Development of a Rapid LC-MS/MS Method for the Determination of Emerging Fusarium mycotoxins Enniatins and Beauvericin in Human Biological Fluids

Abstract

A novel method for the simultaneous determination of enniatins A, A1, B and B1 and beauvericin, both in human urine and plasma samples, was developed and validated. The method consisted of a simple and easy pretreatment, specific for each matrix, followed by solid phase extraction (SPE) and detection by high performance liquid chromatography-tandem mass spectrometry with an electrospray ion source. The optimized SPE method was performed on graphitized carbon black cartridges after suitable dilution of the extracts, which allowed high mycotoxin absolute recoveries (76%–103%) and the removal of the major interferences from the matrix. The method was extensively evaluated for plasma and urine samples separately, providing satisfactory results in terms of linearity (R2 of 0.991–0.999), process efficiency (>81%), trueness (recoveries between 85% and 120%), intra-day precision (relative standard deviation, RSD < 18%), inter-day precision (RSD < 21%) and method quantification limits (ranging between 20 ng·L−1 and 40 ng·L−1 in plasma and between 5 ng·L−1 and 20 ng·L−1 in urine). Finally, the highly sensitive validated method was applied to some urine and plasma samples from different donors.

Dispersive Solid-Phase Extraction using Magnetic Carbon Nanotube Composite for the Determination of Emergent Mycotoxins in Urine Samples

“…The LODs and LOQs were calculated using the criteria of 3 and 10 times the signal-to-noise ratio (S/N), respectively. Low LOQs were obtained for all the target mycotoxins, which were similar to [14,17] or lower than [15,16,18] those obtained with other analytical methods described in the literature.…”

“…The determination of ENNA, ENNA1, ENNB, ENNB1, and BEA has been carried out in urine [14][15][16][17][18][19], and serum [14][15][16]18,[20][21][22][23][24], from both humans and animals, but also in feces samples [15,16,18] and in different organs and tissues from animals [25][26][27][28]. The vast majority of these analytical methods are based on LC-MS/MS, although LC coupled to high resolution mass spectrometry (HRMS) has also been proposed [17][18][19].…”

“…Regarding sample treatment, solid-phase extraction (SPE) [14,26,27] and liquid-liquid extraction (LLE) using ethyl acetate or acetonitrile [15,16,18,[21][22][23][25][26][27][28] are the most commonly used. Miniaturized techniques like dispersive liquid-liquid microextraction (DLLME) have also been proposed [24] and, recently, Rodríguez-Carrasco et al [19] compared and evaluated three different sample preparation approaches (dilute and shoot, DLLME, and salting-out liquid-liquid extraction (SALLE)) for the determination of ENNB and its phase I metabolites in human urine samples, concluding that SALLE showed satisfactory validation results.…”

Development and validation of ultra-high-performance liquid chromatography–tandem mass spectrometry methods for the simultaneous determination of beauvericin, enniatins (A, A1, B, B1) and cereulide in maize, wheat, pasta and rice

“…Examples are beauvericin (BEA) and the related enniatins A, A1, B, B1 (ENNs), both produced by several Fusarium species. Their presence has been reported in cereals from several countries and in human biological fluids [6][7][8]. Recently EFSA published an opinion on the presence of ENNs and BEA in food and feed, but the lack of relevant toxicity data prevented a risk assessment [9].…”

QuEChERS Purification Combined with Ultrahigh-Performance Liquid Chromatography Tandem Mass Spectrometry for Simultaneous Quantification of 25 Mycotoxins in Cereals

“…The successful application of this method has been reported in many products, including cereals and their products [16], spices [17], nuts and seeds [18], Madeira wine [19], human breast milk [20], sesame butter [21], noodles [22], eggs [23], human biological fluids [24], and baby food [25]. In order to reduce the matrix effects (MEs), which can result in unsatisfactory recoveries, additional purification with sorbents such as octadecyl silica (C18), primary secondary amine (PSA), and graphitized carbon black (GCB) are commonly used.…”