Chemical and toxicological alterations of zearalenone under ozone treatment

Our work mainly studied the elimination of zearalenone (ZEN) from corn flour by ozone treatment. We found four degradation products, after separation and identification by UPLC-ESI-QTOF-MS, named as Compound 1 (m/z 335.18), Compound 2 (m/z 351.19), Compound 3 (m/z 321.19) and Compound 4 (m/z 367.18). Then, one main transformation pathway was predicted on the basis of molecular weight and the reaction mechanism of ozone. We had also detected two of the degradation products by our modified UPLC-MS/MS method in real samples—contaminated corn flour. We screened the toxicity of the parent ZEN compound as well as the ozone induced decomposition products with BALB/c mice to evaluate the safety of our method in vivo. Therefore, aqueous ozone was demonstrated to effectively degrade ZEN and chemical structure alternations of ZEN after ozone treatment were predicted in both pure ZEN and real contaminated-corn flour samples. Considering the presence of the by-products formed, differences in the toxic effects on mice exposed to ZEN before and after the ozone treatment emphasise the significance of further study on the quality and toxicity of real food samples after ozone treatment.     

Natural co-occurrence of ochratoxin A,ochratoxin B and aflatoxins in Sicilian red wines

The natural occurrence of ochratoxin A, ochratoxin B, aflatoxin B₁, aflatoxin B₂, aflatoxin G₁ and aflatoxin G₂ (OTA, OTB, AFB₁, AFB₂, AFG₁, AFG₂) in red wines was investigated by HPLC/FLD after immunoaffinity column clean-up in 57 market samples produced in Sicily (Italy). The results showed a very low incidence of these mycotoxins in analysed samples, confirming the high degree of quality and safety of Sicilian red wines. The results indicated 71.9% and 64.9% positive samples for OTA and OTB respectively, with an average level of 0.13 μg l^–1, well below the European maximum permitted levels (MLs). The aflatoxin most frequently detected in the samples was AFG₁, present in 57.9% of samples, while the other aflatoxins were rarely present. Recovery experiments were carried out on eight mycotoxin-free red wines spiked with OTA, OTB, AFB₁, AFB₂, AFG₁ and AFG₂ at two different levels. The limits of detection (LODs) in wines were 0.02 µg l^–1 for OTA, 0.04 µg l^–1 for OTB, 0.03 µg l^–1 for AFG₁, AFG₂ and AFB₂, and 0.05 µg l^–1 for AFB₁. A good correlation was found, with good performances in term of precision for the method.     

Improvement of wine aromatic quality using mixtures of lysozyme and dimethyl dicarbonate,with low SO2 concentration

The use of sulphur dioxide (SO₂) in the treatment of foodstuffs presents some problems as it could lead to pseudo-allergies in some people. The aim of this research work was to study the addition of different preservative mixtures and their influence on the concentration of volatile compounds and sensorial quality in wine. To do so, vinifications were carried out using Garnacha must to which lysozyme, dimethyl dicarbonate (DMDC) and mixtures of these with SO₂ were added at different doses (25 and 50 mg l^?1). The results were compared with a control sample to which only SO₂ had been added (50 mg l^?1). In general, mixtures of SO₂ with lysozyme and DMDC favoured the formation of volatile compounds in the wines. Wines obtained from the mixtures of lysozyme and DMDC with 25 mg l^?1 of SO₂ had better sensorial quality than the wines obtained with 50 mg l^?1 as the only preservative used.     

Aflatoxins,ochratoxins and zearalenone in sorghum and sorghum products in Sudan

This survey examined 60 samples of sorghum and 30 samples of sorghum products from three states (Khartoum, Kordofan and Gadarif) of Sudan for aflatoxin B1, B2, G1 and G2 (AFB1, AFB2, AFG1, AFG2), ochratoxin A and B (OTA, OTB) and zearalenone (ZEN), using high performance liquid chromatography with fluorescence detection. The limits of detection and limits of quantification were in the range 0.01–0.6 µg kg^–1 and 0.03–2.0 µg kg^?1, respectively. The frequency of contaminated samples with AFB1 from Khartoum, Gadarif and Kordofan state was 38.1%, 22.2% and 23.8%, respectively. Only two samples of sorghum from Khartoum state were contaminated with OTA (3.3%). Concentrations of OTA and OTB were low and may not cause problems. No sample of sorghum or sorghum products was contaminated with ZEN. Some sorghum samples contained AFB1 concentrations above the European Union regulatory limits. The highest contaminated samples were found in Khartoum state.     

