The use of microelectrodes with AGNES

Absence of gradients and nernstian equilibrium stripping (AGNES) is a new electroanalytical technique designed to determine free heavy metal ion concentrations in solutions. AGNES had been applied, up to date, with conventional equipment such as the hanging mercury drop electrode (HMDE). Due to their much smaller volume, microelectrodes can reach a given preconcentration factor within a much shorter deposition time, so their use for AGNES has been evaluated in this work. For the particular case of the mercury microelectrode deposited onto an Ir disk (radius around 5 lm), AGNES has been successfully used for speciation purposes in the system Pb + PDCA (pyridinedicarboxylic acid). However, due to a relatively large capacitive current, which decays slowly, the limit of quantification for such microelectrodes has only been reduced by one half with respect to that of the HMDE

Computing steady-state metal flux at microorganism and bioanalogical sensor interfaces in multiligand systems. A reaction layer approximation and its comparison with the rigorous solution

In complicated environmental or biological systems, the fluxes of chemical species at a consuming interface, like an organism or an analytical sensor, involve many coupled chemical and diffusion processes. Computation of such fluxes thus becomes difficult. The present paper describes an approximate approach, based on the so-called reaction layer concept, which enables one to obtain a simple analytical solution for the steady-state flux of a metal ion at a consuming interface, in the presence of many ligands, which are in excess with respect to the test metal ion. This model can be used for an unlimited number of ligands and complexes, without limit for the values of the association/dissociation rate constants or diffusion coefficients. This approximate solution is compared with a rigorous approach for the computation of the fluxes based on an extension of a previously published method (J. Galceran, J. Puy, J. Salvador, J. Cecília, F. Mas and J. L. Garcés, Phys. Chem. Chem. Phys., 2003, 5, 50915100). The comparison is performed for a very wide range of the key parameters: rate constants and diffusion coefficients, equilibrium constants and ligand concentrations. Their combined influence is studied in the whole domain of fully labile to non-labile complexes, via two combination parameters: the lability index, L, and the reaction layer thickness, μ. The results show that the approximate solution provides accurate results in most cases. However, for particular combinations of metal complexes with specific values of L or μ, significant differences between the approximate and rigorous solutions may occur. They are evaluated and discussed. These results are important for three reasons: (i) they enable the use of the approximate solution in a fully reliable manner, (ii) when present, the differences between approximate and rigorous solution are largely due to the coupling of chemical reactions, whose importance can thus be estimated, (iii) due to its simple mathematical expression, the individual contribution of each metal species to the overall flux can be computed

Sorption and fractionation of dissolved organic matter and associated phosphorus in agricultural soil

Molibility of dissolved organic matter (DOM) strongly affects the export of nitrogen (N) and phosphorus (P) from oils to surface waters. To study the sorption an mobility of dissolved organic C and P (DOC, DOP) in soil, the pH-dependent sorption of DOM to samples from Ap, EB, and Bt horizons from a Danish agircultural Humic Hapludult was investigated and a kinetic model applicable in field-scale model tested. Sorption experiments of 1 to 72 h duration were conducted at two pH levels (pH 5.0 and 7.0) and six initial DOC concentrtions (0-4.7 mmol L-1). Most sorption/desorption occurred during the first few hours. Dissolved organic carbon and DOP sorption decreased strongly with increased pH and desorption dominated at pH 7, especially for DOC. Due to fractionation during DOM sorption/desorption at DOC concentrations up to 2 mmol L-1, the solution fraction of DOM was enriched in P indicating preferred leaching of DOP. The kinetics of sorption was expressed as a function of how far the solution DOC or DOP concentrations deviate from "equilibrium". The model was able to simulate the kinetics of DOC and DOP sorption/desorption at all concentrations investigated and at both pH levels making it useful for incorporation in field-scale models for quantifying DOC and DOP dynamics

Metal speciation dynamics in colloidal ligand dispersions. Part 3: Lability features of steady-state systems

A lability criterion is developed for dynamic metal binding by colloidal ligands with convective diffusion as the dominant mode of mass transport. Scanned stripping chronopotentiometric measurements of Pb(II) and Cd(II) binding by carboxylated latex core-shell particles were in good agreement with the predicted values. The dynamic features of metal ion binding by these particles illustrate that the conventional approach of assuming a smeared-out homogeneous ligand distribution overestimates the lability of a colloidal ligand system. Due to the nature of the spatial distribution of the binding sites, the change in lability of a metal species with changing ligand concentration depends on whether the ligand concentration is varied via manipulation of the pH (degree of protonation) or via the particle concentration. In the former case the local ligand density varies, whereas in the latter case it is constant. This feature provides a useful diagnostic tool for the presence of geometrically constrained binding sites

Rates of carbonate cementation associated with sulphate reduction in DSDP/ODP sediments: implications for the formation of concretions

DSDP/ODP porewater profiles in organic carbon-bearing (<5% org. C) sediments commonly show decreases in Ca2+ concentrations and increases in alkalinity over depths where sulphate is being removed by microbial reduction. These Ca2+ depletion profiles represent the combined effect of diffusion, advection and reaction (addition by ion exchange and removal by precipitation mainly as CaCO3 and/or dolomite). A diagenetic model has been used to estimate the rate constant (k) for Ca2+ removal by precipitation during sulphate depletion over depths of 15-150 m, assuming first order kinetics. The rate constants for Ca2+ removal range from 10(-14) to 10(-11) s(-1) in 19 DSDP/ODP sediments, which span a range of bottom water temperatures (0-10 degreesC), lithologies (calcareous to clastic) and sedimentation rates (0.001-0.4 cm year(-1)). Values of k correlate with sedimentation rate (omega) such that log k=1.16 log omega-10.3, indicating that faster rates of Ca2+ removal occur at higher sedimentation rates where there are also higher degrees of saturation with respect to CaCO3 and dolomite. Depth-integrated masses of Ca2+ removed (<100 mumol cm(-2)) during sulphate depletion over these depth ranges are equivalent to a dispersed phase of approximately 1.5 wt.% CaCO3 or 3 wt.% dolomite in a compacted sediment. The complete occlusion of sediment porosity observed in concretions with isotopic signatures suggesting carbonate sourced from sulphate reduction therefore requires more time (a depositional hiatus), more rapid sulphate reduction (possibly by anaerobic methane oxidation) and/or the continued transport of isotopically light carbonate to the concretion site after sulphate reduction has ceased

