Sediment-bound trace metals in Golfe-Juan Bay, northwestern Mediterranean: Distribution, availability and toxicity.

The concentration, potential mobility, cation exchange capacity and toxicity of eight sediment-bound metals in Golfe-Juan Bay, France were examined. Results revealed significant spatial gradient of metal contamination along Golfe-Juan coast. The distribution and concentration of the metals appear to be influenced by the geochemical properties of the sediment, proximity to anthropogenic sources and general water circulation in the bay. The portion of trace metals found in the exchangeable, carbonate, oxidizable and reducible fractions of the sediment constitute 31%-58% of the total sediment-bound trace metal content, suggesting significant potential for remobilization of metals into the water column. Pb and Ni content of the sediment exceed the limits of the French marine sediment quality. Whole sediment extracts showed acute toxicity to marine rotifers. This study concludes that monitoring and management of sediment-bound trace metals in Golfe-Juan Bay are important so as not to underestimate their availability and risk to the marine ecosystems.

Use of neutralized industrial residue to stabilize trace elements (Cu, Cd, Zn, As, Mo, and Cr) in marine dredged sediment from South-East of France.

Management of marine dredged sediments polluted with trace elements is prime issue in the French Mediterranean coast. The polluted sediments possess ecological threats to surrounding environment on land disposal. Therefore, stabilization of contaminants in multi-contaminated marine dredged sediment is a promising technique. Present study aimed to assess the effect of gypsum neutralized bauxaline(®) (bauxite residue) to decrease the availability of pollutants and inherent toxicity of marine dredged sediment. Bauxaline(®), (alumia industry waste) contains high content of iron oxide but its high alkalinity makes it not suitable for the stabilization of all trace elements from multi-contaminated dredged sediments. In this study, neutralized bauxaline(®) was prepared by mixing bauxaline(®) with 5% of plaster. Experiments were carried out for 3 months to study the effect of 5% and 20% amendment rate on the availability of Cu, Cd, Zn, As, Mo, and Cr. Trace elements concentration, pH, EC and dissolved organic carbon were measured in all leachates. Toxicity of leachates was assessed against marine rotifers Brachionus plicatilis. The Results showed that both treatments have immobilization capacity against different pollutants. Significant stabilization of contaminants (Cu, Cd, Zn) was achieved with 20% application rate whereas As, Mo, and Cr were slightly stabilized. Toxicity results revealed that leachates collected from treated sediment were less toxic than the control sediment. These results suggest that application of neutralized bauxaline(®) to dredged sediment is an effective approach to manage large quantities of dredged sediments as well as bauxite residue itself.

Ex-situ evaluation of bauxite residues as amendment for trace elements stabilization in dredged sediment from Mediterranean Sea: A case study.

Stabilization of marine dredged sediments contaminated with multi-elements is a challenging task in choosing the appropriate sorbent and application dosage. The present study investigates the possibility of using bauxite residues (Bauxaline® and Bauxsol) as amendment for the treatment of contaminated sediment. A pilot scale experiment was conducted for three months to stabilize trace elements in composted contaminated sediment sample using 5% by-product amendment. The results showed that after 3months of treatment, cationic trace elements were effectively immobilized but increased leaching of anionic pollutants was observed. Increased leaching of anionic pollutants could be limited by addition of higher quantities of amendments. The total content of available pollutants decreased in stabilized sediments but this treatment has no effect on the classification of waste. The leachates were then evaluated for acute toxicity using estuarine rotifers Brachionus plicatilis. Bauxite residues can be inexpensive choices for the stabilization of cationic pollutants in dredged sediments.

Direct injection method for HPLC/MS/MS analysis of acrylamide in aqueous solutions: application to adsorption experiments.

Polyacrylamides are polymers used in many fields and represent the main source of release of the highly toxic acrylamide in the environment. In this work, a simple, rapid, and sensitive analytical method was developed with HPLC/MS/MS and direct injection for acrylamide analysis in water and adsorption samples. AFNOR standards NF T90-210 and NF T90-220 were used for the analytical method validation and uncertainty estimation. Limit of quantification (LOQ) for acrylamide was 1 µg/L, and accuracy was checked at three acrylamide levels (1, 6, and 10 µg/L). Uncertainties were estimated at 34.2, 22, and 12.4 % for acrylamide concentrations at LOQ, 6 µg/L, and 10 µg/L, respectively. Acrylamide adsorption on clays (kaolinite, illite) and sludge was then studied as a function of pH, time, and acrylamide concentrations. Acrylamide adsorption on kaolinite, illite, and sludge was found to be very weak since adsorption percentages were inferior to 10 %, whatever the pH value and the initial acrylamide concentration. The low affinity of acrylamide for clays and sludge is likely due to its hydrophilic property, small size, and charge neutrality.

