Jin-feng Peng

Determination of formaldehyde in shiitake mushroom by ionic liquid-based liquid-phase microextraction coupled with liquid chromatography

Using ionic liquid as extraction solvent and 2,4-dinitrophenylhydrazine (DNPH) as derivative agent, formaldehyde in shiitake mushroom was determined by liquid-phase microextraction coupled with high-performance liquid chromatography (HPLC). Shiitake mushroom was leached with water and filtrated, then the formaldehyde in filtrate was derivatized with DNPH and extracted simultaneously into a 10mul drop of ionic liquid suspended on the tip of the microsyringe, and finally injected into the HPLC system for determination. The proposed procedure has a detection limit of 5mugl(-1) formaldehyde in extraction solution, thus the mushroom sample filtrate could be diluted with a large ratio to eliminate the influence of sample matrix. The method has a relative standard deviation of 3.5% between days for 53.5mugl(-1) formaldehyde standards. High contents of formaldehyde (119-494mugg(-1) wet weight), which is harmful for human beings, were detected in shiitake mushroom. Therefore, strategies must be taken to prevent the accumulation and strictly control the content of formaldehyde in shiitake mushroom.

Dithizone-functionalized solid phase extraction-displacement elution-high performance liquid chromatography-inductively coupled plasma mass spectrometry for mercury speciation in water samples

A novel and simple solid phase extraction (SPE)-high performance liquid chromatography (HPLC)-inductively coupled plasma mass spectrometry (ICP-MS) method was developed for determination of inorganic mercury (IHg), methylmercury MeHg and ethylmercury (EtHg) in water samples in the present work. The procedure involves pre-functionalization of the commercially available C18 SPE column with dithizone, loading water sample, displacement elution of mercury species by Na(2)S(2)O(3) solution, followed by HPLC-ICP-MS determination. Characterization and optimization of operation parameters of this new SPE procedure were discussed, including eluting reagent selection, concentration of eluting reagent, volume of eluting reagent, effect of NaCl and humic acid in sample matrix. At optimized conditions, the detection limits of mercury species for 100mL water sample were about 3ngL(-1) and the average recoveries were 93.7, 83.4, and 71.7% for MeHg, IHg and EtHg, respectively, by spiking 0.2microgL(-1) mercury species into de-ion water. Stability experiment reveals that both the dithizone-functionalized SPE cartridge and the mercury species incorporated were stable in the storage procedure. These results obtained demonstrate that SPE-HPLC-ICP-MS is a simple and sensitive technique for the determination of mercury species at trace level in water samples with high reproducibility and accuracy.

MCX based solid phase extraction combined with liquid chromatography tandem mass spectrometry for the simultaneous determination of 31 endocrine-disrupting compounds in surface water of Shanghai.

A novel analytical method employing MCX (mixed-mode cationic exchange) based solid phase extraction (SPE) coupled with liquid chromatography tandem mass spectrometry (LC-MS/MS) was developed to detect 31 endocrine-disrupting compounds (EDCs) in surface water samples simultaneously. The target EDCs belong to five classes, including seven estrogens, eight androgens, six progesterones, five adrenocortical hormones and five industrial compounds. In order to simultaneously concentrate the target EDCs and eliminate matrix interferences in the water samples, MCX SPE cartridges were employed for SPE, and then followed by a simple and highly efficient three-step sequential elution procedure. Two electrospray ionization (ESI) detection modes, positive (ESI+) and (ESI-), were optimized for HPLC-MS/MS analysis to obtain the highest sensitivity for all the EDCs. The limits of detection (LODs) were 0.02-1.9 ng L(-1), which are lower than or comparable to these reported in references. Wide linear ranges (LOD-100 ng L(-1) for ESI+ mode, and LOD-200 ng L(-1) for ESI- mode) were obtained with determination coefficients (R(2)) higher than 0.99 for all the compounds. With five internal standards, good recoveries (84.4-103.0%) of all the target compounds were obtained in selected surface water samples. The developed method was successfully applied to investigate the EDCs occurrence in the surface water of Shanghai by analyzing surface water samples from 11 sites. The results showed that nearly all the target compounds (30 in 31) were present in the surface water samples of Shanghai, of which three industrial compounds (4-t-OP, BPA, and BPF) showed the highest concentrations (median concentrations were 11.88-23.50 ng L(-1)), suggesting that industrial compounds were the dominating EDCs in the surface water of Shanghai, and much more attention should be paid on these compounds. Our present research demonstrated that SPE with MCX cartridges combined with HPLC-MS/MS was convenient, efficient and reliable for multiclass analysis of EDCs in surface water.

