A workflow for multiclass determination of 256 pesticides in essential oils by liquid chromatography tandem mass spectrometry using evaporation and dilution approaches: Application to lavandin, lemon and cypress essential oils

Abstract

This paper describes the determination of 256 multiclass pesticides in cypress and lemon essential oils (EOs) by the way of liquid chromatography-electrospray ionization tandem mass spectrometry (LC-ESI/MS/MS) analysis using the scheduled selected reaction monitoring mode (sSRM) available on a hybrid quadrupole linear ion trap (QLIT) mass spectrometer. The performance of a sample preparation of lemon and cypress EOs based on dilution or evaporation under nitrogen assisted by a controlled heating were assessed. The best limits of quantification (LOQs) were achieved with the evaporation under nitrogen method giving LOQs ≤ 10 μg L -1 for 91 % of the pesticides. In addition the very satisfactory results obtained for recovery, repeatability and linearity showed that for EOs of relatively low evaporation temperature, a sample preparation based on evaporation under nitrogen is well adapted and preferable to dilution. By compiling these results with those previously published by some of us on lavandin EO, we proposed a workflow dedicated to multiresidue determination of pesticides in various EOs by LC-ESI/sSRM. Among the steps involved in this worflow, the protocol related to mass spectrometry propose an alternative confirmation method to the classical SRM ratio criteria based on a sSRM survey scan followed by an information-dependent acquisition using the sensitive enhanced product ion (EPI) scan to generate MS/MS spectra then compared to a reference. The submitted workflow was applied to the case of lemon EOs samples highlighting for the first time the simultaneous detection of 20 multiclass pesticides in one EO. Some pesticides showed very high concentration levels with amounts greatly exceeding the mg L -1 . KeywordsPesticides, lemon, cypress, essential oil, LC-MS/MS, sample preparation. IntroductionThe market of EOs is rapidly expanding and generates several billions of dollars every year.[1] The importance and the development of the EOs' market can be explained by the number and diversity of application areas of these natural extracts. Most of these application fields are directly related to human consumption such as cosmetics and perfumes,[2] medicine, [3,4] food, [4][5][6][7] agriculture, [8][9][10][11] as well as aromatherapy. [1,4,12] The cultivation of EOs' raw material (medicinal and aromatic plants) commonly involves the use of pesticides, which can concentrate through the extraction process.[13] This is evidenced by the fact that pesticide residues have been already found in EOs of citrus, [14][15][16][17] boronia, [18] fennel [18] or parsley.[18] However, unlike foodstuffs as water or fruits and vegetables for which maximum residues limits (MRLs) are established and available for consultation in databases (Europe: http://ec.europa.eu/sanco_pesticides/public/index.cfm; Worldwide: http://www.mrldatabase.com), there is no regulation in regards to pesticides contents in EOs. [19] The presence of pesticide residues in EOs can lead to a public health problem, particularly due to the rapid expansion of a...

Allergenic components, biocides, and analysis techniques of some essential oils used in food products

“…There are many studies which were made with MS method followed by GC analysis (Bilia et al, 2002;Nitta et al, 2006;Paraschos et al, 2016;Zribia et al, 2019) and some studies which were combined with other methods (Heravi et al, 2015;Madhumita et al, 2019;Zoubiri & Baaliouamer, 2012). Bio pesticide analysis studies are mostly made with GC or LC methods which are carried out by MS after them (Di Bella et al, 2004;Fillatre et al, 2016;Hakme et al, 2018;Rui-Xing et al, 2020). Taking the median of 0.4 mg/kg, the rat NOAEL could be estimated at ten times less, 0.04 mg/kg.…”

Pesticides in essential oils and selected fragrance extracts. Some examples. A review

“…Fillâtre et al were successful in further developments related to previous studies on lavandin oil . Samples used for these experiments were organically produced orange and cypress oils EOs supplied by a private company.…”

“…LC‐ESI/SRM and LC‐ESI/SRM‐EPI for proper confirmation. Additionally, for the determination of residues that are not amenable to liquid chromatography, the use of gas chromatography is proposed …”

Recent developments in the chromatographic bioanalysis of approved kinase inhibitor drugs in oncology

“…This statement is not a strong argument, as QqQ's are capable of performing large pesticide panels [122], and quantitative assays for multiple drugs almost never analyze more than 10 to 15 components (not including toxicological screening, which are often semi-quantitative).…”