Adsorption of anti-inflammatory and analgesic drugs traces in water on clay minerals.

The aim of this study was to assess the adsorption of four non-steroidal anti-inflammatory drugs (NSAIDs), namely Paracetamol (PRC), Diclofenac (DIC), Ibuprofen (IBU), and Ketoprofen (KET), using both batch and continuous experiments with clay. Various analytical techniques, including XRD, FTIR, SEM coupled to EDX, and Zeta potential, were employed to characterize both raw and calcined clay. XRD and FTIR analyses confirmed the kaolinite nature of the clay. SEM data revealed a lamellar structure formed in the clay after calcination at 550 °C. Adsorption tests were conducted to determine the optimal adsorption conditions. Batch kinetics of adsorption demonstrated rapid adsorption of all four NSAIDs, with the highest adsorption occurring at pH 4 (DIC, IBU, and KET) and pH 6 for PRC, using a concentration of 20 mg L-1 of calcined clay. Additionally, the pseudo-second-order model provided the best fit for all NSAIDs adsorption processes. Maximum adsorption capacities, as determined by the Langmuir model, were 80 mg g-1 for PRC, 238 mg -1g for DIC, 138 mg g-1 for IBU, and 245 mg g-1 for KET. In fixed bed column studies, three dynamic models (Thomas, Adams-Bohart, and Yoon-Nelson) were utilized to describe the breakthrough curves, with linear regression used to identify key characteristics for process design. The fixed bed column adsorption study revealed that DIC exhibited the highest removal efficiency at 98%, while KET, IBU, and PRC were more persistent, with removal efficiencies of 77.1%, 76.7%, and 67.1%, respectively. The Thomas model was deemed appropriate for describing the breakthrough curve. These findings offer valuable insights into the interactions between clay and pharmaceuticals with varying physicochemical properties. They also provide information on the adsorption models, saturation, and adsorption capacities of various pharmaceuticals on natural clays, which can be crucial for further research and environmental remediation efforts.

Non-steroidal anti-inflammatory drugs (NSAIDs) in the environment: Updates on pretreatment and determination methods.

Non-steroidal anti-inflammatory drugs (NSAIDs) are widely used in human and animal health care to reduce persistent inflammation, pain and fever because of their anti-inflammatory, analgesic and antipyretic effects. However, the improper discharge and disposal make it becomes a major contaminant in the environment, which poses a big threat to the ecosystem. For this reason, accurate, sensitive, effective, green, and economic techniques are urgently required and have been rapidly developed in recent years. This review summarizes the advancement of sample preparation technologies for NSAIDs involving solid-phase extraction, solid-phase microextraction, liquid-phase microextraction, QuEChERS, and matrix solid-phase dispersion. Meanwhile, we overview and compare analytical technologies for NSAIDs, including liquid chromatography-based methods, gas chromatography-based methods, capillary electrophoresis, and sensors, particularly the development of liquid chromatography-based methods. Furthermore, we focus on their progress and conduct a comparison between their advantages and disadvantages.

Occurrence, toxicity, impact and removal of selected non-steroidal anti-inflammatory drugs (NSAIDs): A review.

Non-steroidal anti-inflammatory drugs (NSAIDs) are among the most frequently used pharmaceuticals for human therapy, pet therapeutics, and veterinary feeds, enabling them to enter into water sources such as wastewater, soil and sediment, and seawater. The control of NSAIDs has led to the advent of the novel materials for treatment techniques. Herein, we review the occurrence, impact and toxicity of NSAIDs against aquatic microorganisms, plants and humans. Typical NSAIDs, e.g., ibuprofen, ketoprofen, diclofenac, naproxen and aspirin were detected at high concentrations in wastewater up to 2,747,000 ng L-1. NSAIDs in water could cause genotoxicity, endocrine disruption, locomotive disorders, body deformations, organs damage, and photosynthetic corruption. Considering treatment methods, among adsorbents for removal of NSAIDs from water, metal-organic frameworks (10.7-638 mg g-1) and advanced porous carbons (7.4-400 mg g-1) were the most robust. Therefore, these carbon-based adsorbents showed promise in efficiency for the treatment of NSAIDs.

Eu3+ functionalized metal-organic framework for selective monitoring of emerging environmental pollutants non-steroidal anti-inflammatory drugs.

