Evaluation of food chain transfer of the antibiotic oxytetracycline and human risk assessment

There has been recent concern regarding the possibility of antibiotics entering the aquatic food chain and impacting human consumers. This work reports experimental results of the bioconcentration of the antibiotic oxytetracycline (OTC) by the Asian watermeal plant (Wolffia globosa Hartog & Plas) and bioaccumulation of OTC in watermeal and water by the seven-striped carp (Probarbus jullieni). They show, for the first time, the extent to which OTC is able to transfer from water to plant to fish and enter the food chain. The mean bioconcentration factor (dry weight basis) with watermeal was 1.28 × 10³ L kg⁻¹. Separate experiments were undertaken to characterize accumulation of OTC by carp from water and watermeal. These showed the latter pathway to be dominant under the conditions employed. The bioconcentration and biomagnification factors for these processes were 1.75 L kg⁻¹ and 2 × 10⁻⁴ kg g⁻¹ respectively. Using an aqueous concentration range of 0.34–3.0 μg L⁻¹, hazard quotients for human consumption of contaminated fish of 1.3 × 10⁻² to 1.15 × 10⁻¹ were derived.     

裂片石莼和土霉素复合压力下弧菌群落及耐药基因变化特性研究

近年来,水产养殖病源弧菌污染及其耐药性问题备受关注,本研究首次采用宏基因组测序技术分析了海水养殖沉积物在大型海藻裂片石莼（12 g·L^-1）与不同浓度（0、10、100、500 μg·L^-1）土霉素作用3个月后,弧菌群落结构及其耐药基因变化特性.结果表明,经裂片石莼诱导培养后,沉积物中弧菌属相对丰度降低了0.22%,但对弧菌多样性和弧菌耐药基因含量提升明显.裂片石莼和土霉素复合压力下,100 μg·L^-1土霉素对弧菌群落多样性及弧菌耐药基因影响最大,而500 μg·L^-1对其影响最小.沉积物弧菌属共检测出21种耐药基因,多为BL1_fox、BL2be_per、BL2_veb等β-内酰胺类耐药基因.裂片石莼能减少耐药基因tetPB富集,而进一步添加土霉素能诱导产生VatB、BcrA耐药基因.此外,弧菌耐药基因迁移与转化还受弧菌群落结构变化影响.     

Hydrolysis and photolysis of oxytetracycline in aqueous solution

Oxytetracycline ((2Z,4S,4aR,5S,5aR,6S,12aS)-2-(amino-hydroxy-methylidene)-4-dimethylamino-5,6,10,11,12a-pentahydroxy-6-methyl-4,4a,5,5a-tetrahydrotetracene-1,3,12-trione) is a member of tetracycline antibiotics family and is widely administered to farm animals for the purpose of therapeutical treatment and health protection. Increasing attention has been paid to the environmental fate of oxytetracycline and other veterinary antibiotics with the occurrence of these antibiotics in the environment. The hydrolysis and photolysis degradation of oxytetracycline was investigated in this study. Oxytetracycline hydrolysis was found to obey the first-order model and similar rate constant values ranging from 0.094 ± 0.001 to 0.106 ± 0.003 day^{? 1} were obtained at different initial concentration ranging from 10 to 230 μ M. Solution pH and temperature were shown to have remarked effects on oxytetracycline hydrolysis. The hydrolysis in pH neutral solution appeared to be much faster than in both acidic and alkaline solutions. Oxytetracycline half-life decreased from 1.2 × 10² to 0.15 day with the increasing temperature from 4 ± 0.8 to 60 ± 1°C. The presence of Ca^{2 +} made oxytetracycline hydrolytic degradation kinetics deviate from the simple first-order model to the availability-adjusted first-order model and greatly slowed down the hydrolysis. Oxytetracycline photolysis was found to be very fast with a degradation rate constant at 3.61 ± 0.06 day^{? 1}, which is comparable to that of hydrolysis at 60°C. The presence of Ca^{2 +} accelerated oxytetracycline photolysis, implying that oxytetracycline become more vulnerable to sunlight irradiation after chelating with Ca^{2 +}. The photolysis may be the dominant degradation pathway of oxytetracycline in shallow transparent water environment.     

