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Trichothecenes produced by Fusarium species are commonly detected in oats. However, the ratios of the concentrations of free trichothecenes and their conjugates and how they are impacted by different interacting environmental conditions are not well documented. This study aims to examine the effect of water activity (0.95 and 0.98 aw) and temperature (20 and 25 °C) stress on the production of T-2 and HT-2 toxins, deoxynivalenol and their conjugates, as well as diacetoxyscirpenol (DAS). Multiple mycotoxins were detected using liquid chromatography–tandem mass spectrometry from 64 contaminated oat samples. The highest concentrations of HT-2-glucoside (HT-2-Glc) were observed at 0.98 aw and 20 °C, and were higher than other type A trichothecenes in the natural oats' treatments. However, no statistical differences were found between the mean concentrations of HT-2-Glc and HT-2 toxins in all storage conditions analysed. DAS concentrations were generally low and highest at 0.95 aw and 20 °C, while deoxynivalenol-3-glucoside levels were highest at 0.98 aw and 20 °C in the naturally contaminated oats. Emerging mycotoxins such as beauvericin, moniliformin, and enniatins mostly increased with a rise in water activity and temperature in the naturally contaminated oats treatment. This study reinforces the importance of storage aw and temperature conditions in the high risk of free and modified toxin contamination of small cereal grains. [ABSTRACT FROM AUTHOR]

Mycotoxins, as natural products of molds, are often unavoidable contaminants of food and feed, to which the increasingly evident climate changes contribute a large part. The consequences are more or less severe and range from economic losses to worrying health problems to a fatal outcome. One of the best preventive approaches is regular monitoring of food and feed for the presence of mycotoxins. However, even under conditions of frequent, comprehensive, and conscientious controls, the desired protection goal may not be achieved. In fact, it often happens that, despite favorable analytical results that do not indicate high mycotoxin contamination, symptoms of their presence occur in practice. The most common reasons for this are the simultaneous presence of several different mycotoxins whose individual content does not exceed the detectable or prescribed values and/or the alteration of the form of the mycotoxin, which renders it impossible to be analytically determined using routine methods. When such contaminated foods enter a living organism, toxic effects occur. This article aims to shed light on the above problems in order to pay more attention to them, work to reduce their impact, and, eventually, overcome them. [ABSTRACT FROM AUTHOR]

Trichothecenes produced by Fusarium species are commonly detected in oats. However, the ratios of the concentrations of free trichothecenes and their conjugates and how they are impacted by different interacting environmental conditions are not well documented. This study aims to examine the effect of water activity (0.95 and 0.98 aw) and temperature (20 and 25 °C) stress on the production of T-2 and HT-2 toxins, deoxynivalenol and their conjugates, as well as diacetoxyscirpenol (DAS). Multiple mycotoxins were detected using liquid chromatography–tandem mass spectrometry from 64 contaminated oat samples. The highest concentrations of HT-2-glucoside (HT-2-Glc) were observed at 0.98 aw and 20 °C, and were higher than other type A trichothecenes in the natural oats’ treatments. However, no statistical differences were found between the mean concentrations of HT-2-Glc and HT-2 toxins in all storage conditions analysed. DAS concentrations were generally low and highest at 0.95 aw and 20 °C, while deoxynivalenol-3-glucoside levels were highest at 0.98 aw and 20 °C in the naturally contaminated oats. Emerging mycotoxins such as beauvericin, moniliformin, and enniatins mostly increased with a rise in water activity and temperature in the naturally contaminated oats treatment. This study reinforces the importance of storage aw and temperature conditions in the high risk of free and modified toxin contamination of small cereal grains.

Small grain cereals are frequently infected with mycotoxigenic Fusarium fungi. Oats have a particularly high risk of contamination with type A trichothecene mycotoxins; their glucoside conjugates have also been reported. Agronomy practices, cereal variety and weather conditions have been suggested to play a role in Fusarium infection in oats. The current study investigates concentrations of free and conjugated Fusarium mycotoxins in organic and conventional oats grown in Scotland. In 2019, 33 milling oat samples (12 organic, 21 conventional) were collected from farmers across Scotland, together with sample questionnaires. Samples were analysed for 12 mycotoxins (type A trichothecenes T-2-toxin, HT-2-toxin, diacetoxyscirpenol; type B trichothecenes deoxynivalenol, nivalenol; zearalenone and their respective glucosides) using LC-MS/MS. The prevalence of type A trichothecenes T-2/HT-2 was very high (100% of conventional oats, 83% of organic oats), whereas type B trichothecenes were less prevalent, and zearalenone was rarely found. T-2-glucoside and deoxynivalenol-glucoside were the most prevalent conjugated mycotoxins (36 and 33%), and co-occurrence between type A and B trichothecenes were frequently observed (66% of samples). Organic oats were contaminated at significantly lower average concentrations than conventional oats, whereas the effect of weather parameters were not statistically significant. Our results clearly indicate that free and conjugated T-2- and HT-2-toxins pose a major risk to Scottish oat production and that organic production and crop rotation offer potential mitigation strategies. [ABSTRACT FROM AUTHOR]

The fermentation is the main process to form the unique flavor and health benefits of dark tea. Numerous studies have indicated that the microorganisms play a significant part in the fermentation process of dark tea. Dark tea has the quality of “The unique flavor grows over time,” but unscientific storage of dark tea might cause infestation of harmful microorganisms, thereby resulting in the remaining of fungi toxins. Mycotoxins are regarded as the main contributor to the quality of dark tea, and its potential mycotoxin risk has attracted people’s attention. This study reviews common and potential mycotoxins in dark tea and discusses the possible types of masked mycotoxins in dark tea. A summary of the potential risks of mycotoxins and masked mycotoxins in dark tea is presented, intending to provide a reference for the prevention and risk assessment of harmful fungi in dark tea. [ABSTRACT FROM AUTHOR]

Fusarium head blight (FHB) of wheat, caused by the fungus Fusarium graminearum, is associated with grain contamination with mycotoxins such as deoxynivalenol (DON). Although FHB is often positively correlated with DON, this relationship can break down under certain conditions. One possible explanation for this could be the conversion of DON to DON-3-glucoside (D3G), which is typically missed by common DON testing methods. The objective of this study was to quantify the effects of temperature, relative humidity (RH), and preharvest rainfall on DON, D3G, and the D3D/DON relationship. D3G levels were higher in grain from spikes exposed to 100% RH than to 70, 80, or 90% RH at 20 and 25°C across all tested levels of mean FHB index (percentage of diseased spikelets per spike). Mean D3G contamination was higher at 20°C than at 25 or 30°C. There were significantly positive linear relationships between DON and D3G. Rainfall treatments resulted in significantly higher mean D3G than the rain-free check and induced preharvest sprouting, as indicated by low falling numbers (FNs). There were significant positive relationships between the rate of increase in D3G per unit increase in DON (a measure of conversion) and sprouting. As FN decreased, the rate of D3G conversion increased, and this rate of conversion per unit decrease in FN was greater at relatively low than at high mean DON levels. These results provide strong evidence that moisture after FHB visual symptom development was associated with DON-to-D3G conversion and constitute valuable new information for understanding this complex disease-mycotoxin system. [ABSTRACT FROM AUTHOR]

