Multi-Endpoint Acute Toxicity Assessment of Organic Compounds Using Large-Scale Machine Learning Modeling.

In recent years, alternative animal testing methods such as computational and machine learning approaches have become increasingly crucial for toxicity testing. However, the complexity and scarcity of available biomedical data challenge the development of predictive models. Combining nonlinear machine learning together with multicondition descriptors offers a solution for using data from various assays to create a robust model. This work applies multicondition descriptors (MCDs) to develop a QSTR (Quantitative Structure-Toxicity Relationship) model based on a large toxicity data set comprising more than 80,000 compounds and 59 different end points (122,572 data points). The prediction capabilities of developed single-task multi-end point machine learning models as well as a novel data analysis approach with the use of Convolutional Neural Networks (CNN) are discussed. The results show that using MCDs significantly improves the model and using them with CNN-1D yields the best result (R2train = 0.93, R2ext = 0.70). Several structural features showed a high level of contribution to the toxicity, including van der Waals surface area (VSA), number of nitrogen-containing fragments (nN+), presence of S-P fragments, ionization potential, and presence of C-N fragments. The developed models can be very useful tools to predict the toxicity of various compounds under different conditions, enabling quick toxicity assessment of new compounds.

Fragmentation of polypropylene into microplastics promoted by photo-aging; release of metals, toxicity and inhibition of biodegradability.

The widespread presence of microplastics (MP) in water represents an environmental problem, not only because of the harmful effects of their size and potential to vector other pollutants, but also because of the release of additives, degradation products and residues contained in the polymer matrix. The latter includes metallic catalysts, which are often overlooked. This study focuses on the photo-aging of polypropylene (PP) and the resulting structural changes that promote its fragmentation microplastics (PP-MPs) and release of metals, as well as the resulting toxicity of leachates and their potential to inhibit biodegradation of organics in water. The pristine, photo-aged and waste PP are ground under the same regime to assess susceptibility to fragmentation. Obtained PP-MPs are submitted to leaching tests; the release of organics and metals is monitored by Total Organic Carbon (TOC) and Inductively Coupled Plasma Mass Spectrometry (ICP-MS) analysis, respectively. The leachates are assessed for their toxicity against Vibrio fischeri, Daphnia magna and Pseudokirchneriella subcapitata and their influence on the biodegradability of the glucose solution. Photo-aging induced changes in the crystallinity and morphology of the PP and manifested in the abundance of smaller MPs, as revealed by the particle size distribution. In the case of pristine PP, all particles were > 100 µm in size, while aged PP yielded significant mass fraction of MPs <100 µm. The toxicity of leachates from aged PP-MPs is higher than that of pristine and exhibits a positive correlation with portion of metals released. The biodegradability of glucose is strongly inhibited by PP-MPs leachates containing a mixture of metals in trace concentrations.

An Atomic-Level Perspective on the interactions between Organic Pollutants and PET particles: A Comprehensive Computational Investigation.

Microplastics (MPs) have recently attracted a lot of attention worldwide due to their abundance and potentially harmful effects on the environment and on human health. One of the factors of concern is their ability to adsorb and disperse other harmful organic pollutants in the environment. To properly assess the adsorption capacity of MP for organic pollutants in different environments, it is pivotal to understand the mechanisms of their interactions in detail at the atomic level. In this work, we studied interactions between polyethylene terephthalate (PET) MP and small organic pollutants containing different functional groups within the framework of density functional theory (DFT). Our computational outcomes show that organic pollutants mainly bind to the surface of a PET model via weak non-bonding interactions, mostly hydrogen bonds. The binding strength between pollutant molecules and PET particles strongly depends on the adsorption site while we have found that the particle size is of lesser importance. Specifically, carboxylic sites are able to form strong hydrogen bonds with pollutants containing hydrogen bond donor or acceptor groups. On the other hand, it is found that in such kind of systems π-π interactions play a minor role in adsorption on PET particles.

Biomass Pyrolysis-Derived Biochar: A Versatile Precursor for Graphene Synthesis.