The influence of some biological antioxid ants on the light emission from the oxytetracycline oxidation reaction

The effect of the Superoxide radical (O₂ ^–)‐, hydroxyl radical (HO')‐inhibitors, singlet oxygen (¹O₂)‐quenchers and catalase on the light emission during autoxidation reaction of oxytetracycline was measured. The influence of the ¹O₂‐quenchers was investigated quantitatively and the rate constants were established.     

Comparison of two screening level risk assessment approaches for six disinfectants and pharmaceuticals

For three examples of both groups (the disinfectants biphenylol, 4-chloro-m-cresol and triclosan and the pharmaceuticals ivermectin, ibuprofen and oxytetracycline) a relative initial risk assessment (RIRA) was performed assuming a standard emission of 1 kg/d to the most relevant environmental compartment. In addition the hazard of the compounds was evaluated based upon their persistence, toxicity and bioaccumulative properties (PTB). Both estimated and measured parameters were used for this purpose. In addition to an analysis of the risks of the pharmaceuticals and disinfectants per se, the capacity to discern between the intrinsic risk of different compounds is evaluated for both criteria used. It is concluded that the RIRA has a higher discriminative value and yields more information compared to the PTB-criterion.     

分散固相萃取/高效液相色谱法测定土霉素菌渣中土霉素的残留量

文章拟建立一种从土霉素菌渣中提取并检测土霉素残留量的高效液相色谱法。用甲醇和冰乙酸作为提取剂提取样品,用分散固相萃取的方法净化样品,净化药剂为石墨化碳黑(GCB)和C18。通过加标回收实验,用高效液相色谱仪检测样品中土霉素含量。选用的色谱柱为PLRP-S,流动相为甲醇和0.05 mol/L草酸,两者比例为35:65(V:V)。检测波长为355 nm,柱温30℃。经检测,土霉素在0.1~2 000 mg/L范围内线性相关系数大于0.999,线性良好。1.0,4.0及8.0mg/g 3个加标水平的土霉素平均回收率范围是80.85%~109.59%,相对标准偏差(RSD)为2.45%~6.38%。土霉素菌渣中土霉素残留量平均为4.741 mg/g。实验表明,该方法具有简单、方便、快速、准确性强、灵敏度高的特点,可以应用于土霉素的分析检测。     

Development of an efficient extraction method for oxytetracycline in animal manure for high performance liquid chromatography analysis

Oxytetracycline (2-(amino-hydroxy-methylidene)-4-dimethylamino-5,6,10,11,12a-pentahydroxy-6-methyl-4,4a,5,5a-tetrahydrotetracene-1,3,12-trione) is a major member of the tetracycline antibiotics family of which are widely administered to animals in concentrated animal feeding operations for purposes of therapeutical treatment and health protection. With the disposal of animal manure as fertilizer into agricultural land, tetracyclines enter the environment. However, tetracyclines chelate with multivalent cations and proteins, resulting in low extraction efficiencies from animal manure for tetracycline residue analysis. In this study an efficient extraction method for oxytetracycline from steer manure using methanol/water solution amended with chelating organic acid was developed for the analysis of high performance liquid chromatography. The effect of species and amount of amendment acids, shaking time, methanol/water ratio, manure weight, and repeated times of extraction was investigated. It was optimized to amend 2.5 g citric acid and 1.1 g oxalic acid with 10.0 g manure sample in a 50-ml centrifuge tube and extract with 15 ml methanol/water (9:1 in volume) by vigorously shaking for 30 min in a reciprocating shaker. After centrifugation at 11,000 rpm, supernatant is collected. Sample was extracted for a total of 3 times. The developed extraction method was further applied to extract oxytetracycline from fresh and aged cow manure, swine and poultry manure, and soil. Satisfactory recoveries ranging from (84.1 ± 2.4) % to (102.0 ± 3.1) % were obtained, demonstrating that the optimized extraction method is robust for oxytetracycline from different manure sample matrixes.     

