加速溶剂萃取―气相色谱―质谱法测定土壤中酞酸酯类有机物

建立了土壤中酞酸酯类的加速溶剂萃取（ASE）―气相色谱―质谱（GC-MS）测定方法。通过对萃取溶剂和层析柱的优化选择,得出优化萃取条件。同时,实验过程中采用铬酸洗液对实验器皿进行清洗,有效控制了环境中酞酸酯对样品的污染。该优化方法结果显示：平均加标回收率为89.5%～106.0%,相对标准偏差为1.5%～5.8%,检出...     

快速溶剂萃取-气相色谱/质谱法分析血液中的甲卡西酮

建立血液中甲卡西酮快速溶剂萃取（ASE）-气相色谱/质谱（GC/ MS）分析的新方法. 通过优化 ASE 的萃取条件（溶剂、温度及时间）,对血液中的甲卡西酮进行有效提取,之后用 GC/ MS 进行定性、定量分析. 方法检出限为0. 02 mg / L,定量限为0. 1 mg / L. 血液中甲卡西酮在0. 5、1. 0 和2. 0 mg / L 3 个添加水平的平均回收率在96. 70% ~99. 27%之间,甲卡西酮在0. 1 ~ 50 mg / L 的浓度范围内线性良好. 方法快速、简便、高效且操作自动化,适用于血液中甲卡西酮的检验鉴定.     

Expanding the number of phthalates monitored in house dust

Phthalates have been used as plasticisers for several decades in various industry and consumer products. A method was developed for the determination of 13 not commonly monitored phthalates in household dust. The method was based on solvent extraction using sonication, sample clean-up by solid phase extraction (SPE), and analysis using isotope dilution gas chromatography-tandem mass spectrometry (GC/MS/MS). The method was applied to the analysis of dust samples collected using two vacuum sampling techniques from 38 urban Canadian homes: a sample of fresh or ‘active’ dust (FD) collected by technicians and a composite sample taken from the household vacuum cleaner (HD). Spearman rank correlations between HD and FD samples were significant for six phthalates with median concentrations above their method detection limits (MDLs), suggesting that the HD samples provide comparable results with FD samples. Seven phthalates were detected and quantified in a Canada-wide set of 126 household dust samples, among which six phthalates were detected at frequencies higher than 87%, with median (range) concentrations of 1.9 (<0.42–240) (μg/g) for diisohexyl phthalate (DIHxP), 3.8 (<0.16–260) (μg/g) for di-n-heptyl phthalate (DHepP), 6.6 (<1.1–1170) (μg/g) for diisooctyl phthalate (DIOP), 1.1 (<0.12–390) (μg/g) for di-n-octyl phthalate (DOP), 6.3 (<0.16–430) (μg/g) for dinonyl phthalate (DNP), and 1.8 (<0.18–850) (μg/g) for di-n-decyl phthalate (DDP). High detection frequencies and widely scattered concentration levels of these phthalates in this preliminary set of 126 samples suggested a high variability in potential exposure to phthalates in Canadian homes. NIST SRM 2585 (organic contaminants in house dust) was also analysed; eight phthalates were detected, with concentrations ranging from 6.0 μg/g for DOP to 79 μg/g for DIHxP. The results from SRM 2585 may contribute to the certification of phthalate concentration values in this SRM.     

A novel and rapid extraction protocol for sensitive and accurate determination of prochloraz in orange juice samples: Vortex‐assisted spraying‐based fine droplet formation liquid‐phase microextraction before gas chromatography–mass spectrometry

A novel, ecofriendly, and easy extraction and preconcentration method named as vortex‐assisted spraying‐based fine droplet formation liquid‐phase microextraction was proposed for the determination of prochloraz at trace levels in orange juice samples by gas chromatography–mass spectrometry (GC‐MS). In this novel system, extraction solvent is dispersed by the help of spraying apparatus instead of dispersive solvent. Various parameters of the method were carefully optimized to increase signal‐to‐noise ratio of the analyte. Under the optimum chromatographic and extraction conditions, limit of detection and limit of quantification were calculated as 3.2 and 10.8 μg/kg, respectively. Moreover, enhancement in quantification power for the GC‐MS system was determined as 372 folds based on LOQ comparison. Relative recovery results for orange juice samples were found to be between 95.0–107.7% by utilizing matrix matching calibration. Furthermore, the developed method may be used to efficiently and simply extract other organic compounds for their determinations in several matrices.     

