Degradation Of Clofibric Acid Research Articles

Degradation of clofibric acid by ozonation assisted by Co-Ce-SBA-15: Role of interfacial electron migration

Restrained by the sluggish Ce redox cycle, Ce-SBA-15 exhibited the low electron transfer toward O3 activation. To this end, cobalt‑cerium co-doped SBA-15 with three-dimensional pore structure was designed using urea-assisted hydrothermal method and its activity was evaluated using Clofibric acid (CA) as target pollutant. XRD and N2 adsorption-desorption characterizations suggested that Co-Ce-SBA-15 possessed a three-dimensional pore structure with high order degree. py-FTIR, O2-TPD, H2-TPR, and in situ electrochemical characterizations indicated that compared with Ce-SBA-15 and Co-SBA-15, Co-Ce-SBA-15 had greater Lewis acid strength, electron transfer ability and oxygen reducibility. Co-Ce-SBA-15/O3 achieved the greater CA removal and mineralization rate, with 98.7 % CA removal and 58.3 % TOC removal were obtained in 90 min. Co-Ce-SBA-15/O3 process would be inhibited by the coexisting Cl−, NO3− and SO42−. Co-Ce-SBA-15 demonstrated the greater ozone utilization rate than those of monometallic SBA-15. Lewis acidic sites of Co and Ce were the main sites for activating O3. DFT results suggested that the obvious electron transfer existed among O3, Co and Ce Lewis acid sites. The conversion of Co3+/Co2+ and Ce4+/Ce3+ accelerated the interfacial electron transfer, which favored for conveying O3 into •OH. •OH was the primary reactive oxygen species involved in degrading CA. 8 kinds of intermediates were found during CA degradation and the possible degradation route was proposed. This study deepened the understanding of the cooperative effect of Co and Ce in catalytic ozonation process.

Mechanistic study of visible light driven photocatalytic degradation of clofibric acid using Fe-based metal organic frameworks (MOFs)

Although a series of past studies proved the potential usage of Fe-based metal-organic frameworks (MOFs) as photocatalysts, there remains a knowledge gap of the photocatalytic mechanism stemming from the challenge to separate the simultaneous sorption and photocatalytic degradation. Thus, this article aimed to suggest a novel approach by desorbing target molecules during photocatalysis to excavate the underlying mechanisms of sorption and photocatalytic degradation. In this study, two Fe-based MOFs, MIL-101(Fe) and MIL-101(Fe)–NH2, were selected to remove clofibric acid under visible light irradiation. Prior to photocatalysis, sorption mechanism was uncovered based on the sorption kinetic, isotherm, thermodynamic interpretation, and of its dependence on solution pH. The results inferred that the primary sorption mechanism was through the π-π interaction between the benzene ring of clofibric acid and the organic ligand of Fe-based MOFs. Based on these results, photocatalytic mechanism could be independently or jointly assessed during the photocatalytic degradation of clofibric acid. Subsequently, the application of the Tauc method and XPS spectra revealed that the bandgap structure of Fe-based MOFs had the potential to oxidize clofibric acid by producing ROS through the electron excitation upon visible-light illumination. On top of that, the amine functionalization of Fe-based MOF altered the structural moiety that led to an additional strong acid-base interaction with clofibric acid but a decrease in the bandgap limiting the ROS production during photocatalytic activity.

Freezing-enhanced chlorination of organic pollutants for water treatment.

Freezing has been reported to accelerate chemical reactions and thus affect the fate of pollutants in the environment. However, little research has been conducted on the potential effects of freezing on the chlorination process. This study aimed to explore the freezing-enhanced chlorination process by comparing the oxidation of clofibric acid (CA) by chlorine in ice (at -20 °C) to the same reaction in water (at 25 °C). The degradation of CA, which was negligible in water, was significantly accelerated in ice. This acceleration can be attributed to the freeze concentration effect that occurs during freezing, which excludes solutes such as chlorine, CA and protons from the ice crystals, leading to their accumulated concentration in the liquid brine. The increased concentration of chlorine and protons in the liquid brine leads to higher rates of CA oxidation, supporting the freeze concentration effect as the underlying cause for the accelerated chlorination of CA in ice. Moreover, the chlorine/freezing system was also effective in the degradation of other organic pollutants. This highlights the environmental relevance and significance of freezing-enhanced chlorination in cold regions, particularly for the treatment of organic contaminants.