Mycotoxins, as natural products of molds, are often unavoidable contaminants of food and feed, to which the increasingly evident climate changes contribute a large part. The consequences are more or less severe and range from economic losses to worrying health problems to a fatal outcome. One of the best preventive approaches is regular monitoring of food and feed for the presence of mycotoxins. However, even under conditions of frequent, comprehensive, and conscientious controls, the desired protection goal may not be achieved. In fact, it often happens that, despite favorable analytical results that do not indicate high mycotoxin contamination, symptoms of their presence occur in practice. The most common reasons for this are the simultaneous presence of several different mycotoxins whose individual content does not exceed the detectable or prescribed values and/or the alteration of the form of the mycotoxin, which renders it impossible to be analytically determined using routine methods. When such contaminated foods enter a living organism, toxic effects occur. This article aims to shed light on the above problems in order to pay more attention to them, work to reduce their impact, and, eventually, overcome them.

The study determined the occurrence of deoxynivalenol (DON), zearalenone (ZEN) and their metabolites in staple cereals from Southwest Nigeria. Sixty composite samples of maize, sorghum and millet were evaluated for DON, ZEN and their masked forms; 3-acetyldeoxynivalenol (3Ac-DON), 15-acetyldeoxynivalenol (15Ac-DON), α-zearalenone (α-ZEL) and β-zearalenone (β-ZEL). Deoxynivalenol did not co-occur with ZEN in maize, sorghum and millet samples in contrast to previous reports. Only the masked forms; 3Ac-DON occurred in few maize samples within the range

Small grain cereals are frequently infected with mycotoxigenic Fusarium fungi. Oats have a particularly high risk of contamination with type A trichothecene mycotoxins; their glucoside conjugates have also been reported. Agronomy practices, cereal variety and weather conditions have been suggested to play a role in Fusarium infection in oats. The current study investigates concentrations of free and conjugated Fusarium mycotoxins in organic and conventional oats grown in Scotland. In 2019, 33 milling oat samples (12 organic, 21 conventional) were collected from farmers across Scotland, together with sample questionnaires. Samples were analysed for 12 mycotoxins (type A trichothecenes T-2-toxin, HT-2-toxin, diacetoxyscirpenol; type B trichothecenes deoxynivalenol, nivalenol; zearalenone and their respective glucosides) using LC-MS/MS. The prevalence of type A trichothecenes T-2/HT-2 was very high (100% of conventional oats, 83% of organic oats), whereas type B trichothecenes were less prevalent, and zearalenone was rarely found. T-2-glucoside and deoxynivalenol-glucoside were the most prevalent conjugated mycotoxins (36 and 33%), and co-occurrence between type A and B trichothecenes were frequently observed (66% of samples). Organic oats were contaminated at significantly lower average concentrations than conventional oats, whereas the effect of weather parameters were not statistically significant. Our results clearly indicate that free and conjugated T-2- and HT-2-toxins pose a major risk to Scottish oat production and that organic production and crop rotation offer potential mitigation strategies.

Animal feed (including forage and silage) can be contaminated with mycotoxins. Here, 200 maize silage samples from around China were collected in 2019 and analyzed for regulated mycotoxins, masked mycotoxins (deoxynivalenol, 3-acetyldeoxynivalenol, 15-acetyldeoxynivalenol, and deoxynivalenol-3-glucoside), and emerging mycotoxins (beauvericin, enniatins, moniliformin, and alternariol). Deoxynivalenol and zearalenone were detected in 99.5% and 79.5% of the samples, respectively. Other regulated mycotoxins were detected in fewer samples. The highest deoxynivalenol and zearalenone concentrations were 3600 and 830 μg/kg, respectively. The most commonly detected masked mycotoxin was 15-acetyldeoxynivalenol, which was detected in 68.5% of the samples and had median and maximum concentrations of 61.3 and 410 μg/kg, respectively. The emerging mycotoxins beauvericin, alternariol, enniatin A, enniatin B1, and moniliformin were detected in 99.5%, 85%, 80.5%, 72.5%, and 44.5%, respectively, of the samples but at low concentrations (medians <25 μg/kg). The samples tended to contain multiple mycotoxins, e.g., the correlation coefficients for the relationships between the concentrations of beauvericin and deoxynivalenol, deoxynivalenol and zearalenone, and zearalenone and beauvericin were 1.0, 0.995, and 0.995, respectively. The results indicated that there needs to be more awareness of the presence of one or more masked and emerging mycotoxins in maize silage in China. [ABSTRACT FROM AUTHOR]

Despite its nutritional value, wheat grain can be contaminated with mycotoxins, which cause toxic effects when ingested, and this contamination may persist during food processing. Among the mycotoxins found in wheat and its derivatives, DON, a mycotoxin belonging to trichothecene group B, stands out for its prevalence and range. Processing parameters, such as the time and temperature of thermal treatment used in food preparation, are important to mitigate mycotoxin contamination. Studies have shown that interconversion can occur between DON and its derivatives and interaction with macromolecules during food processing. However, it may also bind or disconnect with macromolecules after the digestion process, resulting in underestimation of trichothecene exposure by wheat product consumption. In this review, focus will be placed on the main studies of trichothecenes occurrence in wheat and their derivatives, as well as which processing step reduces trichothecene contamination. There are few studies focusing on nivalenol occurrence despite its toxic effects. The trends are focused on DON and its conversion into D3G during the food processing steps. There is still little standardization in food production, which has complicated comparisons and the identification of the product that represents the greatest risk to human health. The main challenge for public policy to prevent damage to human health is the evaluation of trichothecenes bioaccessibility along the wheat supply chain. • DON is the most studied trichothecene in wheat-based food matrices. • Processing parameters affect DON levels in wheat products. • There are processing parameters that reduces DON concentration. • DON interconversion in D3G occurs in wheat products. [ABSTRACT FROM AUTHOR]

Animal feed (including forage and silage) can be contaminated with mycotoxins. Here, 200 maize silage samples from around China were collected in 2019 and analyzed for regulated mycotoxins, masked mycotoxins (deoxynivalenol, 3-acetyldeoxynivalenol, 15-acetyldeoxynivalenol, and deoxynivalenol-3-glucoside), and emerging mycotoxins (beauvericin, enniatins, moniliformin, and alternariol). Deoxynivalenol and zearalenone were detected in 99.5% and 79.5% of the samples, respectively. Other regulated mycotoxins were detected in fewer samples. The highest deoxynivalenol and zearalenone concentrations were 3600 and 830 μg/kg, respectively. The most commonly detected masked mycotoxin was 15-acetyldeoxynivalenol, which was detected in 68.5% of the samples and had median and maximum concentrations of 61.3 and 410 μg/kg, respectively. The emerging mycotoxins beauvericin, alternariol, enniatin A, enniatin B1, and moniliformin were detected in 99.5%, 85%, 80.5%, 72.5%, and 44.5%, respectively, of the samples but at low concentrations (medians

