Mineralization Of Ibuprofen Research Articles

Novel composite of Zn/Ti-layered double hydroxide coupled with MXene for the efficient photocatalytic degradation of pharmaceuticals

In the present study, a hybrid photocatalyst of Zn/Ti layered double hydroxide (LDH) coupled with MXene – Ti3C2 was synthesized for the first time and applied in photocatalytic degradation of acetaminophen and ibuprofen, two commonly present in the natural environment and prone to accumulate in the aquatic ecosystem pharmaceuticals. The effect of MXene content (0.5 wt%, 2.5 wt%, and 5 wt%) on the photocatalytic activity of LDH/MXene composite was investigated. The composite of LDH/MXene containing 2.5 wt% of MXene revealed the highest photocatalytic activity in the degradation of acetaminophen (100% within 40 min) and ibuprofen (99.7% within 60 min). Furthermore, an improvement in acetaminophen and ibuprofen mineralization was observed for the composite material. Meanwhile, the introduction of interfering ions (Na+, Ca2+, Mg2+, Cl−, SO42−) in the model seawater did not affect the removal efficiency of both pharmaceuticals. The photocatalytic experiment performed in the four subsequent cycles, as well as FTIR, TEM, and XPS analyses after the photodegradation process confirmed the excellent stability and reusability of the prepared composite material. In order to evaluate the effect of various reactive oxidizing species (ROS) on the photocatalytic process, the trapping experiment was applied. It was noticed that •O2− had the main contribution in photocatalytic degradation of acetaminophen, while •OH and h+ mainly affected the degradation of ibuprofen. Finally, based on the results of Mott Schottky analysis, bandgap calculation, and ROS trapping experiment, the possible mechanism for pharmaceuticals degradation was proposed. This research illustrates the feasibility and novelty of the treatment of pharmaceuticals by LDH/MXene composites, implying that MXene plays a significant role in the electron-hole separation and thus high photocatalytic activity.

An electro-peroxone-based multi-pronged strategy for the treatment of ibuprofen and an emerging pharmaceutical wastewater using a novel graphene-coated nickel foam electrode

Conventional treatment technologies are inefficient in mineralizing emerging contaminants such as pharmaceuticals and personal care products (PPCPs), leading to their presence even in treated effluents. Such contaminants dwell in the water bodies for long, causing endocrine disruption and chronic toxicity to human and aquatic life. In this study, a novel three-dimensional graphene-coated nickel foam (Gr-NF) is explored for its performance in electro-peroxone process for the removal of ibuprofen, a non-steroidal anti-inflammatory drug and a model pharmaceutical contaminant. Furthermore, a benchmark study comparing the relative performance of the Gr-NF electrode, with a commonly used Reticulated Vitreous Carbon (RVC) electrode was carried out. In addition, the performance of electro-peroxone with two other common oxidation processes, viz. electrolysis and ozonation were critically compared.The Gr-NF electrode was subjected to several material characterization techniques to understand its structural and chemical characteristics. Typically, •OH radical generation can be achieved only during electro-peroxone. Here, interestingly, we observed •OH generation even during electrolysis using the Gr-NF electrode. Mineralization capacity of Gr-NF was found to be about two times that of RVC. Moreover, 87.0% mineralization of ibuprofen was achieved within 60 minutes. Mechanisms for in situ•OH generation are proposed. Degradation by-products of ibuprofen, along with their mechanisms were studied. The Gr-NF-based electro-peroxone system was also investigated for the treatment of a real pharmaceutical wastewater where it showed promise as a multi-pronged treatment strategy, with 75.0% TOC mineralization within 8 h, 99.7% disinfection within 5 minutes, 85.9% of decolorization, 78.0% of TSS removal within 180 minutes, and 85.0% removal of turbidity within 5 h. The study proves the enhanced performance of Gr-NF electrode over conventional ones such as RVC, along with enhanced capability of •OH radical generation, which makes it an attractive electrode for use in electro-peroxone.

Bimetallic Cu/Fe Catalysts for Ibuprofen Mineralization

At present, the use of conventional wastewater processes is becoming increasingly challenging, mainly due to the presence of biorecalcitrant organic matter. Advanced oxidation processes such as Fenton, Fenton-like and hybrid processes have been successfully employed for the treatment of highly concentrated and toxic non-biodegradable pollutants. Here, a series of bimetallic catalysts, based on Cu/Fe supported over ZrO2, were investigated for the mineralization of ibuprofen with a heterogeneous Fenton-like reaction. The materials were prepared by incipient wetness impregnation and characterized by standard techniques. Temperature-programmed experiments highlighted the promotion of the reduction in CuO due to the synergistic effects of the coupled redox cycles of copper (Cu2+/Cu+) and iron (Fe+3/Fe+2). 5%Cu-5%Fe/ZrO2 not only displays the highest ibuprofen mineralization (83%) under optimum conditions but also exploits its activity in a wider range of pH (3–5) with extremely low metal leaching. The recycling of bimetallic catalysts reveals that only the 5%Cu-5%Fe/ZrO2 system is able to provide sustainable activity in heterogeneous Fenton process.

