Pharmaceutical Industry Wastewater Research Articles

Synthesis of oxygen vacancies rich CeO2-xNx/GCN hybrid nanostructure with great active interfaces for electrochemical detection of antiviral levofloxacin in pharmaceutical samples

COVID-19 is an emerging viral infectious disease. Severe respiratory problems are considered an important syndrome of COVID-19 in humans. Levofloxacin (LEV), a promising fluoroquinolone antibacterial agent/therapeutic agent for influenza virus (H1N1)-induced pneumonia drug. These have been used as a potent antidote for acute respiratory tract infections. Owing to its excellent pharmacokinetic properties such as potential antiviral and scavenging activity, LEV has been used in controlling and treating COVID-19 during infectious emergencies. Even taking over the dosage of LEV and disposing of the embryonic toxic nature of LEV residues in the pharmaceutical research industry can cause adverse effects on the public health and environment. For this purpose, the development of great analytical tools is important to the detection of antiviral LEV for human health safety and environmental protection. In this work, we report a nitrogen (N) doped strategy to construct the enriched oxygen vacancies (OVs) on CeO2-xNx/GCN-2 hybrid nanostructure as an efficient electrocatalyst for the ultrasensitive detection of antiviral LEV. The effect of the N doping into the CeO2 (CeO2-xNx) lattice with increasing the large amount of OVs and boosted their redox properties (Ce4+→Ce3+), thus provided that a great electrochemically active site. Although the abundant OVs were conformed on the CeO2-xNx/GCN-2 from the peak-area ratio of Ce3+/Ce4+ and O2/O1 by X-ray photoelectron spectroscopy (XPS) assay. Owing to the strong electronic coupling between the OV-rich CeO2-xNx and the conductive GCN surface, thus CeO2-xNx/GCN-2 heterojunction achieved superior analytical performance for LEV oxidation with a good linear range from 0.01 μM to 710 μM, and detection limits of 5.6 nM (S/N = 3), and sensitivity 24.711 μA μM−1 cm−2 at a very low working potential (0.7 V). The proposed hybrid sensor also exploited to the analysis of the pharmaceutical industry wastewater, pharmaceutical tablet and human urine samples with a satisfactory recovery rate.

Development of Fe/HNT and Fe/HNT-Al2O3 composite catalysts and application in successive treatment processes for pharmaceutical industry wastewater

The pharmaceutical industry wastewater (PIW) was treated by successive use of electro Fenton (EF) and photocatalytic oxidation (PcO) processes. Nano-particular powdered Fe/HNT (Iron/Halloysite nanotube) heterogeneous semiconductor catalyst was initially produced with Fe(OH)3 sludge modification precipitated after EF process. Thus, photocatalyst material was produced from the waste sludge and used in the PcO process. Photocatalyst Fe/HNT powder was immobilized on a three-dimensional (3D) reticulated Al2O3 ceramic support to enable rapid recovery of the catalyst from the PcO reactor system. Particle morphology and chemical configuration of the heterogeneous catalysts were analyzed with SEM (Scanning Electron Microscopy)-EDS (Energy-Dispersive X-ray spectrometry), UV-DRS (Ultraviolet Diffuse Reflectance Spectra) and XRD (X-ray diffraction). The Fe/HNT layer was calcined at three different temperatures (350, 450 and 600 °C). The optimum temperature was determined as 350 °C for better photocatalytic performance and practical reasons such as energy consumption. The successive use of EF + PcO processes for degradation of three different PIW samples was investigated by using two catalyst forms (nanoparticle and reticulated) and light sources (visible and sun light). The max TOC removal efficiency by EF + sun light-PcO (with Fe/HNT) successive treatment process was obtained as 78.4 %. Besides, the energy consumption value was calculated for optimum process state and calculated as 48.8 kWh/kg TOC at the EF + sun light-PcO (with Fe/HNT) successive treatment process.

