Claire Gérente

Application of Chitosan for the Removal of Metals From Wastewaters by Adsorption—Mechanisms and Models Review

Chitin is the worlds second most abundant naturally occurring polysaccharide. Much of this is disposed of as waste from seafood crustacean, mainly in shrimps, prawns, crabs, and lobsters, where it occurs as a significant component in the shells/exoskeletons of crustacea. Due to its widespread abundance, its chemical and physical versatility, and the problems of its disposal as a waste material, a wide range of value-added applications of chitin and chitosan is being initiated, investigated, and developed. The widely ranging value-added applications of chitin and chitosan are presented in this review. Chitin and its derivative, chitosan, both highly stable and difficult to degrade materials, can be obtained as 10–20% w/w from the waste seafood shells by suitable chemical processing. One of the significant developments in the new range of applications is the study of the ability of chitosan, as a potentially major environmental treatment material, to remove metal ions from wastewaters. Chitosan is the deacetylated form of chitin, and this process produces a chain of amino groups along the chitosan structure. Many researchers are now looking at the ability of this amino group to adsorb metal ions from industrial wastewaters and leachates. This review presents the developments in this area and identifies the defficiences in existing chitosan research by reviewing the equilibrium studies carried out to determine the capacity of chitosan for various metal ions. Then the kinetic studies are reviewed, as well as the solution methodologies adopted by various researchers to explain and model the rate of adsorption of the metal ions from solution. Both equilibrium knowledge and kinetic knowledge are required in order to design commercial treatment systems.

Phosphate removal from synthetic and real wastewater using steel slags produced in Europe

Electric arc furnace steel slags (EAF-slags) and basic oxygen furnace steel slags (BOF-slags) were used to remove phosphate from synthetic solutions and real wastewater. The main objective of this study was to establish an overview of the phosphate removal capacities of steel slags produced in Europe. The influences of parameters, including pH, and initial phosphate and calcium concentrations, on phosphate removal were studied in a series of batch experiments. Phosphate removal mechanisms were also investigated via an in-depth study. The maximum capacities of phosphate removal from synthetic solutions ranged from 0.13 to 0.28 mg P/g using EAF-slags and from 1.14 to 2.49 mg P/g using BOF-slags. Phosphate removal occurred predominantly via the precipitation of Ca-phosphate complexes (most probably hydroxyapatite) according to two consecutive reactive phases: first, dissolution of CaO-slag produced an increase in Ca(2+) and OH(-) ion concentrations; then the Ca(2+) and OH(-) ions reacted with the phosphates to form hydroxyapatite. It was found that the release of Ca(2+) from slag was not always enough to enable hydroxyapatite precipitation. However, our results indicated that the Ca(2+) content of wastewater represented a further source of Ca(2+) ions that were available for hydroxyapatite precipitation, thus leading to an increase in phosphate removal efficiencies.

Removal of metal ions from aqueous solution on low cost natural polysaccharides - Sorption mechanism approach

Abstract The fixation of Cu2+, Ni2+ and Pb2+ on sugar beet pulp, a low-cost material, has been studied. After a simple treatment of the sorbent, the results have shown that the mode of fixation depends on the metal. The key part of the mode of fixation is attributed to ion exchange, while a non-negligible part of adsorption could sometimes occur. As far as lead ions are concerned, 25% of their fixation capacities are due to adsorption mechanism at pH 4. The overall uptake is at a maximum at pH 6 and gives up to 60 mg g−1 for Pb2+, 30 mg g−1 for Cu2+ and 12 mg g−1 for Ni2+, which seems to be removed exclusively by ion exchange. These capacities increase with the pH. Diffusion models have been tested on samples of different particle size, and they have suggested a transfer to the intraparticular sites.

