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Water contamination with pharmaceuticals has become an evident environmental challenge. Treatment processes such as electrochemical oxidation (EO) and adsorption have limitations in the simultaneous removal of pharmaceuticals from water. Therefore, this study examined the potential of coupled process (EO followed by adsorption) in binary pharmaceuticals (acetaminophen (ACM) + ciprofloxacin (CIP)) removal from water, with an emphasis on coupled process optimization. Consequently, optimized coupled process conditions including current density (22 mA/cm 2 ), pH (5.5), EO time (40 min), adsorbent dose (0.1 g/L) and adsorption time (60 min) were obtained. Under optimal conditions, removal efficiencies of 94.6% (ACM)+92% (CIP), 94.07% (ACM)+91.15% (CIP), and > 99.8% (ACM + CIP) were recorded for 20 mg/L (ACM + CIP) removal in EO, adsorption and EO + adsorption, respectively. Further, the coupled process was employed in multiple pharmaceuticals (20 mg/L of ACM + CIP + ATN (atenolol) + AMX (amoxicillin)) removal from water and removal of > 97.56% (ACM + CIP + ATN + AMX) was achieved. Removal efficiencies of ACM (83.35%) + CIP (73.1%) + ATN (68.52%) + AMX (63.05%) and ACM (80.37%) + CIP (66.5%) + ATN (73.07%) + AMX (60.5%) were obtained in EO and adsorption, respectively. The noted lower removal efficiencies in EO and adsorption are associated with the diverse nature of the pharmaceuticals, limited adsorbent active sites, and the shared utilization of reactive oxygen species (ROS) among the pharmaceuticals in EO. The total organic carbon (TOC) removal of 40.24%, and 99% and chemical oxygen demand (COD) removal of 72.45%, and 99.6% were obtained under optimal conditions of EO, and coupled process, respectively. These findings indicate that the pharmaceuticals are only partially mineralized in EO and the subsequent adsorption effectively eliminated the remaining target pharmaceuticals, and degradation by-products from water. Additionally, integrating EO with adsorption reduced the electrical energy consumption of the EO process from 31.6 kWh/m³ to 6 kWh/m³ under optimal conditions. Overall, coupling EO with adsorption offers the utmost advantages when removing multiple pharmaceuticals from complex water matrices., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Ciprofloxacin (CIP) is one of the most widely used antibiotics to treat bacterial infections. Consequently, there is concern that it may contaminate water resources due to its high usage level. It is therefore necessary to monitor, trace, and reduce exposure to these antibiotic residues. In the current study, the extraction of CIP from water was performed using a green adsorbent material based on cellulose/polyvinyl alcohol (PVA) decorated with mixed metal oxides (MMO). This cellulose/MMO/PVA adsorbent was synthesized using a simple sol-gel method. The prepared adsorbent materials were then characterized using a range of methods, including scanning electron microscopy, energy-dispersive X-ray spectroscopy, gas adsorption analysis, X-ray diffraction, and Fourier Transform infrared. The impact of pH, adsorbent dose, contact time, and CIP concentration on ciprofloxacin extraction were examined. The equilibrium and kinetic adsorption data were well described using the Freundlich model (R 2  = 0.965). The optimum conditions for CIP adsorption were: pH = 4.5; adsorbent dosage = 0.55 g·L -1 ; contact time = 83 min; and initial CIP concentration = 2 mg·L -1 . The adsorption capacity of the cellulose/MMO/PVA adsorbent for CIP removal was ∼19 mg·g -1 (CIP removal = 86.48 %). This study shows that cellulose/MMO/PVA adsorbents have potential for removing contaminants from aqueous environments., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Biochar is considered a promising biosorbent for harmful organic pollutants in aqueous media. However, only a limited number of biochars derived from industrial sludges have been utilized due to their problematic high ash content and heavy metal leaching. In this study, a highly effective biochar was prepared as a superabsorbent for ciprofloxacin (CIP) from chemical manufacturing plant sludge via K 2 CO 3 -activated pyrolysis, and its CIP removal behavior was evaluated. Unlike sewage sludge, chemical manufacturing plant sludge contains low SiO 2 , resulting in an ultra-pure carbon (95.4%) based biochar with almost negligible ash content. As the pyrolysis temperature increased from 400 to 800 °C, the ordered graphitic carbon structure transformed into an amorphous carbon phase, and most oxygen-containing groups disappeared. However, the pore size significantly decreased to ∼4.5 nm due to the corrosive carbon volatilization caused by K 2 CO 3 , resulting in an extremely large surface area of 2331.8 m 2 /g. Based on its large surface area and porous carbon structure, the activated biochar at 800 °C (CAB-800) exhibited an outstanding CIP adsorption capacity of 555.56 mg/g. The CIP adsorption isotherm, kinetic, and thermodynamic studies were systematically investigated. The CIP adsorption on CAB-800 was mainly attributed to π-π interactions and hydrogen bond formation, with electrostatic interactions partially contributing to the adsorption reaction. From pH 2 to 12, CAB-800 showed an excellent CIP adsorption capacity of over 316.7 mg/g, with adsorption favored under acidic conditions. Except for HCO 3 - and CO 3 2- , the presence of anions and humic acids did not significantly affect CIP adsorption capacity. These results demonstrate that biochar produced from chemical manufacturing industry sludge via K 2 CO 3 activation is a highly feasible material for the removal of CIP from aqueous media., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Well-dispersed MIL-100(Fe) nanoparticles were synthesized under mild conditions and used to construct a photo-Fenton system (VMH system) with the assistance of visible-light irradiation and hydrogen peroxide. In such a VMH system, the MIL-100(Fe) has a high specific surface area and provides numerous Fe 3+ active sites, thus accelerating the reaction of Fe 3+ with photo-generated electrons under visible-light irradiation and generates Fe 2+ , and then the acquired Fe 2+ can activate H 2 O 2 to generate ⋅ OH, accompanying with the oxidation of Fe 2+ to Fe 3+ . Hence, the in-situ recycling of Fe 2+ /Fe 3+ promotes the generation of ·OH, thus making the VMH system exhibits promising photocatalytic activity. The removal rate of ciprofloxacin in the VMH system is as high as 95.2% within 120 min photo-Fenton reaction, which is about 26 times higher than that of the Visible light/MIL-100(Fe) system. Moreover, the VMH system also exhibits strong degradation ability to other typical antibiotics, such as tetracycline, norfloxacin and cephalexin, and maintains high cyclic stability, revealing great practical application potential in the purification of antibiotic wastewater.

The prevalent presence of pharmaceuticals in aquatic ecosystems underscores the necessity for developing cost-effective techniques to remove them from water. The utilization of affordable precursors in producing activated carbon, capable of rivaling commercial alternatives, remains a persistent challenge. The adsorption of diclofenac and ciprofloxacin onto a novel pinewood-derived activated carbon (FPWAC) was explored, employing a sequential activation process involving ammonium nitrate (NH 4 NO 3 ) treatment followed by sodium hydroxide (NaOH) activation. The produced FPWAC was then thoroughly characterized by employing several techniques. The removal of diclofenac and ciprofloxacin in water and real wastewater effluent was examined in batch tests. The optimum removal conditions were an FPWAC dosage of 1 g L -1 , pH 6, mixture concentration of 25 mg L -1 , and a temperature of 25 °C. The FPWAC was able to remove both pharmaceuticals for up to six cycles, with more than 95% removal for water and 90% for wastewater in the first cycle. The adsorption performance fitted well with the non-linear Freundlich isotherm for both pollutants. The kinetics of adsorption of diclofenac followed a pseudo-first-order model, while ciprofloxacin showed adherence to the pseudo-second-order model. FPWAC proved its potency as a low-cost adsorbent for pharmaceutical removal from wastewater., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

The transport of carbamazepine, ciprofloxacin and sulfamethoxazole in the different pores of activated carbon in an aqueous solution is a dynamic process that is entirely dependent on the intrinsic parameters of these molecules and of the adsorbent. The macroscopic processes that take place are analyzed by interfacial diffusion and reaction models. Modeling of the experimental kinetic curves obtained following batch treatment of each solute at 2 µg/L in tap water showed (i) that the transport and sorption rates were controlled by external diffusion and intraparticle diffusion and (ii) that the effective diffusion coefficient for each solute, with the surface and pore diffusion coefficients, were linked by a linear relationship. A statistical analysis of the experimental data established correlations between the diffusional parameters and some geometrical parameters of these three molecules. Given the major discontinuities observed in the adsorption kinetics, the modeling of the experimental data required the use of traditional kinetic models, as well as a new kinetic model composed of the pseudo first or second order model and a sigmoidal expression. The predictions of this model were excellent. The solubility of each molecule below 60 °C was formulated by an empirical expression.

