Removal of drug dexamethasone from aqueous matrices using low frequency ultrasound: Kinetics, transformation products, and effect of microplastics.

Sonochemical oxidation was employed for the degradation of the drug dexamethasone (Dex). The oxidation at 20 kHz followed pseudo-first-order kinetics and increased with applied ultrasound power density. Acoustic cavitation at 71 W/L was able to eliminate 500 µg/L of dexamethasone from ultrapure water at inherent pH in less than 60 min. The oxidation was enhanced at pH 3 and decreased at increased Dex concentration. Scavenging experiments with tert-butanol showed that hydroxyl radicals play a crucial role in decomposition, where the reaction mainly occurs on the gas-liquid interface of the formed cavities. The addition of chloride did not affect Dex removal, while in the presence of 10 mg/L of humic acid or bicarbonate, the apparent kinetic constant decreased from 0.0423 ± 0.004 min-1 to about 0.03 ± 0.002 min-1. The rate in secondary effluent was 3.3 times lower than in ultrapure water due to the complexity of the actual matrix. Six transformation products were identified via high resolution LC-MS during the sonochemical oxidation of 3 mg/L Dex in ultrapure water. The presence of polyethylene or polystyrene microplastics slightly enhanced DEX sonodegradation. The effect of ultrasound irradiation at 71 W/L for 60 min on the microplastics surfaces was inconsiderable.

Heat-activated persulfate for the degradation of micropollutants in water: A comprehensive review and future perspectives.

This work is a critical review of the most important studies that have dealt with heat-activated persulfate to degrade persistent micropollutants in the last six years. The effect of the different operating parameters is discussed, wherein in all cases, the efficiency was favored at higher temperatures and oxidant concentrations. Particular emphasis was given to the effect of the aqueous matrix. Since heat activation is a homogeneous process based on the production of free radicals, in most of the studies presented, the removal of pollutants decreases as the complexity of the aqueous matrix increases except in cases where secondary oxidative species are produced that are selective with specific pollutants. It has also been observed that the change in toxicity usually follows the removal of the parent compound despite the formation of several by-products. Nowadays, combining different processes for the simultaneous activation of persulfate seems to be gaining ground. A hybrid process is an interesting strategy to reduce costs and increase efficiency, especially in real wastewater. In this light, the most interesting studies of hybrid systems for the destruction of micropollutants in recent years based on thermally activated persulfate are also summarized. Finally, some steps are proposed for future research towards the industrial application, including the study of chemical mixtures, the integrated toxicity assessment, the examination of simultaneous disinfection and decomposition of pollutants into real wastewater, the estimation of the required costs, and energy the combination of processes and their coupling with renewable sources, and the design of pilot plants and the scale-up of the hybrid processes.

Solar light induced photocatalytic removal of sulfamethoxazole from water and wastewater using BiOCl photocatalyst.

The photocatalytic activity of bismuth oxychloride (BiOCl) toward sulfamethoxazole (SMX) elimination was investigated. BiOCl was synthesized according to a simple method using thiourea. Its physicochemical characteristics were determined by nitrogen physisorption, X-Ray diffraction, diffuse reflectance spectroscopy, scanning electron microscopy and transmission electron microscopy. Simulated solar irradiation and 1 g/L BiOCl, could effectively remove 0.5 mg/L SMX in less than 90 min. An increase in SMX concentration from 0.25 mg/L to 4 mg/L decreased the observed kinetic constant. Concerning the pH effect, it was found that under alkaline conditions SMX removal was slightly hindered. The water matrix's influence on SMX removal was explored, carrying out experiments in real water matrices, (bottled water (BW) and secondary effluent (WW)). Interestingly SMX removal was not practically altered in WW secondary effluent, but it was slightly hindered in BW bottled water. Experiments, performed in synthetic matrices, revealed that the presence of bicarbonates and chlorides slightly slowed down degradation kinetics, while humic acid enhanced SMX removal at concentrations up to 10 mg/L. Finally, an enhancement on SMX degradation was observed in the presence of persulfate. Quenching experiments of potential reactive species revealed that SMX degradation takes place mainly through reaction with hydroxyl radicals and photogenerated electrons.