Aflatoxins and ochratoxin A in flour: a survey of the Serbian retail market

This report presents data on the occurrence of aflatoxins (AF) and ochratoxin A in different types of flour marketed in Serbia. A total of 114 samples of wheat, buckwheat, rye, oat, barley, rice, millet and corn flour were collected in the period 2012–2016 and analysed using high performance liquid chromatography with fluorescence detection. Among flours other than corn, AFB1 was quantified only in rice, while ochratoxin A (OTA) was found in 29% of the samples. In corn flours the percentage of positive samples varied greatly over the years: AFB1 7.1–80.0%, OTA 30.0–40.6%, with a co-occurrence of 7.1–34.4%. Overall 5.2% of flours other than corn and 10.7% of corn flours exceeded the maximum levels (MLs) for AFB1 and/or OTA. The highest recorded levels were 8.80 μg kg^?1 of AFB1 (corn) and 23.04 μg kg^?1 of OTA (rye). Overall mean contamination levels of corn flours were 0.53 μg kg^?1 of AFB1 and 0.46 μg kg^?1 of OTA.     

Analysis of Ochratoxin A in Wine by High-Resolution UHPLC-MS

A method for determination of ochratoxin A (OTA) in wines using a new-solid phase extraction clean-up procedure followed with ultra performance liquid chromatography (UHPLC)-Orbitrap MS based on two scan events (full-scan Fourier transform mass spectrometer [FTMS] and higher energy-induced collision dissociation[HCD] data-dependent MS/MS) in positive ionization mode has been developed. The limit of detection (LOD) was estimated at 0.46 μg l^?1 for white wine, 0.53 and 0.54 μg l^?1 for rosé and red wines, respectively. The limit of quantification (LOQ) was estimated at 1.57 μg l^?1 in white wine, 1.77 and 1.81 μg l^?1 in rosé and red wines. Recovery experiments were carried out with spiked samples at three concentration levels (2, 5 and 10 μg l^?1). The OTA recoveries in spiked white wine samples varied from 69.6 % to 99.8 %, while the recoveries for rosé and red wine samples were in the range of 63.0–110.2 % and 63.6–103.2 %, respectively. Finally, based on the results, it is concluded that the combination of C18 cartridge with conventional particle packed columns and UHPLC LTQ-Orbitrap XL is an appropriate procedure for OTA analysis in wines.     

Occurrence of biogenic amines in beers produced with malted organic Emmer wheat (Triticum dicoccum)

Because several groups of microorganisms are able to decarboxylate amino acids, the presence of biogenic amines (BA) can be seen as an index of the microbiological quality of the brewing process. BAs were quantified for the first time in the intermediate products and craft beers produced with malted organic Emmer wheat (Triticum dicoccum) in a small size brewery in order to assess the possible presence of critical control points related to biological hazard in the brewing process. BA levels in beers produced exclusively from malted organic Emmer wheat were between 15.4 and 25.2 mg l^–1 in the samples of light beer (Lt) and between 8.9 and 15.3 mg l^–1 in double malt beers (DM) ready for consumption (the beers stored for 90 days at 1–2°C). Cadaverine and tyramine were the main BAs in the Lt and DM beers, respectively. Increased concentrations of BAs seemed to be more related to the heat treatment of the processing product during mashing and wort boiling, rather than to the fermentation process. Much lower concentrations were found in finished beers obtained from 50% malted organic Emmer wheat and 50% malted barley (up to 3.2 mg l^–1) or from 30% malted Emmer wheat (up to 8.3 mg l^–1). Thus, Emmer wheat malt can be a useful alternative to wheat and spelt for the production of beer with a limited content of BA, if the processing technology is kept under control.     