In this work, novel dummy molecularly imprinted membranes (MIMs) were fabricated using the nylon-66 (NY-66) membranes as the subtracts based on an eco-friendly "sandwich" technology with less consumption of organic reagents at mild conditions for recognition and extraction of enrofloxacin (ENR) and ciprofloxacin (CIP) in egg samples. The prepared MIMs were characterized by SEM, ATR-FTIR and TGA, showing the successful construction of uniform and porous polymers on the surface of membranes. A series of adsorption affinity tests were investigated, indicating the prepared materials had specific recognition capacity and excellent stability as novel sorbents. Furthermore, Box-Benhnken design (BBD) and single factor investigations were applied to optimize pretreatment procedures, coupling with Ultra High Performance Liquid Chromatograph (UHPLC) detection. The method showed a good correlation (r 2 >0.9999) within the linear range of 5.0~5000.0 µg kg -1 , and limit of detection (LOD) of ENR and CIP were 0.3 and 0.7 µg kg -1 , respectively. The mean recovery ranged from 84.5% to 97.0% within relative standard deviations (RSDs) of 10.2%. Finally, ENR and CIP were not detected in 3 batches of egg samples. The current study developed the dummy MIMs as sorbents combined with UHPLC analysis for extraction and detection of target analytes in food matrices., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021. Published by Elsevier B.V.)

A reliable and efficient method for the simultaneous extraction and determination of antibiotics of ciprofloxacin and levofloxacin from milk was developed with solid phase extraction based on tailored adsorbent materials of deep eutectic solvents modified phenolic resin (DES-R-SPE). Six types of polyhydric alcohol-based hydrophilic DESs were prepared to modify the phenolic resin with the compositions of 3-aminophenol as a functional monomer, glyoxylic acid as a crosslinker, and polyethylene glycol 6000 as a porogen. And the prepared DES-Rs showed better extraction capacities for the target analytes than the unmodified phenolic resin because of more hydrogen bonding and electrostatic interactions supplied by DESs. The choline chloride-glycerol-based resin (DES 1 -R) with the highest adsorption amounts was selected and the adsorption behavior of it was studied with static adsorption and the dynamic adsorption performance; the adsorption process followed Freundlich isotherm (R 2  ≥ 0.9337) and pseudo-second-order (R 2  ≥ 0.9951). The present DES 1 -R-SPE method showed good linear range from 0.5 to100 μg mL -1 (R 2  ≥ 0.9998), good recoveries of spiked milk samples (LEV, 96.7%; CIP, 101.5%), and satisfied repeatability for intra-day and inter-day (LEV, RSD≤5.4%; CIP, RSD≤4.6%).

Monodisperse restricted-access media bi-functional monomers with molecularly imprinted polymers (RAM-MIPs) were constructed using surface-initiated atom transfer radical polymerization. They were used as solid-phase extraction (SPE) adsorbents to enrich sarafloxacin (SAR) residues from egg samples, and influences on their performance were investigated. Optimum synthesis of RAM-MIPs was achieved by combining a bi-functional monomer (4-vinylpyridine-co-methacrylic acid, 1:3) with an 8:1:32:8 ratio of a template molecule, cross-linker, and restricted-access functional monomer. The SAR imprinting factor of RAM-MIPs was 6.05 and the selectivity coefficient between SAR and other fluoroquinolones was 1.86-2.64. Compared with traditional MIPs, the RAM-MIPs showed better SAR enrichment and selectivity during extraction of a complex protein-containing solution. Empty SPE cartridges were filled with RAM-MIP microspheres as SPE adsorbents. The limit of quantitation for SAR was 4.23 ng g -1 (signal-to-noise ratio = 10) and the mean SAR recovery from spiked egg samples was 94.0-101.3%. Intra-day and inter-day relative standard deviations were 1.1-9% and 1.5-3.3%, respectively., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

In anaerobic bioreactors, the electrons produced during the oxidation of organic matter can potentially be used for the biological reduction of pharmaceuticals in wastewaters. Common electron transfer limitations benefit from the acceleration of reactions through utilization of redox mediators (RM). This work explores the potential of carbon nanomaterials (CNM) as RM on the anaerobic removal of ciprofloxacin (CIP). Pristine and tailored carbon nanotubes (CNT) were first tested for chemical reduction of CIP, and pristine CNT was found as the best material, so it was further utilized in biological anaerobic assays with anaerobic granular sludge (GS). In addition, magnetic CNT were prepared and also tested in biological assays, as they are easier to be recovered and reused. In biological tests with CNM, approximately 99% CIP removal was achieved, and the reaction rates increased ≈1.5-fold relatively to the control without CNM. In these experiments, CIP adsorption onto GS and CNM was above 90%. Despite, after applying three successive cycles of CIP addition, the catalytic properties of magnetic CNT were maintained while adsorption decreased to 29 ± 3.2%, as the result of CNM overload by CIP. The results suggest the combined occurrence of different mechanisms for CIP removal: adsorption on GS and/or CNM, and biological reduction or oxidation, which can be accelerated by the presence of CNM. After biological treatment with CNM, toxicity towards Vibrio fischeri was evaluated, resulting in ≈ 46% detoxification of CIP solution, showing the advantages of combining biological treatment with CNM for CIP removal.

In the current study, eco-structured and efficient removal of the veterinary fluoroquinolone antibiotic sarafloxacin (SARA) from wastewater has been explored. The adsorptive power of four agro-wastes (AWs) derived from pistachio nutshells (PNS) and Aloe vera leaves (AV) as well as the multi-walled carbon nanotubes (MWCNTs) has been assessed. Adsorbent derived from raw pistachio nutshells (RPNS) was the most efficient among the four tested AWs (%removal '%R' = 82.39%), while MWCNTs showed the best adsorptive power amongst the five adsorbents (%R = 96.20%). Plackett-Burman design (PBD) was used to optimize the adsorption process. Two responses ('%R' and adsorption capacity ' q e ') were optimized as a function of four variables (pH, adsorbent dose 'AD' (dose of RPNS and MWCNTs), adsorbate concentration [SARA] and contact time 'CT'). The effect of pH was similar for both RPNS and MWCNTs. Morphological and textural characterization of the tested adsorbents was carried out using FT-IR spectroscopy, SEM and BET analyses. Conversion of waste-derived materials into carbonaceous material was investigated by Raman spectroscopy. Equilibrium studies showed that Freundlich isotherm is the most suitable isotherm to describe the adsorption of SARA onto RPNS. Kinetics' investigation shows that the adsorption of SARA onto RPNS follows a pseudo-second order (PSO) model.

An ultrasound-assisted ionic liquid (IL) salting-out microextraction system was developed and applied for the extraction of quinolone antibiotics from urine. A precipitate was formed from the salt and IL, and it acted as the sorbent for the analytes. The precipitate containing the analyte was separated by filtration, redissolved, and the solution then was evaporated. The resulting extract was redissolved for high-performance liquid chromatographic analysis. Several parameters, including type and volume of IL, the type and amount of salts, sample pH, temperature and extraction time were optimized. Under the optimal experimental conditions, the limits of detection for fleroxacin and ciprofloxacin were 3.12 and 4.97 μg L-1, respectively. When the present method was applied to real urine sample analysis, the analyte recoveries ranged from 82.3 to 106.8%. This ultrasound-assisted IL salting-out microextraction system had the characteristics of high recoveries, shorter separation time and easy-to-perform collection procedure, which yielded the method to have potential for wide application., (© The Author(s) 2020. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.)

