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 75 min of the sono-assisted photocatalytic treatment, the complete degradation of CIP (10 mg/L) was accomplished under the condition as follows: g-C3N4/NH2-UiO-66 (Zr), 0.6 g/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.

A new MOF-based modified adsorbent for the efficient removal of Hg(ii) ions from aqueous media: isotherms and kinetics.

Herein, a new MOF-based modified adsorbent for the efficient removal of Hg(ii) ions from water media was successfully prepared. Initially, a MOF nanocomposite was synthesized and applied as an efficient adsorbent for the removal of the target heavy metal ion. Following the synthesis, the MOF-based modified adsorbent was identified and characterized by SEM, XRD and FT-IR analytical instruments. The impact of several key variables such as pH of aqueous solution, adsorbent dosage, contact time, and initial concentration of the analyte of interest on the adsorption efficiency was also investigated in detail. Under the optimal conditions established (pH, 3; dose of adsorbent, 0.4 g L-1; contact time, 40 min and the analyte's concentration of 1 mg L-1) the removal efficiency of 96.3% for Hg(ii) was obtained. The results of the studies on the isotherm and kinetics of adsorption revealed that the adsorption process of Hg(ii) matched with the Langmuir isotherm (R2 > 0.990) and the pseudo 2nd-order kinetic models (R2 > 0.998). Additionally, reuse of the applied adsorbent for five consecutive tests exhibited a small percentage of drop (about 8%) in the removal efficiency of the target ion. Finally, the results indicated that the MOF-based modified compound could be potentially applied as a highly efficacious adsorbent for the discharge of Hg(ii) from aquatic media.

Efficient removal of oxytetracycline antibiotic from aqueous media using UV/g-C3N4/Fe3O4 photocatalytic process.

Residual pharmaceuticals in the environment are a class of emerging pollutants that endanger human health. Tetracycline's family, including oxytetracycline (OTC), are known as one of the most produced and consumed antibiotics worldwide. The g-C3N4/Fe3O4 nanocomposite with high level of catalytic efficiency features suitable performance in water/wastewater treatment. Therefore, in the present study, this nanocomposite was applied to remove the oxytetracycline from the aqueous environment. In this research study, g-C3N4/Fe3O4 nanocomposite (serving as catalyst) was initially synthesized by a simple hydrothermal method. The effect of key operating parameters such as initial solution pH, dose of catalyst, contact time and initial concentration of OTC in aqueous solutions was investigated under UV irradiation. In addition, COD and TOC tests, the kinetics and the effect of radical scavengers on the applied photocatalytic process were all evaluated. The maximum removal efficiency of OTC (99.8 %) was achieved under the following conditions: neutral solution pH 7; catalyst dose, 0.7 g/L; and an initial OTC concentration of 5 mg/L. The data showed that the kinetics of the reaction followed the first-order model with R2 of 0.9755. The respective COD and TOC efficiency values for the applied photocatalytic process were determined to be 87 and 59 %, respectively. In addition, the lowest removal efficiency of OTC was observed in the presence of tert-butanol radical scavengers, and OH radicals played a main role. The UV/g-C3N4/Fe3O4 photocatalytic process proved to be highly efficient for the removal of OTC antibiotic and could be potentially applied for the removal of other pollutants from aqueous solutions.

Biosolids, an important route for transporting poly- and perfluoroalkyl substances from wastewater treatment plants into the environment: A systematic review.