Evaluation of an in-injection port thermal desorption-gas chromatography/mass spectrometry method for analysis of non-polar organic compounds in ambient aerosol samples

Thermal desorption coupled with gas chromatography/mass spectrometry (TD-GC/MS) is an alternative to solvent extraction (SE)-based GC/MS (SE-GC/MS) for the analysis of non-polar organic compounds in filter or impactor-collected aerosols. TD-GC/MS has no sample pretreatment and requires a small filter aliquot for detecting individual organic compounds. The performance of an in-injection port TD-GC/MS is evaluated for polycyclic aromatic hydrocarbons (PAHs), n-alkanes, iso-/anteiso-alkanes, hopanes, steranes, branched alkanes, cyclohexanes, alkenes, and phthalates in standards and ambient air samples. Replicate analysis for 132 organic compounds showed relative standard deviations <10%, with the majority <5%. Accuracy for 15 PAHs, determined with NIST standard reference material (SRM) 1649a urban dust, was within +/-5% of the certified values. TD-GC/MS and SE-GC/MS method comparisons for 14 Hong Kong ambient samples agreed within 11% for 106 non-polar compounds. For 19 Tong Liang, China samples, agreement was within 13% for 23 PAHs.     

Development and evaluation of an enzyme-linked immunosorbent assay (ELISA) method for the measurement of 2,4-dichlorophenoxyacetic acid in human urine

An enzyme-linked immunosorbent assay (ELISA) method was developed to quantitatively measure 2,4-dichlorophenoxyacetic acid (2,4-D) in human urine. Samples were diluted (1:5) with phosphate-buffered saline containing 0.05% Tween and 0.02% sodium azide, with analysis by a 96-microwell plate immunoassay format. No clean up was required as dilution step minimized sample interferences. Fifty urine samples were received without identifiers from a subset of pesticide applicators and their spouses in an EPA pesticide exposure study (PES) and analyzed by the ELISA method and a conventional gas chromatography/mass spectrometry (GC/MS) procedure. For the GC/MS analysis, urine samples were extracted with acidic dichloromethane (DCM); methylated by diazomethane and fractionated by a Florisil solid phase extraction (SPE) column prior to GC/MS detection. The percent relative standard deviation (%R.S.D.) of the 96-microwell plate triplicate assays ranged from 1.2 to 22% for the urine samples. Day-to-day variation of the assay results was within ±20%. Quantitative recoveries (>70%) of 2,4-D were obtained for the spiked urine samples by the ELISA method. Quantitative recoveries (>80%) of 2,4-D were also obtained for these samples by the GC/MS procedure. The overall method precision of these samples was within ±20% for both the ELISA and GC/MS methods. The estimated quantification limit for 2,4-D in urine was 30 ng/mL by ELISA and 0.2 ng/mL by GC/MS. A higher quantification limit for the ELISA method is partly due to the requirement of a 1:5 dilution to remove the urine sample matrix effect. The GC/MS method can accommodate a 10:1 concentration factor (10 mL of urine converted into 1 mL organic solvent for analysis) but requires extraction, methylation and clean up on a solid phase column. The immunoassay and GC/MS data were highly correlated, with a correlation coefficient of 0.94 and a slope of 1.00. Favorable results between the two methods were achieved despite the vast differences in sample preparation. Results indicated that the ELISA method could be used as a high throughput, quantitative monitoring tool for human urine samples to identify individuals with exposure to 2,4-D above the typical background levels.     

