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This work describes the development of an HPLC-FLD methodology for the separation of five fluoroquinolones (ciprofloxacin, enrofloxacin, sarafloxacin, norfloxacin and levofloxacin) followed by optimization of the DLLME process for the clean-up and preconcentration of enrofloxacin in samples of seawater and river water. The mobile phase used for the chromatographic separation consisted of methanol: phosphate buffer (NaHPO4 H2O 0.04 M pH 3 with H3PO4 85 %), gradient eluted at a ratio of 20:80 (v:v). The mobile phase flow was maintained at 1.2 mL min-1. For the ultrasonic-assisted dispersive liquid liquid microextraction (UA-DLLME), the following conditions were used: 8 mL of sample with pH adjusted to 8, extraction solvent: 500 μL of chloroform, dispersive solvent: 500 μL of acetonitrile; samples were vortexed and sonicated for 2 minutes, each. The enrichment factor (EF) was 54.7 and the recovery was 70 %, achieving a limit of detection (LOD) of 0.11 μg L-1. Repeatability and intermediate reproducibility presented values of relative standard deviation (RSD) lower than 2 %. Finally, the optimized method was applied to the analysis of water and enrofloxacin was detected in both water samples with a concentration of 0.20 μg L-1 in the river and 0.12 μg L-1 in the seawater. However, recovery tests performed to evaluate the water matrices' effects on the extraction performance, presented recoveries of 72±6.1 for river water and 27±8.3 for seawater. These results demonstrate that hereby developed method is only suitable for water samples with a low salinity content. published

In this work, a liquid-liquid microextraction methodology using solidified floating organic drop (SFODME) was combined with liquid chromatography and UV/Vis detection to determine non-steroidal anti-inflammatory drugs (NSAIDs) naproxen (NPX), diclofenac (DCF), and mefenamic acid (MFN) in tap water, surface water, and seawater samples. Parameters that can influence the efficiency of the process were evaluated, such as the type and volume of the extractor and dispersive solvents, effect of pH, agitation type, and ionic strength. The optimized method showed low detection limits (0.09 to 0.25 μg L-1), satisfactory recovery rates (90 to 116%), and enrichment factors in the range between 149 and 199. SFODME showed simplicity, low cost, speed, and high concentration capacity of the analytes under study. Its use in real samples did not demonstrate a matrix effect that would compromise the effectiveness of the method, being possible to apply it successfully in water samples with different characteristics. published

In this work the dispersive liquid-liquid microextraction technique (DLLME) is presented as an important alternative to the classical extraction methods and was used to extract and concentrate estrogens’ before its quantification by HPLC in environmental water samples. For the evaluation of the analytical methodology, the following conditions were used: sample volume 8 mL, extraction solvent 200 μL of chlorobenzene, and dispersive solvent 2000 μL of acetone. The enrichment factor (EF) was 140 for estrone, 202 for 17β-estradiol (E2), and 199 for 17α-ethinylestradiol (EE2). Limit of detection was 20 ng L−1 for E1, 3.1 ng L−1 for E2, and 2.7 ng L−1 for EE2. Repeatability and intermediate reproducibility presented values of relative standard deviation lower than 10%. Finally, recovery tests were performed to evaluate the water matrices’ effects on the extraction performance, resulting in recoveries between 76 and 110% in surface water and between 84 and 109% in wastewater.

In view of a simple after-use separation, the potentiality of producing magnetic activated carbon (MAC) by intercalation of ferromagnetic metal oxide nanoparticles in the framework of a powder activated carbon (PAC) produced from primary paper sludge was explored in this work. The synthesis conditions to produce cost effective and efficient MACs for the adsorptive removal of pharmaceuticals (amoxicillin, carbamazepine, and diclofenac) from aqueous media were evaluated. For this purpose, a fractional factorial design (FFD) was applied to assess the effect of the most significant variables (Fe3+ to Fe2+ salts ratio, PAC to iron salts ratio, temperature, and pH), on the following responses concerning the resulting MACs: Specific surface area (SBET), saturation magnetization (Ms), and adsorption percentage of amoxicillin, carbamazepine, and diclofenac. The statistical analysis revealed that the PAC to iron salts mass ratio was the main factor affecting the considered responses. A quadratic linear regression model A = f(SBET, Ms) was adjusted to the FFD data, allowing to differentiate four of the eighteen MACs produced. These MACs were distinguished by being easily recovered from aqueous phase using a permanent magnet (Ms of 22&ndash, 27 emu g&minus, 1), and their high SBET (741&ndash, 795 m2 g&minus, 1) were responsible for individual adsorption percentages ranging between 61% and 84% using small MAC doses (35 mg L&minus, 1).

