Katja Lehnert

Differentiation of Refined and Virgin Edible Oils by Means of the trans- and cis-Phytol Isomer Distribution

The differentiation of nonrefined (e.g., cold-pressed) and refined edible oils is an important task in food control because of the higher commercial value of the former. Here, we explored the suitability of the relative abundance of cis-phytol as a marker for authentication of nonrefined edible oils. Phytol, the tetramethyl-branched, monoenoic alcohol, is found widespread in nature as a part of chlorophyll. In chlorophyll, only trans-phytol is found. In this study, we present a method for the analysis of the phytol isomers, considering that traces of cis-phytol (contributing 0.1% to the phytol content) can be determined next to trans-phytol. For this purpose, phytol was gathered with the unsaponifiable matter from the oil, trimethylsilylated, and analyzed by gas chromatography coupled to mass spectrometry. With this method, 27 samples of edible oils (16 refined and 11 nonrefined edible oils) were analyzed for the abundance of cis-phytol relative to trans-phytol. In the nonrefined oils (e.g., olive oil, rapeseed oil, maize oil, and sunflower oil), cis-phytol contributed 0.1% (n = 3) or less (n = 8) to the phytol content. In contrast, the refined olive oils (n = 4) contained a share of 1.3-3% cis-phytol; the refined rapeseed oil (n = 3) contained a share of 0.7-1.0% cis-phytol; and the refined sunflower oil (n = 4) contained a share of 0.3-0.9% cis-phytol. Only one refined pomegranate kernel did not contain cis-phytol. The phytol concentration was not suited to distinguish nonrefined from refined oils. In contrast, our data suggest that the virtual absence of cis-phytol can be used as a marker for nonrefined (e.g., cold-pressed) edible oils.

Thorough analysis of polyhalogenated compounds in ray liver samples off the coast of Rio de Janeiro, Brazil

IntroductionFive liver samples of two different ray species (Gymnura altavela and Zapteryx brevirostris) off the coast of Rio de Janeiro, Brazil, were analyzed for their pollution with anthropogenic and naturally occurring organohalogen compounds.Material and methodsThe samples were extracted with accelerated solvent extraction, and after a clean-up procedure, organohalogen compounds were separated by a modified group separation on activated silica. Subsequent analyses were done by targeted and non-targeted gas chromatography–mass spectrometry in the electron capture negative ion mode.Results and discussion“Classic” organohalogen compounds such as polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), and technical 1,1,1-trichloro-2,2-di(4-chlorophenyl)ethane (DDT) were detected and quantified. PCBs generally exceeded the parts per million level and represented up to 90% of the total contamination of the ray livers. High concentrations were also detected for p,p′-DDE. Non-targeted full scan investigations lead to the detection of an abundant trichlorinated compound which was identified as a new DDT metabolite in biota. Different PBDE congeners and several halogenated natural products were quantified as well. In addition, polychlorinated terphenyls were identified and analyzed in the two species. Moreover, both ray species showed different fatty acid patterns and stable carbon isotope signatures.ConclusionsThe two ray species showed high concentrations of organohalogen compounds in their liver tissue. Varied δ13C values by up to 3.1‰ indicated that the two ray species were living in different habitats.

Identification of a fungi-derived terrestrial halogenated natural product in wild boar (Sus scrofa).

In this study, we identified and quantitated a tetrachlorinated compound found at high concentrations in some samples of the meat of free-ranging wild boar (Sus scrofa) from Southern Germany. Mass spectrometric analysis indicated that the compound was a tetrachloromethoxyphenol isomer, and the subsequently synthesized tetrachloro-p-methoxyphenol was identical with the unknown compound in wild boar. Tetrachloro-p-methoxyphenol is a known secondary metabolite of basidiomycetous fungi, which in turn are regular feed items of the wild boar. It is extremely likely that the wild boar have accumulated tetrachloro-p-methoxyphenol by exploiting basidiomycetes. The highest concentration in the samples (n = 22) was ~1 mg/kg lipids tetrachloro-p-methoxyphenol. This concentration was higher than that of polychlorinated biphenyls (PCBs) and dichlorodiphenyltrichloroethane (DDT) in any of the samples. Some samples did not contain tetrachloro-p-methoxyphenol, which indicates varied preferences in fungi by wild boars. Our data suggest that during their entire evolution, humans have been in contact with the natural product tetrachloro-p-methoxyphenol by consuming wild boars.

