液相色谱-串联质谱法测定饮用水中6类12种药品和个人护理品

建立了同时检测饮用水中6大类共12种典型药品和个人护理品(Pharmaceuticals and personal care products,PPCPs)的自动固相萃取-液相色谱-电喷雾三重四极杆串联质谱(ASPE-HPLC--ESI-MS/MS)方法.样品经ASPE(自动固相萃取)富集提取后,40℃氮吹至近干,用甲醇-水溶液(20∶80,V/V)定容至1 mL后测定.采用正离子和负离子多反应监测离子模式(MRM)定性分析,针对不同扫描模式优化流动相条件,两次进样分析.在低、中、高的3个添加水平下,12种PPCPs的方法回收率为60.8%—110%,相对标准偏差为2.0%—14.0%;检出限(LOD)为0.02—1.5 ng·L-1,定量限(LOQ)为0.06—5 ng·L-1.应用该方法调查了北京市饮用水中PPCPs污染状况,结果表明,9种PPCPs(氧氟沙星、脱水红霉素、磺胺甲恶唑、卡马西平、舒必利、普萘洛尔、萘普生、苯扎贝特和双酚A)在不同饮用水水样中被检出,最高浓度为苯扎贝特34.47 ng·L-1.该方法操作简单、灵敏度高、选择性强,符合饮用水样品中痕量污染物检测要求.     

固相萃取-高效液相色谱-串联质谱法测定地表水中40种抗生素

建立了固相萃取-高效液相色谱-串联质谱法(HLB-HPLC-MS9种氟喹诺酮类(QNs)、7种大环内酯类(MCs)、3种四环素类(TCs)、2种氯霉素类(CAPs)和4种其他类(Others)共40种抗生素的分析方法.通过重点优化水样不同pH值、乙二胺四乙酸二钠(Na2EDTA)加入量、色谱条件和质谱参数等确定了最佳分析条件.水样经HLB固相萃取柱富集净化,采用Agilent Zorbax Rrhd Eclipse Plus C18 (2.1 mm×50 mm,1.8μm)色谱柱分离,正、负离子模式分别采集,正离子模式采用0.2%甲酸-2 mmol乙酸铵水溶液和甲醇-乙腈(V/V,1∶1)作流动相梯度洗脱分离38种单体;负离子模式采用纯水和甲醇-乙腈(V/V,1∶1)作流动相梯度分离2种单体,多重反应监测模式分析,内标法定量.结果显示:目标分析物线性范围在1.00—200 ng·mL~(-1)之间,相关系数r2均大于0.99,方法检出限在0.002—0.270 ng·L~(-1)之间,地表水加标回收率在61.0%—149%之间,相对标准偏差(RSD)在1.2%—32%之间.方法成功应用于贵阳市南明河12个地表水分析,共检出34种抗生素,其中大环内酯类检出浓度最高,平均浓度为257 ng·L~(-1).     

在线固相萃取-液相色谱-串联质谱法同时检测海水养殖水体中15种药物

采用在线固相萃取-液相色谱-串联质谱联用(On-line SPE-LC-MS/MS)技术,建立海水循环水养殖系统中磺胺类(磺胺甲基异恶唑、磺胺噻唑、磺胺嘧啶、磺胺甲基嘧啶、磺胺二甲嘧啶)、大环内酯类(克拉霉素、脱水红霉素)、喹诺酮类(恩诺沙星、氧氟沙星、诺氟沙星)、四环素类(金霉素、四环素、土霉素)13种抗生素及孔雀石绿、隐色孔雀石绿共15种药物的同时检测方法,为循环水养殖海水中部分有机污染物的检验鉴定提供依据.采用0.1%(V/V)甲酸水溶液和0.1%(V/V)甲酸的乙腈-甲醇(1∶1,V/V)溶液为分析流动相,水样经简单酸化处理后直接进样0.9 mL进行On-line SPE-LCMS/MS检测,经在线固相萃取柱富集后,经过梯度洗脱分离,串联质谱多反应监测模式进行定性、定量分析测定.结果表明,15种目标化合物在1—100 ng·L^-1范围内均具有良好的线性响应,方法检出限范围为0.02—1.00 ng·L^-1,定量限范围为0.06—3.00 ng·L^-1.采用该方法对山东省烟台市某水产公司2个海水循环水养殖系统的15...     