Ochratoxin A in wines,musts and grape juices from Spain

A survey on the occurrence of ochratoxin A (OTA) in 240 grape‐based beverages was carried out. Red and white wines from four different Spanish Designations of Origin (n = 160), musts (n = 20), grape juices (n = 10), ordinary wines (n = 20), special wines (Malaga, muscatel, sherry, vermouth, etc) (n = 20) and sparkling wines (n = 10) were assayed for OTA content using immunoaffinity column clean‐up and high‐performance liquid chromatography with fluorimetric detection (detection limit 0.05 µg l^?1). Forty‐three (17.9%) of the samples tested contained detectable levels of OTA. The overall mean OTA concentration in red and white wines of Designations of Origin was 0.30 and 0.18 µg l^?1 respectively (ranges 0.05–3.19 and 0.05–1.13 µg l^?1 respectively). The percentage of wine samples with detectable amounts of OTA was higher for red (18.3%) than for white (10%) wines. OTA was also found in two of 10 red ordinary wines (0.68 and 4.24 µg l^?1), whereas none of 10 white ordinary wines contained OTA. The mean OTA amount detected in sparkling wines was 0.44 µg l^?1 (range 0.14–0.71 µg l^?1). Two of 20 must samples contained OTA at low levels (0.08 and 0.18 µg l^?1), while none of 10 grape juice samples contained OTA. Highest amounts of OTA were found in special wines (45%), with a maximum of 15.25 µg l^?1 in a muscatel sample. Copyright © 2004 Society of Chemical Industry     

Lead excretion in milk of accidentally exposed dairy cattle

Lead (Pb) exposure in dairy cattle is associated with economic losses due to mortality and treatment costs, but with production animals there is also risk to the human food chain. The first objective of this study was to quantify the Pb concentration in milk from Pb-exposed cattle. The second objective was to correlate blood and milk Pb concentrations from individual cows. The third objective was long-term monitoring to determine the duration of milk contamination after exposure ceased. A dairy herd of more than 100 cows was accidentally exposed to Pb-contaminated feed. Milk and blood were collected for Pb analysis. Serial collection of milk samples continued for 2.5 years. The initial concentration of Pb in bulk tank milk was 0.0999 mg l^–1. The highest milk Pb concentration from an individual cow was 0.4657 mg l^–1 and the highest blood Pb concentration was 1.216 mg l^–1. One milk sample collected at the end of the study (day 922) contained 0.0117 mg Pb l^–1 of Pb. The calculated relationship between milk (y) and blood (x) Pb concentration was ln(y) = 3.4(x) – 2.21 (R² = 0.98).     

磁控双色上转换荧光适配体传感器同时检测玉米和燕麦粉中的赭曲霉毒素A与玉米赤霉烯酮

目的 建立上转换荧光法同时检测食品中赭曲霉毒素A（ochratoxin A,OTA）与玉米赤霉烯酮（zearalenone,ZEN）的含量 方法 利用溶剂热法合成了两种油酸封端的核壳型上转换纳米材料,通过表面改性法和戊二醛法制备了表面分别偶联OTA、ZEN适配体的核壳型上转换荧光探针。同时制备了表面原位生长四氧化三铁纳米颗粒的二硫化钼纳米片,作为淬灭剂。OTA、ZEN和适配体特异性结合后,通过磁分离后检测溶液的荧光强度值,从而实现OTA和ZEN浓度的检测。结果 该方法在最佳检测条件下,OTA与ZEN的浓度在0.05~500.00 ng/mL的线性检测范围内,与两种上转换荧光探针的荧光强度的对数值呈良好的线性关系,相关系数分别为0.9949和0.9972,对OTA的检测限为3.97×10-2 ng/mL,对ZEN的检测限为3.11×10-2 ng/mL,应用于玉米粉和燕麦粉中OTA和ZEN的检测,加标回收率为91.7%~109.4%。结论 该方法成功检测灵敏度较高,并具有较好的特异性,可用于食品中OTA和ZEN的高灵敏检测。     

Microbial decontamination of black pepper by ozone and the effect of the treatment on volatile oil constituents of the spice