Graphene, a two-dimensional carbon allotrope with a honeycomb structure, has emerged as a material of immense interest in diverse scientific and technical domains. It is mainly produced from graphite by mechanical, chemical and electrochemical exfoliation. As renewable energy and source utilization increase, including bioenergy from forest and woody residues, processed, among other methods, by pyrolysis treatment, it can be expected that biochar production will increase too. Thus, its useful applications, particularly in obtaining high-added-value products, need to be fully explored. This study aims at presenting a comprehensive analysis derived from experimental data, offering insights into the potential of biomass pyrolysis-derived biochar as a versatile precursor for the controlled synthesis of graphene and its derivatives. This approach comprehended the highest energy output and lowest negative environmental footprint, including the minimization of both toxic gas emissions during processing and heavy metals' presence in the feedstock, toward obtaining biochar suitable to be modified, employing the Hummers and intercalation with persulfate salts methods, aiming at deriving graphene-like materials. Material characterization has revealed that besides morphology and structural features of the original wooden biomass, graphitized structures are present as well, which is proven clearly by Raman and XPS analyses. Electrochemical tests revealed higher conductivity in modified samples, implying their graphene-like nature.

Effect of Aging on Physicochemical Properties and Size Distribution of PET Microplastic: Influence on Adsorption of Diclofenac and Toxicity Assessment.

Microplastics (MPs) are detected in the water, sediments, as well as biota, mainly as a consequence of the degradation of plastic products/waste under environmental conditions. Due to their potentially harmful effects on ecosystems and organisms, MPs are regarded as emerging pollutants. The highly problematic aspect of MPs is their interaction with organic and inorganic pollutants; MPs can act as vectors for their further transport in the environment. The objective of this study was to investigate the effects of ageing on the changes in physicochemical properties and size distribution of polyethylene terephthalate (PET), as well as to investigate the adsorption capacity of pristine and aged PET MPs, using pharmaceutical diclofenac (DCF) as a model organic pollutant. An ecotoxicity assessment of such samples was performed. Characterization of the PET samples (bottles and films) was carried out to detect the thermooxidative aging effects. The influence of the temperature and MP dosage on the extent of adsorption of DCF was elucidated by employing an empirical modeling approach using the response surface methodology (RSM). Aquatic toxicity was investigated by examining the green microalgae Pseudokirchneriella subcapitata. It was found that the thermooxidative ageing process resulted in mild surface changes in PET MPs, which were reflected in changes in hydrophobicity, the amount of amorphous phase, and the particle size distribution. The fractions of the particle size distribution in the range 100-500 µm for aged PET are higher due to the increase in amorphous phase. The proposed mechanisms of interactions between DCF and PET MPs are hydrophobic and π-π interactions as well as hydrogen bonding. RSM revealed that the adsorption favors low temperatures and low dosages of MP. The combination of MPs and DCF exhibited higher toxicity than the individual components.

Structural Features Promoting Photocatalytic Degradation of Contaminants of Emerging Concern: Insights into Degradation Mechanism Employing QSA/PR Modeling.

Although heterogeneous photocatalysis has shown promising results in degradation of contaminants of emerging concern (CECs), the mechanistic implications related to structural diversity of chemicals, affecting oxidative (by HO•) or reductive (by O2•-) degradation pathways are still scarce. In this study, the degradation extents and rates of selected organics in the absence and presence of common scavengers for reactive oxygen species (ROS) generated during photocatalytic treatment were determined. The obtained values were then brought into correlation as K coefficients (MHO•/MO2•-), denoting the ratio of organics degraded by two occurring mechanisms: oxidation and reduction via HO• and O2•-. The compounds possessing K >> 1 favor oxidative degradation over HO•, and vice versa for reductive degradation (i.e., if K << 1 compounds undergo reductive reactions driven by O2•-). Such empirical values were brought into correlation with structural features of CECs, represented by molecular descriptors, employing a quantitative structure activity/property relationship (QSA/PR) modeling. The functional stability and predictive power of the resulting QSA/PR model was confirmed by internal and external cross-validation. The most influential descriptors were found to be the size of the molecule and presence/absence of particular molecular fragments such as C - O and C - Cl bonds; the latter favors HO•-driven reaction, while the former the reductive pathway. The developed QSA/PR models can be considered robust predictive tools for evaluating distribution between degradation mechanisms occurring in photocatalytic treatment.

