Xiangfan Piao

Gas purge microsyringe extraction for quantitative direct gas chromatographic-mass spectrometric analysis of volatile and semivolatile chemicals.

Sample pretreatment before chromatographic analysis is the most time consuming and error prone part of analytical procedures, yet it is a key factor in the final success of the analysis. A quantitative and fast liquid phase microextraction technique termed as gas purge microsyringe extraction (GP-MSE) has been developed for simultaneous direct gas chromatography-mass spectrometry (GC-MS) analysis of volatile and semivolatile chemicals without cleanup process. Use of a gas flowing system, temperature control and a conventional microsyringe greatly increased the surface area of the liquid phase micro solvent, and led to quantitative recoveries of both volatile and semivolatile chemicals within short extraction time of only 2 min. Recoveries of polycyclic aromatic hydrocarbons (PAHs), organochlorine pesticides (OCPs) and alkylphenols (APs) determined were 85-107%, and reproducibility was between 2.8% and 8.5%. In particular, the technique shows high sensitivity for semivolatile chemicals which is difficult to achieve in other sample pretreatment techniques such as headspace-liquid phase microextraction. The variables affecting extraction efficiency such as gas flow rate, extraction time, extracting solvent type, temperature of sample and extracting solvent were investigated. Finally, the technique was evaluated to determine PAHs, APs and OCPs from plant and soil samples. The experimental results demonstrated that the technique is economic, sensitive to both volatile and semivolatile chemicals, is fast, simple to operate, and allows quantitative extraction. On-site monitoring of volatile and semivolatile chemicals is now possible using this technique due to the simplification and speed of sample treatment.

Automatic heating and cooling system in a gas purge microsyringe extraction

The gas purge microsyringe extraction (GP-MSE) technique offers quantitative and simultaneous extraction, and rapid gas chromatographic-mass spectrometric determination of volatile and semivolatile chemicals is possible. To simplify the application, a new automatic temperature control system was developed here. Stable heating and cooling over a wide range of temperatures were achieved using a micro-heater and thermoelectric cooler under varying gas flow conditions. Temperatures could be accurately controlled in the range 20-350°C (heating) and 20 to -4°C (cooling). Temperature effects on the extraction performance of the GP-MSE were experimentally investigated by comparing the recoveries of polycyclic aromatic hydrocarbons (PAHs) under various experimental conditions. A sample treatment was completed within 3 min, which is much less than the time required for chromatographic analysis. The recovery of chemicals determined ranged from 81 to 96%. High reproducibility data (RSD ≤ 5%) were obtained for direct extraction of various analytes in spiked complex plant and biological samples. The data show that the heating and cooling system has potential applications in GP-MSE system for the direct determination of various kinds of volatile and semivolatile chemicals from complex matrices without any, or only minor, sample pretreatment.

Gas flow headspace liquid phase microextraction

There is a trend towards the use of enrichment techniques such as microextraction in the analysis of trace chemicals. Based on the theory of ideal gases, theory of gas chromatography and the original headspace liquid phase microextraction (HS-LPME) technique, a simple gas flow headspace liquid phase microextraction (GF-HS-LPME) technique has been developed, where the extracting gas phase volume is increased using a gas flow. The system is an open system, where an inert gas containing the target compounds flows continuously through a special gas outlet channel (D=1.8mm), and the target compounds are trapped on a solvent microdrop (2.4 microL) hanging on the microsyringe tip, as a result, a high enrichment factor is obtained. The parameters affecting the enrichment factor, such as the gas flow rate, the position of the microdrop, the diameter of the gas outlet channel, the temperatures of the extracting solvent and of the sample, and the extraction time, were systematically optimized for four types of polycyclic aromatic hydrocarbons. The results were compared with results obtained from HS-LPME. Under the optimized conditions (where the extraction time and the volume of the extracting sample vial were fixed at 20min and 10mL, respectively), detection limits (S/N=3) were approximately a factor of 4 lower than those for the original HS-LPME technique. The method was validated by comparison of the GF-HS-LPME and HS-LPME techniques using data for PAHs from environmental sediment samples.