The pervasive presence of poly- and perfluoroalkyl substances (PFAS) in diverse products has led to their introduction into wastewater systems, making wastewater treatment plants (WWTPs) significant PFAS contributors to the environment. Despite WWTPs' efforts to mitigate PFAS impact through physicochemical and biological means, concerns persist regarding PFAS retention in generated biosolids. While numerous review studies have explored the fate of these compounds within WWTPs, no study has critically reviewed their presence, transformation mechanisms, and partitioning within the sludge. Therefore, the current study has been specifically designed to investigate these aspects. Studies show variations in PFAS concentrations across WWTPs, highlighting the importance of aqueous-to-solid partitioning, with sludge from PFOS and PFOA-rich wastewater showing higher concentrations. Research suggests biological mechanisms such as cytochrome P450 monooxygenase, transamine metabolism, and beta-oxidation are involved in PFAS biotransformation, though the effects of precursor changes require further study. Carbon chain length significantly affects PFAS partitioning, with longer chains leading to greater adsorption in sludge. The wastewater's organic and inorganic content is crucial for PFAS adsorption; for instance, higher sludge protein content and divalent cations like calcium and magnesium promote adsorption, while monovalent cations like sodium impede it. In conclusion, these discoveries shed light on the complex interactions among factors affecting PFAS behavior in biosolids. They underscore the necessity for thorough considerations in managing PFAS presence and its impact on environmental systems.

UiO66-NH2-TiO2/NiF photoanode for photocatalytic fuel cell by towards simultaneous treatment of antibiotic wastewater and electricity generation.

Environmental destruction, water crisis, and clean energy are among the very important challenges worldwide based on sustainable development goals. Photocatalytic fuel cell, a potential candidate for converting chemical energy into electrical energy through a pollution-free method, holds promise in addressing these challenges. In this regard, we investigated the response of a photoanode covered with UiO66-NH2-TiO2/NiF on a porous nickel foam as an attractive electrochemical response to remove antibiotics from aqueous solution and simultaneously produce electricity using a one-step hydrothermal synthesis. Nickel foam with its fine structure provides a suitable space for the interaction of light, catalyst, and efficient mass transfer of reactive molecules. It appears that it can be used as a competitive electrode in fuel cells. In order to investigate the properties of the photocatalyst, structural analyses including XRD, FESEM, FTIR, and UV-vis DRS were utilized. Additionally, polarization and electrochemical tests such as chronoamperometry and EIS were measured to further examine the electrochemical features of the PFC photoanode system. The obtained results under optimal conditions (SMZ concentration = 20 ppm, pH = 6, irradiation time = 120 min) were as follows: removal efficiency of 91.7%, Pmax = 16.98 µW/cm2, Jsc = 96.75 µA/cm2, Voc = 644 mV. The light-induced current flow in UiO66-NH2-TiO2/NiF exhibited prominent and reproducible photocurrent responses, indicating efficient and stable charge separation in TiO2/NiF composite materials, which is a promising strategy for pollutant removal and simultaneous electricity generation.

Utilization of the copper recovered from waste printed circuit boards as a metal precursor for the synthesis of TiO2/magnetic-MOF(Cu) nanocomposite: Application in photocatalytic degradation of pesticides in aquatic solutions.

In this study, a number of leaching solutions (H2SO4, CuSO4 and NaCl) and an electrochemical method were used together for the separation of Cu from waste printed circuit boards. Secondly, the magnetic-MOF(Cu) was synthesized using the Cu recovered from waste printed circuit boards. Thereafter, TiO2/mag-MOF(Cu) composite was prepared and its photocatalytic activity was assessed in the photo degradation of two prominent organophosphorus pesticides, namely malathion (MTN) and diazinon (DZN). The catalytic structure of the MOF-based composite was fully characterized by various analyses such as XRD, SEM, EDAX, FT-IR, VSM and UV-vis. The obtained analyses confirmed the successful synthesis of TiO2/mag-MOF(Cu) composite. The synthesized composite exhibited highly efficient in the degradation of both pollutants under the following conditions: pH 7, contaminant concentration 1 mg/L, the catalyst dosage of 0.4 g/L, visible light intensity 75 mW/cm2 and reaction time of 45 min. First order kinetic model was best suited with the experimental results (R2: 0.97-0.99 for different MTN and DZN concentrations). Trapping studies revealed that superoxide radicals (O2•-) played an important role during the degradation process. Furthermore, the catalyst demonstrated a superb recovery as well as high stability over five cyclic runs of reuse. In addition, the total organic carbon (TOC) analysis showed over 83% and 85% mineralization for MTN and DZN, respectively. The combined system of TiO2/mag-MOF(Cu)/Vis also exhibited a great level of efficiency and feasibility in the treatment of tap water and treated wastewater samples. It is concluded that TiO2/mag-MOF(Cu) could be used as an excellent catalyst for the photodegradation of MTN and DZN in aqueous solution.

