Browsing by Person "Vetter, Walter"

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Acrocomia aculeata fruits from three regions in Costa Rica: An assessment of biometric parameters, oil content and oil fatty acid composition to evaluate industrial potential
(2020) Alfaro-Solís, Jose David; Montoya-Arroyo, Alexander; Jiménez, Víctor M.; Arnáez-Serrano, Elizabeth; Pérez, Jason; Vetter, Walter; Frank, Jan; Lewandowski, Iris
Due to increased global demand for vegetable oils, diversification of the supply chain with sustainable sources is necessary. Acrocomia aculeata has recently gained attention as a multi-purpose, sustainable crop for oil production. However, the information necessary for effective selection of promising varieties for agricultural production is lacking. The aim of this study was to assess variability in fruit morphology and oil composition of individual Acrocomia aculeata plants growing wild in different climatic regions of Costa Rica. Fruits at the same ripening stage were collected at three locations, and biometric features, oil content, fatty acid composition of oils from kernels and pulp, as well as fiber composition of husks were determined. Biometric parameters showed high variability among the regions assessed. Moreover, oil content and relative proportions of unsaturated fatty acids were higher at the most tropical location, whereas lauric acid content was lowest under these conditions, indicating a potential environmental effect on oil composition. Pulp oil content correlated positively with annual precipitation and relative humidity, but no clear relation to temperature was observed. The oil chemical composition was similar to that reported for Elaeis guineensis, suggesting that Acrocomia aculeata from Costa Rica may be a suitable alternative for industrial applications currently based on African palm oil. Analysis of husks as a coproduct revealed the possibility of obtaining materials with high lignin and low water and ash contents that could be used as a solid bioenergy source. In conclusion, Acrocomia aculeata oil is a promising alternative for industrial applications currently based on African palm oil and byproducts of its oil production could find additional use as a renewable energy source.
Analysis of highly polar anionic pesticides in food of plant and animal origin by ion chromatography and tandem mass spectrometry with emphasis on addressing adverse effects caused by matrix co-extractives
(2024) Schäfer, Ann-Kathrin; Vetter, Walter; Anastassiades, Michelangelo
Residues of various highly polar pesticides and their metabolites are commonly found in numerous food products. Some of these compounds, such as glyphosate, are not only used in large amounts in agriculture, but are also controversially discussed in public. Here, we present a method, employing ion chromatography (IC) coupled to tandem mass spectrometry (IC-MS/MS), for the analyses of glyphosate, aminomethyl phosphonic acid (AMPA), N -acetyl-glyphosate (NAGly), fosetyl, and 10 further highly polar pesticides and metabolites in various plant and animal matrices following a minimal sample preparation by means of the QuPPe method. Thorough investigations showed that an AS19 column enabled the analysis of all 14 compounds within 30 min. The best sensitivity could be obtained with the make-up solvent acetonitrile being admixed to the mobile phase at a 1:2 flow rate ratio. Matrix effects were thoroughly studied in terms of ion suppression and retention time shifts. Conductivity detection was used to monitor elution profiles of matrix co-extractives in comparison with matrix effect profiles obtained by continuous post-column infusion of a mix with 13 highly polar pesticides and metabolites. These tests indicated that a fivefold dilution of QuPPe extracts was suitable for the routine analysis of samples for MRL-conformity, as it considerably reduced matrix effects maintaining sufficient sensitivity and high recovery rates in eight different commodities. The suitability of the final method for its application in routine analysis was verified by the analysis of >130 samples containing incurred residues where the results were compared with two existing LC-MS/MS methods.