Visible-Light Activation of Persulfate or H2O2 by Fe2O3/TiO2 Immobilized on Glass Support for Photocatalytic Removal of Amoxicillin: Mechanism, Transformation Products, and Toxicity Assessment.

Fe2O3/TiO2 nanocomposites were fabricated via a facile impregnation/calcination technique employing different amounts iron (III) nitrate onto commercial TiO2 (P25 Aeroxide). The as-prepared Fe2O3/TiO2 nanocomposites were characterized by X-ray diffraction (XRD), Raman spectroscopy (RS), scanning electron microscopy/energy-dispersive spectroscopy (SEM/EDXS), X-ray photoelectron spectroscopy (XPS), Brunauer-Emmett-Teller analysis (BET), electron impedance spectroscopy (EIS), photoluminescence spectroscopy (PL), and diffuse reflectance spectroscopy (DRS). As a result, 5% (w/w) Fe2O3/TiO2 achieved the highest photocatalytic activity in the slurry system and was successfully immobilized on glass support. Photocatalytic activity under visible-light irradiation was assessed by treating pharmaceutical amoxicillin (AMX) in the presence and absence of additional oxidants: hydrogen peroxide (H2O2) and persulfate salts (PS). The influence of pH and PS concentration on AMX conversion rate was established by means of statistical planning and response surface modeling. Results revealed optimum conditions of [S2O82-] = 1.873 mM and pH = 4.808; these were also utilized in presence of H2O2 instead of PS in long-term tests. The fastest AMX conversion possessing a zero-order rate constant of 1.51 × 10-7 M·min-1 was achieved with the photocatalysis + PS system. The AMX conversion pathway was established, and the evolution/conversion of formed intermediates was correlated with the changes in toxicity toward Vibrio fischeri. Reactive oxygen species (ROS) scavenging was also utilized to investigate the AMX conversion mechanism, revealing the major contribution of photogenerated h+ in all processes.

Effect of Functionalized Benzene Derivatives as Potential Hole Scavengers for BiVO4 and rGO-BiVO4 Photoelectrocatalytic Hydrogen Evolution.

Sustainable hydrogen production is one of the main challenges today in the transition to a green and sustainable economy. Photocatalytic hydrogen production is one of the most promising technologies, amongst which BiVO4-based processes are highly attractive due to their suitable band gap for solar-driven processes. However, the performance of BiVO4 alone in this role is often unsatisfactory. Herein we report the improvement of BiVO4 performance with reduced graphene oxide (rGO) as a co-catalyst for the photoelectrochemical water splitting (PEC-WS) in the presence of simple functionalized benzene derivatives (SFBDs), i.e., phenol (PH), benzoic acid (BA), salicylic acid (SA), and 5-aminosalicylic acid (5-ASA) as potential photogenerated hole scavengers from contaminated wastewaters. Linear sweep voltammetry and chronoamperometry, along with electrochemical impedance spectroscopy were utilized to elucidate PEC-WS performance under illumination. rGO has remarkably improved the performance of BiVO4 in this role by decreasing photogenerated charge recombination. In addition, 5-ASA greatly improved current densities. After 120 min under LED illumination, 0.53 µmol of H2 was produced. The type and concentration of SFBDs can have significant and at times opposite effects on the PEC-WS performance of both BiVO4 and rGO-BiVO4.

Structural features promoting adsorption of contaminants of emerging concern onto TiO2 P25: experimental and computational approaches.

