A new magnetic adsorbent of eggshell-zeolitic imidazolate framework for highly efficient removal of norfloxacin.

Many effluents contain various antibiotics commonly, where the simultaneous removal of them is a big challenge. In this study, the magnetic biocomposite (eggshell-zeolitic imidazolate framework) was designed and synthesized by green and facile method. Zeolitic imidazolate framework-8 (ZIF-8) particles were stabilized on the surface of magnetic eggshell (Fe3O4-ES), generating a new Fe3O4-ES/ZIF-8 adsorbent, which was also fully characterized using FTIR, XRD, SEM and BET techniques. Thereafter, norfloxacin (NOR) adsorption processes were investigated through different influencing factors (dosage, concentration, pH and temperature). The Langmuir adsorption isotherm could confirm a maximum removal efficiency of 80.13% for NOR. Kinetic studies illustrated that the pseudo-first-order model was in line with the experimental data of the simultaneous removal of NOR. Moreover, the magnetic nature of the adsorbent caused an easy separation from the aqueous solution.

Rapid and selective extraction of norfloxacin from milk using magnetic molecular imprinting polymers nanoparticles.

The magnetic molecular imprinting polymers nanoparticles (MMIPs NPs) for the extraction of norfloxacin (NOR) were prepared by self-polymerization of dopamine onto the surface of (3-Aminopropyl)triethoxysilane (APTES)-modified Fe3O4 NPs. The MMIPs NPs were characterized by FT-IR spectroscopy, XRD, VSM and TEM. The characterization results show that the MMIPs NPs possess superparamagnetic characteristic with the saturated magnetization value of 38.6 emu/g, and the average particle size of about 14.3 nm. Furthermore, the adsorption performance of the MMIPs NPs was evaluated by the static, dynamic, selective adsorption and reusability experiments. The adsorption capacity of MMINs NPs for NOR is 14.2 mg/g with an imprinted factor of 2.1. About 82.4-102.4% of the added NOR (20, 40, 60 µg/mL) were recovered from fortified milk samples with MMIPs NPs as sorbent. Moreover, the MMIPs NPs can be reused for at least six times.

Preparation of porous magnetic molecularly imprinted polymers for fast and specifically extracting trace norfloxacin residue in pork liver.

Here, magnetic molecularly imprinted polymers were designed for norfloxacin via oil-in-water emulsifier-free emulsion method. It was prepared by simply mixing norfloxacin, methacrylic acid-co-ethylene glycol dimethacrylate copolymer, and Fe3 O4 together at room temperature. Characterized by multiple analytical tools, the particle size, pore size, pore volume, specific surface area, and saturation magnetization of the product were about 30 µm, 10-500 nm, 2.92 mL/g, 105.84 m2 /g, and 3.052 emu/g, respectively. And the adsorption capacity was high at 27.04 mg/g towards norfloxacin. Combined with ultra high performance liquid chromatography, it was used to determine norfloxacin in real samples. Average recoveries were above 77.44% with relative standard deviations between 1.21 and 6.85% at three spiked levels (n = 3) for lake water and pork liver. The determination was achieved for the most complex biosample pork liver spiked with norfloxacin low to 30 ng/g, about 100 times less than the maximum residue limit regulated by Commission of the European Communities. All evidences demonstrated that the magnetic molecularly imprinted polymers can be used in practice for monitoring norfloxacin either in environmental water or meat product with high accuracy and reliability.

Development of doubly porous composite adsorbent for the extraction of fluoroquinolones from food samples.

A doubly porous microcomposite polyaniline/graphene oxide/octadecyl-bonded silica magnetite (PANI/GOx/C18-SiO2-Fe3O4) alginate adsorbent was developed and employed to extract fluoroquinolones. The Fe3O4 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-SiO2-Fe3O4 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.