Antifungal properties of bioactive compounds isolated from Fucus vesiculosus supercritical carbon dioxide extract
(2024) Tyśkiewicz, Katarzyna; Rüttler, Felix; Tyśkiewicz, Renata; Nowak, Artur; Gruba, Marcin; Wziątek, Anita; Dębczak, Agnieszka; Sandomierski, Michał; Vetter, Walter; Cacciola, Francesco
The exploration of natural antifungal substances from algal origins is significant due to the increasing resistance of pathogens to conventional antifungal agents and the growing consumer demand for natural products. This manuscript represents the inaugural investigation into the antifungal attributes of bioactive compounds extracted from Fucus vesiculosus via supercritical carbon dioxide (scCO2) extraction utilizing contemporary countercurrent chromatography (CCC). In aligning with the prospective utilization of this extract within the agricultural sector, this study also serves as the preliminary report demonstrating the capability of Fucus vesiculosus scCO2 extract to enhance the activity of plant resistance enzymes. The fractions obtained through CCC were subjected to evaluation for their efficacy in inhibiting the macrospores of Fusarium culmorum. The CCC methodology facilitated the successful separation of fatty acids (reaching up to 82.0 wt.% in a given fraction) and fucosterol (attaining up to 79.4 wt.% in another fraction). All CCC fractions at the concentration of 1.0% were found to inhibit 100% of Fusarium culmorum growth. Moreover, Fucus vesiculosus scCO2 extract was able to activate plant resistance enzymes (Catalase, Ascorbic Peroxidase, Guaiacol Peroxidase, Phenylalanine Ammonia-Lyase, and Phenylalanine Ammonia-Lyase Activity).
Characterization of the major odor-active compounds in fresh rhizomes and leaves of Houttuynia cordata by comparative aroma extract dilution analysis
(2025) Xu, Zhenli; Liu, Jing; Kreissl, Johanna; Oellig, Claudia; Vetter, Walter; Steinhaus, Martin; Frank, Stephanie; Rodov, Victor
Houttuynia cordata is a culinary herb from Asia. Its edible rhizomes and leaves have a fishy aroma, the molecular background of which was unknown. A comparative aroma extract dilution analysis applied to fresh rhizomes and leaves resulted in 44 and 41 odorants, respectively, 38 of which were present with FD factors ≥1 in both samples. The odorant with the highest FD factors, whether in the rhizomes or leaves, was identified as metallic, soapy, fishy smelling 3-oxododecanal. Toward clarifying its tautomeric composition, quantum calculations suggested a predominance of the enol forms in the plant. However, the form perceived at the sniffing port during GC–O remained unclear.
Chlorinated paraffins in hinges of kitchen appliances
(2021) Sprengel, Jannik; Vetter, Walter
Chlorinated paraffins (CPs) are anthropogenic pollutants of growing environmental concern. These highly complex mixtures of thousands of homologs and congeners are usually applied as additives in lubricants or as flame retardants and plasticizers in polymers and paints. Recent studies indicated the presence of high amounts of CPs in the kitchen environment whose sources could not be unequivocally identified. One option was the use of CPs as or in lubricants of hinges. To test this hypothesis, we performed wipe tests on lubricants on 29 hinges of different types of kitchen appliances (refrigerators, baking ovens, dishwashers, freezers, microwave oven, pasta machine, food processor, steam cooker) and analyzed them for short-chain CPs (SCCPs) and medium-chain CPs (MCCPs). CPs were detected in 21 samples (72%). Per wipe, SCCP concentrations ranged between 0.02 and 10 µg (median 0.23 µg), while MCCPs ranged from 0.09 to 750 µg (median 1.0 µg). Highest MCCP amounts (380 and 750 µg per wipe, respectively) were determined in new and unused appliances. A medium correlation between SCCP content and appliance age was observed, but no additional statistic correlation between SCCP/MCCP amount and appliance type or manufacturer could be observed. CPs released from hinges by volatilization, abrasion, and cleaning processes could enter the environment and come in contact with persons living in the corresponding households.
Countercurrent chromatographic fractionation followed by gas chromatography/mass spectrometry identification of alkylresorcinols in rye
(2020) Hammerschick, Tim; Wagner, Tim; Vetter, Walter
Alkylresorcinols (5-alkyl-1,3-dihydroxybenzenes, ARs) are bioactive phenolic lipid compounds which are particularly abundant in rye and partly other cereals. In this study on ARs, whole rye grain extracts were gained with cyclohexane/ethyl acetate (46/54, w/w). Silylated extracts were used to develop a gas chromatography with mass spectrometry method in the selected ion monitoring mode (GC/MS-SIM) for the sensitive detection of conventional ARs along with keto-substituted (oxo-AR) and ring-methylated ARs (mAR) with 5-alkyl chain lengths of 14 to 27 carbon atoms and 0 to 4 double bonds in one run. Analysis was performed by countercurrent chromatographic (CCC) fractionation using the solvent system n-hexane/ethyl acetate/methanol/water (9/1/9/1, v/v/v/v). Subsequent GC/MS-(SIM) analysis of 80 silylated CCC fractions enabled the detection of 74 ARs in the sample. The CCC elution of the ARs followed the equivalent chain length (ECL) rule in which one double bond compensated the effect of two (additional) carbon atoms. Novel or rarely reported ARs were detected in virtually all classes, i.e. saturated AR (AR14:0), even-numbered monounsaturated AR isomers (AR16:1-AR26:1), triunsaturated ARs (AR25:3), oxo-ARs (AR17:0 oxo, AR19:1 oxo, AR21:2 oxo, AR23:2 oxo) and odd-numbered methyl-ARs (mAR15:0-mAR23:0). Positions of the double bonds of monounsaturated ARs and oxo-ARs were determined with the help of dimethyl disulfide (DMDS) derivatives.
