Degradation Of Pharmaceuticals Research Articles

Degradation of pharmaceuticals and other emerging pollutants employing bi-metal catalysts/magnesium and/or (green) hydrogen in aqueous solution.

Contaminations by pharmaceuticals, personal care products, and other emerging pollutants in water resources have become a seriously burgeoning issue of global concern in the first third of the twenty-first century. As societal reliance on pharmaceuticals continues to escalate, the inadvertent introduction of these substances into water reservoirs poses a consequential environmental threat. Therefore, the aim of this study was to investigate reductive degradation, particularly, catalytic hydrogenation regarding model pollutants such as diclofenac (DCF), ibuprofen (IBP), 17α-ethinylestradiol (EE2), or bisphenol-A (BPA), respectively, in aqueous solutions at lab scale. Iron bimetals (zero valent iron, ZVI, and copper, Cu, or nickel, Ni) as well as zero valent magnesium (Mg, ZVM) in combination with rhodium, Rh, or palladium, Pd, as hydrogenation catalysts (HK), were investigated. Studies were executed through various short-term batch experiments, with multiple sample collections, over a total range of 120min. The results indicated that DCF was attenuated at over 90 % when exposed to Fe-Cu or a Fe-Ni bimetal (applied as a single model pollutant). However, when DCF was part of a mixture alongside with IBP, EE2, and BPA, the attenuation efficacy decreased to 79 % with Fe-Cu and 23 % with Fe-Ni. Conversely, both IBP and BPA exhibit notably low attenuation levels with both bimetals, less than 50 %, both deployed as single substances or in mixtures. No reaction (degradation) products could be identified employing LC-MS, but sometimes a release of the parent pollutant when applying an acetic acid buffer could be noted to a certain extent, suggesting adsorption processes on corrosion products such as iron hydroxide and/or oxides. Surprisingly, Mg in combination with Rh (Rh-HK) or Pd (Pd-HK) showed a significantly rapid decrease in the concentrations of DCF, EE2, and BPA, in part up to approximately 100 %, that is, within a few minutes only in part due to hydrogenation degradation reactions (related reaction products could actually be identified by LC-MS; adsorption processes were not observed here). Moreover, kinetic modeling of the DCF degradation with Mg-Rh-HK was conducted at different temperatures (15 °C, 20 °C, 25 °C, 35 °C) and varied initial concentrations (2.5mg/L, 5.0mg/L, 7.5mg/L, 10.0mg/L). The outcomes prove that the degradation of DCF at the Rh-HK's surface followed a modified first-order kinetics, most probably by catalytic hydrodehalogenation and subsequent hydrogenation of the aromatic moieties (molecular hydrogen was provided by the corrosion of Mg). From the determined reaction rate constants at four different temperatures, the activation energy was estimated to be 59.6kJ/mol by means of the Arrhenius equation what is in good agreement with similar results reported in the literature. This coupled hydrodehalogenation and hydrogenation approach may be upscaled into a new promising technical process for comprehensively removing such pharmaceuticals and similar pollutants in sewage plants in a single step, furthermore, even in combination with adsorption by activated carbon and/or ozonation which have already been established at some sewage plants in Switzerland and Germany recently.

Solvothermally Grown Oriented WO3 Nanoflakes for the Photocatalytic Degradation of Pharmaceuticals in a Flow Reactor.

Contamination by pharmaceuticals adversely affects the quality of natural water, causing environmental and health concerns. In this study, target drugs (oxazepam, OZ, 17-α-ethinylestradiol, EE2, and drospirenone, DRO), which have been extensively detected in the effluents of WWTPs over the past decades, were selected. We report here a new photoactive system, operating under visible light, capable of degrading EE2, OZ and DRO in water. The photocatalytic system comprised glass spheres coated with nanostructured, solvothermally treated WO3 that improves the ease of handling of the photocatalyst and allows for the implementation of a continuous flow process. The photocatalytic system based on solvothermal WO3 shows much better results in terms of photocurrent generation and photocatalyst stability with respect to state-of-the-art WO3 nanoparticles. Results herein obtained demonstrate that the proposed flow system is a promising prototype for enhanced contaminant degradation exploiting advanced oxidation processes.

