液相色谱串联质谱测定纺织品中的四溴双酚A

采用固相萃取/超快速液相色谱-串联质谱技术(SPE/UFLC-MS/MS)建立了纺织品中四溴双酚A的测定方法。样品经甲醇超声提取,C_(18)-SPE净化后分析,在串联质谱电喷雾(ESI)离子多反应监测(MRM)模式下检测,以保留时间以及特征离子对进行定性、定量分析。实验结果表明,四溴双酚A在1.0~100.0μg/L范围内呈良好的线性关系。称样量为1.0 g时,方法的定量下限为1.0μg/kg。平均回收率为80.9%~95.3%,相对标准偏差(RSDs)为2.3%~5.9%。所建方法快速、准确、灵敏,可用于纺织中四溴双酚A的分析测定。     

液相色谱-质谱法同时测定塑料制品中的双酚A和四溴双酚A

建立了高效液相色谱-质谱同时测定塑料制品中的双酚A(BPA)和四溴双酚A(TBBP-A)的方法。采用超声波萃取技术萃取样品。系统地考察了前处理条件、色谱条件和质谱参数。实验表明,在50 ℃条件下,加入20 mL二氯甲烷对塑料样品中的BPA和TBBP-A超声提取60 min可获得较好的提取效果。以甲醇和水为流动相,采用液相色谱-质谱联用分离和检测BPA和TBBP-A。该方法的线性范围为0.1～2.0 mg/L; BPA和TBBP-A检出限分别为0.01 mg/kg和0.02 mg/kg;回收率为85.4%～97.6%。该方法分离时间短,操作简便,实用性强,灵敏度高,适用于塑料制品中双酚A和四溴双酚A的残留分析。     

液相色谱-串联质谱法测定污水处理厂水样中双酚A、四溴双酚A及烷基酚类化合物

近年来,双酚A、四溴双酚A及烷基酚类化合物由于其对水生生物的内分泌干扰作用受到越来越广泛的关注。污水处理厂是处理这类化合物的重要途径,研究目标物在其中的浓度分布对于探明此类物质在环境中的暴露水平具有重要意义,而建立相应的分析测定方法则是开展上述研究的基础。本研究建立了同时测定污水处理厂水样中双酚A、四溴双酚A及6种烷基酚类化合物的反相液相色谱-电喷雾串联质谱分析方法。结果发现,以ZORBAX Eclipse Plus C18色谱柱(150 mm×2.1 mm,3.5μm)为分离柱,乙腈和0.02%(v/v)氨水溶液为梯度洗脱的流动相,电喷雾质谱负离子模式下目标化合物在11 min内分离;在1~100μg/L范围内,双酚A、四溴双酚A及6种烷基酚类化合物的峰面积与质量浓度的线性关系良好(R2≥0.998),方法定量限为2.0~20 ng/L;添加水平分别为0.2、2、20μg/L时,目标化合物的平均回收率分别为64.3%~118.0%、65.9%~100.5%、70.3%~102.7%,相对标准偏差均小于7.1%。基于上述方法,对江苏省某工业园区污水处理厂水样中相关物质进行检测,出水中检出5种目标化合物,质量浓度范围为11.9~3 015.3 ng/L。结果表明,该方法准确可靠、灵敏度高,适用于污水处理厂水样中相关烷基酚类化合物的检测。     

分子印迹固相萃取检测罐装食品中双酚A

以双酚A为模板分子,3-氨基丙基乙氧基硅烷为功能单体,通过溶胶-凝胶反应合成双酚A分子印迹纳米硅胶微球。以印迹微球为固相萃取吸附剂,优化固相萃取条件,确定二氯甲烷为上样溶剂。固相萃取选择性实验表明,在双酚A及其结构类似物四溴双酚A、双酚C、壬基酚的混合物溶液中,印迹萃取柱对双酚A具有良好的选择性能,回收率达到90.7%。浓度为2.5和5μmol/L的加标罐装食品样品,经印迹萃取柱预处理,液相色谱检测得到回收率72%～84%,相对标准偏差2.9%～4.4%。     