Factors affecting the performance of a pharmaceutical wastewater treatment plant: Characterization of effluent and environmental risk

Pharmaceutical industries produce a huge volume of emerging pollutants (EPs) that pose a threat to the aqueous environment. Biological processes have shown their inefficacy in treating many pharmaceutical products. The study assessed physicochemical parameters, EPs, heavy metals in pharmaceutical industrial wastewater, and the removal efficiency (RE) of an aerobic biological treatment plant. The study also assessed the contamination levels and risk using several indices, such as the Canadian Council of Ministers of the Environment Water Quality Index (CCME-WQI), heavy metal pollution index (HPI), heavy metal evaluation index (HEI), and risk quotients index (RQs). The study found that the treated water quality was poor, having antibiotics, nonsteroidal anti-inflammatory drugs, and others, along with several transformation products (TPs) and heavy metals, which were unsafe for consumption with high environmental risk. The analysis results showed that the RE for TSS, BOD5, COD, TDS, and EC were found to be 91.80%, 86.81%, 72.29%, 72.20%, and 65.60%, respectively, where the values of BOD5, COD, NO3−, and PO43− in the effluent were still higher than the permissible limits of the ECR (2023). However, the RE for heavy metals was in the order of Cu (84.62%) > Fe (65.04%) > Mn (63.3%) > Zn (60.58%) > Cd (53.85%) > Ni (54.12%) > Pb (42.42%) > Cr (38%), where Cr and Cd concentrations were still higher than the permissible limit of DoE (2019). The Pearson correlation and PCA suggested that EC, TDS, TSS, DO, BOD5, and COD were the most correlating and contributing variables. This study argued that metal-ligand behaviors mainly affect the removal efficiency of the treatment plant by lowering the removal rate of heavy metals and pharmaceutical products.

Phytotoxicity and genotoxicity assessment of organic and inorganic contaminants detected in pharmaceutical industrial wastewaters using Vigna radiata and Allium cepa

The discharged effluent of pharmaceutical industrial wastewater treatment plants (PIWWTPs) exhibits substantial environmental toxicity due to the intricate combination of organic and inorganic pollutants. This study assessed the phytotoxicity, genotoxicity, and cytotoxicity of untreated and treated pharmaceutical industrial wastewater (PIWW). Most of the physicochemical parameters viz. COD, BOD, EC, sulfide, sulfate, nitrate, phosphate, grease, phenols, and metal concentrations viz. B, Cr, Ca, Cd, Cu, Zn, Pb, Hg, and As in untreated wastewater (UTW) were noted beyond the permissible limit and remained higher in treated wastewater (TW). The findings revealed that the performance of PIWWTP was woefully inadequate. The GC-MS spectra of UTW and TW revealed the presence of various organic contaminants. The toxicological studies showed that the UTW had a high degree of phytotoxicity, which persisted even after the treatment as it inhibited the seed germination in Vigna radiata. The seed germination was inhibited up to 70% and 50% tested at 50% concentration of UTW and TW respectively. Genotoxicity was measured by determining mitotic index and chromosomal aberrations in Allium cepa root apex grown in untreated and treated PIWW. Compared to the negative control, the mitotic index dropped to 85% and 75% at the 50% concentrations of UTW and TW, respectively. Chromosomal aberrations were also found in the cellular mass of root apex growing in both UTW and TW. According to the findings, it is unsafe for the environment to release PIWW that has not been properly treated, as this could pose serious risks to environmental health.

Efficient treatment of veterinary pharmaceutical industrial wastewater by catalytic ozonation process: degradation of enrofloxacin via molecular ozone reactions.

The study focused on the efficacious performance of bimetallic Fe-Zn loaded 3A zeolite in catalytic ozonation for the degradation of highly toxic veterinary antibiotic enrofloxacin in wastewater of the pharmaceutical industry. Batch experiments were conducted in a glass reactor containing a submerged pump holding catalyst pellets at suction. The submerged pump provided the agitation and recirculation across the solution for effective contact with the catalyst. The effect of ozone flow (0.8-1.55mg/min) and catalyst dose (5-15g/L) on the enrofloxacin degradation and removal of other conventional pollutants COD, BOD5, turbidity was studied. In batch experiments, 10g of Fe-Zn 3A zeolite efficiently removed 92% of enrofloxacin, 77% of COD, 69% BOD5, and 61% turbidity in 1L sample of pharmaceutical wastewater in 30min at 1.1mg/min of O3 flow. The catalytic performance of Fe-Zn 3A zeolite notably exceeded the removal efficiencies of 52%, 51%, 52%, and 59% for enrofloxacin, COD, BOD5, and turbidity, respectively, achieved with single ozonation process. Furthermore, an increase in the biodegradability of treated pharmaceutical industrial wastewater was observed and made biodegradable easily for subsequent treatment.

