M.A. Martín-Lara

Study of Cr (III) biosorption in a fixed-bed column

This research analyzes the potential use of the olive stone as a low-cost biosorbent for Cr (III) from aqueous solutions in a continuous system. First, experiments were carried out in fixed-bed column to test the influence of various parameters on breakthrough and saturation time. The breakthrough and saturation time increase with the decrease of the flow rate. The same effect is shown when the bed depth is increased. The olive stone sorption capacity, q(e), increases as the inlet Cr (III) concentration increases until a value close to 0.800 mg/g is reached, then q(e) remains constant. Column data obtained at different conditions were described using the Adams-Bohart, Thomas, Yoon and Nelson, and Dose-Response models. The breakthrough curve prediction by the Adams-Bohart and Dose-Response models were found to be very satisfactory. In particular, the Adams-Bohart model can be used to represent the initial region of breakthrough curve, whereas the Dose-Response model is the one which best reproduces the whole curve for all the inlet Cr (III) concentrations used. Finally, a study of pH evolution was carried out. The pH increases at the beginning, subsequently decreasing as time passes until practically reaching the initial value.

Chemical treatment of olive pomace : Effect on acid-basic properties and metal biosorption capacity

In this study, olive pomace, an agricultural waste that is very abundant in Mediterranean area, was modified by two chemical treatments in order to improve its biosorption capacity. Potentiometric titrations and IR analyses were used to characterise untreated olive pomace (OP), olive pomace treated by phosphoric acid (PAOP) and treated by hydrogen peroxide (HPOP). Acid-base properties of all investigated biosorbents were characterised by two main kinds of active sites, whose nature and concentration were determined by a mechanistic model assuming continuous distribution for the proton affinity constants. Titration modelling denoted that all investigated biosorbents (OP, PAOP and HPOP) were characterised by the same kinds of active sites (carboxylic and phenolic), but with different total concentrations with PAOP richer than OP and HPOP. Single metal equilibrium studies in batch reactors were carried out to determine the capacity of these sorbents for copper and cadmium ions at constant pH. Experimental data were analysed and compared using the Langmuir isotherm. The order of maximum uptake capacity of copper and cadmium ions on different biosorbents was PAOP>HPOP>OP. The maximum adsorption capacity of copper and cadmium, was obtained as 0.48 and 0.10 mmol/g, respectively, for PAOP. Metal biosorption tests in presence of Na(+) in solution were also carried out in order to evaluate the effect of chemical treatment on biomass selectivity. These data showed that PAOP is more selective for cadmium than the other sorbents, while similar selectivity was observed for copper.

Biosorption kinetics of Cd (II), Cr (III) and Pb (II) in aqueous solutions by olive stone.

A by-product from olive oil production, olive stone, was investigated for the removal of Cd (II), Cr (III) and Pb (II) from aqueous solutions. The kinetics of biosorption are studied, analyzing the effect of the initial concentration of metal and temperature. Pseudo-first-order, pseudo-second-order, Elovich and intraparticle diffusion models have been used to represent the kinetics of the process and obtain the main kinetic parameters. The results show that the pseudo-second order model is the one that best describes the biosorption of the three metal ions for all the range of experimental conditions investigated. For the three metal ions, the maximum biosoption capacity and the initial biosorption rate increase when the initial metal concentration rises. However, the kinetic constant decreases when the initial metal concentration increases. The temperature effect on biosorption capacity for Cd (II) and Cr (III) is less significant; however, for Pb (II) the effect of temperature is more important, especially when temperature rises from 25 to 40oC. The biosorption capacity at mmol/g of olive stone changes in the following order: Cr>Cd>Pb. Thus, for an initial concentration of 220 mg/l, a maximum sorption capacity of 0.079 mmol/g for Cr (III), 0.065 mmol/g for Cd (II) and 0.028 mmol/g for Pb (II) has been obtained.

Sorption of Cr (VI) onto Olive Stone in a Packed Bed Column: Prediction of Kinetic Parameters and Breakthrough Curves

This paper investigates the ability of olive stone to remove chromium (VI) ions from aqueous solution in a packed bed up-flow column with an internal diameter of 1.5 cm. The experiments were performed with a bed height of 15 g (13.4 cm) and a flow rate of 2 mL/min. To predict the breakthrough curves and to determine the characteristic parameters of the column useful for process design, four kinetic models; Adams-Bohart, Thomas, Yoon-Nelson, and Dose-Response models were applied to the experimental data. All models were found suitable for describing the whole or a definite part of the dynamic behavior of the column. The simulation of the whole breakthrough curve was effective with the Dose-Response model, but the initial part of the breakthrough was best predicted by the Adams-Bohart model. On the other hand, the results indicated that, at pH values of this work, approximately 50% of Cr (VI) is biosorbed by olive stone and the other 50% is reduced to Cr (III), both processes being of equal importance. Therefore, a two-stage biosorption process was developed. The goal of these final experiments was to confirm that Cr (III) [the Cr (VI) reduction product] was also effectively sorbed by olive stone in a second column.

Combustion of a Pb(II)-loaded olive tree pruning used as biosorbent

The olive tree pruning is a specific agroindustrial waste that can be successfully used as adsorbent, to remove Pb(II) from contaminated wastewater. Its final incineration has been studied in a thermobalance and in a laboratory flow reactor. The study aims at evaluating the fate of Pb during combustion, at two different scales of investigation. The flow reactor can treat samples approximately 10(2) larger than the conventional TGA. A detailed characterization of the raw and Pb(II)-loaded waste, before and after combustion is presented, including analysis of gas and solids products. The Pb(II)-loaded olive tree pruning has been prepared by a previous biosorption step in a lead solution, reaching a concentration of lead of 2.3 wt%. Several characterizations of the ashes and the mass balances proved that after the combustion, all the lead presents in the waste remained in ashes. Combustion in a flow reactor produced results consistent with those obtained in the thermobalance. It is thus confirmed that the combustion of Pb(II)-loaded olive tree pruning is a viable option to use it after the biosorption process. The Pb contained in the solid remained in the ashes, preventing possible environmental hazards.

