Cadmium and lead interaction with diatom surfaces: A combined thermodynamic and kinetic approach

International audienceThis 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. Adsorption kinetics was studied as a function of pH and initial metal concentration in sodium nitrate solution and in culture media. Kinetic data were consistent with a two-step mechanism in which the loss of a water molecule from the inner coordination sphere of the metal is rate limiting. Reversible adsorption experiments, with 3 h of exposure to metal, were performed as a function of pH (2 9), metal concentration in solution (10?9 10?3 M), and ionic strength (10?3 1.0 M). 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. Measurements of electrophoretic mobilities (?) revealed negative surface potential for AMIN diatom, however, the absolute value of ? decreases with increase of [Pb2+]aq suggesting the metal adsorption on negative surface sites. These observations allowed us to construct a surface complexation model (SCM) 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. In the full range of investigated Cd concentration, the SCM is able to describe the concentration of adsorbed metal as a function of [Cd2+]aq without implying the presence of high affinity, low abundance sites, that are typically used to model the metal interactions with natural multi-component organic substances. At the same time, Cd fast initial reaction requires the presence of ?highly reactive sites? those concentration represents only 2.5 3% of the total amount of carboxylic sites. For reversible adsorption experiments, the dominating carboxylic groups, whose concentration is allowed to vary within the uncertainty of experimental acid base titrations, are sufficient to reproduce the metal adsorption isotherms. Results of this study strongly suggest that laboratory experiments performed in a wide range of metal to biomass ratios, represent robust and relatively simple method for assessing the distribution of metals between aqueous solution and planktonic and periphytic biomass in natural settings

Speciation of Zn Associated with Diatoms Using X-ray Absorption Spectroscopy

International audienceThe long- and short-term interactions between zinc, an essential but also toxic element, and freshwater and marine diatoms are not well understood partly because of a lack of information on Zn speciation on the surface and inside the cells. In this work, interactions of aqueous Zn super(2+) with marine (Skeletonema costatum) and freshwater (Achnanthidium minutissimum, Navicula minima, and Melosira varians) diatoms were studied using conventional macroscopic techniques, while the local atomic structure of metal ions adsorbed on their surface or incorporated into the cells was characterized by in-situ Zn K-edge X-ray absorption fine structure (XAFS) spectroscopy on both intact and liophylized samples. At the cell surface for all diatom species studied, Zn was tetrahedrally coordinated with oxygen at similar to 2.00 plus or minus 0.02 Ae and monodentately bonded to one or two carboxylate groups; these results are consistent with the surface speciation model developed from macroscopic adsorption experiments. The atomic environment of Zn incorporated into freshwater diatoms during long-term growth in normal nutrient media was distinctly different from that of adsorbed Zn: it was dominated by O (and/or N) neighbors in a tetrahedral arrangement at 1.97 plus or minus 0.02 Ae in the first atomic shell, with the presence of 1 phosphorus and 2 carbons in the Zn second shell. Contrasting speciation of intracellular zinc was revealed for the marine species Skeletonema costatum in which Zn was coordinated to 2 O/N atoms and 2 sulfur groups in the form of cysteine-histidine complexes and/or zinc thiolate clusters. These new structural data strongly suggest: (i) the predominant >R-COO super(-) ligand binding of Zn at the diatom surface; (ii) the nonspecific storage of Zn in the form of carboxylate/phosphate groups inside the cell of freshwater species; and (iii) the highly specific thiol- ligand coordination of intracellular zinc for marine S. costatum species

Interaction between zinc and freshwater and marine diatom species: Surface complexation and Zn isotope fractionation