Herein, we have developed a photocatalytic, fluorescent bismuth phosphate@graphene oxide (BiPO 4 @GO) based magnetic nano-sized-molecularly imprinted polymer (MMIP) for detection, removal, and degradation of ciprofloxacin (CIP) via atom transfer radical polymerization (ATRP) process. CIP is a very popular antibiotic, but their heavy doses in recent time, made them an environmental threat. The imprinted polymer was synthesized using N-vinyl caprolactam, N, N-methylene bis-acrylamide, ZnFe 2 O 4 nanoparticle, and Bi(PO 4 )@GO as a biocompatible monomer, crosslinker, magnetic moiety, and photocatalyst, respectively. The characterization of the molecularly imprinted polymer was systematically evaluated by electrochemical techniques, X-ray diffraction, fluorescence spectroscopy, scanning electron microscopy, etc. The prepared BiPO 4 @GO modified CIP-imprinted magnetic polymer (BiPO 4 @GO-MMIPs) shows high selectivity towards their template/target analyte (i.e., CIP) and used for their visual (via fluorescence study) and trace level detection (via the electrochemical study) in various kind of complex matrix. The dual behaviour i.e. electrochemical and optical sensing of CIP was successfully achieved in a good linear range of 39.0 to 740.0 μg L -1 with detection of limit (LOD) of 0.39 μg L -1 for electrochemical study and 39.0 to 328.0 μg L -1 and LOD of 0.40 μg L -1 for optical study. The prepared BiPO 4 @GO-MMIPs were successfully used for the detection of CIP from complex matrix like blood serum, whole blood, and milk sample as well as removal and degradation of CIP with good efficiency., Competing Interests: Declaration of competing interest None., (Copyright © 2020 Elsevier B.V. All rights reserved.)

A number of porous g-C3N4 nanosheet/Ag3PO4/NCDs (PCNNS/AP/NCDs) with little amounts of Ag3PO4 were synthesized via an in situ sedimentation-calcination method. The PCNNS/AP/NCDs photocatalyst exhibited excellent photocatalytic performance for the photocatalytic degradation of tetracycline (TC) under visible light irradiation at a removal rate of 90.5% in 40 min. The study of the reaction kinetics of the as-prepared samples was in accordance with the pseudo-second-order kinetics, with the correlation coefficient (R2) being greater than 0.9776. Meanwhile, the photocatalyst was capable of degrading ciprofloxacin (CIP), and showed good performance even under actual water conditions with natural sunlight irradiation, indicating that the photocatalyst has wide practical applications. In addition, the photocatalytic performance and the XRD and FTIR spectra showed no obvious changes even after four photocatalytic degradation cycles, which revealed the high stability of the PCNNS/AP/NCDs photocatalyst. Furthermore, the possible degradation pathways of TC and the possible Z-scheme mechanism were proposed with ˙O2- and h+ as the main active species contributing to photocatalytic degradation. The results provide a novel insight into the fabrication of Z-scheme PCNNS/AP/NCDs and introduce them as an efficient visible-light-responsive photocatalyst for use in practical applications.

A green synthesis approach was conducted to prepare amine-functionalized bio-graphene (AFBG) as an efficient and low cost adsorbent that can be obtained from agricultural wastes. In this study, bio-graphene was successfully used to remove Ciprofloxacin (CIP) from synthetic solutions. The efficacy of adsorbent as a function of operating variables (i.e. pH, time, AFBG dose and CIP concentration) was described by a polynomial model. A optimal99.3% experimental removal was achieved by adjusting the mixing time, AFBG dose, pH and CIP concentration to 58.16, 0.99, 7.47, and 52.9, respectively. Kinetic model revealed that CIP diffusion into the internal layers of AFBG controls the rate of the process. Furthermore, the sorption process was in monolayer with a maximum monolayer capacity of 172.6 mg/g. Adsorption also found to be favored under higher CIP concentrations. The thermodynamic parameters (ΔG°<0, ΔH°>0, and ΔS°>0) demonstrated that the process is endothermic and spontaneous in nature. The regeneration study showed that the AFBG could simply regenerated without significant lost in adsorption capacity., Competing Interests: No Conflict of interest.

Adverse effects of pharmaceutical emerging contaminants (PECs), including antibiotics, in water supplies has been a global concern in recent years as they threaten fresh water security and lead to serious health problems to human, wildlife and the environment. However, detection of these contaminants in water sources, as well as food products, is difficult due to their low concentration. Here, we prepared a new family of magnetic molecular imprinted polymer (MMIP) networks for binding antibiotics via a microemulsion polymerization technique using vinyl silane modified Fe 3 O 4 magnetic nanoparticles. The cross-linked polymer backbone successfully integrated with 20-30 nm magnetic nanoparticles and generated a novel porous polymeric network structure. These networks showed a high binding capacity for both templates, erythromycin and ciprofloxacin at 70 and 32 mg/g. Both MMIPs were also recyclable, retaining 75 % and 68 % of the binding capacity after 4 cycles. These MMIPs have showed a clear preference for binding the template molecules, with a binding capacity 4- to 7-fold higher than the other antibiotics in the same matrix. These results demonstrate our MMIP networks, which offered high binding capacity and selectivity as well as recyclability, can be used for both removal and monitoring hazardous antibiotic pollutants in different sources/samples and food products., Competing Interests: Declaration of Competing Interest There is no conflict of interest to declare., (Copyright © 2019 Elsevier B.V. All rights reserved.)

A doubly porous microcomposite polyaniline/graphene oxide/octadecyl-bonded silica magnetite (PANI/GOx/C18-SiO 2 -Fe 3 O 4 ) alginate adsorbent was developed and employed to extract fluoroquinolones. The Fe 3 O 4 facilitated rapid and convenient for the separation of the adsorbent from sample solutions. The double porosity of the alginate hydrogel enhanced the surface area of the polyaniline coating. The developed method exhibited good linearity of 0.0010-50 μg L -1 for danofloxacin; 0.0050-50 μg L -1 for norfloxacin, ciprofloxacin and enrofloxacin; and 0.010-50 μg L -1 for sarafloxacin and difloxacin. The limits of detection were between 0.001 and 0.010 μg L -1 with RSD below 9.0%. The PANI/GOx/C18-SiO 2 -Fe 3 O 4 adsorbent was utilized to extract fluoroquinolones from honey, milk and egg samples and satisfactory extraction recoveries were achieved ranged from 80 to 98%. The developed adsorbent has good stability which can be reused up to 7 times, is simple to prepare and convenient to use for the extraction fluoroquinolones., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