Effect of the presence of chromium (III) on the removal of lead (II) from aqueous solutions by agricultural wastes.

The influence of the presence of Cr (III) on the biosorption of Pb (II) by three olive wastes (olive stone, the two-phase olive mill solid, and olive tree pruning) was investigated in a batch system in terms of equilibrium isotherm and adsorption yield. The results show that the three olive wastes have greater affinity for lead than for chromium and the best results are achieved at pH=5. The presence of chromium in the solution reduces the percentage of lead removal suggesting that there is a competition between the two metals for the binding sites, and that the biosorbent retains both species presenting more affinity for lead. Simultaneous biosorption phenomena of Pb (II) and Cr (III) on the three solid wastes were expressed by multicomponent isotherms. The extended Freundlich-type and Sips-type models were found to exhibit good fit to the experimental data for olive stone and olive tree pruning, respectively.

Biosorption of Cu2+ in a packed bed column by almond shell: optimization of process variables

Abstract This paper presents the ability of a low-cost biosorbent, almond shell, to remove Cu(II) ions from aqueous solution. Biosorption capacity of almond shell to removal Cu(II) was studied in a packed bed column. The effect of various parameters, flow rate, initial copper concentration, and mass of biosorbent, was analyzed. A 23 factorial experiment design was carried out to optimize some of the factors directly affecting the biosorption of copper onto almond shell. The results have shown that initial concentration of Cu(II) is the most influential factors in biosorption capacity, while the most important factors in total copper removal are the flow rate and mass of biosorbent. The biosorption capacity of almond shell presented a maximum when the operational conditions are: flow rate, 6 mL/min; initial copper concentration, 100 mg/L; and mass of almond shell, 5 g; while the parameters which give the maximum value of % removal of Cu(II) are: flow rate, 2 mL/min; initial copper concentration, 40 mg/L; a...

Assessment of the removal mechanism of hexavalent chromium from aqueous solutions by olive stone

The objectives of this study were to study the removal mechanism of Cr(VI) by natural olive stone (OS) and to present a sequential-batch process for the removal of total chromium (original Cr(VI) and Cr(III) derived from reduction of Cr(VI) during biosorption at acidic conditions). First, experiments were conducted varying pH from 1 to 4, and showed that a combined effect of biosorption and reduction is involved in the Cr(VI) removal. Then, X-ray photoelectron spectroscopy and desorption tests were employed to verify the oxidation state of the chromium bound to OS and to elucidate the removal mechanism of Cr(VI) by this material. The goal of these tests was to confirm that Cr(III) is the species mainly absorbed by OS. Finally, the possibility of total chromium removal by biosorption in a sequential-batch process was analyzed. In the first stage, 96.38% of Cr(VI) is removed by OS and reduced to Cr(III). In the second stage, approximately 31% of the total Cr concentration was removed. However, the Cr(III) released in the first stage is not completely removed, and it could suggest that the Cr(III) could be in a hydrated compound or a complex, which could be more difficult to remove under these conditions.

Comparative study of isotherm parameters of lead biosorption by two wastes of olive-oil production

Batch isotherm studies were carried out on a laboratory scale: (i) to investigate the effectiveness to remove lead of two wastes (olive stone (OS) and olive tree pruning (OTP)), untreated and chemically treated; and (ii) to examine the applicability of various adsorption isotherms to fit the experimental data. Results from tests were analyzed using seven equilibrium isotherm correlations (Langmuir, Freundlich, Dubinin-Radushkevich, Temkin, Redlich-Peterson, Sips, and Toth equations). The sum of the squares of the errors was determined for each isotherm and the Langmuir equation provided the best fit. Chemical treatments increased the biosorption properties of these materials. The maximum biosorption capacities were: 6.33, 49.13, 14.83, and 38.93 mg g(-1) for untreated OS, HNO3-OS, H2SO4-OS, and NaOH-OS, respectively, and 26.72, 86.40, 72.78, and 123.80 mg g(-1) for untreated OTP, HNO3-OTP, H2SO4-OTP, and NaOH-OTP, respectively. Finally, the loss of mass for each waste (13.9, 14.3, and 36.8% for HNO3-OS, H2SO4-OS, and NaOH-OS and 35.1, 27.5, and 46.7% for HNO3-OTP, H2SO4-OTP, and NaOH-OTP, respectively) was taken into account and an effectiveness coefficient was determined for each adsorbent material.

Evaluation of biosorption of copper ions onto pinion shell

Abstract Biosorption of Cu(II) by pinion shell (PS) was investigated in batch and packed-bed systems. The biosorbent was characterized by elemental analysis, potentiometric titrations, surface area and pore size distribution, and Fourier transform infrared (FTIR) analyses. Potentiometric titrations and FTIR spectroscopy indicated the presence of functional groups in the PS, some of which were involved in the sorption process. Batch adsorption experiments were carried out as a function of solution pH, particle size, biosorbent dosage, contact time, and initial metal ion concentration. The rate of the biosorption process followed pseudo-second-order kinetics, while the sorption equilibrium data well fitted to the Langmuir and Freundlich isotherm models. The maximum monolayer Cu(II) biosorption capacity was 4.29 mg/g at 25°C. Finally, the dynamic biosorption studies were carried out using a packed-bed column and the main column parameters were determined. The present study suggests that the PS can be used as...