A Generic Liquid Chromatography−Tandem Mass Spectrometry Exposome Method for the Determination of Xenoestrogens in Biological Matrices

Preindl, Karin; Braun, Dominik; Aichinger, Georg; Sieri, Sabina; Fang, Mingliang; Marko, Doris; Warth, Benedikt

doi:10.1021/acs.analchem.9b02446

Cited by 61 publications

(32 citation statements)

References 49 publications

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“…The mean (maximum) concentration of OTA and ZEN were relatively lower in this study compared to previously reported data from Cameroon [30] and Nigeria [38]. However, the extremely high detection rate of 82% for total ZEN is somehow worrisome given the high xenoestrogenic potential of ZEN and its phase I biotransformation products [43]. Recent studies further highlighted that ZEN is prone to synergistic mixture effects [44,45] and able to pass the placental barrier and thus exposure of mothers is likely to result in in utero exposure of the unborn child [46].…”

Section: Discussioncontrasting

confidence: 79%

Assessment of urinary biomarkers of mycotoxin exposure in adults from Cameroon

Abia

Tchana

Djonabaye

et al. 2020

Preprint

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Background In Cameroon dietary staples are contaminated with diverse toxic fungal metabolites, known as mycotoxins. Aflatoxins and fumonisins are of particular public health concern, particularly in relation to cancer and/or early life stunting. Mixtures of these toxins are predicted from food measures, and in this work, the levels and frequencies of urinary mycotoxin biomarkers are reported in Cameroonian adults. Methods A single first void urine sample was collected from 89 adults (aged range: 28–85, male 39, female 50) from the city of Yaoundé, Centre Region, Cameroon. Urines were tested for eight distinct mycotoxins using measures of both parent compounds and/or their metabolites by Liquid Chromatography tandem mass spectrometry (LC-MS/MS). Results Altogether seven distinct mycotoxins, aflatoxin, fumonisin, deoxynivalenol, zearalenone, nivalenol, ochratoxin A and citrinin, (or their metabolites) were observed in urine samples. At least one mycotoxin was detected in all of the urine samples, 87 (97.8%) of which were above the method’s quantification limit. Aflatoxin M1 was detected in 42% (n.d. − 0.21 µg L− 1) of samples of which about a quarter additionally contained fumonisin B1. Of the remaining toxins deoxynivalenol, zearalenone, ochratoxin A, nivalenol and citrinin were present in 78%, 99% 95%, 53%, and 87% of the samples respectively. Alternariol was not detected in any sample. Mixtures of mycotoxins in the samples were frequently observed with 64 samples (72%) containing more than five mycotoxins. Estimates of intake exceeded the TDIs for fumonisin (n = 4), deoxynivalenol (n = 1) and zearalenone (n = 2), no TDI is set for aflatoxin. Conclusions This study reveals frequent co-exposure of Cameroonian individuals to a complex mixture of toxic and carcinogenic mycotoxins, with mixtures of aflatoxin and fumonisin a particular priority from a public health standpoint.

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Section: Discussioncontrasting

confidence: 79%

Assessment of urinary biomarkers of mycotoxin exposure in adults from Cameroon

Abia

Tchana

Djonabaye

et al. 2020

Preprint

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“…The polar analytes TeA, AA-III and AOH-and AME-sulfates, as well as the included perylene quinones, demonstrated better peak shapes with basic eluents. However, the overall signal-to-noise ratio was most favorable with 0.3 mM NH 4 F as eluent A (Preindl et al 2019;Yanes et al 2011). Despite the still interfering matrix suppression in fecal samples, the overall performance was most suitable using this eluent A and MeOH as eluent B.…”