Virulence genes contributing to Aeromonas hydrophila pathogenicity in Oreochromis niloticus

Bacterial diseases are the main cause of high economic loss in aquaculture, particularly gram-negative bacteria. This study was conducted for the isolation and identification of Aeromonas and Pseudomonas spp. from diseased fish. Twenty-two Aeromonas and sixteen Pseudomonas isolates were recovered from diseased Nile tilapia (Oreochromis niloticus) raised in eight earthen ponds in Elhox, Metoubes, Kafrelsheikh, Egypt. The recovered isolates were further identified using PCR as 22 Aeromonas hydrophila, 11 Pseudomonas aeruginosa, and 5 Pseudomonas fluorescens isolates. The 22 A. hydrophila isolates were screened for the presence of four virulence genes. Sixteen of the isolates (72.72%) were positive for the aerolysin gene (aer); 4 (18.18%) harbored the cytotoxic enterotoxin gene (act); and 2 (9.09%) carried the hemolysin A gene (hylA) while the cytotonic heat-stable enterotoxin gene (ast) was absent from all the tested isolates. The pathogenicity test indicated the direct relationship between the mortality percentage and the genotype of the tested A. hydrophila isolates as the mortality rates were 63.3 and 73.3% for isolates with two virulence genes (aer+ & act+, and aer+ and hylA+, respectively), followed by 40, 53.3, and 56.6% for isolates with only one virulence gene (hylA, act, and aer, respectively) and 20% for isolates lacking virulence genes. Based on the sensitivity test, the multi-antibiotic resistance profiles were as follows: 90.9% of the A. hydrophila isolates were sensitive to florfenicol and doxycycline; then 68.18% were susceptible to oxytetracycline, norfloxacin, and ciprofloxacin; and 63.63% were susceptible to sulfamethoxazole-trimethoprim, while only 27.27 and 4.5% were sensitive to erythromycin and cephradine, respectively, and all the isolates were resistant to amoxicillin and ampicillin

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Synergistic effects of anionic surfactants on adsorption of norfloxacin by magnetic biochar derived from furfural residue.

Norfloxacin (NOR) is a persistent organic pollutant and can be effectively removed from effluent by adsorption of biochar. However, the presence of other emerging contaminants, such as surfactants, will potentially alter adsorption performance of norfloxacin by biochar and the molecular-scale mechanisms of the interaction between surfactants and biochar remain poorly understood. In this study, adsorption of norfloxacin on magnetic biochar prepared with iron-containing furfural residue (FRMB) in the presence or absence of anionic surfactants was investigated. The adsorption of NOR was significantly affected by the initial pH and anionic surfactants-sodium dodecyl sulfate (SDS) and sodium dodecyl benzene sulfonate (SDBS). In the presence of SDS and SDBS, the maximum sorption capacities of NOR were 2.33 and 1.97 times higher than that in the absence of surfactants, reached to 698.6 mg g-1 and 589.9 mg g-1, respectively. The optimal pH condition which was 4 indicated that electrostatic adsorption played a decisive role in the adsorption process after introduction of SDS/SDBS. The adsorption data were fitted well by the Elovich model and Freundlich model at the optimal conditions in which both SDS and SDBS were hemimicelle (0.8 mM SDS or 0.4 mM SDBS), indicating surface heterogeneity of FRMB and the adsorption mechanism was related to the assembly of surfactants on biochar. FTIR results showed that FRMB and SDS/SDBS interacted through hydrophobic action, and more complex or aggregates were formed between the NOR and biochar/SDS/SDBS. This work highlights the synergistic enhancement effects of tested surfactants on the removal of NOR by magnetic biochar from aqueous systems.

Construction of M-BiVO4/T-BiVO4 isotype heterojunction for enhanced photocatalytic degradation of Norfloxacine and Oxygen evolution reaction.

