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Understanding the transfer of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in farm animals is essential for ensuring food safety, but such information for suckler ewes (Ovis aries) has been lacking. This work quantifies the accumulation, tissue distribution, and depuration kinetics of PCDD/Fs in these animals. Six suckler ewes (EXP group) were exposed to PCDD/Fs through contaminated hay (2.3–12.7 ng toxic-equivalent kg–1dry matter) and then allowed to depurate by switching to noncontaminated hay from 29 days of lactation. Four control ewes were fed continuously with noncontaminated hay. At different time points covering depuration, weaning and slaughter, PCDD/F analysis of milk (three time points), blood and sternal adipose tissue (five time points), Longissimus thoracismuscle, liver, and empty body homogenate at slaughter (188 days of depuration) was performed. A relevant PCDD/F bioaccumulation was observed from oral intake in milk and adipose tissue (biotransfer factors of 1.24 and 1.06 day kg–1lipids for the sum toxic-equivalent, respectively) in the EXP ewes, especially for penta- and hexa-chlorinated congeners. The EXP ewes’ adipose tissue started at 10-fold the EU maximum level (ML) and showed depuration below the ML after 130 days. Specific PCDD/F accumulation in the ewe liver was observed, especially for dibenzofurans. These toxicokinetic data can inform recommendations to ensure the chemical safety of sheep food products.

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.

Non-dioxin-like polychlorinated biphenyls (ndl-PCBs) are a subclass of persistent bioaccumulative pollutants able to enter the food chain. We investigated the transfer of ndl-PCBs from contaminated feed into meat and liver of fattening chickens. A total of 48 chicks were divided into five treatment and one control groups. Treated animals were fed with contaminated diets (11.7 ± 0.4 μg/kg sum of indicator ndl-PCBs; 88% dry matter (DM)) before slaughter for different subperiods of time: 16, 23, 28, 32, and 36 days for groups 1–5, respectively. One day after the end of each subperiod, three animals per group were slaughtered to determine the congener-specific ndl-PCB content. All remaining animals were fed the control feed until slaughter on day 37 to probe depuration. We used these data to generate congener-specific physiologically based toxicokinetic (PBTK) models for indicator ndl-PCBs. The models show that PCBs 28, 138, 153, and 180 form a more slowly eliminated cluster (with an observed transfer rate into meat over 74% and observed half-lives over 8.7 days) than PCBs 52 and 101 (with a transfer rate under 13% and half-lives under 2.6 days). Our simulations show that ndl-PCB levels in feed lower than 3.9 (long 56-day) or 4.4 μg/kg (short 37-day fattening period) would be necessary to ensure the current maximum level in muscle meat (fat basis), according to EU Regulations 1881/2006 and 1259/2011. The PBTK models are made available in the Python and Food Safety Knowledge Exchange formats.

The group of per- and polyfluoroalkyl substances (PFAS) comprises thousands of chemicals, which are used in various industrial applications and consumer products. In this study, a feeding experiment with laying hens and feed grown on a contamination site was conducted, and PFAS were analyzed in the feed and eggs to assess the transfer of PFAS into eggs. A targeted analysis of perfluoroalkyl acids (PFAAs) and different sulfonamides was performed. Additionally, the total oxidizable precursor (TOP) assay was modified by fully oxidizing small amounts of the samples instead of oxidizing their extracts in order to overcome potential losses during extraction. Targeted analysis showed the presence of known PFAAs and four sulfonamides in the feed and egg yolk samples. In the plant-based feed, short-chain PFAAs, methyl and ethyl perfluorooctane sulfonamidoacetic acid (Me- and EtFOSAA), and perfluorooctane sulfonic acid (PFOS) were the most abundant PFAS. In the eggs, PFOS, FOSAA, and its alkylated homologues showed the highest concentrations. The TOP assay revealed the presence of substantial amounts of precursors with different chain lengths from C4 to C8. The highest relative increase of PFOA after oxidation was observed in egg yolk from the end of the exposure period (828%). The results of this study demonstrate the transfer of PFAAs and their precursors into hens’ eggs and emphasize the contribution of (known and unidentified) precursors to the overall PFAS burden in edible products. The modified TOP assay approach was shown to be a powerful tool to better assess the total burden of samples with PFAS.

