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    固相萃取-超高效液相色谱-串联质谱法测定饮用水中18种典型药品和个人护理品

    UPLC-MS/MS Determination of 18 Typical Pharmaceutical and Personal Care Products in Drinking Water with Enrichment by Separation on Solid Phase Extraction

    • 摘要: 取饮用水样1.0 L,用0.2 μm滤膜过滤。滤液以5 mL·min-1的流量通过活化后的HLB固相萃取柱(SPE),使18种被测物在柱上分离富集。先后用水10 mL和15%(体积分数)甲醇溶液10 mL淋洗HLB柱,随即用甲醇15 mL洗脱吸附于柱上的被测物。收集洗脱液并于30℃下吹氮,使其体积蒸缩至200 μL,加水定容至1.0 mL,离心10 min,取其上清液,用0.22 μm针式过滤器过滤后,取其滤液在仪器工作条件下进行超高效液相色谱-串联质谱(UPLC-MS/MS)分析。选用Waters UPLCTM BEH C18色谱柱作为分离柱,用不同比例的(A)8 mmol·L-1甲酸铵溶液含0.1%(体积分数,下同)甲酸和(B)体积比为1∶1甲醇-乙腈混合液(含1%甲酸)的混合液作为流动相,将色谱柱上的被测物进行梯度洗脱,18种分析物可在34 min内达到较好的分离。在MS/MS分析中选择电喷雾离子源正离子(ESI+)和多反应监测(MRM)模式进行测定。所涉及18种被测物的质量浓度均在15 μg·L-1内与其对应的色谱峰面积呈线性关系,其检出限(3S/N)为5~50 pg·L-1。以超纯水和自来水为基质进行加标回收试验,回收率分别为64.4%~113%和78.2%~116%,测定值的相对标准偏差(n=5)分别为1.6%~19%和2.8%~18%。对采自全国不同区域的7个水厂的实样按方法进行分析,其中有3份水样中检出4-乙酰氨基安替比林的含量高于1 ng·L-1;在所测7份水样中均测得卡马西平和吡喹酮,其含量均低于1 ng·L-1;还在3~5份水样中测得含量1 ng·L-1的四咪唑、磺胺甲恶唑、磺胺噻唑和磺胺二甲基嘧啶等化合物。

       

      Abstract: 1.0 L of drinking water sample was taken and filtered through 0.22 μm filtering membrane, and the filtrate was passed through the activated HLB SPE column at a flow-rate of 5 mL·min-1 to have the 18 typical pharmaceutical and personal-care products (PPCPs) enriched and separated on the SPE column. The column was then rinsed with 10 mL of water and 10 mL of 15% (φHCOOH) methanol solution successively. The 18 analytes were eluted from the SPE column with 15 mL of methanol and the eluate was collected and evaporated to ca. 200 μL by N2-blowing at 30℃. Water was added to the residue to make its volume to 1.0 mL, and after centrifugation for 10 min, the supernatant was taken and filtered through an injection filter, and the filtrate was used for UPLC-MS/MS analysis under the instrumental working conditions. Waters UPLCTM BEH C18 column was used for chromatographic separation with mobile phase mixtures composing of (A) 8 mmol·L-1 HCOONH4 solution0.1% formic acid (volume fraction, the same below) and (B) mixture of CH3OH-CH3CN at a volume ratio of 1:1 (1% formic acid) in various proportions, to elute the 18 analytes from the chromatographic column by gradient elution. The 18 analytes were well saparated within 34 min. ESI+ mode and MRM mode were adopted in MS/MS determination. Linear relationships between values of peak areas and mass concentration of the 18 analytes were found in the same range within 15 μg·L-1. Values of detection limit (3S/N) found were in the range from 5 to 50 pg·L-1. Recovery tests were made by standard addition method using extrapure water and tap water as matrixes, giving results of recovery in the ranges of 64.4%-113% and 78.2%-116% respectively, and values of RSDs (n=5) found were ranged from 1.6% to 19% (for extrapure water) and from 2.8% to 18% (for tap water). Drinking water samples were collected from 7 water works in various regions of our country, and were analyzed by the proposed method. 4-Acetylaminoantipyrine with contents over 1 ng·L-1 were found in 3 of the 7 samples; carbamazepine and praziquantel in amounts lower than 1 ng·L-1 were found in all the 7 samples; and imidazole, sulfamethoxazole, sulfathiazole, sulfamethazine etc. in amounts less than 1 ng·L-1 were found in 3 to 5 among the 7 samples.

       

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