The study of the structural features affecting the adsorption of organics, especially contaminants of emerging concern (CECs), onto TiO2 P25 in aqueous medium has far-reaching implications for the understanding and modification of TiO2 P25 in the roles such as an adsorbent and photocatalyst. The effect of pH and γ(TiO2 P25) as variables on the extent of removal of organics by adsorption on TiO2 P25 was investigated by response surface methodology (RSM) and quantitative structure-property relationship (QSPR) modeling. Experimentally determined coefficients of adsorption were used as responses in RSM, yielding a quadratic polynomial equation (QPE) for each of the studied organics. Furthermore, coefficients (A, B, C, D, E, and F) obtained from QPEs were used as responses in QSPR modeling to establish their dependence on the structural features of the studied organics. The functional stability and predictive power of the resulting QSPR models were confirmed with internal and external cross validation. The influence of structural features of organics on the adsorption process is explained by molecular descriptors included in the derived QSPR models. The most influential descriptors on the adsorption of organics on TiO2 P25 are found to be those correlated with ionization potential, molecular mass, and volume, then molecular fragments (e.g., -CH =) and particular topological features such as C and N atoms, or two heteroatoms (e.g., N and N or O and Cl) at certain distance. Derived QSPR models can be considered as robust predictive tools for evaluating efficiency of adsorption processes onto TiO2 P25, providing insights into influential structural features facilitating adsorption process.

Enhanced photo-degradation of N-methyl-2-pyrrolidone (NMP): Influence of matrix components, kinetic study and artificial neural network modelling.

This study investigates the degradation of N-methyl-2-pyrrolidone (NMP) by UV-C and UV-C/PMS-treatment processes. The degradation of NMP was less than 2% by UV-C photolysis. To enhance the degradation, PMS was used as a source of sulphate (SO4• -) and hydroxyl (HO•) radicals in the UV-C photolysis treatment system. The operational parameters such as initial pH and concentration of NMP and PMS and water matrix elements were studied to understand their effects on degradation. At pH = 6.3, λ = 260 nm, initial concentration of NMP = 10 mg/L, PMS = 300 mg/L and carbonate ion = 150 mg/L, the degradation of NMP was found to be 97.5%, along with 26.86% of TOC removal. The bicarbonate ions, nitrate ions, and chloride ions showed the inhibitory effect on the degradation of NMP. The NMP degradation was governed by pseudo first order kinetics. SO4• - was found to be the dominating degradation species through the radical quenching studies. The intermediates formed during the degradation were identified through LC-MS analysis, and a degradation pathway was proposed. The experimental data was successfully validated through the application of the developed ANN model. The R2 between expected and experimental outcomes was 0.97. The developed ANN model was successful in predicting the degradation of NMP in the given reaction conditions with the prediction accuracy of 90.91% and RMSE of 3.54.

Environmental aspects of UV-C-based processes for the treatment of oxytetracycline in water.

This study is focused on oxytetracycline (OTC) degradation by direct photolysis (UV-C) and photobased advanced oxidation processes (AOPs) (UV-C/H2O2 and UV-C/S2O82-). OTC degradation pathways were revealed by LC-MS/MS and GC-MS/MS analyses. The evolution/degradation profiles of 12 detected byproducts were correlated with changes in biodegradability and toxicity toward Vibrio fischeri recorded during the treatment. Both photobased AOPs yielded higher OTC degradation and mineralization rates than direct photolysis. The OTC degradation pathway was found to be rather specific regarding the main reactive species (HO• or SO4•-)/mechanism, yielding different patterns in toxicity changes, while biodegradability profiles were less affected. Biodegradability was correlated with the observed degradation and mineralization kinetics. The recorded toxicity changes indicate that byproducts formed by initial OTC degradation are more toxic than the parent pollutant. The prolonged treatment resulted in the formation of byproducts that contributed to a decrease in toxicity and an increase in biodegradability, as particularly emphasized in the case of UV-C/S2O82-.

Performance of UV/acetylacetone process for saline dye wastewater treatment: Kinetics and mechanism.