On the industrial symbiosis of alumina and iron/steel production: Suitability of ferroalumina as raw material in iron and steel making.

The biggest challenge for our society, in order to foster the sustainable circular economy, is the efficient recycling of wastes from industrial, commercial, domestic and other streams. The transition to a circular economy is the goal of the European Commission's Circular Economy Action, which was first launched in 2015. In 2020 the above action plan announced initiatives along the entire life cycle of the product, with the aim to make sustainable products the norm in the EU. Therefore, it is anticipated that the above action will result in an increase in Europe's economic competitiveness, sustainability, resource efficiency and resource security. Within this context, the suitability of ferroalumina as a raw material in the blast furnace is investigated. Ferroalumina is the product of the high-pressure filter press dewatering process of the Greek red mud generated during the production of alumina by means of the Bayer cycle. Ferroalumina is a low-cost raw material and its possible charging in the blast furnace and/or steelmaking aggregates is a step towards industrial symbiosis, where the wastes, namely by-products, of an industry or an industrial process, become the raw materials for another. In the present work the effect of ferroalumina addition as a raw material was examined by smelting ferroalumina, blast furnace-slag, lime and scrap at 1550°C in a graphite crucible and a constant slag basicity. The increase of the alumina content in the slag improves the desulfurization capacity. Moreover, the silicon exchange between slag and metal was examined. The results indicate that the alkalis' capacity of the slag increases with the addition of ferroalumina. The analysis of the finally obtained slag suggests that it could be suitable for utilization in slag-cement production.

Degradation of sulfamethoxazole with persulfate using spent coffee grounds biochar as activator.

In the present study, biochar from spent coffee grounds was synthesized via pyrolysis at 850 °C for 1 h, characterized and employed as catalyst for the degradation of sulfamethoxazole (SMX) by persulfate activation. A variety of techniques, such as physisorption of N2, scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray diffraction, thermogravimetric analysis, and potentiometric mass titration, were employed for biochar characterization. The biochar has a surface area of 492 m2/g, its point of zero charge is 6.9, while mineral deposits are limited. SMX degradation experiments were performed mainly in ultrapure water (UPW) at persulfate concentrations between 100 and 1000 mg/L, biochar concentrations between 50 and 200 mg/L, SMX concentrations between 500 and 2000 µg/L and initial solution pH between 3 and 10. Real matrices, besides UPW, were also tested, namely bottled water (BW) and treated wastewater (WW), while synthetic solutions were prepared spiking UPW with bicarbonate, chloride, humic acid or alcohols. Almost complete removal of SMX can be achieved using 200 mg/L biochar and 1000 mg/L sodium persulfate (SPS) within 75 min. The presence of biochar is important for the degradation process, while the activity of the biochar increases linearly with SPS concentration. Degradation follows a pseudo-order kinetic model and the rate increases with increasing biochar concentration and decreasing SMX concentration. Although SMX adsorption onto the biochar surface is favored at acidic conditions, degradation proceeds equally fast regardless of the initial solution pH. Reactions in either real matrix are slower, resulting in 55% SMX removal in 60 min for WW. Bicarbonate causes severe inhibition as only 45% of SMX can be removed within 75 min in UPW. The addition of alcohol slightly inhibits degradation suggesting that the reaction pathway is either under electron transfer control or due to the generation of surface oxygen radicals with higher oxidation potential than the homogeneously produced radicals.

Electrochemical oxidation of butyl paraben on boron doped diamond in environmental matrices and comparison with sulfate radical-AOP.

The electrochemical oxidation (EO) of butyl paraben (BP) over boron-doped diamond (BDD) anode was studied in this work. Emphasis was put on degradation performance in various actual water matrices, including secondary treated wastewater (WW), bottled water (BW), surface water (SW), ultrapure water (UW), and ultrapure water spiked with humic acid (HA). Experiments were performed utilizing 0.1 M Na2SO4 as the electrolyte. Interestingly, matrix complexity was found to favor BP degradation, i.e. in the order WW ~ BW > SW > UW, thus implying some kind of synergy between the water matrix constituents, the reactive oxygen species (ROS) and the anode surface. The occurrence of chloride in water matrices favors reaction presumably due to the formation of chlorine-based oxidative species, and this can partially offset the need to work at increased current densities in the case of chlorine-free electrolytes. No pH effect in the range 3-8 on degradation was recorded. EO oxidation was also compared with a sulfate radical process using carbon black as activator of sodium persulfate. The matrix effect was, in this case, detrimental (i.e. UW > BW > WW), pinpointing the different behavior of different processes in similar environments.