Contamination Characteristics，Detection Methods，and Control Methods of Antibiotic Resistance in Pharmaceutical Wastewater

Pharmaceutical industry wastewater contains a large number of emerging pollutants such as antibiotics， antibiotic resistant bacteria （ARBs）， and antibiotic resistance genes （ARGs）. The present biological water treatment processes cannot effectively remove these pollutants. Eventually， they are discharged into various water bodies or penetrate into soil with the effluent， causing environmental pollution and affecting human health. Therefore， exploring the pollution characteristics of antibiotics， ARBs， and ARGs in pharmaceutical wastewater and knowing the methods to detect and control antibiotic resistance pollution in wastewater are crucial for reducing the contamination of antibiotics and ARGs and assessing the ecological risks of antibiotic resistance. Aiming at the problem of antibiotic resistance pollution in a pharmaceutical wastewater treatment plant （PWWTPs）， the pollution status of antibiotics， ARBs， and ARGs in pharmaceutical wastewater was discussed. Different assessment methods of antibiotic resistance in pharmaceutical wastewater were summarized. Finally， the wastewater treatment technologies commonly used to remove antibiotics and ARGs in PWWTPs were summarized in order to provide a theoretical basis for the ecological risk assessment and scientific control of antibiotics and ARGs in the environment.

Silver (Ag) doped graphitic carbon nitride (g-C3N4) photocatalyst for enhanced degradation of Ciprofloxacin (CIP) under visible light irradiation

Pharmaceutical industry wastewater is causing an increased risk of resistant pharmaceutical micropollutants (PMP) e.g. antibiotic resistant bacteria (super bug) in the ecosystem. Amongst variety of wastewater treatment approaches, Advanced oxidation processes (AOPs) employing photocatalysis provides a cost-effective and sustainable approach for fixation of PMP in an economical and efficient manner to counter the potential risks. Until today, tremendous efforts have been made to trig the performance of photocatalytic wastewater treatment, with the key focus on development of cost-effective, efficient and a moderately stable photocatalyst. Such attempts succeeded with different types of photocatalysts using different synthesis techniques. In recent years, graphitic carbon nitride (GCN) has emerged as one of the cost effective, moderately stable, nontoxic and efficient photocatalyst, and has been scarcely studied specifically for pharmaceutical micropollutants (PMPs) degradation. Hence, considering these factors alongside the facile synthesis and moderate optical absorption of GCN, an effort was made in the present work with effective customization of GCN i.e. silver (Ag) doping to extend light absorption in visible light range which may enhance the photocatalytic performance for Ciprofloxacin (CIP) degradation. The optimization of photocatalytic performance was executed with varied Ag dopant content to obtain an optimum sample with supreme photocatalytic activity for the maximum degradation of CIP, a common antibiotic. The best Ag-doped GCN sample (0.1 AGCN) exhibits a photocatalytic degradation efficiency of 84%, which is 2.15 times greater than pure GCN (39%). The obtained results showed that the strategy of Ag doping substantially enhances the photocatalytic performance, thus offering an efficient mean for developing visible light active photocatalyst for PMP removal and encouraging further research. The photocatalytic performance of the prepared samples was evaluated by degradation of CIP under visible light irradiation. Several characterization techniques were used to characterize and analyze the prepared samples, such as X-ray diffraction (XRD), Scanning electron microscopy (SEM), Raman spectroscopy, Fourier Transform Infrared (FTIR) spectroscopy, UV Visible absorption, and Photoluminescence (PL) spectroscopy.

An integrated system combining electrochemical oxidation and filtration processes to remove chlorine from pharmaceutical industry wastewater

This research devised an efficient method to treat wastewater generated from heparin production at a local Taiwanese company. The approach combined electrochemical techniques with filtration processes to manage the wastewater, which exhibited high levels of total dissolved solids (TDS), chemical oxygen demand (COD), organic matter, and chlorine concentration, requiring treatment before disposal or potential reuse. A specialized electrochemical oxidation (EO) system was customized for processing 500 mL of solution at a 2A current, working in tandem with an activated carbon filter chamber. Various experiments were conducted, altering potential and adsorption times, to understand their correlation in eliminating the identified pollutants in pharmaceutical wastewater. Notably, sample 4 (S4), following an electrolysis process at 2A-12 V in 5 h and subsequent adsorption by 10 g of activated carbon for 60 min, exhibited remarkable efficacy Specifically, this treatment regime facilitated the removal of over 90 % (from 14,750 to 1422 mg/L) of chlorine concentration, 91 % (from 1.12 to 0.09 a.u.) of turbidity, and 88 % (from 22,676 to 2786 mg/L) of COD from the effluent stream. These favorable outcomes were attributed to the conversion of chlorine ions into hypochlorous acid, renowned for its potent antibacterial properties in eliminating organic compounds, as well as the robust adsorption capabilities of activated carbon. This study underscores the viability of employing surface adsorption and electrochemical processes in tandem, utilizing low input currents and brief treatment durations, to treat pharmaceutical wastewater effectively.