Bimetallic Bi/Cu0-catalyzed persulfate-based advanced oxidation processes towards clofibric acid degradation in wastewater

Clofibric acid (CFA), an important blood-lipid regulatory drug is an emerging organic pollutant and widely reported in water resources. A novel bimetallic, bismuth/zero valent cupper (Bi/Cu0) catalyst was prepared which showed better physiological, structural, and catalytic properties than Cu0. The Bi/Cu0 effectively catalyzed persulfate (S2O82−) and caused 85% degradation of CFA. The Bi coupling improved reusability and stability of Cu0. The use of alcoholic and anionic radical scavengers and analyzing change in [S2O82−]0 proved that Bi/Cu0/S2O82− yield hydroxyl radicals (●OH) and sulfate radicals (SO4●–). The ●OH and SO4●– showed faster reaction with CFA, i.e., 4.65 × 109 and 3.82 × 109 M−1 s−1 and degraded CFA into four degradation products. Under optimal conditions of [Bi/Cu0]0 = 1.0 g/L and [S2O82−]0 = 40 mg/L, 99.5% degradation of the 10 mg/L of CFA was achieved at 65 min. Temperature showed promising effects on the removal of CFA by Bi/Cu0/S2O82− and caused 98% removal at 323 K than 75% at 298 K at 32 min. The temperature effects were used to calculate activation energy, enthalpy, and rate constant of CFA degradation. The Bi/Cu0/S2O82− showed effective removal of CFA in real water samples also. The ecotoxicity study confirmed non-toxic product formation which suggests high capability of the proposed technology in the treatment of CFA.

Performance, community structure, metabolic pathway, and mechanism in a three-dimensional electrocatalytic biofilter (3DEBF) for the degradation of multiple concentrations of clofibric acid (CA)

A three-dimensional electrocatalytic biofilter (3DEBF) was constructed to remove clofibric acid (CA). This study compared the effectiveness of 3DEBF and biological aerated filter (BAF) in the removal of refractory CA, examined the effects of influent CA concentrations (0.1, 0.3, 0.5, 0.7, and 1.0 mg/L) on microbial community, and proposed a possible 3DEBF degradation mechanism. Results indicated that the average removal efficiency of 3DEBF reached a peak (76.09%) at 0.7 mg/L, which was 14.43% higher than that of BAF. Based on the microbial community analysis, the significant enrichment of Rhodobacter, Mycobacterium, and Sphingopyxis in 3DEBF was associated with the effect of the CA concentration and the electric field. The degradation pathway indicated that xenobiotics biodegradation and metabolism, membrane transport and replication and repair related genes were upregulated in 3DEBAF. Moreover, CA degradation is based on a combination of adsorption, electrochemical oxidation, and biodegradation.

Factors hindering the degradation of pharmaceuticals from human urine in an iron-activated persulfate system

This study investigated the degradation of clofibric acid (CFA), bezafibrate (BZF), and sulfamethoxazole (SMX) in synthetic human urine using a novel mesoporous iron powder-activated persulfate system (mFe-PS system), and identified the factors limiting their degradation in synthetic human urine. A kinetic model was established to expose the radical production in various reaction conditions, and experiments were conducted to verify the modeling results. In the phosphate-containing mFe-PS system, the 120 min removal efficiency of CFA decreased from 95.1% to 76.6% as the phosphate concentration increased from 0.32 to 6.45 mmol/L, but recovered to 90.5% when phosphate concentration increased to 16.10 mmol/L. Meanwhile, the increased concentration of phosphate from 0.32 to 16.10 mmol/L reduced the BZF degradation efficacy from 91.5% to 79.0%, whereas SMX removal improved from 37.3% to 62.9%. The mFe-PS system containing (bi)carbonate, from 4.20 to 166.70 mmol/L, reduced CFA and BZF removal efficiencies from 100% to 76.8% and 80.4%, respectively, and SMX from 83.5% to 56.7% within a 120-min reaction time. In addition, alkaline conditions (pH ≥ 8.0) inhibited CFA and BZF degradations, while nonacidic pH (pH ≥ 7.0) remarkably inhibited SMX degradation. Results of the kinetic model indicated the formation of phosphate (H2PO4·/HPO4·−) and/or carbonate radicals (CO3·−) could limit pharmaceutical removal. The transformation products (TPs) of the pharmaceuticals revealed more incompletely oxidized TPs occurred in the phosphate- and (bi)carbonate-containing mFe-PS systems, and indicated that H2PO4·/HPO4·− mainly degraded pharmaceuticals via a benzene ring-opening reaction while CO3·− preferentially oxidized pharmaceuticals via a hydroxylation reaction.