Effect of the Mediterranean diet on the faecal long-chain fatty acid composition and intestinal barrier integrity: An exploratory analysis of the randomised controlled LIBRE trial
(2024) Seethaler, Benjamin; Basrai, Maryam; Neyrinck, Audrey M.; Vetter, Walter; Delzenne, Nathalie M.; Kiechle, Marion; Bischoff, Stephan C.
We recently showed that adherence to the Mediterranean diet increased the proportion of plasma n-3 PUFA, which was associated with an improved intestinal barrier integrity. In the present exploratory analysis, we assessed faecal fatty acids in the same cohort, aiming to investigate possible associations with intestinal barrier integrity. Women from the Lifestyle Intervention Study in Women with Hereditary Breast and Ovarian Cancer (LIBRE) randomised controlled trial, characterised by an impaired intestinal barrier integrity, followed either a Mediterranean diet (intervention group, n 33) or a standard diet (control group, n 35). At baseline (BL), month 3 (V1) and month 12 (V2), plasma lipopolysaccharide-binding protein, faecal zonulin and faecal fatty acids were measured. In the intervention group, faecal proportions of palmitoleic acid (16:1, n-7) and arachidonic acid (20:4, n-6) decreased, while the proportion of linoleic acid (18:2, n-6) and α linoleic acid (18:3, n-3) increased (BL-V1 and BL-V2, all P < 0·08). In the control group, faecal proportions of palmitic acid and arachidic acid increased, while the proportion of linoleic acid decreased (BL-V1, all P < 0·05). The decrease in the proportion of palmitoleic acid correlated with the decrease in plasma lipopolysaccharide-binding protein (ΔV1-BL r = 0·72, P < 0·001; ΔV2-BL r = 0·39, P < 0·05) and correlated inversely with adherence to the Mediterranean diet (Mediterranean diet score; ΔV1-BL r = –0·42, P = 0·03; ΔV2-BL r = -0·53, P = 0·005) in the intervention group. Our data show that adherence to the Mediterranean diet induces distinct changes in the faecal fatty acid composition. Furthermore, our data indicate that the faecal proportion of palmitoleic acid, but not faecal n-3 PUFA, is associated with intestinal barrier integrity in the intervention group.