Preparation and evaluation of molecularly imprinted solid-phase micro-extraction fibers for selective extraction of phthalates in an aqueous sample

A novel molecularly imprinted polymer (MIP) that was applied to a solid-phase micro-extraction (SPME) device, which could be coupled directly to gas chromatograph and mass spectrometer (GC/MS), was prepared using dibutyl phthalate (DBP) as the template molecule. The characteristics and application of this fiber were investigated. Electron microscope images indicated that the MIP-coated solid-phase micro-extraction (MI-SPME) fibers were homogeneous and porous. The extraction yield of DBP with the MI-SPME fibers was higher than that of the non-imprinted polymer (NIP)-coated SPME (NI-SPME) fibers. The MI-SPME fibers had a higher selectivity to other phthalates that had similar structures as DBP. A method was developed for the determination of phthalates using MI-SPME fibers coupled with GC/MS. The extraction conditions were optimized. Detection limits for the phthalate samples were within the range of 2.17-20.84 ng L⁻¹. The method was applied to five kinds of phthalates dissolved in spiked aqueous samples and resulted in recoveries of up to 94.54-105.34%, respectively. Thus, the MI-SPME fibers are suitable for the extraction of trace phthalates in complicated samples.     

Rapid determination of acetone in human blood by derivatization with pentafluorobenzyl hydroxylamine followed by headspace liquid-phase microextraction and gas chromatography/mass spectrometry

In the current work, a simple, rapid, accurate and inexpensive method was developed for the determination of acetone in human blood. The proposed method is based on derivatization with O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine hydrochloride (PFBHA), followed by headspace liquid-phase microextraction (HS-LPME) and gas chromatography/mass spectrometry (GC/MS). In the present method, acetone in blood samples was derivatized with PFBHA and acetone oxime formed in several seconds. The formed oxime was enriched by HS-LPME using the organic solvent film (OSF) formed in a microsyringe barrel as extraction interface. Finally, the enriched oxime was analyzed by GC/MS in electron ionization (EI) mode. HS-LPME parameters including solvent, syringe plunger withdrawal rate, sampling volume, and extraction cycle were optimized and the method reproducibility, linearity, recovery and detection limit were studied. The proposed method was applied to determination of acetone in diabetes blood and normal blood. It has been shown that derivatization with HS-LPME and GC/MS is an alternative method for determination of the diabetes biomarker, acetone, in blood samples.     

超声辅助乳化液液微萃取-气相色谱-质谱分析水中的人工合成麝香

将超声辅助乳化与液液微萃取技术结合,建立了水体中人工合成麝香的气相色谱-质谱分析方法.优化前处理条件,包括萃取剂、萃取剂体积、萃取时间、萃取温度及离子强度的选择.结果表明:在10 mL水样中,加入50 μL氯苯作为萃取剂,4 0 MHz超声10 min,混匀,以4000 r/min离心10 min,移取下层有机相进样分析,效果佳.样品的富集倍数可达200倍,8种人工合成麝香在0.005～0.4 μg/L范围内线性关系良好,相关系数均大于0.994;检出限为0.3～0.5 ng/L;水样中加标回收率为96.2％～102.9％;相对标准偏差为2.3％～4.1％.本方法灵敏、快速、准确,可满足环境水样中痕量人工合成麝香监测的质控要求.     