The application of bioassay using Daphnia magna for the evaluation of hospital and pharmaceutical industry wastewater containing Active Pharmaceutical Ingredients (APIs) toxicity

Several groups of Contaminants of Emerging Concern (CECs) including Active Pharmaceutical Ingredients (APIs) can influence ecosystem even at low levels of exposure. The concentration of APIs often belongs to the class of micropollutants, so that toxicity tests should be developed using sensitive test organisms. In this research we developed a potential sensitive Daphnia magna to evaluate the toxicity of APIs-containing wastewater from the total of 7 hospitals and pharmaceutical industries in Greater Bandung, West Java, Indonesia. Physico-chemical parameters that were analyzed including pH, BOD5, COD, TSS, Total N, and Phenol, according to the Ministry of Environment Regulation No. 5/2014. To determine the LC50 values, the Whole Effluent Toxicity (WET) method was applied. The results showed that the maximum concentration of pH, BOD5, COD, TSS, Total N, and Phenol of the pharmaceutical industries WWTP effluents were 7.9, 293 mgL-1, 418 mgL-1, 37 mgL-1, 10.7 mgL-1, and 0.188 mgL-1, respectively. These values have fulfilled the effluent standards. However, based on the acute toxicity testing using WET method, it was found that the minimum LC50 value of those WWTP effluents was 6.51% or equal to the TUa value of 15.35. Based on the TUa toxicity class, this effluent was categorized to be high acute toxic (10 ≤ TUa < 100).

Nutrient sequestration and lipid production potential of Chlorella vulgaris under pharmaceutical wastewater treatment: experimental, optimization, and prediction modeling studies.

The efficient management and treatment of pharmaceutical industry wastewater (PIWW) have become a serious environmental issue due to its high toxicity. To overcome this problem, the present study deals with the phycoremediation of PIWW using Chlorella vulgaris microalga isolated from the Ganga River at Haridwar, India. For this, response surface methodology (RSM) and artificial neural network (ANN) tools were used to identify the best reduction of total phosphorus (TP) and total Kjeldahl's nitrogen (TKN) based pollutants along with the lipid production efficiency of C. vulgaris. Three different concentrations of pharmaceutical wastewater (0, 50, and 100%), operating temperatures (20, 25, and 30 °C), and light intensity (2000, 3000, and 4000 lx) were used to design the phycoremediation experiments having 6:18 h of dark/light period and reactor functional volume of 15L. Findings revealed that C. vulgaris was good enough to remove maximum TP (90.35%), TKN (83.55%) along 20.88% of lipid yield at 25.62 °C temperature, 60.73% PIWW concentration, and 4000 lx of light intensity, respectively. Based on the model performance and validation results, ANN showed more accuracy as compared to the RSM tool. Therefore, the findings of this study showed that C. vulgaris is capable of treating PIWW efficiently along with significant production of lipid content which can further be used in various applications including biofuel production.

Economic evaluation for anoxic biological system integrated with external membrane for pharmaceutical wastewater treatment

The integrated system of biological treatment (anoxic /activated sludge ) and ultrafiltration membrane economic study was investigated. The biological treatment results indicate that the performance of pharmaceutical industrial wastewater treatment using activated sludge with an anoxic zone was enhanced by increasing the ability of the pre-acclimatized activated sludge to degrade organic compounds in the industrial wastewater. The residues compounds from biologically treated water were treated by UF membrane and gave a separation efficiency of 99.4%. The results indicate that using the (anoxic /activated sludge) biological treatment step as a pretreatment step before the membrane can provide high-efficiency removal of the contamination of all drug compounds in the wastewater. An economic evaluation of the system was investigated and the calculations indicate that the unit capital cost of the estimated system per cubic meter was 1.27 $/m3, which was lower than the estimated traditional cost.