Einfluss moderner Pflanzenschutzmittel auf die Mobilität von POP-belasteten Agrarflächen am Beispiel von DDT
ein Feldversuch
(2023) Neitsch, Julia Simone; Vetter, Walter
Due to their recalcitrance, the chloropesticide DDT and its structurally related compounds (DDX) are difficult to degrade. Consequently, farmers are still frequently confronted with DDX contamination in their fields that was left over from the 1960s. This problem is particularly prevalent in contaminated soils that are intended to cultivate plants of the Cucurbitaceae family. These plants release so-called root exudates, which function as natural surfactants that mobilize the DDX present in the soils. Furthermore, surfactants are a common constituent of modern plant protection product (PPP) formulations, which can likewise cause DDX mobilization. The higher mobility of DDX caused by these surfactants can result in the absorption and accumulation of chlorinated pesticides in plants. The side effects of such surfactant-containing PPP formulations have historically been overlooked in the context of standard spraying protocols. The potential mobilization of DDX in soils and its accumulation in Cucurbita pepo due to the surfactants present in standard PPPs formulations was investigated using two field trials. One field was treated with a conventional PPP, while the other was treated with a biological PPP; a control field was left untreated, within which pumpkins were cultivated. Soil samples were taken before and after the application of PPP. The DDX content was subsequently determined in extracts from the soil phase samples and soil water fractions. The background DDX contamination of the soils was comparable in all three test fields. The comparative evaluation showed that the field treated with the biological PPP formulation exhibited a considerable increase in DDX mobility compared to the untreated and conventionally cultivated areas (Paper 1). An analysis of its respective water fraction revealed that it was more contaminated with DDX than the control treatments. This increase suggests a higher bioavailability that can be traced back to the presence of surfactants and oils in the PPP formulations (Paper 1). This higher bioavailability may have been accompanied by an increase in the DDX uptake of the cultivated plants. Furthermore, it was found that treatment with specific formulations of emulsifiable concentrates (EC) promoted DDX mobilization. This mobilizing effect was most likely due to the differing composition of the surfactant and proportions of oils in the PPPs. The second field test focused on differential DDX accumulation in Cucurbita pepo cv. Howden by different PPPs. Fields were treated with PPP in accordance with the official spraying plans and regulations set out by the Federal Ministry of Food and Agriculture (BMEL). Samples from the pumpkin plants roots, shoots, as well as the pumpkins themselves were taken during the cultivation period. The DDX content in the roots from the control fields and the fields with conventional PPP treatments remained virtually unchanged; however, the DDX content increased in the biologically treated area (Paper 2). The pumpkin shoots did not exhibit any increases in DDX concentration during the growing phase regardless of the field sampled. However, an increased DDX content was detected in the shoots of the plants in all test fields shortly before harvesting. At the end of the growing phase, fruits from the biologically treated area showed a higher DDX content than those from the control and conventionally treated areas. In addition, the most critical DDT metabolite, DDE, was found to have been transported to distant parts of the plant, while DDD was detectable in the roots and shoots but not in the fruits of the pumpkins (Paper 2). An assessment of the results of both experiments confirmed a direct correlation between DDX mobilization in the soil and plant uptake. In addition, the bioaccumulation factors of the biologically treated areas were markedly higher than those seen in the conventionally treated and control areas. The results of the field trials show that the mobilization of DDT, as well as the likely mobilization of other lipophilic contaminants, can become problematic for farmers using surfactant-containing EC formulations. However, this observation also provides opportunities for improved phytoremediation by applying EC formulations with high mobilization potentials. The field trials indicate that the mobilizing effects of DDT prompted by EC mixtures depend on the surfactant content in the PPP formulations as well as environmental conditions such as soil conditions, soil water content, and precipitation. Unravelling the optimal range of surfactant-rich formulations and environmental conditions could lead to a promising strategy for soil phytoremediation.
Enrichment and structural assignment of geometric isomers of unsaturated furan fatty acids
(2023) Müller, Franziska; Conrad, Jürgen; Hammerschick, Tim; Vetter, Walter
Furan fatty acids (FuFAs) are valuable minor fatty acids, which are known for their excellent radical scavenging properties. Typically, the furan moiety is embedded in an otherwise saturated carboxyalkyl chain. Occasionally, these classic FuFAs are accompanied by low amounts of unsaturated furan fatty acids (uFuFAs), which additionally feature one double bond in conjugation with the furan moiety. A recent study produced evidence for the occurrence of two pairs of E -/ Z -uFuFA isomers structurally related to saturated uFuFAs. Here, we present a strategy that allowed such trace compounds to be enriched to a level suited for structure determination by NMR. Given the low amounts and the varied abundance ratio of the four uFuFA isomers, the isolation of individual compounds was not pursued. Instead, the entire isomer mixture was enriched to an amount and purity suitable for structure investigation with contemporary NMR methods. Specifically, lipid extracted from 150 g latex, the richest known source of FuFAs, was subsequently fractionated by countercurrent chromatography (CCC), silver ion, and silica gel column chromatography. Analysis of the resulting mixture of four uFuFAs isomers (2.4 mg in an abundance ratio of 56:23:11:9) by different NMR techniques including PSYCHE verified that the structures of the two most abundant isomers were E -9-(3-methyl-5-pentylfuran-2-yl)non-8-enoic acid and E -9-(3-methyl-5-pent-1-enylfuran-2-yl)nonanoic acid. Additionally, we introduced a computer-based method to generate an averaged chromatogram from freely selectable GC/MS runs of CCC fractions without the necessity of pooling aliquots. This method was found to be suitable to simplify subsequent enrichment steps.