Comparison of mineral-based amendments for ex-situ stabilization of trace elements (As, Cd, Cu, Mo, Ni, Zn) in marine dredged sediments: a pilot-scale experiment.

Trace element pollution of marine dredged sediments is an emerging problem all over the world. Comparing to other wastes, trace elements stabilization is more difficult both due to the wide range of contaminants present in the marine sediments and their inherent physicochemical properties. In this study, a pilot-scale experiment was performed to stabilize As, Cd, Cu, Mo, Ni, and Zn in a multi-contaminated sediment sample using hematite, zero-valent iron and zeolite. Results showed that iron-based amendments were able to reduce the leaching and the bioavailability of trace elements in the sediment sample, while zeolite was unsuitable. Chemical stabilization through iron-based amendments seems to be a promising approach as a low-cost alternative to traditional stabilization methods involving chemical reagents.

Toxicity assessment of silica nanoparticles, functionalised silica nanoparticles, and HASE-grafted silica nanoparticles.

Numerous nanomaterials have recently been developed, and numerous practical applications have been found in water treatment, medicine, cosmetics, and engineering. Associative polymers, such as hydrophobically modified alkali-soluble emulsion (HASE) systems are involved in several applications and have been extensively studied due to their ability to form three-dimensional networked gels. However, the data on the potential environmental effects of this polymers are scarce. The aim of this study is to assess the effect of functionalisation of silica nanoparticles, and coupling of functionalised silica nanoparticles to the associative polymer HASE on their toxicity. Thus, acute and chronic toxicity tests included a modified acute test (72 h) using daphnies, algae, and plants as model organisms. Gradient of toxicity varied with the tested organisms. Our results revealed that the functionalised nanoparticules and NP grafted polymer cause a global decrease in toxicity compared to commercial nanoparticule and HASE polymer.

Batch and column studies of the stabilization of toxic heavy metals in dredged marine sediments by hematite after bioremediation.

The management of dredged sediments is an important issue in coastal regions where the marine sediments are highly polluted by metals and organic pollutants. In this paper, mineral-based amendments (hematite, zero-valent iron and zeolite) were used to stabilize metallic pollutants (As, Cd, Cu, Mo, Ni, Pb, and Zn) in a contaminated marine sediment sample. Mineral-based amendments were tested at three application rates (5 %, 10 %, and 15 %) in batch experiments in order to select the best amendment to perform column experiments. Batch tests have shown that hematite was the most efficient amendment to stabilize inorganic pollutants (As, Cd, Cu, Mo, Ni, Pb, and Zn) in the studied sediment. Based on batch tests, hematite was used at one application rate equal to 5 % to conduct column experiments. Column tests confirmed that hematite was able to decrease metal concentrations in leachates from stabilized sediment. The stabilization rates were particularly high for Cd (67 %), Mo (80 %), and Pb (90 %). The Microtox solid phase test showed that hematite could decrease significantly the toxicity of stabilized sediment. Based on batch and column experiments, it emerged that hematite could be a suitable adsorbent to stabilize metals in dredged marine sediment.

Toxicity of TiO(2) nanoparticles to cladocerans, algae, rotifers and plants - effects of size and crystalline structure.

With the rapid development of nanotechnology, there is an increasing risk of human and environmental exposure to nanotechnology-based materials. However, the data on the potential environmental effects of nanoparticles are scarce. The aim of this study is to assess the effect of particle size and crystal structure (anatase and rutile) of titanium dioxide on their toxicity. Thus, acute and chronic toxicity tests included a modified acute test (72 h) using daphnies and algae, rotifers and plants as model organisms. Gradient of toxicity varied with the tested biological organisms. Our results revealed that TiO(2) nanoparticles in anatase crystal structure are toxic in the entire set of tests conducted. However, at highconcentration, through their antimicrobial properties, they significantly promoted growth of roots. Because of its lipophilicity, the rutile crystalline structure of TiO(2) NPs form larger aggregates in aqueous medium; then they have less effect on biological organisms, and thus a lower toxicity than the anatase crystalline form of TiO(2). We also demonstrated that exposure duration, aggregation and concentrations are contributing factors in nanoparticles-mediated toxicity.

