Extraction of Triterpenic Acids and Phytosterols from Apple Pomace with Supercritical Carbon Dioxide: Impact of Process Parameters, Modelling of Kinetics, and Scaling-Up Study.

Apple pomace, a byproduct of juice production, is a rich source of bioactive compounds and nutrients. Supercritical fluid extraction was proposed as a method for a fast and selective extraction of hydrophobic compounds with a pharmaceutical potential from this matrix. Chromatographic analysis showed that the pomace contained significant amounts of such substances, the most abundant of them were ursolic acid, oleanolic acid, and ß-sitosterol. The solubility was chosen as a primary factor for a selection of the extraction conditions; the best results were acquired for a temperature of 80 °C and a pressure of 30 MPa. The equation proposed by Chrastil was applied for the description of the impact of the process parameters on the solubility of the analytes; the obtained values of coefficients of determination were satisfactory, despite the fact that the equation was developed for binary systems. The extraction curves obtained during the experiments were used for the description of the process kinetics using the Broken plus Intact Cell model. The impact of the temperature, pressure, and flow rate of carbon dioxide on the mass transfer phenomena was investigated. The data obtained allowed the prediction of the extraction curve for the process conducted on the larger scale.

Modified Fusarium Mycotoxins in Cereals and Their Products-Metabolism, Occurrence, and Toxicity: An Updated Review.

Mycotoxins are secondary fungal metabolites, toxic to humans, animals and plants. Under the influence of various factors, mycotoxins may undergo modifications of their chemical structure. One of the methods of mycotoxin modification is a transformation occurring in plant cells or under the influence of fungal enzymes. This paper reviews the current knowledge on the natural occurrence of the most important trichothecenes and zearalenone in cereals/cereal products, their metabolism, and the potential toxicity of the metabolites. Only very limited data are available for the majority of the identified mycotoxins. Most studies concern biologically modified trichothecenes, mainly deoxynivalenol-3-glucoside, which is less toxic than its parent compound (deoxynivalenol). It is resistant to the digestion processes within the gastrointestinal tract and is not absorbed by the intestinal epithelium; however, it may be hydrolysed to free deoxynivalenol or deepoxy-deoxynivalenol by the intestinal microflora. Only one zearalenone derivative, zearalenone-14-glucoside, has been extensively studied. It appears to be more reactive than deoxynivalenol-3-glucoside. It may be readily hydrolysed to free zearalenone, and the carbonyl group in its molecule may be easily reduced to α/ß-zearalenol and/or other unspecified metabolites. Other derivatives of deoxynivalenol and zearalenone are poorly characterised. Moreover, other derivatives such as glycosides of T-2 and HT-2 toxins have only recently been investigated; thus, the data related to their toxicological profile and occurrence are sporadic. The topics described in this study are crucial to ensure food and feed safety, which will be assisted by the provision of widespread access to such studies and obtained results.

Natural Occurrence of Nivalenol, Deoxynivalenol, and Deoxynivalenol-3-Glucoside in Polish Winter Wheat.

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.

Dietary risk evaluation for 28 polycyclic aromatic hydrocarbons (PAHs) in tea preparations made of teas available on the Polish retail market.

The aim of this work was to assess dietary risk resulting from consumption of polycyclic aromatic hydrocarbons (PAHs) with tea infusions. To this end, levels of 28 PAHs in black, green, red and white teas available on the Polish retail market have been assessed. Profiles and correlation between concentrations of individual PAHs have been identified. A model study on transfer of PAHs from tea leaves into tea preparations has been conducted. Relatively high concentrations of 28 evaluated PAHs have been found in 58 tested samples of black, green, red and white teas sampled on the Polish retail market. Total concentration ∑28PAH ranged from 57 to 696 µg kg-1 with mean 258 µg kg-1 (dry tea leaves). The most mature tea leaves fermented to a small degree contained relatively the highest PAH levels among all four tested tea types. Relatively low PAH transfer rates into tea infusions and limited volumes of the consumed tea keep the risks associated with PAH dietary intake at a safely low level. The worst-case scenario dietary intake values were 7.62/0.82/0.097 ng kg-1 b.w. day-1 (estimated on the basis of the maximum found concentrations 696/113/23 µg kg-1 and maximum observed transfer rates 24/16/9%) for ∑28PAH/∑PAH4/B[a]P, respectively. MOE values calculated using the above worst case estimates exceeded 700,000 and 400,000 (BMDL10 0.07 and 0.34 mg kg-1 b.w. day-1) for B[a]P and PAH4, respectively. Both B[a]P and PAH4 concentrations may be used as indicators of total PAH concentration in tea leaves; PAH4 slightly better fits low molecular weight PAHs. Several correlations between various PAHs/groups of PAHs have been identified, the strongest one (R2 = 0.92) between PAH4 and EU PAH 15+1.