Visible Light-Assisted Degradation of Sulfamethoxazole on 2D/0D Sulfur-Doped Bi2O3/MnO2 Z-Scheme Heterojunction Immobilized Photocatalysts.

Retrieving the spent photocatalysts from the reaction system is always a challenging task. Therefore, the present work is focused on immobilizing sulfur-doped-Bi2O3/MnO2 (S-BOMO) heterojunction photocatalysts over different support matrices and evaluating their performance for the removal of sulfamethoxazole (SMX) in water under visible light. Our findings revealed S-BOMO coated clay beads (S-BOMO CCB) achieving more than 86% (240 min) SMX degradation ∼3, ∼1.3, and ∼2 times higher compared to S-BOMO coated on the different substrates, including glass beads, floating stones, and polymer material substrates, respectively. Mott-Schottky measurements confirmed the construction of the Z-scheme heterojunction involving MnO2 and 2S-Bi2O3. This Z-scheme mechanism, along with its narrow band gap of 1.58 eV, resulted in a rapid spatial transfer of the photogenerated charge carriers between the semiconductors and is believed to enhance the overall photocatalytic activity of the nanocomposite. Radical trapping and electron paramagnetic resonance results clearly established the active role of hydroxyl radicals and hydrogen peroxide in the degradation of SMX. Further, the 2S-BOMO CCB demonstrated excellent stability and photocatalytic activity over multiple runs. According to the sensitivity analysis and the results of anion effect experiments, phosphate and sulfate ions exhibit a significant impact on sulfamethoxazole degradation. Toxicity analysis revealed that 2S-BOMO CCB and sulfamethoxazole degradation byproducts were apparently innocuous. Additionally, the practical applicability of 2S-BOMO CCB was examined in various real water matrices, with the degradation efficiency followed the order: tap water < groundwater < surface water < hospital wastewater < municipal wastewater < pharmaceutical industry wastewater. The economic assessment revealed the reduction in the overall cost of the immobilized 2S-BOMO following the recovery process. Overall, the findings of this work provided critical insights into the synthesis and performance of incredibly effective and stable immobilized photocatalysts for the degradation of pharmaceutical pollutants.

Synthesis of S-type heterostructure π-COF for photocatalytic tetracycline degradation

Photocatalytic oxidation is a promising technology for wastewater treatment. It is a more desirable method than other conventional wastewater treatment approaches due to its low cost, environmental friendly, and capability to completely degrade pollutants into environmentally safe products under appropriate conditions. Among some photocatalysts, covalent organic frameworks with high photoactivity are recognized as stable and feasible materials for this purpose. In this work, highly-effective photocatalyst of S-type heterostructure π-COF was successfully synthesized by using ultrasonic delamination treatment sp2c-COF nanosheets (sp2c-NS) and py-NH2-COF nanosheets (Py-NH2-NS) via a secondary solvent heating method. The preparation was initiated by synthesizing sp2c-COF and py-NH2-COF successfully adopting pyrene templates by solvothermal method. The study focused on physicochemical characterization and photocatalytic activity of π-COF. The photocatalytic ability of π-COF was carried out to degrade tetracycline under visible light. The results indicate that π-COF not only shows excellent photocatalytic activity for tetracycline degradation of 94.8 % at 90 min under visible light illumination, but also has good photocatalytic degradation performance at wide initial pH values, coexisting ions, and actual water sources. Surprisingly, it has excellent stability and recyclability, it can afford high oxidative degradation (87.3 %) even after 5 successive recycles. The degradation mechanism was discussed by various methods such as active species trapping experiment, electron paramagnetic resonance determination and related electrochemical analysis. In addition, the main degradation intermediate products and the possible pathways of TC degradation were detected and proposed according to LC − MS technology. This work provided a new strategy for the preparation of hetero-structured COF which could be served as an advantageous photocatalyst for the treatment of pharmaceutical industry wastewater.