To conquer the issues of poor compatibility, confined intimate contact and limited improvement of charge anti-recombination process of a traditional heterojunction formed by interfacing of two different semiconductors, a simplistic strategy has been espoused for the fabrication of isotype heterojunction flanked with two dissimilar crystal phases of a single semiconducting material. Herein, we account the fabrication of an in-situ formed M-BiVO4/T-BiVO4 (MT-BiVO4) isotype heterojunction by a simple co-precipitation method followed by altering the calcinations temperatures. The physico-chemical properties of the fabricated MT-BiVO4 isotype hetrojunctions were analyzed by using X-ray diffraction (XRD), Field emission scanning electron microscopy (FESEM), Transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and UV-Visible Diffuse reflectance spectroscopy (UV-Vis DRS) techniques. The FESEM image of MT-BiVO4 photodeposited by Au and MnOx particles was provided strong evidence for the spatial separation of photogenerated charge carriers between M and T phase of BiVO4 in an isotype heterojunction. The interfacing of T-BiVO4 with M-BiVO4 in an isotype heterojunction affords the well-built close contact between them was confirmed by the High resolution transmission electron microscopy (HRTEM) analysis. The photocatalytic reactions of all the prepared MT-BiVO4 isotype heterojunctions were examined by monitoring the degradation of Norfloxacine and oxygen evolution reaction under visible light irradiation. The optimized 65% MT-BiVO4 isotype heterojunction discloses higher photocatalytic activity around 91% of Norfloxacine degradation in 150 min and 808 µmol of O2 evolution in 2 h under visible light irradiation. On the other hand, the photoelectrochemical measurements reveals that the optimized 65% MT-BiVO4 isotype heterojunction exhibits superior photocurrent i.e. 584 µA/cm2 which is approximately 5.1 and 25.3 times higher than the neat T-BiVO4 and M-BiVO4, and these results are well consistent with the photocatalytic activities. The higher PEC and photocatalytic activities are due to the well-built close contact, superior compatibility and matching band structure between T-BiVO4 and M-BiVO4, which provides strapping driving force for the efficient enhancement of charge separation process. The Electrochemical impedance spectroscopy (EIS), photoluminescence (PL), photoelectrochemical (PEC) and bode analysis confirms the effectual diminish of charge recombination process in MT-BiVO4 isotype heterojunction relative to the neat materials. The chronoamperometric analysis authenticated that the isotype heterojunctions are more stable than the neat materials.

Enteromorpha prolifera-derived Fe3C/C composite as advanced catalyst for hydroxyl radical generation and efficient removal for organic dye and antibiotic.

Enteromorpha prolifera-derived Fe3C/C composite has been fabricated through a facile one-step calcination method. As an advanced Fenton-like catalyst, the obtained Fe3C/C composite displayed high catalytic reactivity to generate hydroxyl radicals. It is worth to note that the removal rate of methylene blue (MB) could effectively reach 100% in a wide pH range (pH = 2˜12) and the maximum degradation capacity of the composite is 660 mg/g. The stability and reusability of Fe3C/C composite catalyst have also been tested, which could remain the removal rate at 100% after 6 consecutive runs. To illustrate the practical application possibility, the Fe3C/C composite catalyst was used for degradation of papermaking and dyeing waste water, which could reduce the COD (chemical oxygen demand) value to less than 50. Additionally, the antibiotic norfloxacin (NOR) could also be catalytically removed by the Fe3C/C composite and the possible removal pathway has also been proposed. The excellent removal performance of Fe3C/C composite for MB and NOR may be attributed to the synergistic effect between porous carbon adsorption and Fe3C catalysis. This study not only provides novel insights into recycling of waste biomass, but also paves a new way for the application of Fe3C/C in dyes and antibiotics waste water treatment areas.

Chitosan-based sorbent for efficient removal and extraction of ciprofloxacin and norfloxacin from aqueous solutions.

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 m2.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.

[Evaluation of Performance of an Aminated Rosin-based Resin for Adsorption of Norfloxacin from Aqueous Solutions].

