Non-steroidal Anti-inflammatory Drugs In Water Research Articles

Biomass-Tuned Reduced Graphene Oxide@Zn/Cu: Benign Materials for the Cleanup of Selected Nonsteroidal Anti-inflammatory Drugs in Water.

The persistent increase in the amount of nonsteroidal anti-inflammatory drugs such as ibuprofen (IBP) and diclofenac (DCF) in water bodies is alarming, thereby calling for a need to be addressed. To address this challenge, a bimetallic (copper and zinc) plantain-based adsorbent (CZPP) and reduced graphene oxide modified form (CZPPrgo) was prepared by facile synthesis for the removal of ibuprofen (IBP) and diclofenac (DCF) in water. Both the CZPP and CZPPrgo were characterized by different techniques such as Fourier transform infrared spectroscopy (FTIR), X-ray diffraction analysis (XRD), scanning electron microscopy (SEM), and pHpzc analysis. FTIR and XRD confirmed the successful synthesis of the CZPP and CZPPrgo. The adsorption of the contaminants was carried out in a batch system, and several operational variables were optimized. The adsorption is affected by the initial concentration of the pollutants (5-30 mg·L-1), the adsorbent dose (0.05-0.20 g), and pH (2.0-12.0). The CZPPrgo has the best performance with maximum adsorption capacities of 148 and 146 mg·g-1 for removing IBP and DCF from water, respectively. The experimental data were fitted into different kinetic and isotherm models; the removal of IBP and DCF follows the pseudo-second order, which can be best explained by the Freundlich isotherm model. The reuse efficiency was above 80% even after four adsorption cycles. This shows that the CZPPrgo is a promising adsorbent for removing IBP and DCF in water.

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.

Highly sensitive and simultaneous electrochemical determinations of non-steroidal anti-inflammatory drugs in water using nanostructured carbon-based paste electrodes

Simple and fast simultaneous quantifications in water of anti-inflammatory drugs, which belong to the emerging pollutants, represents a great challenge for water quality control. The development of electrochemical methods to meet the simultaneous and concomitant detection requirements depends mainly on the electrode material. The fullerene‑carbon nanofiber (FULL/CNF) and graphene‑carbon nanotubes (GR/CNT) paste electrodes as sensing elements were employed for the first time for the determination of diclofenac (DCF), naproxen (NPX) and ibuprofen (IBP) simultaneously and concomitantly. The comparative morphostructural and electrochemical characterizations of both electrodes were achieved by scanning electron microscopy (SEM) and cyclic voltammetry (CV). Differential-pulsed voltammetry (DPV), chronoamperometry (CA) and multiple-pulsed amperometry (MPA) were used for detection tests. FULL/CNF electrode was suitable to develop a simultaneous DPV-based detection methodology that allowed reaching the lowest limit of detections of 0.230 nM for DCF, 0.310 nM for NPX and 0.180 nM for IBP. GR/CNT electrode did not provide stability for DPV-based detection, but the lowest limits of detection of 0.149 nM for DCF, 0.809 nM for NPX and 0.640 nM for IBP were achieved by MPA-based methodology. Both electrodes, linked to specific detection technique, showed good reproducibility, stability and ability to measure DCF, NPX and IBP simultaneously in aqueous solution. The satisfactory results achieved by analysis of real surface water sample (Bega River, Timisoara city, Romania) indicated that the proposed voltammetric and amperometric methodologies using both electrodes have great potential for practical applications in analysis of different water samples.

A New Date Stone Biochar for Effective Solid Phase Extraction of Non-steroidal Anti-inflammatory Drugs in Water

A New Date Stone Biochar for Effective Solid Phase Extraction of Non-steroidal Anti-inflammatory Drugs in Water

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 8898ng/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.

Determination of five nonsteroidal anti-inflammatory drugs in water by dispersive solid phase extraction-ultra performance liquid chromatography-tandem mass spectrometry based on metal-organic framework composite aerogel