在线固相萃取-高效液相色谱-串联质谱法测定地表水中8种全氟化合物

建立了在线固相萃取-高效液相色谱-串联质谱法(On-Line SPE-HPLC-MS/MS)检测地表水中8种全氟化合物(perfluorinated compounds,PFCs)的分析方法.该方法用电喷雾离子源(ESI)在选定的多反应监测(MRM)负模式下确定目标化合物并使用同位素内标法定量,测定了地表水中的PFCs. 8种PFCs的样品加标回收率在82.1%—103%之间,线性范围在0.66—500 ng·L^-1之间,相关系数(R²)在0.991—0.998之间,精密度(RSD)在3.95%—6.29%之间,检出限(LOD)在0.20—2.43 ng·L^-1之间,定量限(LOQ)在0.66—8.09 ng·L^-1之间.方法应用于大凌河及小清河地表水的分析,分析结果与该领域其他研究的结果一致,表明该方法具有实际应用意义.     

超高效液相色谱-串联质谱法同时测定环境水样中的15种抗生素

采用固相萃取/超高效液相色谱-串联质谱法,建立了水样中磺胺类、四环素类、氟喹诺酮类、大环内酯类和氯霉素类15种抗生素的同时测定方法.水样经HLB固相萃取柱富集,ACQUITY UPLC BEH C_(18)色谱柱分离,以乙腈和5 mmol·L~(-1)乙酸铵溶液(含0.1%甲酸)为流动相梯度洗脱,电喷雾离子源-串联质谱多反应监测模式检测.结果表明,同时测定15种抗生素的线性范围为5—100μg·L~(-1)(相关系数均大于0.997),检出限为2.1—22.0 ng·L~(-1),定量限为6.9—71.8 ng·L~(-1);空白水样在加标水平为5、10、20μg·L~(-1)时,抗生素的回收率为50.1%—109.0%,相对标准偏差为0.4%—8.5%(n=7).用本文建立的方法检测某农业小流域环境水样,发现5类抗生素可被不同程度检出,浓度范围为0.1—106.2 ng·L~(-1).     

固相萃取-高效液相色谱-串联质谱法测定水体中三苯乙烯基苯酚聚氧乙烯醚

本研究建立了固相萃取结合高效液相色谱-串联质谱测定水体中痕量三苯乙烯基苯酚聚氧乙烯醚(TSPEOn,n=6—29)的方法.水样经HLB柱富集,用10 mL二氯甲烷-甲醇混合溶液(1∶1)洗脱,将洗脱液氮吹至近干后,用乙腈定容至0.5 mL.采用C18(2.1 mm×50 mm,5μm)+Silica(2.1 mm×150 mm,4μm)串联色谱柱,以乙腈和2 mmol·L~(-1)乙酸铵水为流动相,在电喷雾正离子、多反应监测模式下对TSPEOs进行定性分析,外标法进行定量分析.结果表明,TSPEOn(n=6—29)在0.06—512.5μg·L~(-1)浓度范围内线性关系良好,线性相关系数在0.989—0.999之间,方法检出限为0.001—0.22 ng·L~(-1),定量限为0.004—0.72 ng·L~(-1),平均回收率在67.4%—103.3%之间,相对标准偏差为0.7%—14.8%,该方法可用于实际地表水样中痕量TSPEOn(n=6—29)的测定.     

固相萃取-超高效液相色谱-串联质谱法测定污水中16种全氟和多氟烷基化合物

建立了以固相萃取-超高效液相色谱-串联质谱同时测定污水中16种全氟和多氟烷基化合物(PFASs)的方法.样品经固相萃取柱富集浓缩,采用BEH-C18色谱柱(2.1 mm×100 mm,1.7μm),以甲醇和5 mmol·L-1乙酸铵溶液(pH=9)为流动相梯度淋洗,负离子多反应监测模式进行定性和定量分析,内标法定量.1...     

