Pharmaceuticals In Wastewater Samples Research Articles

Modeling and optimization of triclosan biodegradation by the newly isolated Bacillus sp. DL4: kinetics and pathway speculation.

Triclosan is a widely used antibacterial agent and disinfectant, and its overuse endangered ecological safety and human health. Therefore, reducing residual TCS concentrations in the environment is an urgent issue. Bacillus sp. DL4, an aerobic bacterium with TCS biodegradability, was isolated from pharmaceutical wastewater samples. Response surface methodology (RSM) and artificial neural network (ANN) were carried out to optimize and verify the different condition variables, and the optimal growth conditions of strain DL4 were obtained (35°C, initial pH 7.31, and 5% v/v). After 48h of cultivation under the optimal conditions, the removal efficiency of strain DL4 on TCS was 95.89 ± 0.68%, which was consistent with the predicted values from RSM and ANN models. In addition, higher R2 value and lower MSE and ADD values indicated that the ANN model had a stronger predictive capability than the RSM model. Whole genome sequencing results showed that many functional genes were annotated in metabolic pathways related to TCS degradation (e.g., amino acid metabolism, xenobiotics biodegradation and metabolism, carbohydrate metabolism). Main intermediate metabolites were identified during the biodegradation process by liquid chromatography-mass spectrometry (LC-MS), and a possible pathway was hypothesized based on the metabolites. Overall, this study provides a theoretical foundation for the characterization and mechanism of TCS biodegradation in the environment by Bacillus sp. DL4.

Development and Validation of UFLC-MS/MS Analytical Method for the Simultaneous Quantification of Antibiotic Residues in Surface Water, Groundwater, and Pharmaceutical Waste Water Samples from South India.

Antibiotic residues in pharmaceutical wastewater pose a significant environmental concern due to their potential role in fostering antimicrobial resistance. South Indian pharmaceutical companies produce a wide range of antibiotics. As a result, the industries that discharge water may include antibiotic residues, which could be harmful to the environment. In this study, a novel, quick, accurate, and sensitive approach for the simultaneous detection of 11 antibiotics was established, and triple quadrupole mass spectrometry, ultra-fast liquid chromatography-tandem mass spectrometry (UFLC-MS/MS), and selective solid-phase extraction (SPE) were used for validation. Utilizing a mixed mode reversed-phase/cation-exchange cartridge (SPE using Strata X, 33 μm), the single-cartridge extraction procedure was performed and validated. Relative standard deviations for most of the antibiotics ranged from 3.5 to 0.56 with recoveries ranging from 57 to 85%. The samples were injected into the UFLC-MS/MS apparatus at a volume of 10 μL for analysis. The auto sampler cooler temperature was kept at 150 °C, while the column temperature was kept at 40 °C. After validation, the technique was determined to be linear in the range of 2.0-1000.0 ng/mL. The retention period for antibiotics was between 1.2 and 1.5 min. Antibiotics transitions for multiple reaction monitoring| were between 235.1/105.9 and 711.5/467.9 m/z. The method of analysis took 2.5 min to run completely. Antibiotic residues were efficiently analyzed using the established analytical approach in pharmaceutical wastewater (influent and effluent), surface, and groundwater. Eleven antibiotics were found in the water samples during examination with concentrations ranging between 2.313 and 95.744 ng/L. The procedure was shown to be much more environmentally friendly than other contemporary methods based on the green analytical procedure index's evaluation of greenness. Blue applicability grade index tool indicated the developed method's practicality in comparison with that of other reported method.

A selective dispersive liquid-liquid micro-extraction technique for trace level pollutants enrichment of pharmaceutical residues from hospital wastewaters followed by liquid chromatographic analysis