Cadmium and lead adsorption by a natural polysaccharide in MF membrane reactor: experimental analysis and modelling

In the present work, Pb(2+) and Cd(2+) adsorption onto a natural polysaccharide has been studied in membrane reactors. The process involves a stirred semi-batch reactor for the adsorption step and a microfiltration (MF) process in order to confine the particles. Due to their lower affinity for the biosorbent, Cd(2+) ions were found to breakthrough the process faster than Pb(2+) cations. The experimental results showed the technical feasibility of the pilot. A mass balance model based on the Langmuir equilibrium isotherm was used to describe the adsorption process. This relation is able to predict experimental data under different operating conditions: the adsorbent and metal concentrations, and the permeate flow rate. Based on these results, it is demonstrated that the biosorbent studied represents an interesting low-cost solution for the treatment of metal ions polluted waters.

Biosorption of Cu(II) from aqueous solution by Fucus serratus: surface characterization and sorption mechanisms.

In this work, the brown alga Fucus serratus (FS) used as a low cost sorbent has been studied for the biosorption of copper(II) ions in batch reactors. Firstly, the characterization of the surface functional groups was performed with two methods: a qualitatively analysis with the study of FT-IR spectrum and a quantitatively determination with potentiometric titrations. From this latter, a total proton exchange capacity of 3.15 mmolg(-1) was extrapolated from the FS previously protonated. This value was similar to the total acidity of 3.56 mmolg(-1) deduced from the Gran method. Using the single extrapolation method, three kinds of acidic functional groups with three intrinsic pK(a) were determined at 3.5, 8.2 and 9.6. The point of zero net proton charge (PZNPC) was found close to pH 6.3. Secondly, the biosorption of copper ions was studied. The equilibrium time was about 350 min and the adsorption equilibrium data were well described by the Langmuirs equation. The maximum adsorption capacity has been extrapolated to 1.60 mmolg(-1). The release of calcium and magnesium ions was also measured in relation to the copper biosorption. Finally, the efficiency of this biosorbent in natural tap water for the removal of copper was also investigated. All these observations indicate that the copper biosorption on FS is mainly based on ion exchange mechanism and this biomass could be then a suitable sorbent for the removal of heavy metals from wastewaters.

Potential of Aquatic Macrophytes as Bioindicators of Heavy Metal Pollution in Urban Stormwater Runoff

The concentrations of heavy metals in water, sediments, soil, roots, and shoots of five aquatic macrophytes species (Oenanthe sp., Juncus sp., Typha sp., Callitriche sp.1, and Callitriche sp.2) collected from a detention pond receiving stormwater runoff coming from a highway were measured to ascertain whether plants organs are characterized by differential accumulations and to evaluate the potential of the plant species as bioindicators of heavy metal pollution in urban stormwater runoff. Heavy metals considered for water and sediment analysis were Cd, Cr, Cu, Ni, Pb, Zn, and As. Heavy metals considered for plant and soil analysis were Cd, Ni, and Zn. The metal concentrations in water, sediments, plants, and corresponding soil showed that the studied site is contaminated by heavy metals, probably due to the road traffic. Results also showed that plant roots had higher metal content than aboveground tissues. The floating plants displayed higher metal accumulation than the three other rooted plants. Heavy metal concentrations measured in the organs of the rooted plants increased when metal concentrations measured in the soil increased. The highest metal bioconcentration factors (BCF) were obtained for cadmium and nickel accumulation by Typha sp. (BCF = 1.3 and 0.8, respectively) and zinc accumulation by Juncus sp. (BCF = 4.8). Our results underline the potential use of such plant species for heavy metal biomonitoring in water, sediments, and soil.