Effluent decontamination by the ibuprofen-mineralizing strain, Sphingopyxis granuli RW412: Metabolic processes.

The high global consumption of ibuprofen and its limited elimination by wastewater treatment plants (WWTPs), has led to the contamination of aquatic systems by this common analgesic and its metabolites. The potentially negative environmental and public health effects of this emerging contaminant have raised concerns, driving the demand for treatment technologies. The implementation of bacteria which mineralize organic contaminants in biopurification systems used to decontaminate water or directly in processes in WWTPs, is a cheap and sustainable means for complete elimination before release into the environment. In this work, an ibuprofen-mineralizing bacterial strain isolated from sediments of the River Elbe was characterized and assayed to remediate different ibuprofen-polluted media. Strain RW412, which was identified as Sphingopyxis granuli, has a 4.48Mb genome which includes plasmid sequences which harbor the ipf genes that encode the first steps of ibuprofen mineralization. Here, we confirm that these genes encode enzymes which initiate CoA ligation to ibuprofen, followed by aromatic ring activation by a dioxygenase and retroaldol cleavage to unequivocally produce 4-isobutylcatechol and propionyl-CoA which then undergo further degradation. In liquid mineral salts medium, the strain eliminated more than 2mM ibuprofen within 74h with a generation time of 16h. Upon inoculation into biopurification systems, it eliminated repeated doses of ibuprofen within a few days. Furthermore, in these systems the presence of RW412 avoided the accumulation of ibuprofen metabolites. In ibuprofen-spiked effluent from a municipal WWTP, ibuprofen removal by this strain was 7 times faster than by the indigenous microbiota. These results suggest that this strain can persist and remain active under environmentally relevant conditions, and may be a useful innovation to eliminate this emerging contaminant from urban wastewater treatment systems.

Effıcıent photocatalytıc degradatıon of the pharmaceutical ibuprofen over Fe-FSM-16 photo-catalyst under UV ırradıatıon

ABSTRACT Iron doped mesoporous silica (Fe-FSM-16) synthesized by ultrasonic method was used as photo-catalyst for the photo-degradation of ibuprofen (IBP) under UV light. Fe-FSM-16 was characterized by various physicochemical techniques. The effect of the photo-catalyst dose, the effect of pH and the IBP concentration were examined to enhance the IBP photo-degradation. The removal of the IBP was monitored by UV-visible spectrophotometer and liquid chromatography, and the IBP mineralization was measured by the determination of the total organic carbon (TOC) and the chemical oxygen demand (COD). Fe-FSM-16 has a large surface area (181.8 m2.g–1) and an indirect optical band gap energy (Eg = 1.52 eV). The IBP photo-degradation in aqueous solution was achieved in the presence of Fe-FSM-16 and the enhanced reactivity was caused by the presence of iron nanoparticles present inside the FSM structure and dispersed on the FSM.

Efficient Photocatalytic Degradation of Ibuprofen under Visible Light Irradiation Using Silver and Cerium Co‐Doped Mesoporous TiO2

AbstractWater contamination by pharmaceutical compounds has become one of the most serious problem for environment. The use of solar illumination as a renewable energy associated to nanomaterials is an alternative solution for disinfection of wastewater. Therefore, there is a great challenge in green chemistry research to synthesize robust and efficient catalysts for the degradation of organic pollutant under visible light. In this study, we describe new ways to decorated mesoporous TiO2 with cerium (Ce) and silver (Ag) nanoparticles. Indeed, mesoporous TiO2 was co‐doped with Ag and Ce using two different methods: co‐impregnation (Co‐IMP) and co‐deposition precipitation with urea (Co‐DPU). The prepared catalysts were characterized using different analytical techniques such as X‐ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X‐ray spectroscopy (EDX), diffuse reflectance spectroscopy (DR/UV‐vis) and N2 adsorption/desorption. The effect of the preparation method has been evaluated in the photodegradation of ibuprofen (IBP) under visible light irradiation. The obtained results underlined the improvement of photocatalytic activity of mesoporous TiO2 by metals under visible light. A mineralization of IBP up to 98 % was achieved after 4 h irradiation for the catalyst prepared by co‐deposition precipitation with urea. Therefore, this catalyst could be suitable for the treatment of pharmaceuticals in aqueous media using solar light as the energy source.

