Adsorption of Organic Dyes on Magnetic Iron Oxide Nanoparticles. Part I: Mechanisms and Adsorption-Induced Nanoparticle Agglomeration.

This series of two papers is devoted to the effect of organic dye (methylene blue, MB; or methyl orange, MO) adsorption on the surface of either bare or citrate-coated magnetic iron oxide nanoparticles (IONPs) on their primary agglomeration (in the absence of an applied magnetic field) and secondary field-induced agglomeration. The present paper (Part I) is focused on physicochemical mechanisms of dye adsorption and adsorption-induced primary agglomeration of IONPs. Dye adsorption to oppositely charged IONPs is found to be mostly promoted by electrostatic interactions and is very sensitive to pH and ionic strength variations. The shape of adsorption isotherms is correctly reproduced by the Langmuir law. For the particular MB/citrated IONP pair, the maximum surface density of adsorbed MB seems to correspond to the packing density of an adsorbed monolayer rather than to the surface density of the available adsorption sites. MB is shown to form H-aggregates on the surface of citrate-coated IONPs. The effective electric charge on the IONP surface remains nearly constant in a broad range of surface coverages by MB due to the combined action of counterion exchange and counterion condensation. Primary agglomeration of IONPs (revealed by an exponential increase of hydrodynamic size with surface coverage by MB) probably comes from correlation attractions or π-stacking aromatic interactions between adsorbed MB molecules or H-aggregates. From the application perspective, the maximum adsorption capacity is 139 ± 4 mg/g for the MB/citrated IONP pair (pH = 4-11) and 257 ± 16 mg/g for the MO/bare IONP pair (pH ∼ 4). Citrated IONPs have shown a good potential for their reusability in water treatment, with the adsorption efficiency remaining about 99% after nine adsorption/desorption cycles.

A review on the potential uses of red mud as amendment for pollution control in environmental media.

Red mud is a solid waste of bauxite processing by Bayer process which involves caustic digestion of Al-containing mineral for alumina production. The global inventory of red mud waste reached an estimated amount of 4 billion tons in 2015, increasing at an approximate rate of 120 million tons per year. Therefore, its management is becoming a global environmental issue for the protection of environment, and the need for awareness in this regard is becoming crucial. Although red mud is not considered as a hazardous material in many countries, its high alkalinity and fine particle size may pose significant environmental threat, and it is found to be an interesting material for environmental remediation purposes due to rich iron content. This paper provides a review of possible remedial applications of red mud in various environmental compartments. Modification of red mud creates novel opportunities for cost-effective and efficient removal of metal ions, inorganic anions, dyes, and phenols from wastewater and acid mine drainage. Re-vegetation of red mud disposal sites, treatment of metal-contaminated acidic soils presents the usefulness of this material but less research has been done so far to investigate its use in the stabilization of polluted sediments. On the other hand, leaching and eco-toxicological tests have also revealed that red mud does not pose high toxicity to the environment making it suitable for the treatment of contaminated media. Nevertheless, neutralization of red mud is recommended for its safe disposal and secure application in any environmental media.

Functionalized and grafted TiO2, CeO2, and SiO2 nanoparticles-ecotoxicity on Daphnia magna and relevance of ecofriendly polymeric networks.

Effects of functionalization and grafting of TiO2, CeO2, and SiO2 nanoparticles (NPs) were investigated, and toxicity of pristine, functionalized, and grafted NP towards Daphnia magna was measured. Surface functionalization of NP with amine groups decreased hydrophobicity of NP. When NPs were hydrophilic, they were less toxic than hydrophobic NP towards D. magna. Grafting agents influenced toxicity: no toxicity of NP was observed when bio-based and hydrogenated synthetic polymers were used, whereas perfluorinated polymers induced a higher toxicity.

Capping of marine sediments with valuable industrial by-products: Evaluation of inorganic pollutants immobilization.

In-situ capping of polluted sediment is considered as an inexpensive and effective treatment technology to immobilize contaminants in a short time. In this remediation technique sediments are capped by placing a layer of sand, clean sediment or other materials over sediments in order to mitigate risk. In this study, low cost industrial by products (bauxaline, steel slag, and mixture of the two products) were applied as capping agents. A bench scale laboratory experiment in aquariums was performed to evaluate their effects on Cd, Zn, As, and Cr mobility from an artificially contaminated marine sediment. Without capping, all the contaminants are constantly released with various kinetic depending of mineral oxidation or dissolution or leaching. Nevertheless, release did not exceed 31% of the initial amount of pollutant. Capping sediment with steel slag, bauxaline and their mixture totally captured Cd, Zn, and As. In the case of Cr, only steel slag actively blocked its release. A kinetic model was developed to model As and Cr release, with and without capping. The release times for Cr and As from the sediment were close to 6 days. In the presence of capping agents, the capture time for Cr was found to be 57 days for steel slag, and 7 days for bauxaline. Despite a high capture time, steel slag was the best capping agent since bauxaline matrix was a source of Cr and rapidly released it (release time = 1 day). The results indicated that steel slag and its mixture additive can be used as potential capping materials for the remediation of contaminated sites due to their significant entrapping of Cd, Zn, As, and Cr.

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.

Adsorption of nickel ions by oleate-modified magnetic iron oxide nanoparticles.

In this work, magnetic nanoparticles of iron oxide (MNPs) were synthesized, and then the surface was recovered with an oleate double layer in order to investigate the ability of this material to adsorb nickel ions. First, the solution chemistry of oleate ions was investigated in order to determine the critical micellar concentration (CMC) value and the arrangements of ions above the CMC. Then, the synthesized oleate-modified MNP was characterized (TEM, DLS, XRD, FTIR, zeta potential, magnetometry). Finally, adsorption experiments were carried out as a function of pH and as a function of nickel concentration in 0.1 g L-1 suspensions of oleate-modified MNP. The results show that CMC of oleate ranges from 1 to 2.5∙10-3 mol L-1. Above CMC, arrangement of oleate ions as droplets, vesicles, or micelles depends on pH and influences the average size and solution absorbance. Potentiometric titrations allowed determining a pKa value of 7.8 for sodium oleate. The high stability in aqueous suspensions and characterization of oleate-modified MNP confirm that oleate ions are arranged as a bilayer coating at the surface of MNP. Retention of nickel was found to be highly dependent on pH, with a maximum adsorption (90%) beginning from pH = 7.5. The sorption isotherms were well fitted with the Langmuir model and the maximum nickel adsorption capacities were found to be 44 and 80 mg g-1 for pH = 6.8 and 7.2, respectively. The efficient removal of nickel combined with the magnetic properties of the NMP make the oleate-modified MNP an interesting water purification tool.

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.

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.

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.

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.

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.

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.

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.

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.