Effects of pH and Temperature on the Stability of Fumonisins in Maize Products.

This paper is a study of the stability of fumonisins in dough based on maize flour prepared in a phosphate buffer with a pH of 3.5, 5.5 or 7.5 and baked at a temperature within the range of 100-250 °C. Buffers with various pH values were tested, since it is well-known that pH may significantly influence interactions of fumonisins with other substances. A standard analytical procedure was used to determine the concentration of free fumonisins. Hydrolysis in an alkaline medium was then applied to reveal the hidden forms, while the total fumonisins concentations was determined in another measurement. The total concentration of fumonisins was statistically higher in pH = 3.5 and pH = 5.5 than the concentration of free fumonisins; no similar difference was found at pH = 7.5. The applied phosphate buffer pH 7.5 may enhance solubility of fumonisins, which would increase extraction efficiency of free analytes, thereby decreasing the difference between concentrations of total and free fumonisins. Hydrolysed B1 fumonisin (HFB1) and partially hydrolysed B1 fumonisin (isomers a and b: PHFB1a and PHFB1b, respectively) were the main investigated substances. For baking temperatures below 220 °C, fumonisins were slightly more stable for pH = 5.5 than for pH = 3.5 and pH = 7.5. In both of these latter cases, the concentration of partially hydrolysed fumonisins grew initially (up to 200 °C) with an increase in the baking temperature, and then dropped. Similar behaviour was observed for free HFB1, which may suggest the following fumonisin degradation mechanism: initially, the tricarballylic acid (TCA) groups are removed from the molecules, and next, the HFB1 molecules disintegrate.

Levels of Selected Persistent Organic Pollutants (PCB, PBDE) and Pesticides in Honey Bee Pollen Sampled in Poland.

Chemical plant protection is a commonly discussed factor potentially responsible for decline in pollinators and other beneficial insect populations. Various groups of chemicals including persistent organic pollutants could impact a bee colony's welfare and are reported to be present in bee tissue and apiary products. The aim of this work was to evaluate the presence of selected persistent organic pollutant and pesticide residues in bee pollen originating from different geographical regions of Poland. Pesticide residues were identified in 60% of tested bee pollen samples. The compounds identified were mainly active ingredients of fungicide preparations. Insecticide active ingredients were up to 30% of the identified residues. The triazole fungicide tebuconazole and the neonicotinoid insecticide thiacloprid were the most frequently found pesticides in pollen. The highest pesticide concentration was determined for prothioconazole (356 µg kg-1). Mean concentrations of chlorinated biphenyls-EC6 and EC12 were 194 pg g-1 and 74 pg g-1, respectively. CB # 28 has the greatest share in the EC6 profile (mean 61 pg g-1, 31% contribution). Relatively high contributions were also observed for CBs # 101 (35 pg g-1, 18%), # 138 (36 pg g-1, 19%) and # 153 (33 pg g-1, 17%). CB # 114 and 118 have the highest share in the dioxin-like biphenyls fraction with mean concentrations of 17.6 and 37.6 pg g-1 (respectively 23 and 50%). Mean calculated concentrations of 39 polybrominated diphenyl ether congeners (Σ39 BDE) were 20 ± 27.7 pg g-1. High variability was observed between maximal and minimal determined concentration values. Individual BDEs were found at different frequencies and varying concentration levels. BDEs # 47, 75 and 99 dominated the profile with average concentrations of 3 pg g-1, 3.1 pg g-1, and 2.9 pg g-1, respectively.

Occurrence of 26 Mycotoxins in the Grain of Cereals Cultivated in Poland.

