J. Bouzid

Preparation of activated carbon from Tunisian olive-waste cakes and its application for adsorption of heavy metal ions

The present work explored the use of Tunisian olive-waste cakes, a by-product of the manufacture process of olive oil in mills, as a potential feedstock for the preparation of activated carbon. Chemical activation of this precursor, using phosphoric acid as dehydrating agent, was adopted. To optimize the preparation method, the effect of the main process parameters (such as acid concentration, impregnation ratio, temperature of pyrolysis step) on the performances of the obtained activated carbons (expressed in terms of iodine and methylene blue numbers and specific surface area) was studied. The optimal activated carbon was fully characterized considering its adsorption properties as well as its chemical structure and morphology. To enhance the adsorption capacity of this carbon for heavy metals, a modification of the chemical characteristics of the sorbent surface was performed, using KMnO(4) as oxidant. The efficiency of this treatment was evaluated considering the adsorption of Cu(2+) ions as a model for metallic species. Column adsorption tests showed the high capacity of the activated carbon to reduce KMnO(4) into insoluble manganese (IV) oxide (MnO(2)) which impregnated the sorbent surface. The results indicated also that copper uptake capacity was enhanced by a factor of up to 3 for the permanganate-treated activated carbon.

Heavy metal removal from aqueous solutions by activated phosphate rock.

The use of natural adsorbent such as phosphate rock to replace expensive imported synthetic adsorbent is particularly appropriate for developing countries such as Tunisia. In this study, the removal characteristics of lead, cadmium, copper and zinc ions from aqueous solution by activated phosphate rock were investigated under various operating variables like contact time, solution pH, initial metal concentration and temperature. The kinetic and the sorption process of these metal ions were compared for phosphate rock (PR) and activated phosphate rock (APR). To accomplish this objective we have: (a) characterized both (PR) and (APR) using different techniques (XRD, IR) and analyses (EDAX, BET-N(2)); and, (b) qualified and quantified the interaction of Pb(2+), Cd(2+), Cu(2+) and Zn(2+) with these sorbents through batch experiments. Initial uptake of these metal ions increases with time up to 1h for (PR) and 2h for (APR), after then, it reaches equilibrium. The maximum sorption obtained for (PR) and (APR) is between pH 2 and 3 for Pb(2+) and 4 and 6 for Cd(2+), Cu(2+) and Zn(2+). The effect of temperature has been carried out at 10, 20 and 40 degrees C. The data obtained from sorption isotherms of metal ions at different temperatures fit to linear form of Langmuir sorption equation. The heat of sorption (DeltaH degrees), free energy (DeltaG degrees) and change in entropy (DeltaS degrees) were calculated. They show that sorption of Pb(2+), Cd(2+), Cu(2+) and Zn(2+) on (PR) and (APR) an endothermic process. These findings are significant for future using of (APR) for the removal of heavy metal ions from wastewater under realistic competitive conditions in terms of initial heavy metals, concentrations and pH.

Adsorption of nickel and copper onto natural iron oxide-coated sand from aqueous solutions: study in single and binary systems.

Natural iron oxide-coated sand (NCS), extracted from the iron ore located in North-West of Tunisia, was employed to investigate its capacity to remove copper and nickel from aqueous solutions. The aim of this work was to characterize the considered sorbent (NCS) and to assess the possibility of removing nickel and copper from aqueous solutions by this sorbent. The effects of agitation time, pH, initial metal ion concentration and temperature on the removal of these metals were studied. In order to study the sorption isotherm, two equilibrium models, the Freundlich and Langmuir isotherms, were analyzed. The effect of solution pH on the adsorption onto NCS was studied in the pH range from 2 to 7 and 2 to 9 for copper and nickel respectively. The adsorption was endothermic and the computation of the parameters, DeltaH degrees, DeltaS degrees and DeltaG degrees, indicated that the interactions were thermodynamically favourable. Experiments with Cu and Ni adsorption measured together showed that Cu severely interfered with Ni adsorption to the NCS and vice versa under the conditions of the two coexisted ions adsorption.

Lead removal from aqueous solutions by a Tunisian smectitic clay.