Organophosphate and phthalate esters in standard reference material 2585 organic contaminants in house dust

The levels of 22 phthalate diesters (phthalates) and organophosphate triesters (organophosphates) have been investigated in standard reference material 2585 (SRM 2585) “organic contaminants in house dust.” Ultrasonic-assisted solvent extraction and solid-phase extraction on a Florisil adsorbent were used as the extraction and cleanup steps combined with analysis using gas chromatography–tandem mass spectrometry in positive ion chemical ionization mode. Seven phthalates were detected in the concentration range 1–570 μg/g. Di(2-ethylhexyl) phthalate was the major phthalate present at 570 μg/g. Ten organophosphates were detected in SRM 2585. Tris(2-butoxyethyl) phosphate was the predominant organophosphate at 82 μg/g, and nine organophosphates were determined at concentrations ranging from 0.19 to 2.3 μg/g. Five organophosphates were below the method detection limit, of which two were in level with the procedural blank. The applied extraction and cleanup method was evaluated for the analysis of SRM 2585. The extraction yield was ≥99%, except for tris(2-chloroethyl) phosphate (97%) and diethyl phthalate (98.5%). The problem of calibration curvature is addressed, and it is shown that the use of deuterated standards improves the analysis. The concentrations of ten organophosphate esters were determined in SRM 2585, and seven of these were compared with existing data. To our knowledge, this is the first report of the levels of the seven phthalates esters in SRM 2585 “organic contaminants in house dust.”     

A high-accuracy method of analysis of 19-norandrosterone in human urine as utilised for the international laboratory intercomparison CCQM-P68

A high-accuracy exact-matching isotope dilution mass spectrometry (IDMS) method for 19-norandrosterone (19-NA) in human urine was developed at NMIA for the certification of a freeze-dried human urine reference material (CRM NMIA MX002). The method utilised GC/HRMS analysis following hydrolysis, solvent extraction, HPLC fractionation and derivatisation. The method development included investigation of all potential analytical biases for the different stages of the method and included development of a confirmatory LC/MS/MS method. The measurement uncertainty of the reference method was rigorously investigated with the achieved expanded uncertainty being less than 4% at the 95% level of confidence. The method was used in the Comité Consultatif pour la Quantité de Matière (CCQM) pilot study CCQM-P68 which was an interlaboratory intercomparison for the analysis of 19-NA in human urine in which four national metrology institutes (NMIs) participated in. The agreement in the results from the NMIA method with those from the other NMIs was excellent.     

波兰农产品中农药残留检测技术现状

介绍波兰农产品中农药残留检测技术。波兰的农药残留检测技术标准以欧盟标准为框架,在实际检测过程中各实验室可根据自身仪器设备条件、样品基质及目标农药的性质,自主开发检测方法,但需根据SANCO 12571:2013对方法进行验证,并向波兰认可中心提供验证报告。样品制备技术以基于乙腈提取/分配、Qu ECh ERS净化为主(EN 15662:2008),各实验室对标准中大部分步骤进行了调整和创新,以满足实际工作的需要;一些经改进的经典方法,如基质固相分散法(MSPD)和基于丙酮提取、二氯甲烷萃取的LUKE法在波兰农产品检测实验室也有较为广泛的应用;最终定性定量分析以GC–MS/MS和HPLC–MS/MS法为主,以GC,HPLC和紫外分光光度法等分析方法为辅。     

Trace-level analysis of polychlorinated biphenyls,organochlorine pesticides and polycyclic aromatic hydrocarbons in human plasma or serum by dispersive liquid–liquid microextraction and gas chromatography–tandem mass spectrometry

A method to determine 8 polychlorinated biphenyls (PCBs), 23 organochlorine pesticides (OCPs) and 16 polycyclic aromatic hydrocarbons (PAHs) was described using dispersive liquid–liquid microextraction (DLLME) of a small amount of plasma or serum sample and gas chromatography–tandem mass spectrometry (GC–MS/MS). The appropriate selection of the extraction solvent and dispersing solvent contributes to a high extraction yield and a clean extract. To verify the developed method, the interference, linearity of the calibration curve, detection limit, precision and accuracy were evaluated. The calibration curves were linear by 2–3 orders of magnitude with correlation coefficients above 0.997 in all cases. The LODs of PCBs, OCPs and PAHs were measured in the ranges of 0.0006–0.0029, 0.001–0.029 and 0.0002–0.012 ng/mL. The intraday precision achieved by this method was 2.19–10.3% (PCBs), 1.65–14.3% (OCPs) and 0.91–12.8% (PAHs), and the intraday accuracy 1.56–7.37% (PCBs), 2.34–19.6% (OCPs) and 1.49–15.7% (PAHs). The advantage of this method is that the analysis of PCBs, OCPs, and PAHs can be performed in a single chromatographic run, and the low detection limit enables monitoring of target substances in low exposure general public samples, and the analysis procedure is relatively simple and fast.     