Facile synthesis of mesoporous black N–TiO2 photocatalyst for efficient charge separation and the visible-driven photocatalytic mechanism of ibuprofen degradation

The present study aimed to investigate the photodegradation of ibuprofen (IPF) by using black N–TiO2 under visible LED illumination. The as-synthesized black N–TiO2 nanoparticles were characterized by field emission scanning electron microscope (FESEM) equipped with energy dispersive X-ray spectrometer (EDS) detector, transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), UV visible diffuse reflectance spectroscopy (UV-DRS), and Brunauer–Emmett–Teller (BET) techniques. The potential photocatalytic activity of the synthesized nanoparticles was assessed by degradation and mineralization of IPF under visible LED light irradiation. Compared to N–TiO2, the black N–TiO2 exhibited higher degradation (96%) and mineralization (81%) efficiency for IPF under selected operational conditions. We observed that codoping of N and Ti3+ narrowed the band gap (2.1 eV) and decreased the recombination of photogenerated carriers. Pseudo-first order kinetic model was best fitted with the experimental results (R2 > 0.99 for different IPF concentrations). Radical-scavenging tests showed that hydroxyl radicals (•OH), holes (h+), and superoxide radicals (•O2−) are involved in the photocatalytic degradation of IPF, however •OH and •O2− played more important roles. The energy consumption of the system for different initial IPF concentrations was around 16.6–38.7 kWh/m3, indicating that the LED-black N–TiO2 process is energy-efficient. The results revealed that the photocatalytic activity of the black N–TiO2 is not changed much, even after 5 cycles, demonstrating its excellent photocatalytic stability and reusability. According to the findings, LED-black N–TiO2 process has the potential to be applied for facile removal of contaminants of emerging concern (CECs) such as IPF from water resources.

Degradation of ibuprofen by UVA-LED/TiO2/persulfate process: Kinetics, mechanism, water matrix effects, intermediates and energy consumption

In this study, UVA-LED/TiO2/persulfate process was used to degrade ibuprofen (IBP). The results showed that addition of persulfate into the UVA-LED/TiO2 system significantly enhanced the degradation of IBP by inhibiting the electron-hole recombination, with a pseudo-first-order rate constant (kobs) increased by 2.7 times when 0.5 mM persulfate was added. The kobs increased linearly with the concentration of TiO2, while higher IBP initial concentration lowered the degradation rate. HO• contributed most to IBP degradation as suggested by a steady-state kinetic model. The investigation of the effects of water matrix indicated that alkaline condition, existence of humic acid, bicarbonate ion, chloride ion and sulfate ion inhibited the IBP degradation. The mineralization of IBP and decay of PS by UVA-LED/TiO2/persulfate process were both quite slow. Five intermediates were detected and the decomposition pathways were proposed based on the frontier electron densities (FEDs) theory. The electrical energy per order (EEO) of IBP was varied from 0.029 kWh/m3 to 0.243 kWh/m3, showing a relatively low energy cost of UVA-LED/TiO2/persulfate process. The results of this work indicate that UVA-LED/TiO2/persulfate is a powerful and promising process for the degradation of IBP.

Ibuprofen oxidative degradation in the presence of Fenton-catalyst based on MgFe<sub>2</sub>O<sub>4</sub> nanoparticles

Catalytic properties of MgFe2O4 nanoparticles during oxidative destruction of non-steroidal anti-inflammatory drug ibuprofen were studied. The influence of the conditions of the catalytic process on the efficiency of ibuprofen decomposition was established. It was shown that at the catalyst content of 0.5 g/L, H2O2 concentration of 20.0 mmol/L and pH of 6.0 for 40 min, a decrease in the ibuprofen concentration from 10.0 mg/L to less than detected limit is achieved. It was found that in the process of catalytic destruction the degree of ibuprofen mineralization reached 100 %. The conducted research shows the prospects of practical application of the developed Fenton-like heterogeneous catalyst for wastewater treatment from pharmaceutically active compounds.