The levels of 26 mycotoxins were determined in 147 samples of the grain of cereals cultivated in five regions of Poland during the 2014 growing season. The HPLC-HRMS (time-of-flight) analytical technique was used. An analytical procedure to simultaneously determine 26 mycotoxins in grain was developed, tested and verified. Samples from eastern and southern Poland were more contaminated with mycotoxins than the samples from northern and western Poland. Toxins produced by Fusarium fungi were the main contaminants found. Some deoxynivalenol (DON) was found in 100% of the tested samples of wheat (Osiny, Borusowa, Werbkowice), triticale, winter barley and oats, while the maximum permissible DON level (as defined in the EU Commission Regulation No. 1881/2006) was exceeded in 10 samples. Zearalenone (ZEN), DON metabolites and enniatins were also commonly found. The presence of mycotoxins in grain reflected the prevailing weather conditions during the plant flowering/earing stages, which were favorable for the development of blight. Among all investigated wheat genotypes, cv. Fidelius was the least contaminated, while Bamberka, Forkida and Kampana were the most contaminated. However, the single-factor ANOVA analysis of variance did not reveal (at a statistical significance level α = 0.05) any differences between levels of mycotoxins in individual genotypes. Triticale was the most contaminated grain among all of the tested varieties. ZEN, DON and the sum of 3-acetyldexynivalenol and 15-acetyldeoxynivalenol (3- and 15-ADON) were found in 100% of the tested triticale samples at concentrations within the 4-86, 196-1326 and 36-374 µg·kg(-1) range, respectively. Of particular concern was the fact that some "emerging mycotoxins" (enniatins) (in addition to commonly-known and legally-regulated mycotoxins) were also found in the tested triticale samples (enniatin B (Enn-B), enniatin B1 (Enn-B1), enniatin A-1 (Enn-A1), 100% of samples, and enniatin A (Enn-A), 70% of samples). Depending on the toxin, they were found at levels between 8 and 3328 µg·kg(-1).

Intra-strains diversity of expression of polymorphic PKS4 gene in comparison in zearalenone production by Fusarium graminearum during in vitro cultivation.

Filamentous fungi belonging to the Fusarium genus are responsible for large economic losses due to their high pathogenicity and toxigenicity. Fusarium sp. may produce variety of mycotoxins, one of them is zearalenone (ZEA). The presence of the PKS4 gene shows the possibility of zearalenone biosynthesis by Fusarium sp. In this study, in four Fusarium graminearum and one Fusarium poae strains the presence of PKS4 genes and ZEA concentrations were determined. The presence of the PKS4 gene was confirmed by classical polymerase chain reaction (PCR) in three of four strains of F. graminearum. One strain with no PKS4 gene detected was found while still producing ZEA. In the present study, a real-time PCR assay has been successfully performed for the relative expression of Fusarium strains based on new designed primers targeting the PKS4 gene involved in ZEA biosynthesis. Result shows that P56/4 strain of F. graminearum has the highest mRNA level, in the range of 12, what correlates to the high production of this mycotoxin. In this study, a real-time PCR assay has been successfully developed for the prediction of the production of ZEA by F. graminearum strains by PCR real-time techniques based on primers targeting the gene, PKS4, involved in ZEA biosynthesis. The special significance was pointed to occurring genes polymorphism.

Simultaneous separation of chlorinated/brominated dioxins, polychlorinated biphenyls, polybrominated diphenyl ethers and their methoxylated derivatives from hydroxylated analogues on molecularly imprinted polymers prior to gas/liquid chromatography and mass spectrometry.

Polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs), polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) are important contaminants in the environment. In recent years also polybrominated dibenzo-p-dioxins/dibenzofurans (PBDD/Fs) have been reported as emerging environmental stressors. It has been suggested that hydroxylated polybrominated biphenyl ethers (OH-BDEs) are important - may be even the most important - precursors of brominated dioxins/furans. The aim of this study was to develop a robust, time-saving analytical procedure to collectively separate in animal tissues such compounds prior to determination of individual substances with a gas/liquid chromatograph coupled to an ion trap/time-of-flight mass spectrometer (GC/IT-MS or UPLC/TOF-MS). Two OH-CB/BDE separation methods including alkaline extraction and molecularly imprinted polymers (MIP) were compared. Performance of both methods was validated: absolute recovery values were in the 47-90% range depending on the compound, while recovery relative standard deviation was below 20% in most cases. Levels of the studied compounds have been assessed in some real life samples.

Photochemistry of tetra- through hexa-brominated dioxins/furans, hydroxylated and native BDEs in different media.