Determination of residual solvents in pharmaceuticals by thermal desorption-GC/MS.

A novel method for the determination of residual solvents in pharmaceuticals by thermal desorption (TD)-GC/MS has been established. A programmed temperature pyrolyzer (double shot pyrolyzer) is applied for the TD. This method does not require any sample pretreatment and allows very small amounts of the sample. Directly desorbed solvents from intact pharmaceuticals (ca. 1 mg) in the desorption cup (5 mm x 3.8 mm i.d.) were cryofocused at the head of a capillary column prior to a GC/MS analysis. The desorption temperature was set at a point about 20 degrees C higher than the melting point of each sample individually, and held for 3 min. The analytical results using 7 different pharmaceuticals were in agreement with those obtained by direct injection (DI) of the solution, followed by USP XXIII. This proposed TD-GC/MS method was demonstrated to be very useful for the identification and quantification of residual solvents. Furthermore, this method was simple, allowed rapid analysis and gave good repeatability.     

Determination of Hexabromocyclododecane in Expanded Polystyrene and Extruded Polystyrene Foam by Gas Chromatography-Mass Spectrometry

A gas chromatography-mass spectrometry (GC/MS) method for the determination of hexabromocyclododecane (HBCD) in expanded polystyrene and extruded polystyrene foam (EPS/XPS) was developed. The EPS/XPS samples were ultrasonically extracted with acetone and the extracts were purified by filtration through a microporous membrane (0.22 μm) and solid-phase extraction. The samples were analyzed using a GC/MS using the selected ion monitoring mode. The ions 157, 319 and 401 were selected as the qualitative ions, while ion 239 was chosen as the quantitative ion. An HBCD standard working solution with a concentration range of 1.0–50.0 mg/L showed good linearity. The detection limit of HBCD was 0.5 mg/kg, meeting the LPC limit (<100 or 1000 mg/kg). Six laboratories were selected to verify the accuracy of the method, and 10 samples were tested. The interlaboratory relative standard deviation range was 3.68–9.80%. This method could play an important role in controlling HBCD contamination in EPS/XPS.     

Quantitative analysis using gas chromatography/combustion/isotope ratio mass spectrometry and standard addition of intrinsically labelled standards (SAIL)--application to isoflavones in foods

We have investigated a novel application of gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS) for the quantitative analysis of the isoflavones in food matrices. Previous methods have been hampered by the lack of analytical standards to introduce early enough in the extraction procedure to allow compensations for losses at all stages of the procedure. In this work we have produced standard materials that can be added at the initial extraction, by intrinsically labelling soya plants by growing them in an atmosphere enriched in the stable isotope of carbon in CO(2). On analysis these plants were shown to contain phytoestrogens at a high (up to 20%) level of enrichment. The dried plant material has been used to estimate the isoflavone concentrations of a set of spiked flours. For daidzein the methodology was shown to produce results comparable to those achieved by GC/MS techniques. The method was less successful for genistein, possibly due to the greater fragility of this compound under the conditions required for the analysis.     