Background and objectives: Conjugation of mycotoxins in the phase II metabolism of plants results in modified mycotoxins such as glucosides and malonyl‐glucosides. However, malonyl‐glucosides have not yet been completely elucidated for zearalenone (ZEN). Thus, the aim of this study was to produce and isolate malonyl‐glucosides of ZEN for an unambiguous identification by NMR spectroscopy. Findings: Zearalenone was incubated in plant cell suspension cultures of wheat, soy, and tobacco, and phase II metabolites were analyzed by using LC‐DAD‐MS, ‐HRMS, and NMR spectroscopy. Four main metabolites of ZEN were detected in the cell extracts and identified as two glucosides (attached in positions 14 and 16) and their 6´‐malonyl derivatives. Conclusions: Zearalenone‐malonyl‐glucosides should be incorporated in future analyses of modified mycotoxins because of their potential relevance for food and feed safety. Significance and novelty: For the first time, the structures of the two malonyl‐glucosides of ZEN were unambiguously identified by NMR spectroscopy after preparative isolation as 14‐O‐(6'‐O‐malonyl‐β‐D‐glucopyranosyl)ZEN and 16‐O‐(6'‐O‐malonyl‐β‐D‐glucopyranosyl)ZEN. [ABSTRACT FROM AUTHOR]

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Fusarium mycotoxins are common contaminants in cereals and often co-occur with plant-derived mycotoxin sugar conjugates. Several of these modified mycotoxins are not degraded in the small intestine and hence carried through to the large intestine where microbial transformation may occur. This study aims to assess the gastrointestinal stability of the trichothecenes HT-2 toxin (HT-2), HT-2-β-glucoside (HT-2-Glc), diacetoxyscirpenol (DAS), DAS-α-glucoside (DAS-Glc) and fumonisin B1 (FB1), N-(1-deoxy-d-fructos-1-yl) fumonisin-B1 (NDF-FB1). All tested modified mycotoxins were stable under upper gastrointestinal (GI) conditions. In faecal batch culture experiments, HT-2-Glc was hydrolysed efficiently and no further microbial biotransformation of HT-2 was observed. DAS-Glc hydrolysis was slow and DAS was de-acetylated to 15-monoacetoxyscripenol. NDF-FB1 was hydrolysed at the slowest rate and FB1 accumulation varied between donor samples. Our results demonstrate that all tested modified mycotoxins are stable in the upper GI tract and efficiently hydrolysed by human gut microbiota, thus potentially contributing to colonic toxicity. Hence the microbial biotransformation of any novel modified mycotoxins needs to be carefully evaluated. [ABSTRACT FROM AUTHOR]

Masked mycotoxins are biologically modified phase II metabolites formed by plant defense mechanisms through glucosylation catalyzed by uridine diphosphate -glucosyltransferases. Most of the current reports focus on the occurrence of masked mycotoxins in Europe, America, Africa, and cover other geographic regions, e.g. China and Japan. High proportions of masked mycotoxins co-occurring with their parent forms in various cereal-based food and feedstuff could clearly increase total exposures and pose additional health risks to humans and animals. In contrast to the parent mycotoxins, the data on the toxicity of masked mycotoxins are still scarce, however, the poor existing information showed that masked mycotoxins generally exhibit significant in vitro and in vivo toxicities lower than those of their parent forms, especially for deoxynivalenol-3-glucoside, which is the only thoroughly investigated masked mycotoxin. Although the lower toxicity level of masked mycotoxins, these are probably hydrolyzed into their free forms by intestinal microorganisms in the digestive tract of mammals and thus contribute to unpredicted toxicity. The metabolic characteristics of reported masked mycotoxins are species-specific. The most relevant animal model of human sensitivity, the pig, is most sensitive to masked mycotoxins. This review focuses on updates in the current knowledge on country-specific natural-occurrence data in global surveys, as well as in vitro and in vivo toxicology and metabolic investigations of masked mycotoxins. [ABSTRACT FROM AUTHOR]

The Fusarium mycotoxin deoxynivalenol (DON) is a common contaminant of cereals and is often co-occurring with its modified forms DON-3-glucoside (D3G), 3-acetyl-DON (3ADON) or 15-acetyl-DON (15ADON). A stable-isotope dilution liquid chromatography-tandem mass spectrometry (LC-MS/MS) based method for their determination in cereals was developed and validated for maize. Therefore, 13C-labelled D3G was enzymatically produced using 13C-DON and [13C6Glc]-sucrose and used as an internal standard (IS) for D3G, while uniformly 13C labelled IS was used for the other mycotoxins. Baseline separation was achieved for the critical peak pair DON/D3G, while 3ADON/15ADON could not be fully baseline separated after testing various reversed phase, fluorinated phase and chiral LC columns. After grinding, weighing and extracting the cereal samples, the raw extract was centrifuged and a mixture of the four 13C-labelled ISs was added directly in a microinsert vial. The subsequent analytical run took 7 min, followed by negative electrospray ionization and selected reaction monitoring on a triple quadrupole MS. Maize was used as a complex cereal model matrix for validation. The use of the IS corrected the occurring matrix effects efficiently from 76 to 98% for D3G, from 86 to 103% for DON, from 68 to 100% for 15ADON and from 63 to 96% for 3ADON.

Fungal secondary metabolites frequently contaminate agricultural products implying a potential toxicological concern for consumers. We report a food survey investigating 17 Alternaria mycotoxins in tomato sauce, sunflower seed oil and wheat flour. Matrix-dependent median concentrations of the most frequently studied toxins, namely alternariol (AOH), alternariol monomethyl ether (AME), tenuazonic acid, and tentoxin ranged between 1.2 and 6.6, 0.5–1.3, 66–161, and 0.1–0.5 ng/g. Additionally, the modified toxins AOH-3-sulfate (up to 2.1 ng/g) and AME-3-sulfate (up to 17.5 ng/g) were detected in 9% and 34% of tomato sauces accounting for 7–100% of their parent toxin concentrations. The barely studied perylene quinones altertoxin I and alterperylenol were determined in all matrices with concentrations of up to 6 and 48 ng/g, respectively. The contamination patterns of sample subgroups were compared considering multiple factors (e.g. country of origin, type of agriculture, vendor, food processing). Samples from organic agriculture showed comparably higher median and maximum concentrations of the investigated Alternaria toxins, but also national and vendor-specific (supermarket chains vs. online stores) quality requirements for agricultural crops and food processing in the case of sunflower seed oils seem to affect the Alternaria toxin contamination patterns in food commodities. Overall, the presented study contributes comprehensive Alternaria toxin occurrence data which is necessary for future risk assessments evaluating potentially caused health concerns for consumers. • Up to nine of 17 Alternaria toxins were determined in food samples. • Detected levels of modified toxins indicate their relevance for risk assessment. • Barely studied perylene quinones determined at considerable concentrations. • Organic agriculture does not directly correlate with mycotoxin contamination. [ABSTRACT FROM AUTHOR]

