Experimental Study on the Transfer of Polychlorinated Biphenyls (PCBs) and Polychlorinated Dibenzo-p-dioxins and Dibenzofurans (PCDD/Fs) into Milk of High-Yielding Cows during Negative and Positive Energy Balance.

Dioxin-like polychlorinated biphenyls (dl-PCBs) as well as polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) are a major concern for food safety, especially in fat-containing foods of animal origin, such as milk. Due to the lipophilic character of PCDD/Fs and PCBs, it is of special interest to explore whether the metabolic state of high-yielding cows influences the transfer rates into milk. Five German Holstein cows were orally exposed to a mixture of 17 PCDD/Fs, 12 dl-PCBs, and 6 non-dioxin-like PCBs (ndl-PCBs) for two dosing periods of 28 days each. The first period covered the negative energy balance (NEB) after calving, while the second period addressed the positive energy balance (PEB) in late lactation. Each dosing period was followed by a depuration period of around 100 days. During the NEB phase, the transfer rates of 14 PCDD/Fs and 7 dl-PCBs quantified were significantly (p ≤ 0.1) higher compared to the PEB phase, indicating an influence of the metabolic state on the transfer. Furthermore, the congener-specific transfer rates (0.3-39%) were in the range of the results from former studies. This indicates that the milk yield of the exposed cows is not the only determining factor for the transfer of these congeners into milk.

Barbecue conditions affect contents of oxygenated and non-oxygenated polycyclic aromatic hydrocarbons in meat and non-meat patties.

The contents of eight oxygenated polycyclic aromatic hydrocarbons (OPAHs; anthracene-9,10-dione, benzo[a]anthracene-7,12-dione, 11H-benzo[b]fluorene-11-one, 6H-benzo[cd]pyren-6-one, 7H-benzo[de]anthracene-7-one, 9,10-dihydro-8H-benzo[a]pyren-7-one, fluoren-9-one, and naphthacene-5,12-dione) and six PAHs (anthracene, fluorene, and PAH4) were investigated in barbecued meat and non-meat patties. The patties were prepared with ten setups (six replicates, each) of barbecue conditions defined by grill type, grate height, heating medium, and barbecue time. The highest median contents were observed with a disposable grill (OPAHs: 46.3 µg/kg; PAHs: 40.7 µg/kg) and a charcoal grill (OPAHs: 29.6 µg/kg; PAHs: 23.3 µg/kg). Fluoren-9-one and anthracene-9,10-dione were the dominant compounds within OPAHs, but also the four toxicologically most relevant OPAHs were detected with a total up to 11.8 µg/kg. Pairs of OPAHs and corresponding PAHs did not show strong correlations, as individual OPAHs and PAHs were affected differently by the barbecue conditions. No suitable markers for OPAH prediction could be found. We recommend to include OPAHs in future PAH investigations.

A sensitive GC-HRMS method for the simultaneous determination of parent and oxygenated polycyclic aromatic hydrocarbons in barbecued meat and meat substitutes.

A sensitive GC-HRMS method was developed to analyze six polycyclic aromatic hydrocarbons (PAH; anthracene, benzo[a]anthracene, benzo[a]pyrene, benzo[b]fluoranthene, chrysene, and fluorene) and eight oxygenated PAHs (OPAH; anthracene-9,10-dione, benzo[a]anthracene-7,12-dione, 7H-benz[de]anthracene-7-one, 11H-benzo[b]fluorene-11-one, 6H-benzo[cd]pyren-6-one, 9,10-dihydro-8H-benzo[a]pyren-7-one, fluoren-9-one, and naphthacene-5,12-dione) in barbecued meat and meat substitutes. After optimization of the conditions of the sample preparation, consisting of accelerated solvent extraction (ASE) and solid-phase extraction (SPE), high recoveries (PAH 72-109%; OPAH 74-106%) were obtained. The linear regression of the matrix calibration resulted in high correlation coefficients (0.959-0.999). For the first time, reasonably low limits of detection (PAH 0.03-0.17 µg/kg; OPAH 0.04-0.43 µg/kg) were achieved, allowing the analysis of samples barbecued under practical relevant conditions. In charcoal grilled samples, the sum content of the seven detected OPAHs (5.7-62.4 µg/kg) was higher than the sum content of the six PAHs (1.4-36.7 µg/kg). However, 9,10-dihydro-8H-benzo[a]pyren-7-one was not detected in these samples.

Influence of Smoking and Barbecuing on the Contents of Anthraquinone (ATQ) and Polycyclic Aromatic Hydrocarbons (PAHs) in Frankfurter-Type Sausages.

The contents of anthraquinone (ATQ) and polycyclic aromatic hydrocarbons (anthracene (ANT) and PAH4) in smoked Frankfurter-style sausages were investigated depending on various smoking conditions. During smoking, the smoke generator, the smoking duration, the type of wood, and some more plant-specific parameters were tested. The sausages were also barbecued on a charcoal grill. The lowest mean contents of all analytes were observed when friction smoke was used (ATQ < limit of quantification (LOQ); ANT < LOQ; PAH4 < limit of detection (LOD)) and the highest when the settings of ventilations flaps were changed (ANT 36.3 µg/kg; PAH4 2.2 µg/kg) or at an intensive smoke density (ATQ 3.2 µg/kg). The contents increased with the smoking time, but irregularities were detected after 10 min. The use of different types of wood had no influence on the ATQ content but affected the PAH content. In barbecued samples, ATQ and ANT contents were detected at the level of friction smoke and maximum PAH4 contents were found above the exposure during smoking. Due to the varying influence of the smoking parameters on the two analytes, there was no direct correlation between the contents of ATQ and ANT in all smoking experiments.

Dioxin and polychlorinated biphenyl analysis: automation and improvement of clean-up established by example of spices.

To analyze polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDDs/PCDFs) and polychlorinated biphenyls (PCBs) in spices by gas chromatography-mass spectrometry, a new clean-up method had to be developed owing to the high content of essential oils in the samples. A solid-phase extraction (SPE) column with activated silica endowed with sulfuric acid and sodium hydroxide was used. Under these conditions, clean-up was achieved using at least 5-7 g of pepper and even higher amounts of other spices. The automatized clean-up comprised three additional chromatographic steps after accelerated solvent extraction (ASE) followed by gel permeation: chromatography on a florisil SPE column, extract cleaning with the above-mentioned silica SPE column and chromatography with an activated charcoal column. On the basis of this automatized clean-up, a method that is more effective, rapid, simplified and economical than the available methods for PCDD/PCDF and PCB analysis is proposed. In model studies, the average recoveries for PCDDs/PCDFs ranged between 82.6% and 105.6% and for the PCBs between 71.3% and 113.3%.