Non-steroidal anti-inflammatory drugs (NSAIDs), as a new water pollutant emerging in recent years, has potential hazards to the environment. The difficult degradation characteristics of NSAIDs lead to long-term accumulation in the natural environment, which will inevitably cause incalculable damage to human health. In this work, for practical application considerations, MIL-53(Al) type MOF [Al(OH)(TDC)]‧1.5H2O‧0.7DMF (MIL-53-TDC, TDC = 2,5-thiophene dicarboxylic acid) with good water stability is selected as the sensing main body. The ligand TDC was chosen for two reasons: one is as an antenna ligand, which can sensitize Eu3+ ions to emit characteristic fluorescence; the other is as binding site that the sulfur atoms on the thiophene ring can introduce Eu3+ ions through coordination. Thus, Eu3+ functionalized MIL-53-TDC hybrid materials (Eu@MIL-53-TDC) were developed as a fluorescence sensor for the detection of two kinds of NSAIDs, S-ibuprofen (S-IBP) and diclofenac (DCF). The concentration range of S-IBP and DCF detected by the prepared sensors is 0.001-0.07 mM (LOD = 0.5 µM) and 0.0005-0.1 mM (LOD = 0.2 µM), respectively. Moreover, this sensor not only can achieve rapid (3 min) and sensitive analysis of these two NSAIDs but also has a satisfactory recovery for the detection of S-IBP and DCF in serum and tap water.

Localization of Sesquiterpene Lactones Biosynthesis in Flowers of Arnica Taxa.

Arnica montana is a valuable plant with high demand on the pharmaceutical and cosmetic market due to the presence of helenalin (H) and 11α, 13-dihydrohelenalin (DH) sesquiterpene lactones (SLs), with many applications and anti-inflammatory, anti-tumor, analgesic and other properties. Despite the great importance of these compounds for the protection of the plant and their medicinal value, the content of these lactones and the profile of the compounds present within individual elements of florets and flower heads have not been studied so far, and attempts to localize these compounds in flower tissues have also not been conducted. The three studied Arnica taxa synthesize SLs only in the aerial parts of plants, and the highest content of these substances was found in A. montana cv. Arbo; it was lower in wild species, and a very small amount of H was produced by A. chamissonis. Analysis of dissected fragments of whole inflorescences revealed a specific distribution pattern of these compounds. The lactones content in single florets increased from the top of the corolla to the ovary, with the pappus calyx being a significant source of their production. Histochemical tests for terpenes and methylene ketones indicated the colocalization of lactones with inulin vacuoles.

Effect of biosolids amendment on the fate and mobility of non-steroidal anti-inflammatory drugs (NSAIDs) in a field-based lysimeter cell study.

Non-steroidal anti-inflammatory drugs (NSAIDs) are widely used globally to treat and prevent illness. Biosolids change physico-chemical characteristics of soil and can affect the mobility of NSAIDs. A field-based lysimeter study evaluated the effect of three rates (0, 7, and 28 Mg ha-1) of alkaline treated biosolids (ATB) on the leaching potential of naproxen (NPX), ibuprofen (IBF), and ketoprofen (KTF) over 34 days in a sandy loam textured soil. Although all three NSAIDs in the lysimeter cells vertically migrated to deeper soil depths after spiking, the sum of all NPX, IBF, and KTF detected in the leachate samples from all treatments were only 0.03%, 0.02%, and 0.04% of the initial spiking mass to the surface soil, respectively. A mass balance analysis indicated a low accumulation of these compounds in the soil at the end of the study (Day 34) from all treatments with only 4.8%, 0.5%, and 0.7% of initial spiked NPX, IBF, and KTF, respectively. Application of ATB significantly increased soil pH and organic matter (OM) content of the soils but did not impact retention of the compounds in the soil profile. Overall, all three NSAIDs in the present study presented low mobility in the loamy sand textured agricultural soil.

Green alga Chlamydomonas reinhardtii can effectively remove diclofenac from the water environment - A new perspective on biotransformation.