Graphical abstract Highlights • Characterization of 7 novel nivalenol (NIV)- and NIV-3-glucoside (NIV3 G) metabolites in rats. • Development of LC–MS/MS based methods for analysis of NIV(3 G) metabolites in rat excrements. • Similar metabolization of NIV and deoxynivalenol in rats, but with different metabolite patterns. • NIV3 G is largely hydrolyzed in the GI tract of rats, but also extensively further metabolized. • The systemic exposure to NIV is roughly 30 times lower after NIV3 G consumption than after NIV dosage. Abstract Plant-derived mycotoxin conjugates like deoxynivalenol-3-glucoside can be partly hydrolyzed to their aglycones in vivo , albeit to different extent depending on the mycotoxin conjugate and on the animal species. The aim of this work was to investigate the metabolization of the trichothecene mycotoxin nivalenol (NIV) and the fate of its modified form NIV-3-glucoside (NIV3G) in rats. To that end, 350 μg/kg body weight of NIV and the equimolar dose of NIV3G were administered to six rats by gavage in a 5 × 6 design and excreta were collected for 2 days after each treatment. For further analysis of NIV and NIV3G metabolites in rat urine and feces, seven novel NIV- and NIV3G metabolites including NIV sulfonates (NIVS) 1, 2 and 3, deepoxy-NIV (DNIV), DNIV sulfonate 2, NIV3G sulfonate (NIV3GS) 2 and NIV-3-glucuronide were produced, isolated and characterized. Subsequently, LC–MS/MS based methods for determination of NIV, NIV3G and their metabolites in excreta samples were developed, validated and applied. The biological recoveries of administered toxins in the form of their fecal and urinary metabolites were 57 ± 21% for NIV and 94 ± 36% for NIV3G. The majority of NIV and NIV3G metabolites was excreted into feces, with DNIV and NIVS 2 as major NIV metabolites and NIV3GS 2 and DNIV as major metabolites of NIV3G. Only 1.5% of the administered NIV3G was recovered in urine, with NIV3G itself as major urinary metabolite. The biological recovery of free NIV in urine was approximately 30 times lower after treatment with NIV3G than after administration of NIV, indicating that exposure of rats to NIV3G results in lower toxicity than exposure to NIV. [ABSTRACT FROM AUTHOR]

Highlights • DON increased up to 150% during mashing. • Important reduction of DON (60%), ZEA (99%) and fumonisins (90%) after the first 30 min of wort boiling. • DON and FB1 were not completely reduced in none of the samples. Abstract The fate of deoxynivalenol, deoxynivalenol-3-glucoside, 3- and 15-acetyl-deoxynivalenol, zearalenone, α- and β-zearalenol and fumonisins (fumonisin B 1 and fumonisin B 2) through mashing and wort boiling was studied. Three different mycotoxin contamination scenarios were considered. In almost all samples an increase in the level of mycotoxins in wort was observed during mashing followed by a decrease after just 30 min of the process, with levels remaining constant until the end of boiling. Deoxynivalenol and its metabolites were reduced to their initial level contained in the malt before mashing, or even lower, however in none of the samples they were completely eliminated. Zearalenone was not quantitated at the end of boiling, although there was a significant initial level of ZEN. β-Zearalenol remained unaltered during the process. Fumonisins were reduced by between 50 and 100 per cent during mashing and boiling. [ABSTRACT FROM AUTHOR]

The presence of mycotoxins in cereal grain is a very important food safety issue with the occurrence of masked mycotoxins extensively investigated in recent years. This study investigated the variation of different Fusarium metabolites (including the related regulated, masked, and emerging mycotoxin) in maize from various agriculture regions of South Africa. The relationship between the maize producing regions, the maize type, as well as the mycotoxins was established. A total of 123 maize samples was analyzed by a LC-MS/MS multi-mycotoxin method. The results revealed that all maize types exhibited a mixture of free, masked, and emerging mycotoxins contamination across the regions with an average of 5 and up to 24 out of 42 investigated Fusarium mycotoxins, including 1 to 3 masked forms at the same time. Data obtained show that fumonisin B1, B2, B3, B4, and A1 were the most prevalent mycotoxins and had maximum contamination levels of 8908, 3383, 990, 1014, and 51.5 µg/kg, respectively. Deoxynivalenol occurred in 50% of the samples with a mean concentration of 152 µg/kg (max 1380 µg/kg). Thirty-three percent of the samples were contaminated with zearalenone at a mean concentration of 13.6 µg/kg (max 146 µg/kg). Of the masked mycotoxins, DON-3-glucoside occurred at a high incidence level of 53%. Among emerging toxins, moniliformin, fusarinolic acid, and beauvericin showed high occurrences at 98%, 98%, and 83%, and had maximum contamination levels of 1130, 3422, and 142 µg/kg, respectively. Significant differences in the contamination pattern were observed between the agricultural regions and maize types.

Zearalenone-14-glucoside (ZEN-14G), a key modified mycotoxin, has attracted a great deal of attention due to the possible conversion to its free form of zearalenone (ZEN) exerting toxicity. In this study, the toxicokinetics of ZEN-14G were investigated in rats after oral and intravenous administration. The plasma concentrations of ZEN-14G and its major five metabolites were quantified using a validated liquid chromatography tandem mass spectrometry (LC-MS/MS) method. The data were analyzed via non-compartmental analysis using software WinNonlin 6.3. The results indicated that ZEN-14G was rapidly hydrolyzed into ZEN in vivo. In addition, the major parameters of ZEN-14G following intravenous administration were: area under the plasma concentration−time curve (AUC), 1.80 h·ng/mL; the apparent volume of distribution (VZ), 7.25 L/kg; and total body clearance (CL), 5.02 mL/h/kg, respectively. After oral administration, the typical parameters were: AUC, 0.16 h·ng/mL; VZ, 6.24 mL/kg; and CL, 4.50 mL/h/kg, respectively. The absolute oral bioavailability of ZEN-14G in rats was about 9%, since low levels of ZEN-14G were detected in plasma, which might be attributed to its extensive metabolism. Therefore, liquid chromatography high-resolution mass spectrometry (LC-HRMS) was adopted to clarify the metabolic profile of ZEN-14G in rats’ plasma. As a result, eight metabolites were identified in which ZEN-14-glucuronic acid (ZEN-14GlcA) had a large yield from the first time-point and continued accumulating after oral administration, indicating that ZEN-14-glucuronic acid could serve a potential biomarker of ZEN-14G. The obtained outcomes would prompt the accurate safety evaluation of ZEN-14G.

