水环境中抗生素的分布、累积及生态毒理效应

抗生素持续大量使用带来的环境污染和潜在的生态风险已经引起广泛关注。总结了国内外相关研究成果,对水环境中抗生素的污染源及残留水平进行了分析,对抗生素在水生生物体内的累积规律给予了评述,同时对抗生素的生态毒理效应进行了探讨。鉴于我国水环境中抗生素的污染现状,建议未来加强环境相关浓度下抗生素在生物体内的分布与转化、食物链迁移与放大,以及多种抗生素联合效应等方面的研究。     

Spectroscopic study of the degradation of antibiotics and the generation of representative EfOM oxidation products in ozonated wastewater

This study examined effects of ozonation on thirteen fluoroquinolone, macrolide and lincosamide antibiotics present in municipal wastewater. Transformations of effluent organic matter (EfOM) caused by ozonation were characterized using absorbance/fluorescence spectroscopy and high performance size exclusion chromatography (HPSEC). Concentrations of aldehydes and carboxylic acids generated via the oxidation of EfOM were also determined. The absorbance and fluorescence of ozonated wastewater decreased with increasing ozone dose or treatment time. HPSEC data showed that these phenomena corresponded to the oxidation of all EfOM fractions, with some preference towards the degradation of the EfOM molecules with high apparent molecular weight. The removal of antibiotics and production of aldehydes and carboxylic acids were strongly correlated with the changes in both EfOM absorbance and fluorescence. Applications of a model describing the concurrent degradation of trace level contaminants and relative changes of EfOM emission allowed achieving a good fitting between the experimental and modeled ΔC/C₀ vs. ΔA/A₀ and ΔC/C₀ vs. ΔF/F₀ data.     

Soil contamination with antibiotics in a typical peri-urban area in eastern China: Seasonal variation, risk assessment, and microbial responses

The prevalence and persistence of antibiotics in soils has become an emerging environmental issue and an increasing threat to soil security and global public health. The problem is more severe in areas undergoing rapid urbanization; however, the ecological risks of antibiotics, seasonal variability, and associated soil microbial responses in peri-urban soils have not been well-explored. The seasonal soil sampling campaigns were conducted in a typical peri-urban watershed in eastern China to investigate distribution of antibiotics. The results demonstrated higher mean concentrations of most antibiotic compounds in winter than in summer in peri-urban soils. The seasonal variations of norfloxacin, enrofloxacin, and ciprofloxacin were more significant than those of other antibiotics, due to their higher migration ability and bioavailability. An ecological risk assessment demonstrated that chlortetracycline, ciprofloxacin, doxycycline, and ofloxacin can pose high risks to soil microorganisms. Furthermore, the coexistence of multiple antibiotics obviously poses higher risks than individual compounds. A redundancy analysis demonstrated that tetracyclines mainly showed negative correlations with Firmicutes and Chloroflexi, and quinolones showed obviously negative correlations with Acidobacteria, Gemmatimonadetes, and Nitrospirae, suggesting potential inhibition from antibiotics on biological activities or biodegradation processes. However, the persistence of antibiotics in soil results in a significant decrease in bacterial diversity and a change in dominant species. Our results provide an overview of the seasonal variability of antibiotics and the associated effects on bacterial communities in peri-urban soils. The results can provide scientific guidance on decreasing soil contamination with antibiotics to enhance soil security in similar areas.     

Fate of antibiotics and antibiotic resistance genes in a full-scale restaurant food waste treatment plant: Implications of the roles beyond heavy metals and mobile genetic elements

Is our food safe and free of the crisis of antibiotics and antibiotic resistance(AR)?And will the derived food waste(FW) impose AR risk to the environment after biological treatment? This study used restaurant FW leachates flowing through a 200 tons-waste/day biological treatment plant as a window to investigate the fate of antibiotics and antibiotic-resistance genes(ARGs) during the acceptance and treatment of FW. Sulfonamides(sulfamethazine, sulfamethoxazole) and quinolones(ciprofloxacin, enrofloxacin, ofloxacin) were detected during FW treatment, while tetracyclines, macrolides and chloramphenicols were not observable. ARGs encoding resistance to sulfonamides, tetracyclines and macrolides emerged in FW leachates.Material flow analysis illustrated that the total amount of antibiotics(except sulfamethazine) and ARGs were constant during FW treatment processes. Both the concentration and total amount of most antibiotics and ARGs fluctuated during treatment, physical processes(screening, centrifugation, solid–liquid and oil–water separation) did not decrease antibiotic or ARGs concentrations or total levels permanently; the affiliated wastewater treatment plant appeared to remove sulfonamides and most ARGs concentrations and total amount. Heavy metals Ni,Co and Cu were important for disseminating antibiotics concentrations and MGEs for distributing ARGs concentrations. Humic substances(fulvic acids, hydrophilic fractions), C-associated and N-associated contents were essential for the distribution of the total amounts of antibiotics and ARGs. Overall, this study implied that human food might not be free of antibiotics and ARGs, and FW was an underestimated AR pool with various determinants. Nonetheless, derived hazards of FW could be mitigated through biological treatment with well-planned daily operations.     