The use of unicellular algae to remove xenobiotics (including drugs) from wastewaters is one of the rapidly developing areas of environmental protection. Numerous data indicate that for efficient phycoremediation three processes are important, i.e. biosorption, bioaccumulation, and biotransformation. Although biosorption and bioaccumulation do not raise any serious doubts, biotransformation is more problematic since its products can be potentially more toxic than the parent compounds posing a threat to organisms living in a given environment, including organisms that made this transformation. Thus, two questions need to be answered before the proper algae strain is chosen for phycoremediation, namely what metabolites are produced during biotransformation, and how resistant is the analyzed strain to a mixture of parent compound and metabolites that appear over the course of culture? In this work, we evaluated the remediation potential of the model green alga Chlamydomonas reinhardtii in relation to non-steroidal anti-inflammatory drugs (NSAIDs), as exemplified by diclofenac. To achieve this, we analysed the susceptibility of C. reinhardtii to diclofenac as well as its capability to biosorption, bioaccumulation, and biotransformation of the drug. We have found that even at a relatively high concentration of diclofenac the algae maintained their vitality and were able to remove (37.7%) DCF from the environment. A wide range of phase I and II metabolites of diclofenac (38 transformation products) was discovered, with many of them characteristic rather for animal and bacterial biochemical pathways than for plant metabolism. Due to such a large number of detected products, 18 of which were not previously reported, the proposed scheme of diclofenac transformation by C. reinhardtii not only significantly contributes to broadening the knowledge in this field, but also allows to suggest possible pathways of degradation of xenobiotics with a similar structure. It is worth pointing out that a decrease in the level of diclofenac in the media observed in this study cannot be fully explained by biotransformation (8.4%). The mass balance analysis indicates that other processes (total 22%), such as biosorption, a non-extractable residue formation, or complete decomposition in metabolic cycles can be involved in the diclofenac disappearance, and those findings open the prospects of further research.

Development of a detection method for 10 non-steroidal anti-inflammatory drugs residues in four swine tissues by ultra-performance liquid chromatography with tandem mass spectrometry.

The ultra-performance liquid chromatography with tandem mass spectrometry (UPLC-MS/MS) detection method was developed for the residues of 10 NSAIDs (salicylic acid, acetylsalicylic acid, acetaminophen, diclofenac, tolfenamic acid, antipyrine, flunixin meglumine, aminophenazone, meloxicam, metamizole sodium) in swine muscle, liver, kidney, and fat. Swine tissue samples were extracted by phosphorylated acetonitrile with the addition of an appropriate amount of internal standard working solution, defatted with acetonitrile-saturated n-hexane, and purified by Hydrophile-Lipophile Balance (HLB) solid-phase extraction column, then separated by UPLC BEH shield RP18 column with 0.1% formic acid in water/0.1% formic acid in acetonitrile with gradient elution, which was detected in the multiple reaction monitoring (MRM) modes. The correlation coefficient of the standard curve equation is greater than 0.99, and the coefficient of variation within and between batches is less than 14.4%. We evaluated the analytical method using two green assessment tools. The method established in this study met the requirements of NSAID residue analysis and provides analytical tools for determining and confirming NSAIDs in swine tissue samples. This is the first report on the simultaneous determination of 10 NSAIDs in four swine tissues by the UPLC-MS/MS method and accurate quantification using deuterated internal standards.

Determination and risk assessment of pharmaceutical residues in the urban water cycle in Selangor Darul Ehsan, Malaysia.

The environmental fate of non-steroidal anti-inflammatory drugs (NSAIDs) in the urban water cycle is still uncertain and their status is mainly assessed based on specific water components and information on human risk assessments. This study (a) explores the environmental fate of NSAIDs (ibuprofen, IBU; naproxen, NAP; ketoprofen, KET; diazepam, DIA; and diclofenac, DIC) in the urban water cycle, including wastewater, river, and treated water via gas chromatography-mass spectrophotometry (GCMS), (b) assesses the efficiency of reducing the targeted NSAIDs in sewage treatment plant (STP) using analysis of variance (ANOVA), and (c) evaluates the ecological risk assessment of these drugs in the urban water cycle via teratogenic index (TI) and risk quotient (RQ). The primary receptor of contaminants comes from urban areas, as a high concentration of NSAIDs is detected (ranging from 5.87 × 103 to 7.18 × 104 ng/L). The percentage of NSAIDs removal in STP ranged from 25.6% to 92.3%. The NAP and KET were still detected at trace levels in treated water, indicating the persistent presence in the water cycle. The TI values for NAP and DIA (influent and effluent) were more than 1, showing a risk of a teratogenic effect. The IBU, KET, and DIC had values of less than 1, indicating the risk of lethal embryo effects. The NAP and DIA can be classified as Human Pregnancy Category C (2.1 > TI ≥ 0.76). This work proved that these drugs exist in the current urban water cycle, which could induce adverse effects on humans and the environment (RQ in high and low-risk categories). Therefore, they should be minimized, if not eliminated, from the primary sources of the pollutant (i.e., STPs). These pollutants should be considered a priority to be monitored, given focus to, and listed in the guideline due to their persistent presence in the urban water cycle.