Deoxynivalenol (DON) is a protein synthesis inhibitor produced by the Fusarium species, which frequently contaminates grains used for human or animal consumption. We treated a wheat suspension culture with DON or one of its acetylated derivatives, 3-acetyl-DON (3-ADON), 15-acetyl-DON (15-ADON) and 3,15-diacetyl-DON (3,15-diADON), and monitored the metabolization over a course of 96 h. Supernatant and cell extract samples were analyzed using a tailored LC-MS/MS method for the quantification of DON metabolites. We report the formation of tentatively identified DON-15-O-β-D-glucoside (D15G) and of 15-acetyl-DON-3-sulfate (15-ADON3S) as novel deoxynivalenol metabolites in wheat. Furthermore, we found that the recently identified 15-acetyl-DON-3-O-β-D-glucoside (15-ADON3G) is the major metabolite produced after 15-ADON challenge. 3-ADON treatment led to a higher intracellular content of toxic metabolites after six hours compared to all other treatments. 3-ADON was exclusively metabolized into DON before phase II reactions occurred. In contrast, we found that 15-ADON was directly converted into 15-ADON3G and 15-ADON3S in addition to metabolization into deoxynivalenol-3-O-β-D-glucoside (D3G). This study highlights significant differences in the metabolization of DON and its acetylated derivatives.

The aim of this review is to provide a brief overview of analytical methods used for the determination of deoxynivalenol and its modified forms deoxynivalenol-3-β-D-glucoside, 3-acetyl-deoxynivalenol and 15-acetyl-deoxynivalenol in beer. The analytical methods discussed involve gas chromatography coupled with flame ionization detection, electron capture detection and mass spectrometry as well as liquid chromatography hyphenated to ultra-violet detection and mass spectrometry. Special attention was paid to sample preparation. Immunochemical methods such as enzyme-linked immunosorbent assays (ELISAs) which represent efficient tools for fast screening of beer with no sample purification are also discussed.

Zearalenone (ZEN) major biotransformation pathways described so far are based on glycosylation and sulfation, although acetylation of trichothecenes has been reported as well. We investigated herein the ZEN acetylation metabolism route in micropropagated durum wheat leaf, artificially contaminated with ZEN. We report the first experimental evidence of the formation of novel ZEN acetylated forms in wheat, attached both to the aglycone backbone as well as on the glucose moiety. Thanks to the advantages provided by high-resolution mass spectrometry, identification and structure annotation of 20 metabolites was achieved. In addition, a preliminary assessment of the toxicity of the annotated metabolites was performed in silico focusing on the toxicodynamic of ZEN group toxicity. All the metabolites showed a worse fitting within the estrogen receptor pocket in comparison with ZEN. Nevertheless, possible hydrolysis to the respective parent compounds (i.e., ZEN) may raise concern from the health perspective because these are well-known xenoestrogens. These results further enrich the biotransformation profile of ZEN, providing a helpful reference for assessing the risks to animals and humans.ᅟ [ABSTRACT FROM AUTHOR]

Plant-derived phase II metabolites of T-2 toxin (T2) and HT-2 toxin (HT2) were first described in 2011 and further characterized in the following years. Since then, some efforts have been made to understand their biosynthesis, occurrence, toxicity, toxicokinetics, and finally relevance for consumers. Thus, the probably most important question is whether and how these metabolites contribute to toxicity upon hydrolysis either during food processing or the gastrointestinal passage. To answer this question, firstly, knowledge on the correct stereochemistry of T2 and HT2 glucosides is important as this affects hydrolysis and chemical behavior. So far, contradictory results have been published concerning the number and anomericity of occurring glucosides. For this reason, we set up different strategies for the synthesis of mg-amounts of T2, HT2, and T2 triol glucosides in both α and ß configuration. All synthesized glucosides were fully characterized by NMR spectroscopy as well as mass spectrometry and used as references for the analysis of naturally contaminated food samples to validate or invalidate their natural occurrence. Generally, 3-O-glucosylation was observed with two anomers of HT2 glucoside being present in contaminated oats. In contrast, only one anomer of T2 glucoside was found. The second aspect of this study addresses the stability of the glucosides during thermal food processing. Oat flour was artificially contaminated with T2 and HT2 glucosides individually and extruded at varying initial moisture content and temperature. All four glucosides appear to be more stable during food extrusion than the parent compounds with the glucosidic bond not being hydrolyzed. [ABSTRACT FROM AUTHOR]

Mycotoxins produced by Alternaria fungi are ubiquitous food contaminants, but analytical methods for generating comprehensive exposure data are rare. We describe the development of an LC-MS/MS method covering 17 toxins for investigating the natural occurrence of free and modified Alternaria toxins in tomato sauce, sunflower seed oil, and wheat flour. Target analytes included alternariol (AOH), AOH-3-glucoside, AOH-9-glucoside, AOH-3-sulfate, alternariol monomethyl ether (AME), AME-3-glucoside, AME-3-sulfate, altenuene, isoaltenuene, tenuazonic acid (TeA), tentoxin (TEN), altertoxin I and II, alterperylenol, stemphyltoxin III, altenusin, and altenuic acid III. Extensive optimization resulted in a time- and cost-effective sample preparation protocol and a chromatographic baseline separation of included isomers. Overall, adequate limits of detection (0.03-9 ng/g) and quantitation (0.6-18 ng/g), intermediate precision (9-44%), and relative recovery values (75-100%) were achieved. However, stemphyltoxin III, AOH-3-sulfate, AME-3-sulfate, altenusin, and altenuic acid III showed recoveries in wheat flour below 70%, while their performance was stable and reproducible. Our pilot study with samples from the Austrian retail market demonstrated that tomato sauces (n = 12) contained AOH, AME, TeA, and TEN in concentrations up to 20, 4, 322, and 0.6 ng/g, while sunflower seed oil (n = 7) and wheat flour samples (n = 9) were contaminated at comparatively lower levels. Interestingly and of relevance for risk assessment, AOH-9-glucoside, discovered for the first time in naturally contaminated food items, and AME-3-sulfate were found in concentrations similar to their parent toxins. In conclusion, the established multi-analyte method proved to be fit for purpose for generating comprehensive Alternaria toxin occurrence data in different food matrices.ᅟ [ABSTRACT FROM AUTHOR]

The presence of mycotoxins in cereal grain is a very important food safety factor. The occurrence of "masked" mycotoxins has been intensively investigated in recent years. In this study, the occurrence of nivalenol, deoxynivalenol-3-glucoside, and deoxynivalenol in 92 samples of winter wheat from Polish cultivars was determined. The frequency of the occurrence of deoxynivalenol and nivalenol in the samples was 83% and 70%, respectively. The average content of the analytes was: for deoxynivalenol 140.2 µg/kg (10.5-1265.4 µg/kg), for nivalenol 35.0 µg/kg (5.1-372.5 µg/kg). Deoxynivalenol-3-glucoside, the formation of which is connected with the biotransformation pathway in plants, was present in 27% of tested wheat samples; its average content was 41.9 µg/kg (15.8-137.5 µg/kg). The relative content of deoxynivalenol-3-glucoside (DON-3G) compared to deoxynivalenol (DON) in positive samples was 4-37%. Despite the high frequency of occurrence of these mycotoxins, the quality of wheat from the 2016 season was good. The maximum content of DON, as defined in EU regulations (1250 µg/kg), was exceeded in only one sample. Nevertheless, the presence of a glycosidic derivative of deoxynivalenol can increase the risk to food safety, as it can be hydrolyzed by intestinal microflora. [ABSTRACT FROM AUTHOR]

