Solar Photocatalytic Decolorization and Detoxification of Industrial Batik Dye Wastewater Using P(3HB)‐TiO2 Nanocomposite Films

Solar photocatalytic decolorization and detoxification of batik dye wastewater using titanium dioxide (TiO₂) immobilized on poly‐3‐hydroxybutyrate (P(3HB)) film was studied. The effects of initial dye concentration, catalyst concentration, P(3HB) film thickness, and fabrication methods of the nanocomposite films were evaluated against methylene blue, a standard organic dye. It was observed that 0.4 g of P(3HB)‐40 wt% TiO₂ removed 96% of the color under solar irradiation. P(3HB) and TiO₂, mixed concurrently in chloroform followed by stirring for 24 h showed a more even distribution of the photocatalyst on the polymer surface and yielded almost 100% color removal. The photocatalytic films were able to completely decolorize real industrial batik dye wastewater in 3 h and induced a chemical oxygen demand (COD) reduction of 80%. Reusability of the 0.4 g P(3HB)‐40 wt% TiO₂ film in decolorizing the batik dye wastewater was also possible as it gave a high consistent value of decolorization percentage (>80%) even after the sixth repeated usage. Recovery step of the photocatalysts was also not required in this simple treatment system. The decolorized batik dye wastewater had less/no toxic effects on mosquito larvae, Aedes aegypti, and microalgae, Scenedesmus quadricauda indicating simultaneous detoxification process along with the decolorization process.     

Photochemical activity and characterization of the complex of humic acids with iron(III)

This study examined the effects of humic acids (HA) and Fe(III)–HA complex on the photodegradation of atrazine, one of the most widely used herbicides. It was shown that the photolysis of atrazine proceeded via first-order reaction kinetics and that atrazine photodegradation was inhibited by the presence of HA, whereas the rate for atrazine photolysis was promoted in solutions containing both HA and Fe(III). Interactions of Fe(III) with HA were characterized by SEM, EDX, UV–Vis and FTIR, revealing that Fe(III)–HA complex was formed by ligand exchange between oxygen groups of HA and Fe(III). Using fluorescence spectrometry the stability constant (K_c) and the fraction of fluorophores available for complexation (f) were obtained as log K_c = 4.28 and f = 74%. Photoformed Fe(II) by ligand-to-metal charge-transfer (LMCT) within the Fe(III)–HA complex was the most important factor involved in photolysis of atrazine, since Fe(II) was the reactant to generate hydroxyl radical. Thus, the rate of atrazine photodegradation in natural sunlit waters is dependent on both the amount of iron present and the interaction between HA and iron.     

Effect of environmental factors on photodegradation of polycyclic aromatic hydrocarbons (PAHs) in the water-soluble fraction of Kuwait crude oil in seawater

Photodegradation of PAHs in the water-soluble fraction of Kuwait crude oil in seawater was investigated under various environmental factors (temperature, light intensity, oxygen levels and presence of a sensitizer) in laboratory conditions. All factors investigated had significant effect on the degradation rates of PAHs. At 15 °C almost all PAHs optimally degraded at an oxygen level of 4 ppm. For lower molecular weight PAHs a light intensity of 500 W/m² in the presence of the sensitizer worked well. Higher molecular weight PAHs degraded at faster rates at a light intensity 750 W/m². At 30 °C, most of the PAHs degraded optimally at an oxygen level of 0 ppm and light intensity of 500 or 750 W/m² in presence of the sensitizer. At 40 °C, most of PAHs degraded optimally at low oxygen concentrations (0 and 4 ppm) and a light intensity of 500 W/m² in the presence of the sensitizer. Linear regression indicated that for most of the compounds, light intensity had the greatest effect on degradation rates.     

Photodegradation of autochthonous and allochthonous dissolved organic matter in a natural tropical lake

Dissolved organic carbon (DOC) is one of the most abundant fractions of organic matter in aquatic systems and plays an important role in the dynamics of aquatic environments, controlling both the penetration and the underwater light radiation climate. DOC can be photodegraded by light, thus facilitating biodegradation, especially in regions where the incidence of solar radiation is high, such as higher altitudes and lower latitudes. This study quantified the photodegradation of dissolved organic material in a natural tropical lake surrounded by native forests (Brazilian Atlantic Forest) through two experiments: i) the first experiment exposed concentrated autochthonous, allochthonous, and lake water to in situ solar radiation; ii) this experiment also exposed the same organic material to artificial UV radiation in an incubator under controlled conditions. The quality and quantity of dissolved organic carbon were measured using indices based on carbon absorbance and fluorescence spectrum. In the in situ experiment, it was observed that the DOC degradation profile of the concentrated allochthonous and autochthonous organic material were distinct from each other in the absorbance indices, and the lake water mostly resembled the latter one. On the other hand, we did not see evidence of any significant difference among treatments in the laboratory experiment. An increase in the SR index and a concomitant decrease in the fluorescence of humic compounds and SUVA₂₅₄ over time were observed. In both experiments, the amount of degraded organic material over time was low and some possible explanations are discussed.     

