Photoelectrocatalysis driven by visible light offers a new and potentially powerful technology for the remediation of water contaminated by organo-xenobiotics. In this study, the performance of a visible light-driven photoelectrocatalytic (PEC) batch reactor, applying a tungsten trioxide (WO3) photoelectrode, to degrade the model pollutant 2,4-dichlorophenol (2,4-DCP) was monitored both by toxicological assessment (biosensing) and chemical analysis. The bacterial biosensor used to assess the presence of toxicity of the parent molecule and its breakdown products was a multicopy plasmid lux-marked E. coli HB101 pUCD607. The bacterial biosensor traced the removal of 2,4-DCP, and in some case, its toxicity response suggests the identification of transient toxic intermediates. The loss of the parent molecule, 2,4-DCP determined by HPLC, corresponded to the recorded photocurrents. Photoelectrocatalysis offers considerable potential for the remediation of chlorinated hydrocarbons, and that the biosensor based toxicity results identified likely compatibility of this technology with conventional, biological wastewater treatment. Visible light-driven photoelectrocatalysis has potential as a remediation technology in wastewater treatment.

The effects of elevated O3 on photosynthetic properties in adult beech trees (Fagus sylvatica) were investigated in relation to leaf mass per area as a measure of the gradually changing, within-canopy light availability. Leaves under elevated O3 showed decreased stomatal conductance at unchanged carboxylation capacity of Rubisco, which was consistent with enhanced δ13C of leaf organic matter, regardless of the light environment during growth. In parallel, increased energy demand for O3 detoxification and repair was suggested under elevated O3 owing to enhanced dark respiration. Only in shade-grown leaves, light-limited photosynthesis was reduced under elevated O3, this effect being accompanied by lowered Fv/Fm. These results suggest that chronic O3 exposure primarily caused stomatal closure to adult beech trees in the field regardless of the within-canopy light gradient. However, light limitation apparently raised the O3 sensitivity of photosynthesis and accelerated senescence in shade leaves.

Leaching of Cu and Zn from a composite of discarded antifouling paint residues ([Cu] = 288 mg g−1; [Zn] = 96 mg g−1) into natural sea water has been studied over a period of 75 h. Total Cu and Zn were released according to a pseudo first-order reaction, with rate constants on the order of 0.3 and 2.5 (mg L−1)−1 h−1, respectively, and final concentrations equivalent to the dissolution of about 8 and 2% of respective concentrations in the composite. Time-distributions of hydrophobic metals, determined by solid phase extraction-methanol elution, were more complex. Net release of hydrophobic Cu was greater in the absence of light than under a sequence of light–dark cycles; however, hydrophobic Zn release was not detected under the former conditions but contributed up to 50% of total aqueous Zn when light was present. These observations are interpreted in terms of the relative thermodynamic and photolytic stabilities of biocidal pyrithione complexes. Hydrophobic Cu and Zn leached from antifouling paint particles into sea water appear to be pyrithione complexes.

The delafossite CuCrO₂ is a promising candidate for the visible light driven catalysis. The NO₂ ⁻ removal by photoelectrochemical process is studied under mild conditions, close to that encountered in the natural environment. CuCrO₂ exhibits a long term chemical stability with a corrosion rate of 0.34 μmol m⁻² year⁻¹ in KCl (0.5 M). A forbidden band of 1.3 eV has been evaluated from the diffuse reflectance spectrum. The flat band potential (-0.07 V SCE) determined from the Mott-Schottky plot is close to the photocurrent onset potential (0 V SCE). Hence, the conduction band is positioned at -1.08 V SCE and thus lies below the NO₂ ⁻ level leading to a feasible reduction upon visible illumination. The conversion occurs in less than ~5 h with a quantum efficiency of ~0.5%. The possibility of identifying the reaction products via the intensity-potential characteristics was explored by using standard solutions. The decrease of the conversion rate over time is attributed to the competitive water reduction. In absence of catalyst, NO₂ ⁻ is oxidized to NO₃ ⁻ in air equilibrated solution and the reaction follows a first order kinetic with a half life of 21 h, NO₃ ⁻ has been identified by iodometry through copper titration.

Photodegradation of four pharmaceuticals (i.e. carbamazepine, ibuprofen, ketoprofen and 17α-ethinylestradiol) in aqueous media was studied using a solar light simulator (Xe lamp irradiation) and sunlight experiments. These experiments were carried out in river and seawater and compared to distilled water. The latter was used to evaluate the direct photodegradation pathways. Irradiation time was up to 400 min and 24 days for the solar light simulator and sunlight assays, respectively. Pharmaceutical photodegradation followed a first-order kinetics and their half-lives calculated in every aqueous matrix. Moreover, the sensitizing effect of DOC was evaluated by comparison with the kinetics obtained in distilled waters. Ketoprofen was rapidly transformed via direct photolysis in all the waters under both sunlight (t ₁/₂ = 2.4 min) and simulated solar light simulator test (t ₁/₂ = 0.54 min). Under xenon lamp radiation, ibuprofen and 17α-ethinylestradiol were photodegraded at moderate rate with half-lives from 1 to 5 h. Finally, carbamazepine had the lowest photodegradation rate (t ₁/₂ = 8-39 h) attributable to indirect photodegradation. Indeed, its elimination was strongly dependent on the DOC concentration present in solution. Finally, several ketoprofen photoproducts were identified and plotted against solar light simulator irradiation time. Accordingly, the photodegradation pathway of ketoprofen was postulated.