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
-
摘要: 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。Abstract: 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.
-
Key words:
- antibiotics /
- aquaculture /
- detection methods /
- residual levels
-
-
Liu H, Su J. Vulnerability of China's nearshore ecosystems under intensive mariculture development[J]. Environmental Science and Pollution Research, 2017, 24(10):8957-8966 Cao L, Naylor R L, Henriksson P J, et al. China's aquaculture and the world's wild fisheries[J]. Science, 2015, 347(6218):133-135 Moffitt C M, Cajascano L. Blue growth:The 2014 FAO state of world fisheries and aquaculture[J]. Fisheries, 2014, 39(11):552-553 Wang Q D, Cheng L, Liu J S, et al. Freshwater aquaculture in PR China:Trends and prospects[J]. Reviews in Aquaculture, 2016, 7(4):283-302 Gothwal R, Shashidhar T. Antibiotic pollution in the environment:A review[J]. Clean-Soil Air Water, 2015, 43(4):479-489 Rigos G, Bitchava K, Nengas I, et al. Antibacterial drugs in products originating from aquaculture:Assessing the risks to public welfare[J]. Mediterranean Marine Science, 2010, 11(1):33-41 Zhang Q Q, Ying G G, Pan C G, et al. Comprehensive evaluation of antibiotics emission and fate in the river basins of China:Source analysis, multimedia modeling, and linkage to bacterial resistance[J]. Environmental Science and Technology, 2015, 49(11):6772-6782 Kumar K, Gupta S C, Chander Y, et al. Antibiotic use in agriculture and its impact on the terrestrial environment[J]. Advances in Agronomy, 2005, 87(5):1-54 Rico A, Phu T M, Satapornvanit K, et al. Use of veterinary medicines, feed additives and probiotics in four major internationally traded aquaculture species farmed in Asia[J]. Aquaculture, 2013, 412-413(2):231-243 Conkle J L, Lattao C, White J R, et al. Competitive sorption and desorption behavior for three fluoroquinolone antibiotics in a wastewater treatment wetland soil[J]. Chemosphere, 2010, 80(11):1353-1359 Baquero F, Martínez J L, Cantón R, et al. Antibiotics and antibiotic resistance in water environments[J]. Current Opinion in Biotechnology, 2008, 19(3):260-265 Kim H Y, Yu S H, Lee M J, et al. Radiolysis of selected antibiotics and their toxic effects on various aquatic organisms[J]. Radiation Physics and Chemistry, 2009, 78(4):267-272 Landers T F, Cohen B, Wittum T E, et al. Areview of antibiotic use in food animals:Perspective, policy, and potential[J]. Public Health Reports, 2012, 127(1):4-22 骆健美,卢学英,张敏卿.微波萃取技术及其应用[J].化工进展, 2001, 20(12):46-49 Luo J M, Lu X Y, Zhang M Q. Mircrowave aided extraction technique and its application[J]. Chemical Industry and Engineering Progress, 2001, 20(12):46-49(in Chinese)
Huang Y J, Cheng M M, Li W H, et al. Simultaneous extraction of four classes of antibiotics in soil, manure and sewage sludge and analysis by liquid chromatographytandem mass spectrometry with the isotope-labelled internal standard method[J]. Analytical Methods, 2013, 5(15):3721-3731 Blackwell P A, Lützhøft H H, Ma H P, et al. Ultrasonic extraction of veterinary antibiotics from soils and pig slurry with SPE clean-up and LC-UV and fluorescence detection[J]. Talanta, 2004, 64(4):1058-1064 Luo Y, Xu L, Rysz M, et al. Occurrence and transport of tetracycline, sulfonamide, quinolone, and macrolide antibiotics in the Haihe River basin, China[J]. Environmental Science and Technology, 2011, 45(5):1827-1833 Hu W, Ma L L, Guo C S, et al. Simultaneous extraction and determination of fluoroquinolones, tetracyclines and sulfonamides antibiotics in soils using optimised solid phase extraction chromatography-tandem mass spectrometry[J]. International Journal of Environmental Analytical Chemistry, 2012, 92(6):698-713 Léon Bouyou P A, Weisser J J, Strobel B W. Determination of sulfadiazine in phosphate-and DOC-rich agricultural drainage water using solid-phase extraction followed by liquid chromatography-tandem mass spectrometry[J]. Analytical and Bioanalytical Chemistry, 2014, 406(20):5019-5030 Spongberg A L, Witter J D. Pharmaceutical compounds in the wastewater process stream in Northwest Ohio[J]. Science of the Total Environment, 2008, 397(1):148-157 徐琳,罗义,徐冰洁.海河底泥中12种抗生素残留的液相色谱串联质谱同时检测[J].分析测试学报, 2010, 29(1):17-21 Xu L, Luo Y, Xu B J. Simultaneous determination for 12 antibiotics in sediments of Haihe River by HPLC-MS/MS method[J]. Journal of Instrumental Analysis, 2010, 29(1):17-21(in Chinese)