An aminated rosin-based resin (ARBR) was synthesized as a novel environmentally-friendly adsorbent for removal of Norfloxacin (NOR) from aqueous solutions. Its features were characterized by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and surface area measurements (BET). The effects of resin dosage, pH, and ionic strength on the ARBR adsorption properties of NOR were investigated by batch experiments. Results showed that the NOR adsorption amounts increased with pH in the range from 2.0 to 6.0, but decreased at higher pH (8-10). The adsorption process of NOR followed a pseudo-second rate model and could be fitted to the Langmuir isotherm, with calculated maximum monolayer adsorption capacity of 30.29 mg·g-1 at pH 6.0 and 20℃. Thermodynamic calculations showed that the adsorption of NOR was a spontaneous and endothermic process and could be attributed to a combination of electrostatic interactions and hydrogen bonding. Furthermore, the adsorbed NOR on ARBR could be efficiently desorbed by 0.1 mol·L-1 HCl to regenerate the resin. After five adsorption-desorption recycles, ARBR had a stable adsorption performance and could be recycled. The adsorption performance is better than that of various commercial resins, and these research results contribute to the development of applications of rosin derivatives and their utilization in the environmental control of micro pollutants.

Optimization of process conditions for preparation of activated carbon from waste Salix psammophila and its adsorption behavior on fluoroquinolone antibiotics.

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 (H3PO4). Response surface methodology based on Box-Behnken design was used to optimize the prepared conditions of activated carbon. The effects of concentration of H3PO4, 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 H3PO4 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.

Magnetic copper-based metal organic framework as an effective and recyclable adsorbent for removal of two fluoroquinolone antibiotics from aqueous solutions.

Fe3O4/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. Fe3O4/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, Fe3O4/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 Fe3O4/HKUST-1 was 44 emu g-1, which was sufficient for the separation of the Fe3O4/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 Fe3O4/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 Fe3O4/HKUST-1, both electrostatic and π-π interactions may be important.

QbD approach by computer aided design and response surface methodology for molecularly imprinted polymer based on magnetic halloysite nanotubes for extraction of norfloxacin from real samples.

This article describes the development, optimization, and evaluation of a novel composite imprinted polymer, on the basis of magnetic halloysite nanotubes (MHNTs-MIPs) using "Quality by Design (QbD)" approach combining computer simulation and response surface methodology. Norfloxacin, methacrylic acid, and ethylene glycol dimethacrylate were used as template, functional monomer and cross-linker, respectively. As a comparison, two MHNTs-MIPs have been prepared with the most suitable functional monomer methacrylic acid (MAA) along with acrylamide (AM). To explain the adsorption behavior, adsorption kinetics and isotherms were studied. Magnetic halloysite nanotubes molecularly imprinted polymers prepared from MAA (MHNTs-MIP1) displayed a high adsorption capacity (349 µg mg-1) toward NOR. A magnetic imprinting solid phase extraction method coupled with high performance liquid chromatography (MHNTs-MISPE-HPLC-UV) was developed for the determination of NOR in serum and water samples, by applying MHNTs-MIP as a sorbent. The recoveries from 83.76% to 103.30% in water and from 90.46% to 99.78% in serum were obtained. Besides remarquable mechanical properties and specific recognition of MHNTs-MIP toward template molecule. It could be also collected and separated fastly by external magnetic field. Moreover, MHNTs-MIPs could be reused for several cycles with the recovery range from 83.25% to 100.96% for water sample and from 85.65% to 100.33% for serum sample. These analytical results of serum and water samples showed that the proposed method based on MHNTs-MIPs is applicable for fast and selective extraction of therapeutic agents from biological fluids and environmental water.

Removal of norfloxacin in deionized, municipal water and urine using rice (Oryza sativa) and coffee (Coffea arabica) husk wastes as natural adsorbents.