Section: Development Of the Analytical Methodsmentioning

confidence: 99%

Bioavailability, metabolism, and excretion of a complex Alternaria culture extract versus altertoxin II: a comparative study in rats

et al. 2019

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Despite the frequent infection of agricultural crops by Alternaria spp., their toxic secondary metabolites and potential food contaminants lack comprehensive metabolic characterization. In this study, we investigated their bioavailability, metabolism, and excretion in vivo. A complex Alternaria culture extract (50 mg/kg body weight) containing 11 known toxins and the isolated lead toxin altertoxin II (0.7 mg/kg body weight) were administered per gavage to groups of 14 Sprague Dawley rats each. After 3 h and 24 h, plasma, urine and feces were collected to determine toxin recoveries. For reliable quantitation, an LC-MS/MS method for the simultaneous detection of 20 Alternaria toxins and metabolites was developed and optimized for either biological matrix. The obtained results demonstrated efficient excretion of alternariol (AOH) and its monomethyl ether (AME) via feces (> 89%) and urine (> 2.6%) after 24 h, while the majority of tenuazonic acid was recovered in urine (20 and 87% after 3 and 24 h, respectively). Moreover, modified forms of AOH and AME were identified in urine and fecal samples confirming both, mammalian phase-I (4-hydroxy-AOH) and phase-II (sulfates) biotransformation in vivo. Despite the comparably high doses, perylene quinones were recovered only at very low levels (altertoxin I, alterperylenol, < 0.06% in urine and plasma, < 5% in feces) or not at all (highly genotoxic, epoxide-holding altertoxin II, stemphyltoxin III). Interestingly, altertoxin I was detected in all matrices of rats receiving altertoxin II and suggests enzymatic de-epoxidation in vivo. In conclusion, the present study contributes valuable information to advance our understanding of the emerging Alternaria mycotoxins and their relevance on food safety.

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“…Table S3). ZEN was recently shown to cross the placental barrier and exhibit synergistic toxic effects with other xenoestrogens (Vejdovszky et al, 2017a,b;Preindl et al, 2019;Warth et al, 2019). Hence, this finding needs to be confirmed in further surveys.…”

Section: Proof-of-principle Application Of the Integrated Quechers-spmentioning

confidence: 92%

Exposure to Mycotoxin-Mixtures via Breast Milk: An Ultra-Sensitive LC-MS/MS Biomonitoring Approach

et al. 2020

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Exposure to natural food contaminants during infancy may influence health consequences later in life. Hence, breast milk may serve as a vehicle to transport these contaminants, including mycotoxins, from mothers to their infants. Analytical methods mostly focused on single exposures in the past, thus neglecting co-occurrences and mixture effects. Here, we present a highly sensitive multi-biomarker approach by a sophisticated combination of steps during sample preparation including a Quick, Easy, Cheap, Effective, Rugged and Safe (QuEChERS) extraction followed by a solid phase extraction (SPE) cleanup and utilizing stable isotopes for compensating challenging matrix effects. The assay was validated in-house, reaching limits of detection (LOD) for all 34 analytes in the range of 0.1 to 300 ng/L with satisfying extraction efficiencies (75-109%) and stable intermediate precisions (1-18%) for most analytes. Compared to a similar multi-mycotoxin assay for breast milk, LOD values were decreased by a factor of 2-60x enabling the assessment of chronic low-dose exposures. The new method was applied to a small set of Nigerian breast milk samples (n = 3) to compare results with already published data. Concentration levels of samples that were found to be contaminated before could be confirmed. In addition, other mycotoxins were determined in all three samples, for example the newly investigated alternariol monomethyl ether (AME) was found for the first time in this biological fluid at concentrations up to 25 ng/L. Moreover, in a pooled Austrian sample obtained from a milk bank, trace amounts of multiple mycotoxins including AME (1.9 ng/L), beauvericin (5.4 ng/L), enniatin B (4.7 ng/L), enniatin B 1 (

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A Generic Liquid Chromatography−Tandem Mass Spectrometry Exposome Method for the Determination of Xenoestrogens in Biological Matrices

Cited by 61 publications

References 49 publications

Assessment of urinary biomarkers of mycotoxin exposure in adults from Cameroon

Assessment of urinary biomarkers of mycotoxin exposure in adults from Cameroon

Bioavailability, metabolism, and excretion of a complex Alternaria culture extract versus altertoxin II: a comparative study in rats

Exposure to Mycotoxin-Mixtures via Breast Milk: An Ultra-Sensitive LC-MS/MS Biomonitoring Approach

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