The study investigated ciprofloxacin (CIP) adsorption capacity of the novel biomaterials prepared from banyan aerial roots by simple thermochemical modification. Pretreated banyan aerial root fibers were modified with a green reagent citric acid (1 M) at 90, 120 and 150 °C, which enhanced the fiber adsorption capacity revealed by characterization and adsorption tests. Several characterization methods were applied to exploring the surface morphologies and physicochemical properties of unmodified banyan aerial roots (UBARs) and modified banyan aerial roots (T-MBARs, T stands for the modification temperature). Based on SEM images and N 2 adsorption/desorption isotherms, the modification resulted in decrease of the specific surface area owing to cellulose molecular linking. In that case, the improved CIP adsorption of MBARs might be attributed to the larger carboxyl quantity and stronger electronegativity manifested via FTIR spectra and zeta potential analysis. Through the adsorption experiments, the optimal pH value of 8 and the suitable absorbent dosage of 0.03 g were obtained. The simulation results showed that the Freundlich model can fit the adsorption thermodynamic data quite well, while the kinetic data was simulated preferably by the pseudo-second-order kinetic equation signifying the chemical adsorption process, and the intra-particle diffusion was involved in the adsorption consisted of three stages. The findings of batch experiments under diverse operations represented that MBARs purified aqueous CIP better than UBARs, closely related to the superior electronegativity. Both characterization and adsorption studies illustrated the dominant role of electrostatic interaction during CIP removal, accompanied by hydrogen bonding and diffusion interaction besides. The present work suggested that MBAR fibers could possess a promising application to ciprofloxacin potent removal from aqueous solutions., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Large-scale abuse of antibiotics has led to serious environmental problems. Some conventional adsorbents such as several biopolymer gels have poor adsorption performance and inadequate mechanical properties. In this paper, carbon nanotubes (CNTs) and graphene oxide (GO), were combined with sodium alginate (SA) to improve the adsorption performance and other properties of traditional adsorbents. With the help of hydrogen peroxide and l-cysteine (L-cys), carbon nanotubes/l-cysteine@graphene oxide/sodium alginate (CNTs/L-cys@GO/SA) triple-network composite hydrogels were prepared. Compared with traditional hydrogels and the double-network hydrogels that are currently being developed, these triple-network composite hydrogels can exploit their three-dimensional structure to improve their adsorption capacity. The independent triple-network structure increases the three-dimensional space, so there are more pores and pollutant adsorption sites to achieve the high-efficient removal of ciprofloxacin. And the adsorption capacity of CNTs/L-cys@GO/SA hydrogels can reach 181 mg g -1 and 200 mg g -1 at 25 °C and 15 °C respectively in weak acidity environment. In fact, CNTs/L-cys@GO/SA hydrogels show better property at low temperature. In addition, the thermal stability, mechanical properties and swelling ability of the triple-network hydrogels have also been improved. The independent multilayer network can retain the excellent properties of the original materials and make the internal space of hydrogels larger. These multinetwork hydrogels have great potential for removing pollutants from wastewater. In addition, the CNTs/L-cys@GO/SA hydrogels show the higher adsorption capacity of ciprofloxacin under the conditions of weak acidity, low temperature and low inorganic salt concentration, so the removal of ciprofloxacin by hydrogels can also be promoted by changing environmental conditions., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Zwitterionic pharmaceuticals and personal care products can interact with adsorbents in different ways due to their various properties. In this work, the effects of hydrophobicity and electrostatic potential were explored through the adsorption of ciprofloxacin (CPX) and tetracycline (TC) onto multifunctional resins. Nonionic surface interaction was dominant for the adsorption on high-surface-area resin GMA10. Thereinto, hydrophobic and π-π interaction dominant for hydrophobic CPX and hydrophilic TC, respectively. Electrostatic interaction played an important role for high-anion-exchange-capacity resin GMA90. Upon their adsorption onto GMA50 resin, the relatively separated positive and negative electrostatic potentials of CPX +- due to the greater distance (∼12.33 Å) between the anionic and cationic groups led to electrostatic attraction and interaction (Ea = 8.64 ± 0.31 kJ/mol) and the vertical orientation of molecule on the surface. However, TC +-0 displayed nonionic surface interaction (Ea = 7.96 ± 0.14 kJ/mol) due to its relatively neutral electrostatic potential arising from the adjacent functional groups. Hence, the surface of GMA50 was covered with TC +-0 molecules adsorbed parallel to the surface, thereby restricting TC +-0 adsorption. Coexisted with monovalent salts, CPX adsorption was facilitated due to the salting-out effect. By contrast, the salting-out effect for TC was extremely weak, and TC adsorption was restrained due to the competitive adsorption of salts., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Numerous of pollutants threaten our planet, for instance plastic wastes causes a huge potential risk on the environment in addition to many of emergened pollutants as pharmaceutical residue in aquatic environments which affecting ecological balance and in-turn affecting human health. Accordingly, this research proposed an innovative facile, one-step synthesis of functionalized magnetic fullerene nanocomposite (FMFN) via catalytic thermal decomposition of sustainable poly (ethylene terephthalate) bottle wastes as feedstock and ferrocene as a catalyst and precursor of magnetite. Growth mechanism of FMFN was discussed and batch experiments were achieved to examine its adsorption efficiency in relation to Ciprofloxacin antibiotic. Different adsorption parameters including time, initial Ciprofloxacin concentration, and solution temperature were investigated and optimized using Response Surface Methodology (RSM) model. In addition, a study on the antibiotic adsorption process impact on the organisms of an ecosystem was conducted using E. coli DH5α, and results validated method's efficiency in overcoming problem of appearance of antibiotic-resistant microbes., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Ciprofloxacin has been frequently detected in water environment, and its removal has become a significant public concern. Biochar-supported nanoscale zero-valent iron (BC/nZVI) to activate hydrogen peroxide (H 2 O 2 ) has many advantages on promoting the removal of organic contaminants. In this paper, the BC/nZVI activating H 2 O 2 degradation of ciprofloxacin was systematically investigated by experimental and theoretical approaches. The morphologies and property analysis showed that nZVI particles distributed uniformly on the biochar surface, which mainly include  - OH, >CO and COC and CO groups. Different reaction conditions were compared to define the optimal conditions for ciprofloxacin removal in BC/nZVI/H 2 O 2 system. More than 70% of ciprofloxacin was removed in the optimal conditions: acidic condition (pH 3∼4), low doses of H 2 O 2 (20 mM), and temperature of 298 K. The hydroxyl radical ( • OH) oxidation was the primary pathway in BC/nZVI/H 2 O 2 degradation of ciprofloxacin process. The theoretical calculation indicated that hydrogen atom abstraction (HAA) pathways were the dominant oxidation pathways contributing 92.3% in overall second‒order rate constants (k) of • OH and ciprofloxacin. The current results are valuable to evaluate the application of BC/nZVI activating H 2 O 2 degradation of ciprofloxacin and other fluoroquinolone antibiotics in water treatment plants., (Copyright © 2019 Elsevier B.V. All rights reserved.)

The abuse of antibiotics is becoming increasingly serious, particularly in offshore aquaculture areas. Double-network polymer gel has good prospects for environmental application for the removal of antibiotics. In this work, κ-Carrageenan/Sodium Alginate (κ-car/SA) double-network hydrogels were designed and synthesized with enhanced mechanical properties, anti-swelling, and adsorption capacity. It was found that the intermolecular interaction and viscosity tend to increase with the increasing concentration of κ-carrageenan. The swelling degree of the composite hydrogel in NaCl solution presented a decreasing trend with the increase of carrageenan. SA can effectively improve the mechanical properties of κ-carrageenan composite gel and enhance its compressive resistance and elasticity. Ciprofloxacin (CIP) was used as the model pollutant for testing the adsorption performance. The results show that the Langmuir-Freundlich isotherm model is more suitable for fitting the adsorption isotherm data of CIP on gel beads, which indicates that κ-car/SA hydrogels have heterogeneous surface and different binding sites. κ-car/SA composite double-network hydrogels exhibit excellent adsorption properties for CIP (229 mg/g). The optimal adsorption capacity of κ-car/SA composite hydrogels was obtained at pH 4, and the adsorption capacity of the hydrogels increased with increasing ion concentration. FTIR spectroscopy and the Zeta potential test analyses showed that the adsorption mechanism may be explained by hydrogen bonding and the electrostatic interactions between κ-car/SA composite hydrogels and CIP. The formation of the new double-network hydrogel provided good properties and development potential for the adsorption of antibiotic in water., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Antibiotics in the effluents of municipal wastewater treatment plants (WWTP) may create selective pressures to induce antibiotic resistance in bacteria downstream. This study evaluates ciprofloxacin (CIP) removal by a freshwater alga, Scenedesmus dimorphus, to assess the efficacy of algae-based tertiary treatment in reducing effluent-induced CIP resistance. Results show significant CIP removal in light-exposed samples without algae and experimental algae (EA) samples: 53% and 93%, respectively, over 144 h. A residual antibiotic potency assay reveals that untreated CIP is significantly more growth-inhibiting to a model bacterium (Escherichia coli) than the algae-treated and light-exposed samples during short exposures (6 h). Adaptive laboratory evolution (ALE), again using E. coli, reveals that treated samples exhibit reduced capacity to elicit CIP resistance during sustained exposures compared to untreated CIP. Finally, observed CIP resistance in the CIP-exposed ALE lineages is corroborated via genotype characterization, which reveals the presence of resistance-associated mutations in gyrase subunit A (gyrA) that are not present in ALE lineages exposed to algae treated or light-exposed samples. As such, algae-mediated tertiary treatment could be effective in suppressing CIP resistance in bacterial communities downstream from WWTP. In addition, ALE is useful for assessing the potential of wastewater-relevant samples to elicit antibiotic resistance downstream., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