International audienceThis work is devoted to characterization of zinc interaction in aqueous solution with two marine planktonic (Thalassiosira weissflogii = TW, Skeletonema costatum = SC) and two freshwater periphytic species (Achnanthidium minutissimum = AMIN, Navicula minima = NMIN) by combining adsorption and electrophoretic measurements with surface complexation modeling and by assessing Zn isotopes fractionation during both long term uptake and short term adsorption on diatom cells and their frustules. Reversible adsorption experiments were performed at 25 and 5 °C as a function of exposure time (5 min to 140 h), pH (2 to 10), zinc concentration in solution (10 nM to 1 mM), ionic strength (I = 0.001 to 1.0 M) and the presence of light. While the shape of pH-dependent adsorption edge is almost the same for all four species, the constant-pH adsorption isotherm and maximal Zn binding capacities differ by an order of magnitude. The extent of adsorption increases with temperature from 5 to 25 °C and does not depend on light intensity. Zinc adsorption decreases with increase of ionic strength suggesting competition with sodium for surface sites. Cell number-normalized concentrations of sorbed zinc on whole cells and their silica frustules demonstrated only weak contribution of the latter (10 20%) to overall zinc binding by diatom cell wall. Measurements of electrophoretic mobilities (?) revealed negative diatoms surface potential in the full range of zinc concentrations investigated (0.15 760 ?mol/L), however, the absolute value of ? decreases at [Zn] > 15 ?mol/L suggesting a change in surface speciation. These observations allowed us to construct a surface complexation model for Zn binding by diatom surfaces that postulates the constant capacitance of the electric double layer and considers Zn complexation with carboxylate and silanol groups. Thermodynamic and structural parameters of this model are based on previous acid base titration and spectroscopic results and allow quantitative reproduction of all adsorption experiments. Although Zn adsorption constants on carboxylate groups are almost the same, Zn surface adsorption capacities are very different among diatom species which is related to the systematic differences in their cell wall composition and thickness. Measurements of Zn isotopic composition (66Zn/(64Zn)) performed using a multicollector ICP MS demonstrated that irreversible incorporation of Zn in cultured diatom cells produces enrichment in heavy isotope compared to growth media (?66Zn(solid solution) = 0.27 ± 0.05, 0.08 ± 0.05, 0.21 ± 0.05, and 0.19 ± 0.05? for TW, SC, NMIN, and AMIN species, respectively). Accordingly, an enrichment of cells in heavy isotopes (?66Zn(solid solution) = 0.43 ± 0.1 and 0.27 ± 0.1? for NMIN and AMIN, respectively) is observed following short-term Zn sorption on freshwater cells in nutrient media at pH ? 7.8. Finally, diatoms frustules are enriched in heavy isotopes compared to solution during Zn adsorption on silica shells at pH ? 5.5 (?66Zn(solid solution) = 0.35 ± 0.10?). Measured isotopes fractionation can be related to the structure and stability of Zn complexes formed and they provide a firm basis for using Zn isotopes for biogeochemical tracing

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

International audienceThis 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

An Isotopic Exchange Kinetic Model to Assess the Speciation of Metal Available Pool in Soil: The Case of Nickel

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Study of diatoms/aqueous solution interface. I. Acid-base equilibria and spectroscopic observation of freshwater and marine species

International audienceThis work reports on a concerted study of diatom-water interfaces for two marine planktonic ( Thalassiosira weissflogii= TW, Skeletonema costatum= SC) and two freshwater periphytic species ( Achnanthidium minutissimum= AMIN, Navicula minima= NMIN). Proton surface adsorption was measured at 25°C, pH of 3 to 11 and ionic strength of 0.001 to 1.0 M via potentiometric titration using a limited residence time reactor. Electrophoretic mobility of living cells and their frustules was measured as a function of pH and ionic strength. Information on the chemical composition and molecular structure of diatoms surfaces was obtained using FT-IR (in situ attenuated total reflectance) and X-ray Photoelectron Spectroscopy (XPS). The surface area of living cells and their frustules in aqueous solutions was quantified using Small Angle X-ray Scattering Spectroscopy (SAXS). These observations allowed us to identify the nature and to determine the concentration of the major surface functional groups (carboxyl, amine and silanol) responsible for the amphoteric behavior of cell surfaces in aqueous solutions. Taking into account the relative proportion of surface sites inferred from XPS and FT-IR measurements, a surface complexation model of diatom-solution interfaces was generated on the basis of surface titration results. The cell-normalized ratios of the three major surface sites {>COOH}: {>NH 3}: {>SiOH} are 1:1:0.1, 1:10:0, 1:1:0.4 and 1:1:0.3 for TW, SC, AMIN and NMIN, respectively. The total amount of proton/hydroxyl active surface sites for investigated species ranges from 1 (NMIN) to 9 (SC) mmol/g dry weight. Normalization of these site densities to the area of siliceous skeleton yields values between 0.3 (NMIN) and 0.9 mmol/m 2 (SC) which are an order of magnitude higher than corresponding values for organic-free frustules or amorphous silica. This suggests that the amphoteric properties and possibly the affinity for metal adsorption of diatom cultures are essentially controlled by the 3-D organic layers covering the silica frustule

Evidence of Zn isotopic fractionation in a soil-plant system of a pristine tropical watershed (Nsimi, Cameroon)

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Study of Ni exchangeable pool speciation in ultramafic and mining environments with isotopic exchange kinetic data and models.