The adsorption of Pb(2+) ions onto Tunisian smectite-rich clay in aqueous solution was studied in a batch system. Four samples of clay (AYD, AYDh, AYDs, AYDc) were used. The raw AYD clay was sampled in the Coniacian-Early Campanian of Jebel Aïdoudi in El Hamma area (South of Tunisia). AYDh and AYDs corresponds to AYD activated by 2.5 mol/l hydrochloric acid and 2.5 mol/l sulphuric acid, respectively. AYDc corresponds to AYD calcined at different temperatures (100, 200, 300, 400, 500 and 600 degrees C). The raw AYD clay was characterized by X-ray diffraction, chemical analysis, infrared spectroscopy and coupled DTA-TGA. Specific surface area of all the clay samples was determined from nitrogen adsorption isotherms. Preliminary adsorption tests showed that sulphuric acid and hydrochloric acid activation of raw AYD clay enhanced its adsorption capacity for Pb(2+) ions. However, the uptake of Pb(2+) by AYDs was very high compared to that by AYDh. This fact was attributed to the greater solubility of clay minerals in sulphuric acid compared to hydrochloric acid. Thermic activation of AYD clay reduced the Pb(2+) uptake as soon as calcination temperature reaches 200 degrees C. All these preliminary results were well correlated to the variation of the specific surface area of the clay samples. The ability of AYDs sample to remove Pb(2+) from aqueous solutions has been studied at different operating conditions: contact time, adsorbent amount, metal ion concentration and pH. Kinetic experiments showed that the sorption of lead ions on AYDs was very fast and the equilibrium was practically reached after only 20 min. The results revealed also that the adsorption of lead increases with an increase in the solution pH from 1 to 4.5 and then decreases, slightly between pH 4.5 and 6, and rapidly at pH 6.5 due to the precipitation of some Pb(2+) ions. The equilibrium data were analysed using Langmuir isotherm model. The maximum adsorption capacity (Q(0)) increased from 25 to 25.44 mg/g with increasing temperature from 25 to 40 degrees C. Comparative study between sulphuric acid activated clay (AYDs) and powder activated carbon (PAC) for the adsorption of lead was also conducted. The results showed that sulphuric acid activated clay is more efficient than PAC.

Adsorption of a textile dye "Indanthrene Blue RS (C.I. Vat Blue 4)" from aqueous solutions onto smectite-rich clayey rock.

The adsorption of a textile dye, namely, Indanthrene Blue RS (C.I. Vat Blue 4) onto smectite-rich clayey rock (AYD) and its sulphuric acid-activated products (AYDS) in aqueous solution was studied in a batch system with respect to contact time, pH, and temperature. The adsorbents employed were characterized by X-ray diffraction, infrared spectroscopy and specific surface area, cation exchange capacity and point of zero charge were also estimated. The effect of contact time on dye adsorption showed that the equilibrium was reached after a contact time of 40 min for the both adsorbents. The optimum pH for dye retention was found 6.0 for AYDS and 7.3 for AYD. The equilibrium adsorption data were analysed using the Langmuir and Freundlich isotherms. The adsorption capacities (Q(m)) for AYD and AYDS were found 13.92 mg/g and 17.85 mg/g, respectively. The effect of temperature on the adsorption was also investigated; adsorption of Indanthrene Blue RS is an endothermic process. This study demonstrates that all the considered adsorbents can be used as an alternative emerging technology for water treatment.

Impact of orthophosphate addition on biofilm development in drinking water distribution systems.

The contamination of the water distribution network results from fixed bacteria multiplication (biofilm) on the water pipe walls, followed by their detachment and their transport in the circulating liquid. The presence of biofilms in distribution networks can result in numerous unwanted problems for the user such as microbial contamination of the distributed water and deterioration of the network (bio-corrosion). For old networks, lead-containing plumbings can be a serious cause of worry for the consumer owing to the release of lead ions in the circulating water. Among the solutions considered to reduce the presence of lead in drinking water, the addition of orthophosphates constitutes an interesting alternative. However, the added orthophosphate may cause--even at low doses--additional microbial growth. The main objective of this study was to evaluate the impact of the orthophosphate treatment on the biofilm development in the water supplied by the Joinville-le-Pont water treatment plant (Eau de Paris, France). For this purpose, a laboratory pilot plant was devised and connected to the considered water network. Two quantification methods for monitoring the biofilm formation were used: the enumeration on R2A agar and the determination of proteins. For the biofilm detachment operation, an optimization of the rinsing step was firstly conducted in order to distinguish between free and fixed biomass. The data obtained showed that there was a linear relation between both quantification methods. They also showed that, for the tested water, the bacterial densities were not affected by orthophosphate addition at a treatment rate of 1mg PO(4)(3-)/L.

