter and preserve organic carbon, but the role of iron in the preservation of organic matter in sediments has not been clearly established.

Acid-base behavior of the gaspeite (NiCO3(s)) surface in NaCl solutions.

Gaspeite is a low reactivity, rhombohedral carbonate mineral and a suitable surrogate to investigate the surface properties of other more ubiquitous carbonate minerals, such as calcite, in aqueous solutions. In this study, the acid-base properties of the gaspeite surface were investigated over a pH range of 5 to 10 in NaCl solutions (0.001, 0.

Proton/calcium ion exchange behavior of calcite.

The characterization of the proton sorptive properties of calcite in aqueous solutions at 25 +/- 1 degrees C over a relatively wide range of chemical conditions (7.16 View Article and Find Full Text PDF

Theoretical insights into the hydrated (10.4) calcite surface: structure, energetics, and bonding relationships.

Roothaan-Hartree-Fock molecular orbital methods were applied to investigate the ground-state structural, energetic properties, and bonding relationships of the hydrated (10.4) calcite surface. The adsorption of water molecules was modeled at the 6-31G(d,p) level of theory using Ca(n)(CO(3))(n) slab cluster models (4 View Article and Find Full Text PDF

Photoferrotrophs thrive in an Archean Ocean analogue.

Considerable discussion surrounds the potential role of anoxygenic phototrophic Fe(II)-oxidizing bacteria in both the genesis of Banded Iron Formations (BIFs) and early marine productivity. However, anoxygenic phototrophs have yet to be identified in modern environments with comparable chemistry and physical structure to the ancient Fe(II)-rich (ferruginous) oceans from which BIFs deposited. Lake Matano, Indonesia, the eighth deepest lake in the world, is such an environment.

Comparative study of nanoscale surface structures of calcite microcrystals using FE-SEM, AFM, and TEM.

The bulk morphology and surface features that developed upon precipitation on micrometer-size calcite powders and millimeter-size cleavage fragments were imaged by three different microscopic techniques: field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM) of Pt-C replicas, and atomic force microscopy (AFM). Each technique can resolve some nanoscale surface features, but they offer different ranges of magnification and dimensional resolutions. Because sample preparation and imaging is not constrained by crystal orientation, FE-SEM and TEM of Pt-C replicas are best suited to image the overall morphology of microcrystals.

Mercury methylation in the epilithon of boreal shield aquatic ecosystems.

Methylation rates by periphyton growing on the rocky shore of a remote boreal shield lake were measured over diurnal cycles at temperatures representative of summer and fall conditions. The measurements were carried out in vitro with natural communities grown on artificial Teflon substrates submerged along the lake's shore for 1-2 years. At temperatures above 20 degrees C, epilithon Hg methylation rates were fast and reached a steady state within 12 h upon exposure to 2 ng L(-1) of inorganic mercury.

Total mercury and methylmercury accumulation in periphyton of Boreal Shield lakes: influence of watershed physiographic characteristics.

Little is known about Hg accumulation in littoral communities, especially in periphyton biofilm of unperturbed lakes. The objectives of this study were to investigate and establish relationships between total mercury (THg) and methylmercury (MeHg) concentrations in periphyton communities of Boreal lakes and watershed physiographic and lake morphometric characteristics. This study was carried out on 23 Boreal Canadian Shield lakes located between 47-50 degrees N and 73-77 degrees W.

1H-NMR study of Na alginates extracted from Sargassum spp. in relation to metal biosorption.

The use of a number of species of marine brown algae in the implementation of bioremediation strategies for toxic heavy metals is being considered and evaluated. The biosorption capacity of these algae for heavy metals resides mainly in a group of linear polysaccharides known as alginates that occur as a gel in the algal thallus. The potential for selective metal binding by the biomass of two species of Sargassum was evaluated by 1H-NMR (nuclear magnetic resonance) following a high temperature, alkaline extraction and purification of their alginate polysaccharide.

A review of the biochemistry of heavy metal biosorption by brown algae.

The passive removal of toxic heavy metals such as Cd(2+), Cu(2+), Zn(2+), Pb(2+), Cr(3+), and Hg(2+) by inexpensive biomaterials, termed biosorption, requires that the substrate displays high metal uptake and selectivity, as well as suitable mechanical properties for applied remediation scenarios. In recent years, many low-cost sorbents have been investigated, but the brown algae have since proven to be the most effective and promising substrates. It is their basic biochemical constitution that is responsible for this enhanced performance among biomaterials.

Metal selectivity of Sargassum spp. and their alginates in relation to their alpha-L-guluronic acid content and conformation.

The discovery of a consistent and unusual enrichment in homopolymeric alpha-L-guluronic acid G-blocks in alginates extracted from a suite of Sargassum brown algae is described in this study. 1H NMR spectroscopy was used to characterize these alginates which display homopolymeric guluronic acid block (G-block) frequency values (F(GG)) between 0.37 and 0.