Photoreactivity of chromophoric dissolved organic matter transported by the Mackenzie River to the Beaufort Sea

The photoreactivity of chromophoric dissolved organic matter (CDOM) transported to Arctic shelf environments by rivers has only recently been studied and its quantitative role in Arctic shelf biogeochemistry has received little attention. Sunlight exposure experiments were performed on CDOM collected over a three year period (2002 to 2004) from river, estuary, shelf, and gulf regions of the Western Canadian Arctic. Decreases in CDOM absorption, synchronous fluorescence (SF), and dissolved organic carbon (DOC) concentration were followed after 3 days of exposure, and in two experiments, six optical cutoff filters were used to incrementally remove ultraviolet radiation incident on the samples. Apparent quantum yields for CDOM photobleaching (AQY_ble) and for DOC photomineralization (AQY_min) were computed, as were two AQY spectra (_ble and _min) for the Mackenzie River and a sample from the Mackenzie Shelf. The photoreactivity of Mackenzie River CDOM was highest after break-up and peak discharge and lowest in late summer. The half-lives of CDOM and DOC were estimated at 3.7 days and 4.8 days, respectively, when Mackenzie River water was exposed to full sunlight. Photobleaching of Mackenzie River CDOM fluorescence after most UV-B wavelengths were removed increased the correlation between the river and offshore waters in the Beaufort Sea. When light attenuation from particle- and CDOM-rich river water was considered for the Mackenzie Shelf, our photodegradation models estimated around 10% loss of absorption and < 1% DOC loss, suggesting that sunlight exposure does not substantially degrade CDOM on Arctic shelves.     

A mechanistic study on the photodegradation of Irgarol-1051 in natural seawater

The kinetics of the photoinduced degradation and transformation of the antifouling booster biocide, Irgarol-1051, in natural coastal seawater was studied. The measured first-order rate constant for the degradation of Irgarol-1051 was 4.02 ± 0.1 × 10⁻⁴ h⁻¹, while the rate constant for the formation of 2-methylthio-4-tert-butylamino-6-amino-s-triazine (M1), the most dominant degradation product of Irgarol-1051, was 4.6 ± 0.1 × 10⁻⁵ h⁻¹. This considerably slower rate suggested that the transformation of Irgarol-1051 to M1 may not be the predominant pathway of the photodegradation process. During the photodegradation study, a new s-triazine species was observed in the degradation mixtures which, together with M1, appeared immediately upon photolysis and continued to accumulate in the degradation mixture throughout the entire study duration. This is in contrast to the behaviour of the recently identified degradation product of Irgarol-1051, 3-[4-tert-butylamino-6-methylthiol-s-triazin-2-ylamino]- propionaldehyde (M2), which was only detected in the degradation mixture after a long induction period. High-resolution tandem mass spectrometric analysis hinted that the new degradation product (M4) may possess a terminal alcohol and is likely to be an N-allylic alcohol derivative of M1. This suggests that M4 may, indeed, be a precursor of M2 via redox transformation at its N-allylic alcohol functionality.     

Photocatalytic Degradation of Dye C.I. Direct Blue 78 Using TiO2 Nanoparticles Immobilized on Recycled Wool‐Based Nonwoven Material

This paper discusses the possibility of immobilization of TiO₂ nanoparticles onto recycled wool‐based nonwoven material, which can be utilized for removal of dyes from wastewater. The photocatalytic activity of TiO₂ nanoparticles deposited on the nonwoven material was evaluated in the aqueous solution of direct dye C.I. Direct Blue 78 under the UV illumination. Nonwoven material modified with TiO₂ nanoparticles provides complete removal of dye from the solution already after 4–6 h of UV illumination. However, photodegradation of the dye adsorbed on the nonwoven material was obtained within 24 h of UV illumination. The rate of dye adsorption and photodegradation depends on the amount of deposited TiO₂ nanoparticles. The increase of initial dye concentration induced decrease in photocatalytic efficiency of immobilized TiO₂ nanoparticles. The highest photodegradation rate was achieved in acidic conditions. Elevated temperatures positively affected the removal of dye from solution. Photocatalytic activity of TiO₂ nanoparticles deposited on nonwoven material was preserved after three photodegradation cycles.     

The partitioning of Triclosan between aqueous and particulate bound phases in the Hudson River Estuary

The distribution of Triclosan within the Hudson River Estuary can be explained by a balance among the overall effluent inputs from municipal sewage treatment facilities, dilution of Triclosan concentrations in the water column with freshwater and seawater inputs, removal of Triclosan from the water column by adsorption to particles, and loss to photodegradation. This study shows that an average water column concentration of 3 ± 2 ng/l (in the lower Hudson River Estuary) is consistent with an estimate for dilution of average wastewater concentrations with seawater and calculated rates of adsorption of Triclosan to particles. An average Triclosan sediment concentration of 26 ± 11 ng/g would be in equilibrium with the overlying water column if Triclosan has a particle-to-water partitioning coefficient of k_d  10⁴, consistent with laboratory estimates.