Transformations of Selected Fusarium Toxins and Their Modified Forms During Malt Loaf Production.

An increasing number of studies have found that modified mycotoxins, such as free mycotoxins, naturally occur in food, and severely impact food safety. The present study investigated concentrations of trichothecenes nivalenol (NIV), deoxynivalenol (DON), and zearalenone (ZEN), together with their modified forms, nivalenol-3-glucoside (NIV-3G), deoxynivalenol-3-glucoside (DON-3G), and zearalenone-14-glucoside (ZEN-14G) and zearalenone-14-sulfate (ZEN-14S), respectively, at successive stages of malt loaf production (flour, dough kneading/fermentation, loaf baking). Toxins in bakery products originate in flour produced from wheat grain that is naturally contaminated with Fusarium culmorum. Mycotoxin concentrations were determined using high-performance liquid chromatography-high resolution mass spectrometry, and did not significantly change during the successive stages of bread production. After the dough kneading/fermentation stage, concentrations of NIV-3G and DON-3G were slightly increased, whereas those of ZEN and ZEN-14S were slightly decreased. The largest average decrease (21%) was found in ZEN-14G. After the baking stage, the average concentrations of NIV-3G, DON-3G, ZEN-14S, and ZEN-14G in the loaf crumb and crust decreased by 23%, 28%, 27%, and 20%, respectively, compared with those in the dough. During this technical process, the concentration of ZEN-14G in loaf crumb significantly decreased by an average of 48%, and those of ZEN, ZEN-14S, and ZEN-14G in loaf crust decreased by an average of 29%, 42%, and 48%, respectively. Considering the possibility of modified mycotoxins degradation to free forms, as well as the ability to synthesize them from free forms during technological processes, it would be prudent to consider them together during analysis.

Background levels of polycyclic aromatic hydrocarbons and legacy organochlorine pesticides in wheat sampled in 2017 and 2018 in Poland.

Both polycyclic aromatic hydrocarbons (PAHs) and legacy organochlorine insecticides (OCPs), including DDT, are dangerous chemical contaminants. The aims of this study were to (i) determine background levels of PAHs and legacy OCPs for wheat samples collected in 2017 and 2018 in Poland, (ii) identify differences between levels in wheat harvested in various regions of Poland, (iii) evaluate differences in contamination sources manifested by the profiles of the identified chemicals, (iv) identify possible correlations between different classes of chemicals present in wheat, and (v) assess the health risks associated with the presence of PAHs and OCPs in Polish wheat. Average concentrations found in the samples were 0.09 ± 0.03 µg kg-1 for benzo[a]pyrene (BaP) (formerly used as a single PAH marker), 0.43 ± 0.16 for the more recently introduced collective PAH 4 marker (benzo[a]anthracene + benzo[a]pyrene + chrysene + benzo[b]fluoranthene), and 1.07 ± 0.68 µg kg-1 for DDT and its metabolites. The PAH profiles indicated contamination from combustion-related emission sources (liquid fossil fuels, coal, biomass). Health risks associated with the presence of PAHs and OCPs in cereals were assessed using the margin of exposure (MOE) approach. The MOE values calculated based on the highest concentrations found in this study exceeded 50,000 for both BaP and PAH 4. The calculated worst-case scenario value for DDT and metabolites was as low as 0.3% of the respective tolerable daily intake (TDI) value. Assessment of dietary risk has shown that the presence of the two contaminant classes in Polish wheat grains is of low concern.

Biogenic Amines and Free Amino Acids in Traditional Fermented Vegetables-Dietary Risk Evaluation.

Biogenic amines (BAs) are low molecular weight organic bases. BAs occurring naturally in living organisms are responsible for a number of vital functions, including (in humans) secretion of gastric acids, controlling body temperature, differentiation and growth of cells, immune reactions, and brain activity. However, if oversupplied with food, BAs may cause food poisoning and produce undesirable effects. Nine BAs and eight free amino acids (FAAs) were determined in 85 samples of 19 different varieties of fermented vegetables available on the Polish retail market. Both BA and FAA levels differed significantly among various varieties of the studied fermented vegetables. Averages for the sum of all tested BAs ranged from 30.29 ± 16.43 mg·kg-1 in fermented olives to 612.1 ± 359.33 mg·kg-1 in fermented Brussels sprout. BA profiles were dominated by putrescine (42%), tyramine (20%), cadaverine (18%), and histamine (8%); jointly, the four amines amounted to 88% of all nine studied BAs. The combined level of the latter four BAs was calculated for each vegetable variety as the so-called BA index (BAI). On that basis, the risk of BA-related adverse health effects has been assessed as high/medium/low in 6/3/10 of all 19 studied varieties of fermented vegetables. Brussels sprout and broccoli turned out to be the most risky vegetables from that point of view (BAI above 400 mg·kg-1). FAA levels ranged from 54.8 ± 12.76 (fermented olives) to 3917.42 ± 1528.73 mg·kg-1 (fermented garlic). The high content of FAAs may increase the risk of forming toxic amounts of BAs, depending on characteristics of the current and added microflora as well as on environmental and technological conditions the product is subjected to.