Application of a modified MWCNT-based d-µSPE procedure for determination of bisphenols in soft drinks.

Herein, a facile dispersive micro-solid phase extraction (d-µSPE) procedure using carboxylated multi-walled carbon nanotubes modified with silver nanoparticles (Ag/MWCNTs-COOH) was successfully developed for the adsorption and subsequent determination of low levels of two well-known contaminants, namely bisphenol A and S (BPA and BPS) in water and soft drink samples. The detection and measurement of the above-mentioned compounds were performed by HPLC-UV instrument. The applied d-µSPE procedure has several advantages such as rapidity, high degree of sensitivity, precision and efficiency. A combination of polar/non-polar interactions seems to play a key role in the adsorption process. Under the optimized conditions, the calibration curves were linear over the concentration range of 1-500 µg/L for the both targets. The practical limit of quantifications (LOQ) for the both analytes were determined to be 1.0 µg/L. The average relative recoveries obtained from the fortified samples varied between 92 and 110% with the relative standard deviations (RSD%) of 2.9-9.5%.

Efficient photocatalytic degradation of metronidazole from aqueous solutions using Co/g-C3N4/Fe3O4 nanocomposite under visible light irradiation.

Herein, the efficient degradation of a highly consumed antibiotic known as metronidazole (MNZ) in aqueous solutions using Co/g-C3N4/Fe3O4 nanocomposite under visible light irradiation was accomplished. Initially, the photocatalyst (Co/g-C3N4/Fe3O4) was synthesized by a simple hydrothermal method and then characterized by several analytical techniques, namely EDS, SEM, XRD, UV-vis DRS, and FTIR. The efficiency of the synthesized photocatalyst with regard to the degradation of the studied antibiotic (MNZ) under visible light irradiation was fully evaluated. The influential operational parameters affecting the efficiency of the degradation process such as pH (2-10), nanocomposite dosage (0.2-1 g/L), MNZ concentration (5-20 mg/L), and irradiation time (0-80 min) were optimized. The results revealed that the maximum degradation efficiency for MNZ was obtained under the following conditions: irradiation time of 60 min, pH = 8, MNZ concentration of 5 mg/L, and photocatalyst dosage of 0.7 g/L. In addition, the degradation of MNZ followed the pseudo-first-order kinetic model. The best rate constant (k) value was determined to be 0.0102 min-1 with the correlation coefficient (R2) of 0.992. According to the results of the quenching tests, it was found out that hydroxyl radicals (OH°) were the main species responsible for the MNZ degradation. Furthermore, the applied photocatalyst (Co/g-C3N4/Fe3O4) exhibited a high level of recovery and stability after five cycles of reuse. Co/g-C3N4/Fe3O4/Vis system exhibited an excellent performance in the treatment of wastewater and real water samples. Finally, it was concluded that the synthesized nanocomposite could be potentially used as a promising and suitable photocatalyst in the degradation of other antibiotics.

The superior adsorption capacity of 2,4-Dinitrophenol under ultrasound-assisted magnetic adsorption system: Modeling and process optimization by central composite design.