Assessment of novel hybrid treatment wetlands as nature‐based solutions for pharmaceutical industry wastewater treatment

AbstractThis study investigated the use of nature‐based solutions for treating real pharmaceutical industry wastewater in Jordan. A pilot‐scale hybrid treatment wetland (TW) equipped with local zeolite was employed, comprising a tidal flow TW and a horizontal subsurface flow TW. This system was efficient in treating pharmaceutical wastewater with removal efficiencies of 61.4%, 52.6%, 60.1%, and 61.9% for chemical oxygen demand, total phosphorus, total nitrogen, and NH4+‐N, respectively. The final effluent met Jordanian standards for the reuse of treated wastewater in irrigation (Class B). Five pharmaceuticals, namely, enrofloxacin, ciprofloxacin, ofloxacin, lincomycin, and trimethoprim, demonstrated nearly completed removal (93.6–99.9%). Moderated removal performances (59.2–68.2%) were observed for two compounds, flumequine and sulfaquinoxaline. However, three pharmaceuticals, namely, carbamazepine, diclofenac, and sulfadimidine, showed limited removal performances (1.1–20.5%). This study supported the feasibility of using nature‐based solutions for treating pharmaceutical wastewater and highlighted that future studies are required to optimize this strategy for removing a broader range of pharmaceuticals.

Magnetically separable MnFeCoNiCu-based high entropy alloy nanoparticles for photocatalytic oxidation of antibiotic cocktails in different aqueous matrices

Destroying persistent organic pollutants via photocatalytic advanced oxidation processes is critical for sustainable water management. In spite of the tremendous progress in developing highly effective and durable photocatalysts in recent decades, inferior optical absorption and rapid charge recombination considerably restrict their application on a commercial scale. In order to address these issues, herein we have constructed MnFeCoNiCu-based high entropy alloy (HEA) nanoparticles (NPs), through a facile and straightforward procedure, and showcase its superiority over conventional photocatalysts in degrading some typical antibiotics (viz., sulfamethoxazole, SMX; ofloxacin, OFX; and ciprofloxacin, CFX). The equimolar HEA-NPs feature n-type semiconducting properties, improved light trapping ability, and reduced charge recombination. Consequently, a high degradation of 95 %, 94 %, and 89 % for SMX, OFX, and CFX, respectively, can be achieved in the presence of MnFeCoNiCu NPs under visible light illumination, without any serious risks of secondary contamination. In order to better evaluate the photocatalytic performance of MnFeCoNiCu NPs, particularly from a practical perspective, the removal of antibiotic pollutants from multicomponent systems is also investigated. The average treatment efficiency for a ternary mixture of SMX, OFX, and CFX in different aqueous matrices decreases in the order of deionized water (∼82 %) < tap water (∼86 %) < river water (∼78 %) < hospital wastewater (∼60 %) < domestic wastewater (∼57 %) < pharmaceutical industry wastewater (∼47 %). Further, the expended HEA-NPs can be conveniently recovered from the reaction system by applying an external magnetic field, allowing recurrent usage, without any substantial alteration in their microstructure and performance. These demonstrations of satisfactory photocatalytic activity under a diverse spread of realistic environmental conditions, excellent durability, and inexpensive retrieval endorse the application potential of MnFeCoNiCu NPs in decentralized water treatment systems.

Developing a versatile and resilient PVDF/CeO2@GO-COOH photocatalytic membrane for efficient treatment of antibiotic-contaminated wastewater

This study focuses on enhancing the performance of PVDF membranes by incorporating CeO2 photocatalyst in combination with carboxyl-functionalized graphene oxide (GO-COOH). The carboxyl groups of GO-COOH serve a dual purpose: providing anchoring sites for CeO2 and enhancing the interfacial interaction with the polymer. The PVDF/CeO2@GO-COOH membranes were fabricated using sequence of physical blending and phase inversion processes, resulting in significantly improved internal structure with an average pore size diameter of 1.20–1.35 nm. Moreover, the CeO2@GO-COOH photocatalyst exhibited superior compatibility with PVDF. The as-prepared PVDF/CeO2@GO-COOH photocatalytic membranes (PMs) demonstrated remarkable photocatalytic activity, outperforming PVDF/CeO2, achieving degradation efficiencies of 85.55 % for ciprofloxacin and 84.82 % for sulfanilamide (both at 20 mg/L) under UV irradiation for 150 min. Photo-filtration experiments confirmed the synergistic effect of molecular separation and photodegradation, resulting in the removal of 99.5 % of ciprofloxacin and 79.5 % of sulfanilamide, coupled with a relatively high pure water flux of 115.44 L.m−2.h−1. The PM also exhibited excellent stability, self-cleaning properties, and reusability, with a flux recovery rate (FRR) of 97.5 % after five cycles of use. Finally, the PVDF/CeO2@GO-COOH membrane holds great promise for the treatment of pharmaceutical industry wastewater, offering a comprehensive solution that combines efficient pollutant degradation, high permeate flux, stability, and reusability.