Porphyrin-based magnetic porous organic polymer for efficient magnetic solid phase extraction of nonsteroidal anti-inflammatory drugs from water.

The ubiquitous occurrence of nonsteroidal anti-inflammatory drugs (NSAIDs) in the environmental water system has drawn significant concerns due to their adverse effects. The accurate monitoring the content of them is of great significance but challenging in terms of the complex matrix and trace concentration. In this work, a porphyrin-based magnetic porous organic polymer composite (PM-POP) was prepared through a solvent-free synthetic method. Owing to the highly porous structure and strong affinities, the as-prepared PM-POP could be utilized as a highly efficient adsorbent for the magnetic solid phase extraction (MSPE) of NSAIDs. Combining with the high-performance liquid chromatography separation with ultraviolet detector (HPLC-UV), a sensitive analytical method was established, which exhibited wide linear ranges (0.1-400 µg/L) and large enrichment factors (EFs) (39.5-82.9 folds) along with good precision (intra-day RSD ≤ 4.9%) and repeatability (inter-day RSD ≤ 8.4%). Ultimately, it was applied to determinate trace NSAIDs in practical water samples successfully, demonstrating its good application prospect in environmental analysis.

Magnetic Solid-Phase Extraction Based on Magnetite-Multiwalled Carbon Nanotubes of Non-Steroidal Anti-Inflammatories from Water Followed by LC-ESI-MS/MS.

An analytical method based on liquid chromatography-electrospray ionization-tandem mass spectrometry detection (LC-ESI-MS/MS) has been developed for the determination of pharmaceutical compounds in water samples. Five non-steroidal anti-inflammatory drugs (NSAIDs) namely Naproxen, Ketoprofen, Piroxicam, Diflunisal and Celecoxib were investigated. Magnetic solid phase extraction (MSPE) was used for sample pre concentration of water samples and magnetic carbon nanotubes (Fe3O4-MWCNTs) were considered as solid phase extraction sorbent. Important parameters influencing the extraction efficiency such as nature and volume of eluent, sample pH and adsorbent mass were optimized. The developed MSPE method involved 75 mg of Fe3O4-MWCNTs sorbent, 5 mL of water sample at pH = 4 and 5 mL of 10% ammonia in methanol in the elution step. Under the optimized extraction conditions, linearity, detection and quantification limits and reproducibility were evaluated. The proposed method was successfully applied to the analysis of NSAIDs in surface waters, and mean recoveries of all the NSAIDs were above 90% with relative standard deviations < 17%. The detection and quantification limits were comprised between 0.05-3.6 ng.mL-1 and 0.2-11.9 ng.mL-1, respectively.

Liquid chromatography-quadrupole orbitrap and liquid chromatography-tandem mass spectrometry system for rapid identification and quantitation of thirty nonsteroidal anti-inflammatory drugs and acetaminophen in illegal products.

RATIONALE: As the public interest in healthcare increases, illegal dietary supplements, foods, and drugs containing unauthorized pharmaceutical ingredients, including nonsteroidal anti-inflammatory drugs (NSAIDs) and acetaminophen, have been identified. Excessive and unintentional consumption is toxic to the gastrointestinal tract, kidneys, and liver; therefore, these pharmaceuticals must be monitored using analytical methods. METHODS: A rapid and reliable analysis system involving liquid chromatography-quadrupole orbitrap mass spectrometry (LC-Q-Orbitrap/MS) and liquid chromatography-tandem mass spectrometry (LC/MS/MS) was established and validated to identify and quantify 30 NSAIDs and acetaminophen. In addition, we obtained the MS2 spectrum for each component with the proposed structure of the fragment ions. RESULTS: The analytical method was applied to 505 samples of illicitly distributed dietary supplements, foods, and pharmaceuticals. Non-steroidal analgesics were detected in 126 samples. Carbamazepine (42.9%) and diclofenac (30.2%) were the most detected components in the samples; other pharmaceutical adulterants were also detected in some cases. Additionally, we present the identification of an unknown component, dexamethasone (799 µg/g), using LC-Q-Orbitrap/MS in a sample containing the unknown component with meloxicam (15.4 mg/g). CONCLUSIONS: The developed analysis system, consisting of qualitative analysis using LC-Q-Orbitrap/MS and quantitative analysis using LC/MS/MS, can rapidly and accurately identify and quantify NSAIDs and acetaminophen while also identifying non-analytical components.