The aim of this study was to investigate (i) the behavior of native PBDEs during UV irradiation in different media, (ii) the possibility of their transformation into hydroxylated PBDEs in aqueous media, and (iii) the photochemistry/levels of brominated dioxins/furans formed from hydroxylated PBDEs. Debromination leading to the formation of a wide range of low-brominated congeners was the main path of photocatalyzed transformations of PBDEs. In organic solvents other than toluene, BDEs degraded in line with the pseudo first order kinetics (10-20 min half-life, depending on congener type and reaction medium). Irradiated BDE 209 congener behaved quite differently than lower-brominated BDEs: detectable amounts of various bromo-benzenes were found. That suggests that UV irradiation of BDE 209 leads to cleavage of the ether bound between the congener's aromatic rings. Formation of bromophenyl bromo-methyl-biphenyl ethers or benzyl-bromophenoxybenzenes was observed in irradiated PBDE toluene-based solutions. The total concentration of OH-BDEs found in the reaction medium did not exceed 0.2% of the initial precursor mass. Moreover, lower-brominated congeners detected in the reaction medium indicate subsequent debromination of OH-BDEs or hydro-debromination of the degraded congeners. Brominated dioxins and low levels of furans were observed in samples containing OH-BDEs. The total mass of dioxins did not exceed 3.5% of the initial precursor mass.

Fate of PBDEs during food processing: Assessment of formation of mixed chlorinated/brominated diphenyl ethers and brominated dioxins/furans.

The aim of this study was to evaluate effects of food processing on PBDE levels, in particular influence of heat treatment on degradation of PBDEs, including possible formation of chlorinated diphenyl ethers or brominated dioxins/furans as degradation products. It was shown that PBDEs heated in the presence of chlorine (from either organic or inorganic sources) formed mixed chlorinated/brominated diphenyl ethers. However, no PCDEs were formed in the presence of lipids. Lipid medium increased stability of PBDEs exposed to UV irradiation. Profile of congeners formed in result of the debromination reaction was significantly different than profiles observed by some other authors in aliphatic organic solvents. Grilling processes increased concentrations (calculated on the fresh product basis) of the studied compounds by 4-8/22-34% for electric/coal grill, respectively. Depending on the congener and on the applied heat treatment, PBDE mass in pork meat after grilling dropped by 26-53%. No detectable quantities of either brominated dioxins or furans were formed during thermal processing of food containing typical levels of PBDEs.

Preliminary study on brominated dioxins/furans and hydroxylated/methoxylated PBDEs in Baltic cod (Gadus morhua) liver. Comparison to the levels of analogue chlorinated co-occurring pollutants.

Low pg levels of PBDD/Fs in 0.8-38.9 pg g(-1) (fat) range (mean 14.2 pg g(-1)) observed in the tested cod liver samples were significantly lower than levels of their chlorinated analogues (25.1-95.9 range, 37.7 mean pg g(-1) fat). Brominated furans dominated the congener profile. Elevated levels of OH-/MeO-BDE were however observed with mean concentrations at 2769±1319 and 5441±2918 pg g(-1) (fat) respectively. The observed congener profiles with the predominance of 6-OH-BDE 47 and the relatively high proportion between the native and hydroxylated compounds indicate on natural origin of those compounds or at least presence of various exposure sources. A large fraction of studied samples did not comply with the currently standing EU regulations concerning PCBs and chlorinated dioxins (11%), especially as regards non-dioxin like PCBs (88%).

Application of Liquid Chromatography/Ion Trap Mass Spectrometry Technique to Determine Ergot Alkaloids in Grain Products.

A liquid chromatography/ion trap mass spectrometry-based method to determine six ergot alkaloids and their isomers is presented. The samples were cleaned on neutral alumina-based solid-phase extraction cartridges. The following method parameters were obtained (depending on the analyte and spiking level): method recovery from 63.0 to 104.6%, relative standard deviation below 18%, linear range from 1 to 325 µg/kg, linear correlation coefficient not less than 0.98. The developed analytical procedure was applied to determine the levels of ergot alkaloids in 65 samples of selected rye-based food products (flour - 34 samples, bran - 12 samples, rye - 18 samples, flakes - 1 sample). Measurable levels of alkaloids were found in majority of the analysed samples, particularly in rye flour. Additionally, alkaloids were determined in ergot sclerotia isolated from rye grains. Total content was nearly 0.01% (97.9 mg/kg). However, the alkaloid profile was dominated by ergocristine at 45.6% (44.7 mg/kg), an alkaloid not commonly found in the tested food products. Ergocorninine at 0.2% (0.2 mg/kg) was the least abundant alkaloid.