Dietary risk evaluation of acrylamide intake with bread in Poland, determined by two comparable cleanup procedures.

Acrylamide is regarded as a food chemical contaminant. The aims of this work included: (i) to develop sample cleanup procedures applicable for determination of AA in soft bread samples; (ii) to determine AA levels in soft bread available in retail trade in Poland and to compare them with currently standing benchmark levels; (iii) to determine dietary risk related to AA in soft bread. The procedure based on ion-exchange solid phase extraction was more suitable to obtain LOQs corresponding to AA concentrations in soft bread samples. AA levels found in bread samples were in 3.6-163 µg kg-1 range. AA levels varied greatly from sample to sample, which suggests that both food composition and manufacturing processes play a crucial role in AA generation. When considering reference point for neoplastic effects, Margin of Exposure calculated for AA taken with soft bread ranged between 543 and 3,035.

Selected Trichothecenes in Barley Malt and Beer from Poland and an Assessment of Dietary Risks Associated with their Consumption.

Eighty-seven samples of malt from several Polish malting plants and 157 beer samples from the beer available on the Polish market (in 2018) were tested for Fusarium mycotoxins (deoxynivalenol (DON), nivalenol (NIV)), and their modified forms ((deoxynivalenol-3-glucoside (DON-3G), nivalenol-3-glucoside (NIV-3G), 3-acetyldeoxynivalenol (3-AcDON)). DON and its metabolite, DON-3G, were found the most, among the samples analyzed; DON and DON-3G were present in 90% and 91% of malt samples, and in 97% and 99% of beer samples, respectively. NIV was found in 24% of malt samples and in 64% of beer samples, and NIV-3G was found in 48% of malt samples and 39% of beer samples. In the malt samples, the mean concentration of DON was 52.9 µg/kg (range: 5.3-347.6 µg/kg) and that of DON-3G was 74.1 µg/kg (range: 4.4-410.3 µg/kg). In the beer samples, the mean concentration of DON was 12.3 µg/L (range: 1.2-156.5 µg/L) and that of DON-3G was 7.1 µg/L (range: 0.6-58.4 µg/L). The concentrations of other tested mycotoxins in the samples of malt and beer were several times lower. The risk of exposure to the tested mycotoxins, following the consumption of beer in Poland, was assessed. The corresponding probable daily intakes (PDIs) remained a small fraction of the tolerable daily intake (TDI). However, in the improbable worst-case scenario, in which every beer bottle consumed would be contaminated with mycotoxins present at the highest level observed among the analyzed beer samples, the PDI would exceed the TDI for DON and its metabolite after the consumption of a single bottle (0.5 L) of beer.

Contamination of Wheat Cultivated in Various Regions of Poland during 2017 and 2018 Agricultural Seasons with Selected Trichothecenes and Their Modified Forms.