Dispersive solid-phase extraction of non-steroidal anti-inflammatory drugs in water and urine samples using a magnetic ionic liquid hypercrosslinked polymer composite.

In this work, Friedel-Crafts alkylation was successfully applied to prepare a magnetic ionic liquid hypercrosslinked polymer composite (Fe3O4@IL-HCP), which was subsequently employed as magnetic solid-phase extraction (MSPE) adsorbent for the isolation and enrichment of trace non-steroidal anti-inflammatory drugs (NSAIDs). The developed composite was comprehensively characterized using various techniques, with the results indicating that it possessed high saturation magnetization (39.44 em g - 1), large specific surface area (175 m2g - 1), and high adsorption capacity for NSAIDs. The adsorption behavior and mechanisms were also investigated in detail. NSAIDs were adsorbed onto the Fe3O4@IL-HCP sorbent via a heterogeneous multilayer process consisting of hydrogen bonding and π-π and electrostatic interactions. Additionally, the composite's large surface area and multiple active sites enabled extraction equilibrium within 6 min. By coupling with high performance liquid chromatography (HPLC), the developed MSPE/HPLC method was applied for the determination of selected NSAIDs in water and urine samples. The developed method displayed wide linear ranges, low limits of detection (0.12-0.30 ng mL-1 and 0.15-1.5 ng mL-1 in water and urine samples, respectively), sufficient recoveries (92.8-109%), and good precision (relative standard deviations ≤ 4.6%). Thus, the findings of this work provide an appealing alternative for the extraction and determination of trace NSAIDs in environmental water and biological samples.

Rapid Determination of Non-Steroidal Anti-Inflammatory Drugs in Urine Samples after In-Matrix Derivatization and Fabric Phase Sorptive Extraction-Gas Chromatography-Mass Spectrometry Analysis.

Fabric phase sorptive extraction (FPSE) has become a popular sorptive-based microextraction technique for the rapid analysis of a wide variety of analytes in complex matrices. The present study describes a simple and green analytical protocol based on in-matrix methyl chloroformate (MCF) derivatization of non-steroidal anti-inflammatory (NSAID) drugs in urine samples followed by FPSE and gas chromatography-mass spectrometry (GC-MS) analysis. Use of MCF as derivatizing reagent saves substantial amounts of time, reagent and energy, and can be directly performed in aqueous samples without any sample pre-treatment. The derivatized analytes were extracted using sol−gel Carbowax 20M coated FPSE membrane and eluted in 0.5 mL of MeOH for GC-MS analysis. A chemometric design of experiment-based approach was utilized comprising a Placket−Burman design (PBD) and central composite design (CCD) for screening and optimization of significant variables of derivatization and FPSE protocol, respectively. Under optimized conditions, the proposed FPSE-GC-MS method exhibited good linearity in the range of 0.1−10 µg mL−1 with coefficients of determination (R2) in the range of 0.998−0.999. The intra-day and inter-day precisions for the proposed method were lower than <7% and <10%, respectively. The developed method has been successfully applied to the determination of NSAIDs in urine samples of patients under their medication. Finally, the green character of the proposed method was evaluated using ComplexGAPI tool. The proposed method will pave the way for simper analysis of polar drugs by FPSE-GC-MS.

A composite adsorbent of graphene quantum dots, mesoporous carbon, and molecularly imprinted polymer to extract nonsteroidal anti-inflammatory drugs in milk.