This work aimed at the microwave-assisted production of activated carbon (AC) from primary paper mill sludge (PS) for the adsorption of antibiotics from water. Production conditions, namely pyrolysis temperature, pyrolysis time and activating agent (KOH):PS ratio, were optimized as a function of product yield, specific surface area (SBET), total organic carbon (TOC) content and adsorptive removal percentage of two target antibiotics (amoxicillin (AMX) and sulfamethoxazole (SMX)). Under the optimized conditions (pyrolysis at 800 °C during 20 min and a KOH:PS ratio of 1:5), a microporous AC (MW800-20-1:5, with SBET = 1196 m2 g-1, TOC = 56.2% and removal of AMX and SMX = 85% and 72%, respectively) was produced and selected for further kinetic and equilibrium adsorption studies. The obtained results were properly described by the Elovich reaction-based kinetic model and the Langmuir equilibrium isotherm, with maximum adsorption capacities of 204 ± 5 mg g-1 and 217 ± 8 mg g-1 for AMX and SMX, respectively. Considering the satisfactory comparison of these results with the performance of commercial and alternative AC produced by conventional pyrolysis, this work demonstrated the feasibility of the microwave-assisted production of environmentally and energetically sustainable waste-based AC to be applied in the efficient removal of antibiotics from water., This work is a contribution to the project WasteMAC (POCI-01-0145-FEDER-028598) funded by FCT – Fundação para a Ciência e a Tecnologia, I.P., through national funds, and the co-funding by the FEDER, within the PT2020 Partnership Agreement and Compete 2020. Thanks are also due for the financial support to CESAM (UIDB/50017/2020+UIDP/50017/2020), to FCT/MEC through national funds, and the co-funding by the FEDER, within the PT2020 Partnership Agreement and Compete 2020. Marta Otero, Vânia Calisto and Guilaine Jaria are thankful to FCT for the Investigator Program (IF/00314/2015), the Scientific Employment Stimulus (CEECIND/00007/2017) and a PhD grant (SFRH/BD/138388/2018), respectively. María V. Gil acknowledges support from a Ramón y Cajal grant (RYC-2017-21937) of the Spanish government, co-financed by the European Social Fund (ESF).

The adsorption of pharmaceutical substances using carbonaceous materials, such as activated carbon (AC), biochar (BC) and hydrochar (HC), has received substantial attention by researchers working on water treatment, due to the simplicity, low-cost and high performance of this process. In order to widen the potentiality of these carbonaceous materials and to overcome some of their limitations, particularly the inefficient separation of powdered formulations from treated water, the incorporation of magnetic nanoparticles has been explored. The recovery of magnetic carbon materials (MCM) from the treated water can be attained by applying an external magnetic field, avoiding inefficient and costly filtration and centrifugation processes, typically applied in the case of non-magnetic carbonaceous adsorbents. In the last ten years, some work has been devoted to the preparation of MCM specifically from AC (MCACM), biochar (MCBCM) and hydrochar (MCHCM). This review aims to present the different aspects of using MCM in water treatment, namely in the removal of pharmaceutical compounds. The synthesis routes used to produce MCM, their physical, morphologic and chemical features, and their application in the removal of these micro-organic contaminants from water will be assessed. The advantages and disadvantages of using MCM in water treatment, and their comparative performance with the carbonaceous non-magnetic precursors will be also discussed in this review. published