Effect of baking on reduction of free and hidden fumonisins in gluten-free bread.

The aim of the present work was to assess the influence of the baking process on the fumonisin content in gluten-free bread. The dough was made using two methods: without sourdough and with sourdough. Fumonisins were determined using high-performance liquid chromatography with ion-trap mass spectrometry. This study showed that the bread baking process caused a statistically significant drop in the mean concentration of free fumonisins: the reduction levels were 30 and 32% for the direct and sourdough-based methods, respectively. The lower reduction after baking was observed for hidden fumonisins: 19 and 10%, respectively. The presence of some compounds (such as proteins or starch) capable of stabilizing fumonisins during the baking process might be responsible for the observed increase in the hidden-to-free ratio from an initial 0.72 in flour to 0.83 in bread made from sourdough and to 0.95 in sourdough-free bread.

Influence of hen breeding type on PCDD/F, PCB & PBDE levels in eggs.

The aim of this study was to assess levels of PCDD/Fs, PCBs and PBDEs in free range eggs and in farm eggs available on the Polish retail market. Congener profiles that might be used to identify different sources of contamination have also been assessed. Generally higher mean values of PCDD/F, PCB and PBDEs found in free range eggs than in farm eggs reflect occurrence of highly contaminated samples. However, medians were similar in both groups; PCDD/F medians were even higher in farm eggs. High concentrations (accompanied by changed congener profile) indicate contamination sources other than environmental background. Congener profiles and absolute concentration values found in majority of the tested samples from both groups were typical for environmental background of the studied persistent organic pollutants. Due to their small market share free range eggs do not seem to pose any essential threat to human health.

Seasonal variability of polychlorinated biphenyls (PCBs) and polychlorinated diphenyl ethers (PBDEs) congener profiles in butter in Poland: dietary risk evaluation.

Various statistical methods have been employed to analyse in details seasonal diversification of polychlorinated biphenyl (PCB)/polybrominated diphenyl ether (PBDE) congener profiles found in butter fat. The variability of the PCB/PBDE congener profiles indicates the presence of various sources of the milk fat contamination. The obtained results suggest that the environmental chemical background has the highest share in the contamination sources pattern. Ion trap mass spectrometry coupled to high-resolution gas chromatography with semi-permeable membrane dialysis sample cleanup was used for determination of PCBs and PBDEs in milk fat. Determined butter fat PCB profiles were similar to the profiles characteristic for Aroclor 1254 technical mixture. Our data indicate that dietary intake of PCB/PBDE with milk and milk products may be estimated to be about 717.5 pg kg b.w.(-1) day(-1) for six-indicator PCBs, 0.329 (equivalent toxicity, TEQ) pg kg b.w.(-1) day(-1) for 12 DL PCBs and 50 pg kg b.w.(-1) day(-1) for PBDEs (sum of 14 congeners).

Polychlorinated biphenyls (PCBs), polychlorinated diphenyl ethers (PBDEs) and organochlorine pesticides in selected cereals available on the Polish retail market.

Polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), and organochlorine pesticides (DDT, HCH, HCB, chlordane, endrin, dieldrin, aldrin, nitrophene, metoxychlor) are man-made chemicals manufactured for numerous applications. The aim of this study was to assess levels of PCBs, PBDEs, and organochlorine pesticides in selected types of cereals available on the Polish retail market. 191 samples of various cereals have been analyzed in total. Average EC6 concentrations ranged from 56.4 (snacks) to 442.2 pg g(-1) (bran) while the concentration of 12 dioxin-like PCBs was in 15 (groats)-37.6 pg g(-1) (snacks) range. Mean dioxin equivalency concentration calculated as lower bound results in 2005 TEF values amounted to 0.120 ± 0.445 pg TEQ g(-1), while 0.091 ± 0.338 pg TEQ g(-1) if 1998 TEF values were used. Average concentration of all 14 studied BDEs (∑14 BDE) was 112 ± 80 pg g(-1), while average concentration of 13 BDEs excluding BDE #209 was only 15 ± 6 pg g(-1). Pesticide concentrations observed in the analyzed samples were generally low in comparison to maximum residue levels (MRLs) actually permitted by the European Union. However, MRLs were exceeded in 7 out of all 191 analyzed samples. Total concentration of DDT isomers in one of the tested bran samples was as high as 0.053 mg kg(-1). DMDT concentrations slightly above MRL = 0.01 mg kg(-1)were observed in 6 other samples (2 × bran, 1 × children porridge, 2 × snacks and 1 × bread). This study has shown that levels of PCBs, PBDEs and organochlorine pesticides in cereal products available on the Polish market are generally low. However, elevated levels of individual pollutants were observed in several instances.