Ionic liquids as mobile phase additives for high-performance liquid chromatography separation of phenoxy acid herbicides and phenols

In this present study, 1-butyl-3-methylimidazolium chloride ([C(4)MIM]Cl), 1-octyl-3-methylimidazolium chloride ([C(8)MIM]Cl), and 1-decyl-3-methylimidazolium chloride ([C(10)MIM]Cl) were adopted as mobile phase additives in the high performance liquid chromatography (HPLC) to simultaneously separate phenoxy acid herbicides and phenols at neutral pH. It was found that by using 20 mM of [C(4)MIM]Cl, baseline separation and good chromatograms for all the acid compounds were obtained on a normal reversed-phase C(18) column. The retention time of the target acid compounds shortened with the increase of the alkyl chain length and the concentrations of ionic liquids, probably due to the delocalization of the positive charge on the imidazolium cation, the repulsion between chlorine ions of ionic liquids and the acid compounds, as well as the stereo-hindrance effect. The mechanism with ionic liquids as mobile additives for the separation of acid compounds was discussed.

Direct chemical vapour generation-flame atomization as interface of high performance liquid chromatography-atomic fluorescence spectrometry for speciation of mercury without using post-column digestion

A high performance liquid chromatography-direct chemical vapour generation-flame atomization-atomic fluorescence spectrometry (HPLC-CVG-FA-AFS) system for speciation of methylmercury (MeHg+), inorganic mercury (Hg2+) and ethylmercury (EtHg+) without using post-column digestion is developed and characterized. In this novel system, organomercurial species separated by chromatography were transformed to their hydrides by KBH4, further atomized in the flame atomizer and detected by AFS. The conventionally used on-line UV or microwave digestion system was omitted, and no oxidation reagent was needed, which significantly simplified the instrumentation. Under the optimized conditions, the detection limits were 0.2, 0.4 and 0.4 µg L−1 (as Hg) for MeHg+, Hg2+, and EtHg+ (100 µL injection), which corresponds to absolute detection limits of 0.02, 0.04 and 0.04 ng (as Hg) for MeHg+, Hg2+, and EtHg+, respectively. The sensitivity of the developed method was comparable with the conventional high performance liquid chromatography-UV digestion-cold vapour generation-atomic fluorescence spectrometry (HPLC-UV-CVG-AFS) system. Validation with biological certified reference materials showed that the proposed method is simple and accurate for mercury speciation.

Simultaneous solid phase extraction coupled with liquid chromatography tandem mass spectrometry and gas chromatography tandem mass spectrometry for the highly sensitive determination of 15 endocrine disrupting chemicals in seafood.

This study aimed to develop a sensitive and reliable multi-residue method for the determination of trace amounts of endocrine disrupting chemicals including five phthalate esters (PAEs), five monoalky phthalate esters (MPEs), four alkylphenols (APs) and bisphenol A (BPA) in seafood. Ultrasonic liquid extraction was selected for extraction based on acetonitrile, instead of frequently-used n-hexane, due to its lower background of PAEs. Application of solid phase extraction (SPE) with primary secondary amine (PSA, 1g/6 mL) cartridge achieved the relatively low matrix effects for MPEs and BPA in seafood. To our knowledge, it is the first study reporting about simultaneous extraction and purification of PAEs, MPEs, APs and BPA in biota samples. To obtain the maximum sensitivity, both liquid chromatography tandem mass spectrometry (LC-MS/MS) and gas chromatography tandem mass spectrometry (GC-MS/MS) were applied for analysis. This method was validated and tested on fish, mollusk and prawn. Sufficient linearity was verified by Mandels fitting test for the matrix-matched calibrations used in this study for MPEs, APs and BPA, between 0.5 ng/g and 200 ng/g or 400 ng/g. And correlation coefficients of all calibrations suppressed 0.99 for all analytes. Good recoveries were obtained, ranging from 60% to 127% for most compounds. The sensitivity was good with method detection limits (MDLs) of 0.015-2.2 ng/g wet weight (ww) for all compounds. Most MDLs are much lower than those in previous reports. The sensitive method was then applied on real fish, mollusk and prawn samples from the Yangtze River Delta sea area (China), and all the target compounds were detected with the maximum concentrations of PAEs, MPEs, APs and BPA up to 219.3 ng/g ww, 51.4 ng/g ww, 62.0 ng/g ww and 8.6 ng/g ww, respectively.