超高效液相色谱串联质谱法检测鱼体中的全氟化合物

采用超高效液相色谱-串联质谱联用法(UPLC-ESI-MS/MS),建立了检测1种贝类和2种鱼类的肌肉组织中11种全氟化合物(PFCs)的分析方法.采用碱液消解做为样品前处理法,选Carbon/NH2双层SPE小柱做为净化小柱,并以ACQUITY UPLC BEH C18为分析柱,甲醇和2 mmol.L-15%甲醇乙酸铵溶液为梯度淋洗液.所选定的11种全氟化合物在6 min内就可以达到良好分离,外标法定量.平均回收率在72.1%—93.6%之间,相对标准偏差在0.6%—9.5%之间,实际检出限在3.4—26.7 pg.g-1.     

Determination of 27 pharmaceuticals and personal care products (PPCPs) in water: The benefit of isotope dilution

• Isotope dilution method was developed for the determination of 27 PPCPs in water. • The established method was successfully applied to different types of water samples. • The correction effect of corresponding 27 ILSs over 70 d was investigated. • Benefit of isotopic dilution method was illustrated for three examples. Pharmaceuticals and personal care products (PPCPs) are a unique group of emerging and non-persistent contaminants. In this study, 27 PPCPs in various water samples were extracted by solid phase extraction (SPE), and determined by isotope dilution method using liquid chromatography coupled to tandem triple quadruple mass spectrometer (LC-MS/MS). A total of 27 isotopically labeled standards (ILSs) were applied to correct the concentration of PPCPs in spiked ultrapure water, drinking water, river, effluent and influent sewage. The corrected recoveries were 73%–122% with the relative standard deviation (RSD)<16%, except for acetaminophen. The matrix effect for all kinds of water samples was<22% and the method quantitation limits (MQLs) were 0.45–8.6 ng/L. The developed method was successfully applied on environmental water samples. The SPE extracts of spiked ultrapure water, drinking water, river and wastewater effluent were stored for 70 days, and the ILSs-corrected recoveries of 27 PPCPs were obtained to evaluate the correction ability of ILSs in the presence of variety interferences. The recoveries of 27 PPCPs over 70 days were within the scope of 72%–140% with the recovery variation<37% in all cases. The isotope dilution method seems to be of benefit when the extract has to be stored for long time before the instrument analysis.     

Determination and occurrence of endocrine disrupting compounds,pharmaceuticals and personal care products in fish (Morone saxatilis)

Endocrine disrupting compounds (EDCs), pharmaceuticals and personal care products (PPCPs) have attracted much attention due to widespread contamination in aquatic environment. In this study, we determined 13 EDCs and PPCPs in fish blood, bile and muscle by using gas chromatography-mass spectrometry (GC-MS). The limits of quantitation (LOQ) were in the ranges of 0.23–2.54, 0.22–2.36 ng·mL⁻¹, and 0.24–2.57 ng·g⁻¹ dry weight (dw) for fish blood, bile and muscle, respectively. Recoveries of target compounds spiked into sample matrices and passed through the entire analytical procedure ranged from 65% to 95%, from 60% to 92% and from 62% to 91% for blood, bile and muscle, respectively. The methods were applied to the analysis of fish from a lake in California. Target compounds were relatively low in bile, and only bisphenol A (BPA) and diclofenac were measurable near the LOQ. Seven of 13 compounds were detected in blood, with total concentrations up to 39 ng·mL⁻¹. Only BPA was frequently found in muscle, with mean concentration of 7.26 ng·g⁻¹ dw. The estimated daily intake of BPA through fish consumption for U.S. resident was significantly lower than the tolerable daily intake recommended by the European Food Safety Authority. This study showed that the exposure to the bisphenol A from fish diet is unlikely to pose a health risk.     