In this study a dispersive liquid-liquid micro-extraction (DLLME) method was utilized for extraction of trace pharmaceuticals in wastewater samples. Factors influencing the extraction performances were tested and accordingly 900 µL dichloroethane as the extraction solvent, 1400 µL acetonitirle as dispersive solvent, 10 min extraction time at 4000 rpm centrifugation, and pH 5 were found optimum. Acetonitrile and 0.2% formic acid in water were used as eluent. The column temperature was maintained at 25 °C and the optimum detection wavelengths of 273 nm for sulfamethoxazole and 280 nm for ciprofloxacin were used. For both the analytes, the coefficients of determinations (r2) were found to vary from 0.9989 to 0.9997, confirming good linearity in the concentration range of 0.005-100 µg mL-1 for sulfamethoxazole and 0.01-100 µg mL-1 for ciprofloxacin. The LOD and LOQ were in the range of 0.78-1.58 ng mL-1 and 2.24-5.28 ng mL-1, respectively; the RSDs were 0.41-3.21% for intra-day precision and 0.37-6.44% for inter-day precision. The concentrations of the three pharmaceuticals determined ranged from 0.76-1.53 μg mL-1 in the wastewater samples collected from Black Lion Hospital. However, ciprofloxacin and doxycycline were not detected and only low concentration of sulfamethoxazole was detected in the wastewater samples collected from Menelik II Hospital.
 KEY WORDS: Antibiotics, DLLME, Dispersive solvent, Hospital wastewater
 Bull. Chem. Soc. Ethiop. 2024, 38(1), 27-42. DOI: https://dx.doi.org/10.4314/bcse.v38i1.3

Unmodified and rGO-modified Zn/Al layered double hydroxides; nanoadsorbents employed for the solid phase extraction/HPLC determination of naproxen

The applicability of two layered double hydroxide adsorbents, that is, Zn/Al LDH and the reduced graphene oxide-modified Zn/Al-rGO LDH for the solid phase extraction-preconcentration of naproxen followed by HPLC determination is evaluated and compared. The adsorbents are characterized by using XRD, FT-IR, FE-SEM, BET, and TEM techniques. The optimization of parameters affecting the extraction procedure included pH and sample solution volume, amount of the adsorbents, adsorbent/sample solution contact time, type, concentration, and volume of the desorption solution, and the time required for desorption process was performed by using univariate method. It is assumed that the uptake of anionic form of naproxen is taken place via the ion exchange mechanism with interlayer carbonate anions of the studied LDHs. The applicability of the adsorbents is evaluated by the determination of naproxen in human urine, hospital, and pharmaceutical wastewater samples. The obtained linear ranges by employing the unmodified and modified LDHs for the determination of naproxen in pharmaceutical wastewater were found to be 10–530 µg L−1 (R 2 = 0.9999) and 5–630 µg L−1 (R 2 = 0.9999), respectively. The limits of detection and enrichment factor were appraised as 5.1 µg L−1 and 42 by employing Zn/Al LDH, and 3.1 µg L−1 and 54.5 by using Zn/Al-rGO LDH. Both investigated LDHs are able to be used in solid phase extraction-preconcentration of naproxen in real samples. However, the evaluated figures of merit reveal that the modified Zn/Al-rGO LDH is more efficient adsorbent than the unmodified Zn/Al LDH for the extraction of naproxen.

A magnetic sorbent based on Zn-NiFe2O4@Ni-Al layered double hydroxide nanocomposite for the pre-concentration and quantification of mefenamic acid by differential pulse voltammetry

A novel magnetic sorbent was introduced involving a zinc–nickel ferrite@nickel–aluminum layered double hydroxide (Zn-NiFe2O4@Ni-Al LDH) nanocomposite. The Zn-NiFe2O4@Ni–Al LDH was synthesized through a co-precipitation method, and characterized using several techniques. The nanocomposite was shown to be an efficient sorbent for the pre-concentration of mefenamic acid prior to its detection by differential pulse voltammetry using a glassy carbon electrode modified with carbon nanotubes. To achieve the best extraction efficiency, the effects of various parameters such as pH, the sorbent dosage, extraction time, elution conditions, and sample volume were studied and optimized. Under the optimized experimental conditions, the calibration plot was linear in two concentration ranges from 50 to 100 nM (R2 = 0.9944) and 100–700 nM (R2 = 0.9913). The limit of detection was calculated to be 6.3 nM, and the precision of the method in the terms of intra-day and inter-day relative standard deviations (n = 5; mefenamic acid concentration = 100 nM) were 1.4% and 2.4%, respectively. The accuracy of the method was assessed by analyzing a pharmaceutical dosage form of the analyte, and comparing the results with those obtained from a standard method. To evaluate the applicability of the method, it was applied for trace determination of mefenamic acid in tablet, human plasma, urine, and pharmaceutical wastewater samples, and the satisfactory relative recovery values (96.0–103.1%) were attained for the spiked samples. The easy separation from the solution by applying an external magnet, high surface area, high stability in the strong alkaline solutions, and high reusability (more than 60 adsorption/desorption cycles) are some advantages of the synthesized nanosorbent.