The use of ozone as a substitute for ethylene oxide to decontaminate whole black peppercorn and ground black pepper and the effects of ozone on the volatile oil constituents of the spice were studied. Black peppercorns were immersed in water and sparged with ozonised air (ozone concentration, 6·7 mg litre^?1) for 10 min at an air flow rate of 6 litre min^?1. This treatment reduced the microbial population of peppercorn by 3–4 log numbers. Ground black pepper with various moisture levels was sparged with ozonised air for up to 6 h. This treatment reduced the microbial population by 3–6 log numbers, depending on the moisture content of the spice. Higher moisture content led to a greater reduction in microbial load. The volatile oil constituents of the spice with and without ozone treatment were extracted with isopropyl ether and analysed by gas chromatography and gas chromatography-mass spectrometry. Ozone treatment of ground black pepper resulted in the oxidation of certain volatile oil constituents while the treatment had no significant effect on the volatile oil constituents of whole peppercorn.     

Fluoride content of soft drinks,nectars, juices,juice drinks,concentrates, teas and infusions marketed in Portugal

A potentiometric method using a fluoride combination ion-selective electrode was validated and used to analyse 183 samples, including soft drinks, juices, nectars, juice drinks, concentrates, teas and infusions marketed in Portugal. The fluoride levels were higher in extract-based soft drinks, juice drinks and juice, with fluoride values of 0.86 ± 0.35, 0.40 ± 0.24 and 0.37 ± 0.11 mg l^?1, respectively. The lowest fluoride concentration was found in infusion samples (0.12 ± 0.01 mg l^?1), followed by teas and carbonated soft drinks with fluoride concentrations of 0.16 ± 0.12 and 0.18 ± 0.07 mg l^?1, respectively. Nectars, concentrates and juice-based drinks had similar fluoride concentrations of 0.33 ± 0.16, 0.29 ± 0.12 and 0.25 ± 0.14 mg l^?1, respectively. The fluoride concentrations in all these samples would only contribute intakes below the acceptable daily intake (ADI = 0.05 mg kg^?1 body weight day^?1), indicating that, individually, these beverages cannot induce fluoride toxicity in the population group of children.     

Determination of the exposure parameters that maximise the concentrations of the anaesthetic/sedative eugenol in rainbow trout (Oncorhynchus mykiss) skin-on fillet tissue

Studies were conducted to determine the anaesthetic/sedative concentrations and durations that would maximise anaesthetic/sedative residue concentrations in rainbow trout (Oncorhynchus mykiss) skin-on fillet tissue. Rainbow trout (167–404 g) were exposed to 50 mg l^?1 AQUI-S^® 20E (10% active ingredient, eugenol) in 17°C freshwater for durations up to 1440 min, 100 and 250 mg l^?1 AQUI-S^® 20E for durations up to 240 min, and 500 and 1000 mg l^?1 AQUI-S^® 20E for durations up to 90 min. Fish exposed to 100 mg l^?1 AQUI-S^® 20E for durations of 30, 60, 120 and 240 min had the greatest eugenol concentrations in the fillet tissue, 50, 58, 54 and 62 µg g^?1, respectively. All other exposure concentrations and durations resulted in significantly lower eugenol concentrations, i.e. all < 39 µg g^?1.     

Effect of post-harvest treatments on the occurrence of ochratoxin A in raw cocoa beans

Cocoa beans are the principal raw material for chocolate manufacture. Moulds have an important place in the change in the quality of cocoa beans due to their role in the production of free fatty acids and mycotoxins, namely ochratoxin A (OTA). This study investigated the impact of the key post-harvest treatments, namely the fermentation and drying methods on OTA contamination of raw cocoa beans. Analytical methods for OTA detection were based on solid–liquid extraction, clean-up using an immunoaffinity column, and identification by reversed-phase HPLC with fluorescence detection. Of a total of 104 randomly selected cocoa samples analysed, 32% had OTA contents above 2 µg kg^–1. Cocoa sourced from pods in a bad state of health had a maximum OTA content of 39.2 µg kg^–1, while that obtained from healthy pods recorded 11.2 µg kg^–1. The production of OTA in cocoa beans increased according to the pod-opening delay and reached 39.2 µg kg^–1 after an opening delay of 7 days after harvest, while 6.1 and 11.2 µg kg^–1 were observed when pods were opened after 0 and 4 days. OTA production also seemed to depend considerably to the cocoa fermentation materials. When using plastic boxes for bean fermentation, the OTA production was enhanced and reached an average OTA content of about 4.9 µg kg^–1, while the raw cocoa treated in banana leaves and wooden boxes recorded 1.6 and 2.2 µg kg^–1 on average respectively. In parallel, the OTA production was not really influenced by either the mixing or the duration of the fermentation or the drying materials.     