Facile synthesis of 2D/0D Bi2O3/MnO2 Z-scheme heterojunction for enhanced visible light-assisted photocatalytic degradation of acetaminophen

The construction of heterojunctions is a prominent strategy for improving the photocatalytic activity of semiconductor nanoparticles. In this study, a novel visible-light-driven 2D/0D Bi2O3/MnO2 (BMO) Z-scheme heterojunction was fabricated through a facile room-temperature solution-phase synthesis scheme to achieve enhanced photocatalytic degradation of acetaminophen (ACT). The BMO nanocomposite achieved 94.3% degradation efficiency at 0.0202 min−1 in 120 min, approximately 3.5 and 3.8 times higher than the degradation rate of the individual MnO2 and Bi2O3 photocatalysts, respectively. Based on electron paramagnetic resonance spectra and Mott-Schottky measurements, a Z-scheme heterojunction appeared between the Bi2O3 nanoflakes and MnO2 nanoparticles. The effective charge separation and electron transfer efficiency due to Z-scheme heterojunction and a narrow band gap of 2.10 eV were responsible for the enhanced photocatalytic performance. Further, the intermediates and end products of ACT degradation were identified, and plausible degradation pathways were established. Additionally, the performance of BMO in various real water matrices was evaluated. The degradation efficiency was highest in deionized water, followed by tap water, municipal, hospital, and pharmaceutical industry wastewater. Eventually, a mathematical model based on an artificial neural network has been developed to predict the photocatalytic process. Besides, the excellent photocatalytic performance of the BMO nanocomposite remained intact even after five consecutive cycles. The results of this study elicit crucial insights into synthesizing highly efficient and stable Z-scheme heterojunction photocatalysts to degrade emerging contaminants.

Treatment of Pharmaceutical Industry Wastewater by PhotoelectroFenton Oxidation

The use of Photoelectro-Fenton oxidation to treat real pharmaceutical effluent is an attractiveoption for the elimination of complex and persistent organic contaminants. This advanced oxidation processcombines the electrochemical generation of highly reactive hydroxyl radicals (OH•) with the photochemicaldegradation of by-products, resulting in the efficient removal of pharmaceutical compounds fromwastewater. In the Photoelectro-Fenton process, an appropriate anode material, such as BDD or DSA, isused to generate OH•radicals through the electrochemical oxidation of Fe2+ ions. The addition of a smallamount of Fe2+ and H2O2 facilitates the Fenton reaction, leading to the production of additional OH•radicalsin the solution. The presence of these OH•radicals ensures the effective oxidation of pharmaceuticalpollutants, which are often resistant to conventional wastewater treatment methods. The use of UV orsunlight irradiation further enhances the Photoelectro-Fenton process by promoting thephotodecomposition of intermediate by-products formed during the oxidation process. This simultaneouselectrochemical and photochemical degradation mechanism provides synergistic effects, resulting inenhanced degradation and mineralization of pharmaceutical compounds. Studies have demonstrated thesuccessful application of Photoelectro-Fenton oxidation for the treatment of real pharmaceuticalwastewater, showing significant removal efficiencies for a wide range of pharmaceutical compounds,including antibiotics, analgesics, and hormones. Additionally, the process has been shown to effectivelydegrade recalcitrant by-products and reduce the overall toxicity of the wastewater. However, it is importantto consider factors such as optimal pH, Fe2+ and H2O2 dosages, irradiation intensity, and reaction time toachieve optimal treatment efficiency. Furthermore, the cost-effectiveness and scalability of thePhotoelectro-Fenton process need to be evaluated for its potential implementation in large-scale wastewatertreatment facilities.

Alternative technology for the recovery of butyl acetate with low concentration: high capacity adsorbent and high efficiency adsorption

Industrial pharmaceutical wastewater usually contains butyl acetate (BA) with a concentration of 1 wt%–7 wt%, and the traditional method for BA recovery is distillation with high energy consumption. Adsorption method is developed to recover BA with low concentration for the high efficiency and low energy consumption. Medium polar polyacrylate resins with macroporous structure of 233.1 nm and average particle size of about 526.5 μm are successfully synthesized by suspension polymerization and used for the BA adsorption and desorption. The maximum adsorption capacity reaches 171.1 mg g−1 with relative standard deviation (RSD) value of 0.2%, which is more than twice the results in the literature. The BA desorption rate is 97.0% at 100 °C with RSD value of 0.4%, and the resins are beneficial to the reuse in the adsorption-desorption cycle. The adsorption thermodynamics and kinetics are investigated, and the BA adsorption is a spontaneous and endothermic process with the increase of disorder degree. This process is mainly contributed by physical absorption and agree well with Freundlich model and pseudo-first-order adsorption kinetic model. The adsorption method avoids boiling a large amount of wastewater and hopefully provides a novel alternative technology for the BA recovery.

