小诺霉素发酵废水好氧生物处理试验研究

对具有强抑制性污染物的抗生素小诺霉素发酵废水，选择活性污泥、粉末活性炭（ＰＡＣＴ）、纯氧曝气等３种好氧生物处理法进行了比较试验。根据实验结果，小诺霉素发酵废水的生物降解呈抑制动力学，采用Ｍａｒｑｕａｒｔ方法对动力学模式进行参数估计。ＰＡＣＴ能够有效地降低降解过程中微生物受到的抑制作用，从而明显地改善了生物处理过程动力学。     

Sequential development and exploitation of an exhaustible resource: do monopoly rights promote conservation?

This paper explores the problem of sequential exploitation of exhaustible resources by a monopolist, when a setup cost must be incurred to access the next pool. Under certain circumstances, the monopolist will always follow a more conservationist path of extraction and delay the introduction of new resource pools compared to a social planner. However, with other forms of consumer demand, the monopolist may exhaust the resource more quickly, especially if many new options will follow. These results may apply especially to depletable resources like antibiotics or biotech products, for which significant research and development costs are required, followed by monopoly rights conferred by patents.     

Biodegradation and bio-sorption of antibiotics and non-steroidal anti-inflammatory drugs using immobilized cell process

In the present study, the removal mechanisms of four antibiotics (sulfamethoxazole, sulfadimethoxine, sulfamethazine, and trimethoprim) and four non-steroidal anti-inflammatory drugs (acetaminophen, ibuprofen, ketoprofen, and naproxen) in immobilized cell process were investigated using batch reactors. This work principally explores the individual or collective roles of biodegradation and bio-sorption as removal routes of the target pharmaceuticals and the results were validated by various experimental and analytical tools. Biodegradation and bio-sorption were found as dominant mechanisms for the drug removal, while volatilization and hydrolysis were negligible for all target pharmaceuticals. The target pharmaceuticals responded to the two observed removal mechanisms in different ways, typically: (1) strong biodegradability and bio-sorption by acetaminophen, (2) strong biodegradability and weak bio-sorption by sulfamethoxazole, sulfadimethoxine, ibuprofen and naproxen, (3) low biodegradability and weak bio-sorption by sulfamethazine and ketoprofen, and (4) low biodegradability and medium bio-sorption by trimethoprim. In the sorption/desorption experiment, acetaminophen, sulfamethoxazole and sulfadimethoxine were characterized by strong sorption and weak desorption. A phenomenon of moderate sorption and well desorption was observed for sulfamethazine, trimethoprim and naproxen. Both ibuprofen and ketoprofen were weakly sorbed and strongly desorbed.     

Ecotoxicity evaluation of selected sulfonamides

Sulfonamides (SAs) are a group of antibiotic drugs widely used in veterinary medicine. The contamination of the environment by these pharmaceuticals has raised concern in recent years. However, knowledge of their (eco)toxicity is still very basic and is restricted to just a few of these substances. Even though their toxicological analysis has been thoroughly performed and ecotoxicological data are available in the literature, a systematic analysis of their ecotoxicological potential has yet to be carried out. To fill this gap, 12 different SAs were chosen for detailed analysis with the focus on different bacteria as well as non-target organisms (algae and plants). A flexible (eco)toxicological test battery was used, including enzymes (acetylcholinesterase and glutathione reductase), luminescent marine bacteria (Vibrio fischeri), soil bacteria (Arthrobacter globiformis), limnic unicellular green algae (Scenedesmus vacuolatus) and duckweed (Lemna minor), in order to take into account both the aquatic and terrestrial compartments of the environment, as well as different trophic levels. It was found that SAs are not only toxic towards green algae (EC₅₀ = 1.54-32.25 mg L⁻¹) but have even stronger adverse effect on duckweed (EC₅₀ = 0.02-4.89 mg L⁻¹) than atrazine - herbicide (EC₅₀ = 2.59 mg L⁻¹).     

Antibiotics along an alpine river and in the receiving lake with a catchment dominated by grazing husbandry