Arsenic in marine sediments from French Mediterranean ports: geochemical partitioning, bioavailability and ecotoxicology.

This work investigates arsenic mobility, bioavailability and toxicity in marine port sediments using chemical sequential extraction and laboratory toxicity tests. Sediment samples were collected from two different Mediterranean ports, one highly polluted with arsenic and other inorganic and organic pollutants (Estaque port (EST)), and the other one, less polluted, with a low arsenic content (Saint Mandrier port (SM)). Arsenic distribution in the solid phase was studied using a sequential extraction procedure specifically developed for appraising arsenic mobility in sediments. Toxicity assessment was performed on sediment elutriates, solid phases and aqueous arsenic species as single substance using the embryo-toxicity test on oyster larvae (Crassostrea gigas) and the Microtox test with Vibrio fischeri. Toxicity results showed that all sediment samples presented acute and sub-chronic toxic effects on oyster larvae and bacteria, respectively. The Microtox solid phase test allow to discriminate As-contaminated samples from the less contaminated ones, suggesting that toxicity of whole sediment samples is related to arsenic content. Toxicity of dissolved arsenic species as single substance showed that Vibrio fischeri and oyster larvae are most sensitive to As(V) than As(III). The distribution coefficient (Kd) of arsenic in sediment samples was estimated using results obtained in chemical sequential extractions. The Kd value is greater in SM (450 Lkg(-1)) than in EST (55 Lkg(-1)), indicating that arsenic availability is higher for the most toxic sediment sample (Estaque port). This study demonstrates that arsenic speciation play an important role on arsenic mobility and its bioavailability in marine port sediments.

Effect of temperature on the sorption of europium on alumina: microcalorimetry and batch experiments.

The determination of enthalpies of reactions (aqueous and surface complexation) is used in this work to model the temperature effect on the adsorption processes. Microcalorimetry experiments were carried out to determine the enthalpy of adsorption of europium on γ-alumina at 25 °C. The stability constants at 50 °C were then calculated with the van't Hoff equation, and a 2-pK approach was used to model the adsorptive behavior of Eu on alumina at 50 °C, as a function of pH. The results have shown that the adsorption of Eu(3+) on the alumina surface is weakly endothermic. In the experimental conditions considered in the present study, the temperature has only a small effect on the adsorption reaction.

Ex situ remediation of contaminated sediments using mineral additives: assessment of pollutant bioavailability with the Microtox solid phase test.

The aim of this work is to assess the potential ecotoxicological effects of contaminated sediments treated with mineral additives. The Microtox solid phase test was used to evaluate the effect of mineral additives on the toxicity of sediment suspensions. Four Mediterranean port sediments were studied after dredging and bioremediation: Sample A from navy harbor, sample B from commercial port and samples C and D from pleasure ports. Sediment samples were stabilized with three mineral additives: hematite, zero-valent iron and zeolite. Results show that all studied mineral additives can act as stabilizer agent in highly contaminated sediments (A and C) by decreasing dissolved metal concentrations and sediment toxicity level. On the contrary, for the less contaminated samples (B and D) hematite and zeolite can provoke toxic effect towards Vibrio fischeri since additive particles can favor bacteria retention and decrease bioluminescence emission.

Influence of uranium on bacterial communities: a comparison of natural uranium-rich soils with controls.

This study investigated the influence of uranium on the indigenous bacterial community structure in natural soils with high uranium content. Radioactive soil samples exhibiting 0.26% - 25.5% U in mass were analyzed and compared with nearby control soils containing trace uranium. EXAFS and XRD analyses of soils revealed the presence of U(VI) and uranium-phosphate mineral phases, identified as sabugalite and meta-autunite. A comparative analysis of bacterial community fingerprints using denaturing gradient gel electrophoresis (DGGE) revealed the presence of a complex population in both control and uranium-rich samples. However, bacterial communities inhabiting uraniferous soils exhibited specific fingerprints that were remarkably stable over time, in contrast to populations from nearby control samples. Representatives of Acidobacteria, Proteobacteria, and seven others phyla were detected in DGGE bands specific to uraniferous samples. In particular, sequences related to iron-reducing bacteria such as Geobacter and Geothrix were identified concomitantly with iron-oxidizing species such as Gallionella and Sideroxydans. All together, our results demonstrate that uranium exerts a permanent high pressure on soil bacterial communities and suggest the existence of a uranium redox cycle mediated by bacteria in the soil.