Natural seaweed waste as sorbent for heavy metal removal from solution

Biosorption is a suitable heavy metal remediation technique for the treatment of aqueous effluents of large volume and low pollutant concentration. However, today industrial applications need the selection of efficient low‐cost biosorbents. The aim of this work is to investigate brown alga such as Fucus serratus (FS) as a low‐cost biosorbent, for the fixation of metallic ions, namely Cu2+, Zn2+, Pb2+, Ni2+, Cd2+ and Ce3+, in a batch reactor. Biosorption kinetics and isotherms have been performed at pH 5.5. For all of the studied metallic ions, the equilibrium time is about 450 min and a tendency based on the initial sorption rate has been established: Ce3+ > Zn2+ > Ni2+ > Cu2+ > Cd2+ > Pb2+. The adsorption equilibrium data are well described by the Langmuir equation. The sequence of the maximum adsorption capacity is Pb2+ ≈ Cu2+ ≫ Ce3+ ≈ Ni2+ > Cd2+ > Zn2+ and values are ranged between 1.78 and 0.71 mmol g−1. These results indicate that the FS biomass is a suitable biosorbent for the removal of heavy metals from wastewater and can be tested in a dynamic process. The selected pilot process involves a hybrid membrane process: a continuous stirred tank reactor is coupled with a microfiltration immersed membrane, in order to confine the FS particles. A mass balance model is used to describe the adsorption process and the breakthrough curves are correctly modelled. Based on these results, it is demonstrated that FS is an interesting biomaterial for the treatment of water contaminated heavy metals.

Mechanisms of Cr(III) and Cr(VI) removal from aqueous solutions by sugar beet pulp

Abstract The removal of three‐ and hexavalent chromium from aqueous solutions using sugar beet pulp as biosorbent substrate was performed. The kinetics of Cr(III) and Cr(VI) removal were studied at 20.0 ± 0.5 °C and under various experimental conditions. The Cr(III) ions were adsorbed onto the biosorbent by ion‐exchange mechanism with Ca2+ cations. The influence of solution pH was found to greatly affect the adsorption efficiency of Cr(VI). Cr(VI) removal was largely involved in a reduction mechanism with the appearance of Cn(III) ions in the solution.

Application of sludge-based carbonaceous materials in a hybrid water treatment process based on adsorption and catalytic wet air oxidation

This paper describes a preliminary evaluation of the performance of carbonaceous materials prepared from sewage sludges (SBCMs) in a hybrid water treatment process based on adsorption and catalytic wet air oxidation; phenol was used as the model pollutant. Three different sewage sludges were treated by either carbonisation or steam activation, and the physico-chemical properties of the resultant carbonaceous materials (e.g. hardness, BET surface area, ash and elemental content, surface chemistry) were evaluated and compared with a commercial reference activated carbon (PICA F22). The adsorption capacity for phenol of the SBCMs was greater than suggested by their BET surface area, but less than F22; a steam activated, dewatered raw sludge (SA_DRAW) had the greatest adsorption capacity of the SBCMs in the investigated range of concentrations (<0.05 mol L(-1)). In batch oxidation tests, the SBCMs demonstrated catalytic behaviour arising from their substrate adsorptivity and metal content. Recycling of SA_DRAW in successive oxidations led to significant structural attrition and a hardened SA_DRAW was evaluated, but found to be unsatisfactory during the oxidation step. In a combined adsorption-oxidation sequence, both the PICA carbon and a selected SBCM showed deterioration in phenol adsorption after oxidative regeneration, but a steady state performance was reached after 2 or 3 cycles.

Engineered Biofilms for Metal Ion Removal

Firstly, biofilm and biosorbents are defined. Mechanisms of interactions between metal ions and biofilm are discussed in terms of diffusion, mass transfer and sorption. In a second step, different processes using biofilm to remove heavy metal in aqueous solutions are presented. The continuously stirred processes are described for metal ion removal in wastewater by biofilm coating particles. In this case, the equilibrium data obtained with isotherm curves show a good adsorption of several metal ions onto biofilm. Examples of adsorption capacities for a large number of microorganisms and heavy metal ions are presented. The fixed bed reactors packed with grains coated with a biofilm are efficient to get a sorption (adsorption or ion exchange) of cations. The pressure drop is calculated with classical equations. Some values such as adsorption capacities and breakthrough times are got from the breakthrough curves. Several models (Adams-Bohart, mass transfer, and homogeneous surface diffusion models) are applied to get design data. A new approach using neural network to model breakthrough curves is proposed and discussed.