Physicochemical analysis and detection of exceptionally high diclofenac concentration in the pharmaceutical wastewaters collected from the production units of national industrial zone, Rawat, Pakistan

The annual growth rate of pharmaceutical industry in Pakistan is 10% and is continuously expanding to fulfill the increasing demand of the rapidly growing population. But inability of the pharmaceutical sector to comply with the environmental standards leads to the introduction of large quantities of various pollutants in the natural environment which presents serious ecological challenges. In this study, effluent wastewater samples from 14 manufacturing units of the pharmaceutical industries of the National Industrial Zone, Rawat, Pakistan, were collected and characterized for physicochemical parameters including color, odor, pH, electric conductivity, temperature, total dissolved solids, total suspended solids, salinity, dissolved oxygen (DO), chemical oxygen demand (COD), nitrates, sulfates and phosphates according to the standard methods. The detection and quantification of diclofenac (DCF)—one of the commonly prescribed drugs in Pakistan—were carried out in the pharmaceutical wastewater samples (PWWSs) using HPLC-PAD. Exceptionally high concentration of the diclofenac was detected in the industrial disposal of MB-12 (311,495 µg L−1). PWWSs were analyzed using chemometric techniques including principal factor analysis (PFA) and cluster analysis (CA). PFA explained almost 81.48% of the total variance by the newly extracted four components and complemented the strong Pearson’s correlation coefficient (r) of DCF concentrations to that of the levels of COD, r = 0.752, and DO, r = − 0.609, in PWWSs. Six clusters were generated during similar wastewater characteristics-based CA dendrogram, in which reverse osmosis-treated PWWSs were observed to cluster with the untreated PWWSs, suggesting the need to adopt an advance and better wastewater treatment methods by the pharmaceutical industries.

Multivariate analysis of heavy metals in pharmaceutical wastewaters of National Industrial Zone, Rawat, Pakistan

Water is the basic necessity of life, and its quality affects biological processes. Anthropogenic activities increase concentration of harmful pollutants like heavy metals in the environment. The current study is the first attempt for the assessment of heavy metals in the wastewaters released from pharmaceutical industries of the National Industrial Zone, Rawat, Pakistan. The metal concentrations depicted the following trend: Fe » Zn > Ni > Pb > Mn > Cr6+ > Cd > Cu. Mn, Cu and Zn were recorded within the maximum permissible limits of Pakistan National Environmental Quality Standards (Pak-NEQS) and World Health Organization (WHO) in all the pharmaceutical wastewater samples; but Cd, Pb, Fe, Cr6+ and Ni surpassed one or both the admissible limits which can be the potential threat to the underground water resources, aquatic life and human health. The highest concentration was detected for Fe (10.86 ± 0.01 mg.L−1) in the wastewater sample of MB-12, which was much higher than the maximum NEQS limit of 2 mg.L−1. Maximum significant correlations were observed for Cr with various water quality parameters, including dissolved oxygen, phosphates, salinity and Cu during Pearson's correlation analysis. Multivariate techniques including cluster analysis and principal factor analysis were used to extract the latent information from the data set to assess the water quality. Three principal factors were extracted during factor analysis containing high positive factor loadings of Cd, Fe; Cu, Mn; and Pb in the principal factors 1, 2 and 3 respectively, indicating the contribution of the anthropogenic and industrial operations in the water contamination due to the discharge of improperly treated or untreated pharmaceutical wastewater. Cluster analysis based dendrogram resulted in the formation of single cluster containing reverse osmosis treated wastewater samples along with the untreated wastewaters which strongly recommends the need to adopt wastewater treatment methods with efficient processes for proper discharge of their pharmaceutical effluents into fresh waters, thus reducing the potential ecological hazards.

