Photochemical Degradation of Short-Chain Chlorinated Paraffins in Aqueous Solution by Hydrated Electrons and Hydroxyl Radicals

Short-chain chlorinated paraffins (SCCPs) are a complex mixture of polychlorinated alkanes (C10-C13, chlorine content 40-70%), and have been categorized as persistent organic pollutants. However, there are knowledge gaps about their environmental degradation, particularly the effectiveness and mechanism of photochemical degradation in surface waters. Photochemically-produced hydrated electrons (e-(aq)) have been shown to degrade highly chlorinated compounds in environmentally-relevant conditions more effectively than hydroxyl radicals (·OH), which can degrade a wide range of organic pollutants. This study aimed to evaluate the potential for e-(aq) and ·OH to degrade SCCPs. To this end, the degradation of SCCP model compounds was investigated under laboratory conditions that photochemically produced e-(aq) or ·OH. Resulting SCCP degradation rate constants for e-(aq) were on the same order of magnitude as well-known chlorinated pesticides. Experiments in the presence of ·OH yielded similar or higher second-order rate constants. Trends in e-(aq) and ·OH SCCP model compounds degradation rate constants of the investigated SCCPs were consistent with that of other chlorinated compounds, with higher chlorine content producing in higher rate constants for e-(aq) and lower for ·OH. Above a chlorine:carbon ratio of approximately 0.6, the e-(aq) second-order rate constants were higher than rate constants for ·OH reactions. Results of this study furthermore suggest that SCCPs are likely susceptible to photochemical degradation in sunlit surface waters, facilitated by dissolved organic matter that can produce e-(aq) and ·OH when irradiated.

The study of spectral and luminescent properties of humic acids and their impact on the photodegradation process of 2,6-bis(hydroxymethyl)-4-methylphenol

UV photolysis (KrCl excilamp, λrad ~ 222 nm) of aqueous humic acids (HAs) samples was carried out without and in the presence of 2,6-bis(hydroxymethyl)-4-methylphenol. The samples of HAs fractions were obtained from Aldrich Chemical Co and prepared from peat of Arkhangelsk region. The presence of Aldrich humic acid in the solution has a essential effect on the processes of phenolic compound photochemical degradation under the action of light from the excilamp.

OPTIMIZATION OF PROTECTIVE COATING COMPONENTS OF THERMOMODIFIED WOOD TO THE EXPOSURE OF WATER

Paints and varnishes are used to a large extent to protect wood surfaces in outdoor conditions, as they are easy to maintain and reapply. Also, when developing a coating, manufacturers are guided by the need to obtain a number of properties that generally determine its ability to protect against moisture. To obtain a protective coating that meets the specified requirements, it is necessary that the components that make up the coating belong directly to the group of protective materials or form such compounds under operating conditions, be able to adhere to the surface of the product. It was found that thermal modification provides a decrease in water absorption of wood. Additional processing of the wood surface helps to reduce moisture absorption by 2 times, and for samples modified at a temperature of 220 °C – 3 times. Geometric dimensional stability is also improved by a factor of 2. The effect of heat treatment on the water absorption of wood is somewhat less – for samples modified at 190 and 220 °C for more than 10 hours. Protective substances for thermally modified wood provided similar protection of open thermally modified surfaces of wood from the effects of water. The positive effect of thermal modification on a decrease in the level of water absorption has been established. It has been proven that it is temperature that has a significant effect on such changes. Since the protective coating is also susceptible to photochemical degradation, it is very important to renew it in a timely manner in accordance with the manufacturer's instructions for the pleasant appearance of wood surfaces during external use. The optimal ratio of components in the surface layer of thermally modified wood has been determined, which ensures the fulfillment of the task, namely for a mixture of oil and wax: the density of a wood – 724 kg/m3; oils – 70.0%; wax – 17.5%. Therefore, such treatment is beneficial for the protection and aesthetic appeal of wood products.

Investigation of the Aquatic Photolytic and Photocatalytic Degradation of Citalopram

This study investigated the direct and indirect photochemical degradation of citalopram (CIT), a selective serotonin reuptake inhibitor (SSRI), under natural and artificial solar radiation. Experiments were conducted in a variety of different operating conditions including Milli-Q (MQ) water and natural waters (lake water and municipal WWT effluent), as well as in the presence of natural water constituents (organic matter, nitrate and bicarbonate). Results showed that indirect photolysis can be an important degradation process in the aquatic environment since citalopram photo-transformation in the natural waters was accelerated in comparison to MQ water both under natural and simulated solar irradiation. In addition, to investigate the decontamination of water from citalopram, TiO2-mediated photocatalytic degradation was carried out and the attention was given to mineralization and toxicity evaluation together with the identification of by-products. The photocatalytic process gave rise to the formation of transformation products, and 11 of them were identified by HPLC-HRMS, whereas the complete mineralization was almost achieved after 5 h of irradiation. The assessment of toxicity of the treated solutions was performed by Microtox bioassay (Vibrio fischeri) and in silico tests showing that citalopram photo-transformation involved the formation of harmful compounds.