A simple,rapid and novel method based on salting-out assisted liquid–liquid extraction for ochratoxin A determination in beer samples prior to ultra-high-performance liquid chromatography coupled to tandem mass spectrometry

A novel, simple, easy and cheap sample treatment strategy based on salting-out assisted liquid-liquid extraction for ochratoxin A (OTA) ultra-trace analysis in beer samples using ultra-high-performance liquid chromatography-tandem mass spectrometry determination was developed. The factors involved in the efficiency of pre-treatment were studied employing factorial design in the screening phase and the optimal conditions of the significant variables on the analytical response were evaluated using a central composite face-centred design. Consequently, the amount of salt ((NH₄)₂SO₄), together with the volumes of sample, hydrophilic (acetone) and nonpolar (toluene) solvents, and times of vortexing and centrifugation were optimised. Under optimised conditions, the limits of detection and quantification were 0.02 µg l^?1 and 0.08 µg l^?1 respectively. OTA extraction recovery by SALLE was approximately 90% (0.2 µg l^?1). Furthermore, the methodology was in agreement with EU Directive requirements and was successfully applied for analysis of beer samples.     

臭氧降解玉米中赭曲霉毒素A的效果及对玉米脂肪酸的影响

针对粮食贮藏过程中真菌污染造成的食用安全性问题,探讨臭氧在玉米储藏中的应用可行性。以玉米中易污染的赭曲霉毒素A(OTA)为研究对象,在不同质量浓度臭氧,不同处理时间下,考察臭氧对OTA的降解效果,以及对玉米脂肪酸的影响。结果表明：30g/m3臭氧处理120min或者60g/m3臭氧处理90min能将80μg/L的OTA标准品几乎降解完全;利用60g/m3臭氧处理10h能有效的将玉米中污染80μg/kg OTA降解到安全范围(5μg/kg)以下,并且臭氧处理对玉米脂肪酸无显著影响。说明臭氧可有效降解玉米储藏中污染的OTA,并且不会破坏其中的不饱和脂肪酸,初步证明臭氧在玉米储藏中应用的可行性。     

Evaluation of an ozone–slurry ice combined refrigeration system for the storage of farmed turbot (Psetta maxima)

The use of ozonised slurry ice was investigated as a new refrigeration system for the storage of farmed turbot (Psetta maxima). With this purpose in mind, an ozone generator device was coupled to a slurry ice system working subzero at −1.5 °C. The ozone concentration was adjusted to a redox potential of 700 mV, and the slurry ice biphasic mixture was prepared at a 40% ice/60% water ratio and 3.3% salinity. Certain biochemical parameters indicative of fish freshness, such as the rate of nucleotide degradation or TMA-N formation, were not significantly affected by the presence of ozone in the slurry ice mixture. However, storage in ozonised slurry ice significantly slowed down the mechanisms responsible for lipid hydrolysis and lipid oxidation in farmed turbot. Storage in ozonised slurry ice also led to significantly (p < 0.05) lower counts of both total aerobes and psychrotrophic bacteria in both turbot muscle and skin, as compared with the control batch stored without ozone. Sensory analyses confirmed an extended shelf life of turbot specimens stored in ozonised slurry ice; these maintaining “A” sensory quality up to day 14, while the counterpart batch stored in slurry ice kept this quality only up to day 7. The combination of ozone and slurry ice may be recommended for the chilling and storage of farmed turbot with a view to extending its shelf-life.     

