Detoxification agents based on magnetic nanostructured particles as a novel strategy for mycotoxin mitigation in food
Introduction
Public concern about food safety has shown a remarkable increase during the last decades, all over the world. In this context, the presence of chemical contaminants in the food chain has particular relevance, since it constitutes one of the main health threats (Pérez-Ortega et al., 2017). Among chemical contaminants, mycotoxins are toxic compounds produced by fungi, which contaminate food commodities and foodstuffs (Zhang et al., 2013). Mycotoxins with the greatest impact, in terms of toxicity and occurrence, are aflatoxins B1, B2, G1, and G2 (AFB1, AFB2, AFG1, AFG2); deoxynivalenol (DON); zearalenone (ZEN); fumonisin B1 (FB1); ochratoxin A (OTA); and patulin (PAT) (Marroquín-Cardona, Johnson, Phillips, & Hayes, 2014). After ingestion, these compounds cause a broad range of toxic effects in humans and animals, damaging several organs such as liver or kidney, and affecting the gastrointestinal, reproductive and immune systems (Sainz, González-Jartín, Aguín, Mansilla, & Botana, 2018). In addition, aflatoxins are potent carcinogens (Creppy, 2002). Therefore, sanitary administrations have adopted regulations establishing their maximum tolerable levels in food and feed. However, the list and variety of mycotoxins affecting natural products is large, and their elimination is nowadays very limited (Sainz, Alfonso, & Botana, 2015).
Toxins produced by Fusarium species (DON, ZEN, FB1, T-2 and HT-2 toxins) are usually found in cereals, while Aspergillus and Penicillium toxins (OTA, PAT and aflatoxins) can contaminate apples, pears, grapes, dry fruits, peanuts, cereals and other food commodities (Sainz et al., 2018). Mycotoxins are not usually affected by technological treatments employed during food production (Pascari, Ramos, Marin, & Sanchis, 2018). Consequently, mycotoxins can be detected in processed food like beverages such as beer, wines, juice or milk, flours for human consumption, feed for animals, etc (Abdallah et al., 2016, Bhat et al., 2010, Peters et al., 2017). Specifically, beer brewed from malted barley and other cereals infected in the field by species of Fusarium can contain several toxins. In fact, Fusarium toxins like DON, ZEN or FB1 are usually found in industrially produced beer (Pascari et al., 2018). On the other hand, the actual growing trend of producing beer by hand is becoming a problem since these brewages present, in some occasions, toxins concentrations above the Tolerable Daily Intake (Peters et al., 2017).
Once a food commodity is contaminated with mycotoxins, physical removal of contaminated raw material (manual sorting of grains or fruits), the addition of chemical binders or modifiers or enzymatic treatments can be used to reduce or eliminate these compounds (Karlovsky et al., 2016, Taheur et al., 2019). Chemical detoxification may be achieved under alkaline or acidic conditions applying high temperatures. In addition, some mycotoxins can be degraded by enzymes. These processes have however two main drawbacks: first, mycotoxins can result in metabolites of higher or unknown toxicity and second, both chemicals and modified toxins remain in the treated matrix, increasing the number of unwanted compounds (Jard, Liboz, Mathieu, Guyonvarc’h, & Lebrihi, 2011). Since chemical detoxification of food is not authorized by the European Union, new strategies are needed to ameliorate food from a toxicological point of view (EC No. 1881/2006). In this regard, the combination of nanotechnology and magnetic separation can provide a new detoxifying methodology with a wide application in the field of food and water treatment. In water remediation, nanostructured and nanoreactive membranes have been applied for water filtration allowing the elimination of, among others, bacteria and viruses, metal ions, trichloroethylene, polycyclic aromatic hydrocarbons as well as pesticides. Moreover, iron oxide nanoparticles were proposed for removing heavy metals from the aqueous systems (Dave and Chopda, 2014, Theron et al., 2008).