Study of spatial and temporal distribution of antimicrobial in water and sediments from caging fish farms by on-line SPE-LC-MS/MS

An on-line solid phase extraction liquid chromatography-tandem mass spectrometry (SPE-LC-MS/MS) method for the determination of 12 antimicrobials in sediment and surface water was developed and validated. Furthermore, the spatial and temporal antimicrobials distributions in the sediment and in the water of four fish farms located in the hydroelectric dam of Ilha Solteira Reservoir in Brazil were investigated over four seasons in three sampling sites: at the fish cages, 100 and 1,000 m downstream far from the cages. The method was performed using an Agilent Zorbax 80 SB-C8 column (9.4 × 15 mm, 5 µm) as the loading column, and the Agilent Zorbax Eclipse Plus C18 column (3.0 × 100 mm, 3.5 µm) as a separation column within a run time of 13 min. The limits of quantification were less than 9 ng·L^?1 for the antibiotics in water and 16 µg·kg^?1 in sediment; the recovery ranged from 80 to 119%, with a variation coefficient less than 11%, and the repeatability was lower than 15%. Oxytetracycline was found in the water in all sample seasons. However, florfenicol was identified in April and October 2013 and January 2014, and tetracycline was present in July 2013. Regarding the sediment, oxytetracycline and tetracycline were found in all sampling periods, but chlortetracycline was only identified in January 2014. The spatial distribution of antimicrobials showed that the main pollution source came from the fish farms. This study demonstrated that the proposed method is reliable for the monitoring of antimicrobials in water and sediments and it showed contamination in both matrices from Ilha Solteira Reservoir.     

抗生素在沉积物中的吸附机制及其影响因素

抗生素作为医疗业和农业使用量最大的药物之一,由于其本身的特性,很容易进入沉积物一水环境中。抗生素在沉积物中的吸附过程是影响抗生素的反应活性、可移动性、持久性及生物可利用性的关键过程。本文选择四环素类、喹诺酮类、磺胺类和大环内酯类4类常用抗生素,在总结了这4类抗生素在湖泊沉积物中污染状况的基础上,分析了抗生素在沉积物中的吸附机制,并归纳论述了pH值、盐度、重金属离子、表面活性剂以及水动力条件对其在沉积物上吸附的影响机制。     

Sorption of tylosin and sulfamethazine on solid humic acid

Tylosin(TYL) and sulfamethazine(SMT) are ionizable and polar antimicrobial compounds,which have seeped into the environment in substantial amounts via fertilizing land with manure or sewage. Sorption of TYL and SMT onto humic acid(HA) may affect their environmental fate. In this study, the sorption of TYL and SMT on HA at different conditions(pH, ionic strength) was investigated. All sorption isotherms fitted well to the Henry and Freundlich models and they were highly nonlinear with values of n between 0.5 and 0.8, which suggested that the HA had high heterogeneity. The sorption of TYL and SMT on HA decreased with increasing p H(2.0–7.5), implying that the primary sorption mechanism could be due to cation exchange interactions between TYL~+/SMT~+ species and the functional groups of HA.Increasing ionic strength resulted in a considerable reduction in the K_d values of TYL and SMT,hinting that interactions between H bonds and π–π EDA might be an important factor in the sorption of TYL and SMT on HA. Results of Fourier transform infrared(FT-IR) and ~13C-nuclear magnetic resonance(NMR) analysis further demonstrated that carboxyl groups and O-alkyl structures in the HA could interact with TYL and SMT via ionic interactions and H bonds,respectively. Overall, this work gives new insights into the mechanisms of sorption of TYL and SMT on HA and hence aids us in assessing the environmental risk of TYL and SMT under diverse conditions.     

Decomposition and mineralization of cefaclor by ionizing radiation: kinetics and effects of the radical scavengers