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The development of a reliable procedure for the synthesis of the 16-glucoside and 16-sulfate of the resorcylic acid lactone (RAL) type compound zearalenone is presented. Different protective group strategies were considered and applied to enable the preparation of glucosides and sulfates that are difficult to access up to now. Acetyl and p-methoxybenzyl protection led to undesired results and were shown to be inappropriate. Finally, triisopropylsilyl-protected zearalenone was successfully used as intermediate for the first synthesis of the corresponding mycotoxin glucoside and sulfate that are highly valuable as reference materials for further studies in the emerging field of masked mycotoxins. Furthermore, high stability was observed for aryl sulfates prepared as tetrabutylammonium salts. Overall, these findings should be applicable for the synthesis of similar RAL type and natural product conjugates.

Food raw materials can contain the mycotoxin ochratoxin A (OTA). Thermal processing of these materials may result in decreased OTA levels but also in the formation of the thermal isomerization product 2′R-ochratoxin A (2′R-OTA). So far, only 2′R-OTA levels reported from 15 coffee samples in 2008 are known, which is little when compared to the importance of coffee as a food and trading good. Herein, we present results from a set of model experiments studying the effect of temperatures between 120 °C and 270 °C on the isomerization of OTA to 2′R-OTA. It is shown that isomerization of OTA starts at temperatures as low as 120 °C. At 210 °C and above, the formation of 25% 2′R-OTA is observed in less than one minute. Furthermore, 51 coffee samples from France, Germany, and Guatemala were analyzed by HPLC-MS/MS for the presence of OTA and 2′R-OTA. OTA was quantified in 96% of the samples, while 2′R-OTA was quantifiable in 35% of the samples. The highest OTA and 2′R-OTA levels of 28.4 µg/kg and 3.9 µg/kg, respectively, were detected in coffee from Guatemala. The OTA:2′R-OTA ratio in the samples ranged between 2.5:1 and 10:1 and was on average 5.5:1. Besides coffee, 2′R-OTA was also for the first time detected in a bread sample and malt coffee powder.

Deoxynivalenol (DON) is the most prevalent trichothecene in Europe and its occurrence is associated with infections of Fusarium graminearum and F. culmorum, causal agents of Fusarium head blight (FHB) on wheat. Resistance to FHB is a complex character and high variability occurs in the relationship between DON content and FHB incidence. DON conjugation to glucose (DON-3-glucoside, D3G) is the primary plant mechanism for resistance towards DON accumulation. Although this mechanism has been already described in bread wheat and barley, no data are reported so far about durum wheat, a key cereal in the pasta production chain. To address this issue, the ability of durum wheat to detoxify and convert deoxynivalenol into D3G was studied under greenhouse controlled conditions. Four durum wheat varieties (Svevo, Claudio, Kofa and Neodur) were assessed for DON-D3G conversion; Sumai 3, a bread wheat variety carrying a major QTL for FHB resistance (QFhs.ndsu-3B), was used as a positive control. Data reported hereby clearly demonstrate the ability of durum wheat to convert deoxynivalenol into its conjugated form, D3G.

The mycotoxin zearalenone may contaminate food and feed worldwide upon infections by Fusarium spp. of plants and raw materials intended for human and animal consumption. Currently, contamination by zearalenone and congeners pose concern for health due to xenoestrogenic effects. However, while zearalenone and the main reduced metabolites are well-known xenoestrogens, some plant metabolites that may enter the food chain have been observed aside. Among them, zearalenone-14-glucoside may be abundant in the edible parts of infected plants, thereby entering significantly the human diet and animal feeding. On the basis of previous works, the lack of xenoestrogenicity for this compound per se was taken for granted, while neglecting the direct proof of estrogenic activity and considering the hydrolysis as a possible source of estrogenically active metabolites. The present work investigated the xenoestrogenicity of zearalenone-14-glucoside, in comparison to zearalenone, deepening the underlying molecular mechanisms through an integrated in vitro/in silico approach. On the basis of our results, zearalenone-14-glucoside effectively stimulated a xenoestrogenic response in cells, but such stimulus can be entirely attributable to the hydrolysis phenomenon, as the glycosylated form turned out to be unable to effectively bind and activate the estrogens receptors. [ABSTRACT FROM AUTHOR]

Food processing, especially thermal treatment, may have implications on mycotoxins in products available for consumers. This research work aimed to study how mycotoxin levels may be influenced by modifying the technological parameters of both whole grain and cocoa biscuit-making processes. The study was mainly focused on the following mycotoxins: deoxynivalenol, deoxynivalenol-3-glucoside, and the minor metabolite culmorin. Special emphasis was given to the recipe formulation, and to the baking conditions, using an industrial-scale operation, starting from naturally contaminated raw materials. Exploiting the power of Design of Experiments (DoE) and a dedicated LC-MS/MS method, the complexity of the different processes was investigated. The models obtained within this study showed a high goodness-of-fit suggesting that the pH and the baking time play important roles for minimizing mycotoxins in the final products, while the recipe formulation has an impact on the mycotoxins extractability by affecting the biscuit microstructure. [ABSTRACT FROM AUTHOR]

Masked mycotoxins are plant metabolites of mycotoxins which co-contaminate common cereal crops. Since their discovery, the question has arisen if they contribute to toxicity either directly or indirectly through the release of the parent mycotoxins. Research in this field is rapidly emerging and the aim of this review is to summarize the latest knowledge on the fate of masked mycotoxins upon ingestion. Fusarium mycotoxins are the most prevalent masked mycotoxins and evidence is mounting that DON3Glc and possibly other masked trichothecenes are stable in conditions prevailing in the upper gut and are not absorbed intact. DON3Glc is also not toxic per se, but is hydrolyzed by colonic microbes and further metabolized to DOM-1 in some individuals. Masked zearalenone is rather more bio-reactive with some evidence on gastric and small intestinal hydrolysis as well as hydrolysis by intestinal epithelium and components of blood. Microbial hydrolysis of ZEN14Glc is almost instantaneous and further metabolism also occurs. Identification of zearalenone metabolites and their fate in the colon are still missing as is further clarification on whether or not masked zearalenone is hydrolyzed by mammalian cells. New masked mycotoxins continuously emerge and it is crucial that we gain detailed understanding of their individual metabolic fate in the body before we can assess synergistic effects and extrapolate the additive risk of all mycotoxins present in food. [ABSTRACT FROM AUTHOR]