Insights into the Time Evolution of Slowly Photodegrading Contaminants

Photochemical degradation plays an important role in the attenuation of many recalcitrant pollutants in surface freshwaters. Photoinduced transformation kinetics are strongly affected by environmental conditions, where sunlight irradiance plays the main role, followed by water depth and dissolved organic carbon (DOC). Apart from poorly predictable weather-related issues, fair-weather irradiance has a seasonal trend that results in the fastest photodegradation in June and the slowest in December (at least in temperate areas of the northern hemisphere). Pollutants that have first-order photochemical lifetimes longer than a week take more than one month to achieve 95% photodegradation. Consequently, they may experience quite different irradiance conditions as their photodegradation goes on. The relevant time trend can be approximated as a series of first-order kinetic tracts, each lasting for one month. The trend considerably departs from an overall exponential decay, if degradation takes long enough to encompass seasonally varying irradiance conditions. For instance, sunlight irradiance is higher in July than in April, but increasing irradiance after April and decreasing irradiance after July ensure that pollutants emitted in either month undergo degradation with very similar time trends in the first 3–4 months after emission. If photodegradation takes longer, pollutants emitted in July experience a considerable slowdown in photoreaction kinetics as winter is approached. Therefore, if pollutants are photostable enough that their photochemical time trend evolves over different seasons, degradation acquires some peculiar features than cannot be easily predicted from a mere analysis of lifetimes in the framework of simple first-order kinetics. Such features are here highlighted with a modelling approach, taking the case of carbamazepine as the main example. This contaminant is almost totally biorecalcitrant, and it is also quite resistant to photodegradation.

Influence of Oxygen Ion Migration from Substrates on Photochemical Degradation of CH3NH3PbI3 Hybrid Perovskite

Measurements of XPS survey, core levels (N 1s, O 1s, Pb 4f, I 3d), and valence band (VB) spectra of CH3NH3PbI3 (MAPbI3) hybrid perovskite prepared on different substrates (glass, indium tin oxide (ITO), and TiO2) aged under different light-soaking conditions at room temperature are presented. The results reveal that the photochemical stability of MAPbI3 depends on the type of substrate and gradually decreases when glass is replaced by ITO and TiO2. Also, the degradation upon exposure to visible light is accompanied by the formation of MAI, PbI2, and Pb0 products as shown by XPS core levels spectra. According to XPS O 1s and VB spectra measurements, this degradation process is superimposed on the partial oxidation of lead atoms in ITO/MAPbI3 and TiO2/MAPbI3, for which Pb–O bonds are formed due to the diffusion of the oxygen ions from the substrates. This unexpected interaction leads to additional photochemical degradation.

Titanium Dioxide and Its Applications in Mechanical, Electrical, Optical, and Biomedical Fields

Titanium dioxide (TiO2), owing to its non-toxicity, chemical stability, and low cost, is one of the most valuable ceramic materials. TiO2 derived coatings not only act like a ceramic protective shield for the metallic substrate but also provide cathodic protection to the metals against the corrosive solution under Ultraviolet (UV) illumination. Being biocompatible, TiO2 coatings are widely used as an implant material. The acid treatment of TiO2 promotes the attachment of cells and bone tissue integration with the implant. In this chapter, the applications of TiO2 as a corrosion inhibitor and bioactive material are briefly discussed. The semiconducting nature and high refractive index of TiO2 conferred UV shielding properties, allowing it to absorb or reflect UV rays. Several studies showed that a high ultraviolet protection factor (UPF) was achieved by incorporating TiO2 in the sunscreens (to protect the human skin) and textile fibers (to minimize its photochemical degradation). The rutile phase of TiO2 offers high whiteness, and opacity owing to its tendency to scatter light. These properties enable TiO2 to be used as a pigment a brief review of which is also addressed in this chapter. Since TiO2 exhibits high hardness and fracture toughness, the wear rate of composite is considerably reduced by adding TiO2. On interacting with gases like hydrogen at elevated temperatures, the electrical resistance of TiO2 changes to some different value. The change in resistance can be utilized in detecting various gases that enables TiO2 to be used as a gas sensor for monitoring different gases. This chapter attempts to provide a comprehensive review of applications of TiO2 as an anti-corrosion, wear-resistant material in the mechanical field, a UV absorber, pigment in the optical sector, a bioactive material in the biomedical field, and a gas sensor in the electrical domain.