Mass spectra of methyl esters of brominated fatty acids and their presence in soft drinks and cocktail syrups

RATIONALE Brominated vegetable oil (BVO) is frequently used as a solubility transmitter in soft drinks. Being banned in Europe and Japan but permitted in the United States and Canada, there is a need for analytical methods suitable for use in food control. Brominated fatty acids in BVO are usually determined by gas chromatography (GC) after their conversion into the corresponding methyl esters. METHODS GC with mass spectrometry (MS) was used to record the electron ionization (EI) and negative ion chemical ionization (NICI) mass spectra of relevant brominated fatty acid methyl esters synthesized for this purpose. Brominated fatty acids obtained from transesterified BVO from soft drink and syrup samples were also analyzed. RESULTS GC/NICI-MS was the most sensitive method for the detection of brominated fatty acids but GC/EI-MS was found to be more suited for quantification due to the formation of more selective fragment ions in the higher mass range. Suitable ions were selected for determination of the methyl esters of brominated fatty acids in the selected ion monitoring (SIM) mode. Artifacts produced by the transesterification of BVO with boron trifluoride were observed and discussed. BVO was also quantified in three syrup samples commercially produced for use in cocktails/long drinks. In one of the syrup samples that tested positive, BVO was not labelled in the ingredient list. Bromination experiments produced evidence that one or more Br2 -18:0 isomers identified as a shoulder peak of threo-9,10-dibromooctadecanoic acid in several soft drink and syrup samples originated from the bromination of partly hydrogenated plant oil. CONCLUSIONS BVO was determined for the first time in syrup samples. Attention should be paid to the problem of BVO occurring unlabeled in soft drinks and cocktail syrups imported from North America.

Quantification of bromophenols in Islay whiskies.

Two single malt whiskies from the Scottish island Islay, i.e., Laphroiag and Lagavulin, are characterized by an iodine-like flavor associated with marine environments. In this study we investigated if this flavor impression could be due to bromophenols which are character impact compounds of marine fish and shrimps. In this study we developed a method suited for the determination of dibromo- and tribromophenols in whisky. Aliquots were O-acetylated, and quantification was carried out with gas chromatography with electron-capture negative ion mass spectrometry (GC/ECNI-MS). Both Islay whiskies contained more than 400 ng/L bromophenols with 2,6-dibromophenol being the most relevant homologue (>300 ng/L, respectively). These concentrations are at least 1 order of magnitude higher than the taste threshold of 2,6-dibromophenol in water. A third Islay whisky, Bowmore, contained ∼100 ng/L bromophenols while seventeen other whiskies from other regions in Scotland as well as from the USA, Ireland, and Germany contained at least 1 order of magnitude less than the two whiskies with the marine taste. Accordingly, bromophenols may contribute to the marine flavor and taste of Laphroaig and Lagavulin.

Anaerobic transformation of four abundant organochlorine pesticide residues (B8-1413, B9-1679, oxychlordane, p,p‵-DDE) in extracts of Antarctic skua eggs by the isolated bacterium Sulfurospirillum multivorans

Residues of halogenated pollutants bioaccumulated in eggs of the south polar skua (Catharacta maccormicki) from the Antarctic were extracted, purified, and fractionated. The target fraction which contained the bulk of the chloropesticides was concentrated and incubated with cell suspensions of the isolated bacterium Sulfurospirillum multivorans (formerly Dehalospirillum multivorans). S. multivorans was previously identified as a good anoxic transformer of several halogenated compounds. The compounds of technical toxaphene 2-endo,3-exo,5-endo,6-exo,8,8,10,10-octachlorobornane (B8-1413, also known as P-26) and 2-endo,3-exo,5-endo,6-exo,8,8,9,10,10-nonachlorobornane (B9-1679, also known as P-50) as well as 1,1-dichloro-2,2-bis(p-chlorophenyl)ethene (p,p′-DDE) and 1-exo,2-exo,4,5,6,7,8,8-octachloro-2,3-exo-epoxy-3a,4,7,7a-tetrahydro-4,7-methanoindene (oxychlordane) were present at a sufficiently high concentration and hence useful for studying the anaerobic transformation by the bacterium. When treated with S. multivorans, B8-1413 and B9-1679 were almost quantitatively transformed within 1 day. For B9-1679, the major metabolite was found to be 2-endo,3-exo,5-endo,6-exo,8,9,10-heptachlorobornane (B7-1001). Compared to the toxaphenes, transformation of oxychlordane and p,p′-DDE was significantly slower. Even after seven days, about 10% of the initial pool was detected in the extracts. 1-chloro-2,2-bis(p-chlorophenyl)ethene (p,p′-DDMU) was identified as a transformation product of p,p′-DDE. The four compounds in this study comprise some of the most persistent chloropesticide residues found in marine birds. In case there is sufficient transformation before they reach the top predators, the bioaccumulative potential can be significantly reduced.