The toxicity of composted sediments from Mediterranean ports evaluated by several bioassays.

This work investigates the ecotoxicological evaluation of contaminated dredged sediments from French Mediterranean navy harbour (A), commercial port (B) and two composite specimens (C) and (D) coming from the mixture of A and B with other port sediments. The toxicity of elutriates from these sediments is estimated using embryo-toxicity test, Microtox® solid phase test, LuminoTox, phytotoxicity tests and genotoxicity test. Bioassay responses are not clearly correlated with chemical contamination in the whole sediment and vary as a function of tested organisms. The highest contaminated samples (A and C) are almost always more toxic than the less contaminated samples (B and D). Among composite sediments, the mixture effect with other sediments is not efficient to decrease toxicity in sample C, suggesting that other parameters influence toxicity level such as particle size or organic matter content. These parameters should be taken into consideration in order to improve the efficiency of the mixture process and produce composite sediments with low toxicity.

Ecotoxicological evaluation of Mediterranean dredged sediment ports based on elutriates with oyster embryotoxicity tests after composting process.

The ecotoxicological effect of dredged sediments was estimated by embryo-larval toxicity of the oyster Crassosstrea gigas in sediment elutriates (filtered and unfiltered). The study covers the main ports from the French Mediterranean coast. Composted sediments from a navy harbour (A), a commercial port (B) and two composite specimens (C and D) obtained after mixing various sediments were taken into consideration. Effective concentrations affecting 50% of larvae (EC50) were obtained from different elutriate concentrations (from 0 to 100%). Toxicity results obtained from filtered elutriates decreased according to the following gradient: sample A (5.68%), B (20.50%), C (37.60%) and D (47.17%). Chemical concentrations in whole sediments were in agreement with those in elutriates. Among the measured contaminants in elutriates, Cu and Zn resulted as the main contributors to toxicity. Dissolved organic carbon played an important role by exerting a protective effect against the toxicity of dissolved Cu. Toxicity results were interpreted on the basis of toxicity scores to give indication about sediment quality which provided more severe judgement than risk score based on chemical concentrations in sediments.

Sorption of Cr(VI) onto natural iron and aluminum (oxy)hydroxides: effects of pH, ionic strength and initial concentration.

The aim of this work is to study the performances of removal of hexavalent chromium from aqueous solution by three different oxy-hydroxides: hematite, goethite and alpha-alumina. Batch experiments were conducted to measure the effects on adsorption of Cr(VI) of different parameters such as pH of the medium, ionic strength, and initial concentration. Results showed that the adsorption of Cr(VI) depends strongly on the pH, but is independent of ionic strength for hematite and goethite. For alpha-alumina, adsorption is strongly dependent on pH values and ionic strength. Equilibrium studies showed that Cr(VI) had a high affinity in an acidic medium, but decreased as solution pH increased. Equilibrium isotherms were measured experimentally. Results were analyzed by the Langmuir and Freundlich equations using linearized correlation coefficient at room temperature. The characteristic parameters for each isotherm have been determined. Langmuir equation was found to fit the equilibrium data for Cr(VI) adsorption.

Acid-base properties of the alumina surface: influence of the titration procedures on the microcalorimetric results.

The enthalpy changes associated with the protonation and deprotonation of an alumina surface have been determined on the basis of microcalorimetry experiments and acid-base potentiometric titrations at 25 degrees C. It has been shown that the results may vary significantly according to the experimental procedure. In order to do so, the potentiometric and microcalorimetric titrations have been carried out first from an acidic pH to basic pH and second from a pH near the pH(zpc) of alumina to acidic or basic pH. It has been demonstrated that the pK(a) values deduced from the potentiometric titrations are the same whatever the experimental protocol whereas the only way to obtain meaningful enthalpies of proton exchange is to carry out microcalorimetric titrations by starting around the point of zero charge.

