Adsorption mechanisms of metal cations from water on an oxidized carbon surface.

Adsorption of Cr(III), Mn(II), Cu(II) and Zn(II) on an oxidized activated carbon cloth was studied. Its surface chemistry was characterized by potentiometric titration. This technique revealed the amount of surface oxygen functionalities and their acidity constant distribution. The acidity constant range involved in the metal cation adsorption was obtained from this distribution. Metal cation adsorption increased with higher adsorption temperature due to the increase in the negative surface charge of the oxidized activated carbon. Adsorption was by proton exchange and the number, amount and strength of the surface acid groups involved could be obtained. The proton exchange was by an inner-sphere or outer-sphere surface metal complex formation mechanism. In the case of divalent cation adsorption, the increase in temperature changed the adsorption mechanism from outer-sphere to inner-sphere. However, the adsorption mechanism of Cr(III) was outer-sphere and independent of temperature. Adsorption capacity augmented with the increase in the charge-to-size ratio of the hexa-aquo cations. In addition, the adsorption capacity of divalent cations increased with the rise in stability of the surface metal complex formed.

Batch and column adsorption of herbicide fluroxypyr on different types of activated carbons from water with varied degrees of hardness and alkalinity.

There has been little research into the effects of the water hardness and alkalinity of surface waters on the adsorption of herbicides on activated carbons. The aim of this study was to determine the influence of these water characteristics on fluroxypyr adsorption on different activated carbons. At low fluroxypyr surface concentrations, the amount adsorbed from distilled water was related to the surface hydrophobicity. Surface area of carbons covered by fluroxypyr molecules ranged from 60 to 65%. Variations in fluroxypyr solubility with water hardness and alkalinity showed a salting-in effect. Calcium, magnesium and bicarbonate ions were adsorbed to a varied extent on the activated carbons. The presence of fluroxypyr in solution decreased their adsorption due to a competition effect. K(F) from the Freundlich equation linearly increased with water hardness due to salt-screened electrostatic repulsions between charged fluroxypyr molecules. The amount adsorbed from distilled water was largest at high fluroxypyr solution concentrations, because there was no competition between inorganic ions and fluroxypyr molecules. The column breakthrough volume and the amount adsorbed at breakthrough were smaller in tap versus distilled water. Carbon consumption was lower with activated carbon cloth than with the use of granular activated carbon.

Adsorption and thermal desorption of the herbicide fluroxypyr on activated carbon fibers and cloth at different pH values.

Adsorption of fluroxypyr was studied at pH values between 2 and 10 and at temperatures of 298 and 313 K. Adsorption capacity decreased when the solution pH increased. This was explained by changes in fluroxypyr solubility and in dispersive and electrostatic adsorbent-adsorbate interactions with the increase in pH. The highest adsorption was found at pH 2, when the solubility was the lowest and only dispersive interactions operated. An increase in temperature produced a decrease in adsorption capacity. Thermal desorption of fluroxypyr up to 1073 K left a residue on the carbon surface, which increased with higher adsorption pH. Differential thermogravimetry (DTG) profiles showed two desorption peaks at pH values of 2 and 4 and only one peak at pH values of 7 and 10. The appearance of one or two peaks may be related to the type of adsorbate-adsorbent interactions established during adsorption. The predominance of electrostatic interactions favours the strongly bound or chemisorbed fluroxypyr. One important conclusion is that the highest amounts of fluroxypyr are adsorbed and thermally desorbed when there are only non-electrostatic interactions between fluroxypyr molecules and carbon surface. Activation desorption energy and pre-exponential factor were obtained from the shift in temperature of desorption peaks with higher heating rate.

Kinetics of diuron and amitrole adsorption from aqueous solution on activated carbons.

A study was conducted on the adsorption kinetics of diuron and amitrole from aqueous solutions on activated carbons of different particle sizes and on an activated carbon fiber. Different kinetic models were applied to the experimental results obtained. A pseudo-second-order rate equation fitted the adsorption kinetics data better than a pseudo-first-order rate equation. Amitrole showed faster adsorption kinetics compared with diuron because of the smaller size of the former herbicide, despite its lower driving force for adsorption. Both reaction rate constants increased when the particle size decreased. The activated carbon fiber and the activated carbon of smallest particle size (0.03 mm) showed similar adsorption kinetics. The intraparticle diffusion rate constant increased with higher initial concentration of herbicides in solution and with lower particle size of the adsorbent. This is because the rise in initial concentration increased the amount adsorbed at equilibrium, and the reduction in particle size increased the number of collisions between adsorbate and adsorbent particles. Demineralization of the activated carbon with particle size of 0.5mm had practically no effect on the adsorption kinetics.