This study evaluates a novel adsorbent for ciprofloxacin (CPX) removal from water using a composite derived from municipal solid waste biochar (MSW-BC) and montmorillonite (MMT). The composite adsorbent and pristine materials were characterized using powder X-Ray Diffraction (PXRD), Fourier-Transform Infrared (FTIR) spectroscopy, and Scanning Electron Microscope (SEM) before and after the adsorption. Batch experiments were conducted to study the mechanisms involved in the adsorption process. Ciprofloxacin sorption mechanisms were interpreted in terms of its pH-dependency and the distribution coefficients. The SEM images confirmed the successful binding of MMT onto the MSW-BC through flaky structure along with a porous morphology. Encapsulation of MMT onto MSW-BC was exhibited through changes in the basal spacing of MMT via PXRD analysis. Results from FTIR spectra indicated the presence of functional groups for both pristine materials and the composite that were involved in the adsorption reaction. The Hill isotherm model and pseudo-second-order and Elovich kinetic models fitted the batch sorption data, which explained the surface heterogeneity of the composite and cooperative adsorption mechanisms. Changes made to the MSW-BC through the introduction of MMT, enhanced the active sites on the composite adsorbent, thereby improving its interaction with ionizable CPX molecules giving high sorption efficiency., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Water contamination with antibiotics is a serious environmental threat. Ciprofloxacin (CIP) is one of the most frequently detected antibiotics in water. Herein, silica-based magnetic nanosorbents prepared using three seaweed polysaccharides, alginic acid, κ- and λ-carrageenan, were developed and evaluated in the uptake of ciprofloxacin. The sorbents were firstly characterized in detail to assess their morphology and composition. A systematic investigation was conducted to study the adsorption performance towards CIP, by varying the initial pH, contact time and initial CIP concentration. The maximum adsorption capacity was 464, 423 and 1350 mg/g for particles prepared from alginic acid, κ- and λ-carrageenan respectively. These high values indicate that these materials are among the most effective sorbents reported so far for the removal of CIP from water. The kinetic data were consistent with the pseudo-second-order model. The CIP adsorption on λ-carrageenan particles followed a cooperative process with sigmoidal isotherm that was described by the Dubinin-Radushkevich model. The high charge density of λ-carrageenan and the propensity of CIP molecules to self-aggregate may explain the cooperative nature of CIP adsorption. The sorbents were easily regenerated in mild conditions and could be reused in CIP removal up to 4 times without a significant loss of adsorptive properties., (Copyright © 2019 Elsevier B.V. All rights reserved.)

This study examined the removal of varying concentrations of the antibiotic Ciprofloxacin (CIP) over the long-term (120 days) in an anaerobic membrane bioreactor (AnMBR). The results showed that 50-76% CIP was removed with 0.5-1.5 mg CIP/L in the feed, although at 4.7 mg/L its removal efficiency decreased to <20%. It was found that biological degradation was the main mechanism for removing CIP, while adsorption onto the sludge only contributed a small fraction, and an even smaller fraction was due to the waste sludge discharged. CIP was biodegraded to some degree in the AnMBR, with some intermediate compounds detected using LC-MS/MS and GC-MS. This work showed the effectiveness of an AnMBR in removing CIP at low concentrations of <1.5 mg/L, and hence may be an effective treatment for removing other antibiotics from wastewater., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

An environmentally friendly and low-cost material based on cellulose filter paper modified with β-cyclodextrin (β-CD) was designed to uptake and elute drugs for water purification. To carry out the work, a β-CD derivative was first obtained through reaction of β-CD with N-(hydroxymethyl) acrylamide (NMA), and then β-CD-NMA was grafted on cellulose by means of the Fenton's reaction. The CD-grafted cellulose paper was characterized by ATR-FTIR analysis, SEM images, and mechanical properties. CD-functionalized (F1) and non-functionalized (NF) papers were tested in aqueous media containing an antibiotic (ciprofloxacin) or a non-steroidal anti-inflammatory drug (diclofenac) covering a wide range of salinity levels. Ciprofloxacin was similarly adsorbed by both papers through ionic interactions, while diclofenac was selectively and remarkably captured by the CD-functionalized filter (up to 25 mg g -1 from saline medium under biorelevant conditions; ca. 60 mg g -1 Langmuir isotherm model). Effects of diclofenac concentration, volume of medium, and incubation time on the amount adsorbed were investigated in detail. Elution tests involved the combination of several organic solvents and alkaline solutions and revealed that acetonitrile:NaOH 10 mM aq. solution (50:50, v/v) allows for an effective recovery of the previously trapped diclofenac. Application of ultrasounds shortened the process to 10 min. Reusability of F1 papers was also evaluated. Overall, the CD-grafted cellulose paper appears as a suitable material for bioremediation and analytical purposes., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

We present an integral smartphone-based whole-cell biosensor, LumiCellSense (LCS), which incorporates a 16-well biochip with an oxygen permeable coating, harboring bioluminescent Escherichia coli bioreporter cells, a macro lens, a lens barrel, a metal heater tray, and a temperature controller, enclosed in a light-impermeable case. The luminescence emitted by the bioreporter cells in response to the presence of the target chemicals is imaged by the phone's camera, and a dedicated phone-embedded application, LCS&#95;Logger, is employed to calculate photon emission intensity and plot it in real time on the device's screen. An alert is automatically given when light intensity increases above the baseline, indicating the presence of the target. We demonstrate the efficacy of this system by the detection of residues of an antibiotic, ciprofloxacin (CIP), in whole milk, with a detection threshold of 7.2 ng/mL. This value is below the allowed maximum as defined by European Union regulations.

Nanosheets prepared from magnesium oxide, chitosan and graphene oxide (MgO/Chit/GO) were hydrothermally synthesized and used as a sorbent for removal of ciprofloxacin and norfloxacin from aqueous solutions. Residual antibiotics in sample were determined by HPLC/UV instrument. The sorbent was characterized by FTIR, XRD, BET, SEM, and TEM. Its high adsorption capacity is attributed to the high surface area (294 m 2 .g -1 ) as compared to bare MgO/chit or bare GO. The pore size of the mesoporous sorbent typically is 15 Å. The adsorption isotherms for the two model antibiotics studied (norfloxacin, ciprofloxacin) can be described with the Langmuir model, and the maximum adsorption capacities are 1111 and 1000 mg.g -1 for ciprofloxacin and norfloxacin, respectively. The analysis of the kinetic data revealed that the synthesized sorbent followed pseudo-second-order kinetics and the maximum equilibrium was at over 120 and 150 min for ciprofloxacin and norfloxacin, respectively. Therefore, it is introduced as an economical, eco- friendly, and high-performance sorbent for removal of antibiotics from aqueous solutions. Graphical abstract Schematic presentation of dispersion of magnesium oxide/chitosan/graphene oxide (MgO/chit/GO) nanosheets in waste water for removal of ciprofloxacin and norfloxacin as water pollutants.

In this study, humic acid coated biochar (HA-BC) and chitosan were combined to prepare an adsorbent with enhanced reactivity for the removal of ciprofloxacin (CIP). With initial CIP concentrations of 250 mg/L, the maximum adsorbed amount was 154.89 mg/g. Removal rates reached equilibrium after 12 h, obeying the pseudo second-order kinetic model. Adsorption isotherm data was better fitted to the Langmuir isotherm model. The sorption capacity of humic acid-biochar/chitosan hydrogel beads (HBCB) decreased by 11.42%, 6.66%, 9.32%, and 23.92% in the presence of NaCl, NaNO 3 , Na 2 SO 4 , and Na 3 PO 4 , respectively. A complex mechanism was found to be responsible for the adsorptive removal of CIP including, hydrogen bonding, π-π electron donor-acceptor (EDA) interactions and hydrophobic interactions. After four regeneration steps, sorption capacity remained sufficient (61.23 mg/g). These removal results indicate that HBCB is durable and effective for long term CIP removal., (Copyright © 2019 Elsevier Inc. All rights reserved.)