Sono-assisted photocatalytic degradation of ciprofloxacin in aquatic media using g-C3N4/MOF-based nanocomposite under visible light irradiation.

This research study is centered on the sono-assisted photocatalytic degradation of a well-known antibiotic (ciprofloxacin; CIP) in aquatic media using a g-C3N4/NH2-UiO-66 (Zr) catalyst under visible light irradiation. Initially, the catalyst was prepared by a simple method, and its physiochemical features were thoroughly analyzed by XRD, FT-IR, FE-SEM, EDX, EDS-Dot-Mapping, and UV-Vis analytical techniques. After that, the impact of several influential factors affecting the performance of the applied sono-assisted photocatalytic process such as the initial concentration of CIP, solution pH, catalyst dosage, light intensity, and ultrasound power was fully assessed, and the optimal conditions were established. After 75min of the sono-assisted photocatalytic treatment, the complete degradation of CIP (10mg/L) was accomplished under the condition as follows: g-C3N4/NH2-UiO-66 (Zr), 0.6g/L; pH, 5.0, and ultrasound power, light intensity 75 mw/cm2, 200 W/m2. Meanwhile, the photocatalytic degradation of CIP followed the pseudo-first-order kinetic model. In addition, the scavenger experiments demonstrated that OH˚ and O2°- radicals played a key role in the sono-assisted photocatalytic degradation process. It is also acknowledged that the applied catalyst was reused for five consecutive runs with a minor loss observed in its degradation efficiency. In a further experiment, a significant synergistic effect with regard to the degradation of CIP was observed once all three major parameters (visible light, ultrasound waves, and catalyst) were used in combination compared to each used alone. To sum up, it is thought that the integration of g-C3N4/MOF-based catalyst, ultrasound waves, and visible light irradiation could be potentially applied as a promising strategy for the degradation of various pharmaceuticals on account of high degradation performance, simple operation, excellent reusability, and eco-friendly approach.

Porous-carbon/manganese composite catalyst transformed from waste biomass as peroxymonosulfate activator for carbamazepine degradation

Activation of peroxymonosulfate (PMS) with solid catalysts for organic pharmaceutical degradation still faces challenge due to the demand of inexpensive catalysts. In this study, manganese-oxidizing microalgae (MOM) and its associated biogenic manganese oxides (BMO) were employed to prepare biomass-transformed porous-carbon/manganese (B-PC/Mn) catalyst through high-temperature calcination (850 °C). Remarkably, 100 % of carbamazepine (CBZ) was degraded within 30 min in the B-PC/Mn/PMS system. The degradation kinetic constant was 0.1718 min−1, which was 44.0 times higher than that of the biomass-transformed porous carbon mixed with MnOx activated PMS system. 1O2 was generated in the B-PC/Mn/PMS system, which is responsible for CBZ degradation. The MOM-BMO-associated structure greatly increased the specific surface areas and the contents of the C = O and pyrrolic-N groups, which facilitated PMS activation. The structure also induced the generation of Mn5C2, which exhibited a strong adsorption towards PMS. This study provides a novel strategy for preparing catalysts by using waste biomass.

Addressing challenges of BiVO4 light-harvesting ability through vanadium precursor engineering and sub-nanoclusters deposition for peroxymonosulfate-assisted photocatalytic pharmaceuticals removal

In this study, we present a complex approach for increasing light utilisation and peroxymonosulfate (PMS) activation in BiVO4-based photocatalyst. This involves two key considerations: the design of the precursor for BiVO4 synthesis and interface engineering through CuOx sub-nanoclusters deposition. The designed precursor of ammonium methavanadate (NH4VO3, NHV) leads to reduction in particle size, better dispersion and improved light harvesting ability, confirmed by the calculations of the local volume rate of photon absorption (LVRPA) using the Six-Flux Radiation Absorption-Scattering model. The morphological changes result in a significant improvement in photocatalytic activity under visible light for the degradation of pharmaceuticals (naproxen and ofloxacin) compared to the commercial NH4VO3. Additionally, CuOx sub-nanoclusters were deposited on designed BiVO4 and characterised using X-ray absorption near edge structure (XANES). The presence of sub-nanoclusters enhanced charge carriers separation, resulting in an increase in the apparent rate constants of 1.60 and 3.32-times for photocatalytic NPX and OFL removal, respectively. The application of obtained Vis light active photocatalysts in the presence of 0.1 mM PMS resulted in remarkably more efficient degradation of NPX (100 % within 60 min) and OFL (98.2 % within 120 min). PMS/Vis420/CuOx/BiVO4 system exhibited high stability and reusability in the subsequent cycles of photodegradation. However, high PMS dosage induced Bi leaching which may cause the instability of the photocatalyst. Finally, to address the environmental implications of pharmaceutical removal and adhere to the Guidelines for drinking-water quality, toxicity assessments using Vibrio fischeri bacteria were performed and compared to a quantitative structure–activity relationship (QSAR) model.