Despite the versatility that nanotechnology can offer to the agrifood sector, only recently food business operators have introduced these novelties (Magro et al., 2016). Several applications have been developed in the field of food science including enhancement of food security by extending storage duration or allowing contaminants detection or favoring the bioavailability of some compounds like coenzyme Q10 or some vitamins (He & Hwang, 2016). However, little research has been done about the elimination of natural toxins from food and beverages through the use of nanotechnology (Abd-Elsalam et al., 2017, Magro et al., 2016). Some applications developed for the reduction of mycotoxins from aqueous solutions include chitosan-coated Fe3O4 particles for PAT decontamination, magnetic carbon nanocomposites for AFB1 adsorption, graphene oxide modified with chitosan particles for the simultaneous reduction of AFB1, OTA and ZEA, and the use of naked maghemite nanoparticles for citrinin removal from fungal suspensions (Abbasi Pirouz et al., 2018, Luo et al., 2017, Magro et al., 2016, Zahoor and Ali Khan, 2016). Other types of adsorbents were also studied in recent years. For instance, modified montmorillonites were proposed for the simultaneous removal of AFB1 and ZEN, and sugar beet pulp for the uptake of ZEN (Akar et al., 2018, Wang et al., 2019). On the other hand, the use of different types of polymers showed good results in the removal of ZEN from aqueous solutions and OTA from red wine (Carrasco-Sánchez et al., 2018, Poór et al., 2018).
In this work, we present a green methodology to extract toxins from liquid solutions and beverages, by using biocompatible magnetic nanostructures with a high binding affinity to a variety of toxins, acting as detoxifying agents that are magnetically separated from the matrix. Three sets of magnetic nanostructured cleaning agents with well-differentiated sizes and compositions have been prepared in order to test the efficacy of their surface area and chemical affinity for removing a large set of conventional mycotoxins.
Section snippets
Chemicals and reagents
Water was purified in a Millipore Milli-Q Plus system (Millipore, Bedford, MA). Acetonitrile and acetic acid (glacial, 100%) were supplied by Panreac Quimica S.A. (Barcelona, Spain). Formic acid was from Merck (Madrid, Spain), ammonium formate from Fluka (Buchs, Switzerland), and ultrafree-MC centrifugal filters with Durapore membrane (0.22 μm pore size) from Millipore (Billerica, MA). Solid standards of mycotoxins (DON, ZEN, FB1) were purchased from Sigma (Madrid, Spain) and certified
Results and discussion
Several mycotoxins can be present in beer and other beverages such as wine or fruit juices, so methods allowing the elimination or reduction of these compounds are necessary to ameliorate final products and make them safer for consumption. Hence, the purpose of this work was the development and the use of magnetic nanostructures that allow the elimination of the main types of naturally occurring mycotoxins.
We have measured the adsorption capacity of 25 magnetic nanocomposites with different
Conclusion
Nanostructured materials with activated carbon, bentonite and aluminium hydroxide are able to eliminate up to 87% of mycotoxins from aqueous solutions, with a maximum adsorption capacity of 450 µg of toxin per each g of nanoparticle. On the other hand, alginate and mixtures of alginate and activated carbon particles, graphene oxide or pectin are able to remove up to 70% of mycotoxins, having a maximum adsorption of 598 ng/g. Particles composed of mixtures of alginate and activated carbon or
Acknowledgments
The research leading to these results has received funding from the following FEDER cofunded-grants. From Conselleria de Cultura, Educacion e Ordenación Universitaria, Xunta de Galicia, 2017 GRC GI-1682 (ED431C 2017/01). From CDTI and Technological Funds, supported by Ministerio de Economía, Industria y Competitividad, AGL2014-58210-R, AGL2016-78728-R (AEI/FEDER, UE), ISCIII/PI16/01830 and RTC-2016-5507-2, ITC-20161072. From European Union POCTEP 0161-Nanoeaters -1-E-1, Interreg AlertoxNet
Conflict of interest
None.
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