A ng/L Level LC-MS Method Using Membrane SPE as Sampling Technology: Determination of Nine Halobenzoquinones in Potable Water.

A promising method was established for the determination of nine halobenzoquinones (HBQs) in potable water by membrane solid-phase extraction (MSPE) pretreatment and the liquid chromatography-mass spectrometry (LC-MS) method. A 500 mL water sample was taken for enrichment by the SDB-RPS membrane, which was previously activated by methanol and ultrapure water. The sample was eluted with methanol and re-dissolved with the initial mobile phase after nitrogen blowing. Then, it was detected in negative ion mode using the working curve, and HBQs were quantified by the external standard method. The linearity was satisfactory in the concentration range of 4-1000 ng/L, with correlation coefficients of 0.9963~0.9994. The recoveries were 73.5~126.6% at three spiked levels, with relative standard deviations (RSDs) of 6.8~15.5%. The limits of detection (LOD, S/N = 3) values were 0.1~0.7 ng/L. The results demonstrate that the MSPE-LC-MS method is reliable, rapid, and sensitive for the simultaneous analysis of nine HBPs in potable water.

Simultaneous determination of the residues of anesthetics and sedatives in fish using LC-QLIT-MS/MS combined with DSPE.

Liquid chromatography coupled with quadrupole linear ion trap tandem mass spectrometry (LC-QLIT-MS/MS) technology operated in electrospray ionization (ESI) was developed for tracing anesthetic (AETs) and sedatives (SDTs) in fish. Sampling procedure was achieved by using acetonitrile extraction followed by dispersive solid phase extraction (DSPE) clean-up. Under the optimized laboratory conditions, reliable qualitative confirmation was obtained through the multiple reaction monitoring-information dependent acquisition-enhanced product ion (MRM-IDA-EPI) mode. Results indicated a favorable linear in the concentration range of 1-100 µg∙kg-1 (0.1-10 µg∙kg-1 for MS-222), with regression coefficient not less than 0.9997. The detection limit ranges from 0.03 to 0.4 µg∙kg-1 (S/N = 3). The validated method was applied to determine AETs and SDTs in fish with satidfied recoveries of 86.3 %-111.7 % and the relative standard deviations (RSD) of 1.9 %-8.9 % (n = 6). Practical samples analysis indicated that the proposed method is simple, rapid, sensitive and accurate for identification of AETs and SDTs.

Rapid and selective determination of 9 nitrosamines in biological samples using ultra-high performance liquid chromatography-triple quadrupole linear ion trap mass spectrometry.

A sensitive, selective and convenient method for the simultaneous determination of 9 nitrosamines (NAs) in biological samples was developed using isotope dilution ultra-high performance liquid chromatography-triple quadrupole linear ion trap mass spectrometry (UPLC-QTRAP-MS). Multiple reaction monitoring-information dependent acquisition-enhanced product ion (MRM-IDA-EPI) scan mode was performed to eliminate false positive results, and the whole detection procedure was characterized by less time consuming and simple sample preparation. 9 NAs were separated through a T3 column with the gradient elution of acetonitrile and water, and detected by UPLC-QTRAP-MS with an atmospheric pressure chemical ionization (APCI) source in the positive mode. The quantitative analysis was carried out via the isotope internal standard method with a matrix calibration curve. Under the optimized conditions, good linearity for the 9 NAs was achieved in the range of 0.2-20 µg L-1 with correlation coefficients (r) higher than ≥0.9991, and the limits of detection and limits of quantitation were 0.02-0.1 µg L-1 (S/N = 3) and 0.06-0.3 µg L-1 (S/N = 10), respectively. Satisfactory recoveries ranging from 79.4% to 108.0% were obtained, and the precision of the proposed method, indicated by the relative standard deviations (RSDs), was 2.3-12.9%. The matrix effect study showed that NDMA, NMOR and NMEA presented a matrix suppression effect, NDPHA displayed a matrix enhancement effect, and the matrix effects of the other 5 analytes could be ignored. Real application of the developed method in 13 urine and 24 plasma samples demonstrated that NDBA, NPIP and NPYR occurred in both urine and plasma samples with the concentration of 0.038-0.60 µg L-1, while other NAs were not detected. Such a method was sensitive and selective, and could be applied to the rapid qualitative and quantitative analysis of the 9 NAs in biological samples.

Three-dimensional ionic liquid functionalized magnetic graphene oxide nanocomposite for the magnetic dispersive solid phase extraction of 16 polycyclic aromatic hydrocarbons in vegetable oils.

In this paper, a novel three-dimensional ionic liquid functionalized magnetic graphene oxide nanocomposite (3D-IL@mGO) was prepared, and used as an effective adsorbent for the magnetic dispersive solid phase extraction (MSPE) of 16 polycyclic aromatic hydrocarbons (PAHs) in vegetable oil prior to gas chromatography-mass spectrometry (GC-MS). The properties of 3D-IL@mGO were characterized by scanning electron micrographs (SEM), X-ray photoelectron spectroscopy (XPS), vibrating sample magnetometer (VSM). The 3D-IL@mGO, functionalized by ionic liquid, exhibited high adsorption toward PAHs. Compared to molecularly imprinted solid phase extraction (MISPE), the MSPE method based on 3D-IL@mGO had less solvent consumption and low cost, and was more efficent to light PAHs in quantitative analysis. Furthermore, the rapid and accurate GC-MS method coupled with 3D-IL@mGO MSPE procedure was successfully applied for the analysis of 16 PAHs in eleven vegetable oil samples from supermarket in Zhejiang Province. The results showed that the concentrations of BaP in 3 out of 11 samples were higher than the legal limit (2.0µg/kg, Commission Regulation 835/2011a), the sum of 8 heavy PAHs (BaA, CHR, BbF, BkF, BaP, IcP, DaA, BgP) in 11 samples was between 3.03µg/kg and 229.5µg/kg. Validation results on linearity, specificity, accuracy, precision and stability, as well as on application to the analysis of PAHs in oil samples demonstrated the applicability to food safety risk monitoring in China.

Simultaneous determination of seven synthetic colorants in wine by dispersive micro-solid-phase extraction coupled with reversed-phase high-performance liquid chromatography.

A novel and effective dispersive micro-solid-phase extraction (d-µ-SPE) using ethanediamine-functionalized magnetic Fe3O4 polymer (EDA-MP) as an efficient adsorbent in wine sample was developed. Based on this, a simple and time-saving analytical method for the simultaneous determination of seven synthetic colorants (i.e., tartrazine, amaranth, carmine, sunset yellow, allura red, brilliant blue and erythrosine) in wine by reversed-phase high-performance liquid chromatography with an ultraviolet detector was established. The experimental parameters, including the chromatographic retention behavior of studied synthetic colorants, the effect of the usage amount of cross-linking monomer, the effect of the usage amount of EDA-MP on the recovery and the recyclability of the adsorbents, were studied in detail. The results showed that the EDA-MP could be reused efficiently at least six times. Under optimized conditions, the recoveries for all analytes were in the range of 88.6-105.2%, with the intraday relative standard deviations (RSDs) ranging from 2.1 to 8.2% and the interday RSDs ranging from 3.4 to 8.7%, and all the analytes had good linearities in the tested ranges with correlation coefficients (r(2)) >0.9995. The limits of quantification for seven synthetic colorants were between 0.12 and 0.45 mg L(-1). The developed method was successfully applied to wine samples, and it was confirmed that the EDA-MP particles were highly effective d-µ-SPE materials.