This paper reports an investigation of the effects of a trihydroxamate siderophore, desferrioxamine B (DFO-B), and a common biological ligand, oxalate, on the steady-state dissolution of goethite at pH 5 and 25 jC. The main goal of our study was to quantify the adsorption of the ligands and the dissolution of goethite they promote in a two-ligand system. In systems with one ligand only, the adsorption of oxalate and DFO-B each followed an L-type isotherm. The surface excess of oxalate was approximately 40 mmol kg À 1 at solution concentrations above 80 AM, whereas the surface excess of DFO-B was only 1.2 mmol kg À 1 at 80 AM solution concentration. In the two-ligand systems, oxalate decreased DFO-B adsorption quite significantly, but not vice versa. For example, in solutions containing 40 AM DFO-B and 40 AM oxalate, 30% of the DFO-B adsorbed in the absence of oxalate was displaced. The mass-normalized dissolution rate of goethite in the presence of DFO-B alone increased as the surface excess of the ligand increased, suggesting a ligand-promoted dissolution mechanism. In systems containing oxalate only, mass-normalized goethite dissolution rates were very low at concentrations below 200 AM, despite maximal adsorption of the ligand. At higher oxalate concentrations (up to 8 mM), the steady-state dissolution rate continued to increase, even though the surface excess of adsorbed ligand was essentially constant. Chemical affinity calculations and dissolution experiments with variation of the reactor flow rate showed that far-from-equilibrium conditions did not obtain in systems containing oxalate at concentrations below 5 mM. The dissolution rate in the presence of DFO-B at solution concentrations between 1 and 80 AM was approximately doubled when oxalate was also present at 40 AM solution concentration. The dissolution rate in the presence of oxalate at solution concentrations between 0 and 200 AM was increased by more than an order of magnitude when DFO-B was also present at 40 AM solution concentration. Chemical affinity calculations showed that, in systems containing DFO-B, goethite dissolution was always under far-from-equilibrium conditions, irrespective of the presence of oxalate. These results were described quantitatively by a model rate law containing a term proportional to the surface excess of DFO-B and a term proportional to that of oxalate, with both surface excesses being determined in the twoligand system. The pseudo first-order rate coefficient in the DFO-B term has the same value as measured for goethite dissolution in the presence of DFO-B only, while the rate coefficient in the oxalate term must be measured in the two-ligand system, since it is only in this system that far-from-equilibrium conditions obtain. These latter conditions do not exist in the system containing oxalate only, but they do exist in the DFO-B/oxalate system because the siderophore is able to remove Fe(III) from all Fe -oxalate complexes rapidly, leaving the uncomplexed oxalate ligand in solution free to react again wit...

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Clay-supported TiO 2 photocatalysts can potentially improve the performance of air treatment technologies via enhanced adsorption and reactivity of target volatile organic compounds (VOCs). In this study, a bench-top photocatalytic flow reactor was used to evaluate the efficiency of hectorite-TiO 2 and kaolinite-TiO 2 , two novel composite materials synthesized in our laboratory. Toluene, a model hydrophobic VOC and a common indoor air pollutant, was introduced in the air stream at realistic concentrations, and reacted under UVA (λ max = 365 nm) or UVC (λ max = 254 nm) irradiation. The UVC lamp generated secondary emission at 185 nm, leading to the formation of ozone and other short-lived reactive species. Performance of clay-TiO 2 composites was compared with that of pure TiO 2 (Degussa P25), and with UV irradiation in the absence of photocatalyst under identical conditions. Films of clay-TiO 2 composites and of P25 were prepared by a dip-coating method on the surface of Raschig rings, which were placed inside the flow reactor. An upstream toluene concentration of ~170 ppbv was generated by diluting a constant flow of toluene vapor from a diffusion source with dry air, or with humid air at 10, 33 and 66 % relative humidity (RH). be partially attributed to the contribution of gas phase reactions by short-lived radical species. When the reaction rate was normalized to the light irradiance, T r /I λ , the UV/TiO 2 reaction under UVA irradiation was more efficient for samples with a higher content of TiO 2 (P25 and Hecto-TiO 2 ), but not for Kao-TiO 2 . In all cases, reaction rates