Volume 6 • Issue 7 • 1000464
J Food Process Technol
ISSN: 2157-7110 JFPT, an open access journal
Open Access Research Article
Kafouris et al., J Food Process Technol 2015, 6:7
DOI: 10.4172/2157-7110.1000464
*Corresonding author: Demetris Kafouris, State General Laboratory, Ministry of
Health, Kimonos 44, 1451 Nicosia, Cyprus, Tel: +357 22 809167; Fax: +357 22
316434; E-mail: dkafouris@sgl.moh.gov.cy
Received April 15, 2015; Accepted May 14, 2015; Published May 21, 2015
Citation: Kafouris D, Christofdou M, Christodoulou M, Christou E, Ioannou-Kakouri E
(2015) A Validated UPLC-MS/MS Multi-mycotoxin Method for Nuts and Cereals for
the Offcial Control in Cyprus within the EU Requirements. J Food Process Technol
6: 464. doi:10.4172/2157-7110.1000464
Copyright: © 2015 Kafouris D, et al. This is an open-access article distributed under
the terms of the Creative Commons Attribution License, which permits unrestricted
use, distribution, and reproduction in any medium, provided the original author and
source are credited.
Abstract
The validation of a rapid, reliable and sensitive method for the simultaneous determination of Afatoxins (AFB
1
, AFB
2
, AFG
1
,
AFG
2
), Ochratoxin A, Zearalenone, Deoxynivalenol, Fumonisins B
1
and B
2
, T-2 and HT-2 toxins, in nuts (peanuts, pistachio and
almonds) and cereals (maize and wheat) is reported. The method was developed and validated to fulfl the requirements of the
offcial control of mycotoxins according to EU legislation. This method is based on a single extraction step using an acetonitrile/
water mixture followed by the analysis of the diluted crude extract using ultra high performance liquid chromatography with tandem
mass spectrometry (UPLC-MS/MS). The MS/MS detection was carried out using an electro spray-ionization interface (ESI) in
positive ion mode. Matrix-matched calibration was used for the quantifcation of the mycotoxins, because of the absence of further
clean up steps that reduce suppression/enhancement matrix effects. The method performance characteristics were determined
after spiking blank samples on multiple levels. The mean recoveries of mycotoxins in spiked nuts ranged from 74.4% to 131.7%,
while in cereals ranged from 52.8% to 113.9%. Relative standard deviations were lower than 20.4% for all target mycotoxins.
Limits of detection and quantifcation for nuts and cereals ranged 0.08-30.0 and 0.25-99.0 μg/Κg, respectively.
A Validated UPLC-MS/MS Multi-mycotoxin Method for Nuts and Cereals
for the Official Control in Cyprus within the EU Requirements
Demetris Kafouris*, Maria Christofdou, Markela Christodoulou, Eftychia Christou and Eleni Ioannou-Kakouri
State General Laboratory, Ministry of Health, Kimonos 44, 1451 Nicosia, Cyprus
Keywords: Multiycotoxin analysis; UPLC-MS/MS; Nuts; Cereals;
Afatoxins; Ochratoxin A, Zearalenone; Deoxynivalenol; Fumonisins;
T-2 toxin; HT-2 Toxin
Introduction
Mycotoxins are natural chemical contaminants produced as toxic
secondary metabolites by some fungal species such as Aspergillus,
Penicillium and Fusarium. Mycotoxin formation is afected by several
biological factors, by harvesting, storage and processing conditions,
insect damage in agricultural crops and fnally by climate changes
(temperature, humidity) [1,2]. Consumption of food and feed
contaminated with mycotoxins can cause severe efects on animal
and human health, from allergic responses to cancer and death. Due
to their high occurrence, the most common and widely investigated
mycotoxins in food and feed, regulated by the European Union
legislation [3,4] are: Afatoxins (AFB
1
, AFB
2
, AFG
1
, AFG
2
), Ochratoxin
A (OTA), trichothecenes [Deoxynivalenol (DON), T-2 and HT-2
toxins], Fumonisins (FB
1
, FB
2
) and Zearalenone (ZON) [5-7]. AFs are
primarily produced by Aspergillus favus and Aspergillus parasiticus
and are among the most carcinogenic substances known. AFs are
signifcant in nuts, maize and cereal grains [1,8]. OTA has been found
in cereals (wheat, barley, oats and maize), spices and dried fruits
and is primarily nephrotoxic and considered to be a possible human
carcinogen. OTA is produced by Aspergillus ochraceus, Penicillium
verrucosum and Penicillium viridicatum. Fumonisins, trichothecenes
and ZON are produced by Fusarium species. Tese mycotoxins are
mostly found in cereals, especially in maize [1,8]. Fumonisins have
cancer promoting activity and mostly responsible for esophageal
carcinoma. ZON can cause oestreogenic efects such as infertility,
abortion and cervical cancer. Trichothecenes are related with fatal and
chronic toxicoses. Tey inhibit DNA and protein synthesis, and they
are responsible for outbreaks of acute diseases of the digestive system
such as nausea, vomiting, diarrhea, dizziness and headache [1,7].
Several analytical (chemical and biochemical) methods have
been developed for the determination of individual mycotoxins afer
immunoafnity column clean-up [9-15]. Chromatographic methods
commonly used for the quantitative determination of mycotoxins
in foodstufs includes thin layer chromatography (TLC) [16], high
performance liquid chromatography (HPLC) coupled with ultraviolet
(UV), photo diode array (PDA), fuorescence detectors (FLD) or
mass spectrometry (MS), and gas chromatography (GC) coupled with
electron capture (ECD), fame ionization (FID) or MS detectors [17].
Due to the high toxicity and occurrence of mycotoxins, rapid and
reliable screening methods need to be developed for their identifcation
and quantifcation in foodstuf in order to ensure safety and compliance
with the legislation.
For the past years, multi-target methods for the simultaneous
detection and quantifcation of diferent, co-occurring mycotoxins
have been developed to replace the single analyte methods. Most of
these methods are based on the combination of high- or ultra-high-
performance liquid chromatography with tandem [18-21] or high-
resolution [22,23] mass spectrometry. A major advantage of LC-MS-
based multi-target methods is the elimination of the need for sample
derivatization, in addition with the high selectivity and sensitivity.
Furthermore, such multi-target methods are suitable for the analysis
of highly variable mycotoxin concentrations. Mycotoxins present
a great diversity in their physicochemical properties, therefore the
optimization of an efective and efcient extraction procedure is of
great importance. Mixtures of water with high amounts of methanol
or acetonitrile (>70 %) are appropriate as extraction solvents for most
mycotoxins. However, for fumonisins, higher extraction recoveries
are achieved when the water proportion is increased and/or the pH
of the solvent is decreased [19]. For the cleanup, multi-target methods
use simple “dilute-and-shoot” approaches [19-20,24,25], solid phase
extraction [21,26,27], immunoafnity columns [28,29] and, more
recently QuEChERS methodology (Quick, Easy, Cheap, Efective,
Journal of Food
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ISSN: 2157-7110