Elucidation of different forms of organic carbon in marine sediments from the Atlantic coast of Spain using thermal analysis coupled to isotope ratio and quadrupole mass spectrometry

Analysis of river, estuary and marine sediments from the Atlantic coast of Spain using thermogravimetry–differential scanning calorimetry–quadrupole mass spectrometry–isotope ratio mass spectrometry (TG–DSC–QMS–IRMS) was used to (a) distinguish bulk chemical hosts for C within a sediment and humic acid fraction, (b) track C pools with differing natural C isotope ratios and (c) observe variation with distance from the coast. This is the first application of such a novel method to the characterisation of organic matter from marine sediments and their corresponding humic acid fractions. Using thermal analysis, a labile, a recalcitrant and a refractory carbon pool can be distinguished. Extracted humic fractions are mainly of recalcitrant nature. The proportion of refractory carbon is greatest in marine sediments and humic acid fractions. Quadrupole mass spectrometry confirmed that the greatest proportion of m/z 44 (CO₂) and m/z 18 (H₂O) were detected at temperatures associated with recalcitrant carbon (510–540 °C). Isotope analysis detected progressive enrichment in δ¹³C for the sediment samples with an increase in marine influence. Isotopic heterogeneity in the refractory organic matter in marine sediments could be due to products of anthropogenic origin or natural combustion products. Isotope homogeneity of humic acids confirms the presence of terrigenous C in marine sediments, allowing the terrestrial input to be characterised.     

An electrochemical study of pyrite oxidation in the presence of carbon coatings in cyanide medium

The anodic and cathodic behaviour of pyrite with clay and different carbon coatings of activated carbon, graphite and carbonaceous matter in cyanide medium was investigated using the potentiodynamic method. The presence of clay coating did not change the polarisation curve appearance for either the anodic oxidation of pyrite or the cathodic reduction of oxygen or the potential of the current plateau, but only decreased the plateau current especially at a higher coating thickness. The presence of the carbon coatings marginally shifted the rest potential for pyrite to a more anodic position and slightly changed the polarisation curve appearance for pyrite oxidation. The current density for pyrite oxidation largely increased in the presence of the carbon coatings, the potential at the plateau shifted to more cathodic positions, and the plateau width became smaller. These effects became more noticeable at a higher coating thickness. The activated carbon, graphite and carbonaceous matter coatings performed similarly in affecting pyrite oxidation at a similar thickness. The carbon coatings significantly increased the limiting current densities for oxygen reduction on pyrite, and the limiting current plateau became steeper at a higher coating thickness. The carbon coatings increased the limiting current density for oxygen reduction to a similar extent at a low coating thickness, but increased to varied extents at a higher coating thickness. The carbon coatings also greatly increased the cathodic current density for gold reduction on pyrite. The enhancement of pyrite oxidation and oxygen or gold reduction on pyrite by the carbon coatings was likely attributed to the electrochemical interaction between pyrite and the carbon materials with electron-rich surfaces and high conductivity. The presence of the carbon coatings significantly increased the oxidation of pyrite in aerated cyanide solutions and the preg-robbing of pyrite especially at a higher coating thickness.     

Paleoproterozoic (2155–1970 Ma) evolution of the Guiana Shield (Transamazonian event) in the light of new paleomagnetic data from French Guiana

We present a comprehensive paleomagnetic study on Paleoproterozoic (2173–2060 Ma) plutonic and metamorphic rocks from French Guiana, representative of the full range of the main Transamazonian tectonothermal steps. Twenty-seven groups of directions and poles were obtained from combination of 102 sites (613 samples) based on age constraint, similar lithology and/or geographical proximity. Paleomagnetic results show variations between rocks of different ages which are supposed to be characteristic of magnetizations acquired during uplift and cooling of successive plutonic pulses and metamorphic phases. This is also reinforced by positive field tests (baked contact and reversal tests). Recent U/Pb and Pb/Pb on zircon and complementary ⁴⁰Ar/³⁹Ar on amphibole and biotite allow questioning the problem of magnetic ages relative to rock formation ages. Estimated magnetic ages, based on amphibole dating as a proxy, enable us to construct a Guiana Shield apparent polar wander path for the 2155–1970 Ma period. It is also possible to present paleolatidudinal evolution and continental drift rates related to specific Transamazonian tectonic regimes.French Guiana and probably the Guiana Shield were located at the Equator from ca. 2155 to 2130 Ma during the Meso-Rhyacian D1 magmatic accretion phase, related to subduction of Eorhyacian oceanic crust. After closure of the Eorhyacian Ocean and collision of West African and Amazonian plates, the Guiana Shield moved. The first evolution towards 60° latitude, occurs after 2080 Ma, during the Neorhyacian D2a post collisional sinistral transcurrent phase. During the Late Rhyacian D2b phase, up to 2050 Ma, the Guiana Shield reaches the pole and starts to move to lower latitudes on an opposite meridian. By the Orosirian D2c phase, from ca. 2050 to 1970 Ma, the Guiana Shield reaches the Equator.Based on the amphibole ⁴⁰Ar/³⁹Ar dates, we estimate the continental drift between 12 and 16 cm/y for the Meso to Late Rhyacian period followed by a lower rate between 9 and 14 cm/y up to Orosirian time. This study highlights rock ages and magnetic ages are prerequisite to any continental reconstruction especially when it is shown continental drift is important for a 100–200 Ma time period. Our results confirm the possibility of APWP construction on Paleoproterozoic plutonic rocks but suggest improvement will rely on the combination with multidisciplinary approaches such as structural geology and multi-method radiometric dating.     