A composite magnetic adsorbent was developed by embedding graphene quantum dots (GQDs), silica-modified magnetite (Fe3O4-SiO2), and mesoporous carbon (MPC) into a molecularly imprinted polymer (GQDs/Fe3O4-SiO2/MPC/MIP). The adsorbent was applied to extract nonsteroidal anti-inflammatory drugs (NSAIDs) in milk. The MIP was formed via a sol-gel copolymerization using flurbiprofen, diflunisal, and mefenamic acid as template molecules, 3-aminopropyltriethoxysilane as a monomer, and tetraethyl orthosilicate as a cross-linker. GQDs and MPC enhanced affinity binding between NSAIDs and the adsorbent through π-π stacking, hydrogen bonding, and hydrophobic interaction. The Fe3O4-SiO2 nanoparticles embedded in the composite adsorbent enabled its rapid isolation from the sample solution. The extracted NSAIDs were quantified by high-performance liquid chromatography and exhibited good linearity from 1.0 to 100.0 µg L-1 for flurbiprofen and 0.5 to 100.0 µg L-1 for diflunisal and mefenamic acid, respectively. The limits of detection ranged from 0.5 to 1.0 µg L-1. Recoveries of NSAIDs from spiked milk samples ranged from 81.4 to 93.7%, with RSDs below 7%. The reproducibility of the fabricated adsorbent was good and in the optimal conditions, the developed adsorbent could be used for up to six extraction-desorption cycles.

Polyimidazolyl acetate ionic liquid grafted on cellulose filter paper as thin-film extraction phase for extraction of non-steroidal anti-inflammatory drugs from water.

Recently, pharmaceuticals and personal care products in the water environment exhibited potential risks to both human and aquatic organisms. In order to improve the sensitivity and accuracy of pharmaceutical detection, the polyimidazolyl acetate ionic liquid was synthesized by Radziszewski reaction and coated on cellulose filter papers as a thin-film extraction phase for extraction of non-steroidal anti-inflammatory drugs from water. The attenuated total reflection-infrared spectrometry, thermogravimetric analysis, and scanning electron microscope analyses demonstrated that the polyimidazolyl acetate ionic liquid was successfully prepared and attached to the surface of the cellulose filter paper through chemical bonding. The adsorption capacity of the homemade thin-film extraction material for the four non-steroidal anti-inflammatory drugs was greater than 8898 ng/cm2 under the optimum conditions, and the desorption rate was over 90%. Then, a paper-based thin-film extraction phase-high-performance liquid chromatography-tandem mass spectrometry method was established for the extraction of non-steroidal anti-inflammatory drugs in water. This method provided limits of detection and limits of quantification were in the range of 0.02-0.15 and 0.17-0.50 µg/L, respectively. Hence, the obtained thin-film extraction phase showed excellent recovery and reproducibility for the target non-steroidal anti-inflammatory drugs with carboxyl groups from water.

Electrochemically deposition of metal-organic framework onto carbon fibers for online in-tube solid-phase microextraction of non-steroidal anti-inflammatory drugs.

Electrochemical deposition has been proposed as a promising approach for in situ immobilization of metal-organic framework (MOF) on conductive surfaces. It is favorable as it is time-saving, green, and does not require vigorous reaction conditions, which can be applied to the synthesis and immobilization of extraction materials for fiber in-tube solid phase microextraction. In this work, PPF-1 was immobilized on the surface of the carbon fibers by electrochemical method. The novel method overcame the problems including strict conditions and time-consuming operation. The modified carbon fibers were packed into the PEEK tube for extraction and analysis of three non-steroidal anti-inflammatory drugs (NSAIDs), which performed good extraction efficiency due to strong hydrogen bonding, hydrophobic interaction and π-π interaction between PPF-1 and analytes. The established method obtained good enrichment performance (enrichment factor between 230-540), low limits of detection (between 0.01-0.03 ng/mL), good linearity and good reproducibility (RSDs≤4.93%), which was successfully applied for the quantitative analysis of NSAIDs in human plasma samples.

MIL-101(Fe)@TiO2 nanotube composite material is used for the solid phase extraction of non-steroidal anti-inflammatory drugs under the synergy of multiple interactions.

