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Liquid chromatography versus supercritical fluid chromatography coupled to mass spectrometry: a comparative study of performance for multiresidue analysis of pesticides.

ABSTRACT: Abundant studies have been published evaluating different parameters of reverse-phase liquid chromatography (LC) and supercritical fluid chromatography (SFC), both coupled to electrospray (ESI)/mass spectrometry (MS) for pesticide residue analysis. However, there is a lack of a comprehensive comparative study that facilitates deep knowledge about the benefits of using each technique. In the present study, the same mass spectrometer was used coupled to both liquid and supercritical fluid chromatographies with a multiresidue method of 215 compounds, for the analysis of pesticide residues in food samples. Through the injection of the spiked extracts, separate experiments were conducted. A study of the optimum ion source temperature using the different chromatography modes was performed. The results were evaluated in terms of sensitivity with tomato, leek, onion, and orange as representative fruit and vegetable matrices. The compounds which reported the highest area values in each chromatography were evaluated through their substance groups and polarity values. The impact of matrix effects obtained in tomato matrix was similar for both cases; however, SFC clearly showed better results in analyzing matrices with a higher number of natural co-extracted compounds. This can be explained by the combination of two effects: (i) chromatography separation and (ii) ion source efficiency. The chromatographic elution presented different profiles of matrix components, which had diverse impact on the coelution with the analytes, being more beneficial when SFC was used in the matrices studied. The data showed that the best results obtained in SFC are also related to a higher ionization efficiency even when the ESI emitter tip was not optimized for SFC flow. In the present study a comprehensive evaluation of the benefits and drawbacks of these chromatography modes for routine pesticide residue analysis related to target compounds/commodities is provided.

SUBMITTER: Cutillas V

PROVIDER: S-EPMC8437864 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:An ultrahigh-performance liquid chromatography in combination with high-resolution mass spectrometry Thermo Q-Extractive Focus Orbitrap MS has been introduced for analysis of multiclass pesticides in vegetable samples collected in Hanoi, Vietnam. Multiclass pesticides were separated on the Thermo Hypersil Gold PFP column utilizing a gradient of the mobile phase consisting of 5 mM ammonium formate, 0.1% formic acid in deionized water, and methanol. The target analytes were detected in the full-scan mode on Thermo Scientific Q-Exactive Focus Orbitrap MS for quantitation at the optimum operating conditions. These conditions included, but not limit to, the resolution of 70000 at the full width at half maximum in both positive and negative mode, mass range from 80 to 1000 m/z, and optimized parameters for the heated electrospray ionization source. The identification of the analytes in real samples was based on retention times, mass to charge ratios, mass accuracies, and MS/MS spectra at the confirmation mode with the inclusion list of target analytes. The mass accuracies of target analytes were from -4.14 ppm (dinotefuran) to 1.42 ppm (cinosulfuron) in the neat solvent and from -3.91 ppm (spinosad D) to 1.29 ppm (cinosulfuron) in the matrix-matched solution. Target analytes in the vegetable-based matrix were extracted by the QuEChERS method. Some critical parameters of the analytical method such as linearity, repeatability, limit of detection, and limit of quantitation have been evaluated and implemented. Excellent LOD and LOQ of the developed method were achieved at the range of 0.04-0.85 and 0.13-2.9 μg·kg-1, respectively. Intraday and interday repeatability of the analytical signal (peak area, n=6) of the developed method were below 3% and 10%, correspondingly. The matrix effect, extraction recovery, and overall recovery were fully investigated by spiking experiments. Experimental results demonstrated that the ionization suppression or enhancement was the main contribution on the overall recoveries of target analytes. Finally, the in-house validated method was applied to pesticides screening in vegetables samples in local villages in Hanoi, Vietnam. The concentrations of all target analytes were below limit of quantitation and lower than US-FDA or EU maximum residue levels.

Project description:Supercritical fluid chromatography (SFC) is frequently used for the analysis and separation of non-polar metabolites, but remains relatively underutilised for the study of polar molecules, even those which pose difficulties with established reversed-phase (RP) or hydrophilic interaction liquid chromatographic (HILIC) methodologies. Here, we present a fast SFC-MS method for the analysis of medium and high-polarity (-7?cLogP?2) compounds, designed for implementation in a high-throughput metabonomics setting. Sixty polar analytes were first screened to identify those most suitable for inclusion in chromatographic test mixtures; then, a multi-dimensional method development study was conducted to determine the optimal choice of stationary phase, modifier additive and temperature for the separation of such analytes using SFC. The test mixtures were separated on a total of twelve different column chemistries at three different temperatures, using CO2-methanol-based mobile phases containing a variety of polar additives. Chromatographic performance was evaluated with a particular emphasis on peak capacity, overall resolution, peak distribution and repeatability. The results suggest that a new generation of stationary phases, specifically designed for improved robustness in mixed CO2-methanol mobile phases, can improve peak shape, peak capacity and resolution for all classes of polar analytes. A significant enhancement in chromatographic performance was observed for these urinary metabolites on the majority of the stationary phases when polar additives such as ammonium salts (formate, acetate and hydroxide) were included in the organic modifier, and the use of water or alkylamine additives was found to be beneficial for specific subsets of polar analytes. The utility of these findings was confirmed by the separation of a mixture of polar metabolites in human urine using an optimised 7min gradient SFC method, where the use of the recommended column and co-solvent combination resulted in a significant improvement in chromatographic performance.

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Liquid chromatography versus supercritical fluid chromatography coupled to mass spectrometry: a comparative study of performance for multiresidue analysis of pesticides.

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