A fast gas chromatography coupled with electron capture negative ion mass spectrometry in selected ion monitoring mode screening method for short‐chain and medium‐chain chlorinated paraffins
(2022) Schweizer, Sina; Schulz, Tobias; Vetter, Walter
Rationale: Chlorinated paraffins (CPs) are a group of anthropogenic pollutants that consist of complex mixtures of polychlorinated n-alkanes of different chain lengths (~C10 to C30). Persistence, bioaccumulation, toxicity, and long-range transport of short-chain chlorinated paraffins (SCCPs, C10- to C13-CPs) have prompted their classification as persistent organic pollutants (POPs) by the Stockholm Convention in 2017. Due to the varying chain lengths and chlorination degrees, quantification of SCCPs and medium-chain chlorinated paraffins (MCCPs, C14- to C17) using gas chromatography coupled with electron capture negative ion mass spectrometry in selected ion monitoring mode (GC/ECNI-MS-SIM) is not only challenging but also very time consuming. In particular, up to eight GC runs per sample are required for the comprehensive GC/ECNI-MS-SIM quantification of SCCPs and MCCPs. These efforts are high especially if the samples do not contain CPs above the limit of detection (LOD), subsequently. Methods: We developed a semi-quantitative and sensitive method for the examination of SCCPs and MCCPs in one GC run. This GC/ECNI-MS-SIM screening method was based on the recording of Cl− (m/z 35 and 37), Cl2− (m/z 70 and 72), and HCl2− (m/z 71 and 73) isotope ions and evaluation of the ratios between them. Results: Correctness of the results of the screening method was verified by analysis of edible oils with and without CPs, CP standards, as well as a technical CP mixture. Polychlorinated biphenyls (PCBs) and other polyhalogenated aromatic compounds, as well as brominated flame retardants, do not form all of the fragment ions analyzed by the screening method. Conclusions: After the screening, only CP-positive samples may need to be measured in detail. Measurement time will already be gained in the case of ~10% samples without CPs.
Fate of free and bound phytol and tocopherols during fruit ripening of two Capsicum cultivars
(2020) Krauß, Stephanie; Hermann-Ene, Vanessa; Vetter, Walter
Phytol and tocopherols and their fatty acid esters (PFAE and TFAE) are isoprenoid lipid components which can be found for instance in vegetables. Their behavior during maturation of fruits and vegetables could reveal valuable information on their biosynthetic formation and biological function. As pods of the genus Capsicum contain considerable amounts of both PFAE and TFAE, two cultivars (i.e. Capsicum annuum var. Forajido and Capsicum chinense var. Habanero) were grown in a greenhouse project. The date of flowering and fruit formation of each blossom was noted and fruits were harvested in four specific periods which corresponded with different stages of ripening, i.e. unripe, semi-ripe, ripe and overripe. Quantification by means of gas chromatography mass spectrometry and creation of development profiles strongly supported the suggestion that PFAE and TFAE were formed as storage molecules during fruit ripening and parallel degradation of chlorophyll. Additionally, compound-specific carbon isotope ratios (δ13C values (‰)) of originally in PFAE and chlorophyll bound phytol ultimately proved that PFAE, besides tocopherols, serve as sink for the cytotoxic phytol moiety released from chlorophyll degradation during fruit ripening. Furthermore, color measurements were successfully implemented to simplify the usually cumbersome separation of chili fruits into different ripening degrees.
Furan fatty acid amounts and their occurrence in triacylglycerols of white asparagus (Asparagus officinalis) from the German market
(2023) Müller, Franziska; Bauer, Vanessa; Vetter, Walter
Vegetables including asparagus contain a wide range of fatty acids, mainly stored in triacylglycerols. One class of interesting minor fatty acids is the family of furan fatty acids (FuFAs) because of their antioxidant properties. Since FuFAs have not been studied previously in asparagus (Asparagus officinalis L.), we developed and applied a simplified method for their analysis in 20 fresh and three preserved samples. Four FuFAs were detected with clear dominance of the dimethyl‐substituted FuFAs (D‐FuFAs) 11D5 and 9D5 as well as small amounts of the monomethyl‐substituted FuFAs (M‐FuFAs) 11M5 and 9M5. The total amounts of FuFAs in fresh white asparagus ranged from 1.4 to 4.6 mg/100 g dry weight (mean 3.0 mg/100 g dry weight). Subsequent LC‐Q‐Orbitrap‐HRMS measurements enabled the detection of 22 different FuFA‐containing TAGs. These were predominantly found together with one or two polyunsaturated fatty acid.
