A comparative study of the human urinary mycotoxin excretion patterns in Bangladesh, Germany, and Haiti using a rapid and sensitive LC-MS/MS approach

Abstract

An improved "dilute and shoot" LC-MS/MS multibiomarker approach was used to monitor urinary excretion of 23 mycotoxins and their metabolites in human populations from Asia (Bangladesh), Europe (Germany), and the Caribbean region (Haiti). Deoxynivalenol (DON), deoxynivalenol-3-glucuronide (DON-3-GlcA), T-2-toxin (T-2), HT-2-toxin (HT-2), HT-2-toxin-4-glucuronide (HT-2-4-GlcA), fumonisin B1 (FB1), aflatoxins (AFB1, AFB2, AFG1, AFG2, AFM1), zearalenone (ZEA), zearalanone (ZAN), their urinary metabolites α-zearalanol (α-ZEL) and β-zearalanol (β-ZEL), and corresponding 14-O-glucuronic acid conjugates (ZEA-14-GlcA, ZAN-14-GlcA, β-ZEL, α/β-ZEL-14-GlcA), ochratoxin A (OTA), and ochratoxin alpha (OTα) as well as enniatin B (EnB) and dihydrocitrinone (DH-CIT) were among these compounds. Eight urinary mycotoxin biomarkers were detected (AFM1, DH-CIT, DON, DON-GLcA, EnB, FB1, OTA, and α-ZEL). DON and DON-GlcA were exclusively detected in urines from Germany and Haiti whereas urinary OTA and DH-CIT concentrations were significantly higher in Bangladeshi samples. AFM1 was present in samples from Bangladesh and Haiti only. Exposure was estimated by the calculation of probable daily intakes (PDI), and estimates suggested occasional instances of toxin intakes that exceed established tolerable daily intakes (TDI). The detection of individual mycotoxin exposure by biomarker-based approaches is a meaningful addition to the classical monitoring of the mycotoxin content of the food supply.

Mycotoxin mixtures in food and feed: holistic, innovative, flexible risk assessment modelling approach:

“…In total 19 studies were selected for ZEN, and its metabolites. The glucuronide forms ZEN14 ZEN14Oglucuronide was analysed by four authors (Abia et al, 2013;Ezekiel et al, 2014;Gerding et al, 2015;Cirlini et al, 2017). There is only one study in the dataset who analysed ZEN together with its phase I and glucuronides forms (Mauro et al, 2015).…”

Biomarker der internen Exposition gegenüber toxikologisch relevanten Kontaminanten in Lebensmitteln

“…Resultate solcher Messungen belegen, dass die AFB1-Exposition in einigen Regionen Asiens und Afrikas bedenklich, in westlichen Industrielän-dern aber verhältnismäßig gering ist [14]. In keiner der Urinproben von erwachsenen Probanden in Deutschland konnte AFM1 detektiert werden [15]. Als Biomarker einer mittelfristigen Exposition kommen spezifische Addukte in DNA-Proben bzw.…”

Challenges in risk assessment of multiple mycotoxins in food

“…Human biomonitoring is considered a quite new frontier for establishing the real human exposure to mycotoxins. Recent results on this domain (Gerding et al, 2014(Gerding et al, , 2015Heyndrickx et al, 2015;Warth et al, 2012a,b) surprisingly revealed a level of exposure to mycotoxins above the widely accepted tolerable daily intake values, especially to DON, highlighting the importance to perform mycotoxin biomonitoring studies. Typical biomarkers of exposure are the parent toxins themselves, protein or DNA adducts, and/or major phase I or phase II metabolites (e.g.…”

“…The use of β-glucuronidase-assisted hydrolysis (in order to increase the levels of the parent toxins) (Ahn et al, 2010;Shephard et al, 2013;Solfrizzo et al, 2011Solfrizzo et al, , 2014Wallin et al, 2015), immunoaffinity columns (IAC) (Ahn et al, 2010;Rubert et al, 2011;Shephard et al, 2013;Solfrizzo et al, 2011Solfrizzo et al, , 2014Wallin et al, 2015) and solid-phase extraction (SPE) (Heyndrickx et al, 2015;Njumbe Ediage et al, 2012;Rodríguez-Carrasco et al, 2014a,b;Shephard et al, 2013;Solfrizzo et al, 2011Solfrizzo et al, , 2014Wallin et al, 2015) were applied by some authors as sample preparation and clean-up procedures. However, some studies have also successfully used the so-called dilute and shoot approach by omitting any cleanup procedure (Abia et al, 2013;Ezekiel et al, 2014;Gerding et al, 2014Gerding et al, , 2015Heyndrickx et al, 2015;Shephard et al, 2013;Warth et al, 2012a,b). Although the analysis of mycotoxins in human urine is another important data source for exposure assessment, some challenges are posed to human mycotoxin multibiomarker approaches.…”

“…Although the analysis of mycotoxins in human urine is another important data source for exposure assessment, some challenges are posed to human mycotoxin multibiomarker approaches. These challenges include the lack of toxicokinetic data on mycotoxins in humans resulting in a lot of uncertainties that should be taken into account when perform a risk assessment based on urinary mycotoxin levels; difficulties to correlate human dietary habits, concurrent mycotoxin contamination of food and consequent presence of these mycotoxins in human urine; obstacles to comparison of obtained results between different studies, considering the differences in age, detection limits, number of subjects included in the study and the analytical performances of the used methods (Gerding et al, 2014; ' Gerding et al, 2014' Gerding et al, , 2015 Haiti 23 1 All studies used urine as biological sample. Liquid chromatography coupled with tandem mass spectrometry was used for analysis in all studies, except for Spain where gas chromatography coupled with tandem mass spectrometry was used.…”