水产养殖水、沉积物中抗生素检测方法优化及残留特征研究

抗生素作为疾病预防和促进生长的药物被广泛用于水产养殖业中,不可避免地造成了周围环境抗生素的残留,从而带来各种潜在风险。为了对水产养殖水和沉积物中的抗生素残留特征进行研究,建立了环境样品中抗生素的富集方法。对沉积物中抗生素的提取溶剂、HLB小柱活化溶剂和洗脱溶剂进行了筛选,利用高效液相色谱串联质谱仪对15种抗生素进行检测分析,并检测了上海市某水产养殖区7个养殖塘2018年9、12月抗生素的残留水平。结果表明,选用乙腈/磷酸盐缓冲溶液(V∶V=1∶1)作为提取溶剂,依此用甲基叔丁基醚、甲醇和超纯水作为活化溶剂,甲醇作为洗脱溶剂时目标抗生素的回收率最高;在养殖塘水体中共检测出10种抗生素,检出浓度中间值依次为:磺胺类>甲氧苄啶>阿莫西林>氟喹诺酮类>喹乙醇>四环素类和呋喃唑酮。养殖塘沉积物中共检测出13种抗生素,检出浓度中间值依次为:氟喹诺酮类>四环素类>磺胺类>甲氧苄啶>喹乙醇>阿莫西林和呋喃唑酮;不同品种的养殖塘中抗生素的检出种类均不相同,其中青鱼塘和白水鱼塘10种、虾塘9种、扣蟹塘仅5种。对比抗生素检出浓度发现:氟喹诺酮类抗生素在鱼类养殖塘中检出浓度最高,磺胺甲恶唑仅在蟹塘检出,喹乙醇在虾塘检出浓度达3 612.85 ng·L~(-1)。9月与12月抗生素的残留水平也存在差异,抗生素在9月的平均含量比12月高。

Optimization of Antibiotic Detection Methods and Residual Characteristics in Aquaculture Water and Sediment

Antibiotics were widely used in aquaculture as a drug for disease prevention, growth promotion, which inevitably lead to antibiotic residues in the surrounding environment, resulting in a variety of potential risks. The antibiotic extracts for sediment samples, the HLB cartridge activation solvents and the elution solvent were screened, and 15 antibiotics were detected by high- performance liquid chromatography-tandem mass spectrometry. The method was employed for the detection of residual levels of antibiotics in 7 kinds of aquaculture ponds of a certain aquaculture area in Shanghai in September and December, 2018. The results turned out that employing acetonitrile/phosphate buffer solution (V:V=1:1) as the extract, methyl tert-butyl ether, methanol and ultrapure water as the activation solvent, and methanol as the elution solvent, the target antibiotics showed the highest recovery rate. A total of 10 antibiotics were detected in the water. The order of the intermediate concentrations of antibiotics was: sulfonamides > trimethoprim > amoxicillin > fluoroquinolones > quinoethanol > tetracyclines and furazolidone. A total of 13 antibiotics were detected in the sediments. The order of the intermediate concentrations of antibiotics was: fluoroquinolones > tetracyclines > sulfonamides > trimethoprim > quinoethanol > amoxicillin and furazolidone. The types and concentrations of antibiotics in different cultured ponds were different. 10 kinds of antibiotics were detected in Mylopharyngodon piceus ponds and Erythroculter ilishaeformis ponds, 9 antibiotics were detected in Penaeus vannamei ponds, and only 5 antibiotics were detected in Eriocheir sinensis H. Milne-Edwards ponds. The highest concentration of fluoroquinolones was detected in fishponds. Sulfamethoxazole was only detected in Eriocheir sinensis H. Milne-Edwards ponds. The concentration of olaquindox in Penaeus vannamei ponds was 3 612.85 ng L^-1. There was also a difference in the concentration of antibiotics detected between September and December, and the average level of antibiotics in September was higher than in December.