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Alternaria toxins in South African sunflower seeds: cooperative study

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Abstract

Sunflower seed samples (N = 80) from different sunflower cultivars originating from different localities in South Africa were analyzed for 15 toxins produced by fungi of the genus Alternaria by means of a simple one-step extraction dilute-and-shoot HPLC-MS/MS approach. References for valine-tenuazonic acid (Val-TeA), altenusin (ALTS), and altenuisol (ALTSOH) were isolated from fungal culture extracts and spectroscopically characterized. Additionally, valine-tenuazonic acid was tested regarding its cytotoxicity in comparison with tenuazonic acid (TeA) and showed less activity on HT-29 cells. Furthermore, alternariol monomethyl ether-3-O-ß-D-glucoside (AME-3G) was produced by fermentation of alternariol monomethyl ether (AME) with the fungus Rhizopus oryzae. The seed samples were analyzed both with and without hulls. The method covers the AAL toxins TA1 and TA2, altenuene (ALT) and iso-altenuene (iso-ALT), altenuisol, altenusin, altertoxin I (ATX-I) and altertoxin II (ATX-II), alternariol (AOH) and alternariol monomethyl ether, alternariol monomethyl ether-3-O-ß-D-glucoside, tenuazonic acid, allo-tenuazonic acid (allo-TeA) and valine-tenuazonic acid, and tentoxin (TEN). More than 80% of the samples were positive for one or more analytes above the respective limit of detection (0.2–23 μg/kg). Alternariol, its monomethyl ether, tentoxin, tenuazonic acid, altenuisol, and valine-tenuazonic acid were found in quantifiable amounts. The highest prevalences were found for tentoxin (73% positive, mean content 13.2 μg/kg, maximum level 130 ± 0.9 μg/kg) followed by tenuazonic acid (51% positive, mean content 630 μg/kg, maximum level 6300 ± 560 μg/kg). The obtained data were further analyzed statistically to identify quantitative or qualitative relationships between the levels of Alternaria toxin in the samples.

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Abbreviations

AAL TA1 :

AAL toxin TA1

AAL TA2 :

AAL toxin TA2

allo-TeA:

Allo-tenuazonic acid

ALT:

Altenuene

ALTS:

Altenusin

ALTSOH:

Altenuisol

AME:

Alternariol monomethyl ether

AME-3G:

Alternariol monomethyl ether-3-O-ß-D-glucoside

AOH:

Alternariol

AR:

Apparent recovery

ATX-I:

Altertoxin I

ATX-II:

Altertoxin II

CAD:

Collision gas pressure

EFSA:

European Food Safety Authority

EPI:

Enhanced product ion spectrum

ER:

Recovery of the extraction step

GS1:

Ion source gas 1

GS2:

Ion source gas 2

HPLC-MS/MS:

High-performance liquid chromatography coupled to tandem mass spectrometry

IS:

Ion spray voltage

iso-ALT:

Iso-altenuene

LOD:

Limit of detection

LOQ:

Limit of quantitation

MMT:

Million metric tons

SRM:

Selected reaction monitoring

SSE:

Signal suppression/enhancement

TeA:

Tenuazonic acid

TEM:

Ion source temperature

TEN:

Tentoxin

TTC:

Threshold of toxicological concern

USDA:

US Department of Agriculture

Val-TeA:

Valine-tenuazonic acid

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Acknowledgements

The authors thank Theresa Zwickel (Federal Institute of Risk Assessment, Berlin, Germany) for supply of a reference for altertoxin II. Furthermore, we thank Steffen Lürwer and Angela Klusmeier-König for assistance during sample preparation and Moses Ramusi for collecting sunflower samples.

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Authors and Affiliations

  1. Institute of Food Chemistry, Westfälische Wilhelms-Universität Münster, Corrensstraße 45, 48149, Münster, Germany

    Sebastian Hickert, Lena Hermes, Christine Focke, Benedikt Cramer & Hans-Ulrich Humpf

  2. NRW Graduate School of Chemistry, Wilhelm-Klemm-Str. 10, 48149, Münster, Germany

    Sebastian Hickert & Hans-Ulrich Humpf

  3. Departamento de Física-Química, Faculdade de Ciências Farmacêuticas de Ribeirão Preto, Universidade de São Paulo, 14040-903 Ribeirão Preto, São Paulo, Brazil

    Lucas Maciel Mauriz Marques & Norberto Peporine Lopes

  4. ARC-Grain Crops Institute, Private Bag X1251, Potchefstroom, 2520, South Africa

    Bradley Flett

  5. Unit of Environmental Sciences and Management, North-West University, Private Bag X6001, Potchefstroom, 2520, South Africa

    Bradley Flett

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  1. Sebastian Hickert
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  2. Lena Hermes
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  3. Lucas Maciel Mauriz Marques
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  4. Christine Focke
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  8. Hans-Ulrich Humpf
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Correspondence to Hans-Ulrich Humpf.

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Hickert, S., Hermes, L., Marques, L.M.M. et al. Alternaria toxins in South African sunflower seeds: cooperative study. Mycotoxin Res 33, 309–321 (2017). https://doi.org/10.1007/s12550-017-0290-1

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