A feeding study was performed to examine the bioaccumulation of per- and polyfluoroalkyl substances (PFAS) in laying hens’ tissues and plasma and feed-to-egg transfer rates and half-lives. A 25 day exposure was followed by a 42 day depuration period. A target analysis revealed substantial amounts of the precursors N-methyl and N-ethyl perfluorooctane sulfonamidoacetic acid (Me- and EtFOSAA), perfluorooctane sulfonamidoacetic acid (FOSAA), and perfluorooctane sulfonamide (FOSA). In tissues and eggs, the highest bioaccumulation was found for PFHxS, PFHpS, PFOS, and PFOA. Low levels of PFHxS (all samples), PFOS, and FOSAA (in yolk) were measurable even after the depuration period. The egg elimination half-lives of PFOS and aforementioned precursors were estimated to be 4.3 days, while the transfer rates of PFOS and all precursors taken together were 0.99. The transfer rate of PFOA was around 0.49. PFHxS and PFHpS showed apparent transfer rates of >100%, which is hypothesized to indicate the presence of precursors.

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Beaked redfish (Sebastes mentella) and Greenland halibut (Reinhardtius hippoglossoides) were collected from fishing grounds of the Barents Sea to study the composition and lipid distribution of the muscle tissue. The belly flaps of beaked redfish showed higher lipid contents (mean 4.6%) compared to anterior dorsal muscle. The protein content was relatively constant in all parts (18–19%). The variation in the muscle lipid composition among individual redfish was greater than the variation among different anatomical locations of the fillets. No significant differences were found in the composition of Greenland halibut muscle parts. The protein content was generally low and ranged between 12.2–13.9%. The lipid content varied considerably between approximately 6 and 17%, displaying large variations of the lipid contents between different Greenland halibut individuals from one catch. The variability of lipid content should be considered in the risk assessment and management of lipophilic contaminants in fish fillets. A correlation between water and lipid content was found for both species (r = −0.8750, beaked redfish; r = −0.8732, Greenland halibut).

The mutual information (MI) expansion is applied to two molecular systems to probe algorithms that serve to estimate conformational entropy differences more precisely. The individual terms of the MI expansion are evaluated with a histogram method. Internal coordinates are used to avoid spurious correlations, which would require higher order terms in the MI expansion. Two approaches are applied that compensate for systematic errors that occur with a histogram method: (1) Simulation data are balanced by using the same number of coordinate sets (frames) for both conformer domains considered for the entropy difference computation. Balancing puts fluctuations of the histogram bin contents on the same level for both conformer domains, allowing efficient error cancellation. (2) Bias correction compensates for systematic deviations due to a finite number of frames per bin. Applying both corrections improves the precision of entropy differences drastically. Estimates of entropy differences are compared to thermodynamic benchmarks of a simple polymer model and trialanine, where excellent agreement was found. For trialanine, the average error for the estimated conformational entropy difference is only 0.3 J/(mol K), which is 100 times smaller than without applying the two corrections. Guidelines are provided for efficiently estimating conformational entropies. The program ENTROPICAL, used for the computations, is made available, which can be used for molecular dynamics or Monte Carlo simulation data on macromolecules like oligopeptides, polymers, proteins, and ligands.