An insight into the role of experimental parameters in advanced oxidation process applied for pharmaceutical degradation.

The advanced oxidation process (AOP) is an efficient method to treat recalcitrance pollutants such as pharmaceutical compounds. The essential physicochemical factors in AOP experiments significantly influence the efficiency, speed, cost, and safety of byproducts of the treatment process. In this review, we collected recent articles that investigated the elimination of pharmaceutical compounds by various AOP systems in a water medium, and then we provide an overview of AOP systems, the formation mechanisms of active radicals or reactive oxygen species (ROS), and their detection methods. Then, we discussed the role of the main physicochemical parameters (pH, chemical interference, temperature, catalyst, pollutant concentration, and oxidant concentration) in a critical way. We gained insight into the most frequent scenarios for the proper and improper physicochemical parameters for the degradation of pharmaceutical compounds. Also, we mentioned the main factors that restrict the application of AOP systems in a commercial way. We demonstrated that a proper adjustment of AOP experimental parameters resulted in promoting the treatment performance, decreasing the treatment cost and the treatment operation time, increasing the safeness of the system products, and improving the reaction stoichiometric efficiency. The outcomes of this review will be beneficial for future AOP applicants to improve the pharmaceutical compound treatment by providing a deeper understanding of the role of the parameters. In addition, the proper application of physicochemical parameters in AOP systems acts to track the sustainable development goals (SDGs).

Eat seldom is better than eat frequently: Pharmaceuticals degradation kinetics, enantiomeric profiling and microorganisms in moving bed biofilm reactors are affected by feast famine cycle times

Feast-famine (FF) regimes improved the removal of recalcitrant pharmaceuticals in moving bed biofilm reactors (MBBRs), but the optimal FF cycle remained unresolved. The effects of FF cycle time on the removal of bulk substrates (organic carbon and nitrogen) and trace pharmaceuticals by MBBR are systematically evaluated in this study. The feast to famine ratio was fixed to 1:2 to keep the same loading rate, but the time for the FF cycles varied from 18 h to 288 h. The MBBR adapted to the longest FF cycle time (288 h equaling 48 × HRT) resulted in significantly higher degradation rates (up to +183%) for 12 out of 28 pharmaceuticals than a continuously fed (non-FF) reactor. However, other FF cycle times (18, 36, 72 and 144 h) only showed a significant up-regulation for 2–3 pharmaceuticals compared to the non-FF reactor. Enantioselective degradation of metoprolol and propranolol occurred in the second phase of a two phase degradation, which was different for the longer FF cycle time. N-oxidation and N-demethylation pathways of tramadol and venlafaxine differed across the FF cycle time suggestin the FF cycle time varied the predominant transformation pathways of pharmaceuticals. The abundance of bacteria in the biofilms varied considerably between different FF cycle times, which possibly caused the biofilm to remove more recalcitrant bulk organic C and pharmaceuticals under long cycle times.

Natural Silicates Encapsulated Enzymes as Green Biocatalysts for Degradation of Pharmaceuticals.

Biocatalytic degradation with the use of enzymes has gained great attention in the past few years due to its advantages of high efficiency and environmental friendliness. Novel, cost-effective, and green nanoadsorbents were produced in this study, using natural silicates as an enzyme host matrix for core-shell immobilization technique. With the natural silicate as a core and silica layer as a shell, it was possible to encapsulate two different enzymes: horseradish peroxidase (HRP) and laccase, for removal and degradation of three pharmaceuticals: diclofenac (DFC), carbamazepine (CBZ), and paracetamol (PC). The biocatalysts demonstrated high oxidation rates for the selected pollutants. In particular HRP immobilized fly ash and perlite degraded DFC and PC completely during 3 days of interaction and also showed high degradation rates for CBZ. Immobilized laccase was successful in PC degradation, where up to 70-80% degradation of the compounds with aromatic rings was reported by NMR measurements for a high drug concentration of 10 μg/mL. The immobilization method played a significant role in this process by providing stability and protection for the enzymes over 3 weeks. Furthermore, the enzymes acted differently in the three chosen supports due to their complex chemical composition, which could have an effect on the overall enzyme activity.

