Sample Treatment in Pesticide Residue Determination in Food by High-Resolution Mass Spectrometry: Are Generic Extraction Methods the End of the Road?

2016 ◽  
Vol 99 (6) ◽  
pp. 1395-1402 ◽  
Author(s):  
Roberto Romero-González ◽  
Francisco Javier Arrebola Liébanas ◽  
Rosalía López-Ruiz ◽  
Antonia Garrido Frenich

Abstract The use of high-resolution MS (HRMS) is becoming popular in laboratories for the determination of pesticide residues in food commodities. The recent improvements in the instrumentation have helped to increase the number of active compounds and transformation products that can be monitored within a simple chromatographic run. However, prior to instrumental determination, it is necessary to perform a nonspecific, or generic, sample treatment that allows the efficient extraction of several compounds with very relevant differences in their physical and chemical properties. In this sense, the quick, easy, cheap, effective, rugged, and safe (QuEChERS) method and its several modifications and the “dilute-and-shoot” extraction methodology have already revealed an enormous potential for their use together with chromatographic techniques coupled to HRMS. The potentiality and limitations of such a methodological combination have been evaluated in terms of sensitivity and selectivity when they are applied to the analysis of complex food matrixes. An evaluation of the scope of the methods, in terms of efficiency of the extraction and ionization steps, as well as the matrix effect, has also been carried out. Different solutions for the matrix effect have been considered, including improvement in clean-up steps, sample dilution, and matrix compensation by matrix-matched calibration or by the use of isotopically labeled standards.

Foods ◽  
2020 ◽  
Vol 9 (5) ◽  
pp. 553
Author(s):  
Lorena Manzano-Sánchez ◽  
José Antonio Martínez-Martínez ◽  
Irene Domínguez ◽  
José Luis Martínez Vidal ◽  
Antonia Garrido Frenich ◽  
...  

Nowadays, highly polar pesticides are not included in multiresidue methods due to their physico-chemical characteristics and therefore, specific analytical methodologies are required for their analysis. Laboratories are still looking for a pluri-residue method that encompasses the largest number of polar pesticides. The aim of this work was the simultaneous determination of ethephon, 2-hydroxyethylphosphonic acid (HEPA), fosetyl aluminum, glyphosate, aminomethylphosphonic acid (AMPA), N-acetyl-glyphosate and N-acetyl-AMPA in tomatoes, oranges, aubergines and grapes. For that purpose, an ultra high performance liquid chromatography (UHPLC) coupled to a high resolution single mass spectrometer Orbitrap-MS were used. Different stationary phases were evaluated for chromatographic separation, and among them, the stationary phase Torus DEA provided the best separation of the selected compounds. The QuPPe method was used for the extraction of the analytes, but slight modifications were needed depending on the matrix. The developed method was validated, observing matrix effect in all matrices. Intra- and inter-day precision were estimated, and relative standard deviation were lower than 19%. Recoveries were satisfactory, and mean values ranged from 70% to 110%. Limits of quantification were between 25 and 100 µg kg−1. Finally, the analytical method was applied to different fruits and vegetables (oranges, tomatoes, aubergines and grapes).


2020 ◽  
Author(s):  
Xin Hu ◽  
Douglas Walker ◽  
YongLiang Liang ◽  
Matthew Smith ◽  
Michael Orr ◽  
...  

Abstract Complementing the genome with an understanding of the human exposome is an important challenge for contemporary science and technology. Tens of thousands of chemicals are used in commerce, yet cost for targeted environmental chemical analysis limits surveillance to a few hundred known hazards. To overcome limitations which prevent scaling to thousands of chemicals, we developed a single-step express liquid extraction (XLE), gas chromatography high-resolution mass spectrometry (GC-HRMS) analysis and computational pipeline to operationalize the human exposome. We show that the workflow supports quantification of environmental chemicals in small human plasma (200 µL) and tissue (≤ 100 mg) samples. The method also provides high resolution, sensitivity and selectivity for exposome epidemiology of mass spectral features without a priori knowledge of chemical identity. The simplicity of the method can facilitate harmonization of environmental biomonitoring between laboratories and enable population level human exposome research with limited sample volume.


Author(s):  
Rafaela Rocha Roiffé ◽  
Vinicius Figueiredo Sardela ◽  
Antônio Luís dos Santos Lima ◽  
Daniely Silva Oliveira ◽  
Francisco Radler de Aquino Neto ◽  
...  

Abstract Liquid chromatography coupled to Orbitrap high resolution mass spectrometry was shown to be an adequate technique to control the adulteration of whey protein food supplements with prohibited substances, not declared on the labels. An extraction method combined with an instrumental analysis that allowed for the determination of 105 substances in whey protein food supplements, was established. The pre-treatment of the samples consisted of protein precipitation and solid-phase extraction using weak cation exchange functionalized polymeric sorbent cartridges. The samples were directly analyzed by LC-Orbitrap-HRMS. The selectivity, limit of detection, repeatability, recovery, carryover and matrix effect were estimated as the validation parameters. The repeatability obtained was 96.19% and the recovery 83.80%, but carryover and the matrix effect were not observed. The present method was successfully applied to the analysis of commercial samples, verifying adulteration by diuretics (conivaptan and politiazide) and a stimulant (benfluorex) in seven of the eleven brands evaluated.


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