Intensification of the photodegradation efficiency of an emergent water pollutant through process conditions optimization by means of response surface methodology

Heterogeneous photocatalysis has been increasingly investigated during the past years and has been recognized as a promising technique for clean and safe water purification. The current study exploits the advantage of this technique demonstrating that the removal of a biorefractory water pollutant named clofibric acid can be really improved by photocatalysis through a parametric comprehensive investigation and optimization study based on response surface methodology. Its novelty comes from the approach used to enhance the efficiency of the photocatalytic degradation of clofibric acid. A custom central composite design consisting of 49 trials was applied for process modeling and a quadratic robust model was derived based on the analysis of variance for the optimization of the process parameters. The effective removal of the target molecule with about 70% carbon mineralization was achieved under optimal photocatalytic conditions: 1.5 mg/L as the initial concentration of pollutant, 0.61 g/L catalyst, and an irradiation time of 190 min. Further, it was provided that nitrates play a positive role in the removal of this pollutant, while hydrogenocarbonates slow down its elimination. The ecotoxicity evaluation at different trophic levels confirmed the low toxicity of photodegradation by-products. Data analysis demonstrated that response surface methodology is a reliable approach for the optimization of the interactive effects of photocatalytic process parameters and is able to enhance their performance for the complete elimination of this hardly removed water pollutant.

ZnO-Zn2TiO4 heterostructure for highly efficient photocatalytic degradation of pharmaceuticals.

In this study, ZnO-Zn2TiO4 (ZTM) material was prepared through a novel synthesis method based on a ultrasound-assisted polyol-mediated process followed by calcination at a different temperature. Physical features of the samples were studied by using various analysis techniques including XRD, FT-IR, SEM/EDX, pHPZC, and UV-Vis DRS. Subsequently, the materials were employed as catalysts for the photocatalytic degradation of clofibric acid as a model pharmaceutical contaminant. The photocatalytic performance was evaluated under different conditions of calcination temperature, catalyst dosage, starting concentration, and initial pH of clofibric acid solution. The finding results revealed that hexagonal-tetragonal phases of ZnO-Zn2TiO4 calcined at 600°C (ZTM-600) with an average crystallite size of 97.8Å exhibited the best degradation efficiency (99%). The primary bands characteristic of ZnO and Zn2TiO4 were displayed by FT-IR analysis and the UV-visible DRS confirms the larger absorption capacity in UV-visible regions. The photogenerated electrons are the powerful reactive species involved in clofibric acid photodegradation process. This study shows a promising photocatalyst and provides new sight to rational design the facets of photocatalysis process for enhanced photocatalytic performances and effective wastewater treatment.

Interface engineering of Z-scheme α-Fe2O3/g-C3N4 photoanode: Simultaneous enhancement of charge separation and hole transportation for photoelectrocatalytic organic pollutant degradation

A series of g-C3N4-modified α-Fe2O3 heterostructures are synthesized by deposition on fluorine-doped tin oxide (FTO). The resulting α-Fe2O3/g-C3N4/FTO photoanode (denoted as Fe/CN) show markedly improve photoelectrocatalytic performance, with a photocurrent density (0.18 mA/cm2) that is 5.1 times that of α-Fe2O3 and 9.4 times that of g-C3N4. The suitable charge transport path is observed by interfacial analysis, where the conduction band of g-C3N4 and valence band of α-Fe2O3 shuttled holes and electrons into the electrolyte at accelerated speeds, respectively. Impressively, the Fe/CN photoelectrode achieve the highest pollutant removal efficiency of 99.7% for the photoelectrocatalytic degradation of clofibric acid (CA) under visible-light irradiation, which is expected to be applicable in actual wastewater for environmental protection. Density functional theory (DFT) calculations and intermediate identification shows that the CA degradation pathway involved C–Cl and O–C cleavage. These findings provide an environmentally friendly method to remove emerging contaminants using renewable solar energy.