In silico soil degradation and ecotoxicity analysis of veterinary pharmaceuticals on terrestrial species: first report.

With the aim of persistence property analysis and ecotoxicological impact of veterinary pharmaceuticals on different terrestrial species, different classes of veterinary pharmaceuticals (n=37) with soil degradation property (DT50) were gathered and subjected to QSAR and q-RASAR model development. The models were developed from 2D descriptors under organization for economic cooperation and development guidelines with the application of multiple linear regressions along with genetic algorithm. All developed QSAR and q-RASAR were statistically significant (Internal=R2adj: 0.721-0.861, Q2LOO: 0.609-0.757, and external=Q2Fn=0.597-0.933, MAEext=0.174-0.260). Further, the leverage approach of applicability domain assured the model's reliability. The veterinary pharmaceuticals with no experimental values were classified based on their persistence level. Further, the terrestrial toxicity analysis of persistent veterinary pharmaceuticals was done using toxicity prediction by computer assisted technology and in-house built quantitative structure toxicity relationship models to prioritize the toxic and persistent veterinary pharmaceuticals. This study will be helpful in estimation of persistence and toxicity of existing and upcoming veterinary pharmaceuticals.

Induced S-scheme CoMn-LDH/C-MgO for advanced oxidation of amoxicillin under visible light

The development of low-cost photostable heterostructures with robust interfacial contact is critical for competent photoactivity and practical applications. The solid-state approach was successfully employed for fabrication of novel stacked oval-shaped CoMn-LDH/C-MgO composites with Mn-O-Mg bridges for efficient interfacial charge separation induced by S-scheme charge transfer for degradation of amoxicillin (AMX). The persulfate (PS) activation mechanism was confirmed by Raman analysis using bond length relationship to peak shifts. PS activation rate was 1.8 times of CoMn-LDH/PS for the S-scheme heterojunction with a 99.97 ± 0.16 % removal efficiency after 60 min of irradiation at pH 5.2. S-scheme photocatalytic ozonation increased AMX mineralization rate by up to 8 times compared to ozonation. Antimicrobial studies confirmed bacterial growth inhibition of composites and the by-products of AMX degradation had reduced bacterial growth inhibition compared to AMX. This work demonstrated the development of an S-scheme CoMn-LDH/C-MgO heterojunction as a visible light heterogeneous photocatalyst for degradation of pharmaceuticals.

Unraveling the role of Co(II)-phosphate complex in trace Co(II) activated peroxymonosulfate process for water decontamination with phosphate surrounding

The evolution and role of Co(II)-phosphate complex in pH-dependent peroxymonosulfate (PMS) activation by trace Co(II) for phosphate-contained water decontamination was experimentally and theoretically investigated. The HPO42− species play the most positive effect through forming Co-HPO4 coordination for enhancing radical generation and pharmaceutical degradation (3.59 times) in neutral condition. The reduction of Co(III) to Co(II) was identified as a proton-coupled electron transfer process. In Co(II)/PMS system without phosphate, the protons from the neighboring H2O coordination will bind with the generated SO4•−, inducing proton poisoning effect and in situ radical quenching. While the HPO42− coordination not only modulates the Co 3d electronic structure to optimize the PMS interaction and charge transfer, but also alters the proton affinity to alleviate the proton poisoning effect, securing the radical generation. This study provides insights into the impacts of background factors on advanced oxidation processes and develops strategies for efficient remediation in real (waste)water matrix.