Determination of Geochemical Bio-Signatures in Mars-Like Basaltic Environments

Bio-signatures play a central role in determining whether life existed on early Mars. Using a terrestrial basalt as a compositional analog for the martian surface, we applied a combination of experimental microbiology and thermochemical modeling techniques to identify potential geochemical bio-signatures for life on early Mars. Laboratory experiments were used to determine the short-term effects of biota on the dissolution of terrestrial basalt, and the formation of secondary alteration minerals. The chemoorganoheterotrophic bacterium, Burkholderia sp. strain B_33, was grown in a minimal growth medium with and without terrestrial basalt as the sole nutrient source. No growth was detected in the absence of the basalt. In the presence of basalt, during exponential growth, the pH decreased rapidly from pH 7.0 to 3.6 and then gradually increased to a steady-state of equilibrium of between 6.8 and 7.1. Microbial growth coincided with an increase in key elements in the growth medium (Si, K, Ca, Mg, and Fe). Experimental results were compared with theoretical thermochemical modeling to predict growth of secondary alteration minerals, which can be used as bio-signatures, over a geological timescale. We thermochemically modeled the dissolution of the basalt (in the absence of biota) in very dilute brine at 25°C, 1 bar; the pH was buffered by the mineral dissolution and precipitation reactions. Preliminary results suggested that at the water to rock ratio of 1 × 107, zeolite, hematite, chlorite, kaolinite, and apatite formed abiotically. The biotic weathering processes were modeled by varying the pH conditions within the model to adjust for biologic influence. The results suggested that, for a basaltic system, the microbially-mediated dissolution of basalt would result in “simpler” secondary alteration, consisting of Fe-hydroxide and kaolinite, under conditions where the abiotic system would also form chlorite. The results from this study demonstrate that, by using laboratory-based experiments and thermochemical modeling, it is possible to identify secondary alteration minerals that could potentially be used to distinguish between abiotic and biotic weathering processes on early Mars. This work will contribute to the interpretation of data from past, present, and future life detection missions to Mars

Biophysical Environmental Chemistry: A New Frontier for Chemistry

The paper discusses the position and role of environmental chemistry among the other environmental disciplines. It discusses the various aspects of environmental chemistry and emphasizes the need for developing fundamental studies in biophysical environmental chemistry in order to better understand the functioning of environmental systems. These systems include a large number of various structures in the nanometer to meter range which play key roles on compound fluxes and consequently on the homeostasis of ecosystems and on their disturbance by anthropogenic activities. Both structures and fluxes are presently ill-known and new concepts and methods must be developed in this field. For chemistry, this is a challenging area where supramolecular structures and processes play dominant roles. It is also a challenging field for the development of environmental sciences since detailed and sound physico-chemical processes are needed in macroscopic modeling of compound circulation in ecosystems. In addition, teaching this discipline to chemistry students would allow them to confront complex, structured real systems. This paper also discusses the relationship between biophysical environmental chemistry and the other environmental disciplines within integrated multidisciplinary studies. The structure used at the Faculty of Sciences of the University of Geneva to favour a flexible but efficient integration is briefly described

Changes in LA volume and diameter correlate with mechanisms of recurrence after paroxysmal AF ablation.

Papathanasiou et al point out that the two different methods of LA volume and diameter measurement in our recent publication could limit the significance of the correlations we reported with PV reconnection and non-PV foci as mechanisms of post AF ablation recurrence. While we acknowledge the lack of statistically significant correlations of smaller echo derived LA diameter with PV reconnection or of a larger angiographic LA volume with non-PV foci, the congruent confidence intervals of this correlation suggest a statistical trend. Non-uniform LA dimensional changes as an expression of structural remodelling may also be a possible explanation. Published data indicates that angiographic LA volumes consistently exhibit a positive bias compared to echocardiographic volumes but do provide intra-procedural measurements better correlating with gold standard techniques like CT or MRI. Finally we agree with Papathanasiou et al that dynamic changes in LA dimensions likely correlate with early and late mechanisms of recurrence and merit prospective studies

Electrochemical methods for speciation of trace elements in marine waters. Dynamic aspects

The contribution of electrochemical methods to the knowledge of dynamic speciation of toxic trace elements in marine waters is critically reviewed. Due to the importance of dynamic considerations in the interpretation of the electrochemical signal, the principles and recent developments of kinetic features in the interconversion of metal complex species will be presented. As dynamic electrochemical methods, only stripping techniques (anodic stripping voltammetry and stripping chronopotentiometry) will be used because they are the most important for the determination of trace elements. Competitive ligand ex- change-adsorptive cathodic stripping voltammetry, which should be considered an equilibrium technique rather than a dynamic method, will be also discussed because the complexing parameters may be affected by some kinetic limitations if equilibrium before analysis is not attained and/or the flux of the adsorbed complex is in fluenced by the lability of the natural complexes in the water sample. For a correct data interpretation and system characterization the comparison of results obtained from different techniques seems essential in the articulation of a serious discussion of their meaning