The livestock breeding industries face overuse of antibiotics, which has been intensively studied in recent years. However, the occurrence and fate of antibiotics as well as their potential threats to the aquatic environments in alpine and arid regions remain unclear. This study investigated the relationship of the occurrence and concentrations of antibiotics between the Kaidu River and Bosten Lake in a typical alpine basin in China. Hot spots with antibiotic pollution source were explored. The antibiotic concentrations in river water and suspended sediment (SPS) were 2.20-99.4 ng/L and 1.03-176 ng/g. The dominant antibiotics were tetracyclines, sulphacetamide, and ofloxacin in river water and sulfonamides, clarithromycin, roxithromycin, and ofloxacin in SPS. The apparent differences in pollution sources and landscapes in different reaches led to the obvious spatial patterns of antibiotics in the Kaidu River. Higher partition coefficient of antibiotic between SPS and water phases for sulfonamides than tetracyclines was because that tetracyclines strongly responded to clay contents while sulfonamides significantly responded to organic carbon contents in SPS. There were significant differences in detected antibiotic categories between the river and the lake. Fluoroquinolones (especially ciprofloxacin and enrofloxacin) were detected in the lake while sulphacetamide was only detected in the river. Therefore, the surrounding husbandry and aquaculture around the Bosten Lake was an important antibiotic pollution source in addition to inputs from the Kaidu River. This research suggested that alpine lakes could be an important sink of antibiotics in alpine dry regions, and thus impose greater threats to the aquatic ecosystem.     

Potassium ferrate pretreatment promotes short chain fatty acids yield and antibiotics reduction in acidogenic fermentation of sewage sludge

During the acidogenic fermentation converting waste activated sludge (WAS) into short-chain fatty acids (SCFA), hydrolysis of complex organic polymers is a limiting step and the transformation of harmful substances (such as antibiotics) during acidogenic fermentation is unknown. In this study, potassium ferrate (K₂FeO₄) oxidation was used as a pretreatment strategy for WAS acidogenic fermentation to increase the hydrolysis of sludge and destruct the harmful antibiotics. Pretreatment with K₂FeO₄ can effectively increase the SCFA production during acidogenic fermentation and change the distribution of SCFA components. With the dosage of 0.2 g/g TS, the maximum SCFA yield was 4823 mg COD/L, which is 28.3 times that of the control group; acetic acid accounts for more than 90% of the total SCFA. The higher dosage (0.5 g/g TS) can further increase the proportion of acetic acid, but inhibit the overall performance of SCFA production. Apart from the promotion of hydrolysis and acidogenesis, K₂FeO₄ pretreatment can also simultaneously oxidizes and degrades part of the antibiotics in the sludge. When the dosage is 0.5 g/g TS, the degradation efficacy of antibiotics is the most significant, and the contents of ofloxacin, azithromycin, and tetracycline in the sludge are reduced by 69%, 42%, and 50%, respectively. In addition, K₂FeO₄ pretreatment can also promote the release of antibiotics from sludge flocs, which is conducive to the simultaneous degradation of antibiotics in the subsequent biological treatment process.     

养殖废水中9种大环内酯及林可酰胺类抗生素的同时测定及分析方法研究

采用固相萃取-超高效液相色谱三重四极杆质谱联用法,建立了同时测定养殖废水中9种大环内酯及林可酰胺类抗生素的方法,并对样品pH值、保存时间、洗脱溶剂、上样流速及过滤材质等进行了优化。测定结果表明,pH值为6,过滤材质为聚丙烯（GHP）,上样速度为5 mL/min时,9种抗生素的加标回收率最优,为71.4%～126%,相对标准偏差最小,为2.4%～7.1%,标准曲线的线性最好,相关系数为0.998 5～0.999 5,检出限为0.78～1.22 ng/L。该方法灵敏度高、检出限低、测定结果准确,能够广泛应用于养殖废水中大环内酯及林可酰胺类抗生素残留量的监测分析。     

Antibiotic contamination in a typical water-rich city in southeast China: a concern for drinking water resource safety

Abstract

The occurrence and distribution in the aquatic environment of Nanjing of 49 antibiotics from seven therapeutic classes were investigated using an improved analytical method developed for multiclass target analysis. The results showed that these antibiotics are widely present in the water bodies of this city, with a total concentration of up to 1.958?μg L^?1. The most abundant class was tetracyclines, contributing 43.7% to the total antibiotic burden. Lincomycin was detected in all samples, and the detection rate of clindamycin was 90.5%. An exploratory analysis of the data points was performed by unsupervised pattern recognition (hierarchical cluster analysis, HCA) in an attempt to clarify the pollution level in different sampling areas, and robust cluster solutions grouped the data according to their different antibiotic contaminant profiles. The safety of drinking water resources was emphasized, and the rivers, as the main receiving water body for treated and untreated wastewater in this city, were more seriously contaminated than the surrounding lakes and reservoir, not only in concentration but also in detection frequency, in our study as well as in similar research studies. A correlation analysis between the presence of antibiotics and the environmental factors was conducted, and it was found that antibiotic contamination and water quality were closely connected; the better the water quality, the lower the antibiotic contamination. Positive correlations existed between the antibiotics and tested heavy metals, as well as between antibiotics and boron and arsenic. However, whether these correlations resulted from their reaction or a common source was difficult to determine, and the mechanism requires further exploration.     

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.     

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.