Persulfate activation by modified red mud for the oxidation of antibiotic sulfamethoxazole in water.

Different pre-conditioning treatments were evaluated in order to stabilize red mud, a waste product from bauxite processing, for obtaining heterogeneous catalysts (named as B1-B3) that can be employed as suitable activators of sodium persulfate (SPS) for the degradation of sulfamethoxazole (SMX), a model antibiotic, in water. The presence of Fe3O4 in the composition of the catalysts was found to be a key factor for a suitable activation of SPS, according to the XPS measurements. The oxidation of SMX was successfully fitted to a pseudo-first-order kinetic model (r2 > 0.96), obtaining a 68% removal after 180 min when 0.8 mg/L of SMX was oxidized with 2 g/L of SPS and 2 g/L of catalyst B3. The presence of organic and/or inorganic constituents in the water matrix significantly hindered the degradation rate of SMX, the apparent kinetic constants being from 2 to 3 times lower than that determined in ultrapure water test. The use of ultrasound irradiation coupled to the addition of B3 catalyst improved importantly the SMX oxidation in real aqueous matrices, thus attaining values of removal which almost triplicated the ones obtained in absence of ultrasounds.

Current Trends in the Application of Nanomaterials for the Removal of Emerging Micropollutants and Pathogens from Water.

Water resources contamination has a worldwide impact and is a cause of global concern. The need for provision of clean water is becoming more and more demanding. Nanotechnology may support effective strategies for the treatment, use and reuse of water and the development of next-generation water supply systems. The excellent properties and effectiveness of nanomaterials make them particularly suitable for water/wastewater treatment. This review provides a comprehensive overview of the main categories of nanomaterials used in catalytic processes (carbon nanotubes/graphitic carbon nitride (CNT/g-C3N4) composites/graphene-based composites, metal oxides and composites, metal-organic framework and commercially available nanomaterials). These materials have found application in the removal of different categories of pollutants, including pharmaceutically active compounds, personal care products, organic micropollutants, as well as for the disinfection of bacterial, viral and protozoa microbial targets, in water and wastewater matrices. Apart from reviewing the characteristics and efficacy of the aforementioned nanoengineered materials for the removal of different pollutants, we have also recorded performance limitations issues (e.g., toxicity, operating conditions and reuse) for their practical application in water and wastewater treatment on large scale. Research efforts and continuous production are expected to support the development of eco-friendly, economic and efficient nanomaterials for real life applications in the near future.

Degradation of antibiotic ampicillin on boron-doped diamond anode using the combined electrochemical oxidation - Sodium persulfate process.

In this work, the electrochemical oxidation of antibiotic ampicillin (AMP) on a boron-doped diamond anode in the presence of sodium persulfate (SPS) was investigated (EO/SPS process). Experiments were conducted at AMP concentrations between 0.8 and 3 mg/L, SPS concentrations between 100 and 500 mg/L, current densities between 5 and 110 mA/cm2, in three water matrices (ultrapure water, bottled water and secondary treated wastewater), using 0.1 M Na2SO4 as the supporting electrolyte. AMP degradation follows a pseudo-first order kinetic expression with the apparent rate constant increasing with (i) increasing SPS concentration (from 0.08 min-1 to 0.36 min-1 at 0 and 500 mg/L SPS, respectively, 1.1 mg/L AMP, 25 mA/cm2), (ii) increasing current (from 0.08 min-1 to 0.6 min-1 at 5 and 110 mA/cm2, respectively, 1.1 mg/L AMP, 250 mg/L SPS), and (iii) decreasing AMP concentration (from 0.16 min-1 to 0.31 min-1 at 3 and 0.8 mg/L, respectively, 250 mg/L SPS, 25 mA/cm2). The presence of various anions (mainly bicarbonates) in bottled water did not impact AMP degradation. The observed kinetic constant decreased by 40% in the presence of 10 mg/L humic acid. On the other hand, process efficiency was enhanced almost 3.5 times in secondary effluent due to the electrogeneration of active chlorine species that promote indirect oxidation reactions in the bulk solution. The efficacy of the EO/SPS process was compared to and found to be considerably greater than a process where SPS was activated by simulated solar irradiation at an intensity of 7.3 × 10-7 E/(L.s) (SLR/SPS process). Coupling the two processes (EO/SLR/SPS) resulted in a cumulative, in terms of AMP degradation, effect. The combined process was tested for AMP degradation, mineralization and inhibition to Vibrio fischeri in wastewater; fast AMP removal was accompanied by low mineralization and incomplete toxicity removal.