The removal of the widely used antibiotic norfloxacin (NOR), the presence of which has been reported in natural water, was evaluated using rice (RH) and coffee (CH) husk wastes as adsorbents. Low particle sizes and natural pH in distilled water favored NOR elimination in both materials. In order to investigate the type of adsorption, the data was adjusted to the Langmuir, Freundlich and Redlich-Peterson isotherms. The best fit for the Langmuir and Redlich-Peterson isotherms suggested a monolayer-type adsorption model. Kinetic models of pseudo first and second order were also evaluated, the latter being the most suitable to represent the NOR adsorption phenomenon. Meanwhile, the intraparticle diffusion model indicated that the adsorption of NOR occurs both at the surface and within the pores of the material. Studies performed on thermodynamic aspects such as activation energy (Ea), enthalpy change (ΔH˚) and Gibbs free energy change (ΔG˚) suggest that the physisorption of the pollutant takes place through a spontaneous endothermic process. Additionally, PZC determination, Boehm method, chemical composition, thermodynamic analysis, and FTIR spectra before and after the adsorption of the antibiotic suggest that in CH adsorbents this occurred mainly through electrostatic interactions, while in RH hydrogen bonds also contributed significantly. Finally, the efficiency of natural adsorbents for the removal of NOR was evaluated in synthetic matrices of municipal wastewater and urine, and promising results were obtained despite the complexity of these matrices. The results presented in this work show the potential application of RH and CH residues as a low-cost alternative for the removal of NOR even in complex matrices. However, despite the similarities between the materials, CH waste showed better properties for the removal of the tested NOR due to its higher surface area, lower PZC and higher number of acid groups.

Simultaneous removal of ciprofloxacin, norfloxacin, sulfamethoxazole by co-producing oxidative enzymes system of Phanerochaete chrysosporium and Pycnoporus sanguineus.

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 N1 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.

Elimination of the antibiotic norfloxacin in municipal wastewater, urine and seawater by electrochemical oxidation on IrO2 anodes.

The electrochemical degradation of the fluoroquinolone antibiotic norfloxacin (NOR) on Ti/IrO2 anodes, in several aqueous matrices was evaluated. For this purpose, initially the performance and degradation routes of the technology at several pH values (3.0, 6.5, 7.5 and 9.0) and in the presence of some of the most common anions in real water matrices (Cl-, HCO3-, SO42- and NO3-) were determined. The results showed that the degradation of NOR can occur through both direct elimination at the electrode surface and mediated oxidation, via the electrogeneration of oxidative agents, such as active chlorine species and percarbonate ions, which come from chloride and bicarbonate oxidation, respectively. Conversely, nitrate ions showed to inhibit the efficiency of the system. Concerning the pH, the efficiency of the process in the presence of chloride ions followed the order: 9.0>7.5>6.5>3.0; showing a strong dependence of the NOR speciation, and being the anionic form of the antibiotic the more susceptible to be oxidized. Furthermore, the identification of three primary NOR by-products demonstrated that the initial attack of the active chlorine species, mainly HOCl, occurred at the secondary amine of the piperazine ring followed by chlorination of the benzene ring. The precedent findings were crucial to understand the efficiency of the technology to eliminate NOR in synthetic complex matrices such as seawater, municipal wastewater and urine. The electrochemical oxidation showed to be promissory to eliminate NOR, and its associated antimicrobial activity, in such complexes matrices. Waters at basic pH containing chloride or bicarbonate ions, such as seawater or municipal wastewater showed to be the most adapted to the application of the technology. Additionally, nitrate ions or urea, found in some matrices like fresh urine, reduce the efficiency of the process.

Performance of aerobic granular sludge in a sequencing batch bioreactor exposed to ofloxacin, norfloxacin and ciprofloxacin.