International audienceSoils and ore samples influenced by mining and metallurgical activity were collected in ultramafic soils (UM) complexes of Barro Alto and Niquelândia, in order to determine the contribution of each Ni bearing phases to the total exchangeable pool of Ni, and to point out if this pool was affected by anthropic activities. For this purpose, the IEK-model previously developed by the group (Zelano et al., submitted) was applied, on the basis of IEK experiments performed on pure typical Ni scavengers (serpentines, chlorite, smectite and iron oxydes) from ultramafic systems. For each typical scavenger, this model describes the percentage of Ni associated to exchangeable pool(s) as well as their corresponding kinetic constant(s) of exchange. The mineralogical composition of soil and ore samples and Ni solid speciation were first determined, and the IEK-model was applied on these bases. In almost all samples, an important contribution of serpentine to Ni exchangeable pool was highlighted, ranging between 10% and 45%. The important amount of organic matter (OM) in one of the studied soil samples, allowed to extrapolate generic OM ENi and k parameters, which were introduced in the IEK-model to improve its predictive capability. Obtained results provided evidences of how even a small content (3 wt%) of organic carbon (OC), can represent an important contribution of OM to the total ENi pool (60%). In the investigated ore samples, up to the 60% of ENi was attribute to smectite, responsible for fast ENi pool kinetic evolution. In addition, the model highlighted the role of the Fine Black Ash (FBA), by-products of the pyrometallurgical activity, detected into a soil sample, that is responsible for the 15% of ENi. This approach allowed to determine, for the first time, the relative contribution of each Ni bearing phase to the total exchangeable pool, in terms of concentration and kinetics

Colloids and suspended particulate matters influence on Ni availability in surface waters of impacted ultramafic systems in Brazil

International audienceThe overall objective of this work was to assess the modification of Ni availability and lability consequently to anthropic activity. Surface waters were collected in two ultramafic complexes (Barro Alto and Niquelandia) from Goias State (Brazil) impacted by mining and metallurgical activities. For the nearly first time, Isotopic Exchange Kinetic technique (IEK) was performed on these natural water samples to quantify the pool of isotopically exchangeable Ni from the suspended particulate matter (SPM) in water, defined here as E-Ni(W). The SPM mineralogy was investigated by X-Ray Diffraction (XRD), Scanning and Transmission Electron Microscopy (SEM and TEM). This allowed to establish the link between Ni availability and its solid speciation. Goethite, chlorite, talc and serpentine were identified as the main Ni bearing phases in SPM far from metallurgy (Barro Alto site) while in samples located in the area influenced by metallurgy (Niquelandia) Ni was mainly associated to spherical micrometric particles, related to fly ash produced by the ore combustion. In Niquelandia samples 4,1, value was found ranging between 2.4 and 565 mu g L-1, while in Barro Alto E-Ni(W) was 62 mu g L-1, which corresponds to E-Ni values of 49,000 and 2350 mg kg(-1), in SPM from Niquelandia and Barro Alto, respectively. Moreover, IEK experiments highlighted differences in kinetic of Ni exchanges: the maximum E-Ni(W) value was reached after only 19 hours of interaction in Barro Alto sample, while in Niquelandia ones E-Ni(W) hardly reached 70 to 95% of the maximum after the same period of time. On the one hand, both the low proportion and high velocity of Ni exchanges observed in Barro Alto sample may be attributed to surface complexation on talc, serpentine, chlorite and goethite. On the other hand, both the higher proportion of exchangeable stock and slower isotopic exchanges should be mostly attributed in Niquelandia samples to Ni interaction with the anthropogenic spherical and porous particles of Fe-Mg-Si-Al composition, related to FBA released by metallurgic activity