New perspectives for Advanced Oxidation Processes.

Advanced Oxidation Processes (AOPs) are called to fill the gap between the treatability attained by conventional physico-chemical and biological treatments and the day-to-day more exigent limits fixed by environmental regulations. They are particularly important for the removal of anthropogenic pollutants and for this reason, they have been widely investigated in the last decades and even applied in the treatment of many industrial wastewater flows. However, despite the great development reached, AOPs cannot be considered mature yet and there are many new fields worthy of research. Some of them are going to be briefly introduced in this paper, including hybrid processes, heterogeneous semiconductor photocatalysis, sulphate-radical oxidation and electrochemical advanced oxidation for water/wastewater treatment. Moreover, the use of photoelectrochemical processes for energy production is discussed. The work ends with some perspectives that can be of interest for the ongoing and future research.

Oxidation of bisphenol A in water by heat-activated persulfate.

The heat-activated persulfate oxidation of bisphenol A (BPA), a representative endocrine disrupting compound, was investigated with respect to the effect of several process variables on degradation rates. The activation temperature appears to be the single most important parameter, i.e. a temperature increase from 40 to 70 °C results in an 80-fold rate increase. Regarding initial BPA concentration, the reaction follows a pseudo-first order rate expression, where the kinetic constant decreases from 11.5 10-2 to 3.5 10-2 min-1 when BPA concentration increases from 110 to 440 µg/L. Reactions in actual water matrices, such as bottled water and secondary treated wastewater, are slower than in pure water since various organic/inorganic water constituents compete with BPA for being oxidized by the reactive oxidizing species; this was confirmed with experiments in pure water spiked with humic acid or bicarbonate. Interestingly though, the presence of chloride seems to promote BPA degradation. Furthermore, degradation is favored at near-neutral pH and increased sodium persulfate (SPS) concentrations. Experiments at an increased BPA concentration of 20 mg/L were performed to identify transformation by-products (TBPs), as well as assess the mineralization and toxicity of the treated samples. Liquid chromatography time-of-flight mass spectrometry (LC-TOF-MS) revealed the formation of eleven TBPs of BPA and plausible pathways including hydroxylation, oxidation, cleavage and oligomerization reactions are proposed. Mineralization occurs slower than BPA degradation, while the toxicity to marine bacteria Vibrio fischeri increases during the early stages of the reaction but it progressively decreases thereafter.

Boron-doped diamond oxidation of amoxicillin pharmaceutical formulation: Statistical evaluation of operating parameters, reaction pathways and antibacterial activity.