凝胶渗透色谱-分散固相萃取法同时测定鸡蛋中多溴联苯醚及其衍生物、四溴双酚A和六溴环十二烷

建立了一种同时检测鸡蛋中四溴双酚A(TBBP A)、六溴环十二烷(HBCD)和多溴联苯醚(PBDEs)及其衍生物羟基多溴联苯醚(OH-PBDEs)和甲氧基多溴联苯醚(MeO-PBDEs)的凝胶渗透色谱(GPC)-分散固相萃取(DSPE)-液相色谱-串联质谱(HPLC-MS/MS)和气相色谱-负化学源质谱(GC-NCI/MS)的检测方法。样品经正己烷、二氯甲烷(1∶1,V/V)加速溶剂萃取,凝胶渗透色谱净化后,经100 mg十八烷基键合硅胶(C18)分散固相萃取吸附剂去除杂质,液相色谱-串联质谱和气相色谱-负化学源质谱方法测定,外标法定量。在蛋白和蛋黄样品中添加1.0或5.0μg/kg的目标物,其回收率分别为64.5%~97.2%和65.6%~109.2%(除BDE-85为54.8%,OH-BDE-137为47.4%外),相对标准偏差小于20.2%,定量限为0.01~0.2μg/kg。     

高效液相色谱-串联质谱法同时测定农田土壤中的六溴环十二烷和四溴双酚A

建立了加速溶剂萃取/高效液相色谱-三重四极杆串联质谱(ASE/HPLC-MS/MS)批量检测农田土壤中六溴环十二烷(HBCDs)和四溴双酚A(TBBPA)残留的分析方法。土壤样品经加速溶剂萃取,Sep-pak C18固相萃取柱净化后,在多反应监测(MRM)负离子电喷雾模式下进行HPLC-MS/MS分析。色谱柱为X Bridge C18反相柱(150 mm×2.1 mm×3.5μm),流动相为梯度变化的甲醇和水溶液。在最佳实验条件下,六溴环十二烷和四溴双酚A在0.50~200.0μg/L范围内线性关系良好(r≥0.998),方法检出限(S/N≥3)为1.80~10.0 ng/kg。在1.0~40.0μg/kg添加水平内,平均加标回收率为73.8%~106.9%,相对标准偏差(RSD)为5.8%~11.2%。采用该方法分析了我国某区域内表层土壤样品的HBCDs和TBBPA,得到理想的分析效果。     

液相色谱-串联质谱法测定小型家用电器塑料部件中双酚A

建立了小型家用电器塑料部件中双酚A的液相色谱-串联质谱(LC-MS/MS)检测方法。采用快速溶剂萃取仪对样品进行萃取,以Sep-Pak C18固相萃取柱净化,甲醇-水(含有0.05%氨水)混合液作为流动相,负离子模式下进行MS/MS检测。结果表明: 该方法在5～100 μg/L范围内线性关系良好,相关系数(r2)为0.9991。在10、25和75 μg/kg 3个添加水平下,双酚A的平均回收率为95.2%～109.7%,相对标准偏差均小于3.8%,检出限为10 μg/kg。该方法操作简便,灵敏度高,适用于家用电器塑料部件中双酚A的残留分析。     

固定化离子液体固相萃取-电化学联用测定痕量双酚A

以咪唑改性的苯乙烯型大孔树脂填料制备固相萃取小柱,进行固定化离子液体固相萃取,结合β-环糊精修饰离子液体碳糊电极,发展痕量双酚A的电化学联用快速检测技术。实验优化影响萃取效率的因素,获得最佳萃取条件(萃取填料用量0.4 g,样品体积200 m L,上样液p H 7.0,5 m L甲醇为洗脱溶剂,萃取流速4.5 m L/min)。测得固定化离子液体树脂对双酚A的最大吸附容量为10.1 mg/g,富集倍数为40倍。双酚A的浓度线性范围在2.3~228μg/L,检出限为0.95μg/L。联用方法灵敏、实用性强,用于实际样品中双酚A分析,结果与HPLC方法一致。     

液相色谱-三重四极杆质谱同时测定食品接触材料中双酚A、双酚F与双酚S的迁移量

采用液相色谱-三重四极杆质谱(LC-MS/MS)建立了食品接触材料中双酚A、双酚F和双酚S化合物的同时测定方法。双酚A、双酚F和双酚S在样品中通过与食品模拟物在一定温度、时间接触的状态下迁移到食品模拟物中,以C18色谱柱进行分离,甲醇-氨水为流动相洗脱,采用电喷雾离子源(ESI),多反应监测(MRM)负离子模式进行扫描,同位素内标法定量。结果表明,双酚A、双酚F和双酚S的色谱分离良好,双酚A和双酚F在1~50μg/L质量浓度范围内与其峰面积均呈线性关系,BPS在0.1~50μg/L质量浓度范围内与其峰面积呈线性关系。BPA和BPF的最低检出限为0.3μg/L,BPS的最低检出限为0.05μg/L。加标回收率为83.6%~102.6%,相对标准偏差(RSD)为3.5%~8.9%。该方法快速可靠、准确简便,适用于食品接触材料中双酚A、双酚F和双酚S化合物的检测。     