There has been recent growing interest in the presence of antibiotics in different environmental sectors. One considerable concern is the potential development of antibiotic-resistant bacteria in the environment, even at low concentrations. Cefaclor, one of the beta-lactam antibiotics, is widely used as an antibiotic. Kinetic studies were conducted to evaluate the decomposition and mineralization of cefaclor using gamma radiation. Cefaclor, 30 mg/l, was completely degraded with 1,000 Gy of gamma radiation. At a concentration of 30 mg/l, the removal efficiency, represented by the G-value, decreased with increasing accumulated radiation dose. Batch kinetic experiments with initial aqueous concentrations of 8.9, 13.3, 20.0 and 30.0mg/l showed the decomposition of cefaclor using gamma radiation followed a pseudo first-order reaction, and the dose constant increased with lower initial concentrations. At a given radiation dose, the G-values increased with higher initial cefaclor concentrations. The experimental results using methanol and thiourea as radical scavengers indicated that ()OH radicals were more closely associated with the radiolytic decomposition of cefaclor than other radicals, such as e(aq)(-) or ()H. The radical scavenger effects were tested under O(2) and N(2)O saturations for the enhancement of the TOC percentage removal efficiencies in the radiolytic decomposition of cefaclor. Under O(2) saturation, 90% TOC removal was observed with 100,000 Gy. Oxygen is well known to play a considerable role in the degradation of organic substances with effective chain reaction pathways. According to the effective radical reactions, the enhanced TOC percentage removal efficiencies might be based on the fast conversion reactions of e(aq)(-) and ()H with O(2) into oxidizing radicals, such as O(2)(-) and HO(2)(), respectively. 100% TOC removal was obtained with N(2)O gas at 20,000 Gy, as reducing radicals, such as e(aq)(-) and ()H, are scavenged by N(2)O and converted into ()OH radicals, which have strong oxidative properties. The results of this study showed that gamma irradiation was very effective for the removal of cefaclor in aqueous solution. The use of O(2) or N(2)O, with radiation, shows promise as effective radical scavengers for enhancing the TOC or COD removal efficiencies in pharmaceutical wastewaters containing antibiotics. However, the biological toxicity and interactions between various chemicals during the radiolytic treatment, as well as treatments under conditions more representative of real wastewater will require further studies.     

Multi-function adsorbent-photocatalyst MXene-TiO2 composites for removal of enrofloxacin antibiotic from water

MXenes, a new family of two-dimensional transition metal carbides or nitrides, have attracted tremendous attention for various applications due to their unique properties such as good electrical conductivity, hydrophilicity, and ion intercalability. In this work, Ti₃C₂ MXene, or MX, is converted to MX-TiO₂ composites using a simple and rapid microwave hydrothermal treatment in HCl/NaCl mixture solution that induces formation of fine TiO₂ particles on the MX parent structure and imparts photocatalytic activity to the resulting MX-TiO₂ composites. The composites were used for enrofloxacin (ENR), a frequently found contaminating antibiotic, removal from water. The relative amount of the MX and TiO₂ can be controlled by controlling the hydrothermal temperature resulting in composites with tunable adsorption/photocatalytic properties. NaCl addition was found to play important role as composites synthesized without NaCl could not adsorb enrofloxacin well. Adding NaCl into the hydrothermal treatment causes sodium ions to be simultaneously intercalated into the composite structure, improving ENR adsorption greatly from 1 to 6 mg ENR/g composite. It also slows down the MX to TiO₂ conversion leading to a smaller and more uniform distribution of TiO₂ particles on the structure. MX-TiO₂/NaCl composites, which have sodium intercalated in their structures, showed both higher ENR adsorption and photocatalytic activity than composites without NaCl despite the latter having higher TiO₂ content. Adsorbed ENR on the composites can be efficiently degraded by free radicals generated from the photoexcited TiO₂ particles, leading to high photocatalytic degradation efficiency. This demonstrates the synergetic effect between adsorption and photocatalytic degradation of the synthesized compounds.     

Occurrence of veterinary antibiotics in animal wastewater and surface water around farms in Jiangsu Province, China

The objective of this investigation was to obtain a broad profile of veterinary antibiotics residues in animal wastewater and surface water around large-scale livestock and poultry farms in Jiangsu Province of China. Therefore, 53 samples collected from 27 large-scale animal farms in 11 cities and counties of Jiangsu Province in 2009, were monitored for 10 selected veterinary antibiotics using solid phase extraction and high performance liquid chromatography/electrospray ionization-tandem mass spectrometry (HPLC/ESI-MS/MS) techniques. Ten veterinary antibiotics were found in animal wastewaters, eight antibiotics were detected in pond waters, and animal farm-effluents and river water samples were contaminated by nine antibiotics. The most frequently detected antibiotics were sulfamethazine (75%), oxytetracycline (64%), tetracycline (60%), sulfadiazine (55%) and sulfamethoxazole (51%) which were detected with a maximum concentration of 211, 72.9, 10.3, 17.0 and 63.6 μg L⁻¹, respectively. The maximum concentration of 0.55 μg L⁻¹ for cyromazine, 3.67 μg L⁻¹ for chlortetracycline, 0.63 μg L⁻¹ for sulfadoxine, 39.5 μg L⁻¹ for doxycycline and 0.64 μg L⁻¹ for sulfaquinoxaline were determined in the collected samples. In general, the maximum concentration of the selected veterinary antibiotics was detected in animal wastewaters except for chlortetracycline in animal farm-effluents. In addition, residue levels of selected veterinary antibiotics in animal wastewater and surface water around the farms were related to animal species and have a high spatial variation.