The electrochemical oxidation of a commercial amoxicillin formulation over a boron-doped diamond (BDD) anode was investigated. The effect of initial COD concentration (1-2 g/L), current density (30-50 mA/cm2), treatment time (15-90 min), initial pH (3-9) and electrolyte concentration (2-4 g/L NaCl) on COD removal was assessed through a factorial design methodology. For the range of conditions in question, the first three single effects, as well as the interaction between COD and time were the most important ones in terms of mass of COD removed. Liquid chromatography time-of-flight mass spectrometry (LC-TOF-MS) was employed to identify major transformation by-products (TBPs); thirteen compounds were detected as TBPs of AMX electrochemical degradation, while several others appear in the original formulation. AMX degradation occurs though the following pathways: (i) hydroxylation mainly in the benzoic ring, (ii) opening of ß-lactam ring followed by decarboxylation, hydroxylation and re-arrangement, and (iii) bond cleavage between the carbons of amino and amide groups. Furthermore, the process is accompanied by the release of several ions, i.e. nitrate, sulfate and ammonium. The antibiotic activity of AMX up to 1000 mg/L was tested against Klebsiella pneumoniae and Enterococcus faecalis reference strains; both bacteria are completely inactivated at this concentration but the activity is reduced substantially at lower concentrations. Oxidized samples still exhibit some antibacterial activity (50-60%) which is due to TBPs and active chlorine species present in the liquid phase. The latter are generated from chloride ions and enhance considerably AMX degradation rates.

Boron-doped diamond electrooxidation of ethyl paraben: The effect of electrolyte on by-products distribution and mechanisms.

Ethyl paraben (EP), a representative emerging pollutant of the parabens family, was subject to electrochemical oxidation over a boron-doped diamond (BDD) anode. Experiments were carried out in a single-compartment cell at 10-70 mA cm-2 current density, 200-600 µg L-1 EP concentration, initial solution pH 3-9 and 0.1 M electrolyte concentration. The degradation rate is favored at increased current densities and in the presence of NaCl as the supporting electrolyte, while the pH effect is inconsiderable. For instance, the first order rate constant for the degradation of 200 µg L-1 EP at 30 mA cm-2 was 0.25, 0.1 and 0.07 min-1 with NaCl, Na2SO4 and HClO4, respectively. Degradation in secondary treated wastewater was faster than in pure water presumably due to the action of chloride ions present in the effluent. Liquid chromatography time-of-flight mass spectrometry (LC-TOF-MS) was employed to determine major transformation by-products (TBPs). The route of EP degradation with Na2SO4 involves hydroxylation and demethylation reactions, signifying the role of electrogenerated hydroxyl radicals in the process. Twenty one TBPs were identified with NaCl as the electrolyte, including several chlorinated and non-chlorinated dimers and trimers; these findings suggest that indirect oxidation mediated by chlorine radicals and other chlorine active species also takes place. In this view, the role of the supporting electrolyte is crucial since it can influence both reaction kinetics and pathways.

Solar photocatalysis as disinfection technique: Inactivation of Klebsiella pneumoniae in sewage and investigation of changes in antibiotic resistance profile.

The presence of pathogenic microorganisms in wastewater and their resistant nature to antibiotics impose effective disinfection treatment for public health and environmental protection. In this work, photocatalysis with metal-doped titania under artificial and natural sunlight, chlorination and UV-C irradiation were evaluated for their potential to inactivate Klebsiella pneumoniae in real wastewater. Their overall effect on antibiotic resistance profile and target antibiotic resistance genes (ARGs) was also investigated. In particular, Mn-, Co- and binary Mn/Co-TiO2 were tested resulting in bacterial decrease from 4 to 6 Logs upon 90 min of exposure to simulated solar irradiation. The response of catalysts under natural solar light was insufficient, as only a 2 Log reduction was recorded even after 60 min of treatment. The relative activity of the applied methods for K. pneumoniae inactivation was decreased in the order: photocatalysis with the binary Co/Mn-TiO2 under artificial light > chlorination with dose of 5 mg/L of free chlorine > UV-C irradiation, at an initial bacterial concentration of 107 CFU/mL. The applied methods showed various effects on antibiotic resistance profile in residual cells. Among the tested antibiotics (ampicillin, cefaclor, sulfamethoxazole and tetracycline), considerable changes in MIC values were recorded for cefaclor and tetracycline. Resistance of surviving cells after treatment remained in high levels, reflecting the abundance of the corresponding target ARGs, namely tetA, tetM, sul1, blaTEM and ampC. The notable presence of target ARGs post disinfection raises concerns and makes wastewater effluent a carrier of antibiotic resistance elements into the aquatic environment.

Removal of antibiotics in a parallel-plate thin-film-photocatalytic reactor: Process modeling and evolution of transformation by-products and toxicity.