磁性石墨烯分散固相萃取结合液相色谱-串联质谱法测定水基胶中的双酚A和烷基酚

建立了超高效液相色谱-串联质谱(UPLC-MS/MS)与磁性石墨烯相结合测定水基胶中双酚A、壬基酚和辛基酚的方法。样品提取后,以磁性石墨烯分散固相萃取净化,经BEH C18色谱柱分离。分析物的回收率在81.5%～97.9%之间,日间相对标准偏差(RSDs)小于8.0%。所有化合物均获得了良好的线性系数(r≥0.9996),检出限(LOD)和定量限(LOQ)范围分别为3～8μg/kg和10～26μg/kg。采用该方法对20个水基胶实际样品进行检测,仅有1个样品检出4-正壬基酚。该方法可用于测定水基胶中双酚A和4种烷基酚的含量。     

Highly sensitive determination of tetrabromobisphenol A and bisphenol A in environmental water samples by solid‐phase extraction and liquid chromatography‐tandem mass spectrometry

Using bamboo‐activated charcoal as SPE adsorbent, a novel SPE method was developed for the sensitive determination of tetrabromobisphenol A and bisphenol A in environmental water samples by rapid‐resolution LC‐ESI‐MS/MS. Important parameters influencing extraction efficiency, including type of eluent, eluent volume, sample pH, volume and flow rate, were investigated and optimized. Under the optimal extraction conditions (eluent: 8 mL methanol, pH: 7; flow rate: 4 mL/min; sample volume: 100 mL), low LODs (0.01–0.02 ng/mL), good repeatability (6.2–8.3%) and wide linearity range (0.10–10 ng/mL) were obtained. Satisfied results were achieved when the proposed method was applied to determine the two target compounds in real‐world environmental water samples with spiked recoveries over the range of 80.5–119.8%. All these facts indicate that trace determination of tetrabromobisphenol A and bisphenol A in real‐world environmental water samples can be realized by bamboo‐activated charcoal SPE‐rapid resolution‐LC‐ESI‐MS/MS.     

高通量固相萃取-超高效液相色谱-串联质谱法测定人尿中8种环境酚类内分泌干扰物

建立了人尿中8种环境酚类化合物的96孔板固相萃取-超高效液相色谱-串联质谱(96-well SPE LC-MS/MS)检测方法,其中包括7种双酚类化合物和三氯生。尿样解冻到室温,经β-葡萄糖醛酸苷肽酶/芳基磺酸酯酶37 ℃过夜酶解。实验比较了3种96孔板固相萃取柱和不同淋洗条件对人尿样的净化效果和目标化合物的回收率。结果显示,采用Oasis HLB 96孔板(60 mg)对样品进行萃取和用30%(v/v)乙腈水溶液进行淋洗净化的纯化效果最好。纯化后目标物用甲醇溶液洗脱,经氮气吹干,用0.5 mL甲醇-水(1∶1, v/v)溶液定容,目标化合物用UPLC-MS/MS进行检测。比较了2种分析柱(C₁₈和T3分析柱)以及不同的有机流动相对分离样品中目标物的影响。结果显示,以BEH C₁₈(100 mm×2.1 mm, 1.7 μm)作为分析柱,乙腈/水作为流动相,以流速0.3 mL/min梯度洗脱时,目标物的分离效果最好。质谱条件选择串联质谱负离子电喷雾(ESI^-)多反应监测模式(MRM)进行检测。对样品的基质效应进行评估发现,双酚A、双酚F、双酚S、双酚B和双酚AF的绝对基质效应为3.47%~15.32%,不需要补偿措施;四氯双酚A、四溴双酚A和三氯生的绝对基质效应分别是49.58%(中等基质效应)、71.99%和86.93%(强基质效应),均需要补偿效应。因此,该方法采用了一一对应的同位素内标法抵消基质效应。用6份实际尿样基质评估相对基质效应,8种内标的峰面积的相对标准偏差为3.63%~9.06%,说明相对基质效应稳定。在优化条件下,双酚A和双酚AF在0.50~50 μg/L内、四氯双酚A和双酚S在0.05~50 μg/L内、双酚F和四溴双酚A在0.01~50 μg/L内、双酚B在1.00~50 μg/L内、三氯生在5.00~200 μg/L内线性关系良好,相关系数大于0.9995。方法检出限为0.002~1.09 μg/L,定量限为0.007~3.63 μg/L。3个加标水平的加标回收率为81.0%~101.9%,日内精密度为0.4%~19.4%,日间精密度为2.5%~17.8%。应用该方法对2019-2020年采集的北京地区64份尿样进行测定,结果发现8种目标分析物中,除双酚B和双酚AF未检出外,其余均有检出,其中双酚A和双酚S的检出率最高,分别为100%和96.9%。三氯生、四溴双酚A、四氯双酚A和双酚F的检出率分别为57.8%、46.9%、23.4%和21.9%。尿样中8种目标物含量的中位值以降序排列分别为1.44 μg/L(三氯生)、0.69 μg/L(双酚A)、0.086 μg/L(双酚S)、0.0032 μg/L(四溴双酚A)、0.00050 μg/L (四氯双酚A)、0.00 μg/L(双酚F、双酚B和双酚AF)。以上尿样检测结果显示,北京市居民存在普遍的环境酚类化合物暴露,值得关注。该方法操作简单,定量准确,样品需求量小,有机试剂消耗少,适合大批量样本的测定。     