非甾体类抗炎药(NSAIDs)能在环境水体中长期稳定存在,不仅对生物有慢性毒性还能增加病原体的耐药性,开发可靠的测定水样中痕量非甾体抗炎药的分析方法至关重要。该文制备新型金属有机骨架/壳聚糖复合气凝胶材料Co-UiO-67(bpy)/CS分散固相萃取吸附剂,将其用于环境水体中酮洛芬、萘普生、氟比洛芬、双氯芬酸、布洛芬5种非甾体类抗炎药的富集,结合超高效液相色谱-串联质谱法(UPLC-MS/MS),建立了基于金属有机骨架材料(MOFs)复合气凝胶环境水体中药物残留检测的新方法。为获得最佳的萃取效率,对影响萃取效果的主要因素(材料类型、MOFs用量、萃取时间、水样pH值、离子强度、甲酸体积分数、洗脱时间、洗脱剂体积)进行条件考察及优化。优化结果显示,吸附剂5 min内就可实现目标化合物的完全吸附,用总体积为5 mL的1%甲酸甲醇溶液洗脱6 min,目标化合物就能充分解吸。在最优的固相萃取条件下建立分析方法,结果表明,5种非甾体类抗炎药在各自范围内线性关系良好,线性相关系数均大于0.9937,方法的检出限(LOD)和定量限(LOQ)分别为0.32~2.06 ng/L和1.05~6.78 ng/L。在40、250和1500 ng/L 3个加标水平下进行加标回收试验,5种待测物的平均回收率为74.5%~114.1%。日内、日间相对标准偏差分别为1.3%~12.3%和1.3%~11.5%。将该方法用于实际水样的检测,市政污水检测出微量的酮洛芬和氟比洛芬,含量分别为14.52 ng/L和10.05 ng/L。该方法具有良好的灵敏度、准确度和精密度,操作简便,耗时短,为环境水体中痕量非甾体抗炎药富集检测提供了新方法。

Novel hydrophobic deep eutectic solvents for ultrasound-assisted dispersive liquid-liquid microextraction of trace non-steroidal anti-inflammatory drugs in water and milk samples

In the present study, several novel and natural hydrophobic deep eutectic solvents (HDESs) were prepared, and one of the HDESs composed of guanidinium chloride and thymol was advantageously used to develop an ultrasound-assisted dispersive liquid–liquid microextraction (UA-DLLME) method combined with high-performance liquid chromatography for the determination of four non-steroidal anti-inflammatory drugs (NSAIDs). Several important parameters influencing extraction efficiency were investigated and optimized, including the type and volume of HDES, ultrasound time, solution pH and the amount of salt addition. Under optimal experimental conditions, the method showed good linearity with the determination coefficients (R2) of 0.994–0.999 in the linear range of 5–2000 μg/L, low limits of detection of 0.5–1 μg/L and acceptable recoveries in the range of 79.42%–107.52%. The proposed method was successfully applied for the pretreatment of trace NSAIDs in real water and milk samples, and the results demonstrated the potential of the synthesized HDES for the extraction and determination of contaminants in aqueous samples.

Effect of choline chloride and urea based deep eutectic solvent on the physicochemical properties of salicylic acid and salicylamide at T = (288.15 to 313.15) K

Physicochemical properties of non-steroidal anti-inflammatory drugs (NSAIDs), salicylic acid and salicylamide, in choline chloride and urea based deep eutectic solvent (DES), reline, have been determined at temperature range from 288.15 to 313.15 K. In this work, physicochemical parameters such as apparent molar volume (Vϕ), apparent molar isentropic compressibility (Kϕ,s) and relative viscosities (ηr) are studied for the said NSAIDs in water and aqueous reline solutions. The results indicate that in all cases, the solute–solvent interactions increases with increasing concentration of DES as well as temperature. In addition, the values of viscosity B-coefficient are determined by analyzing Jones-Dole equation. Hepler’s constant (∂2V0ϕ/∂T2) and limiting apparent molar expansivity (E0ϕ) are deduced as well. Finally, the intermolecular interactions are evaluated by making plots among various parameters and discussed in terms of competing interactions present in the ternary systems.

Peroxymonosulfate-assisted g-C3N4@Bi2MoO6 photocatalytic system for degradation of nimesulide through phenyl ether bond cleavage under visible light irradiation

Non-steroidal anti-inflammatory drugs (NSAIDs) are a kind of emerging pollutants that have caused people's concerns. In this work, the catalytic system with perovskite-like material Bi2MoO6 modified graphitic carbon nitride (g-C3N4) combined with peroxymonosulfate (PMS) was constructed to efficiently degrade nimesulide (NIM) in water. After the characterization by various technologies, it was found that the g-C3N4 @ Bi2MoO6 composite possessed an increased specific surface area, enhanced light absorption range, and lower recombination rate of the photogenerated carriers. Thereby the composites displayed stronger photocatalytic activity than pure g-C3N4 and Bi2MoO6. The introduction of PMS not only provided more reactive oxygen species (ROSs) for the photocatalytic system, such as SO4− and 1O2 but also further promoted the transfer of photogenerated electrons. The multiple active species that existed in the system were involved in the photocatalytic process so that 97.4% NIM was degraded with 12 min. The degradation path of NIM was analyzed by LC-MS detection, which revealed that the structure of NIM was decomposed by the cleavage of the phenyl ether bond. The detection results of the total organic carbon (TOC) indicated that the proposed method could enhance the mineralization efficiency of NIM. This work could propose a solution for the rapid removal and degradation of NSAIDs in water.