Water-based gas purge microsyringe extraction coupled with liquid chromatography for determination of alkylphenols from sea food Laminaria japonica Aresh

A novel organic solvent-free mode of gas purge microsyringe extraction, termed water-based gas purge microsyringe extraction, was developed. This technique can directly extract target compounds in wet samples without any drying process. Parameters affecting the extraction efficiency were investigated. Under optimal extraction conditions, the recoveries of alkylphenols were between 87.6 and 105.8%, and reproducibility was between 5.2 and 12.1%. The technique was also used to determine six kinds of alkylphenols (APs) from samples of Laminaria japonica Aresh. The OP and NP were detected in all the samples, and concentrations ranged from 26.0 to 54.5ngg(-1) and 45.0-180.4ngg(-1), respectively. The 4-n-butylphenol was detected in only one sample and its concentration was very low. Other APs were not detected in L. japonica Aresh samples. The experimental results demonstrated that the technique is fast, simple, non-polluting, allows for quantitative extraction, and a drying process was not required for wet samples. Since only aqueous solution and a conventional microsyringe were used, this technique proved affordable, efficient, and convenient for the extraction of volatile and semivolatile ionizable compounds.

Gas purge-microsyringe extraction: A rapid and exhaustive direct microextraction technique of polycyclic aromatic hydrocarbons from plants

Gas purge-microsyringe extraction (GP-MSE) is a rapid and exhaustive microextraction technique for volatile and semivolatile compounds. In this study, a theoretical system of GP-MSE was established by directly extracting and analyzing 16 kinds of polycyclic aromatic hydrocarbons (PAHs) from plant samples. On the basis of theoretical consideration, a full factorial experimental design was first used to evaluate the main effects and interactions of the experimental parameters affecting the extraction efficiency. Further experiments were carried out to determine the extraction kinetics and desorption temperature-dependent. The results indicated that three factors, namely desorption temperature (temperature of sample phase) Td, extraction time t, and gas flow rate u, had a significantly positive effect on the extraction efficiency of GP-MSE for PAHs. Extraction processes of PAHs in plant samples followed by first-order kinetics (relative coefficient R(2) of simulation curves were 0.731-1.000, with an average of 0.958 and 4.06% relative standard deviation), and obviously depended on the desorption temperature. Furthermore, the effect of the matrix was determined from the difference in Eapp,d. Finally, satisfactory recoveries of 16 PAHs were obtained using optimal parameters. The study demonstrated that GP-MSE could provide a rapid and exhaustive means of direct extraction of PAHs from plant samples. The extraction kinetics were similar that of the inverse process of the desorption kinetics of the sample phase.

Novel and rapid method for determination of organophosphorus pesticide residues in edible fungus using direct gas purge microsyringe extraction coupled on-line with gas chromatography–mass spectrometry

In this work a new analytical method for a rapid and simultaneous determination of 28 organophosphorus pesticides (OPPs) residues in edible fungus using gas purge microsyringe extraction (GP-MSE), coupled with on-line gas chromatography-mass spectrometry (GP-MSE-GC-MS) has been developed and optimized. GP-MSE, a novel gas flow liquid-phase microextraction technique, has been then fruitfully used as innovative and one-step extraction procedure, allowing a direct injection into the gas chromatograph coupled with a mass spectrometry detector (GC-MS) system without any further cleaning step. Once optimized, the GP-MSE-GC-MS analysis procedure showed reproducibility values, resolutions, linear responses, detection and quantification limits that allowed to consider this method suitable for the analysis of the 28 OPPs in real samples. Furthermore, OPP recoveries and the relative standard deviations (RSDs) ranged from 85.26% to 100.21%, and from 1.6% to 6.9%, respectively. This procedure was then used for the analysis of real samples and the obtained results were compared with those of ultrasonic extraction-solid phase extraction. Among the 28 OPPs, 14 of them were found in Lentinus edodes and Enoki mushrooms fungus samples, with a total concentrations of 112.7 and 210.7 μg kg(-1), respectively. This work demonstrated then that GP-MSE-GC-MS provided a highly efficient, solvent-saving, accurate and sensitive quantitative analysis method for a rapid determination of OPPs in edible fungus.

Monitoring of phthalates in foodstuffs using gas purge microsyringe extraction coupled with GC-MS.

Phthalate esters (PAEs) are commonly used as nonreactive plasticisers in vinyl plastics to increase the flexibility of plastic polymers. Numerous studies have indicated that the PAEs as a class of endocrine-disrupting chemicals. In addition, the studies have also shown that a major source of human exposure to phthalates is the diet. To date, the largest problem in PAEs analysis is the high blank value because PAEs are widely used in various applications and products. To overcome this shortcoming, gas purge microsyringe extraction (GP-MSE) was applied, which established a new and low-blank-value analytical method for PAE analysis to analyse PAEs in foodstuffs. In this study, GP-MSE was used as a clean-up method, and the overall recoveries ranged from 85.7 to 102.6%, and the RSD was less than 10%. More importantly, this method can overcome the problem of the high blank value in PAE analysis. This method was applied for measuring PAEs in 78 foodstuffs. The results showed that a wide variety of PAE concentrations were found in the different groups, and the content of PAEs (varies from 658 to 1610 ng g(-1) fresh weight) is greatest in seafood. The concentrations were in the following order: DEHP>DBP>DEP≈DMP>BBP≈DNOP. Finally, the daily intake of PAEs was estimated for adults based on the levels of PAEs in foodstuffs. The total EDIdiet values of 3.2 and 12.9 μg kg(-1) bw d(-1) were calculated for DEHP based on the mean and highest concentrations in foodstuffs, respectively.