The furan fatty acids 11M5 and 11D5 can act as activators of human peroxisome proliferator‐activated receptor gamma
(2025) Pospiech, Jonas; Caspi, Ayelet; Vetter, Walter; Kerem, Zohar; Frank, Jan; Kufer, Thomas A.; Pospiech, Jonas; Institute of Nutritional Medicine, University of Hohenheim, Stuttgart, Germany; Caspi, Ayelet; Robert H. Smith Faculty of Agriculture, Food and Environment, The Hebrew University of Jerusalem, Rehovot, Israel; Vetter, Walter; Institute of Food Chemistry (170b), University of Hohenheim, Stuttgart, Germany; Kerem, Zohar; Robert H. Smith Faculty of Agriculture, Food and Environment, The Hebrew University of Jerusalem, Rehovot, Israel; Frank, Jan; Department of Food Biofunctionality, Institute of Nutritional Sciences, University of Hohenheim, Stuttgart, Germany; Kufer, Thomas A.; Institute of Nutritional Medicine, University of Hohenheim, Stuttgart, Germany
Furan fatty acids (FuFA) are a minor class of fatty acids in food that are characterized by a furan ring within the alkyl chain. Furan fatty acids have strong antioxidant properties but their biological functions remain largely elusive. Using molecular docking combined with biomolecular validation, we investigated the regulatory activities of the key furan fatty acids 9M5, 11M5, and 11D5 on human nuclear receptors, including PPARγ, LXR, PXR, FXR, and HNF4α. Using computational methods, 11M5 and 11D5 and to a lesser extend 9M5 were predicted to bind to PPARγ. The activation of both PPARγ1 and PPARγ2 was confirmed in human HEK293T cells and structure‐activity experiments revealed that this was dependent on the furan fatty acid backbone. In summary, our data provide novel insights into the biological activities of furan fatty acids in human cells and indicate that activation of peroxisome proliferator‐activated receptor gamma underlies their beneficial health effects. These findings establish a clear mechanistic basis, supported by the inactivity of related compounds, and we are confident that future expanded studies will further confirm this mechanism.
GC/EI-MS method for the determination of phytosterols in vegetable oils
(2021) Schlag, Sarah; Huang, Yining; Vetter, Walter
Sterols are a highly complex group of lipophilic compounds present in the unsaponifiable matter of virtually all living organisms. In this study, we developed a novel gas chromatography with mass spectrometry selected ion monitoring (GC/MS-SIM) method for the comprehensive analysis of sterols after saponification and silylation. A new referencing system was introduced by means of a series of saturated fatty acid pyrrolidides (FAPs) as internal standards. Linked with retention time locking (RTL), the resulting FAP retention indices (RIFAP) of the sterols could be determined with high precision. The GC/MS-SIM method was based on the parallel measurement of 17 SIM ions in four time windows. This set included eight molecular ions and seven diagnostic fragment ions of silylated sterols as well as two abundant ions of FAPs. Altogether, twenty molecular ions of C27- to C31-sterols with 0–3 double bonds were included in the final method. Screening of four common vegetable oils (sunflower oil, hemp oil, rapeseed oil, and corn oil) enabled the detection of 30 different sterols and triterpenes most of which could be identified.