2,4-Dinitrophenol (DNP) was listed as a priority pollutant; accordingly, DNP-contaminated effluent must be treated before discharging to the receiving resources. In the present study, the hybrid ultrasound-assisted GO-Fe3O4 system was employed to decontaminate DNP solution. Ultrasound irradiation makes the mass transfer of adsorbate improved and Fe3O4 enables GO separation from liquid phase under external magnetic field. The as-synthesized GO-Fe3O4 composite was characterized by SEM, TEM, XRD, FTIR, BET and VSM. A response surface methodology based central composite design (RSM-CCD) was used to estimate and optimize of various variables on DNP removal percentage. Under optimal conditions (pH: 4.45, adsorbent dose: 0.178 g/L, ultrasound frequency: 40.02 kHz and DNP concentration: 50.10 mg/L, maximum adsorption capacity was calculated to be 425.58 mg/g for the ultrasound system, higher than the simple system 309.40 mg/g, indicating the importance of synergistic effect between the ultrasound waves and the adsorption process. The ultrasound-assisted adsorption system showed the better agreement with the Langmuir isotherm (R2 > 0.997), while the results of the stirring system were more consistent with the Freundlich model (R2 > 0.991). The experimental results indicated that the pseudo-second-order kinetic model well fitted by experiment data and rate constant was calculated to be 0.000148 min-1 and 0.000002 min-1 under ultrasound and silent systems, respectively. The rate of desorption under ultrasound was more favorable and reuse of the adsorbent in both systems after 10th consecutive cycles reduced by about 22%. Thermodynamic calculations also confirmed the endothermicity and spontaneity of both systems. Electrostatic attraction, hydrogen bonding, and π -π interactions played key roles during the adsorption of DNP onto the MGO. In conclusion, the outcomes of this study provide valuable information of the ultrasound-assisted GO-Fe3O4 system for practical applications.

Effect of cigarette butt on concentration of heavy metals in landfill leachate: health and ecological risk assessment.

Cigarette butt is known as hazardous waste with numerous toxic and carcinogenic pollutants which impose serious concern for both the environment and human. Heavy metals are recognized as the most common pollutant in the cigarette butts. The concentration of some heavy metals (cadmium, chromium, nickel, lead and zinc) in leachate obtained from the pilot landfill with commingled waste and freshly smoked cigarettes butts were analyzed. The results showed that the addition of 0.76% (in weight) freshly smoked cigarette butts in landfilled waste increased total heavy metal concentration by 4.8%, while addition of 1.3% (in weight) freshly smoked cigarette butts leads to increased 3.72% of total heavy metals concentrations. An increased 10.52% and 3.43% health risk values were found from the leachate of the landfill pilot, where 1% freshly smoked cigarette butt and a littered cigarette were added, respectively. Overall, it can be concluded that cigarette butt landfilling is not recommended for management of this type of waste and is necessary to be replaced with less hazardous ways such as recycling.

A global systematic review, meta-analysis and health risk assessment on the quantity of Malathion, Diazinon and Chlorpyrifos in Vegetables.

It is widely believed that an increasing trend in the production and consumption of vegetables has led to a dramatic rise in the use of pesticides potentially threatening the health of consumers around the world. This systematic study along with meta-analysis has mainly centered on the evaluation of the quantity of three well-known pesticides namely, Malathion (MLT), Diazinon (DZN) and Chlorpyrifos (CPF) in vegetables. In this regard, a comprehensive literature search has been performed over the last decade (January 1, 2011 to June 21, 2020) within the scientific databases including PubMed, Web of Science, and Scopus. Of 1239 articles identified through the database screening, 22 plus 37 data report were retained and included in the meta-analysis phase. Additionally, the probabilistic human health risks for the consumers due to the intake of CPF, DZN and MLT from eating vegetables were estimated by the Monte Carlo Simulated (MCS) method. According to the findings, the maximum quantities of MLT, DZN and CPF in the vegetables were observed in Pakistan (222 µg/kg, 95%CI = 214.94-229.08), Thailand (245.00, 95% CI = 235.2-254.8) and South Korea (440 µg/kg, 95% CI = 437.19-442.81), while the lowest concentration levels were reported in China (1.7 µg/kg, 95% CI = 1.56-1.84), Poland (0.57, 95% CI = 0.46-0.68) and Poland (5.78 µg/kg, 95% CI = 4.40-7.12), respectively. The results of the Egger's and the Begg's tests revealed that no bias with regard to the potential publication was observed. Finally, non-carcinogenic risk assessment results demonstrated that the exposure to the studied pesticides thorough vegetables consumption could not threaten the health of consumers.