Derivatization and liquid chromatography-UV-tandem mass spectrometric analysis of perfluorinated carboxylic acids.

The presence of perfluorocarboxylates (PFCAs) in the environment is of increasing concern due to their possible toxicity to humans and bioaccumulation in organisms. PFCAs are frequently found in river water, sediment and organisms and sometimes even in groundwater. In order to quantitatively determine these PFCAs, a fast derivatization coupled with a liquid chromatography-ultraviolet detector-electrospray ionization-tandem mass spectrometry (LC-UV-ESI-MS/MS) method was developed. The PFCAs were quantitatively converted to their corresponding phenacyl esters using p-bromophenacyl bromide as the derivatization reagent. Under optimized reaction conditions, the conversion yield of the PFCAs ranged from 86 to 92% with low %RSD. The typical derivatization product (p-bromophenacyl bromide perfluorooctanoate) was characterized by (1)H NMR, (13)C NMR, FT-IR and mass spectrometry. UPLC with a BEH C18 column and CAN/H(2)O (8/2, v/v) as a mobile phase were used to separate the derivatives. The analytes were completely eluted within 6 min and multidimensional detection using UV at 260 nm and ESI-MRM in the negative ion mode were carried out. Bromide isotopic characteristic fragment ions appeared in the first Q1 scans, and four daughter ions of the MRMs at m/z [M-H-222](-), [M-H-250](-), [M-H-278](-) and [M-H-316](-) were used for quantification and confirmation. The mass spectral information ensured accurate identification of the analytes even when the sample matrices were complex. The method successfully eliminated the PFCAs background problems originating from polymeric parts in liquid chromatographic systems. The LODs of the method were lower than 5 ng mL(-1), and the relative standard deviation (RSD%) values ranged from 5.2 to 9.8%. The method was successfully applied for the quantification of PFCAs in river water contaminated by industrial wastewater, and this indicated that the method was useful in the determination of PFCAs in environmental samples.

Gas-Purged Headspace Liquid Phase Microextraction System for Determination of Volatile and Semivolatile Analytes

In order to achieve rapid, automatic, and efficient extraction for trace chemicals from samples, a system of gas-purged headspace liquid phase microextraction (GP-HS-LPME) has been researched and developed based on the original HS-LPME technique. In this system, semiconductor condenser and heater, whose refrigerating and heating temperatures were controlled by microcontroller, were designed to cool the extraction solvent and to heat the sample, respectively. Besides, inert gas, whose gas flow rate was adjusted by mass flow controller, was continuously introduced into and discharged from the system. Under optimized parameters, extraction experiments were performed, respectively, using GP-HS-LPME system and original HS-LPME technique for enriching volatile and semivolatile target compounds from the same kind of sample of 15 PAHs standard mixture. GC-MS analysis results for the two experiments indicated that a higher enrichment factor was obtained from GP-HS-LPME. The enrichment results demonstrate that GP-HS-LPME system is potential in determination of volatile and semivolatile analytes from various kinds of samples.

An on-line sample pretreatment technique for the HPLC analysis of plant samples.

A continuous-flow, on-line sample pretreatment technique using a silica gel microsyringe extractor has been developed. All steps including extraction, separation, clean-up, and concentration occur in the microsyringe. The overall sample pretreatment process takes <10 min per sample. Different polarity chemicals in the plant sample are successively extracted and separated, and analyzed in parallel using HPLC-UV and HPLC-UV-MS/MS. Polycyclic aromatic hydrocarbons, alkylphenols, and plant hormones were determined as model compounds for nonpolar, intermediate polarity, and polar fractions, respectively. All the parameters that influence the extraction and separation efficiency of the microsyringe extractor have been optimized and evaluated. Under the optimized conditions, recoveries of target compounds ranged from 78.4 to 101.9%, the RSD was <12.8% and the square of the correlation coefficient was >0.99. Complex plant samples of Sambucus Mandshurica Kitag have been tested using this method. Fluorene, phenanthrene, pyrene, and plant hormones were detected in all the samples, and concentrations ranged from 24.2-34.9, 43.8-67.1, 25.9-29.2, and 14.5~110.8 ng/g, respectively.