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

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

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3612.85 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。

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 3612.85 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.