Separation of polychlorinated dibenzo-p-dioxins/furans, non-ortho/mono/di/tri/tetra-ortho-polychlorinated biphenyls, and polybrominated diphenyl ethers groups of compounds prior to their determination with large volume injection gas chromatography-Quadrupole ion storage tandem mass spectrometry.

Polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs), polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) are important environmental contaminants. Their maximum legally allowable levels in food and environment are in the low pg g(-1) range. Therefore some highly selective and sensitive analytical methods must be used to determine them. Prior to final determination by GC/MS the cleaned-up samples have to be split into some fractions in view of large differences in concentrations of various analytes and existence of numerous chromatographic co-elutions (which in any case cannot be fully avoided). The aim of this study was to: (i) develop a robust, time-saving analytical method to isolate, clean-up and fractionate PCBs, PBDEs and PCDD/Fs prior to their determination with gas chromatography/ion trap mass spectrometry; (ii) assess method performance using laboratory validation data and some certified reference materials; (iii) use the developed method to assess PCB/PBDE/PCDD/F levels in samples of commercially available food. A combination of alumina, florisil, modified silica gel and two carbon columns were used for sample cleanup and fractionation. Separate fractions containing dioxins/furans, PBDE, non-ortho, mono-ortho and di-/tri-/tetra-ortho PCBs were obtained. The method statistical parameters were compatible with 1883/2006 EC Regulation (80-120%, RSD below 15%). The method performance was successfully used to evaluation of some real life food samples.

Fumonisins in plant-origin food and fodder--a review.

Fumonisins are mycotoxins produced by the Fusarium group of fungi commonly found on crops, mainly on maize. Some data suggest that as much as 25% of world crops may be lost because of mycotoxin contamination. Therefore, researchers in many countries (particularly in those in which relatively large amounts of maize are directly consumed by humans) are concerned with fumonisin levels in plant-origin foodstuffs and feeds available in their local markets. There is no doubt the levels are strongly correlated with the climate conditions prevailing in the region in which the maize was cultivated: the hotter the climate, the more serious the problem. Negative consequences of consumption of fumonisin-contaminated food by humans include an increased risk of oesophagus cancer and decreased body mass growth. In recent years some trials have been undertaken to reduce fumonisin levels in food and feed by the application of isothiocyanates naturally occurring in plants or peptidoglycans isolated from lactic acid bacteria (LAB). The results of these studies suggested that some reduction in contamination levels might be achieved. Additionally, some recent studies indicate that Sphingopyxis sp. bacteria produce enzymes that are able to break down the fumonisin molecule. Some fumonisins present in food may be bound/coupled with other compounds, and therefore difficult to detect. Such complexes in which the toxins are masked or hidden may even be at higher levels than the not-bound (free) molecules. The problem of how to evaluate effectively and efficiently the concentration of fumonisins in various foodstuffs is therefore a real-life challenge for scientists.

Application of molecularly imprinted polymers to determine B1, B2, and B3 fumonisins in cereal products.

The aim of this study was to develop an analytical method for qualitative and quantitative determination of the B(1), B(2,) and B(3) fumonisins in cereal products. A LC coupled to an IT-MS was used as the analytical instrument. The AFFINIMIP FumoZON Molecularly Imprinted Polymer SPE cartridges (Polyintell) were used to isolate fumonisins from the analyzed samples and the clean-up step. Statistical parameters evaluated in some validation experiments were as follows: mean recovery 95-106%, precision <17% (expressed as recovery RSD). The developed method was used to determine fumonisins in 49 cereals (42 maize-based and seven wheat-based products). In most cases, concentrations of the studied compounds found in the analyzed samples were low. The highest total concentration of the B(1), B(2), and B(3) fumonisins was found in maize flour samples (range, 26-1102 µg/kg, mean 498 µg/kg).