Influence of anionic, cationic and nonionic surfactants on adsorption and desorption of oxytetracycline by ultrasonically treated and non-treated multiwalled carbon nanotubes

High adsorption capacity of carbon nanotubes (CNTs) may greatly determine the bioavailability and mobility of organic contaminants. The fate of contaminants adsorbed by CNTs may be substantially influenced by surfactants used both in the synthesis and dispersion of CNTs. The aim of this research was to determine the influence of surfactants (nonionic - TX100, cationic - CTAB and anionic - SDBS) on adsorption and desorption of oxytetracycline (OTC) by multiwalled carbon nanotubes (MWCNTs). The surfactants used had a substantial influence on both adsorption and desorption of OTC. The direction of changes depended clearly on the type of surfactant. In case of anionic SDBS, increased adsorption of OTC by MWCNTs was observed. The presence of TX100 and CTAB decreased the adsorption of OTC by MWCNTs significantly. The increase of OTC adsorption after ultrasonic treatment was observed in case of MWCNTs alone and MWCNTs with SDBS and TX100. However, ultrasonic treatment caused OTC adsorption decrease in the presence of CTAB. The change of pH had also an important effect on OTC adsorption in the presence of surfactants. Depending on the surfactant and pH, an increase or decrease of OTC adsorption was observed. The presence of surfactants increased OTC desorption from MWCNTs significantly as follows: SDBS = CTAB < TX100. The results obtained suggest new potential threats and constitute a basis for further research considering the bioavailability and toxicity of antibiotics in the presence of MWCNTs and surfactants.     

新生态MnO_2处理土霉素生产废水的实验研究

用高锰酸钾和硫酸锰反应制得亚微米级新生态MnO2 .采用先石灰法除草酸盐、后用&MnO2 吸附处理CODcr≤ 5 70 0mg/L的土霉素生产废水的方案 ,在pH <3、MnO2 投加量为 30 0ppm及常温常压下 ,则可使COD去除率达到 58.1～ 65 .9% .实验证明 ,新生态MnO2 吸附剂有一定的应用前景     

The effect of oxytetracycline on physiological and enzymatic defense responses in aquatic plant species Egeria densa,Azolla caroliniana,and Taxiphyllum barbieri

Oxytetracycline is an antibiotic widely employed in aquaculture to control and treat bacterial diseases of fish. Due to ineffective wastewater treatment, antibiotic residues from fish ponds are directly released into surface and groundwater affecting the environment. The Green Liver System® is a sustainable and cost-effective water treatment based on the ability of aquatic plants to biotransformation xenobiotics. To expand the application range of this system, Egeria densa, Azolla caroliniana, and Taxiphyllum barbieri were tested in response to oxytetracycline exposure. The aquatic plants were exposed to 0.5, 2.0, 5.0, and 25 μg/L oxytetracycline (n = 4) for 24 h in order to analyze the physiological responses (photosynthetic pigment contents and hydrogen peroxide formation -- H₂O₂), the biotransformation process (activity of glutathione S-transferase), and the antioxidant defense (glutathione reductase; peroxidase; and catalase) responses. There were no statistical differences in the photosynthetic pigment contents and H₂O₂ level between the treatment and control groups in the three aquatic plant species. It can be concluded that oxytetracycline does not provoke physiological damage to the tested species within 24 h of exposure. Nevertheless, the antioxidant defense mechanism was activated. Peroxidase and catalase were the most prominent antioxidant enzymes in the three plant species, whereas glutathione S-transferase activity was significantly increased in A. caroliniana and T. barbieri.