Effects of enhanced zinc and copper in drinking water on spatial memory and fear conditioning

Ingestion of enhanced zinc can cause memory impairments and copper deficiencies. This study examined the effect of zinc supplementation, with and without copper, on two types of memory. Rats raised pre- and post-natally on 10 mg/kg ZnCO₃ or ZnSO₄ in the drinking water were tested in a fear-conditioning experiment at 11 months of age. Both zinc groups showed a maladaptive retention of fearful memories compared to controls raised on tap water. Rats raised on 10 mg/kg ZnCO₃, 10 mg/kg ZnCO₃ + 0.25 mg/kg CuCl₂, or tap water, were tested for spatial memory ability at 3 months of age. Significant improvements in performance were found in the ZnCO₃ + CuCl₂ group compared to the ZnCO₃ group, suggesting that some of the cognitive deficits associated with zinc supplementation may be remediated by addition of copper.     

A surface complexation model for cadmium and lead adsorption onto diatom surface

This work is devoted to the physico-chemical study of cadmium and lead interaction with diatom–water interfaces for two marine planktonic (Thalassiosira weissflogii = TW, Skeletonema costatum = SC) and two freshwater periphytic species (Achnanthidium minutissimum = AMIN, Navicula minima = NMIN) by combining adsorption measurements with surface complexation modeling. Reversible adsorption experiments were performed at 20 °C after 3 h of exposure as a function of pH, metal concentration in solution, and ionic strength. While the shape of pH-dependent adsorption edge is similar among all four diatom species, the constant-pH adsorption isotherm and maximal binding capacities differ. These observations allowed us to construct a surface complexation model for cadmium and lead binding by diatom surfaces that postulates the constant capacitance of the electric double layer and considers Cd and Pb complexation with mainly carboxylic and, partially, silanol groups. Parameters of this model are in agreement with previous acid–base titration results and allow quantitative reproduction of all adsorption experiments.     

Can stable isotopes be used to monitor landfill leachate impact on surface waters?

Bacterially mediated methanogenesis in municipal solid waste landfills has been shown to cause an enrichment of carbon stable isotope ratios of dissolved inorganic carbon and hydrogen stable isotope ratios of water in landfill leachate. In the present study, we investigate the universality of this enrichment in leachate obtained from four diverse landfill sites in New Zealand. At each site, surface water samples upstream and downstream of landfills were analysed to examine the applicability of stable isotope ratios as a tool for monitoring leachate contamination in landfill-associated streams. The design of leachate collection systems, operational history, and landfill location appeared to strongly influence leachate isotopic values and the effectiveness of isotope ratios as an environmental monitoring tool for surface water.     

Geochemical evolution of the Capim River kaolin, Northern Brazil

The Capim River kaolin, located in the eastern Brazilian Amazon, constitutes one of the most important kaolin deposits in the world. Known for its high whiteness, its noble application is in the paper industry. Studies were carried out on samples from the six facies of the deposit (sand kaolin, soft kaolin, lower transition facies, ferruginous crust, upper transition facies and flint kaolin) in order to trace its geochemical evolution. The kaolin developed at the expense of Cretaceous sandy–clayey sediments of the Ipixuna Formation. Intense lateritic processes characterized by ferruginization and deferruginization mechanisms led to the distinction of the different facies.     

Holocene record of productivity in the NW Iberian continental shelf

A multiproxy approach (textural characteristics, heavy metal concentrations and benthic foraminifera data) was adopted to study the OMEX core KSGX 40, collected at the Galicia Mud Deposit (NW Iberian outer continental shelf) and recording the last ca. 4.8 ka cal BP. Geochemical profiles of Fe, Mn, Zn, Co, Cr, Cu, Ni, Pb, Al and Ca show significant temporal variations. Benthic foraminifera productivity proxy suggests that the recorded muddy events were contemporaneous of a higher C_org flux to the marine benthic environment. The higher flux of organic matter, following a long-term intensification of the upwelling and coinciding with a finer sedimentation, led to depressed levels of oxygen beneath the water-sediments interface and to early diagenetic processes of several redox-sensitive elements.     

Platinum and palladium mobility in supergene environment: The residual origin of the Pirogues River mineralization, New Caledonia

Eluvial concentration of platinum-group minerals (PGM) has developed in the south of New Caledonia, from the weathering of a mafic and ultramafic cumulate. The platinum/palladium (Pt/Pd) ratio evolution from the bottom to the top of the weathering profile indicates a chemical mobilization of Pd in supergene environment. The examination by scanning electron microscopy of the residual PGM collected in the weathering profile and their chemical characterization by electronic microprobe show a preservation of the structure and chemical signature (in the core of the grains) of the fresh PGM. This clearly demonstrates that the PGM studied here are residual and are affected by dissolution process.     

Developments in the characterisation of waste materials for environmental impact assessment purposes

The characterisation of waste is entering a new phase with the latest developments of characterisation leaching tests and associated modelling capabilities. The currently applied too simple testing approaches lead to poor choices in waste management. With the increased insight in release controlling processes chemical speciation aspects can be addressed even in the most complex and heterogeneous waste materials. From a composition perspective materials may be highly variable, but often materials are far more consistent in their leaching behaviour. This aspect should be exploited more extensively as it holds the key to treat waste materials in such a way that long term solutions are achieved rather than reaching temporary gains.