Ciprofloxacin Removal via Acid-Modified Red Mud: Optimizing the Process, Analyzing the Adsorption Features, and Exploring the Underlying Mechanism.

In this study, RM (red mud) was acidified with sulfuric acid, and the acidified ARM (acidified red mud) was utilized as an innovative adsorption material for treating antibiotic-containing wastewater. The adsorption conditions, kinetics, isotherms, thermodynamics, and mechanism of ARM for CIP (ciprofloxacin) were investigated. The characterization of the ARM involved techniques such as scanning electron microscopy (SEM), transmission electron microscopy (TEM), Brunauer-Emmett-Teller (BET), X-ray diffraction (XRD), X-ray fluorescence (XRF), thermogravimetric analysis (TGA), and NH3-TPD analysis. Adsorption studies employed a response surface methodology (RSM) for the experimental design. The results showed that ARM can absorb CIP effectively. The RSM optimal experiment indicated that the most significant model terms influencing adsorption capacity were solution pH, CIP initial concentration, and ARM dosage, under which the predicted maximum adsorption capacity achieved 7.30 mg/g. The adsorption kinetics adhered to a pseudo-second-order model, while equilibrium data fitted the Langmuir-Freundlich isotherm, yielding maximum capacity values of 7.35 mg/g. The adsorption process occurred spontaneously and absorbed heat, evidenced by ΔGθ values between -83.05 and -91.50 kJ/mol, ΔSθ at 281.6 J/mol/K, and ΔHθ at 0.86 kJ/mol. Analysis using attenuated total reflection Fourier-transform infrared spectroscopy (ATR-FTIR) indicated a complex reaction between the Al-O in the ARM and the ester group -COO in CIP. The C=O bond in CIP was likely to undergo a slight electrostatic interaction or be bound to the internal spherical surface of the ARM. The findings indicate that ARM is a promising and efficient adsorbent for CIP removal from wastewater.

Efficient Degradation of Ciprofloxacin in Water over Copper-Loaded Biochar Using an Enhanced Non-Radical Pathway.

The development of an efficient catalyst with excellent performance using agricultural biomass waste as raw materials is highly desirable for practical water pollution control. Herein, nano-sized, metal-decorated biochar was successfully synthesized with in situ chemical deposition at room temperature. The optimized BC-Cu (1:4) composite exhibited excellent peroxymonosulfate (PMS) activation performance due to the enhanced non-radical pathway. The as-prepared BC-Cu (1:4) composite displays a superior 99.99% removal rate for ciprofloxacin degradation (initial concentration 20 mg·L-1) within 40 min. In addition, BC-Cu (1:4) has superior acid-base adaptability (3.98~11.95) and anti-anion interference ability. The trapping experiments and identification of reactive oxidative radicals confirmed the crucial role of enhanced singlet oxygen for ciprofloxacin degradation via a BC-Cu (1:4)/PMS system. This work provides a new idea for developing highly active, low-cost, non-radical catalysts for efficient antibiotic removal.

[Red Mud-activated Peroxymonosulfate for Ciprofloxacin Degradation: Efficiency and Mechanism].

In this paper, the effects and mechanism of ciprofloxacin (CIP) degradation with peroxymonosulfate (PMS) catalyzed by solid waste red mud (RM) was firstly studied. The results indicated that RM has large specific surface area (10.96 m2·g-1) and complex pore structure, containing ferric, alumina and calcium oxide, which enhanced ciprofloxacin degradation by PMS effectively. Radical quenching experiments revealed that SO4-·and HO·were contributed to ciprofloxacin oxidation, and the reaction was mainly occurred on RM's surface. An increase in temperature could accelerate CIP degradation, and the corresponding reaction activation energy Ea was about 5.74 kJ·mol-1. Meanwhile, CIP degradation rate increased with PMS concentration and the optimal dosage of RM was 1.0 g·L-1. Eight degradation intermediates were identified using HPLC/MS/MS, and consequently, CIP was degraded mainly through two pathways; the piperazine groups were preferentially attacked by active free radicals. This study further indicated that RM is a cheap catalyst and can be potentially used in the treatment of antibiotic contaminated wastewater.

CCl4-Enhanced Ultrasonic Irradiation for Ciprofloxacin Degradation and Antibiotic Activity.

In this study, an ultrasound/CCl4 system was used to degrade the fluoroquinolone antibiotic, ciprofloxacin, in aqueous solution. The effect of CCl4 concentration and initial solution pH on ciprofloxacin degradation were investigated. The results showed that ciprofloxacin degraded effectively under an ultrasound/CCl4 system, with degradation efficiency increasing from 0.51% to 50.92%, when the CCl4 concentration ranged from 0.0 to 41.4 mmol/L in 40 min. Radical scavenging experiments certified that both •OH and chlorine-containing radicals contributed to ciprofloxacin degradation. Eight intermediates were detected using ultra high-performance liquid chromatography-mass spectrometry (UHPLC-MS) method, including three chloro-intermediates. Based on these results, the possible degradation pathways of ciprofloxacin are proposed. Agar diffusion tests with E. coli and S. aureus showed that ciprofloxacin's antibacterial activity was completely removed in 40 min. This study indicates that an ultrasound/CCl4 system can degrade ciprofloxacin and remove its antibacterial activity, and thus is a promising process for treating fluoroquinolone antibiotics in wastewater.

[Norfloxacin Solution Degradation Under Ultrasound, Potassium Persulfate Collaborative System].

High oxidative sulfate radicals can be produced by potassium persulfate (K2S2O8). The integrated effect of ultrasonic and K2S2O8, on norfloxacin degradation was investigated. The experimental parameters such as K2S2O8 concentration, norfloxacin initial concentration, initial pH value, free radicals quenching agents such as methanol and tert-butyl on norfloxacin degradation were discussed. The results indicated that ultrasonic/K2S2O8, system had an obvious degradation and mineralization effect on norfloxacin. Norfloxacin removal efficiencies were 3.2 and 8.9 times in ultrasonic/K2S2O8 system than those in single K252O8 and ultrasonic oxidation system, respectively. And the reaction followed the first-order kinetics. Norfloxacin removal efficiency varied gently with K2S2O8 concentration. Solution initial pH had a significant effect on norfloxacin degradation, which was attributed to the different oxidizing species under different pH values. The radicals were sulfate radicals under acidic and neutral conditions, and was the combination of sulfate and hydroxyl radicals under alkaline conditions. TOC and agar diffusion test with E. coli showed that 49.12% norfloxacin was mineralized and antibacterial activity was completely removed, with the diameter of E. coli inhibition zone decreased from 45 mm to 14 mm (filter paper diameter). The result implied that ultrasound/K2S2O8 showed promising results as a possible application for treatment of norfloxacin antibiotics wastewater.