We constructed an accurate polyether force field for implicit solvent (IS) molecular dynamics (MD) simulations that matches local and global conformations of 1,2-dimethoxy-ethane (DME) and polyethylene glycol (PEG), respectively. To make appropriate force field adjustments for IS models of PEG, we used long-term MD simulation data of 1 μs in explicit solvent (ES) based on the most recent CHARMM35 ether force field that includes adjustments for PEG in explicit water. In IS models, competition of attractive van der Waals (vdW) interactions between solute−solute and solute−solvent atom pairs is often not considered explicitly. As a consequence, the attractive vdW interactions between solute atom pairs that remain in IS models explicitly can yield equilibrium structures that are too compact. This behavior was observed in the present study comparing MD simulation data of the DME and PEG ES model with corresponding IS models that use generalized Born (GB) electrostatics combined with positive surface energy terms favoring compact structures. To regain balance of attractive vdW interactions for IS models, we considered the IS generalized Born with simple switching (GBSW) model in detail, where we turned off surface energy terms and reduced attractive vdW interactions to 90%, or we used alternatively even slightly negative surface energies. However, to obtain quantitatively the same local and global distributions of PEG conformers as in ES, we needed additional force field adjustments involving torsion potentials and 1−4 and 1−5 atom pair Coulomb interactions. This CHARMM ether force field, specifically optimized for IS simulation conditions, is equally valid for dimeric and polymeric ethylene glycol. To explore the conformational space of PEG with MD simulations, an IS GBSW model requires 2 orders of magnitude less CPU time than the corresponding ES model. About a factor of 5 of this gain in efficiency is due to the lack of solvent viscosity in IS models.

Systematic model investigations of the molecular interactions of fluorinated amino acids within native protein environments substantially improve our understanding of the unique properties of these building blocks. A rationally designed heterodimeric coiled coil peptide (VPE/VPK) and nine variants containing amino acids with variable fluorine content in either position a16or d19within the hydrophobic core were synthesized and used to evaluate the impact of fluorinated amino acid substitutions within different hydrophobic protein microenvironments. The structural and thermodynamic stability of the dimers were examined by applying both experimental (CD spectroscopy, FRET, and analytical ultracentrifugation) and theoretical (MD simulations and MM‐PBSA free energy calculations) methods. The coiled coil environment imposes position‐dependent conformations onto the fluorinated side chains and thus affects their packing and relative orientation towards their native interaction partners. We find evidence that such packing effects exert a significant influence on the contribution of fluorine‐induced polarity to coiled coil folding.

Non-dioxin-like polychlorinated biphenyls (ndl-PCBs) are a subclass of persistent bioaccumulative pollutants able to enter the food chain. Toxicokinetic models for the transfer of the six ndl-PCB congeners (PCBs 28, 52, 101, 138, 153, and 180) from contaminated feed and soil into chicken eggs and meat are presented. Three independent controlled feeding study datasets were used to estimate the model parameters and four studies for evaluating the model performance. The yolk deposition of ndl-PCBs is modeled in a novel way that mimics the physiology of yolk growth and development, resulting in improved prediction of the experimental data without introducing an ad hoc time delay between ovulation and oviposition. Using the models, the highest level of 2.4 μg/kg dry matter (DM) was calculated for the sum of ndl-PCBs in laying hen feed to ensure that the current maximum levels in meat and eggs (40 ng/g fat) will not be exceeded. It is also shown how this highest level in feed should be adapted in case soil, in addition to feed, is also a source of ndl-PCBs for free-range chickens.

Lupin varieties with a low content of quinolizidine alkaloids (QAs) like blue sweet lupin (BSL) have long been used as a protein source for dairy cows. A health concern for humans may arise from the transfer of acute toxic QAs from feed into cow’s milk. This study is the first to quantify the transfer of QAs from BSL into cow’s milk with experimental and modeling methods. Four lactating dairy cows were subjected to two 7 day feeding periods with 1 and 2 kg/d BSL, respectively, each followed by a depuration period. BSL contained 1774 mg/kg dry matter total QAs. Individual milk samples were taken twice daily and QA contents in feed and milk determined with liquid chromatography–tandem mass spectrometry. Transfer of QAs into the milk was already seen with the administration of 1 kg/d BSL, with differences in transfer rates (TRs) between individual QAs. A toxicokinetic model was derived to quantify and predict QA feed-to-food transfer. For the four most prominent QAs, our model shows an α-half-life of around 0.27 d. TRs were obtained for six QAs and were between 0.13 (sparteine) and 3.74% (multiflorine). A toxicological assessment of milk containing QAs as measured in this study indicated a potential health concern.