Photocatalytic degradation of sulfamethoxazole (SMX) antibiotic has been studied under recycling batch and homogeneous flow conditions in a thin-film coated immobilized system namely parallel-plate (PPL) reactor. Experimentally designed, statistically evaluated with a factorial design (FD) approach with intent to provide a mathematical model takes into account the parameters influencing process performance. Initial antibiotic concentration, UV energy level, irradiated surface area, water matrix (ultrapure and secondary treated wastewater) and time, were defined as model parameters. A full of 25 experimental design was consisted of 32 random experiments. PPL reactor test experiments were carried out in order to set boundary levels for hydraulic, volumetric and defined defined process parameters. TTIP based thin-film with polyethylene glycol+TiO2 additives were fabricated according to pre-described methodology. Antibiotic degradation was monitored by High Performance Liquid Chromatography analysis while the degradation products were specified by LC-TOF-MS analysis. Acute toxicity of untreated and treated SMX solutions was tested by standard Daphnia magna method. Based on the obtained mathematical model, the response of the immobilized PC system is described with a polynomial equation. The statistically significant positive effects are initial SMX concentration, process time and the combined effect of both, while combined effect of water matrix and irradiated surface area displays an adverse effect on the rate of antibiotic degradation by photocatalytic oxidation. Process efficiency and the validity of the acquired mathematical model was also verified for levofloxacin and cefaclor antibiotics. Immobilized PC degradation in PPL reactor configuration was found capable of providing reduced effluent toxicity by simultaneous degradation of SMX parent compound and TBPs.

Ultraviolet-activated persulfate oxidation of methyl orange: a comparison between artificial neural networks and factorial design for process modelling.

In this work, the degradation of the azo dye methyl orange in model aqueous solutions by UVC light-induced persulfate oxidation was studied. Five operating parameters that may influence the decolorization kinetics were evaluated, namely, methyl orange (MO) (5-50 mg L(-1)) and sodium persulfate (SPS) (50-150 mg L(-1)) concentration, reaction time (up to 60 min), (un-buffered) solution pH (3-9) and the addition of NaCl (0-500 mg L(-1)). The process was simulated, applying and comparing two methodologies, namely two-level factorial design and an artificial neural network (ANN). It was found that MO concentration is the most influential parameter, followed by the reaction time and SPS concentration, while the effects of solution pH and the addition of sodium chloride are statistically less significant; this order of significance was predicted by both methodologies. The ANN can simulate the process more accurately (i.e. in terms of R(2), mean square error (MSE) and residuals) than factorial design, although it needs significantly larger sets of data and longer computational time.

Study of the generated genetic polymorphisms during the photocatalytic elimination of Klebsiella pneumoniae in water.

Klebsiella pneumoniae is considered to be an emerging pathogen persisting under extreme environmentally stressed conditions. The aim of the present study is the investigation of inactivation rates of this pathogen in water by means of heterogeneous photocatalytic treatment under solar irradiation and the induced genetic variance applying RAPD-PCR as a molecular typing tool. Novel Mn- and Co-doped TiO2 catalysts were assessed in terms of their disinfection efficiency. The reference strain of K. pneumoniae proved to be readily inactivated, since disinfection occurred rapidly (i.e. after only 10 min of treatment) and low levels of bacterial regrowth were recorded in the dark and under natural sunlight. Binary doped titania exhibited the best photocatalytic activity, verifying the synergistic effect induced by composite dopants. Applying RAPD analysis to viable cells after treatment we concluded that increasing the treatment time led to considerable alteration of RAPD profiles and the homology coefficient ranged almost between 35 and 60%. RAPD-PCR proved to be a useful typing molecular tool that under standardized conditions exhibits highly reproducible results. Genetic variation among isolates increased in relation to the period of treatment and prolonged irradiation in each case affected the overall alteration in band patterns. RAPD patterns were highly diverse between treated and untreated isolates when disinfection was performed with the Co-doped titania. The broad spectrum of genetic variance and generated polymorphisms has the potential to increase the already significant virulence of the species.

Acesulfame degradation by thermally activated persulfate: Kinetics, transformation products and estimated toxicity.

