Photooxidation of arsenite under 254 nm irradiation with a quantum yield higher than unity.

Arsenite (As(III)) in water was demonstrated to be efficiently oxidized to arsenate (As(V)) under 254 nm UV irradiation without needing any chemical reagents. Although the molar absorption coefficient of As(III) at 254 nm is very low (2.49 ± 0.1 M(-1)cm(-1)), the photooxidation proceeded with a quantum yield over 1.0, which implies a chain of propagating oxidation cycles. The rate of As(III) photooxidation was highly enhanced in the presence of dissolved oxygen, which can be ascribed to its dual role as an electron acceptor of photoexcited As(III) and a precursor of oxidizing radicals. The in situ production of H2O2 was observed during the photooxidation of As(III) and its subsequent photolysis under UV irradiation produced OH radicals. The addition of tert-butyl alcohol as OH radical scavenger significantly reduced (but not completely inhibited) the oxidation rate, which indicates that OH radicals as well as superoxide serve as an oxidant of As(III). Superoxide, H2O2, and OH radicals were all in situ generated from the irradiated solution of As(III) in the presence of dissolved O2 and their subsequent reactions with As(III) induce the regeneration of some oxidants, which makes the overall quantum yield higher than 1. The homogeneous photolysis of arsenite under 254 nm irradiation can be also proposed as a new method of generating OH radicals.

Photocatalytic oxidation mechanism of As(III) on TiO2: unique role of As(III) as a charge recombinant species.

Using TiO(2) photocatalyst, arsenite, As(III), can be rapidly oxidized to arsenate, As(V), which is less toxic and less mobile in the aquatic environment. Therefore, the TiO(2)/UV process can be employed as an efficient pretreatment method for arsenic contaminated water. Since we first reported in 2002 that the superoxide (or hydroperoxyl radical) plays the role of main oxidant of As(III) in the TiO(2)/UV process, there has been much debate over the true identity of the major photooxidant among superoxides, holes, and OH radicals. The key issue is centered on why the much stronger OH radicals cannot oxidize As(III), and it has been proposed that the unique role of As(III) as an external charge recombination center on the UV-excited TiO(2) particle is responsible for this eccentric mechanism. Although the proposed mechanism has been supported by many experimental evidences, doubts on it were not clearly removed. In this study, we provided direct and undisputed evidence to support the role of As(III) in the charge recombination dynamics using time-resolved transient absorption spectroscopy. The presence of As(III) indeed mediated the charge recombination in TiO(2). Under this condition, the role of the OH radical is suppressed because of the null cycle, and the weaker oxidant, superoxide, should prevail. The role of the superoxide has been previously doubted on the basis of the observation that the addition of excess formic acid (hole scavenger that should enhance the production of superoxides) inhibited the photocatalytic oxidation of As(III). However, this study proved that this was due to the photogeneration of reducing radicals (HCO(2)·) that recycle As(V)/As(IV) back to As(III). It was also demonstrated that the 4-chlorophenol/TiO(2) system under visible light that cannot generate neither OH radicals nor valence band holes converted As(III) to As(V) through the superoxide pathway.

Iodide-mediated photooxidation of arsenite under 254 nm irradiation.

The preoxidation of As(III) to As(V) is a desirable process to increase the removal efficiency of arsenic in water treatment In this work, the photooxidation of As(III) under 254 nm irradiation was investigated in the concentration range of 1-1000 microM in the presence of potassium iodide (typically 100 microM). Although the direct photooxidation of As(III) in water was negligible, the presence of iodide dramatically enhanced the oxidation rate. The quantitative conversion of As(III) to As(V) was achieved. The quantum yields of As(III) photooxidation ranged from 0.08 to 0.6, depending on the concentration of iodide and As(III). The excitation of iodides under 254 nm irradiation led to the generation of iodine atoms and triiodides, which seem to be involved in the oxidation process of As(III). Because the efficiency of iodine atom generation is highly dependent on the presence of suitable electron acceptors,the photooxidation of As(III) was efficient in an air- or N2O-saturated solution but markedly reduced in the N2-saturated solution. The production of H2O2 was also accompanied by the generation of As(V). The addition of excess methanol (OH radical scavenger) did not reduce the photooxidation rate at all, which ruled out the possibility of hydroxyl radical involvement. It was found that the in situ photogenerated triiodides oxidize As(III) with regenerating iodides by completing a cycle. The proposed UV254/KI/As(III) process is essentially an iodide-mediated photocatalysis.

Photocatalytic bacterial inactivation by polyoxometalates.

The photocatalytic inactivation (PCI) of Escherichia coli (Gram-negative) and Bacillus subtilis (Gram-positive) was performed using polyoxometalate (POM) as a homogeneous photocatalyst and compared with that of heterogeneous TiO2 photocatalyst. Aqueous suspensions of the microorganisms (10(7)-10(8)cfu ml(-1)) and POM (or TiO2) were irradiated with black light lamps. The POM-PCI was faster than (or comparable to) TiO2-PCI under the experimental conditions employed in this study. The relative efficiency of POM-PCI was species-dependent. Among three POMs (H(3)PW(12)O(40), H(3)PMo(12)O(40), and H(4)SiW(12)O(40)) tested in this study, the inactivation of E. coli was fastest with H(4)SiW(12)O(40) while that of B. subtilis was the most efficient with H(3)PW(12)O(40). Although the biocidal action of TiO2 photocatalyst has been commonly ascribed to the role of photogenerated reactive oxygen species such as hydroxyl radicals and superoxides, the cell death mechanism with POM seems to be different from TiO2-PCI. While TiO2 caused the cell membrane disruption, POM did not induce the cell lysis. When methanol was added to the POM solution, not only the PCI of E. coli was enhanced (contrary to the case of TiO2-PCI) but also the dark inactivation was observed. This was ascribed to the in situ production of formaldehyde from the oxidation of methanol. The interesting biocidal property of POM photocatalyst might be utilized as a potential disinfectant technology.