广东一饮用水源地河流沉积物及鱼体中氟喹诺酮类(FQs)抗生素残留特征研究

本研究对广东一饮用水源保护区的河流氟喹诺酮类(Fluoroquinolones,FQs)抗生素进行分析.采用高效液相色谱法定性定量分析9个沉积物样品和5种鱼肉及1种鱼内脏中3种FQs—诺氟沙星(Norfloxacin,NOR)、环丙沙星(Ciprofloxacin,CIP)、恩诺沙星(Enrofloxacin,ENR)的残留特征,并与沉积物中有机质、总氮、总磷进行Person相关性分析.结果表明:河流沉积物各点平均值NORCIPENR,最大含量分别为:NOR248.25 ng·g-1,CIP 158.69 ng·g-1,ENR 56.81 ng·g-1;FQs和沉积物有机质、总磷相关系数平均为0.946、0.968(p0.01);5种鱼的鱼肉中FQs的含量可能高于或低于沉积物中FQs含量均值;鳙鱼内脏FQs含量是鱼肉中的3.21~9.53倍.研究结果对保障饮用水安全及水产品生态安全具有重要的意义.     

Toxic interaction mechanism of two fluoroquinolones with serum albumin by spectroscopic and computational methods

To evaluate the toxicity of two fluoroquinolones (FQs), ciprofloxacin (CPFX), and enrofloxacin (ENFX), at the protein level, their binding modes with bovine serum albumin (BSA) were characterized by multiple spectroscopic and molecular docking methods under simulated physiological conditions. On the basis of fluorescence spectra, we concluded that both FQs greatly quenched the fluorescence intensity of BSA, which was attributed to the formation of a moderately strong complex mainly through electrostatic interactions. Besides, CPFX posed more of an affinity threat than ENFX. The molecular docking methods further illustrated that both CPFX and ENFX could bind into the subdomain IIIA of BSA and interact with Arg 508 and Lys 437, the positively charged residues in protein. Furthermore, as shown by the synchronous fluorescence, UV-Visible absorption and circular dichroism data, both CPFX and ENFX could lead to the conformational and microenvironmental changes of BSA, which may affect its physiological function.     

In vitro residual anti-bacterial activity of difloxacin, sarafloxacin and their photoproducts after photolysis in water

Fluoroquinolones like difloxacin (DIF) and sarafloxacin (SARA) are adsorbed in soil and enter the aquatic environment wherein they are subjected to photolytic degradation. To evaluate the fate of DIF and SARA, their photolysis was performed in water under stimulated natural sunlight conditions. DIF primarily degrades to SARA. On prolonged photodegradation, seven photoproducts were elucidated by HR-LC-MS/MS, three of which were entirely novel. The residual anti-bacterial activities of DIF, SARA and their photoproducts were studied against a group of pathogenic strains. DIF and SARA revealed potency against both Gram-positive and -negative bacteria. The photoproducts also exhibited varying degrees of efficacies against the tested bacteria. Even without isolating the individual photoproducts, their impact on the aquatic environment could be assessed. Therefore, the present results call for prudence in estimating the fate of these compounds in water and in avoiding emergence of resistance in bacteria caused by the photoproducts of DIF and SARA.     

Influence of hydraulic retention time on behavior of antibiotics and antibiotic resistance genes in aerobic granular reactor treating biogas slurry

Longer HRT can enhance degradation rate of sulfamethoxazole in granular reactor. Longer HRT can reduce accumulated concentrations of TCs and QNs in sludge. Longer HRT may have increased relative abundances of ARGs in aerobic granules. The behavior of antibiotics and the corresponding resistance genes in aerobic granular reactors for treating biogas slurry under different hydraulic retention times (10.7 h, R1; 8 h, R2) was investigated in this study. The results indicated that the hydraulic retention time could affect the effluent concentrations and removal efficiencies of sulfonamides. The average removal rates of tetracyclines, fluoroquinolones, and sulfonamides were 63%, 46%, and 90% in R1, and 62%, 46%, and 86% in R2, respectively. Although the removal efficiencies of tetracyclines and fluoroquinolones were similar in both reactors, the respective accumulated concentrations of tetracyclines and fluoroquinolones in R1 were 7.00 and 11.15 µg/g SS, which were lower than those in R2 (8.92 and 13.37 µg/g SS, respectively). The difference in the relative abundance of target antibiotic resistance genes between both reactors was not significant, yet the average relative abundances of all target resistance genes in R1 were higher than those in R2 after 45 days of operation. The results of this study suggested that a longer hydraulic retention time could enhance the antibiotic removal ability of aerobic granular sludge, yet it may also increase the risk of surplus sludge utilization from a resistance genes point of view.     

Production of the broad specific monoclonal antibody against sarafloxacin for rapid immunoscreening of 12 fluoroquinolones in meat

The objective of this study was to produce a generic antibody for immunoassay of fluoroquinolone drugs in meat. Two novel haptens of sarafloxacin were synthesized that were used to produce the monoclonal antibodies. The obtained monoclonal antibodies simultaneously recognized 12 fluoroquinolone drugs (sarafloxacin, diflocaxin, marbofloxacin, ofloxacin, ciprofloxacin, enrofloxacin, norfloxacin, pefloxacin, lomefloxacin, amifloxacin, enofloxacin and danofloxacin). After evaluation of different coating antigen/antibody combinations, a heterologous competitive indirect enzyme linked immunosorbent assay (ELISA) was developed to determine the 12 drugs. The crossreactivities to these analytes were in the range of 18%–113% and the limits of detection were in the range of 0.8–6.5 ng/mL depending on the compound. Eight fluoroquinolones licensed as veterinary drugs in China were fortified into blank chicken for ELISA analysis. The recoveries were in the range of 67.6%–94.6% with coefficients of variation lower than 12.4%. Therefore, this method could be used as a screen tool for routine monitoring of the residues of these fluoroquinolone drugs in animal derived foods.     

An insight into the removal of fluoroquinolones in activated sludge process: Sorption and biodegradation characteristics

The detailed sorption steps and biodegradation characteristics of fluoroquinolones(FQs)including ciprofloxacin, enrofloxacin, lomefloxacin, norfloxacin, and ofloxacin were investigated through batch experiments. The results indicate that FQs at a total concentration of 500 μg/L caused little inhibition of sludge bioactivity. Sorption was the primary removal pathway of FQs in the activated sludge process, followed by biodegradation, while hydrolysis and volatilization were negligible. FQ sorption on activated sludge was a reversible process governed by surface reaction. Henry and Freundlich models could describe the FQ sorption isotherms well in the concentration range of 100–300 μg/L. Thermodynamic parameters revealed that FQ sorption on activated sludge is spontaneous, exothermic, and enthalpy-driven. Hydrophobicity-independent mechanisms determined the FQ sorption affinity with activated sludge. The zwitterion of FQs had the strongest sorption affinity, followed by cation and anion, and aerobic condition facilitated FQ sorption. FQs were slowly biodegradable, with long half-lives( 100 hr). FQ biodegradation was enhanced with increasing temperature and under aerobic condition,and thus was possibly achieved through co-metabolism during nitrification. This study provides an insight into the removal kinetics and mechanism of FQs in the activated sludge process, but also helps assess the environmental risks of FQs resulting from sludge disposal.