Uncertainties in the determination of pyrrolizidine alkaloid levels in naturally contaminated honeys and comparison of results obtained by different analytical approaches

The contamination of honey with hepatotoxic pyrrolizidine alkaloids (PAs) is a well-known hazard for food safety. While management strategies and controls of the honey industry aim to reduce the PA levels, uncertainties remain with regard to the safety of regionally produced and marketed honey. In addition, a previous study showed large differences of results obtained after various periods of storage and apparent differences between the analytical results of different laboratories. Therefore, this study aimed at examining these uncertainties by monitoring the impact of storage on the PA and PA N-oxide (PANO) content of two freshly harvested honeys and on possible demixing effects caused by pollen settling. Additionally, three analytical approaches – target analysis with matrix-matched calibration or standard addition and a sum parameter method – were applied for a comparative analysis of 20 honeys harvested in summer 2016. All samples originated from Schleswig-Holstein in Northern Germany where the PA plant Jacobaea vulgaris is currently observed on a massive scale. The results of the time series analyses showed that PANO levels markedly decreased within a few weeks and practically reached the LOD 16 weeks after harvest. Tertiary PAs, by contrast, remained stable and did not increase as a consequence of PANO decrease. The experiments on a putative demixing, which may result in a heterogeneous distribution of PAs/PANOs, revealed that there was no such effect during storage of up to 12 weeks. A comparison of the PA/PANO levels obtained by different analytical approaches showed that in some cases the sum parameter method yielded much higher levels than the target approaches, whereas in other cases, the target analysis with standard addition found higher levels than the other two methods. In summary, the results of this study highlight uncertainties regarding the validity and comparability of analytical results and consequently regarding health risk assessment.     

Supramolecular complexes: Determination of stability constants on the basis of various experimental methods

Stability constants and formation enthalpies of supramolecular complexes of crown ethers and their cyclic and acyclic analogues are determined on the basis of experimental data obtained by different physicochemical methods in the terms of a general approach developed and implemented in the ChemEqui software package. The established regularities of variation of stability of complexes are discussed as dependent on the ligand structure, nature of the cation, solvent, and anion. The applicability of the suggested method of determining complexation selectivity is shown for multicomponent equilibria in solutions.

     

Quality enhancement of the abundant under‐valued crustacean,lobster krill (Munida spp.), during its chilled storage

Lobster krill (Munida genus) represents an under‐valued crustacean frequently caught on European fishing banks. In this work, its sensory, microbiological and biochemical qualities were evaluated during chilled storage. Additionally, the effects of a prestorage antimelanosic treatment consisting of soaking in sodium metabisulphite (SMB) solutions at two different concentrations (0.25% and 0.75%) were also studied. SMB prestorage treatment provided lobster specimens that still exhibited acceptable sensory quality after 10 days of storage, while control specimens were unacceptable at that time. SMB treatment also resulted in a significant (P < 0.05) inhibition of microbial growth, mainly of Enterobacteriaceae, psychrotrophes and proteolytic bacteria. Low lipid oxidation levels were observed for all batches; however, a significantly higher (P < 0.05) retention of polyunsaturated fatty acids was found in SMB‐treated lobster, especially in the 0.75% SMB batch. The results presented here open the way to the potential commercialisation of currently under‐utilised lobster krill as a chilled product.