The Removal of Sulfamonomethoxine (SMM) with Copper Oxide/Zirconium Dioxide (CuO/ZrO2) Nanocomposites by Photocatalytic Degradation in Pharmaceutical Industry Wastewaters and the Evaluation of Microtox (Aliivibrio fischeri) and Daphnia magna Acute Toxicity Assays

In this study, Copper oxide/zirconium dioxide (CuO/ZrO2) nanocomposites (NCs) as a photocatalys was examined during photocatalytic degradation process (PDP) in the efficient removal of Sulfamonomethoxine (SMM) from pharmaceutical industry wastewater (PI ww) plant, İzmir, Turkey. Different pH values (3.0, 4.0, 7.0, 9.0, 10.0 and 12.0), increasing SMM concentrations (5, 10, 20 and 40 mg/l), increasing CuO/ZrO2 NCs concentrations (100, 200, 400, 800 and 1000 mg/l), different CuO/ZrO2 NCs mass ratios (1/2, 2/3, 3/4, 4/4, 4/3, 3/2, 2/1), increasing recycle times (1., 2., 3., 4., 5., 6. and 7.) was operated during PDP in the efficient removal of SMM in PI ww. The characteristics of the synthesized nanoparticles (NPs) were assessed using XRD, DRS, FESEM, EDX, FTIR, TEM and XPS analyses, respectively. The acute toxicity assays were operated with Microtox (Aliivibrio fischeri also called Vibrio fischeri) and Daphnia magna acute toxicity tests. The photocatalytic degradation mechanisms of CuO/ZrO2 NCs and the reaction kinetics of SMM were evaluated in PI ww during PDP. Cost analysis was evaluated for SMM removal with CuO/ZrO2 NCs by PDP in PI ww. ANOVA statistical analysis was used for all experimental samples. Maximum 99.6% SMM removal was obtained during PDP in PI ww, at 350 W UV-vis light irradiation power, at 147 mW/cm2 light intensity, after 120 min, at pH=12.0 and at 25oC, respectively. Maximum 99.2% SMM removal was found with PDP in PI ww, at 5 mg/l SMM, at 350 W UV-vis, at 147 mW/cm2, after 120 min, at pH=12.0 and at 25oC, respectively. Maximum 99.5% SMM removal was measured to 800 mg/l CuO/ZrO2 NCs with PDP in PI ww, at 5 mg/l SMM, at 350 W UV-vis, at 147 mW/cm2, after 120 min, at pH=12.0 and at 25oC, respectively. Maximum 99.4% SMM removal was measured at 4/3wt CuO/ZrO2 NCs mass ratios, at 5 mg/l SMM, at 800 mg/l CuO/ZrO2 NCs, at 350 W UV-vis, at 147 mW/cm2, after 120 min, at pH=12.0 and at 25oC, respectively. Maximum 99.5% SMM recovery was measured in PI ww during PDP, after 1. recycle time, at 5 mg/l SMM, at 800 mg/l CuO/ZrO2 NCs, at 4/3wt CuO/ZrO2 NCs mass rartio, at 350 W UV-vis, at 147 mW/cm2, after 120 min, at pH=12.0 and at 25oC, respectively. 97.31% maximum Microtox acute toxicity removal was found in SMM=20 mg/l after 180 min, and at 60oC. It was observed an inhibition effect of SMM=40 mg/l to Microtox after 180 min, and at 60oC. 93.27% maximum Daphnia magna acute toxicity removal was obtained in SMM=20 mg/l after 180 min, and at 60oC, respectively. It was obtained an inhibition effect of SMM=40 mg/l to Daphnia magna after 180 min and at 60oC. As a result, the CuO/ZrO2 NCs during PDP in PI ww was stable in harsh environments such as acidic, alkaline, saline and then was still effective process. Finally, the combination of a simple, easy operation preparation process, excellent performance and cost effective, makes this CuO/ZrO2 NCs a promising option during PDP in PI ww treatment.