Electrochemical Sensor Based on Poly-L-Tyrosine/AuNCs/PDA-CNTs Nanocomposites for the Detection of 17β-Estradiol in Wastewater

Achieving direct electrochemical detection of 17β-estradiol (E2) at low concentrations remains a challenge due to the weak electrochemical activity of E2. In this study, we report a simple, cheap and sensitive electrochemical sensor based on nanocomposite for the direct detection of E2 in wastewater. The nanocomposite sensing electrode was developed by electrochemical in situ polymerization. Due to the π–π stacking and hydrogen bonding between poly-L-tyrosine (P(L-tyr)) with E2, we prepared P(L-tyr) electrode based on dopamine-modified multi-walled carbon nanotubes (PDA-CNTs) and gold nanoclusters (AuNCs). Then P(L-tyr)/AuNCs/PDA-CNTs/GCE sensing system was obtained. Meanwhile, the synergistic effect of fast electron transfer of AuNCs and the signal amplification effect of PDA-CNTs enables sensitive and direct detection of E2. The results showed that P(L-tyr)/AuNCs/PDA-CNTs/GCE sensor had a linear response to E2 concentration from 0.05 to 10 μmol·l−1 with a detection limit of 7.1 nmol·l−1. Then, the trace amount of E2 in pharmaceutical wastewater samples can be directly detected against several interferences from complex matrix, with recoveries from 91.0 to 107.5%. P(L-tyr)/AuNCs/PDA-CNTs/GCE showed good stability when placed at room temperature. Therefore, it can meet the requirements of the sensitive detection of E2 in complex matrix.

Rapid determination of NSAIDs by capillary and microchip electrophoresis with capacitively coupled contactless conductivity detection in wastewater.

A simple, rapid method using CE and microchip electrophoresis with C4 D has been developed for the separation of four nonsteroidal anti-inflammatory drugs (NSAIDs) in the environmental sample. The investigated compounds were ibuprofen (IB), ketoprofen (KET), acetylsalicylic acid (ASA), and diclofenac sodium (DIC). In the present study, we applied for the first time microchip electrophoresis with C4 D detection to the separation and detection of ASA, IB, DIC, and KET in the wastewater matrix. Under optimum conditions, the four NSAIDs compounds could be well separated in less than 1min in a BGE composed of 20mM His/15mM Tris, pH 8.6, 2mM hydroxypropyl-beta-cyclodextrin, and 10% methanol (v/v) at a separation voltage of 1000-1200V. The proposed method showed excellent repeatability, good sensitivity (LODs ranging between 0.156 and 0.6mg/L), low cost, high sample throughputs,portable instrumentation for mobile deployment, and extremely lower reagent and sample consumption. The developed method was applied to the analysis of pharmaceuticals in wastewater samples with satisfactory recoveries ranging from 62.5% to 118%.

Facile synthesis of electrocatalytically active bismuth oxide nanosheets for detection of palladium traces in pharmaceutical wastewater

Current synthesis routes of bismuth oxide nanosheets (BiONS) are relatively complicated, requiring the use of halogens or metalloids. Herein, a facile method to synthesize BiONS without the addition of halogens or other metalloids was developed. The synthesized BiONS were identified to have flake-shaped structures (300–1000 nm in width) with the thickness of 6–10 nm, which were predominantly made of β-Bi2O3. Such BiONS were applied to modify the surface of screen-printed carbon electrodes (BiONS-SPCEs) for the development of a robust palladium (Pd2+) sensor. After optimizing the electrochemical parameters of the sensor, it was found that the linear sensor response range and limit of detection for Pd2+ were 40–400 and 1.4 ppb, respectively. The electrocatalytic activity of the Pd2+-sensor was validated in the competing environment of other metal and metalloid ions. Real samples collected during a Pd recovery process from pharmaceutical wastewater were used to verify the application of BiONS-SPCEs in control of palladium recovery process. The quantitative results of post recovery palladium concentrations obtained using BiONS-SPCEs in treated pharmaceutical wastewater samples were in good agreement with those obtained by inductively coupled plasma-optical emission spectrometry (ICP-OES). Thus, such Pd2+-sensor provided the possibility of on-site process control of complex industrial samples for obtaining near-instant information that would lead to better management of resources used in the process, and same time assure environmental standards for both recovered products and processed discharge.

A Fully Automated Online SPE-LC-MS/MS Method for the Determination of 10 Pharmaceuticals in Wastewater Samples.