固相萃取-高效液相色谱-串联质谱测定水中8种双酚-二环氧甘油醚

建立了水中8种双酚-二环氧甘油醚(双酚A二缩水甘油醚(BADGE)及其衍生物双酚A(3-氯-2-羟丙基)甘油醚(BADGE·HCl)、双酚A双(3-氯-2-羟丙基)醚(BADGE·2HCl)、双酚A(2,3-二羟丙基)甘油醚(BADGE·H2O)、双酚A双(2,3-二羟丙基)醚(BADGE·2H2O)、双酚A(3-氯-2-羟丙基)(2,3-二羟丙基)醚(BADGE·HCl·H2O)和双酚F-二环氧甘油醚(BFDGE)及其衍生物双酚F双(3-氯-2-羟丙基)醚(BFDGE·2HCl))的固相萃取-高效液相色谱-串联质谱(SPE-HPLC-MS/MS)测定方法。10个饮用水接触涂料样品在室温避光条件下,以超纯水浸泡(24±1)h,然后取200 mL经C18固相萃取柱进行净化浓缩,以C18色谱柱进行分离,以5 mmol/L醋酸铵、甲醇和水为流动相进行梯度洗脱,质谱多反应监测(MRM)模式检测,外标法定量。结果表明,8种双酚-二环氧甘油醚在0.007~5.00μg/L线性关系良好,相关系数均大于0.999 0,该方法对8种双酚-二环氧甘油醚的定量限为7~91ng/L,回收率为79.1%~101%,RSD为4.0%~12%。该方法具有灵敏度高、选择性强的特点,能够满足水中双酚-二环氧甘油醚的快速检测和准确定量。     

Rapid analysis of pesticide residues in drinking water samples by dispersive solid‐phase extraction based on multiwalled carbon nanotubes and pulse glow discharge ion source ion mobility spectrometry

An analytical method based on dispersive solid‐phase extraction with a multiwalled carbon nanotubes sorbent coupled with positive pulse glow discharge ion mobility spectrometry was developed for analysis of 30 pesticide residues in drinking water samples. Reduced ion mobilities and the mass–mobility correlation of 30 pesticides were measured. The pesticides were divided into five groups to verify the separation capability of pulse glow discharge in mobility spectrometry. The extraction conditions such as desorption solvent, ionic strength, conditions of adsorption and desorption, the amounts of multiwalled carbon nanotubes, and solution pH were optimized. The enrichment factors of pesticides were 5.4‐ to 48.7‐fold (theoretical enrichment factor was 50‐fold). The detection limits of pesticides were 0.01～0.77 μg/kg. The linear range was 0.005–0.2 mg/L for pesticide standard solutions, with determination coefficients from 0.9616 to 0.9999. The method was applied for the analysis of practical and spiked drinking water samples. All results were confirmed by high‐performance liquid chromatography with tandem mass spectrometry. The proposed method was proven to be a commendably rapid screening qualitative and semiquantitative technique for the analysis of pesticide residues in drinking water samples on site.     

An efficient biosorption‐based dispersive liquid‐liquid microextraction with extractant removal by magnetic nanoparticles for quantification of bisphenol A in water samples by gas chromatography‐mass spectrometry detection