Few studies have focused on the feasibility of microbial fuel cells (MFCs) for removing quinolones antibiotics and their anti-shock capabilities. After 1.5 years of operation, the removal efficiency of 10 mg/L ciprofloxacin in MFCs increased to 99.00% in 88 h. These results are in accordance with the enhanced activity of biofilms and voltage output of MFCs. Additionally, the anti-shock capacities of the biofilms in MFCs were evaluated by treating ofloxacin and enrofloxacin and operating at different temperature and salinity. These MFCs can remove 87.31% and 40.81% of ofloxacin and enrofloxacin in 72 h, respectively. Even exposed to a low temperature of 10 °C or a salinity of 3%, the MFCs can achieve greater than 50% and nearly 80% of ciprofloxacin removal efficiency, respectively. The enrichment of Alcaligenes and Chryseobacterium contributed mostly to the removal of quinolones antibiotics. This study provides scientific evidences for treating wastewater containing quinolones antibiotics using MFCs., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

High specific surface area activated carbon prepared from endocarp of Jerivá (Syagrus romanzoffiana) (ACJ) was used for ciprofloxacin (CIP) antibiotic removal from aqueous effluents. The activated carbon (AC) was characterized via scanning electron microscope, Fourier transform infrared spectroscopy, N 2 adsorption/desorption, and pH value at the zero-charge point. Avrami kinetic model was the one that best fit the experimental results in comparison to the pseudo-first-order and pseudo-second-order kinetic models. The equilibrium data obeyed the Liu isotherm equation, showing a maximum adsorption capacity of 335.8 mg g -1 at 40 °C. The calculated thermodynamic parameters indicate that the adsorption of CIP was spontaneous and endothermic at all studied temperatures. Also, the free enthalpy changes (∆H° = 3.34 kJ mol -1 ) suggested physical adsorption between CIP and ACJ. Simulated effluents were utilized to check the potential of the ACJ for wastewater purification. The highly efficient features enable the activated carbon prepared from endocarp of Jerivá, an attractive carbon adsorbent, to remove ciprofloxacin from wastewaters.

A tremendous effort has been made for the synthesis and multifunction of environmentally responsive and selective separation membranes. With the bioinspired design of polydopamine (pDA)-assisted inorganic film, we proposed a simple, yet efficient, thermo-responsive cell culture substrate. Herein, a Ag/TiO 2 /pDA-based nanocomposite structure was initially obtained, and the ciprofloxacin-imprinted membranes (MINCMs) with thermo-responsive recognition sites were then synthesized by using NIPAm as backbone monomer. The opto-thermally responsive molecularly imprinted membranes (OT-MIMs) were obtained through in situ reduction of HAuCl 4 on membrane surfaces, Au nanoparticles were used as the light-heat converters. The light-switching principle was elaborated as well as the energy conversions that took place in this system. These conformational changes finally allowed the constructions or destructions of ciprofloxacin-imprinted sites. Due to the formation of the opto-thermally responsive ciprofloxacin-imprinted sites, rapid adsorption dynamics and opto-thermally responsive perm-selectivity toward templates were both achieved. Therefore, 58.65 mg/g of adsorption capacity and 4.91 of permselectivity factor from OT-MIMs were successfully obtained. Importantly, the as-designed bioinspired strategy led to a state-of-the-art design that was capable of reversibly controlling the flow rate (J) of ciprofloxacin from 12.10 to 4.93 mg min -1  cm -2 in less than a few minutes using light., (Copyright © 2018 Elsevier Inc. All rights reserved.)

Fe 3 O 4 /HKUST-1 magnetic copper based metal-organic frameworks (MOF) were synthesized by a simple and facile method and applied as an effective and recyclable adsorbent for the adsorptive removal of two widely used ciprofloxacin (CIP) and norfloxacin (NOR) fluoroquinolone antibiotics (FQAs) from aqueous solutions. Fe 3 O 4 /HKUST-1 was thoroughly characterized, and the major influence factors including solution pH, adsorbent amount and salt concentration were investigated. Compared to the reported adsorbents, Fe 3 O 4 /HKUST-1 has a very high adsorption rate, and it is found that CIP and NOR could be removed within 30 min. Moreover, the maximum adsorption capacities of the magnetic composites toward CIP and NOR reached as high as 538 mg g -1 and 513 mg g -1 , respectively, much higher than those of most of the reported adsorbents for these two FQAs. The saturation magnetization value of Fe 3 O 4 /HKUST-1 was 44 emu g -1 , which was sufficient for the separation of the Fe 3 O 4 /HKUST-1adsorbent from the aqueous solution by the application of an external magnetic field. Additionally, this magnetic material showed a good reusability with the adsorption capability decreasing only slightly after reuse for ten cycles. These results indicated that the magnetic composites Fe 3 O 4 /HKUST-1 may be a promising adsorbent in the decontamination of FQAs from wastewater due to its high adsorption capability, fast kinetics, easy separation from water, and excellent recyclability. The adsorption mechanism was proposed based on the effects of pH on adsorption and on the zeta potential of the adsorbent. For the adsorption of CIP and NOR by Fe 3 O 4 /HKUST-1, both electrostatic and π-π interactions may be important., (Copyright © 2018 Elsevier Inc. All rights reserved.)

Extracellular polymeric substances (EPS) in microbial sludge, fulfils a key role in removal of micro-organic pollutants during biological wastewater treatment. In this study, the authors evaluated the removal of ciprofloxacin (CIP) by sulfate-reducing bacteria (SRB) sludge in a sulfate-reducing up-flow sludge bed (SRUSB) reactor, and examined the role of EPS on CIP removal in an SRB sludge system. The results indicated that CIP was removed efficiently through adsorption and biodegradation by SRB sludge, with adsorption the major removal pathway. EPS also played an important role in CIP adsorption by SRB sludge, and the adsorption mechanisms of CIP by EPS were investigated using the three-dimensional excitation-emission matrix fluorescence spectroscopy technologies combined with parallel factor analysis. The functional groups binding CIP onto EPS were identified through Fourier transform infrared (FTIR) spectra analysis. The results suggested that the static quenching of EPS following CIP adsorption led to formation of an EPS-CIP complex, and that the CIP was mainly bound with tryptophan and tyrosine-like protein substances in EPS with the binding constants of 1.43×10 4 L·mol -1 and 1.02×10 4 L·mol -1 , respectively. The FTIR results suggested that hydroxyl, amino and carboxyl functional groups were mainly responsible for binding of CIP onto EPS. The results revealed the adsorption mechanisms of CIP by EPS in SRB sludge, and enhanced understanding of the role of EPS in sulfur-mediated biological processes for the removal of CIP and other organic micro-pollutants.

A magnetic reed biochar (MBC) was fabricated through chemical coprecipitation first and subsequent pyrolysis of reed stalk powder precipitated with Fe 2+ /Fe 3+ at 873.15 K. The structure and properties of the MBC were characterized using SEM, BET, FTIR, and VSM. Adsorption experiments were carried out to investigate the adsorption behaviors and mechanisms of ciprofloxacin (CIP) and ofloxacin (OFL) onto the MBC. The MBC possessed roughness and pores within its structure and contained a large amount of oxygen-containing functional groups on the surface. The BET surface area of the MBC was 254.6 m 2 ·g -1 , and the total pore volume was 0.257 cm 3 ·g -1 , thus the MBC exhibited a relatively high porosity. The adsorption process was found to be pH and temperature dependent. The relative contributions of adsorbate species (cations, zwitterions, and anions) to overall adsorption varied for different pH values. Thermodynamic parameters indicated that the CIP and OFL adsorption onto MBC was a spontaneous, endothermic, and entropy-increasing process. Kinetics and isotherm data of CIP and OFL adsorption onto MBC were well depicted by the pseudo-second-order model and the Langmuir model. The equilibrium adsorption capacities of CIP and OFL onto MBC were 27.84 mg·g -1 and 22.00 mg·g -1 , respectively. Pore-filling effects, π-π interaction between electron donors and acceptors, hydrogen bonding formation, hydrophobic interaction, and electrostatic interaction may be important mechanisms for CIP and OFL adsorption onto the MBC.