A Zr-MOF@GO-Coated Fiber with High Specific Surface Areas for Efficient, Green, Long-Life Solid-Phase Microextraction of Nonsteroidal Anti-inflammatory Drugs in Water

A composite material featuring a zirconium-based metal–organic framework and graphene oxide (Zr-MOF@GO) was synthesized by a hydrothermal method and bonded to a stainless steel wire with an inorganic binder as a solid-phase microextraction (SPME) fiber for the derivatization-free extraction and analysis of nonsteroidal anti-inflammatory drugs (NSAIDs) coupled with gas chromatography (GC). The force between the Zr-MOF@GO and NSAIDs includes coordination action, H-bonding, and π–πconjugation effect, which results in the better extraction performance than a commercial polyamide fiber. The developed method achieved low detection limits (0.001–0.030 µg L−1, S/N = 3) and wide linear range (0.01–500 µg L−1) with good linearity (R ≥ 0.9970). The fiber coating had a high scratch resistance, which could effectively prevent coating wear and failure due to the friction between the fiber and the casing. Combined with the high thermal and chemical stability, the loss-free service life of the coating reached at least 240 extractions. Particularly, the derivatization-free extraction technique can greatly reduce the extraction time and use of organic solvents, thus maximizing the SPME technology advantages. It is evident that the analysis method is simple, environmentally friendly, and fast for detecting NSAIDs in water with high efficiency and long service life.

A modified zeolite/iron oxide composite as a sorbent for magnetic dispersive solid-phase extraction for the preconcentration of nonsteroidal anti-inflammatory drugs in water and urine samples

This study is the first to use a new ZSM-5 zeolite-based composite decorated with iron oxide magnetic nanoparticles and modified with hexadecyltrimethylammonium bromide surfactant (i.e., HDTMA-ZSM-5/Fe2O3) as an efficient sorbent for magnetic dispersive solid-phase extraction (MDSPE) of nonsteroidal anti-inflammatory drugs in water and urine samples with subsequent measurement by liquid chromatography diode array detection. Experimental factors affecting MDSPE were optimized using a multivariate optimization strategy. The optimum experimental conditions were: amount of sorbent, 40 mg; sample pH, 2.2; NaCl concentration, 2.5%; extraction time, 2 min; eluent solvent, methanol; eluent solvent volume, 424 μL; and elution time, 2 min. The linearity of the method was studied from 3.3 to 400 μg L−1 (N = 8) for ketoprofen, from 1.7 to 400 μg L−1 (N = 8) for felbinac, from 6.6 to 400 μg L−1 (N = 7) for diclofenac and from 9.9 to 400 μg L−1 (N = 6) for ibuprofen. Method repeatability was evaluated at 10 and 200 μg L−1 spiking levels, obtaining coefficients of variation between 2 and 5% (n = 6). Limits of detection, determined empirically, were 1.0 μg L−1 , 0.5 μg L−1, 2.0 μg L−1 and 3.0 μg L−1 for ketoprofen, felbinac, diclofenac and ibuprofen, respectively. Tap water, reservoir water, wastewater and five urine samples were selected to assess method applicability. Recovery values ranged between 86–107% and 80–112% for water and urine samples, respectively, showing negligible matrix effects. Finally, this method was employed to monitor ibuprofen excretion in real urine samples.

Dual functional monomers modified magnetic adsorbent for the enrichment of non-steroidal anti-inflammatory drugs in water and urine samples

According to the molecular properties of non-steroidal anti-inflammatory drugs (NSADs), a new adsorbent for magnetic solid phase extraction (MSPE) was designed and synthesized. Triethyl-(4-vinylbenzyl)aminium chloride and 4-vinylbenzeneboronic acid were utilized as dual functional monomers to copolymerize with divinylbenzene on the surface of pre-modified Fe3O4 nanoparticles. The prepared magnetic adsorbent (Fe3O4@TCVA) was characterized by elemental analysis, Fourier transform infrared, scanning electron microscopy, transmission electron microscopy and vibrating sample magnetometer. Due to the abundant boronic acid, quaternary amine and phenyl groups, the Fe3O4@TCVA displayed satisfactory extraction performance for target NSADs (diclofenac acid, ibuprofen and mefenamic acid) by means of B-N coordination, anion-exchange, π-π and hydrophobic interactions. Under the optimized conditions, the Fe3O4@TCVA/MSPE was combined with high-performance liquid chromatography with diode array detection (HPLC-DAD) to sensitively analyze NSADs in water and human urine samples. Results indicated that the limits of detection for water and urine samples were in the ranges of 0.014–0.031 μg/L and 0.029–0.11 μg/L, respectively. The relative standard deviations for the intra-day and inter-day assay variability were below 10%. The applicability of the proposed Fe3O4@TCVA/MSPE-HPLC-DAD method was demonstrated by the successful extraction and quantification of trace levels of NSADs in real water and human urine samples. Satisfactory spiked recovery and reproducibility were achieved.