Aflatoxins and ochratoxin A in export quality raisins collected from different areas of Pakistan

During 2012–2014, 170 samples of export quality raisins were collected from different vendors in Pakistan. The collected samples were analysed for the presence of aflatoxins (AFs) and Ochratoxin A (OTA) contamination using high-performance liquid chromatography technique. The limit of detection and limit of quantification of AFs/OTA were 0.12/0.10 and 0.36/0.30 µg kg^?1, respectively. Only 5% of the samples were contaminated with AFs, ranging 0.15–2.58 µg kg^?1 with a mean of 0.05 ± 0.26 µg kg^?1. None of the raisin samples exhibited AFs contamination above the maximum limit (ML = 4 µg kg^?1) as set by the European Union (EU). About 72% of the samples were contaminated with OTA, ranging 0.14–12.75 µg kg^?1 with a mean of 2.10 ± 1.9 µg kg^?1. However, in 95.3% of the tested samples, OTA level was lower than the ML of 10 µg kg^?1 as regulated by the EU. Apparently, a strict and continuous monitoring plan, including regulatory limits, improves food safety and quality for all types of commodities.     

Tissue distribution and elimination of deoxynivalenol and ochratoxin A in dietary-exposed Atlantic salmon (Salmo salar)

ABSTRACT

Post-smolt Atlantic salmon (Salmo salar) were fed standard feed with added 2 or 6 mg kg^–1 pure deoxynivalenol (DON), 0.8 or 2.4 mg kg^–1 pure ochratoxin A (OTA), or no added toxins for up to 8 weeks. The experiments were performed in duplicate tanks with 25 fish each per diet group, and the feed was given for three 2-h periods per day. After 3, 6 and 8 weeks, 10 fish from each diet group were sampled. In the following hours after the last feeding at 8 weeks, toxin elimination was studied by sampling three fish per diet group at five time points. Analysis of DON and OTA in fish tissues and plasma was conducted by liquid chromatography-mass spectrometry and high-pressure liquid chromatography with fluorescence detection, respectively. DON was distributed to the liver, kidney, plasma, muscle, skin and brain, and the concentrations in liver and muscle increased significantly from 3 to 8 weeks of exposure to the high-DON diet. After the last feeding at 8 weeks, DON concentration in liver reached a maximum at 1 h and decreased thereafter with a half-life (t_1/2) of 6.2 h. DON concentration in muscle reached a maximum at 6 h and was then eliminated with a t_1/2 = 16.5 h. OTA was mainly found in liver and kidney, and the concentration in liver decreased significantly from 3 to 8 weeks in the high-OTA group. OTA was eliminated faster than DON from various tissues. By using Norwegian food consumption data and kinetic findings in this study, we predicted the human exposure to DON and OTA from fish products through carryover from the feed. Following a comparison with tolerable daily intakes, we found the risk to human health from the consumption of salmon-fed diets containing maximum recommended levels of these toxins to be negligible.     

In vivo toxicity assessment of deoxynivalenol-contaminated wheat after ozone degradation

ABSTRACT

The effect of ozone on deoxynivalenol (DON) detoxification was investigated. Ozone treatment could significantly reduce the levels of DON in wheat; 53% of DON in wheat was decomposed with 90 mg l^–1 of ozone at a flow rate of 15 l min^–1 for 4 h. The safety of DON-contaminated wheats (DCWs) untreated/treated by ozone was also evaluated. Institute of Cancer Research (ICR) mice were divided into a standard diet group and five experimental diet groups for a 51-day orally administration experiment. In the experiment, no remarkable changes in the general appearance of the mice were observed, and all the mice survived until the scheduled necropsy. The results of sub-chronic toxicity indicated that mice fed on DCWs alone had significantly decreased in body weight gain, thymus and spleen weights, ratios of liver, thymus and spleen to body weight, blood indices (red blood cell, haemoglobin, white blood cell), and pro-inflammatory cytokines (interleukin-6 (IL-6), tumour necrosis factor alpha (TNF-α)), while showing a significant increase in alanine aminotransferase, aspartate aminotransferase, blood creatinine and blood urea nitrogen levels. Histopathological examination indicate that DON elicited some degree of toxicity on the liver, kidney and thymus tissue. Mice fed on DCWs treated by ozone mitigated the adverse effects compared with mice fed on DCWs. All the results suggested that the deleterious effects of DON could be highly reduced by ozone, and ozone itself shows minor toxic effects on animals in this process.