Much of the deterioration of water resources is anthropogenically caused as a consequence of the incessant production of chemical compounds to obtain the quality of life that society demands today. This constant presence and harmful accumulation of these pollutants in different ecosystems have seen them emerge as a major concern both for human health and for environmental safety. Scientific advances have succeeded in legislating against, reducing and even eliminating priority pollutants, while new technologies are being constantly developed to identify and treat newly emerging pollutants. The objective of this work is the evaluation of the seawater reverse osmosis membrane as a method for the removal of an antibiotic present in seawater. The novelty of the study is that the tests were undertaken using water of high ionic strength. A critical selection of the antibiotic to be used in the study was carried out. The experiments were performed under constant pressure conditions, employing synthetic seawater in a pilot-scale unit with a commercial spiral-wound reverse osmosis membrane. Results are shown in terms of selectivity of the reverse osmosis process for antibiotic removal. The RO membrane element successfully reject most of the ciprofloxacin (removal rate >90%), with maximum rejection value of 99.96%., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

A procedure based on liquid-liquid extraction (LLE) and phase separation using magnetically stirred salt-induced high-temperature liquid-liquid extraction (PS-MSSI-HT-LLE) was developed to extract and pre-concentrate ciprofloxacin (CIPRO) and enrofloxacin (ENRO) from animal food samples before electroanalysis. Firstly, simple LLE was used to extract the fluoroquinolones (FQs) from animal food samples, in which dilution was performed to reduce interference effects to below a tolerable threshold. Then, adapted PS-MSSI-HT-LLE protocols allowed re-extraction and further pre-concentration of target analytes in the diluted acid samples for simultaneous electrochemical quantification at low concentration levels. To improve the peak separation, in simultaneous detection, a baseline-corrected second-order derivative approach was processed. These approaches allowed quantification of target FQs from animal food samples spiked at levels of 0.80 to 2.00 µmol L -1 in chicken meat, with recovery values always higher than 80.5%, as well as in milk samples spiked at 4.00 µmol L -1 , with recovery values close to 70.0%., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

The wide occurrence of antibiotics in groundwater has raised serious concerns due to their impacts on humans and the ecosystem. Most of the research in groundwater remediation focuses on the exploitation of nano-materials. However, nano-materials have several disadvantages such as high production cost, rapid reduction in permeability, disposal problems, and high sensitivity to environmental conditions. To solve these issues, novel sodium alginate/graphene oxide hydrogel beads (GSA) were synthesised and their effectiveness as permeable reactive barrier (PRB) backfill material in the remediation of ciprofloxacin (CPX)-contaminated groundwater was tested. The adsorption of CPX onto GSA followed the pseudo-second-order kinetic model. The isotherm data followed the Freundlich model. The maximum adsorption capacity was 100 mg g -1 at pH 7.0. The adsorption process was sensitive to contact time, initial CPX concentration and ionic strength. However, it was not pH sensitive. Hydrophobic interaction, electrostatic interaction, ion exchange, H-bonding, and pore filling were proposed to be the main adsorption mechanisms. The effects of flow rate, influent CPX concentration, and ionic strength on the performance of PRB were confirmed through flow-through column experiments and by using a chemical non-equilibrium two-site model. Accordingly, a proper PRB was designed based on hydrogeological conditions. Finally, the lifetime and cost of the PRBs were calculated. The results obtained provided concrete evidence that GSA is a promising adsorbent material for PRBs applications in the remediation of CPX-contaminated groundwater., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Salix psammophila (SP), a solid waste abundantly available, was applied as a precursor to prepare the activated carbon by chemical activation method using phosphoric acid (H 3 PO 4 ). Response surface methodology based on Box-Behnken design was used to optimize the prepared conditions of activated carbon. The effects of concentration of H 3 PO 4 , activation temperature and activation time on the adsorption performance (expressed by the adsorption capacity of ciprofloxacin hydrochloride (CIP) and norfloxacin (NOR)) were investigated. The optimum conditions were obtained using H 3 PO 4 concentration of 67.83%, activation temperature of 567.44 °C and activation time of 86.61 min. The optimum activated carbon (SPAC) was characterized with scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDS), Brunauer-Emmett-Teller (BET) and Fourier transform infrared spectroscopy (FTIR). The adsorption behavior of CIP and NOR on SPAC was carried out and the mechanisms for the adsorption process were proposed. The equilibrium data were fitted by the Freundlich and Langmuir isotherm models, which resulted in 251.9 mg/g and 366.9 mg/g of the maximum monolayer adsorption for CIP and NOR at 25 °C, respectively. The best fitted kinetic model was pseudo-second-order, implying that chemisorption dominated in the adsorption process. This study indicated that activated carbon based on Salix psammophila (SPAC) was an excellent adsorbent for removing fluoroquinolone antibiotics from aqueous solutions.

Ciprofloxacin has been determined with high frequency in studies involving environmental waters matrixes. However, no study evaluating the correlation between the initial pH and molar iron/organic ligand ratio has been published. This paper describes the degradation of the antibiotic ciprofloxacin by the photo-Fenton process using different sources of iron (Fe 2+ , Fe 3+ and Fe 3+ -citrate and Fe 3+ -oxalate, named FeCit and FeOx, respectively) and molar iron/organic ligand ratios at initial pH values of 2.5 and 6.5. The best results at initial pH 2.5 were achieved using FeCit and FeOx at molar iron/organic ligand ratios of 1:1 and 1:3 respectively, when the ciprofloxacin concentration reached values below the quantitation limit of the HPLC after 20 min of treatment. However, at initial pH 6.5, improvements in the results (15% for FeCit, and 46% for FeOx) were achieved by increasing the molar iron/organic ligand ratios to 1:4 (FeCit) and 1:9 (FeOx), respectively. Three transformation products, (C 17 H 19 FN 3 O 4 , m/z 348; C 17 H 21 FN 3 O 5 , m/z 366; and C 13 H 12 FN 2 O 3 , m/z 263) of ciprofloxacin degradation were identified, one of them not yet being reported in the literature (C 17 H 21 FN 3 O 5 , m/z 366). Their formation and degradation was monitored and the initial steps of their formation and degradation were proposed. The results show that the piperazine ring is more susceptible to hydroxyl radical attack than the quinolone ring, which persists in the intermediates identified. Therefore, this process can be a good alternative for the treatment of this type of pollutant at near-neutral conditions., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

In this study, the heterogeneous Fenton oxidation of ciprofloxacin (CIP) in an aqueous solution was examined over the nano-sized magnetite (Fe 3 O 4 ) as a catalyst supplied through high-energy planetary ball milling process. To characterize the magnetite samples after and before ball milling operation, the X-ray diffraction (XRD), High-resolution scanning electron microscopy (HR-SEM), energy-dispersive X-ray spectroscopy (EDX), Brunauer-Emmett-Teller (BET) and Fourier transform infrared spectroscopy (FTIR) analysis were applied. The catalytic properties of the magnetite were considerably improved because of the enhancement in its physical properties, resulted from milling process. The findings also indicated that 6 h ball-milled magnetite demonstrated better properties for elimination of CIP of about 89% following 120 min reaction at optimal conditions of H 2 O 2 12 mM, Fe 3 O 4 1.75 g L -1 , CIP 10 mg L -1 and pH 3.0. The effects of various operational parameters, including the initial pH of the solution, H 2 O 2 initial concentration, catalyst dosage, milling time and CIP initial concentration was investigated. Application of organic and inorganic scavengers considerably decreased the CIP removal efficiency. Correspondingly, with respect to the leached iron values at pH 3, it was concluded that CIP elimination was mainly occurred through heterogeneous Fenton procedure. This process included the adsorption and oxidation phases in which the hydroxyl radicals (OH) played a significant role. GC-MS analysis was used for recording of the generated intermediates of the CIP removal in the course of heterogeneous Fenton process., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Pycnoporus sanguineus could remove 98.5% ciprofloxacin (CIP), 96.4% norfloxacin (NOR), 100% sulfamethoxazole (SMX), and 100% their mixture through biotransformation within 2 d, while Phanerochaete chrysosporium could only remove 64.5% CIP, 73.2% NOR, and 63.3% SMX through biosorption and biotransformation within 8 d, respectively. The efficiencies of antibiotic bioremoval under co-culture were more than that under the pure culture of P. chrysosporium but less than that under the pure culture of P. sanguineus. However, only 2% CIP and 3% NOR under co-culture were detected in the mycelia. In vitro enzymatic degradation and in vivo cytochrome P450 inhibition experiments revealed that laccase and cytochrome P450 could play roles in the removal of above all antibiotics, while manganese peroxidase could only play role in SMX removal. Transformation products of CIP and NOR under the pure culture of P. chrysosporium could be assigned to three different reaction pathways: (i) defluorination or dehydration, (ii) decarboxylation, and (iii) oxidation of the piperazinyl substituent. Additionally, other pathways, (iv) monohydroxylation, and (v) demethylation or deethylation at position N 1 also occurred under the co-culture and pure culture of P. sanguineus. Antibacterial activity of antibiotics could be eliminated after treatments with pure and co-culture of P. chrysosporium and P. sanguineus. The cytotoxicity of the metabolites of SMX and NOR under co-culture was lower than that under the pure culture of P. sanguineus, indicating co-culture is a more environmentally friendly strategy to eliminate SMX and NOR., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