The increasing use of pharmaceuticals, their presence in the aquatic environment, and the associated toxic effects, have raised concerns in recent years. In this work, a new multi-residue analytical method was developed and validated for the determination of 10 pharmaceuticals in wastewaters using online solid-phase extraction (online SPE) and liquid chromatography-tandem mass spectrometry (LC-MS/MS). The compounds included in the method were antineoplastics (cabazitaxel, docetaxel, doxorubicin, etoposide, irinotecan, methotrexate, paclitaxel, and topotecan), renin inhibitors (aliskiren), and antidepressants (maprotiline). The method was developed through several experiments on four online SPE cartridges, three reversed phase chromatography columns, and four combinations of mobile phase components. Under optimal conditions, very low limits of detection (LODs) of 1.30 to 10.6 ng L−1 were obtained. The method was repeatable, with relative standard deviations (RSD, %) for intraday and interday precisions ranged from 1.6 to 7.8 and from 3.3 to 13.2, respectively. Recovery values ranged from 78.4 to 111.4%, indicating the reproducibility of the method. Matrix effects were mainly presented as signal suppression, with topotecan and doxorubicin being the two most affected compounds (31.0% signal suppression). The proposed method was successfully applied to hospital effluents, detecting methotrexate (4.7–9.3 ng L−1) and maprotiline (11.2–23.1 ng L−1). Due to the shorter overall run time of 15 min, including sample preparation, and reduced sample volume (0.9 mL), this on-line SPE-LC-MS/MS method was extremely convenient and efficient in comparison to the classical off-line SPE method. The proposed method was also highly sensitive and can be used for ultratrace quantification of the studied pharmaceuticals in wastewaters, providing useful data for effective environmental monitoring.

Enhanced electro-oxidation performance of FeCoLDH to organic pollutants using hydrophilic structure

Iron-cobalt layered double hydroxides (FeCoLDH) showed superior oxygen evolution reaction (OER) performance, but the sluggish water adsorption and dissociation dynamics restrict its capacity to degrade organic pollutants by electro-oxidation. Herein, enhanced electro-oxidation performance of FeCoLDH with hydrophilic structure was designed and exhibited efficient removal efficiency of tetracycline. Theoretical calculation and characterization results consistently elucidated that the electronic structure of FeCoLDH is optimized by doping phosphorus and depositing copper nanodots (NDs). In addition, the obtained Cu NDs/P-FeCoLDH shows higher degradation ability of tetracycline in all-pH conditions than pristine FeCoLDH. That’s because it owns smaller barrier with 0.6 eV to generate hydroxyl radicals (•OH) than pristine FeCoLDH. Furthermore, it can effectively degrade organic pollutants in seawater, river water and pharmaceutical wastewater samples. This work provides novel and rational electrode materials for electro-oxidation system with practical application potential, which could offer new insights into the fundamental understanding of electrochemistry.

Construction of bacterial consortium for efficient degradation of mixed pharmaceutical dyes.

Synthetic dyes are established colorants in the pharmaceutical industries for the coating and coloration of tablets, capsules, etc. to mark the specific formulation and dosage, improve the stability, and esthetic value. The pharmaceuticals manufacturing process releases large volumes of dye-containing wastewaters, contributing to eco-toxic concerns related to different health risks. In this study, biodegradation of amaranth, sunset yellow, tartrazine, indigo carmine, and quinoline yellow dyes was investigated in the mixed environment. Initially, 24 tolerant bacterial strains were isolated from pharmaceutical wastewater samples, among which 19 strains were found to be non-virulent. Five different consortia were constructed by considering the 19 strains among which C1 consisting of strains DY7, 10, 11, and 18 was found to be the most potential consortium with an overall efficiency of 96.65% dye degradation in the presence of glucose after 15days. The strains DY7, 10, 11, and 18 were identified as members of the Klebsiella genus by 16S rRNA partial sequencing. The cell wall structure, carbohydrate utilization profile, and metabolic characterization were conducted on the selected strains of C1. Among the 25 different antibiotics, DY7 and DY11 exhibited the highest zone of growth inhibition in the presence of cefixime, and DY10 was restricted by chloramphenicol whereas DY18 was found sensitive to ceftazidime/tazobactam.