Retention of nickel from aqueous solutions using iron oxide and manganese oxide coated sand: kinetic and thermodynamic studies

In this study, the removal of nickel ions from aqueous solutions using iron oxide and manganese oxide coated sand (ICS and MCS) under different experimental conditions was investigated. The effect of metal concentration, contact time, solution pH and temperature on the amount of Ni(II) sorbed was studied and discussed. Langmuir and Freundlich isotherm constants and correlation coefficients for the present systems at different temperatures were calculated and compared. The equilibrium process was well described by the Langmuir isotherm model: the maximum sorption capacities (at 29 K) were 2.73 mg Ni/g and 3.33 mg Ni/g of sorbent for ICS and MCS, respectively. Isotherms were also used to evaluate the thermodynamic parameters (ΔG°, ΔH°, ΔS°) of adsorption. The sorption kinetics were tested for the pseudo‐first‐order, pseudo‐second‐order and intra‐particle diffusion models. Good correlation coefficients were obtained for the pseudo‐second‐order kinetic model, showing that the nickel uptake process followed the pseudo‐second‐order rate expression.

Removal of nickel and cadmium from aqueous solutions by sewage sludge ash: Study in single and binary systems

Sewage sludge ash can potentially be used for the removal of metal ions from wastewater because its chemical composition is similar to that of fly ash. The aim of this work was to investigate the adsorptive characteristics of this material, including specific surface area and pH of zero point of charge (pHzpc), and to assess the possibility of removing nickel and cadmium from aqueous solutions by this sorbent. The effects of agitation time, pH, initial metal ion concentration and temperature on the removal of these metals were studied. In order to study the sorption isotherm, two equilibrium models, the Langmuir and Freundlich isotherms, were analysed. The effect of solution pH on the adsorption on to sewage sludge ash was studied in the pH range from 2 to 8. The adsorption was endothermic and the computation of the parameters, ΔH°, ΔS° and ΔG°, indicated that the interactions were thermodynamically favourable. Experiments with Ni and Cd adsorption measured together showed that Cd severely interfered with Ni adsorption to sewage sludge ash and vice versa.

Efficacy of olive mill waste water and its derivatives in the suppression of crown gall disease of bitter almond

Olive mill waste water (OMW) and some of its indigenous bacterial strains were tested in vitro and in planta for their efficacy against crown gall disease caused by Agrobacterium tumefaciens. OMW and polyphenols displayed a high level of antibacterial activity, however the volatile fraction was less efficient as only a bacteriostatic effect was observed. In pot experiments, the percentage of bitter almond rootstock showing symptoms of crown gall was significantly reduced with the dosage rate of OMW 1% as compared to the control (highly natural infected soil treated with water). Five indigenous bacterial strains isolated from OMW exhibited an antagonistic effect against the bacterium. Based on the gene 16S rRNA sequence analysis, one isolate showed 99.2% similarity to known sequences of Bacillus subtilis, one isolate demonstrated high percentage similarities (99.3%) to the genera Bacillus pumilis, and two isolates were associated with Stenotrophomonas maltophilia and Pseudomonas putida 100% and 99.6% similarities respectively. Among these bacteria, the strain B1 proved efficient against the soil borne pathogen in vitro and pot experiments. Our study in controlled conditions suggested that the addition of OMW to soil exerts significant disease suppressiveness against A. tumefaciens.

Batch sorption of Pb(II) ions from aqueous solutions using activated carbon prepared from date stones: equilibrium, kinetic, and thermodynamic studies

AbstractThe sorption of Pb(II) ions onto activated carbon prepared from Tunisian date stones was studied in a batch process. The effects of the main parameters, such as contact time, initial concentration of Pb(II), solution pH, and temperature were studied. The kinetic data were analyzed by applying pseudo-first-order, pseudo-second-order, and Weber-Morris diffusion models. The applicability of Langmuir and Freundlich adsorption isotherms was evaluated to better understand the adsorption process. The results revealed that the equilibrium data were perfectly represented using a Langmuir isotherm. The maximum monolayer adsorption capacity was found to be 38.46 mg/g at 20°C, pH 6, contact time 120 min, and 0.5 g activated carbon. The kinetic data followed closely the pseudo-second-order model. The application of an intraparticle diffusion model revealed that the adsorption mechanism of Pb(II) is a rather complex process and that diffusion is involved in the overall rate of the adsorption process, but it is ...