The existence of the artificial sweetener acesulfame (ACE) in quantities of significance can negatively impact water quality, and its consumption has been associated with deleterious health effects. The present investigation explores the efficacy of heat-activated sodium persulfate (SPS) for eliminating ACE. The complete degradation of 0.50 mg L-1 of ACE was achieved within 45 min under a reaction temperature of 50 °C and 100 mg L-1 of SPS. The impact of thermal decomposition on ACE at a temperature of 60 °C was negligible. This study considers several factors, such as the SPS and ACE loading, the reaction temperature, the initial pH, and the water matrix of the reactor. The results indicate that the method's efficiency is positively correlated with higher initial concentrations of SPS, whereas it is inversely associated with the initial concentration of ACE. Furthermore, higher reaction temperatures and acidic initial pH levels promote the degradation of acesulfame. At the same time, certain constituents of the water matrix, such as humic acid, chlorides, and bicarbonates, can hinder the degradation process. Additionally, the data from LC-QToF-MS analysis of the samples were used to investigate transformation through suspect and non-target screening approaches. Overall, ACE's eight transformation products (TPs) were detected, and a potential ACE decomposition pathway was proposed. The concentration of TPs followed a volcano curve, decreasing in long treatment times. The ecotoxicity of ACE and its identified TPs was predicted using the ECOSAR software. The majority of TPs exhibited not harmful values.

Sonocatalytic degradation of Bisphenol A from aquatic matrices over Pd/CeO2 nanoparticles: Kinetics study, transformation products, and toxicity.

In this work, different ratios of palladium - cerium oxide (Pd/CeO2) catalyst were synthesized and characterized, while their sonocatalytic activity was evaluated for the degradation of the xenobiotic Bisphenol A (BPA) from aqueous solutions. Sonocatalytic activity expressed as BPA decomposition exhibited a volcano-type behavior in relation to the Pd loading, and the 0.25Pd/CeO2 catalyst characterized by the maximum Pd dispersion and lower crystallite size demonstrated the higher activity. Using 500 mg/L of 0.25 % Pd/CeO2 increased the kinetic constant for BPA destruction by more than two times compared to sonolysis alone (20 kHz at 71 W/L). Meanwhile, the simultaneous use of ultrasound and a catalyst enhanced the efficiency by 50.1 % compared to the sum of the individual processes, resulting in 95 % BPA degradation in 60 min. The sonocatalytic degradation of BPA followed pseudo-first-order kinetics, and the apparent kinetic constant was increased with ultrasound power and catalyst loading, while the efficiency was decreased in bottled water and secondary effluent. From the experiments that were conducted using appropriate scavengers, it was revealed that the degradation mainly occurred on the bubble/liquid interface of the formed cavities, while the reactive species produced from the thermal or light excitation of the prepared semiconductor also participated in the reaction. Five first-stage and four late-stage transformation products were identified using UHPLC/TOF-MS, and a pathway for the sonocatalytic degradation of BPA was proposed. According to ECOSAR software prediction, most transformation by-products (TBPs) present lower ecotoxicity than the parent compound, although some remain toxic to the indicators chosen.

Biochar from olive tree twigs and spent malt rootlets as electrodes in Zn-air batteries.

Biochars, i.e. porous carbons obtained by pyrolysis of biomass, can act as electrocatalysts for oxygen evolution and oxygen reduction reaction. In the present work, two biochars have been prepared by using materials of completely different biomass origin: olive-tree twigs and spent malt rootlets (brewery wastes). Both biomass species were subjected to pyrolysis under limited oxygen supply and then they were activated by mixing with KOH and pyrolysis again. The obtained biochars were characterized by several techniques in order to determine their structural characteristics and the composition of their active components. Despite their different origin, the two biochars demonstrated similar structural and compositional characteristics thus highlighting the importance of the pyrolysis and activation procedure. Both biochars were used as electrocatalysts in the operation of rechargeable Zn-air batteries, where they also demonstrated similar electrocatalytic capacities with only a small advantage gained by olive-tree-twigs biochar. Compared to bare nanoparticulate carbon (carbon black), both biochars demonstrated a marked advantage towards oxygen evolution reaction.