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 solution[0.1% 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.
中图分类号 O657.63 DOI 10.11973/lhjy-hx202006004
所属栏目 工作简报
基金项目 上海市卫生体系建设第四轮三年行动计划重点学科建设项目(15GWZK0201)
收稿日期 2019/8/26
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作者单位点击查看
联系人作者刘敏(lium@apm.sh.cn)
备注沈璐,工程师,主要从事色谱分析工作
引用该论文: SHEN Lu,YIN Haowen,LIU Min,WANG Yingzhi. UPLC-MS/MS Determination of 18 Typical Pharmaceutical and Personal Care Products in Drinking Water with Enrichment by Separation on Solid Phase Extraction[J]. Physical Testing and Chemical Analysis part B:Chemical Analysis, 2020, 56(6): 641~649
沈璐,殷浩文,刘敏,王樱芝. 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[J]. 理化检验-化学分册, 2020, 56(6): 641~649
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参考文献
【1】DAUGHTON C G, TERNES T A. Pharmaceuticals a-personal care products in the environment:agents of subtle change?[J]. Environmental Health Perspectives, 1999,107(S6):907-938.
【2】HALLING-SØRENSEN B, NORS NIELSEN S, LANZKY P F, et al. Occurrence,fate a-effects of pharmaceutical substances in the environment-A review[J]. Chemosphere, 1998,36(2):357-393.
【3】QIAO T J, YU Z R, ZHANG X H, et al. Occurrence a-fate of pharmaceuticals a-personal care products in drinking water in Southern China[J]. Journal of Environmental Monitoring, 2011,13(11):3097-3103.
【4】LI N T, YU S L, CHEN W. Occurrence,removal a-risk assessment of pharmaceutical a-personal care products (PPCPs) in an advanced drinking water treatment plant (ADWTP) arou-Taihu Lake in China[J]. Chemosphere, 2016,152:1-9.
【5】PADHYELP, YAO H, KUNG'U F T, et al. Year-long evaluation on the occurrence a-fate of pharmaceuticals,personal care products, a- e-ocrine disrupting chemicals in an urban drinking water treatment plant[J]. Water Research, 2014,51:266-276.
【6】BULL R J, CROOK J, WHITTAKER M, et al. Therapeutic dose as the point of departure in assessing potential health hazards from drugs in drinking water a-recycled municipal wastewater[J]. Regulatory Toxicology a-Pharmacology, 2011,60(1):1-19.
【7】乔铁军,张锡辉,欧慧婷.饮用水中药品和个人护理用品的研究进展[J].给水排水, 2010,36(4):118-125.
【8】王炼,黎源倩,张礼春.超高效液相色谱同时测定奶粉和牛奶中β-内酰胺、喹诺酮和大环内酯类抗生素的残留[J].分析试验室, 2011,30(6):23-27.
【9】贾妍艳,谭建华,徐晨,等.固相萃取-气相色谱-质谱法同时测定水中9种药品及个人护理用品[J].色谱, 2014,32(3):263-267.
【10】刘思思,杜鹃,陈景文,等.加速溶剂萃取-高效液相色谱-串联质谱联用测定莱州湾海水养殖区野生鱼肌肉中19种抗生素及2种磺胺代谢产物残留[J].色谱, 2014,32(12):1320-1325.
【11】胡冠九,陈素兰,穆肃,等.江苏省某市典型饮用水水源中抗生素质量浓度特征[J].水资源保护, 2016,32(3):84-88.
【12】张崇,薛飞群,张丽芳,等.亲水液相色谱-串联质谱法测定羊肌肉组织中安乃近代谢物的残留量[J].食品科学, 2014,35(10):158-162.
【2】HALLING-SØRENSEN B, NORS NIELSEN S, LANZKY P F, et al. Occurrence,fate a-effects of pharmaceutical substances in the environment-A review[J]. Chemosphere, 1998,36(2):357-393.
【3】QIAO T J, YU Z R, ZHANG X H, et al. Occurrence a-fate of pharmaceuticals a-personal care products in drinking water in Southern China[J]. Journal of Environmental Monitoring, 2011,13(11):3097-3103.
【4】LI N T, YU S L, CHEN W. Occurrence,removal a-risk assessment of pharmaceutical a-personal care products (PPCPs) in an advanced drinking water treatment plant (ADWTP) arou-Taihu Lake in China[J]. Chemosphere, 2016,152:1-9.
【5】PADHYELP, YAO H, KUNG'U F T, et al. Year-long evaluation on the occurrence a-fate of pharmaceuticals,personal care products, a- e-ocrine disrupting chemicals in an urban drinking water treatment plant[J]. Water Research, 2014,51:266-276.
【6】BULL R J, CROOK J, WHITTAKER M, et al. Therapeutic dose as the point of departure in assessing potential health hazards from drugs in drinking water a-recycled municipal wastewater[J]. Regulatory Toxicology a-Pharmacology, 2011,60(1):1-19.
【7】乔铁军,张锡辉,欧慧婷.饮用水中药品和个人护理用品的研究进展[J].给水排水, 2010,36(4):118-125.
【8】王炼,黎源倩,张礼春.超高效液相色谱同时测定奶粉和牛奶中β-内酰胺、喹诺酮和大环内酯类抗生素的残留[J].分析试验室, 2011,30(6):23-27.
【9】贾妍艳,谭建华,徐晨,等.固相萃取-气相色谱-质谱法同时测定水中9种药品及个人护理用品[J].色谱, 2014,32(3):263-267.
【10】刘思思,杜鹃,陈景文,等.加速溶剂萃取-高效液相色谱-串联质谱联用测定莱州湾海水养殖区野生鱼肌肉中19种抗生素及2种磺胺代谢产物残留[J].色谱, 2014,32(12):1320-1325.
【11】胡冠九,陈素兰,穆肃,等.江苏省某市典型饮用水水源中抗生素质量浓度特征[J].水资源保护, 2016,32(3):84-88.
【12】张崇,薛飞群,张丽芳,等.亲水液相色谱-串联质谱法测定羊肌肉组织中安乃近代谢物的残留量[J].食品科学, 2014,35(10):158-162.
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