Geometrical and positional isomers of unsaturated furan fatty acids in food
(2022) Müller, Franziska; Hammerschick, Tim; Vetter, Walter
Furan fatty acids (FuFA) are important antioxidants found in low concentrations in many types of food. In addition to conventional FuFA which normally feature saturated carboxyalkyl and alkyl chains, a few previous studies indicated the FuFA co‐occurrence of low shares of unsaturated furan fatty acids (uFuFA). For their detailed analysis, the potential uFuFA were enriched by centrifugal partition chromatography (CPC) or countercurrent chromatography (CCC) followed by silver ion chromatography from a 4,7,10,13,16,19‐docosahexaenoic acid ethyl ester oil, a 5,8,11,14,17‐eicosapentaenoic acid ethyl ester oil and a latex glove extract. Subsequent gas chromatography with mass spectrometry (GC/MS) analysis enabled the detection of 16 individual uFuFA isomers with a double bond in conjugation with the central furan moiety. In either case, four instead of two uFuFA isomers previously reported in food, respectively, were detected by GC/MS. These isomers showed characteristic elution and abundance patterns in GC/MS chromatograms which indicated the presence of two pairs of cis/trans‐isomers (geometrical isomers).
High abundance of pyrrolizidine alkaloids in bee pollen collected in July 2019 from Southern Germany
(2022) Friedle, Carolin; Kapp, Thomas; Wallner, Klaus; Alkattea, Raghdan; Vetter, Walter
Pyrrolizidine alkaloids (PA) are secondary plant defense compounds and known pre-toxins when containing a 1,2-double bond. They are commonly produced by various plants and may thus be present in bee pollen which may be consumed by humans as food supplements. In this study, PA were determined in bee pollen samples from 57 locations in Southern Germany sampled by means of pollen traps in July 2019. Samples were analyzed by using palynological methodology and solid-phase extraction (SPE) followed by LC–MS/MS. In total, 52 pollen samples featured total pyrrolizidine alkaloids (ΣPA) with concentrations up to 48,000 ng/g bee pollen, while the N-oxides (NO) echinatine-NO and rinderine-NO clearly dominated. In contrast, the palynological analysis only detected 33 samples with pollen from PA-producing plants. Accordingly, the results showed that palynological analysis is not sufficient to determine PA in pollen. In addition, a risk assessment was followed to estimate the risk of the detected PA concentrations to humans.
High levels of halogenated natural products in large pelagic fish from the Western Indian Ocean
(2021) Wu, Qiong; Munschy, Catherine; Aminot, Yann; Bodin, Nathalie; Vetter, Walter
Concentrations, profiles and muscle-liver distribution of halogenated natural products (HNPs) and anthropogenic persistent organic pollutants (POPs) were investigated in five large pelagic fish species and one smaller planktivore fish species from the Western Indian Ocean. Analysis of swordfish muscle from the Seychelles revealed the predominance of HNPs, with the highest concentrations found for 2′-methoxy-2,3′,4,5′- tetraBDE (2′-MeO-BDE 68 or BC-2), 6-methoxy-2,2′,4,4′- tetraBDE (6-MeO-BDE 47 or BC-3) and 2,3,3′,4,4′,5,5′-heptachloro-1′-methyl-1,2′-bipyrrole (Q1), along with varied contributions of further HNPs. The mean concentration of ∑HNPs (330 ng/g lw) was one or two orders of magnitude higher than ∑DDTs (60 ng/g lw) and ∑PCBs (6.8 ng/g lw). HNPs (BC-2, BC-3 and Q1) were also predominant in individual samples of three tropical tuna species from the Seychelles and from other regions of the Western Indian Ocean (Mozambique Channel, off Somalia and Chagos Archipelago). Non-targeted gas chromatography coupled with electron capture negative ion mass spectrometry operated in the selected ion monitoring mode (GC/ECNI-MS-SIM) analysis of one swordfish sample indicated low abundance of rarely reported HNPs (three hexachloro-1′-methyl-1,2′-bipyrrole (Cl6-MBP) isomers and pentabromo-1,1′-dimethyl-2,2′-bipyrroles (Br5-DBP)) but no further abundant unscreened polyhalogenated compounds.