As a demonstration of an alternative to the challenges faced with batch pharmaceutical manufacturing including the large production footprint and lengthy time-scale, we previously reported a refrigerator-sized continuous flow system for the on-demand production of essential medicines. Building on this technology, herein we report a second-generation, reconfigurable and 25 % smaller (by volume) continuous flow pharmaceutical manufacturing platform featuring advances in reaction and purification equipment. Consisting of two compact [0.7 (L)×0.5 (D)×1.3 m (H)] stand-alone units for synthesis and purification/formulation processes, the capabilities of this automated system are demonstrated with the synthesis of nicardipine hydrochloride and the production of concentrated liquid doses of ciprofloxacin hydrochloride, neostigmine methylsulfate and rufinamide that meet US Pharmacopeia standards., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A membrane bioreactor (MBR) was used to treat ciprofloxacin (CIP)-contaminated artificial wastewater. The pollutant removal performance and the microbial community structure of the MBR were studied at three different CIP dosages (0 mg·L -1 , 5 mg·L -1 , and 10 mg·L -1 ). The results showed that the sludge concentration in the reactor decreased and then levelled off as the dosage of CIP was increased from 0 mg·L -1 to 5 mg·L -1 and further to 10 mg·L -1 . The mean removal of TOC and COD decreased from 98.40% and 97.80% to 84.20% and 94.10%, respectively, indicating that the CIP negatively influenced the organic removal but the effect was minor. In contrast, the ammonium removal was greatly influenced by the dosage of CIP. When the CIP dosage increased from 0 mg·L -1 to 5 mg·L -1 and further to 10 mg·L -1 , the ammonium removal efficiency decreased from 96.91% to 84.14% and then to 77.80%, and the activity of Nitrosomonas , Alcaligenes , Nitrospira , and Nitrobacter were greatly inhibited. The CIP removal initially increased and then decreased. The mass balance revealed that the removal of CIP in the MBR was principally attributed to biodegradation and sludge adsorption, which accounted for 30.13% and 0.25%, respectively, at a CIP dosage of 5 mg·L -1 and 7.55% and 1.81% at a CIP dosage of 10 mg·L -1 .

Ciprofloxacin (CIP) is one of most used quinolone antibiotics detected frequently in agricultural soils and vegetables. In the present study, variations in microbial community and CIP removal in rhizospheric soils between two cultivars of Brassica parachinensis L. that accumulate higher and lower CIP (Sijiu and Cutai, respectively) were investigated under CIP stress (0mg/kg in CK, 2.94mg/kg in T1, and 67.11mg/kg in T2). The removal rates of CIP in rhizospheric soils of cultivar Sijiu were higher than those of cultivar Cutai, with a significant difference in T2 (48.7%>39.4%, P<0.05). The pyrosequencing of 16S rRNA and ITS gene indicated that the microbial diversity and community structure in rhizospheric soils of the two cultivars varied significantly. Spirochaeta and Trichosporon might be associated with CIP degradation, and higher relative abundances of Trichosporon in rhizoshperic soils of cultivar Sijiu might be responsible for higher CIP removal. Fourteen bacterial genera and ten fungal genera were screened as potential biomarkers for CIP removal process. The community level physiological profiling in rhizospheric soils of the two cultivars under CIP stress differed significantly, and more C substrates that favored CIP removal were observed in rhizoshperic soils of cultivar Sijiu. Our results demonstrate that variations in microbial community and the utilization of C substrates played important roles in differring the CIP removal in rhizospheric soils between the two cultivars., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Adsorption ceramsite (SKC) was prepared with biochar (BC) derived from municipal sludge and kaolin (KL) based on the optimized processing parameters to adsorb ciprofloxacin (CIP) in aqueous solutions. The CIP adsorption mechanism of SKC was investigated by adsorption kinetics and isotherm adsorption models, combined with the analysis of microstructure, pore structure, phase composition, and zeta potential. Furthermore, the heavy metal leaching toxicity was assessed using the toxicity characteristic leaching procedure (TCLP) method. The results showed that SKC, with 60% BC and 40% KL calcining at 1,050℃ for 5 min, showed an outstanding removal efficiency of CIP (65.34%). The pseudo-second-order equation agreed with the adsorption behavior and the Freundlich model described the adsorption process well. The adsorption process was a multilayer adsorption controlled by physical and chemical reactions. The leaching concentration of heavy metals, trapped by the mineral phases in SKC was much lower than that in BC, indicating low ecotoxicological risk. SKC possessed the ability to adsorb CIP with its developed porosity and characteristic mineralogical phases, including silicon aluminum oxide and iron oxide. This work provides a low-cost recyclable sorbing material to remove high concentration CIP from wastewater and offers a new idea for the large-scale safe use of BC.

Solid-phase microextraction with polysulfone and molecularly imprinted polymers as coating on nickel foam were used to adsorb and enrich floxacin drugs. The preparation method is simple and reproducible to obtain the materials with controlled thickness. After evaluation by scanning electron microscope and various adsorption experiments, the materials were used to adsorb analytes in water samples and biological samples. Coupling with chromatographic analysis, the method recoveries are satisfactory with 90.0-104.8% and 79.31-107.1% for water and biological samples. The method repeatability by intra- and interday experiments shows that the RSD values for water and biological samples were 1.0-9.9% and 1.7-10.3%, with the quantitative limits of three floxacin drugs as 3.0-6.2 μg L -1 . Graphical Abstract Preparation diagram of polysulfone material.

Purpose of this study is to report the synthetic procedure of a novel photo catalyst, nano zinc oxide incorporated graphene oxide/nanocellulose (ZnO-GO/NC) for the effective adsorption and subsequent photo degradation of ciprofloxacin (CF), an antibiotic widely used in the poultry. Self cleaning property in cellulose was achieved by introducing a nano zinc oxide incorporated graphene oxide into nanocellulose (NC) matrix. By incorporating nano zinc oxide (ZnO) in graphene oxide (GO), band gap could be tuned to 2.4eV and after the composite formation with NC, the band gap was enhanced to 2.8eV which is in the visible region. Thus the degradation of the CF was achieved under the visible light. Photo degradation was due to electron hole interaction. The step wise modification in the synthesis ZnO-GO/NC was characterized using FT-IR, XRD, SEM, EDS, AFM, DRS-UV and BET N 2 adsorption isotherm techniques. The values of surface area, pore volume and pore radius were found to be 12.68m 2 /g, 0.026mL/g and 12.5nm, respectively. Efficiency in the adsorption process of CF onto ZnO-GO/NC was verified by batch adsorption technique. The optimum pH was found to be 5.5 and dose of the ZnO-GO/NC was optimized as 2.0g/L. Equilibrium was attained at 120min and the adsorption of drug followed second-order kinetics. Sips isotherm was the best fitted model and could explain the nature of interaction of CF with ZnO-GO/NC. The studies revealed that the degradation followed first-order kinetics and the optimum pH for the degradation process was found to be 6.0 and achieved a maximum degradation efficiency of 98.0%. The reusability of ZnO-GO/NC after five consecutive cycles indicated it to be a potential candidate for the removal and degradation of CF from aquatic environment., (Copyright © 2016 Elsevier Inc. All rights reserved.)