Degradation of pharmaceuticals in UV/H2O2 process: EEM-based kinetic model, transformation products and corresponding toxicity evaluation

Advanced oxidation process (AOP) by UV/H2O2 presented excellent performance on removing trace pharmaceuticals in wastewater. Monitoring the removal efficiency of pharmaceuticals rapidly can evaluate the effectiveness of UV/H2O2 process. And evaluating the potential risks of this technology is essential to facilitate its engineering application. In this study, diclofenac, ibuprofen, naproxen, carbamazepine and citalopram, which have potential biological effect to ecological environment, were degraded by UV/H2O2 in wastewater. Results suggested that UV/H2O2 could degrade 5 pharmaceuticals effectively. An EEM-based degradation kinetic model was constructed by combining pseudo first-order kinetic patterns of pharmaceuticals degradation and multiple exponential decay pattern of fluorescence degradation. This model could estimate the removal of pharmaceuticals rapidly and exhibited excellent predictive capability (R2 values > 0.90). Based on suspect and untargeted screening, 40 transformation products (TPs) were identified, with hydroxylation, (de)methylation and decarboxylation being the dominant pathways. Among them, 20 TPs were newly discovered. Furthermore, the predicted toxicity results from Ecological Structure-Activity Relationship (ECOSAR) model suggested that 37.5%− 42.5% of TPs exhibited higher toxicity than parent compounds. The increased toxicity of TPs of DCF and IBP could be attributed to decarboxylation. This study provides a promising and rapid method for monitoring the degradation of pharmaceuticals and estimating the toxicity of TPs. These findings facilitate further evaluation of the practicality and risks associated with the UV/H2O2 process for pharmaceutical removal in wastewater.

Rice husk–based pyrogenic carbonaceous material efficiently promoted peroxymonosulfate activation toward the non-radical pathway for the degradation of pharmaceuticals in water

Pristine pyrogenic carbonaceous material (BRH) obtained from rice husk and modified with FeCl3 (BRH-FeCl3) were prepared and explored as carbocatalysts for the activation of peroxymonosulfate (PMS) to degrade a model pharmaceutical (acetaminophen, ACE) in water. The BRH-FeCl3/PMS system removed the pharmaceutical faster than the BRH/PMS. This is explained because in BRH-FeCl3, compared to BRH, the modification (iron played a role as a structuring agent mainly) increased the average pore diameter and the presence of functional groups such as -COO−, -Si–O−, or oxygen vacancies, which allowed to remove the pollutant through an adsorption process and significant carbocatalytic degradation. BRH-FeCl3 was reusable during four cycles and had a higher efficiency for activating PMS than another inorganic peroxide (peroxydisulfate, PDS). The effects of BRH-FeCl3 and PMS concentrations were evaluated and optimized through an experimental design, maximizing the ACE degradation. In the optimized system, a non-radical pathway (i.e., the action of singlet oxygen, from the interaction of PMS with defects and/or -COO−/-Si–O− moieties on the BRH-FeCl3) was found. The BRH-FeCl3/PMS system generated only one primary degradation product that was more susceptible to biodegradation and less active against living organisms than ACE. Also, the BRH-FeCl3/PMS system induced partial removals of chemical oxygen demand and dissolved organic carbon. Furthermore, the carbocatalytic system eliminated ACE in a wide pH range and in simulated urine, having a low-moderate electric energy consumption, indicating the feasibility of the carbocatalytic process to treat water polluted with pharmaceuticals.

Synthesis of Imprinted Ag-PANI/CdS/Fe3O4/BC Heterojunction Towards Selective Adsorption and Degradation of the Specific Pharmaceuticals

Synthesis of Imprinted Ag-PANI/CdS/Fe3O4/BC Heterojunction Towards Selective Adsorption and Degradation of the Specific Pharmaceuticals

Pharmaceuticals degradation and pathogens inactivation in municipal wastewater: A comparison among UVC photo-Fenton with chelating agents, UVC/H2O2 and ozonation