Solid Phase Extraction and Simultaneous Chromatographic Quantification of some Non-steroidal Anti-inflammatory Drug Residues; an Application in Pharmaceutical Industrial Wastewater Effluent

Two sensitive and selective methods were developed for the simultaneous determination of four commonly used non-steroidal anti-inflammatory drugs (NSAIDs), namely; paracetamol (PCM), diclofenac sodium (DCF), ibuprofen (IBP), and indomethacin (IND) in wastewater effluents. The first method used HPLC for the determination of the studied drugs using a mobile phase consisting of phosphate buffer (pH 3.0) and acetonitrile at a flow rate of 1 mL/min. in gradient elution mode and detection at 220 nm. The separation process was performed on BDS Hypersil Cyano column (250 x 4.6 mm, 5 μm). The second method was a TLC-densitometric one which was performed using n-Hexane: ethyl acetate: acetic acid in the ratio (6:3.5:0.5) as a developing system. The proposed chromatographic methods were successfully applied for the selective determination of the four studied drugs in simulated and real pharmaceutical wastewater samples after their solid-phase extraction.

Exploring magnetic particle surface embedded with imidazole-based deep eutectic solvent for diclofenac removal from pharmaceutical wastewater samples

This article described the use of imidazole-based deep eutectic solvents (DES) as functionalization agent for magnetic particles (Fe3O4) to form novel adsorbent and its application for diclofenac removal from pharmaceutical wastewater samples. A DES system was prepared by using imidazole in conjugation with chlorine chloride (ChCl-BuIM) as the hydrogen bond donor. Morphology, structure, property, and surface groups of the prepared adsorbents were investigated, and the adsorption study conditions were optimized. Results showed that the interaction between heterosporous surface of adsorbents and adsorbate molecules were through chemisorption mechanism. The adsorption was feasible, spontaneous, and exothermic. The analysis was further validated by using the adsorbents to remove diclofenac from pharmaceutical wastewater samples, whereby the percentage of removal was approximately 94.2%− 97.1% with low relative standard deviation (<˂3.01%). Overall, this study not only provided an inexpensive and eco-friendly adsorbent, but also developed a highly promising approach for the removal of diclofenac from pharmaceuticals wastewater samples.

Validation of a liquid chromatography coupled with tandem mass spectrometry method for the determination of drugs in wastewater using a three-phase solvent system.

Pharmaceuticals constitute one of the most important emerging classes of environmental pollutants. A three-phase solvent system of water, water containing 0.1% of formic acid and acetonitrile was successfully used to separate, by liquid chromatography with mass spectrometry (LC-MS), polarity-matched pharmaceuticals, that is, carbamazepine, clarithromycin, and erythromycin, as well as amoxicillin and metformin. Despite of polarity similarities, these pharmaceuticals were completely resolved in the analytical run time of 15 min. The optimized three-phase solvent system based-method was validated for the simultaneous analysis of six matched-polarity pharmaceuticals in wastewater samples. Good linearity (coefficient of determination more than 0.993) and precision (relative standard deviation less than 15.66%) were achieved. Recovery of analytes from the wastewater was between 0.70 and 1.18. Limits of detections ranged from 0.0001 to 0.5114µg/L. No significant matrix effect, evaluated by post extraction addition, was observed in the electrospray ionization (ESI) source. Then, this methodology has been successfully applied to environmental study of pharmaceutical residues occurring in influent and effluent wastewater samples, from the main wastewater treatment plant in Potenza (Basilicata, Southern Italy).

Hybrid adsorption–photocatalysis properties of quaternary magneto-plasmonic ZnO/MWCNTs nanocomposite for applying synergistic photocatalytic removal and membrane filtration in industrial wastewater treatment

A new multifunctional filtration membrane was prepared by twofold advantages of conventional polymeric-membrane as the supporting layer and magneto-plasmonic Ag-doped ZnO@Fe3O4/MWCNTs nanocomposite as the functional layer. Poly acrylic acid (PAA)-modified polyamide (PA) discs (PAA-PA) were applied to increase the hydrophilicity of prepared membrane and X-Ray diffraction (XRD) and scanning electron microscopy (SEM) techniques were used for characterization. The grafting yield of PAA in the pores and on the surface of PA was 17 wt.% and weigh difference between PAA-PA membrane before and after modifying with the photocatalyst was 8.7 mg. The amount of photocatalyst loading in the prepared membrane was obtained 6.49 g m−2. The synergistic effect of photocatalysis and membrane filtration was evaluated by investigating removal efficiency of amoxicillin (AMOX) as model pollutant using photocatalytic filtration concentration (CPF) parameter under a solar-simulated xenon lamp and the prepared photocatalyst-grafted PAA-PA membrane (PC-PAA-PA) was exhibited better removal ability than bare PA. The flux performance and antifouling property of the prepared membrane was investigated using pharmaceutical wastewater samples and the results revealed that the PC-PAA-PA exhibited good multifunctional characteristics such as high photocatalytic property, flux stability, and antifouling potential. The fouling process was performed in triplicate and the results demonstrated good stability of the photocatalyst on the membrane surface during operation. It can be concluded that by using a simple process for grafting of the photocatalyst to the membrane and the excellent antifouling ability of the resulting filter, an efficient reactor with antifouling characteristics can be constructed to produce cleaner water.