Hydroxylated transformation products obtained after UV irradiation of the current-use brominated flame retardants hexabromobenzene, pentabromotoluene, and pentabromoethylbenzene
(2023) Klimm, Alexandra; Vetter, Walter
Hexabromobenzene (HBB), pentabromotoluene (PBT), and pentabromoethylbenzene (PBEB) are current-use brominated flame retardants (cuBFRs) which have been repeatedly detected in environmental samples. Since information on hydroxylated transformation products (OH-TPs) was scarcely available, the three polybrominated compounds were UV irradiated for 10 min in benzotrifluoride. Fractionation on silica gel enabled the separate collection and identification of OH-TPs. For more insights, aliquots of the separated OH-TPs were UV irradiated for another 50 min (60 min total UV irradiation time). The present investigation of polar UV irradiation products of HBB, PBT, and PBEB was successful in each case. Altogether, eight bromophenols were detected in the case of HBB (three Br3-, four Br4-, and one Br5-isomer), and nine OH-TPs were observed in the case of PBT/PBEB (six Br3- and three Br4-congeners). In either case, Br➔OH exchange was more relevant than H➔OH exchange. Also, such exchange was most relevant in meta- and ortho-positions. As a further point, and in agreement with other studies, the transformation rate decreased with decreasing degree of bromination. UV irradiation of HBB additionally resulted in the formation of tri- and tetrabrominated dihydroxylated compounds (brominated diphenols) that were subsequently identified. These dihydroxylated transformation products were found to be more stable than OH-TPs.
Identification and quantification of dicarboxylic fatty acids in head tissue of farmed Nile tilapia (Oreochromis niloticus)
(2021) Lehnert, Katja; Rashid, Mamun M.; Barman, Benoy Kumar; Vetter, Walter
Nile tilapia (Oreochromis niloticus) was grown in Bangladesh with four different feeding treatments as part of a project that aims to produce fish in a cost-effective way for low-income consumers in developing countries. Fillet and head tissue was analysed because both tissues were destined for human consumption. Gas chromatography with mass spectrometry (GC/MS) analyses of transesterified fatty acid methyl ester extracts indicated the presence of ~ 50 fatty acids. Major fatty acids in fillet and head tissue were palmitic acid and oleic acid. Both linoleic acid and polyunsaturated fatty acids with three or more double bonds were presented in quantities > 10% of total fatty acids in fillet, but lower in head tissue. Erucic acid levels were below the newly proposed tolerable daily intake in the European Union, based on the consumption of 200 g fillet per day. Moreover, further analysis produced evidence for the presence of the dicarboxylic fatty acid azelaic acid (nonanedioic acid, Di9:0) in head tissue. To verify this uncommon finding, countercurrent chromatography was used to isolate Di9:0 and other dicarboxylic acids from a technical standard followed by its quantification. Di9:0 contributed to 0.4–1.3% of the fatty acid profile in head tissue, but was not detected in fillet. Fish fed with increasing quantities of flaxseed indicated that linoleic acid was the likely precursor of Di9:0 in the head tissue samples.
In vitro human cell-based TTR-TRβ CALUX assay indicates thyroid hormone transport disruption of short-chain, medium-chain, and long-chain chlorinated paraffins
(2021) Sprengel, Jannik; Behnisch, Peter A.; Besselink, Harrie; Brouwer, Abraham; Vetter, Walter
Over the last decades, short-chain chlorinated paraffins (SCCPs), medium-chain chlorinated paraffins (MCCPs), and long-chain chlorinated paraffins (LCCPs) have become the most heavily produced monomeric organohalogen compound class of environmental concern. However, knowledge about their toxicology is still scarce, although SCCPs were shown to have effects on the thyroid hormone system. The lack of data in the case of MCCPs and LCCPs and the structural similarity with perfluoroalkyl substances (PFAS) prompted us to test CPs in the novel TTR-TR CALUX assay for their thyroid hormone transport disrupting potential. Four self-synthesized and additionally purified single chain length CP mixtures (C10-CPs, C11-CPs, C14-CPs and C16-CPs) and two each of industrial MCCP and LCCP products were tested in parallel with PFOA. All CP mixtures influenced the TTR binding of T4, giving activities of 1,300 to 17,000 µg/g PFOA equivalents and lowest observable effect concentrations (LOELs) of 0.95 to 0.029 mM/L incubate. Highest activities and lowest LOELs were observed for C16-CPs (48.3% Cl content, activity 17,000, LOEL 0.047 mM/L) and a LCCP mixture (71.7% Cl content; activity 10,000; LOEL 0.029 mM/L). A trend of higher activities and lower LOELs towards longer chains and higher chlorination degrees was implied, but could not be statistically confirmed. Irrespectively, the less well examined and current-use LCCPs showed the highest response in the TTR-TRβ CALUX assay.