Rapid monitoring of sulfur mustard degradation in solution by headspace solid-phase microextraction sampling and gas chromatography mass spectrometry

A method using headspace solid-phase microextraction (HS-SPME) followed by gas chromatography/mass spectrometry (GC/MS) analysis has been developed to gain insight into the degradation of the chemical warfare agent sulfur mustard in solution. Specifically, the described approach simplifies the sample preparation for GC/MS analysis to provide a rapid determination of changes in sulfur mustard abundance. These results were found to be consistent with those obtained using liquid-liquid extraction (LLE) GC/MS. The utility of the described approach was further demonstrated by the investigation of the degradation process in a complex matrix with surfactant added to assist solvation of sulfur mustard. A more rapid reduction in sulfur mustard abundance was observed using the HS-SPME approach with surfactant present and was similar to results from LLE experiments. Significantly, this study demonstrates that HS-SPME can simplify the sample preparation for GC/MS analysis to monitor changes in sulfur mustard abundance in solution more rapidly, and with less solvent and reagent usage than LLE.     

Analysis of cholesterol oxidation products by Fast gas chromatography/mass spectrometry

The aim of the present study was to set‐up a Fast gas chromatography/mass spectrometry method for the analysis of cholesterol oxidation products (COPs). A silylated mixture of seven oxysterol standards was injected into a Fast GC/MS system. A capillary GC column (10 m×0.1 mm internal diameter×0.1 μm film thickness) coated with 95% dimethyl‐ and 5% diphenyl‐polysiloxane, was used. The method gave a fast (total analysis time=3.5 min) and satisfactory resolution (R>1.2) of the COPs standards, with a good repeatability and sensitivity, similar to those of conventional GC/MS; recoveries were tested on mice liver. Fast GC/MS method suitability for COPs analysis in food was also tested on an oxidized sardine fillet, which had been previously saponified and purified by NH₂ solid‐phase extraction (SPE); a good repeatability and sensitivity was also obtained. The analytical performance of the Fast GC/MS method for the determination of COPs, together with the consequent significant reduction of the analysis time and consumables, demonstrates that Fast GC/MS represents a valid alternative to conventional GC/MS and evinces the great potential of such an analytical technique, which could be applied for both food and biological samples.     

Determination of the boiling point distribution of sulfur compounds in light cycle oil using GC with a flame photometric detector and pyrolyzer

A method has been developed to determine the boiling point distribution of sulfur compounds in light cycle oils (LCO'S). The method chosen for this analysis was GC with a flame photometric detector (FPD) and pyrolyzer. Tests were carried out to evaluate the recovery efficiency, repeatability, and accuracy of the method. Repeatabilities within 2% were obtained. The recovery of benzothiophenes and dibenzothiophenes was close to 100%; this was important because these are the major sulfur components in LCO's. No hydrocarbon or solvent interferences were observed with the use of the pyrolyzer, even for a 95% solvent level. Comparison with results from other techniques showed that the method accurately determined the levels of sulfur compounds in the LCO boiling point range.     

Fast gas chromatography with solid phase extraction clean-up for ultratrace analysis of pesticide residues in baby food

A sample preparation method based on single solvent phase extraction and solid-phase extraction (SPE-NH2) clean-up is studied in combination with fast capillary gas chromatography (GC) to determine 18 selected pesticides belonging to various chemical classes in apples, the common raw material for baby food production and baby food, at the concentration level < or = 10 microg/kg maximum residual limit (MRL). Possibilities of mass spectrometry (MS) detector and electron capture detector (ECD) in fast gas chromatography (GC) of samples with complex matrice at ultra trace levels of pesticide residues were studied and compared. MS detection in single ion monitoring (SIM) mode provided higher selectivity compared to ECD. Optimisation of extraction as well as the simplifying of the whole process of sample preparation was carried out. Recoveries obtained at concentration level of 5 microg/kg (the required value for limit of quantification (LOQ) in baby food) were >90%, except of dimethoate (77.7%) and captan (46.4%) with MS detection. The obtained LOQs were at least 1 order lower than 5 microg/kg for the majority of compounds. The repeatability of gas chromatography-mass spectrometry (GC-MS) measurements of the matrix matched standards expressed as relative standard deviation was <11% except of captan and cypermethrin.