Kinetic and mechanistic insights into the degradation of clofibric acid in saline wastewater by Co2+/PMS process: a modeling and theoretical study.

Recently, the degradation of non-chlorinated organic pollutants in saline pharmaceutical wastewater by SO4˙−-based advanced oxidation processes (AOPs) has received widespread attention. However, little is known about the oxidation of chlorinated compounds in SO4˙−-based AOPs. This study chose clofibric acid (CA) as a chlorinated pollutant model; the oxidation kinetics and mechanistic pathway were explored in the Co2+/peroxymonosulfate (PMS) system. Notably, a high removal efficiency (81.0%) but low mineralization rate (9.15%) of CA within 120 min were observed at pH 3.0 during Co2+/PMS treatment. Exogenic Cl− had a dual effect (inhibitory then promoting) on CA degradation. Several undesirable chlorinated by-products were formed in the Co2+/PMS system. This demonstrated endogenic chlorine and exogenic Cl− both reacted with SO4˙− to generate chlorine radicals, which participated in the dechlorination and rechlorination of CA and its by-products. Furthermore, SO4˙− was the dominant species responsible for CA degradation at low Cl− concentrations (≤1 mM), whereas Cl2˙− was the predominant radical at [Cl−]0 > 1 mM. A possible degradation pathway of CA was proposed. Our findings suggested that chlorinated compounds in highly saline pharmaceutical wastewater will be more resistant and deserve more attention.

Urea-Assisted Synthesis of Mesoporous TiO2 Photocatalysts for the Efficient Removal of Clofibric Acid from Water.

Mesoporous TiO2 photocatalysts intended for the advanced removal of clofibric acid (CA) from water were synthesized by the sol-gel method in a medium containing cetyl-trimethyl-ammonium bromide (CTAB) and urea, using either ethanol or isopropanol to dilute the TiO2 precursor. The activation of the samples was undertaken at 550, 650 and 750 °C. The XRD revealed that the nature of the solvent resulted in significant differences in the anatase-to-rutile ratios obtained at different temperatures. The specific surface area values were situated between 9 and 43 m2·g−1 and the band gap values were similar for all the samples. The photocatalytic activity of the prepared samples was examined for the degradation of CA, an emergent water contaminant. The photocatalytic tests performed under UV-A irradiation revealed that the photo-reactivity of these materials depends on the calcination temperature. The best results were obtained for the samples calcined at 750 °C, which showed high yields of CA elimination, as well as almost complete mineralization (over 95%) after 180 min of reaction. Good results in terms of catalyst reusability in the reaction were found for the catalyst showing the highest photo-reactivity. Therefore, the samples can be considered good candidates for future water remediation applications.

Construction of heterojunction photoanode via facile synthesis of CoOx/CN nanocomposites for enhanced visible-light-driven photoelectrochemical degradation of clofibric acid