Zou S C, Xu W H, Zhang R J, et al. Occurrence and distribution of antibiotics in coastal water of the Bohai Bay, China:Impacts of river discharge and aquaculture activities[J]. Environmental Pollution, 2011, 159(10):2913-2920 Lei X N, Lu J J, Liu Z L, et al. Concentration and distribution of antibiotics in water-sediment system of Bosten Lake, Xinjiang[J]. Environmental Science and Pollution Research, 2015, 22(3):1670-1678 Chen H, Shan L, Xu X R, et al. Antibiotics in typical marine aquaculture farms surrounding Hailing Island, South China:Occurrence, bioaccumulation and human dietary exposure[J]. Marine Pollution Bulletin, 2015, 90(1-2):181-187 Xu W H, Zhang G, Zou S C, et al. Determination of selected antibiotics in the Victoria Harbour and the Pearl River, South China using high-performance liquid chromatography-electrospray ionization tandem mass spectrometry[J]. Environmental Pollution, 2007, 145(3):672-679 Riaz L, Mahmood T, Khalid A, et al. Fluoroquinolones (FQs) in the environment:A review on their abundance, sorption and toxicity in soil[J]. Chemosphere, 2017, 191:704-720 Gao P P, Mao D Q, Luo Y, et al. Occurrence of sulfonamide and tetracycline-resistant bacteria and resistance genes in aquaculture environment[J]. Water Research, 2012, 46(7):2355-2364 李堃,赵丹莹,郭蒙京.淡水鱼中喹乙醇含量的液相色谱测定法[J].职业与健康, 2013, 29(3):322-324 Li K, Zhao D Y, Guo M J. Determination of olaquindox in freshwater fish by HPLC[J].Occupation and Health, 2013, 29(3):322-324(in Chinese)
Van Doorslaer X, Dewulf J, Van Langenhove H, et al. Fluoroquinolone antibiotics:An emerging class of environmental micropollutants[J]. Science of the Total Environment, 2014, 500-501(1-3):250-269 丁惠君,钟家有,邹斌春,等.环鄱阳湖水产养殖区典型抗生素污染特征[C].北京:第八届全国河湖治理与水生态文明发展论坛, 2016 梁惜梅,施震,黄小平.珠江口典型水产养殖区抗生素的污染特征[J].生态环境学报, 2013(2):304-310 Liang X M, Shi Z, Huang X P. Occurrence of antibiotics in typical aquaculture of the Pearl River Estuary[J]. Ecology and Environmental Sciences, 2013 (2):304-310(in Chinese)
陈永山,章海波,骆永明,等.典型规模化养猪场废水中兽用抗生素污染特征与去除效率研究[J].环境科学学报, 2010, 30(11):2205-2212 Chen Y S, Zhang H B, Luo Y M, et al. A preliminary study on the occurrence and dissipation of antibiotics in swine wastewater[J]. Acta Scientiae Circumstantiae, 2010, 30(11):2205-2212(in Chinese)
Li W H, Shi Y L, Gao L H, et al. Occurrence of antibiotics in water, sediments, aquatic plants, and animals from Baiyangdian Lake in North China[J]. Chemosphere, 2012, 89(11):1307-1315 Xu J, Zhang Y, Zhou C B, et al. Distribution, sources and composition of antibiotics in sediment, overlying water and pore water from Taihu Lake, China[J]. Science of the Total Environment, 2014, 497-498(3):267-273 Jiang L, Hu X L, Yin D Q, et al. Occurrence, distribution and seasonal variation of antibiotics in the Huangpu River, Shanghai, China[J]. Chemosphere, 2011, 82(6):822-828 Arikan O A, Rice C, Codling E. Occurrence of antibiotics and hormones in a major agricultural watershed[J]. Desalination, 2008, 226(1):121-133 Vieno N M, Härkki H, Tuhkanen T, et al. Occurrence of pharmaceuticals in river water and their elimination in a pilot-scale drinking water treatment plant[J]. Environmental Science and Technology, 2007, 41(14):5077-5084 Zheng Q, Zhang R J, Wang Y H, et al. Occurrence and distribution of antibiotics in the Beibu Gulf, China:Impacts of river discharge and aquaculture activities[J]. Marine Environmental Research, 2012, 78(8):26-33 聂湘平,何秀婷,杨永涛,等.珠江三角洲养殖水体中喹诺酮类药物残留分析[J].环境科学, 2009, 30(1):266-270 Nie X P, He X T, Yang Y T, et al. Investigation of quinolones in aquaculture environment of the Pearl River Delta[J]. Environmental Science, 2009, 30(1):266-270(in Chinese)
Gao L H, Shi Y L, Li W H, et al. Occurrence, distribution and bioaccumulation of antibiotics in the Haihe River in China[J]. Journal of Environmental Monitoring, 2012, 14(4):1248-1255 Chen H, Liu S, Xu X R, et al. Tissue distribution, bioaccumulation characteristics and health risk of antibiotics in cultured fish from a typical aquaculture area[J]. Journal of Hazardous Materials, 2018, 343:140-148 马敬中,武冬梅,汪有生.喹乙醇在我国的应用研究进展[J].化学世界, 2008, 49(10):630-633 Ma J Z, Wu D M, Wang Y S. Progress on the study of olaquindox in our country[J]. Chemical World, 2008, 49(10):630-633(in Chinese)
Halling-Sørensen B, Sengeløv G, Ingerslev F, et al. Reduced antimicrobial potencies of oxytetracycline, tylosin, sulfadiazin, streptomycin, ciprofloxacin, and olaquindox due to environmental processes[J]. Archives of Environmental Contamination and Toxicology, 2003, 44(1):7-16 Kim S C, Carlson K. Temporal and spatial trends in the occurrence of human and veterinary antibiotics in aqueous and river sediment matrices[J]. Environmental Science and Technology, 2007, 41(1):50-57 Radke M, Lauwigi C, Heinkele G, et al. Fate of the antibiotic sulfamethoxazole and its two major human metabolites in a water sediment test[J]. Environmental Science and Technology, 2009, 43(9):3135-3141 -
点击查看大图
计量
- 文章访问数: 3714
- HTML全文浏览数: 3714
- PDF下载数: 94
- 施引文献: 0
下载:
