分散固相萃取-气相色谱/串联质谱法测定竹笋中38种持久性有机污染物

建立了同时测定竹笋中9种多环芳烃(PCBs)、16种多氯联苯(PAHs)和13种有机氯农药(OCPs)的分散固相萃取-气相色谱法-串联质谱(DSPE-GC-MS/MS)分析方法。竹笋样品经乙腈提取,以无水MgSO_4、弗罗里硅土和十八烷基键合硅胶吸附剂(C18)作为分散固相萃取净化剂净化,经气相色谱-串联质谱测定,外标法定量。结果表明,方法实现了对38种持久性有机化合物的分离和定量,分析物含量在2~1000μg/L范围内线性关系良好,相关系数在0.9960~0.9998之间;方法检出限范围0.035~5.55μg/kg;38种持久性有机污染物在低、中、高添加浓度下的平均加标回收率为67.6%~113.6%,相对标准偏差为1.7%~9.5%。方法可对竹笋样品中38种持久性有机污染物定性和定量。     

动物源性食品中小分子有机污染物的多类别多残留分析技术的研究进展

综述了近年来动物源性食品中小分子有机污染物的多类别多残留分析技术的研究进展,包括液液萃取法、加速溶剂萃取法、基质分散固相萃取法等提取方法,液液萃取法、低温冷冻法、固相分散萃取法、固相萃取法等净化方法,以及液相色谱法、质谱法、液相色谱-质谱联用等仪器分析方法。还指出了多类别多残留分析方法潜在的研究方向(引用文献64篇)。     

分散固相萃取-气相色谱-质谱法分析蕨菜、黑米中53种农药残留量

采用分散固相萃取(Dispersive solid-phase extraction)样品前处理方法,建立了蕨菜、黑米等生态农产品中53种农药残留的气相色谱一质谱(GC-EI/MS)的分析方法.样品由含0.1%冰醋酸的乙腈提取,以环氧七氯为内标,经分散固相萃取法净化.每种农药选择了合适的离子及其驻留时间,采用气相色谱-...     

基于磁固相萃取-自动前处理分离和富集动物肝脏中的β-受体激动剂

基于磁固相萃取-自动前处理分离和富集动物肝脏中的β-受体激动剂,建立了动物肝脏中3种β-受体激动剂（沙丁胺醇、克伦特罗和莱克多巴胺）残留的液相色谱-串联质谱（LC-MS/MS）分析方法。样品溶液经提取后,采用磁性阳离子吸附剂（M-MCX）结合自动前处理装置进行净化,使用LC-MS/MS检测,同位素内标法进行定量。结果显示,M-MCX较传统混合阳离子固相萃取（MCX）柱的吸附容量高34%,而且节约了吸附材料。结合自动磁固相萃取装置,30 min内可完成8个样品的净化,方法检出限为0.01～0.1μg/kg,平均回收率为88.2%～110.5%,相对标准偏差为2.9%～10.3%。与传统柱填充式固相萃取法相比,本方法具有操作简单、快速、高效等优点,能够满足动物组织样品前处理的批量、自动化处理的需求。     

基质固相分散-气相色谱串联质谱法测定孕妇血清中22种持久性有机污染物

建立了基质固相分散技术-气相色谱串联质谱法(MSPD-GC-QQQ-MS/MS)同时测定孕妇血清中22种持久性有机污染物(艾氏剂、狄氏剂、七氯、灭蚁灵、六六六、多氯联苯和滴滴涕)的方法.血清样品与C18吸附剂混合净化,正己烷溶液洗脱,GC-QQQ-MS/MS测定.采用Agilent J&W DB-35ms (30 m×0.25 mm×0.25 μm)分离,正电子离子源(EI+)模式电离,多反应监测模式(MRM)下进行测定,外标法定量.结果表明,在1.0～1000.0 ng/mL的范围内,22种持久性有机污染物的相关系数均大于0.99;在2.0和20.0 ng/mL的添加水平下,所有持久性有机污染物回收率均在75％～ 115％之间,方法定量限均≤0.15 ng/mL.在比较基质固相分散(MSPD)、液液萃取(LLE)和固相萃取(SPE)提取和净化实际加标血清样品时,MSPD方法的结果中位数更接近真实值,且离散程度最小.本方法适用于人类血清中多种持久性有机物的定性和定量分析.     

链格孢霉毒素样品处理及分析方法研究进展

综述链格孢霉毒素样品处理及分析方法。样品处理方法主要有液液萃取法、固相萃取法、逆流色谱法和基于QuEChERS原则的处理方法等。在固相萃取技术的基础上,又发展了分散固相萃取法和分子印迹固相萃取法。主要分析方法包括液相色谱–质谱联用法、加压毛细管电色谱法和表面增强拉曼光谱法等仪器检测技术以及酶联免疫法、化学发光免疫分析法、生物传感器技术、快速检测试纸和试剂盒等快速检测技术。最后对链格孢霉毒素样品处理及分析方法的发展趋势进行了展望。     

UAE/SPE-GS/MS法同时测定纺织废物中17种氯苯类污染物

本文建立了超声波辅助萃取/固相萃取法-气质联用法(UAE/SPE-GS/MS)同时测定纺织固废物中17种氯苯类污染物的分析方法。从超声萃取溶剂、超声萃取时间、超声萃取温度和固相萃取小柱等前处理条件进行优化,以保留时间定性,外标法定量。结果表明,纺织固废样品在超声50℃的水浴中经二氯甲烷溶剂超声萃取30min后,再通过弗罗里硅土(Florisil)固相萃取柱净化,测得17种氯苯类污染物的回收率为80%～107.6%,相对偏差RSD(n=10)小于5.5%。     

改良QuEChERS-气相色谱-串联质谱法同时测定土壤中17种邻苯二甲酸酯

建立了改良的QuEChERS法,结合气相色谱-串联质谱(GC-MS/MS)检测土壤中17种邻苯二甲酸酯的分析方法.样品用乙腈水溶液提取,NaCl盐析分层,上清液采用磁性氧化石墨烯(Fe3O4-GO)、N-丙基乙二胺(PSA)和无水MgSO4吸附剂分散固相萃取净化,质谱以多反应监测(MRM)模式测定,外标法定量.结果 表...     

新型纳米材料在农产品安全分析中的应用进展

农产品质量安全事关民生福祉，近年来受到了政府和消费者越来越多的关注，建立农产品中农药、兽药、重金属和真菌毒素等污染物高效、快速和灵敏的分离分析新方法，对于保障农产品质量安全具有重要的意义。农产品基质复杂，污染物浓度低，采取适当的样品前处理对农产品中的污染物进行富集净化是非常重要的。固相萃取是目前应用最多的样品前处理技术，其核心吸附剂决定了萃取的选择性和萃取效率。近年来，越来越多的新型材料被用作固相萃取的吸附剂，结合多种萃取模式(固相微萃取、分散固相萃取、磁性固相萃取等),大大提高了目标物的萃取效率、萃取选择性和分析通量。纳米材料具有大的比表面积，对痕量目标物亲和力强，将其作为固相萃取的吸附剂，极大地改善了分析技术的选择性和灵敏度，已经成为农产品中痕量化合物预富集技术的优先选择。本文概述了磁性材料、碳基材料、金属和金属氧化物材料、金属有机骨架材料、有机共价骨架材料等纳米材料的吸附特性，因具有比表面积大、吸附容量高、结构可设计等众多优点，良好的稳定性和优异的物理化学性能使其非常适合作为农产品安全分析中污染物富集净化的吸附剂，结合色谱、光谱、质谱等检测技术，所开发的分析方法成功应用于多种农产...     

固相萃取-GC-MS分析法鉴定生活废水中的半挥发性有机化合物

环境样品分析中,样品的前处理占了很大的比例,传统的液液萃取、KD浓缩器浓缩的样品前处理方式需要大量的溶剂,并且消耗时间长、消耗体力大.近些年来,在环境污染物的鉴别分析中,由于固相萃取、固相微萃取等样品前处理方法,溶剂消耗量少、浓缩、净化效率高、时间体力消耗小而越来越受到亲睐.本文采用ENVI-18固相萃取小柱对生活废水中的污染物进行分离浓缩处理,GC-MS分析鉴别,并与美国EPA半挥发性化合物的分析方法进行对比,只要操作掌握得好,固相萃取法不仅溶剂消耗量小,浓缩、净化效率高,时间体力消耗少,而且鉴别的物质多,在环境污染物的鉴别分析中确实是一个值得推广的好方法.     

母乳中多种含卤持久性有机污染物的联合检测方法

建立了母乳中多种含卤持久性有机污染物(POPs)的联合检测方法,目标化合物主要包括六溴环十二烷(HBCDs)、多溴联苯醚(PBDEs)、多氯联苯(PCBs)和有机氯农药(OCPs)等.样品的前处理采用液液萃取、凝胶渗透色谱(GPC)净化和固相萃取(SPE)等技术,目标化合物经气相色谱-质谱联用仪(GC-MS)、液相色谱-三重四极杆串联质谱联用仪(LC-MS/MS)和气相色谱-三重四极杆串联质谱联用仪(GC-MS/MS)等进行检测.样品通过GPC除去脂肪,然后经SPE柱进一步净化并进行多组分分离,极大程度地减小了生物样品中复杂基质的干扰,适合样品量相对较小的人体样本中多种超痕量POPs的分析.应用灵敏度高、选择性更好的GC-MS/MS对样品中的PCBs和OCPs等进行分析,进一步降低基质的干扰.方法经过小牛血清加标实验验证,稳定可靠.POPs的加标回收率分别为88.7％～98.8％(PBDEs), 88.5％～92.5％(HBCDs), 67.9％～82.3％(PCBs)和81.7％～116.1％(OCPs),方法检出限分别为0.13～1.8 pg/mL(PBDEs), 0.31～1.2 pg/mL(HBCDs), 0.22～1.4 pg/mL(PCBs)和0.20～1.5 pg/mL(OCPs).采用本方法对潍坊地区20例母乳样品进行分析,结果显示,潍坊市母乳中HBCDs, PBDEs, PCBs、HCHs和DDTs的中值浓度分别为2.86, 7.76, 8.84、140和503 ng/g 脂重,此浓度水平与国内其它地区人群相当.     

A comparison of the performance of two chromatographic and three extraction techniques for the analysis of PAHS in sources of drinking water

The aim of this work is to establish a sensitive and reliable method for the analysis of the 16 priority Environmental Protection Agency-defined polycyclic aromatic hydrocarbons (PAHs) found in water samples. Gas chromatography (GC)-mass spectrometry (MS) and high-performance liquid chromatography (HPLC)-fluorescence detection (FLD)-UV techniques are optimized to obtain an adequate resolution of all compounds. Validation of the methods is carried out, and a good performance is observed for both techniques. The HPLC-FLD-UV technique is somewhat more sensitive than the GC-MS technique for the determination of PAHs; thus, the HPLC-FLD-UV method is used to follow up both the solid-phase extraction (SPE) analysis using cartridges and discs and the liquid-liquid extraction (LLE), which are also evaluated for the extraction of the PAHs. Low recoveries between 43% and 79% are obtained using SPE cartridges, and higher values are obtained using SPE discs (56-96%) and LLE (60-105%). Better results are obtained using the LLE technique, and, thus, analysis of real water samples is carried out using this technique. LODs between 0.6 and 21 ng/L and relative standard deviations less than 15% are obtained using a spiked water sample analyzed using the full LLE HPLC-FLD-UV method.     

Simultaneous determination of endocrine disrupting phenolic compounds and steroids in water by solid-phase extraction-gas chromatography-mass spectrometry

A solid-phase extraction (SPE)-gas chromatography (GC)-mass spectrometry (MS) analytical method for the simultaneous separation and determination of endocrine disrupting chemicals (EDCs) from water samples is described in detail. Important and contrasting EDCs including estrone, 17beta-estradiol, 17beta-ethynylestradiol, 16beta-hydroxyestrone, 4-nonylphenol, bisphenol A and 4-tert-octylphenol were selected as the target compounds. The SPE technique, followed by the derivatisation with bis (trimethylsilyl) trifluoroacetamide was used for the extraction recoveries of target compounds from water samples. A number of parameters that may affect the recovery of EDCs, such as the type of SPE cartridges, eluents, as well as water properties including pH value, and concentration of salts and humic substances were investigated. It is shown that the Oasis cartridges produced the best recoveries of target EDCs while ethyl acetate was efficient in eluting EDCs from SPE cartridges. The recovery of some EDCs was enhanced by the addition of salt, but reduced by the increase in pH value and humic acid concentration. The optimised method was further verified by performing spiking experiments in natural river water and seawater matrices, with good recovery and reproducibility for all the selected compounds. The established method was successfully applied to environmental water samples from East and West Sussex, UK, for the determination of the target EDCs.     

Solid- and liquid-phase extraction for the gas chromatographic-tandem mass spectrometric quantification of 2,3-dinor-thromboxane B2 and 2,3-dinor-6-oxo-prostaglandin F1 alpha in human urine

Whole body synthesis of thromboxane A2 is best assessed by quantifying non-invasively its major urinary metabolite, i.e., 2,3-dinor-thromboxane B2 (2,3-dn-TxB2), by gas chromatography-mass spectrometry (GC-MS) or GC-tandem MS. Methods based on these techniques usually require a series of extraction and purification procedures including solid-phase extraction (SPE) and thin-layer chromatography (TLC) or liquid chromatographic separation of authentic or derivatized 2,3-dn-TxB2. Taking advantage of the inherent accuracy of GC-tandem MS and the high selectivity of the extraction of methoximated 2,3-dn-TxB2 on phenylboronic acid SPE cartridges we developed a method that involves only SPE steps prior to quantification by GC-tandem MS. The method was validated by performing in parallel an additional TLC step. Method mean accuracy and precision were of the order of 103% and 95%, respectively. The method allows furthermore co-processing of the same urine sample to quantify accurately and rapidly the major urinary metabolite of prostacyclin, i.e., 2,3-dn-6-oxo-prostaglandin (PG) F1 alpha, by GC-tandem MS. The limit of detection of the method was below each 5 pg of 2,3-dn-TxB2 and 2,3-dn-6-oxo-PGF1 alpha per 5 ml of urine. Our study suggests that dinor metabolites of isothromboxanes and isoprostacyclins are not abundantly present in human urine.     

Comparison of Different Cartridges of Solid Phase Extraction for Determination of Polyphenols in Tobacco by UPLC/MS/MS and Multivariate Analysis

The comparison of solid phase extraction(SPE) for the preconcentration and isolation of polyphenols in tobacco samples was carried out by ultra-high performance liquid chromatography/tandem mass spectrometry (UPLC/MS/MS) and multivariate analysis.Several adsorbing materials of SPE(C18,NH2,SAX and OASIS) were investigated.It was found that the C18 and OASIS cartridges can not only speed up the purification process,but also simplify the SPE operation.A UPLC/MS/MS was used for the determination of polyphenols ...     

Determination of pesticides originating from golf courses by solid-phase extraction and liquid chromatography-tandem mass spectrometry

A multi-residue method using liquid chromatography coupled to triple quadrupole tandem mass spectrometry (LC-MS/MS), associated with solid-phase extraction (SPE), was developed for the determination of 21 pesticides in water samples. The compounds investigated are used for the maintenance of golf courses and ordinarily measured by gas chromatography-mass spectrometry (GC-MS). Electrospray ionisation (ESI) was applied to all compounds, and LC and MS conditions were optimised to measure them under SRM mode. This method showed excellent linearity ranges for all pesticides, with correlation coefficients greater than 0.996. Two kinds of extraction cartridges, namely, styrene divinylbenzene polymer (Sep-Pak PS-2) and divinylbenzene-N-vinylpyrrolidone copolymer (Oasis HLB), were tested and the extraction conditions were optimised. All the pesticides were determined using acetonitrile and ethyl acetate as eluents in both cartridges, and good recoveries (>77%) and repeatability with low relative standard deviations (RSDs, <12%) were achieved from ultra-pure water. In addition, satisfactory recoveries (>76%) and low intra-day and inter-day RSDs (<15%) of all pesticides were also obtained with the Sep-Pak PS-2 cartridge when using river water. The method limits of detection (LODs) ranged between 0.068 (diazinon) and 3.9 (triclopyrbutoxyethyl)?ng?L^?1. The analytical method was successfully applied for the determination of pesticides in surface river water.     

固相萃取/高效液相色谱-串联质谱法同时检测环境水样中24种农药残留

建立了一种固相萃取/高效液相色谱-串联质谱(SPE/HPLC-MS/MS)同时检测水体中24种农药的分析方法。样品用乙腈提取后,经固相萃取小柱富集净化。以乙腈-0.1%(体积分数)甲酸水溶液为流动相梯度洗脱,在电喷雾离子源正离子模式下(ESI+)采用多反应监测(MRM)模式检测。结果显示,24种农药在1~200μg/L范围内具有良好的线性关系,相关系数(r2)均不小于0.998,水样中3个添加水平(5、20、100μg/L)下的回收率为65.9%~127.8%,相对标准偏差(RSD)为0.7%~14.2%;方法检出限为0.05~0.71 ng/L。采用该方法对大连地区10个河流入海口及2个水库的水样进行了检测,12个站位的样品中共检出10种农药,质量浓度为0.2~558.3 ng/L。结果表明,所建立的SPE/HPLC-MS/MS方法高效、灵敏、可靠,可用于实际水体中多种农药的同时检测。     

Quantitative determination of piritramide in human plasma and urine by off- and on-line solid-phase extraction liquid chromatography coupled to tandem mass spectrometry

A method for the liquid chromatography/tandem mass spectrometric (LC/MS/MS) quantification of piritramide, a synthetic opioid, in plasma after conventional off-line solid-phase extraction (SPE) and in urine by on-line SPE-LC/MS/MS in positive electrospray mode was developed and validated. Applicability of the on-line approach for plasma samples was also tested. Deuterated piritramide served as internal standard. For the off-line SPE plasma method mixed cation-exchange SPE cartridges and a 150 x 2 mm C18 column with isocratic elution were used. For the on-line SPE method, a Waters Oasis HLB extraction column and the same C18 analytical column in a column-switching set-up with gradient elution were utilized. All assays were linear within a range of 0.5-100 ng/mL with a limit of detection of 0.05 ng/mL. The intra- and interday coefficients of variance ranged from 1.3 to 6.1% for plasma and 0.5 to 6.4% for urine, respectively. The extraction recovery for the off-line plasma assay was between 90.7 and 100.0%. Influence of matrix effects, and freeze/thaw and long-term stability were validated for both approaches; influence of urine pH additionally for quantification in urine.     

Analysis of unknown organic pollutants in sewage by solid-phase extraction combined with gas chromatography-mass spectrometry

A rapid, simple, and reliable method of solid-phase extraction (SPE) combined with gas chromatography (GC)-mass spectrometry (MS) is developed for the analysis of a wide range of polarity of unknown organic pollutants in sewage. Wastewater samples are extracted by passing them through disposable C(18) cartridges, and the extracts are then analyzed by GC-MS. Different SPE parameters for ten organic compounds in the list of priority pollutants suggested by the China Environmental Protection Agency (EPA) are studied, and their breakthrough volumes are determined. Extraction recoveries for the tested compounds are greater than 60%, except the recovery of 1,2-dichloroethane is 48%. The relative standard deviations are less than 7.8% (n = 3). The developed approach is successfully applied for the identification of organic components in a sewage sample. Over 220 organic pollutants are identified, with 5 of these present in the list of priority pollutants suggested by the U.S. EPA and 4 from the list by the China EPA.     

On-line coupling of solid-phase extraction with mass spectrometry for the analysis of biological samples. II. Determination of clenbuterol in urine using multiple-stage mass spectrometry in an ion-trap mass spectrometer

Solid-phase extraction (SPE) was coupled to ion-trap mass spectrometry to determine clenbuterol in urine. For SPE a cartridge exchanger was used and, after extraction, the eluate was directly introduced into the mass spectrometer. For two types of cartridges, i.e. C18 and polydivinylbenzene (PDVB), the total SPE procedure (including injection of 1 mL urine, washing, and desorption) has been optimised. The total analysis, including SPE, elution, and detection, took 8.5 min with PDVB cartridges, while an analysis time of 11.5 min was obtained with C18 cartridges. A considerable amount of matrix was present after extraction of urine over C18 cartridges, resulting in significant ion suppression. With PDVB cartridges, the matrix was less prominent, and less ion suppression was observed. For single MS, a detection limit (LOD) of about 25 ng/mL was found with PDVB cartridges. With C18 cartridges an LOD of only about 50 ng/mL could be obtained. Applying tandem mass spectrometry (MS/MS) did not lead to an improved LOD due to an interfering compound. However, a considerable improvement in the LOD was obtained with MS3. The selectivity and sensitivity were increased by the combination of efficient fragmentation of clenbuterol and reduction of the noise. Detection limits of 2 and 0.5 ng/mL were obtained with C18 and PDVB cartridges, respectively. The ion suppression was 4 to 45% (concentration range: 250 to 1.0 ng/mL) after extraction of urine using PDVB cartridges, and up to 70% ion suppression was observed using C18 cartridges. With MS4, no further improvement in selectivity and sensitivity was achieved, due to inefficient fragmentation of clenbuterol and no further reduction of noise.