Visible-light-driven photoelectrocatalytic (PEC) oxidation has been explored extensively to develop highly active materials. Herein, a visible-light-active p-Co3O4 and n-g-C3N4 heterojunction (CoOx/CN) photoanode, constructed by simple one-pot calcination, was shown to remove clofibric acid (CA) from water through a PEC process. Compared with pristine g-C3N4, the optimal photoanode (15%-CoOx/CN) exhibited stable and effective PEC performance and CA degradation performance, a 100-fold enhancement in photocurrent density, and around 1.5-fold decreased efficiency over 6 h. The p–n heterojunctions were shown to increased the charge density and conductivity of g-C3N4 for rapid charge transfer. Furthermore, interface contact broadened the visible light absorption and accelerated charge carrier transfer. Notably, the catalysts established p–n heterojunctions, which hindered the bulk recombination of photoinduced carriers and improved the charge separation efficiency. The CoOx/CN photoanodes showed a pair of redox peaks at a potential of 0.3 V vs. Ag/AgCl, indicating good Co3O4 redox behavior under alkaline conditions. The 15%-CoOx/CN photoanode displayed excellent PEC performance of up to 0.16 mA cm−2 in 0.1 M KOH solution at 1.23 V vs. RHE (reversible hydrogen electrode) and long-term stability for up to 12 h. The CoOx/CN photoanodes maintained excellent PEC activities for CA removal, even under acidic and alkaline conditions conditions (pH 3–10). Probable degradation pathway of CA was proposed according to the main degradation intermediates. This study shows that the synergistic effect of p–n heterojunctions in photoelectrodes provides a new approach to the rational application of new photoanode candidates and PEC performance optimization.

Facile synthesis of rGO/Ag@AgCl core-shells nanocomposite and their multifunctional efficacy as a photocatalyst and antimicrobial agent for decontamination of water

An environmentally friendly process for synthesis of rGO/Ag@AgCl Core-shells nanocomposite was developed by Bitter gourd leaf extract. The core-shell morphology was confirmed by STEM-EDX line profile and elemental mapping images. As-synthesized nanocomposite was utilized as photocatalyst for degradation of Clofibric acid (CA) and Naphthol Green B (NGB) from aqueous phase under solar irradiation. As-synthesized nanocomposites showed photodegradation up to 98% of CA and 98.7% of NGB within 40 and 30 min, respectively. Here, we also investigated the optimum amount of nanocomposites for the photodegradation process. ESR analyses confirmed that the active species such as hydroxyl and superoxide anion radicals were mainly accountable for the degradation of organic pollutants. The presence of rGO enhanced the catalytic activity of Ag@AgCl NPs. The as-prepared nanocomposite was also utilized for the removal of biological impurities against bacterial strains. Hence form the present study, it was confirmed that the synthesized rGO-Ag@AgCl nanocomposites act as a potential material for wastewater treatment.

Efficient degradation of clofibric acid by heterogeneous catalytic ozonation using CoFe2O4 catalyst in water

CoFe2O4 (Cobalt ferrite, CF) nanoparticles were prepared, well characterized and applied as efficient solid catalyst in catalytic ozonation, named CF/O3 process, for the removal of emerging organic contaminants (EOCs). The degradation and mineralization of clofibric acid (CA) in CF/O3 process were dramatically enhanced in comparison with those under the O3 system. Surface hydroxyl groups (HGs) were considered as an important factor for ozone decomposition and the reactive oxygen species (ROS) on the catalyst surface were mainly responsible for CA elimination. The contribution and formation of ROS, including hydroxyl radicals (•OH), especially superoxide radicals (O2•−), singlet oxygen (1O2), and hydrogen peroxide (H2O2) were evaluated, and a rational mechanism was elucidated accordingly. Probable degradation pathway of CA was proposed according to the organic intermediates identified. The acute toxicity of the treated solution increased during the first 15 min and then declined rapidly and nearly disappeared as the reaction proceeded. In addition, acceptable catalytic performance of CF/O3 can be obtained for the treatment of other EOCs and the treatment of natural surface water spiked with CA. This work presents an efficient and promising catalytic ozonation technique for the elimination of EOCs in complex water matrices.

Zn/La Mixed Oxides Prepared by Coprecipitation: Synthesis, Characterization and Photocatalytic Studies.