Simultaneous analysis of five taste and odor compounds in surface water using solid-phase extraction and gas chromatography-mass spectrometry

In this paper, a method using solid-phase extraction (SPE) and gas chromatography-mass spectrometry (GC-MS) was developed to simultaneously analyze five taste and odor compounds in surface water, i.e., 2-methylisoborneol (2-MIB), 2,4,6-trichloroanisole (TCA), 2-isopropyl-3-methoxy pyrazine (IPMP), 2-isobutyl-3-methoxy pyrazine (IBMP), and trans-1,10-dimethyl-trans-9-decalol (geosmin, GSM). The mass spectrometry was operated in selective ion monitoring (SIM) mode. Three kinds of SPE columns and three eluting solvents were compared, the C18 column was chosen as optimum SPE column, and methanol was chosen as the optimum eluting solvent. It was found that the method showed good linearity in the range of 1–200 ng·L^-1 and gave detection limits of 0.5–1.5 ng·L^-1 for individual compounds. Good recoveries (93.5%–108%) and relative standard deviations (1.58%–7.31%) were also obtained. Additionally, concentrations of these taste and odor compounds in Jinan’s surface and drinking water were analyzed by applying this method, and the results showed that GSM and 2-MIB were the dominant taste and odor compounds in Jinan’s raw water.     

An efficient resin for solid-phase extraction and determination by UPLCMS/MS of 44 pharmaceutical personal care products in environmental waters

• A hydrophilic resin (GCHM) was facile synthesis and characterized. • Average absolute recovery of GCHM (75.6%) performs better than Oasis^® HLB. • Detection limits of method (SPE-UPLC-MS/MS) ranged between 0.03 and 0.6 ng/L. • 22 PPCPs were determined in environmental waters ranging from 0.5 to 1590 ng/L. In this study, a hydrophilic resin named GCHM was fabricated based on poly(N-vinyl pyrrolidone-co-divinylbenzene), characterized, and applied as a solid-phase extraction (SPE) material. Up to 44 pharmaceuticals and personal care products (PPCPs) belonging to 10 classes were recovered in environmental water samples. Different variables affecting extraction, such as adsorbent amount, sample pH, and loading speed, were optimized. Under optimal conditions, the average absolute recovery of 44 PPCPs was 75.6% using GCHM, indicating a better performance than the commercial Oasis^® HLB. SPE with home-made hydrophilic polymeric sorbent followed by ultra-performance liquid chromatography and tandem mass spectrometry was validated, and the method achieved good linearity (r²>0.991, for all analytes). In addition, the method detection limits of target compounds ranged from 0.03 to 0.6 ng/L. The developed method was applied to determine PPCPs in 10 environmental water samples taken from the Yangtze River, Huaihe River, and Taihu Lake, 1 groundwater sample from Changzhou in Jiangsu Province, 1 wastewater sample from Xiamen and 2 seawater samples from the Jiulong River in Fujian Province, China. In these samples, 22 compounds were determined at levels ranging from 0.5 to 1590 ng/L.     

Simultaneous quantification of several classes of antibiotics in water,sediments, and fish muscles by liquid chromatography-tandem mass spectrometry

Precise and sensitive methods for the simultaneous determination of different classes of antibiotics, including sulphonamides, fluoroquinolones, macrolides, tetracyclines, and trimethoprim in surface water, sediments, and fish muscles were developed. In water samples, drugs were extracted with solid-phase extraction （SPE） by passing 1000 mL of water through hydrophilic lipophilic balanced （HLB） SPE cartridges. Sediment samples were solvent-extracted, followed by tandem SPE （strong anion exchange （SAX） ＋ HLB） clean-ups. Fish muscles were extracted by a mixture of acetonitrile and citric buffer （80：20, v/v） solution, and cleaned by SPE. Liquid chromatography-tandem mass spectrometry （LC-MS/ MS） with multiple reaction monitoring （MRM） detection was employed to quantify all compounds. The recoveries for the antibiotics in the spiked water, sediment, and fish samples were 60.2%-95.8%, 48.1%-105.3%, and 59.8%- 103.4%, respectively. The methods were applied to samples taken from Dianchi Lake, China. It showed that concentrations of the detected antibiotics ranged from limits of quantification （LOQ） to 713.6 ng- L1 （ofloxacin） in surface water and from less than LOQ to 344.8 μg·kg-1 （sulphamethoxazole） in sediments. The number of detected antibiotics and the overall antibiotic concentrations were higher in the urban area than the rural area, indicating the probable role of livestock and human activities as important sources of antibiotic contamination. In fish muscles, the concentration of norfioxacin was the highest （up to 38.5 μg·kg-1）, but tetracyclines and macrolides were relatively low. Results showed that the methods were rapid and sensitive, and capable of determining several classes of antibiotics from each of the water, sediment, and fish matrices in a single run.     