Futility of traditional advanced oxidation processes (AOPs) in saline wastewater treatment has stimulated the quest for novel "halotolerant" chemical oxidation technology. Acetylacetone (AA) has proven to be a potent photo-activator in the degradation of dyes, but the applicability of UV/AA for saline wastewater treatment needs to be verified. In this study, degradation of crystal violet (CV) was investigated in the UV/AA system in the presence of various concentrations of exogenic Cl- or Br-. The results reveal that degradation, mineralization and even accumulation of adsorbable organic halides (AOX) were not significantly affected by the addition of Cl- or Br-. Rates of CV degradation were enhanced by elevating either AA dosage or solution acidity. An apparent kinetic rate equation was developed as r = -d[CV]/dt = k[CV]a[AA]b = (7.34 × 10-4 mM1-(a+b) min-1) × [CV]a=0.16 [AA]b=0.97. In terms of results of radical quenching experiments, direct electron/energy transfer is considered as the major reaction mechanism, while either singlet oxygen or triplet state (3(AA)*) might be involved. Based on identification of degradation byproducts, a possible degradation pathway of CV in the UV/AA system is proposed.

One-Pot Synthesis of Sulfur-Doped TiO2/Reduced Graphene Oxide Composite (S-TiO2/rGO) With Improved Photocatalytic Activity for the Removal of Diclofenac From Water.

Sulfur-doped TiO2 (S-TiO2) composites with reduced graphene oxide (rGO), wt. % of rGO equal to 0.5%, 2.75%, and 5.0%, were prepared by a one-pot solvothermal procedure. The aim was to improve photocatalytic performance in comparison to TiO2 under simulated solar irradiation for the treatment of diclofenac (DCF) in aqueous medium. The obtained composites were characterized for physical-chemical properties using thermogravimetric analysis (TGA), X-ray diffractograms (XRD), Raman, scanning electron microscopy (SEM)/energy dispersive X-ray (EDX), Brauner Emmett Teller (BET), and photoluminescence (PL) analyses, indicating successful sulfur doping and inclusion of rGO. Sulfur doping and rGO have successfully led to a decrease in photogenerated charge recombination. However, both antagonistic and synergistic effects toward DCF treatment were observed, with the latter being brought forward by higher wt.% rGO. The composite with 5.0 wt.% rGO has shown the highest DCF conversion at pH 4 compared to that obtained by pristine TiO2, despite lower DCF adsorption during the initial dark period. The expected positive effects of both sulfur doping and rGO on charge recombination were found to be limited because of the subpar interphase contact with the composite and incomplete reduction of the GO precursor. Consequent unfavorable interactions between rGO and DCF negatively influenced the activity of the studied S-TiO2/rGO photocatalyst under simulated solar irradiation.

Recent Achievements in Development of TiO2-Based Composite Photocatalytic Materials for Solar Driven Water Purification and Water Splitting.

Clean water and the increased use of renewable energy are considered to be two of the main goals in the effort to achieve a sustainable living environment. The fulfillment of these goals may include the use of solar-driven photocatalytic processes that are found to be quite effective in water purification, as well as hydrogen generation. H2 production by water splitting and photocatalytic degradation of organic pollutants in water both rely on the formation of electron/hole (e-/h+) pairs at a semiconducting material upon its excitation by light with sufficient photon energy. Most of the photocatalytic studies involve the use of TiO2 and well-suited model compounds, either as sacrificial agents or pollutants. However, the wider application of this technology requires the harvesting of a broader spectrum of solar irradiation and the suppression of the recombination of photogenerated charge carriers. These limitations can be overcome by the use of different strategies, among which the focus is put on the creation of heterojunctions with another narrow bandgap semiconductor, which can provide high response in the visible light region. In this review paper, we report the most recent advances in the application of TiO2 based heterojunction (semiconductor-semiconductor) composites for photocatalytic water treatment and water splitting. This review article is subdivided into two major parts, namely Photocatalytic water treatment and Photocatalytic water splitting, to give a thorough examination of all achieved progress. The first part provides an overview on photocatalytic degradation mechanism principles, followed by the most recent applications for photocatalytic degradation and mineralization of contaminants of emerging concern (CEC), such as pharmaceuticals and pesticides with a critical insight into removal mechanism, while the second part focuses on fabrication of TiO2-based heterojunctions with carbon-based materials, transition metal oxides, transition metal chalcogenides, and multiple composites that were made of three or more semiconductor materials for photocatalytic water splitting.