Mixed oxides containing zinc and lanthanum were prepared by coprecipitation in alkaline medium, followed by calcination at 400 °C. The initial precipitation product and the calcined form were characterized by Brunauer–Emmett–Teller (BET) method adsorption of nitrogen at −196 °C, Scanning Electron Microscopy/Electron-Probe Microanalysis (SEM/EPM), Ultraviolet—Diffuse Reflectance Spectroscopy (UV-DRS) and Infrared (IR) spectroscopy. The band gap slightly changes from 3.23 eV to 3 eV by calcination. The photocatalytic performance of the solids were investigated in diluted aqueous medium, by using clofibric acid (CA), a stable and toxic molecule used as precursor in some pesticides and drugs, as test compound, possibly found in the wastewaters in low concentrations. The effects of the degradation extent, determined by high performance liquid chromatography (HPLC) and total organic carbon (TOC) measurements, were investigated at different initial concentrations of CA. Within about 60 min the CA degradation is almost total at low concentration values (3 ppm) and reaches over 80% in 180 min for an initial concentration of 50 ppm. Moreover, the CA removal performance of photocatalyst remains excellent after three cycles of use: the removal yield was practically total after 60 min in the first two cycles and reached 95% even in the third cycle.

Kinetic and mechanistic insights into the abatement of clofibric acid by integrated UV/ozone/peroxydisulfate process: A modeling and theoretical study

The feasibility of integrated UV/ozone (O3)/peroxydisulfate (PDS) process for abatement of clofibric acid (CA) was systematically explored in this study with focus on the kinetic simulation and oxidation mechanisms. The results indicated the UV/O3/PDS process was of prominent treatment capability with pseudo-first-order rate constant of CA degradation increased by 65.9% and 86.0% compared to UV/O3 and UV/PDS processes, respectively. A chemical kinetic model was developed and successfully employed to predict CA elimination as well as the specific contributions of UV, hydroxyl radical (•OH) and sulfate radical (SO4•−) under different PDS dosage, pH, natural organic matters, bicarbonate and chloride conditions in UV/O3/PDS process. According to quantum chemical calculation, radical addition on ortho site of isopropoxy substituent and single electron transfer were corroborated to be the dominant reaction channels for the oxidation of CA by •OH and SO4•−, respectively. Additionally, the reactive sites and transformation pathways of CA were proposed via Fukui function calculation and UPLC-Q-TOF-MS analysis. Moreover, the performance of UV/O3/PDS process was further evaluated with regard to the energy demand and bromate formation. This study first proposed a kinetic model in UV/O3/PDS process and elucidated the regioselectivity and products distribution of CA during oxidative treatment.

One-step synthesis of MnOx/g-C3N4 nanocomposites for enhancing the visible light photoelectrochemical oxidation performance

Here, we report enhancement of the photoelectrochemical (PEC) performance of MnOx/graphite-like carbon nitride (g-C3N4) nanocomposites synthesized by one-step thermal decomposition for degradation of clofibric acid (CA). MnOx showed enhanced broadband ultraviolet–visible light regions, efficient charge generation–separation, and enhanced PEC performance when combined with g-C3N4. Photogenerated holes can be efficiently captured by introducing Mn2+/Mn3+/Mn4+ valence band transitions. In addition to a good visible-light response, the MnOx/g-C3N4-10 (g-C3N4 with 10% Mn(NO3)2·6H2O) photoanode showed enhanced photocurrent density of 0.03 × 10−3 A cm−2 at 0.63 V vs. Ag/AgCl, which was approximately 100 times that of pristine g-C3N4. The superoxide radical and positive holes played dominant roles in PEC degradation of CA. The MnOx/g-C3N4-10 photoanode showed the highest photoelectrocatalytic performance under acidic conditions because of electrostatic attraction between the electrode and CA. The CA degradation ratio using the MnOx/g-C3N4-10 photoanode was 100% under visible light in 6 h at pH = 3. This work provides a simple and sustainable strategy to modify g-C3N4 for captured holes to improve PEC degradation of CA, and it is promising for application to different materials in a variety of fields.