Competition between selenium (IV) and silicic acid on the hematite surface.

Competition between selenium (IV) and silicic acid for the hematite (alpha-Fe(2)O(3)) surface has been studied during this work. Single batch experiments have been performed to study separately the sorption of selenium (IV) and silicic acid as a function of the pH. With the help of the 2-pK surface complexation model, experimental data have been fitted using the FITEQL 4.0 program. Two monodentate inner-sphere surface complexes have been used to fit selenite ions retention, triple bond FeSeO(3)(-) and triple bond FeHSeO(3). In order to fit sorption of silicic acid, the two following surface complexes, namely triple bond FeH(3)SiO(4), and triple bond FeH(2)SiO(4)(-), have been used. Using the surface complexation constants coming from these two binary systems, prediction curves of the effect of silicic acid on the retention of selenium (IV) onto hematite have been obtained. Finally, performed experiments showed a competition between selenium (IV) and silicic acid for the surface sites of hematite. Experimental data matched DDLM predictions, confirming the ability of the surface complexation model to predict quantitatively and qualitatively the ternary system selenium (IV)/H(4)SiO(4)/hematite.

Sorption of selenium(IV) onto magnetite in the presence of silicic acid.

Sorption of selenium(IV) and silicic acid onto magnetite (Fe(3)O(4)) was investigated in binary systems, with concentrations of silicic acid under the solubility limit of amorphous silica. Using the double diffuse layer model (DDLM), surface complexation constants of selenium(IV) and H(4)SiO(4) onto magnetite were extracted using Fiteql 4.0. Then, prediction curves of the sorption of selenium(IV) in the presence of silicic acid onto magnetite were obtained, using the calculated surface complexation constants. Finally, laboratory experiments were performed and showed a competition between selenium(IV) and silicic acid for the surface sites of magnetite. Experimental results matched the model predictions, confirming its ability to model qualitatively and quantitatively the ternary system.

Sorption of silicates on goethite, hematite, and magnetite: experiments and modelling.

Sorption of H(4)SiO(4) (including experiments as a function of time, K(d) measurement with different m/v ratios and sorption edges) onto different iron (hydro)oxides as goethite (alpha-FeOOH), hematite (alpha-Fe(2)O(3)), and magnetite (Fe(3)O(4)) has been studied with concentration of silicates under solubility limit. A surface complexation model has been used to account for sorption edge of silicates onto these iron oxide surfaces. It reveals that two types of surface complex namely FeH(3)SiO(4) and FeH(2)SiO(4)(-), are needed to describe properly the experimental observations.

Effect of temperature on the acid-base properties of the alumina surface: microcalorimetry and acid-base titration experiments.

Sorption reactions on natural or synthetic materials that can attenuate the migration of pollutants in the geosphere could be affected by temperature variations. Nevertheless, most of the theoretical models describing sorption reactions are at 25 degrees C. To check these models at different temperatures, experimental data such as the enthalpies of sorption are thus required. Highly sensitive microcalorimeters can now be used to determine the heat effects accompanying the sorption of radionuclides on oxide-water interfaces, but enthalpies of sorption cannot be extracted from microcalorimetric data without a clear knowledge of the thermodynamics of protonation and deprotonation of the oxide surface. However, the values reported in the literature show large discrepancies and one must conclude that, amazingly, this fundamental problem of proton binding is not yet resolved. We have thus undertaken to measure by titration microcalorimetry the heat effects accompanying proton exchange at the alumina-water interface at 25 degrees C. Based on (i) the surface sites speciation provided by a surface complexation model (built from acid-base titrations at 25 degrees C) and (ii) results of the microcalorimetric experiments, calculations have been made to extract the enthalpic variations associated respectively to first and second deprotonation of the alumina surface. Values obtained are deltaH1 = 80+/-10 kJ mol(-1) and deltaH2 = 5+/-3 kJ mol(-1). In a second step, these enthalpy values were used to calculate the alumina surface acidity constants at 50 degrees C via the van't Hoff equation. Then a theoretical titration curve at 50 degrees C was calculated and compared to the experimental alumina surface titration curve. Good agreement between the predicted acid-base titration curve and the experimental one was observed.