Crossover animal trials were performed with intravenous and oral administration of deoxynivalenol-3-β- d-glucoside (DON3G) and deoxynivalenol (DON) to broiler chickens and pigs. Systemic plasma concentrations of DON, DON3G and de-epoxy-DON were quantified using liquid chromatography-tandem mass spectrometry. Liquid chromatography coupled to high-resolution mass spectrometry was used to unravel phase II metabolism of DON. Additionally for pigs, portal plasma was analysed to study presystemic hydrolysis and metabolism. Data were processed via tailor-made compartmental toxicokinetic models. The results in broiler chickens indicate that DON3G is not hydrolysed to DON in vivo. Furthermore, the absolute oral bioavailability of DON3G in broiler chickens was low (3.79 ± 2.68 %) and comparable to that of DON (5.56 ± 2.05 %). After PO DON3G administration to pigs, only DON was detected in plasma, indicating a complete presystemic hydrolysis of the absorbed fraction of DON3G. However, the absorbed fraction of DON3G, recovered as DON, was approximately 5 times lower than after PO DON administration, 16.1 ± 5.4 compared with 81.3 ± 17.4 %. Analysis of phase II metabolites revealed that biotransformation of DON and DON3G in pigs mainly consists of glucuronidation, whereas in chickens predominantly conjugation with sulphate occurred. The extent of phase II metabolism is notably higher for chickens than for pigs, which might explain the differences in sensitivity of these species to DON. Although in vitro studies demonstrate a decreased toxicity of DON3G compared with DON, the species-dependent toxicokinetic data and in vivo hydrolysis to DON illustrate the toxicological relevance and consequently the need for further research to establish a tolerable daily intake. [ABSTRACT FROM AUTHOR]

The Fusarium mycotoxin zearalenone (ZEN) can be conjugated with polar molecules, like sugars or sulfates, by plants and fungi. To date, the fate of these modified forms of ZEN has not yet been elucidated in animals. In order to investigate whether ZEN conjugates contribute to the total ZEN exposure of an individual, ZEN (10 μg/kg b.w.) and equimolar amounts of two of its plant metabolites (ZEN-14-O-β-glucoside, ZEN-16-O-β-glucoside) and of one fungal metabolite (ZEN-14-sulfate) were orally administered to four pigs as a single bolus using a repeated measures design. The concentrations of ZEN, its modified forms and its mammalian metabolites ZEN-14-glucuronide, α-zearalenol (α-ZEL) and α-ZEL-14-glucuronide in excreta were analyzed by high-performance liquid chromatography tandem mass spectrometry (HPLC-MS/MS) based methods. The biological recovery of ZEN in urine was 26% ± 10%, the total biological recovery in excreta was 40% ±8%. Intact ZEN-14-sulfate, ZEN-14-O-β-glucoside and ZEN-16-O-β-glucoside were neither detected in urine nor in feces. After ZEN-14-sulfate application, 19% ± 5% of the administered dose was recovered in urine. In feces, no ZEN metabolites were detected. The total biological recoveries of ZEN-14-O-β-glucoside and ZEN-16-O-β-glucoside in the form of their metabolites in urine were 19% ± 11% and 13% ± 7%, respectively. The total biological recoveries in urine and feces amounted to 48% ± 7% and 34 ± 3%. An explanation for the low biological recoveries could be extensive metabolization by intestinal bacteria to yet unknown metabolites. In summary, ZEN-14-sulfate, ZEN-14-O-β-glucoside, and ZEN-16-O-β-glucoside were completely hydrolyzed in the gastrointestinal tract of swine, thus contributing to the overall toxicity of ZEN. [ABSTRACT FROM AUTHOR]

The spreading of mycotoxic nephropathy in animals/humans was studied. The possible etiological causes provoking this nephropathy were carefully reviewed and analyzed. The natural content of the most frequent nephrotoxic mycotoxins in target feedstuffs/foods were investigated, in addition to their significance for development of renal damages in endemic areas. An estimation of the level of exposure of humans to the nephrotoxic mycotoxin, ochratoxin A (OTA), is made. The possible synergism or additive effects between some target mycotoxins in the development of nephropathy is also covered. The significance of joint mycotoxin interaction and masked mycotoxins, in addition to some newly isolated fungal toxic agents in the complicated etiology of mycotoxic nephropathy ranged in Balkan countries is discussed. The importance of some target fungal species which can induce kidney damages was evaluated. The morphological/ultrastructural, functional and toxicological similarities between human and animal nephropathy are studied. The possible hazard of low content of combinations of some target mycotoxins in food or feedstuff ingested by pigs, chickens or humans under natural conditions is evaluated and a risk assessment was made. Some different but more effective manners of prophylaxis and/or prevention against OTA contamination of feedstuffs/foods are suggested. A survey was made in regard to the best possible ways of veterinary hygiene control of OTA-exposed animals at slaughter time for preventing the entrance of OTA in commercial feedstuffs/food channels with a view to reduce the possible health hazard for humans. The economic efficacy and applicability of such preventive measures is additionally discussed and some practical suggestions are made. [ABSTRACT FROM AUTHOR]

Masked mycotoxins are plant metabolites of mycotoxins that contaminate food and feed. They pose health concern as the shortage of toxicological data forces the lack of regulation worldwide. The present work investigated the toxicological relevance of the masked mycotoxin zearalenone-14-glucoside. In vitro , it shows a lower toxicity in respect to the parent compound. However, the major risks related to the consumption of masked mycotoxins depend on the possibility to undergo hydrolysis. Therefore, the hydrolysis and further transformation of zearalenone-14-glucoside in bovine blood and blood components (i.e. plasma, serum and serum albumin) were monitored using LC/MS-MS analysis to gain insights on the possible systemic fate. Hydrolysis was observed in all matrices, and both cell-dependent and –independent contributions were pointed out. Moreover, further metabolism was observed in the whole blood as zearalenol isomers were found. Serum albumin was identified among the active components, and the protein-ligand interaction was investigated via computational analysis. The blood has been pointed out as possible district of reversion and further activation of zearalenone-14-glucoside, and a similar fate cannot be excluded for other masked mycotoxins. Therefore, the systemic hydrolysis should be evaluated beside the absorption, bioavailability and bioaccessibility to deeply understand the toxicity of masked mycotoxins. [ABSTRACT FROM AUTHOR]

Mycotoxins are likely to be converted into masked forms when subjected to plant metabolism or food processing. These masked forms of mycotoxins together with their prototypes may cause mixture toxicity effects, causing adverse effects on animal welfare and productivity. The structure elucidation of masked mycotoxins is the most challenging task in mycotoxin research due to the limitations of traditional analysis methods. To assist in the rapid identification of masked mycotoxins, we developed a data-driven online prediction tool, MycotoxinDB, based on reaction rules. Using MycotoxinDB, we identified seven masked DONs from wheat samples. Given its widespread applications, we expect that MycotoxinDB will become an indispensable tool in future mycotoxin research. MycotoxinDB is freely available at: http://www.mycotoxin-db.com/.