Increasing the adsorption sites and effective interactions between sorbents and the targets can improve the solid-phase extraction (SPE) efficiency. Herein, based on the advantages of MOFs and TiO2 nanotubes (TiO2 NTs), an MIL-101(Fe)@TiO2 NT composite was prepared and applied to extract non-steroidal anti-inflammatory drugs (NSAIDs) from water samples coupled with high performance liquid chromatography (HPLC). Through characterization, it was established that MIL-101(Fe) was effectively composited on the surface and inside the TiO2 nanotubes, increasing effective adsorption sites. The obtained composite material well retains the structure and functional groups of the two original materials, and while retaining the original force with the target, it achieves a synergistic effect and produces more interactions with the target. Therefore, the extraction efficiency was greatly improved. The recovery efficiency reached 97.7-105.1% with an RSD of less than 6.71%, the detection limit was 0.1-0.2 µg L-1, and the linear range was 1-200 µg L-1 with a determination coefficient of 0.9972-0.9994. Owing to the stability of the two original materials, the composite material could be recycled and reused to extract NSAIDs up to 15 times without a loss of the recovery rate. Satisfactory results were obtained when it was used to extract NSAIDs from the Yellow River. These results indicate that the synthesized MIL-101(Fe)@TiO2 NT material is a promising sorbent to extract NSAIDs at trace concentrations with high efficiency and long lifetimes.

Design and application of molecularly imprinted polymers for adsorption and environmental assessment of anti-inflammatory drugs in wastewater samples.

In this study, a series of molecularly imprinted polymers (MIPs) have been synthesized using separately diclofenac, naproxen, and ibuprofen as templates with three different polymerization approaches. Two functional monomers, methacrylic acid (MAA) and 2-vinylpyridine (2-VP), were tested and ethylene glycol dimethacrylate (EGDMA) was used as crosslinker; also, template-free polymers (NIPs) were synthesized. It was found that the MIP with the highest retention percentage for diclofenac was the one prepared by the emulsion approach and with MAA (98.3%); for naproxen, the one prepared by the bulk polymerization with MAA (99%); and for ibuprofen, the one synthesized by bulk with 2-VP (97.7%). These three MIPs were characterized by scanning electron microscopy, thermogravimetric test, Fourier transform infrared, specific area measurements, and surface charge. It was found that the emulsion method allowed particle size control, while the bulk method gave heterogeneous particles. The three evaluated MIPs exhibited thermal stability up to 300 °C, and it was observed that 2-VP confers greater stability to the material. From the BET analysis, it was demonstrated that the MIPs and NIPs evaluated are mesoporous materials with a pore size between 10 and 20 nm. In addition, the monomer influenced the surface charge of the material, since the MAA conferred an acidic point of zero charge (PZC), while the 2-VP conferred a PZC of basic character. Through adsorption isotherms, it was determined  that there is a higher adsorption capacity of the MIPs at acidic pH following a pseudo-second-order kinetic model. Finally, the MIPs were used to determine the non-steroidal anti-inflammatory drugs (NSAIDs) understudy in San Luis Potosí, México, wastewater, finding concentrations of 0.642, 0.985, and 0.403 mg L-1 for DCF, NPX, and IBP, respectively.

From the pills to environment - Prediction and tracking of non-steroidal anti-inflammatory drug concentrations in wastewater.

The extend of environment pollution by pharmaceuticals is in a stage that required more automatic and integrated solutions. The non-steroidal anti-inflammatory drugs (NSAIDs) are one of the most popular pharmaceutical in the world and emerging pollutants of natural waters. The aim of the paper was to check the correlation of the sales data of selected NSAIDs (ibuprofen, naproxen, diclofenac) and their concentration in the WWTP in order to enable predicting their loads, having only the sales data. For calculations, we apply three discharge scenarios (the fates between purchased to the presence in influents), having in mind that some part of sold mass can be improperly dispose to sewage system. To support predictions, chemical analysis was conducted in two conventional wastewater treatment plants (WWTPs) located in Poland during 2018 and 2020, thereby before and during pandemic situation. The NSAIDs concentration in the influent was higher than that which would be obtained if all of the administrated mass of the pharmaceutical went through the metabolic pathway of transformation. This means that substantial mass of sold NSAIDs in improperly dispose to sewage system, and this factor need to be taken into account in future predictions. Furthermore, results indicate that the variance of naproxen and diclofenac concentrations in the influent has no correlation with relatively stable sales throughout whole year. The pandemic situation had yet no direct effect to diclofenac concentrations in influents, despite observed increasing of sales. It was calculated that more than 60 kg of diclofenac was discharged into the Baltic Sea in 2018, and 20 kg in the first half of 2021 from two tested WWTPs. The presence of 4OH-diclofenac in effluents often in higher concentration compared to diclofenac mean that this still biologically active compound need to be taken into account in future risk assessment.