In this work, emerging advanced oxidation processes (AOPs), namely UVC photo-Fenton with two chelating agents at neutral pH, were compared for the first time to consolidated AOPs, namely, UVC/H2O2 and Ozonation (O3) in the degradation of three pharmaceuticals (PhCs) and pathogens inactivation, in real municipal wastewater (RMWW) at pilot scale. Conventional UVC based AOP (UVC/H2O2 at 50 mg/L of H2O2) was faster, being able to degrade 80% of the sum of PhCs in RMWW after 2.5 min, while the same treatment time was required to achieve 60% removal by photo-Fenton. 60% removal of the sum of PhCs in RMWW by O3 was achieved only after 75 min, at the highest dose investigated (0.45 g O3/ L h). The detection limit (1 CFU/100 mL) for pathogens inactivation was achieved after 120 min by O3 for E. coli, while more time was required for Enterococcus (10 CFU/100 mL after 120 min). Faster inactivation was observed for UVC/H2O2 (15 mg/L), the DL being achieved just within 5 and 10 min for E. coli and Enterococcus, respectively. Accordingly, UVC/H2O2 at 15 mg/L would be an effective solution for simultaneous PhCs removal and bacteria inactivation, showing better performance compared to O3 and UVC photo-Fenton like process.

Improvement of the Carbocatalytic Degradation of Pharmaceuticals in Water by the Use of Ultrasound Waves

A carbonaceous material obtained from wood wastes (SW-Mn) was initially used for the removal of pharmaceuticals in water by a carbocatalytic system. The SW-Mn material adsorbed only 41% of the diclofenac (DCF) and 3% of the valsartan (VAL). Interestingly, SW-Mn activated peroxymonosulfate (PMS) and presented a significant increase in the removal rate of DCF, surpassing 90%, while VAL achieved a 24% removal rate at 20 min of treatment. The carbonaceous material was not effective in activating peroxydisulfate or hydrogen peroxide. Nevertheless, the addition of ultrasound waves at 40 kHz to the carbocatalytic system (SW-Mn +PMS) significantly enhanced VAL degradation, exhibiting a high synergy index (4.98). The routes of the degradation were determined using scavengers, and XPS and EPR analyses, evidencing the main action of singlet oxygen in both carbocatalytic and sonocarbocatalytic systems. It is important to note that radicals also participated in the sonocarbocatalytic process, albeit with a minor contribution. The reuse of SW-Mn was tested during various cycles, showing up to a 39.2% VAL degradation rate after the third consecutive reuse. Moreover, the sonocarbocatalytic system was applied to a sample of irrigation crop water spiked with VAL. The treatment induced a partial elimination of the pollutant due to some interfering effects of the matrix components.

Photoelectrocatalytic degradation of pharmaceuticals promoted by a metal-free g‑C3N4 catalyst

Graphitic carbon nitride (g-C3N4) recently emerged as a remarkable photoelectrocatalyst for water treatment. Advanced oxidation processes (AOPs) consisting of photoelectrocatalytic (PEC) systems are being researched towards the development of sustainable strategies for the complete removal of refractory contaminants from effluents of urban wastewater treatment plants (WWTPs). This work consists of the optimisation of a PEC system, composed of a boron-doped diamond (BDD) anode, titanium cathode, and a suspended g-C3N4 photoelectrocatalyst, for the treatment of both synthetic and real urban waste waters spiked with pharmaceutical active compounds (PhACs). Different working parameters were considered and optimised to improve degradation and mineralisation rates, such as the cathode material, anode-to-cathode distance, electrolyte resistivity, and matrix composition. The optimal conditions allowed removals of 100 % diclofenac, 88 % fluoxetine and 77 % ibuprofen in the complex wastewater matrix. Moreover, it was observed that the presence of other refractory organic molecules offered a greater impediment to PEC treatment than residual co-existing substances. The main oxidative agents were investigated by scavenging experiments, showing that generated holes and reactive oxy-species, i.e. hydroxyl and superoxide radicals, take a major role in the degradation of PhACs. The recyclability of the g-C3N4 suspension as photoelectrocatalyst in the PEC process provides a promising perspective for the development of wastewater treatment units.

Simultaneous degradation and rejection of PPCPs from wastewater in a 3DEO-FO-RO process