通过式固相萃取/超高效液相色谱-串联质谱法测定蔬菜中18种农药残留

建立了超高效液相色谱-串联质谱(UPLC-MS;MS)快速测定蔬菜中18种农药残留的方法.样品经乙腈提取后,经Oasis PRiME HLB固相萃取柱净化,采用ACQUITY UPLC HSS T3 C18(50 mm×2.1 mm,1.8μm)色谱柱进行分离,以0.1%甲酸水溶液和乙腈作为流动相进行梯度洗脱.采用电喷雾电离源、正离子模式下以多反应监测(MRM)进行定性和定量分析.结果表明,18种农药在0.5—50μg·L^-1范围内线性关系良好(r2>0.995),方法最低检出限为0.4—1.5μg·kg^-1,最低定量限为1.4—5.0μg·kg^-1.在韭菜、芹菜、番茄、白菜基质中,5、10、50μg·kg^-1添加水平下的加标回收率为60.2%—126.9%,相对标准偏差(RSD)为0.4%—21.6%(n=3).     

QuEChERS-超高效液相色谱-串联质谱法测定鱼血清中的精神活性物质

本文建立了一种同时测定鱼血清中19种精神活性物质的分析方法.该方法基于QuEChERS方法对样品进行提取和净化,待测物采用超高效液相色谱-串联质谱法(UPLC-MS/MS)进行分析,检测的19种精神活性物质均采用同位素内标法定量.该方法的方法检测限(MDL)范围为0.02-0.06 ng.mE-1,基质效应处于76.7...     

Simultaneous quantification of several classes of antibiotics in water,sediments, and fish muscles by liquid chromatography–tandem mass spectrometry

Precise and sensitive methods for the simultaneous determination of different classes of antibiotics, including sulphonamides, fluoroquinolones, macrolides, tetracyclines, and trimethoprim in surface water, sediments, and fish muscles were developed. In water samples, drugs were extracted with solid-phase extraction (SPE) by passing 1000 mL of water through hydrophilic lipophilic balanced (HLB) SPE cartridges. Sediment samples were solvent-extracted, followed by tandem SPE (strong anion exchange (SAX) + HLB) clean-ups. Fish muscles were extracted by a mixture of acetonitrile and citric buffer (80:20, v/v) solution, and cleaned by SPE. Liquid chromatography–tandem mass spectrometry (LC-MS/MS) with multiple reaction monitoring (MRM) detection was employed to quantify all compounds. The recoveries for the antibiotics in the spiked water, sediment, and fish samples were 60.2%–95.8%, 48.1%–105.3%, and 59.8%–103.4%, respectively. The methods were applied to samples taken from Dianchi Lake, China. It showed that concentrations of the detected antibiotics ranged from limits of quantification (LOQ) to 713.6 ng·L^-1 (ofloxacin) in surface water and from less than LOQ to 344.8 μg·kg^-1 (sulphamethoxazole) in sediments. The number of detected antibiotics and the overall antibiotic concentrations were higher in the urban area than the rural area, indicating the probable role of livestock and human activities as important sources of antibiotic contamination. In fish muscles, the concentration of norfloxacin was the highest (up to 38.5 μg·kg^-1), but tetracyclines and macrolides were relatively low. Results showed that the methods were rapid and sensitive, and capable of determining several classes of antibiotics from each of the water, sediment, and fish matrices in a single run.     

基于液相色谱法分析水环境中大环内酯类抗生素污染的研究进展

大环内酯抗生素广泛使用,在水环境中的残留越来越引起世界关注.本文综述了国内外基于液相色谱技术分析水环境中大环内酯的方法,比较不同预处理法以及分析方法的灵敏度和检出限.固相萃取法可以同时富集和净化,消耗试剂少,方便,野外操作可行,是理想的预处理技术.液相色谱串联质谱技术选择性好、特异性高、灵敏度高,可以检测浓度低于ng.L-1的目标物,是一种可靠理想的分析方法.最后对大环内酯分析研究进行了展望.