Cross-interaction of antibodies within the immunoaffinity columns used in this study facilitated the simultaneous determination of nivalenol (NIV), deoxynivalenol (DON), their glucoside derivatives (NIV-3G, DON-3G), and 3-acetyl-deoxynivalenol (3-AcDON) in wheat grain harvested in various regions of Poland. In Poland, 2018 was a warm, dry agricultural season, and hence, was relatively less favourable for cereal cultivation than 2017. Data on the natural occurrence of NIV-3G in wheat grain are among the first published in the literature. DON was the most frequently found mycotoxin in the tested samples; the percentage occurrence of DON-positive samples was 92% in 2017 and 61% in 2018. Moreover, DON concentrations were generally higher in 2017 samples (5.2⁻1670.7 µg/kg) than those in 2018 samples (range 5.0⁻461.7 µg/kg). A similar pattern was found for DON-3G. However, no statistically significant differences between the samples from the two agricultural seasons were observed for the other three mycotoxins that were analysed, and their concentrations were generally considerably lower. DON was strongly correlated with DON-3G (correlation coefficient r = 0.9558), while NIV was strongly correlated with NIV-3G (r = 0.9442). The percentage occurrence of NIV-3G- and DON-3G-positive samples was 14% in 2017 and 49% in 2018. The NIV-3G/NIV ratio was 5.9⁻35.7%, while the DON-3G/DON ratio range was 3.2⁻53.6%. In 2018, wheat samples from Southern Poland exhibited statistically significantly higher levels of DON than those from Northern Poland. The dry and hot summer of 2018 not only reduced wheat yields, but also limited development of Fusarium spp. Therefore, grain harvested that year was generally contaminated with relatively low levels of mycotoxins. Lower levels of DON were also accompanied by lesser amounts of DON-derivatives.

Endocrine disrupting potency of organic pollutant mixtures isolated from commercial fish oil evaluated in yeast-based bioassays.

The aim of this work was to evaluate the activity of xenobiotic mixtures containing persistent organic pollutants isolated from commercial fish oil samples against sex hormone receptors, including estrogen and androgen. The applied bioassay was based on transgenic yeast strains. The mixtures were extracted from the samples using the semi-permeable membrane dialysis technique and analyzed with gas chromatography/ion trap mass spectrometry. It turned out that mixtures of chemicals isolated from fish oil may interact with human steroid sex hormone receptors in various ways: the tested samples showed both estrogenic and anti-androgenic activity. Calculated 17ß-estradiol equivalents for the tested samples ranged between 0.003 and 0.073 pg g-1 (fat). Anti-androgenic activity expressed as the flutamide equivalent concentration was in the 18.58-216.21 ng g-1 (fat) range. Polychlorinated biphenyls and various DDT metabolites were the main fish oil pollutants influencing the receptors. Additivity and/or synergy between chemicals was observed in the ER/AR mediated response.

Optimized yeast-based in vitro bioassay for determination of estrogenic and androgenic activity of hydroxylated / methoxylated metabolites of BDEs / CBs and related lipophilic organic pollutants.

Persistent organic pollutants (POPs) are known to show endocrine disrupting (ED) activity, including interactions with hormone receptors. The aim of this work was to develop a bioassay applicable for evaluation of ED potency of highly lipophilic metabolites of POPs. To that end, a yeast-based bio-assay protocol was used. Estrogenic / androgenic activity of some native brominated biphenyl ethers (BDEs) / chlorinated biphenyls (CBs), and their hydroxylated / methoxylated metabolites was assessed. Since data (including potency compared to reference native hormones) obtained using different protocols vary, the possibility that yeast transforms POPs into some more potent compounds was first checked; it seems that no such transformation is important from the test applicability standpoint. The developed method was sensitive with EC50 values 6.5*10-11 M and 4.5*10-9 M calculated for E2 and DHT, respectively. Both CBs and BDEs show weak estrogenic activity negatively correlated with the degree of their halogenation, but their metabolites are significantly more potent xenohormones. 4-OH-2,2',4',6'-TeCB was the most potent estrogen receptor (ER) agonist among all tested compounds; its activity was only 1,000 times lower than that of native E2.

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.

Current Knowledge about Oxysterols: A Review.

For years food consumers have been warned that a cholesterol-rich diet may result in atherosclerosis. It is also well known that consumption of large amounts of phytosterols decreases concentration of low-density lipoproteins (LDLs) in blood (LDLs are regarded a key risk factor in development of cardiovascular diseases). However, no scientific evidence has unambiguously proved any direct connection between amount of consumed cholesterol and LDL level in blood. On the other hand, concentration of cholesterol oxidation products, oxysterols, seems to be indeed relevant; for example, they significantly impact appearance of atherosclerotic lesions (plaques). Phytosterols (like sitosterol or campasterol) decrease LDL level in blood, but on the other hand products of their oxidation are toxic. Therefore, it is worth to know influence of phytosterols on living organisms, processes which lead to their formation, and their levels in popular foodstuffs. This paper is an attempt to review literature data on the above aspects, as well as on impact on living organisms of oxidation products of popular sterols.

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).

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.

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.

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.

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.