Ultrasensitive electroanalytical sulfisoxazole sensors amplified with Pd-doped ZnO nanoparticles and modified with 1-hexyl-3-methyl imidazolium bis(trifluoromethylsulfonyl)imide

In this study, an electrochemical sensor has been introduced by incorporating Pd-doped ZnO nanoparticles (ZnO–Pd/NPs) into a carbon paste (CP) matrix amplified by a conductive binder (1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (1H3MIBTMSI), in this case) to determine the concentration of the sulfisoxazole (SFX) drug in urine, tablet, and pharmaceutical wastewater samples.

Three-phase carrier-mediated hollow fiber microextraction based on deep eutectic solvent followed by HPLC–UV for determination of raloxifene and ethinylestradiol in pharmaceutical wastewater treatment plants

Endangering of the aquatic organisms and humans health by entrance of the pharmaceuticals in hydrosphere is becoming an important growing problem in the world. Effluents from wastewater treatment plants (WWTPs) are considered one of the main disposal pathways and incoming load of different pharmaceuticals in hydrosphere. In the present work, a new carrier-mediated hollow fiber liquid phase microextraction (CM-HFLPME) based on deep eutectic solvent (DES) was combined with HPLC–UV and applied for determination of ethinylestradiol (EE) and raloxifene (RLX) in pharmaceutical wastewater samples. The target analytes were extracted from 17 mL of the basic solution with pH 11 into an organic phase, as the supported liquid membrane (SLM) impregnated in the pores of a hollow fiber, and then back-extracted into the acceptor phase locating into the lumen of the hollow fiber. SLM consisted of n-octanol containing N,N,N-cetyltrimethyl ammonium bromide (CTAB), as the carrier, and the acceptor phase contained a mixture of DES and HCl. The important factors including sample pH, extraction time, HCl concentration and CTAB amount were optimized using a central composite design (CCD). Under the optimized conditions, preconcentration factors of RLX and EE were found to be 86 and 53, respectively. The limits of detections (LODs), based on 3S/N, were found to be 5.0 ng/mL for RLX and 10 ng/mL for EE, respectively. The calibration curves of RLX and EE were linear within the ranges of 20–5000 ng/mL (r2 = 0.9980) and 30–5000 ng/mL (r2 = 0.9985), respectively. Relative standard deviation (RSD%) of RLX and EE, based on three replicates at the concentration of 100 ng/mL, was calculated 1.7% and 2.6%, respectively. Finally, the feasibility of the proposed method was successfully confirmed by extraction and determination of RLX and EE in pharmaceutical wastewaters.

Simple determination of amphetamine and methamphetamine in complicated matrices by filter‐based emulsification microextraction followed by high‐performance liquid chromatography

AbstractIn this work, a filter‐based emulsification microextraction method is combined with high‐performance liquid chromatography for a fast, simple, and efficient determination of amphetamine and methamphetamine in the human plasma and pharmaceutical wastewater samples. In this method, in order to enhance the extraction speed without the use of a disperser solvent, the extraction solvent is dispersed as fine droplets in the sample solution, and a filtration step completes the extraction process by separation of the extraction phase from the sample solution. This method is centrifuge‐free, provides a good sample clean‐up, and is totally accomplished in about 60 s. In order to achieve the optimal experimental conditions, the effective parameters involved including the type and volume of the extraction solvent, pH of the sample solution, and ionic strength are thoroughly examined. Under the optimized experimental conditions, the calibration curves were obtained in the range of 3–2000 ng mL−1. The relative standard deviations for the method were in the range of 7.1–9.2% and the limits of detection ranged between 1.0 and 1.5 ng mL−1.