This study investigated for the first time the intestinal transfer of two modified forms of zearalenone (ZEN), zearalenone-14-glucoside (ZEN14Glc) and zearalenone-16-glucoside (ZEN16Glc), using polarized monolayers of Caco-2 cells. The cells were apically exposed to 40 μM of ZEN14Glc, ZEN16Glc and ZEN, separately. Results showed that, after apical administration, ZEN14Glc and ZEN16Glc can be detected in cellular extracts indicating uptake by intestinal cells. Moreover, the glucosylated forms were cleaved to release ZEN, with a different cleavage ability for the two conjugated isomers. In particular, ZEN16Glc seems to be less prone to deglycosylation compared to ZEN14Glc, probably on account of an increased steric hindrance. We could show that human cytosolic β-glucosidase is able to cleave ZEN14Glc liberating ZEN, but is unable to cleave ZEN16Glc.All metabolites could cross the cell membrane and be detected in the apical compartment, while ZEN was also found in the basolateral compartment together with the modified mycotoxin form. [ABSTRACT FROM AUTHOR]

The Fusarium mycotoxins HT-2 toxin (HT2) and T-2 toxin (T2) are frequent contaminants in oats. These toxins, but also their plant metabolites, may contribute to toxicological effects. This work describes the use of 13C-assisted liquid chromatography-high-resolution mass spectrometry for the first comprehensive study on the biotransformation of HT2 and T2 in oats. Using this approach, 16 HT2 and 17 T2 metabolites were annotated including novel glycosylated and hydroxylated forms of the toxins, hydrolysis products, and conjugates with acetic acid, putative malic acid, malonic acid, and ferulic acid. Further targeted quantitative analysis was performed to study toxin metabolism over time, as well as toxin and conjugate mobility within non-treated plant tissues. As a result, HT2-3-O-β-D-glucoside was identified as the major detoxification product of both parent toxins, which was rapidly formed (to an extent of 74% in HT2-treated and 48% in T2-treated oats within one day after treatment) and further metabolised. Mobility of the parent toxins appeared to be negligible, while HT2-3-O-β-D-glucoside was partly transported (up to approximately 4%) through panicle side branches and stem. Our findings demonstrate that the presented combination of untargeted and targeted analysis is well suited for the comprehensive elucidation of mycotoxin metabolism in plants. [ABSTRACT FROM AUTHOR]

The interactions between fungi and plants can yield metabolites that are toxic in animal systems. Certain fungi are known to produce sesquiterpenoid trichothecenes, such as T-2 toxin, that are biotransformed by several mechanisms including glucosylation. The glucosylated forms have been found in grain and are of interest as potential reservoirs of T-2 toxin that are not detected by many analytical methods. Hence the glucosides of trichothecenes are often termed “masked” mycotoxins. The glucoside of T-2 toxin (T2-Glc) was linked to keyhole limpet hemocyanin and used to produce antibodies in mice. Ten monoclonal antibody (Mab)-producing hybridoma cell lines were developed. The Mabs were used in immunoassays to detect T2-Glc and T-2 toxin, with midpoints of inhibition curves (IC50s) in the low ng/mL range. Most of the Mabs demonstrated good cross-reactivity to T-2 toxin, with lower recognition of HT-2 toxin. One of the clones (2-13) was further characterized with in-depth cross-reactivity and solvent tolerance studies. Results suggest Mab 2-13 will be useful for the simultaneous detection of T-2 toxin and T2-Glc.

The development of liquid chromatography-mass spectrometry (LC-MS)/mass spectrometry (MS) methods for the simultaneous detection and quantification of a broad spectrum of mycotoxins has facilitated the screening of a larger number of samples for contamination with a wide array of less well-known “emerging” mycotoxins and other metabolites. In this study, 83 samples of feed and feed raw materials were analysed. All of them were found to contain seven to 69 metabolites. The total number of detected metabolites amounts to 139. Fusarium mycotoxins were most common, but a number of Alternaria toxins also occurred very often. Furthermore, two so-called masked mycotoxins (i.e., mycotoxin conjugates), namely deoxynivalenol-3-glucoside (75% positives) and zearalenone-4-sulfate (49% positives), were frequently detected. Although the observed median concentrations of the individual analytes were generally in the low μg/kg range, evaluating the toxicological potential of a given sample is difficult. Toxicity data on less well-known mycotoxins and other detected metabolites are notoriously scarce, as an overview on the available information on the most commonly detected metabolites shows. Besides, the possible synergistic effects of co-occurring substances have to be considered.

The presence of mycotoxins in cereal grain is a very important food safety factor. The occurrence of “masked” mycotoxins has been intensively investigated in recent years. In this study, the occurrence of nivalenol, deoxynivalenol-3-glucoside, and deoxynivalenol in 92 samples of winter wheat from Polish cultivars was determined. The frequency of the occurrence of deoxynivalenol and nivalenol in the samples was 83% and 70%, respectively. The average content of the analytes was: for deoxynivalenol 140.2 µg/kg (10.5–1265.4 µg/kg), for nivalenol 35.0 µg/kg (5.1–372.5 µg/kg). Deoxynivalenol-3-glucoside, the formation of which is connected with the biotransformation pathway in plants, was present in 27% of tested wheat samples; its average content was 41.9 µg/kg (15.8–137.5 µg/kg). The relative content of deoxynivalenol-3-glucoside (DON-3G) compared to deoxynivalenol (DON) in positive samples was 4–37%. Despite the high frequency of occurrence of these mycotoxins, the quality of wheat from the 2016 season was good. The maximum content of DON, as defined in EU regulations (1250 µg/kg), was exceeded in only one sample. Nevertheless, the presence of a glycosidic derivative of deoxynivalenol can increase the risk to food safety, as it can be hydrolyzed by intestinal microflora.

Fusarium graminearum and Fusarium meridionale are primary contaminants of barley, capable of producing several mycotoxins, mainly type B trichothecenes and zearalenone. Cold plasma decontamination has been gaining prominence, seeking to control the fungal and mycotoxin contamination of food and feed and to improve product quality. To reach this objective, the present study was divided into two parts. In the first part, F. meridionale and F. graminearum strains were exposed to gliding arc plasma jet (GAPJ). Cell viability tests showed the inactivation of F. meridionale after 15-min treatment, whereas F. graminearum showed to be resistant. In the second part, barley grains were treated by GAPJ for 10, 20, and 30 min, demonstrating a reduction of about 2 log CFU/g of the barley's mycobiota, composed of yeasts, strains belonging to the F. graminearum species complex, Alternaria , and Aspergillus . A decrease in DON levels (up to 89%) was observed after exposure for 20 min. However, an increase in the toxin Deoxynivalenol-3-glucoside (D3G) was observed in barley grains, indicating a conversion of DON to D3G.