This study established a novel three-dimensional electrochemical oxidation coupled with forward osmosis and reverse osmosis (3DEO-FO-RO) system with the purpose to achieve simultaneous degradation and rejection of pharmaceuticals and personal care products (PPCPs) in wastewater. 18 frequently detected PPCPs were selected as the target pollutants to prepare the synthetic wastewater with a concentration of 200 μg/L for each pollutant. Ti/IrO2–Ta2O5–SnO2 mesh anode, titanium mesh cathode and Sn–Sb–Bi/γ-Al2O3 particles electrodes were integrated in the 3DEO-FO reactor. Experimental results demonstrated that degradation efficiency exceeding 98.5 % and rejection exceeding 99.4 % for each PPCP were achieved simultaneously in the 3DEO-FO-RO processes at a current density of 1 mA/cm2 after 8 h treatment. Despite variations in applied current density, the 3DEO-FO-RO processes exhibited superior PPCPs removal efficiencies, particularly for refractory compounds, compared to the 2DEO-FO-RO processes. Increased hydroxyl radical (·OH) generation in the 3D reactor was considered to be responsible for the excellent performance. Furthermore, results derived from ultraviolet (UV) absorption spectra and fluorescence excitation-emission matrix (EEM) spectra provided additional validation for the effective removal of PPCPs in the 3DEO-FO-RO processes, along with evidence indicating the decomposition of PPCPs into smaller constituents. Ultimately, the 3DEO-FO-RO process demonstrated its capacity in removing PPCPs from actual secondary effluent from a wastewater treatment plant. This integrated system coupling 3D EO with FO-RO membranes can provide an efficient approach for simultaneous degradation and rejection of trace contaminants for wastewater reuse.

Acetaminophen oxidation under solar light using Fe-BiOBr as a mild Photo-Fenton catalyst

Acetaminophen is an analgesic used as a first-choice treatment for pain and fever. When individuals consume acetaminophen, a portion of the drug is excreted through urine and can end up in wastewater. Water remediation from pharmaceuticals, such as acetaminophen, is required before reaching the environment. This work demonstrates that Fe–BiOBr using the solar photo-Fenton process eliminates acetaminophen at mild pH in aqueous media. Fe-BiOBr is produced using microwave-assisted solvothermal synthesis, and the formation of the BiOBr phase is confirmed with XRD. SEM and TEM demonstrated the flower-like morphology, in which crystallite size reduces as a function of the Fe loading. The chemical environment at the surface of Fe–BiOBr is investigated with XPS. The results are connected with Raman analysis, which suggests the presence of oxygen vacancies in Fe–BiOBr. Furthermore, the effect of Fe in BiOBr is assessed by determining the optical band gap with UV–Vis. The Fe-BiOBr functionality is assessed during acetaminophen degradation. Fe-BiOBr revealed excellent performance in degrading acetaminophen in the first minutes (Q = 10 kJ m−2) under natural sunlight. Results reveal that 1% Fe content in BiOBr can degrade acetaminophen and its main byproduct (30 min, Q = 50 kJ m−2) at pH 5 and using 0.25 gL-1 of catalyst. A synergistic mechanism between heterogeneous photocatalysis and Fenton processes with primary superoxide (•O2–) radical, followed by hydroxyl (•OH) radical and photogenerated holes (h+), is proposed. Our research contributes to the degradation of pharmaceuticals under mild conditions and sunlight irradiation.

Piezo-Photocatalytic Degradation of Pharmaceuticals in Water Using Calcined Natural Sphalerite

This study is the first to report the high performance of calcined natural sphalerite as a heterogeneous catalyst (Catalyst) in the piezo- and photocatalytic degradation of pharmaceuticals (bezafibrate and ceftriaxone) using high-frequency ultrasound (US, 1.7 MHz) and ultraviolet-light-emitting diodes (LED, 365 nm). The kinetic comparison showed that piezo-photocatalysis (LED + US + Catalyst) was more efficient than photocatalysis (LED + Catalyst) for degrading both contaminants in deionized water as well as in surface river water at natural pH (7.9). Despite reducing degradation rates (~1.7 times) in river water due to the scavenging effect of its constituents, ceftriaxone and bezafibrate were degraded by 77% and 48% after 1 h of exposure, respectively. Adding H2O2 increased the corresponding pseudo-first-order rate constants, and the complete degradation of ceftriaxone was achieved. However, the contribution of ultrasound at a given intensity was hidden, which resulted in a similar performance of piezo-photocatalysis and photocatalysis for treating river water. No pronounced synergy between the piezo- and photocatalytic processes was observed in the experimental conditions used. Nevertheless, the H2O2-assisted piezo-photocatalysis using high-frequency US, LED, and natural catalysts can be considered a novel and effective strategy for eliminating pharmaceuticals from real water without pH adjustment.