Heterogeneous photocatalytic degradation of ibuprofen in ultrapure water, municipal and pharmaceutical industry wastewaters using a TiO2/UV-LED system

Degradation and mineralization of ibuprofen (IBU) were investigated using Ultraviolet (UV) Light Emitting Diodes (LEDs) in TiO2 photocatalysis. Samples of ultrapure water (UP) and a secondary treated effluent of a municipal wastewater treatment plant (WWTP), both spiked with IBU, as well as a highly concentrated IBU (230 mg L−1) pharmaceutical industry wastewater (PIWW), were tested in the TiO2/UV-LED system. Three operating parameters, namely, pH, catalyst load and number of LEDs were optimized. The process efficiency was evaluated in terms of IBU removal using high performance liquid chromatography (HPLC) and ultra-high performance liquid chromatography coupled to tandem mass spectrometry (UHPLC-MS/MS). Additionally, the mineralization was investigated by determining the dissolved organic carbon (DOC) content. The chemical structures of transformation products were proposed based on the data obtained using liquid chromatography with a high resolution mass spectrometer ion trap/time-of-flight (LC-MS-IT-TOF). A possible pathway of IBU degradation was accordingly suggested. Bioassays were performed using the marine bacterium Vibrio fischeri to evaluate the potential acute toxicity of original and treated wastewaters. TiO2 heterogeneous photocatalysis was efficient to remove IBU from UP and from PIWW, and less efficient in treating the wastewater from the municipal WWTP. The acute toxicity decreased by ca. 40% after treatment, regardless of the studied matrix.

Mineralization of Ibuprofen and Humic Acid through Catalytic Ozonation

ABSTRACTAdvanced oxidation methods are used to remove traces of pharmaceuticals from aquatic environments. The application of a catalyst improves the total organic carbon removal during ozonation of pharmaceuticals in water. The aim of this study was to use MnO2-CuO/ γ-Al2O3 catalyst for ozonation of ibuprofen (5 mgL−1) and evaluate the effect of the presence of humic acid in the removal process. The presence of the catalyst increased the mineralization percentage of ibuprofen from 27% for noncatalytic ozonation to 55% in the presence of catalyst. The presence of humic acid increased noncatalytic mineralization by 10%. The reusability and stability of the catalyst, and its ability to adsorb reaction by-products were demonstrated.

Surface acidity and reactivity of β-FeOOH/Al2O3 for pharmaceuticals degradation with ozone: In situ ATR-FTIR studies

The surface acidity and reactive activity of β-FeOOH, mesoporous alumina (MA), β-FeOOH/MA were investigated in catalytic ozonation of pharmaceutically active compounds (PhACs) aqueous solution. β-FeOOH/MA showed high efficiency for the degradation and mineralization of ibuprofen and ciprofloxacin. Its surface Lewis acid sites on β-FeOOH/MA were more greatly enhanced compared with those on MA and β-FeOOH. In situ attenuated total reflection FTIR (ATR-FTIR) spectroscopy was used to investigate the interaction of D2O and O3 with the catalysts in aqueous phase under various conditions. The dissociative chemisorptions of D2O occurred at the surface Lewis acid sites of the catalyst. Furthermore, O3 interacted with the surface hydrogen-bonded –O–D and D2O to initiate reactive oxygen species (ROS). The stronger Lewis acid sites of β-FeOOH/MA caused the more chemisorbed water enhancing the interaction with ozone, resulting in higher catalytic reactivity. The observations verified that the Lewis acid sites were reactive centers for the catalytic ozonation of PhACs in water.

Pathways and metabolites of microbial degradation of selected acidic pharmaceutical and their occurrence in municipal wastewater treated by a membrane bioreactor

Laboratory degradation tests with five acidic pharmaceuticals using activated sludge as inocculum under aerobic conditions were performed and microbial metabolites were analysed by liquid chromatography-mass spectrometry (LC-MS). Ketoprofen was partly mineralized as a sole source of carbon and energy and the metabolites determined by LC-MS suggest microbial ketoprofen degradation to proceed along the pathway known for biphenyls and related compounds. Bezafibrate, naproxen and ibuprofen were degraded only cometabolically whereas no transformation was obtained for diclofenac. Some biodegradation intermediates in these batch tests could be tentatively identified by means of LC-MS. The first step in microbial bezafibrate degradation appears to be the hydrolytic cleavage of the amide bond, generating well degradable 4-chlorobenzoic acid as one of the hydrolysis products. As previously found for mammals, ether cleavage and formation of desmethylnaproxen was the initial step in microbial degradation of naproxen. Two isomers of hydroxy-ibuprofen were detected as intermediates in the mineralization of ibuprofen. Laboratory studies suggest that naproxen and ibuprofen can be fully mineralized whereas more stable metabolites occur in microbial ketoprofen and bezafibrate transformation, that may deserve further attention. A LC-MS method for the trace analysis of these metabolites in water was developed and applied to municipal wastewater. Municipal wastewater treatment by a membrane bioreactor may gradually improve the removal of these pharmaceuticals.