Key structural features promoting radical driven degradation of emerging contaminants in water.

Diverse contaminants of emerging concern (CECs) can be found in nowadays aquatic environment, possessing high potential to cause adverse ecological and human health effects. Due to their recalcitrance, conventional water treatment methods are shown to be inadequately effective. Thus, their upgrade by advanced oxidation processes, involving the generation of highly reactive species (HO and SO4-), is highly demanded. In order to assess the susceptibility of CECs by HO and SO4-, as well as to determine the corresponding reaction rate constants kHO and kSO4-, the complex experimental studies has to be maintained. The alternative is the application of modeling approaches which correlate structural characteristics with activities/properties of interest, i.e. quantitative structure activity/property relationship (QSAR/QSPR). In this study kHO and kSO4- of fifteen selected CECs were determined by competitive kinetics, and afterward used to elucidate key structural features promoting their degradation. In that purpose, QSPR models were constructed using multiple linear regression (MLR) combined with genetic algorithm (GA) approach. The models were submitted to the internal and external validation (using additional set of 17 CECs). Selected 3-variable models predicting kHO and kSO4- were characterized with high accuracy and predictivity (R2 = 0.876 and Q2 = 0.847 and R2 = 0.832 and Q2 = 0.778, respectively). Although selected models at the first sight include descriptors derived through complicated calculation procedures, their weighting schemes indicate on their relevance and transparency toward established reaction theories and differences regarding radical type.

Toxicity of aromatic pollutants and photooxidative intermediates in water: A QSAR study.

Extensive commercial use of aromatic hydrocarbons results with significant amounts of these chemicals and related by-products in waters, causing a severe ecological and health threat, thus requiring an increased attention. This study was aimed at developing models for prediction of the initial toxicity of the aromatic water-pollutants (expressed as EC50 and TU0) as well as the toxicity of their intermediates at half-life of the parent pollutant (TU1/2). For that purpose, toxicity toward Vibrio fischery was determined for 36 single-benzene ring compounds (S-BRCs), diversified by the type, number and position of substituents. Quantitative structure-activity relationship (QSAR) methodology paired with genetic algorithm optimization tool and multiple linear regression was applied to obtain the models predicting the targeted toxicity, which are based on pure structural characteristics of the tested pollutants, avoiding thus additional experimentation. Upon derivation of the models and extensive analysis on training and test sets, 4-, 4- and 5-variable models (for EC50 and TU0, TU1/2, respectively) were selected as the most predictive possessing 0.839

Elucidating the Photocatalytic Behavior of TiO2-SnS2 Composites Based on Their Energy Band Structure.

TiO2-SnS2 composite semiconducting photocatalysts with different building component ratios were prepared by hydrothermal synthesis (TiO2-SnS2-HT) and by immobilization of commercial TiO2 and SnS2 particles (TiO2-SnS2-COMM). The band gap values, which determine the catalysts’ photoactivity, were examined by diffuse reflectance spectroscopy and Kubelka⁻Munk transformations. The catalysts’ surface properties: specific surface area, charge and adsorption capacitance at the solid⁻solution interface were characterized using BET analysis, potentiometric titration and electrochemical impedance spectroscopy, respectively. The electronic band structure of TiO2-SnS2 photocatalyst, as the key property for the solar-driven photocatalysis, was deduced from the thermodynamic data and the semiconducting parameters (type of semiconductivity, concentration of the charge carriers, flat band potential) obtained by Mott⁻Schottky analysis. The photoactivity of both composites was studied in photocatalytic treatment of diclofenac (DCF) under simulated solar irradiation and was compared to the benchmark photocatalyst (TiO2 P25) activity. The influence of process parameters, such as pH, H2O2, and composite formulation on the effectiveness of DCF removal and conversion was investigated and discussed by employing response surface modeling (RSM) approach. The photocatalytic efficiency of both composite materials was discussed on the basis of the hetereojunction formation that facilitated the photoelectron transfer, promoting more efficient photocatalytic degradation of DCF.