Feasibility study on applying the iron-activated persulfate system as a pre-treatment process for clofibric acid selective degradation in municipal wastewater

Clofibric acid (CFA) was selected as an example of the widespread micropollutants in municipal wastewater to investigate the feasibility of the application of an iron-activated persulfate (Fe-PS) system for selective micropollutants removal prior to biological wastewater treatment. In pure CFA solution, the CFA degradation rate was accelerated with an increase in oxidant dosage and 2.15 mg·L−1 (0.01 mM) CFA could be completed removed within 30 min with 270 mg·L−1 (1 mM) potassium persulfate (PS) activated by 56 mg·L−1 iron powder (Fe). Although both sulfate radicals (SO4∙−) and hydroxyl radicals (HO∙) were generated in the Fe-PS system, SO4∙− was identified as the dominant oxidant for CFA degradation. To investigate the interference from model compounds in the municipal wastewater, CFA degradation in different concentrations of ammonia or/and glucose solutions, the synthetic municipal wastewater, and real municipal wastewater systems were investigated. A complete removal of CFA was achieved with ammonia or/and glucose interferences. Less than 3% ammonia was removed due to the formation of aminopropyl radicals. About 15% degradation of dissolved organic carbon (DOC) was mainly attributed to the oxidation of glucose by HO∙, Indicating the excellent selective oxidation ability of the Fe-PS system targeting at CFA over glucose. Even though the alkalinity significantly hindered the oxidation of CFA in both synthetic and real municipal wastewater system, the removal efficiency of CFA was significantly higher than that of DOC. The decrease of CFA removal efficiency in municipal wastewater system comparing to the other tests was due to the slow degradation of PS in the system and further hindered the SO4∙− generation. Therefore, the impacts of other impurities in municipal wastewater on the oxidation activities of Fe-PS system should be further investigated. In general, this study confirmed the feasibility of using the Fe-PS system for selective degrading resistant CFA in municipal wastewater.

Degradation of pharmaceuticals from wastewater in a 20-L continuous flow bio-electro-Fenton (BEF) system

The bio-electro-Fenton (BEF) technology has proven to be an effective and energy-saving method for treating wastewaters containing a single pharmaceutical in the lab-scale. However, the continuous degradation of pharmaceuticals in a scaled-up BEF has never been reported. In this study, a 20-L dual-chamber BEF reactor was designed and tested for treating six model pharmaceuticals. The effect of key operational factors including applied voltage, cathode Fe2+ dosage, initial pharmaceuticals concentration and hydraulic retention time (HRT), were assessed. By implementing 0.1 V voltage, 0.3 mM Fe2+ and HRT of 26 h, the six selected pharmaceuticals (500 μg L−1 for each) were removed completely. Moreover, transformation products during clofibric acid degradation, such as 4-chlororesorcinol, were detected and the relevant transformation pathway was proposed. Additionally, it successfully removed these pharmaceuticals in the real wastewater matrix. This paper contributes to scaling-up the BEF process for continuous and effective treating pharmaceuticals-contaminated wastewater.

TiO2-rGO photocatalytic degradation of an emerging pollutant: kinetic modelling and determination of intrinsic kinetic parameters

An intrinsic kinetic model, derived from a suggested reaction photo-mechanism and with an explicit dependence on the local volumetric rate of photon absorption (LVRPA), was developed to simulate the photocatalytic degradation of clofibric acid and the main reaction intermediates, with a new titania-reduced graphene oxide nanocomposite (TiO2-rGO), The proposed reaction mechanism takes into account that graphene behaves as an electron acceptor and, therefore, this effect was included in the derivation of the reaction rate expressions and in the parameters estimation of the kinetic model. The photodegradation of clofibric acid was performed in a slurry photoreactor under different irradiation levels and using several loadings of a TiO2-rGO nanocomposite, prepared by hydrothermal method with a 0.5 wt. % of GO. Absorbed radiation profiles inside the photoreactor were obtained by solving the radiation model with the Monte Carlo method. A photocatalyst loading of 100 mg L−1 gave place to the best photodegradation results. Mass balances were proposed for the main pollutant and their main detected intermediates: p-benzoquinone and 4-chlorophenol. The intrinsic kinetic parameters were obtained for the complete (6-parameters) and simplified (5-parameters) models by comparing the experimental and the theoretical concentration values of all the organic compounds detected. The model proved to be able to predict with good accuracy the concentration evolution of clofibric acid, 4-chlorophenol and p-benzoquinone under several photocatalyst concentrations and irradiation levels. Finally, a very good correlation between calculated and experimental values of clofibric acid concentration was obtained with root-mean-square errors below 11%.