In this work, a simple, fast, sensitive, and environmentally friendly method was developed for preconcentration and quantitative measurement of bisphenol A in water samples using gas chromatography with mass spectrometry. The preconcentration approach, namely biosorption‐based dispersive liquid‐liquid microextraction with extractant removal by magnetic nanoparticles was performed based on the formation of microdroplet of rhamnolipid biosurfactant throughout the aqueous samples, which accelerates the mass transfer process between the extraction solvent and sample solution. The process is then followed by the application of magnetic nanoparticles for easy retrieval of the analyte‐containing extraction solvent. Several important variables were optimized comprehensively including type of disperser solvent and desorption solvent, rhamnolipid concentration, volume of disperser solvent, amount of magnetic nanoparticles, extraction time, desorption time, ionic strength, and sample pH. Under the optimized microextraction and gas chromatography with mass spectrometry conditions, the method demonstrated good linearity over the range of 0.5–500 µg/L with a coefficient of determination of R² = 0.9904, low limit of detection (0.15 µg/L) and limit of quantification (0.50 µg/L) of bisphenol A, good analyte recoveries (84–120%) and acceptable relative standard deviation (1.8–14.9%, n = 6). The proposed method was successfully applied to three environmental water samples, and bisphenol A was detected in all samples.     

Carbon nanotubes as solid-phase extraction sorbents prior to atomic spectrometric determination of metal species: A review

New materials have significant impact on the development of new methods and instrumentation for chemical analysis. From the discovery of carbon nanotubes in 1991, single and multi-walled carbon nanotubes – due to their high adsorption and desorption capacities – have been employed as sorption substrates in solid-phase extraction for the preconcentration of metal species from diverse matrices. Looking for successive improvements in sensitivity and selectivity, in the past few years, carbon nanotubes have been utilized as sorbents for solid phase extraction in three different ways: like as-grown, oxidized and functionalized nanotubes. In the present paper, an overview of the recent trends in the use of carbon nanotubes for solid phase extraction of metal species in environmental, biological and food samples is presented. The determination procedures involved the adsorption of metals on the nanotube surface, their quantitative desorption and subsequent measurement by means of atomic spectrometric techniques such as flame atomic absorption spectrometry, electrothermal atomic absorption spectrometry or inductively coupled plasma atomic emission spectrometry/mass spectrometry, among others. Synthesis, purification and types of carbon nanotubes, as well as the diverse chemical and physical strategies for their functionalization are described. Based on 140 references, the performance and general properties of the applications of solid phase extraction based on carbon nanotubes for metal species atomic spectrometric determination are discussed.     

Preparation of magnetic molecularly imprinted polymer based on multiwalled carbon nanotubes for selective dispersive micro-solid phase extraction of fenitrothion followed by ion mobility spectrometry analysis

A novel molecularly imprinted polymer based on magnetic multiwalled carbon nanotubes was fabricated and applied for selective dispersive micro-solid phase extraction of fenitrothion prior its determination by ion mobility spectrometry. The composite was synthesized using magnetic multiwalled carbon nanotubes as the support. Methacrylic acid was used as the functional monomer, fenitrothion as the template, ethylene glycol dimethacrylate as the cross-linker, and 2,2-azoisobutyronitrile as the initiator. The resultant polymer was characterized by FTIR spectroscopy, X-ray diffraction, field emission scanning electron microscopy, Brunauer–Emmet–Teller analysis, thermogravimetric analysis, and vibrating sample magnetometer techniques. Experimental factors affecting the extraction efficiency such as pH and amount of sorbent were evaluated. Under optimum experimental conditions, the developed method displayed the linear range of 5–220 μg/L with a detection limit of 1.3 μg/L. The intra- and interday relative standard deviations for determination of fenitrothion were 3.6 and 4.7% (n = 6), respectively. Ultimately, the proposed method was used to monitor trace amounts of fenitrothion in fruits, vegetables, and water samples.     

Preconcentration of atrazine and simazine with multiwalled carbon nanotubes as solid-phase extraction disk

A sensitive and selective preconcentration method using solid-phase extraction (SPE) disk, namely multiwalled carbon nanotubes (MWCNTs) disk, is proposed for the determination of atrazine and simazine in water samples. Atrazine and simazine were extracted on MWCNTs disk and then determined by gas chromatography–mass spectrometry (GC/MS). Several parameters on the enrichment factor of the analytes were investigated. The experimental results showed that it was possible to obtain quantitative analysis when the solution pH was 5 using 200 mL of validation solution containing 0.1 μg of triazines and 5 mL of acetone as an eluent. The maximum enrichment factors for atrazine and simazine were 3900 ± 250 and 4000 ± 110, respectively when 200 mL of sample solution volume was used. Relative standard deviations for seven determinations were 6.9% (atrazine) and 3.0% (simazine) under optimum conditions. The linear range of calibration curves were 0.1 to 1 ng mL^{− 1} for each analyte with good correlation coefficients. The detection limits (3S/N) were 2.5 and 5.0 pg mL^{− 1} for atrazine and simazine, respectively. The proposed method was successfully applied to the determination of atrazine and simazine in environmental water samples with high precision and accuracy.