A granular sludge sequencing batch reactor (SBR) was operated for 340 days for treating a synthetic wastewater containing fluoroquinolones (FQs), namely ofloxacin, norfloxacin and ciprofloxacin. The SBR was intermittently fed with FQs, at concentrations of 9 and 32 µM. No evidence of FQ biodegradation was observed but the pharmaceutical compounds adsorbed to the aerobic granular sludge, being gradually released into the medium in successive cycles after stopping the FQ feeding. Overall COD removal was not affected during the shock loadings. Activity of ammonia oxidizing bacteria and nitrite oxidizing bacteria did not seem to be inhibited by the presence of FQs (maximum of 0.03 and 0.01 mM for ammonium and nitrite in the effluent, respectively). However, during the FQs feeding, nitrate accumulation up to 1.7 mM was observed at the effluent suggesting that denitrification was inhibited. The activity of phosphate accumulating organisms was affected, as indicated by the decrease of P removal capacity during the aerobic phase. Exposure to the FQs also promoted disintegration of the granules leading to an increase of the effluent solid content, nevertheless the solid content at the bioreactor effluent returned to normal levels within ca. 1 month after removing the FQs in the feed allowing recovery of the bedvolume. Denaturing gradient gel electrophoresis revealed a dynamic bacterial community with gradual changes due to FQs exposure. Bacterial isolates retrieved from the granules predominantly belonged to α- and γ-branch of the Proteobacteria phylum. The capacity of the system to return to its initial conditions after withdrawal of the FQ compounds in the inlet stream, reinforced its robustness to deal with wastewaters containing organic pollutants.

Phase distribution and removal of pharmaceuticals and personal care products during anaerobic sludge digestion.

The fate and removal of 48 pharmaceuticals and personal care products (PPCPs) during anaerobic digestion of sewage sludge were investigated in four full-scale sewage treatment plants (STPs). We measured concentrations in both the liquid and solid phases of the sludge to compare the distribution ratios (Kd) between phases before and after digestion. The results showed changes in Kd values of PPCPs with carboxyl or amino functional groups, probably due to a shift of dissociation equilibrium with the increase in pH. Sulfamethoxazole and trimethoprim were almost completely degraded (>90%); triclosan, triclocarban, and ofloxacin were moderately degraded (around 30-50%); but carbamazepine was not eliminated. To our knowledge, this is the first report that shows (i) the occurrence and removal of several tens of PPCPs by anaerobic sludge digestion in full-scale municipal STPs and (ii) the change of distribution between the liquid and solid phases during digestion.

Detection of norfloxacin and monitoring its effect on caffeine catabolism in urine samples.

A multi-walled carbon nano tube (MWCNT) modified pyrolytic graphite (MPG) electrode is prepared and applied to detect norfloxacin (NFX) based on its electrochemical reduction. The experimental parameters affecting the NFX determination were optimized in terms of MWCNT amount, pH, reaction time, and square wave frequency. The dynamic range for the NFX analysis ranged between 1.2 and 1000µM with a detection limit of 40.6±3.3nM. The effect of NFX on the catabolism of caffeine has been studied by determining its concentration in the urine samples after the prolonged administration of NFX using the MPG electrode. The results show that the catabolism of caffeine is inhibited by ~65% after five days of NFX administration, consequently the caffeine concentration in the urine sample is increased, which is reflected in terms of ~2.5 times increase in the peak current of caffeine. The determinations of NFX and caffeine were selective and the method was successfully applied in biological fluids and pharmaceutical tablets for the test compound analysis. In future this method can be useful for the selective determination of NFX and studying its effect on caffeine catabolism.

Preparation of graphene/TiO2 composites by nonionic surfactant strategy and their simulated sunlight and visible light photocatalytic activity towards representative aqueous POPs degradation.

A series of graphene/TiO2 composites were fabricated using a single-step nonionic surfactant strategy combined with the solvothermal treatment technique. Their phase structure, morphology, porosity, optical absorption property, as well as composition and structure, were characterized. The as-prepared composites were successfully applied to degrade aqueous persistent organic pollutants (POPs) such as rhodamine B, aldicarb, and norfloxacin in simulated sunlight (λ>320 nm) and visible light (λ>400 nm) irradiation. The degradation mechanism and kinetics of aqueous POPs were studied in detail. The mineralization of aqueous POPs and the recyclability of the composites were also tested in the same condition.