"Dunarea de Jos" University of Galaţi, Faculty of Food Science and Engineering, Str. Domnească 111, 800201 Galaţi, Romania.
RIKILT, Wageningen University and Research, P.O. Box 230, NL-6700 AE Wageningen, The Netherlands.
Sci Total Environ. 2015 Nov 1;532:501-11. doi: 10.1016/j.scitotenv.2015.06.010. Epub 2015 Jun 19.
The occurrence of 67 pharmaceutical and antifungal residues in the Danube river on the Romanian territory was studied by using solid-phase extraction (SPE) and LC-Q Exactive Orbitrap high resolution MS in both full scan (FS) MS and targeted MS/MS modes. A single-laboratory validation procedure was carried out for the determination of 67 compounds in FSMS mode evaluating selectivity, sensitivity, linearity, precision and accuracy. The method showed satisfactory analytical performance. The evaluation of the recovery concluded that 75% of the compounds show recoveries between 85 and 115% and 10% of the compounds show recoveries between 85% and 65%. The level of detection was lower than 5 ng l(-1) for 66% of the compounds, between 5 and 10 ng l(-1) for 22% and between 10 and 25 ng l(-1) for 14% of the compounds. The coefficients of determination R(2) were higher than 0.99 for 79% of the compounds, over a linearity range of 2.5-50 ng l(-1). Targeted MS/MS analysis, performed in addition to the full scan acquisition was used for confirmatory purpose. Twenty samples of Danube water and three of the main tributaries were collected in May, July, August and October 2014. Analysis of the selected water samples revealed the occurrence of 23 compounds such as diclofenac, carbamazepine, sulfamethoxazole, tylosin, indomethacin, ketoprofen, piroxicam, together with antifungals like thiabendazole, and carbendazim. Carbamazepine was detected in 17 samples, the maximum concentration being 40 ng l(-1). The highest concentration reached was 166 ng l(-1) for diclofenac.
本研究采用固相萃取（SPE）和 LC-Q Exactive Orbitrap 高分辨质谱，在全扫描（FS）MS 和靶向 MS/MS 模式下，对罗马尼亚境内多瑙河的 67 种药物和抗真菌残留进行了研究。采用单实验室验证程序，对 FSMS 模式下 67 种化合物的测定进行了选择性、灵敏度、线性、精密度和准确度的评估。该方法表现出良好的分析性能。对回收率的评价表明，75%的化合物回收率在 85%至 115%之间，10%的化合物回收率在 85%至 65%之间。66%的化合物检测限低于 5ng/L，22%的化合物检测限在 5-10ng/L 之间，14%的化合物检测限在 10-25ng/L 之间。79%的化合物的相关系数 R（2）高于 0.99，线性范围为 2.5-50ng/L。除全扫描采集外，还进行了靶向 MS/MS 分析，用于确证目的。2014 年 5 月、7 月、8 月和 10 月采集了多瑙河河水和三条主要支流的 20 个水样。对选定水样的分析显示，出现了 23 种化合物，如双氯芬酸、卡马西平、磺胺甲恶唑、泰乐菌素、吲哚美辛、酮洛芬、吡罗昔康，以及噻苯达唑和多菌灵等抗真菌药物。在 17 个样本中检测到卡马西平，最大浓度为 40ng/L。双氯芬酸的最高浓度达到 166ng/L。