Effect of carbon nanohorns in the radical polymerization of methacrylate monolithic capillary columns and their application as extractant phases

A successful copolymerization of the single-walled carbon nanohorns (SWNHs) with methacrylate monomers was achieved via thermal initiated free-radical polymerization because of the high reactivity of the SWNHs in comparison with other carbon nanostructures. The hybrid solids were deeply characterized in terms of morphology, by scanning electron microscopy (SEM). The effect of the incorporation of the bare or oxidized (o-SWNHs) carbon nanoparticles at different percentages (0–0.5 wt%) in polymerization mixtures to obtain hybrid monolithic capillary columns has been evaluated. In addition, their impact both in the polymerization step and in the extraction capacity was deeply studied. Final hybrid monoliths were applied for the extraction of polycyclic aromatic hydrocarbons and nonsteroidal anti-inflammatory drugs in water and biological samples, respectively. The precision was calculated both intra- and inter-capillaries obtaining satisfactory RSD values of less than 19.1%, which indicated the high robust reproducibility of the extraction procedure and the synthesis method. The accuracy of the method was also evaluated through a recovery study giving good recovery values, which varied between 78% and 112% for PAHs in waters, and 90–114% for NSAIDs in human urine samples.

Front Cover: Magnetic multi-walled carbon nanotubes as a valuable option for the preconcentration of non-steroidal anti-inflammatory drugs in water

Front Cover: Magnetic multi-walled carbon nanotubes as a valuable option for the preconcentration of non-steroidal anti-inflammatory drugs in water

Magnetic multi‐walled carbon nanotubes as a valuable option for the preconcentration of non‐steroidal anti‐inflammatory drugs in water

AbstractWater bodies receive a high discharge of drugs, which can behave as pollutants. Sample preparation with new materials and techniques are necessary to achieve adequate selectivity and sensitivity for the determination of these compounds in waters. In this work, magnetic nanoparticles modified with pristine multi‐walled carbon nanotubes have been used as sorbents in a magnetic solid‐phase extraction method for the determination of ibuprofen, naproxen and diclofenac in natural waters. The synthesis and functionalization of the sorbent are achieved in one single step. Liquid chromatography with ultraviolet and fluorescence detectors was used after sample preparation. The main factors that affect the adsorption and desorption were optimized. Limits of detection were 6.0–9.8 μg L−1 and precision was 1.3–6.1% relative standard deviation. The enrichment factors (4.1–4.8) were close to the preconcentration factor (5) with an amount of sorbent as low as 2.5 mg. Extraction recoveries of 81.3–101.5% were obtained in spiked tap, river and dam water samples. The low amount of adsorbent used and its reusability (up to five times) offers a high economy of use and low waste generation.

Simultaneous enantiomeric analysis of chiral non-steroidal anti-inflammatory drugs in water, river sediment, and sludge using chiral liquid chromatography-tandem mass spectrometry

A sensitive and reliable analytical method for the simultaneous enantiomeric analysis of chiral non-steroidal anti-inflammatory drugs in water, river sediment, and sludge was established.

Determination of non-steroidal anti-inflammatory drugs in water and urine using selective molecular imprinted polymer extraction and liquid chromatography

A selective solid-phase extraction was employed for the improvement of the determination of non-steroidal anti-inflammatory drugs (NSAIDs) in continental water and urine samples. Ketoprofen, naproxen, diclofenac, and ibuprofen were selected as target analytes due to they are the most frequently administered and consumed NSAIDs. These compounds were extracted using molecular imprinted polymers and determined by liquid chromatography with diode array (DAD), and tandem-mass spectrometry (MS–MS) detectors. Performance of DAD and MS–MS detectors was evaluated throughout this study. The obtained limits of quantification, after a 50-fold preconcentration solid-phase extraction, varied from 20 to 30μgL−1 for DAD, and from 0.007 to 0.017μgL−1 for MS–MS for both types of sample matrixes. Quantitative recoveries were found for blank-samples spiked at different NSAIDs concentration levels, ranging from 0.05 to 10mgL−1 for urine and from 0.5 to 500μgL−1 for water. The proposed methodology was applied for the determination of NSAID residues in urine of prescribed individuals, and continental waters.

N,S co-doped TiO2nanoparticles and nanosheets in simulated solar light for photocatalytic degradation of non-steroidal anti-inflammatory drugs in water: a comparative study

Abstract Background In this study, highly visible-light photoactive nitrogen and sulfur co-doped TiO2 (N,S-TiO2) nanoparticles and nanosheets were synthesized via facile sol–gel and hydrothermal methods, respectively. The photocatalytic activities of N,S-TiO2 catalysts were evaluated by degradation of non-steroidal anti-inflammatory drugs, ibuprofen (IBP) and naproxen (NPX), under simulated solar irradiation. Results The N,S-TiO2 nanoparticle is a well-developed mesoporous structure that contains both anatase and rutile phases and a large BET surface area (132 m2 g−1). N,S-TiO2 nanosheets contain a complete anatase phase with a larger mesoporous structure and a smaller BET surface area (64 m2 g−1). The results showed that at catalyst loading of 2.0 g L−1 and pH 6, N,S-TiO2 nanoparticles can degrade 85% and 99.3% of IBP and NPX. At the same conditions, 71.6% of IBP and 99.1% of NPX were degraded by N,S-TiO2 nanosheets in this study. Conclusion The high photocatalytic activity of N,S-TiO2 may be due to synergistic effects of nitrogen and sulfur co-doping into TiO2, resulting in better separation of photogenerated electrons and holes and higher-visible light adsorption. Reusability tests of N,S-TiO2 showed that it could retain its catalytic activity even after six cycles. © 2015 Society of Chemical Industry

Fabrication of aluminum terephthalate metal-organic framework incorporated polymer monolith for the microextraction of non-steroidal anti-inflammatory drugs in water and urine samples

Polymer monolith microextraction (PMME) based on capillary monolithic column is an effective and useful technique to preconcentrate trace analytes from environmental and biological samples. Here, we report the fabrication of a novel aluminum terephthalate metal-organic framework (MIL-53(Al)) incorporated capillary monolithic column via in situ polymerization for the PMME of non-steroidal anti-inflammatory drugs (NSAIDs) (ketoprofen, fenbufen and ibuprofen) in water and urine samples. The fabricated MIL-53(Al) incorporated monolith was characterized by X-ray powder diffractometry, scanning electron microscopy, Fourier transform infrared spectrometry, and nitrogen adsorption experiment. The MIL-53(Al) incorporated monolith gave larger surface area than the neat polymer monolith. A 2-cm long MIL-53(Al) incorporated capillary monolith was applied for PMME coupled with high-performance liquid chromatography for the determination of the NSAIDs. Potential factors affecting the PMME were studied in detail. Under the optimized conditions, the developed method gave the enhancement factors of 46–51, the linear range of 0.40–200μgL−1, the detection limits (S/N=3) of 0.12–0.24μgL−1, and the quantification limits (S/N=10) of 0.40–0.85μgL−1. The recoveries for spiked NSAIDs (20μgL−1) in water and urine samples were in the range of 77.3–104%. Besides, the MIL-53(Al) incorporated monolith was stable enough for 120 extraction cycles without significant loss of extraction efficiency. The developed method was successfully applied to the determination of NSAIDs in water and urine samples.

Innovative sampling and extraction methods for the determination of nonsteroidal anti-inflammatory drugs in water

Two different innovative approaches were used for the determination of nonsteroidal anti-inflammatory drugs (NSAIDs) in water: stir bar sorptive extraction (SBSE) and passive sampling, followed by electrospray ionization liquid chromatography–tandem mass spectrometry.SBSE was developed by comparing EG-Silicone and PDMS stir bars and optimizing main parameters to attain high preconcentration. Quantitative analysis was carried out by mass spectrometry in negative ionization mode and multiple reaction monitoring. The SBSE-LC-MS/MS method provided satisfactory figures of merit with LOD (7.5–71ngL−1) and LOQ (22.5–213ngL−1). The developed method was successfully applied to real samples collected from river water and wastewater effluents. The obtained results showed the presence of all analytes at trace levels, in a wide range of concentrations. The passive sampling approach was carried out by using Polar Organic Chemical Integrative Sampler (POCIS); samplers were deployed for 15 days in river and tap water, allowing to detect analytes at ultra-trace levels. Time-Weighted Average concentration of NSAIDs in river water was estimated in the range 0.33–0.46ngL−1, using the sampling rates previously obtained by means of a simple calibration system.