Reactivation and reuse of TiO2-SnS2 composite catalyst for solar-driven water treatment.

One of the most important features of photocatalytic materials intended to be used for water treatment is their long-term stability. The study is focused on the application of thermal and chemical treatments for the reactivation of TiO2-SnS2 composite photocatalyst, prepared by hydrothermal synthesis and immobilized on the glass support using titania/silica binder. Such a catalytic system was applied in solar-driven treatment, solar/TiO2-SnS2/H2O2, for the purification of water contaminated with diclofenac (DCF). The effectiveness of studied reactivation methods for retaining TiO2-SnS2 activity in consecutive cycles was evaluated on basis of DCF removal and conversion, and TOC removal and mineralization of organic content. Besides these water quality parameters, biodegradability changes in DCF aqueous solution treated by solar/TiO2-SnS2/H2O2 process using simply reused (air-dried) and thermally and chemically reactivated composite photocatalyst through six consecutive cycles were monitored. It was established that both thermal and chemical reactivation retain TiO2-SnS2 activity in the second cycle of its reuse. However, both treatments caused the alteration in the TiO2-SnS2 morphology due to the partial transformation of visible-active SnS2 into non-active SnO2. Such alteration, repeated through consecutive reactivation and reuse, was reflected through gradual activity loss of TiO2-SnS2 composite in applied solar-driven water treatment.

Influence of process parameters on the effectiveness of photooxidative treatment of pharmaceuticals.

In this study, UV-C/H2O2 and UV-C/[Formula: see text] processes as photooxidative Advanced oxidation processes were applied for the treatment of seven pharmaceuticals, either already included in the Directive 2013/39/EU "watch list" (17α- ethynylestradiol, 17ß-estradiol) or with potential to be added in the near future due to environmental properties and increasing consumption (azithromycin, carbamazepine, dexamethasone, erythromycin and oxytetracycline). The influence of process parameters (pH, oxidant concentration and type) on the pharmaceuticals degradation was studied through employed response surface modelling approach. It was established that degradation obeys first-order kinetic regime regardless structural differences and over entire range of studied process parameters. The results revealed that the effectiveness of UV-C/H2O2 process is highly dependent on both initial pH and oxidant concentration. It was found that UV-C/[Formula: see text] process, exhibiting several times faster degradation of studied pharmaceuticals, is less sensitive to pH changes providing practical benefit to its utilization. The influence of water matrix on degradation kinetics of studied pharmaceuticals was studied through natural organic matter effects on single component and mixture systems.

TiO2-SnS2 nanocomposites: solar-active photocatalytic materials for water treatment.

The study is aimed at evaluating TiO2-SnS2 composites as effective solar-active photocatalysts for water treatment. Two strategies for the preparation of TiO2-SnS2 composites were examined: (i) in-situ chemical synthesis followed by immobilization on glass plates and (ii) binding of two components (TiO2 and SnS2) within the immobilization step. The as-prepared TiO2-SnS2 composites and their sole components (TiO2 or SnS2) were inspected for composition, crystallinity, and morphology using Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), X-ray diffraction (XRD), and scanning electron microscopy/energy-dispersive X-ray spectroscopy (SEM/EDX) analyses. Diffuse reflectance spectroscopy (DRS) was used to determine band gaps of immobilized TiO2-SnS2 and to establish the changes in comparison to respective sole components. The activity of immobilized TiO2-SnS2 composites was tested for the removal of diclofenac (DCF) in aqueous solution under simulated solar irradiation and compared with that of single component photocatalysts. In situ chemical synthesis yielded materials of high crystallinity, while their morphology and composition strongly depended on synthesis conditions applied. TiO2-SnS2 composites exhibited higher activity toward DCF removal and conversion in comparison to their sole components at acidic pH, while only in situ synthesized TiO2-SnS2 composites showed higher activity at neutral pH.