Polyfluoroalkyl phosphate esters and perfluoroalkyl carboxylic acids in target food samples and packaging—method development and screening

Polyfluoroalkyl phosphate mono-, di-, and tri-esters (mono-, di-, and triPAPs) are used to water- and grease-proof food packaging materials, and these chemicals are known precursors to perfluoroalkyl carboxylic acids (PFCAs). Existing analytical methods for PAPs lack sample clean-up steps in the sample preparation. In the present study, a method based on ultra performance liquid chromatography coupled to tandem mass spectrometry (UPLC/MS/MS) was developed and optimized for the analysis of mono-, di-, and triPAPs, including a clean-up step for the raw extracts. The method was applied to food samples and their PAP-containing packaging materials. The optimized UPLC/MS/MS method enabled the separation and identification of a total of 4 monoPAPs, 16 diPAPs, and 7 triPAPs in the technical mixture Zonyl®-RP. For sample clean-up, weak anion exchange solid phase extraction columns were tested. PAPs standard solutions spiked onto the columns were separated into a fraction containing neutral compounds (triPAPs) and a fraction with ionic compounds (mono- and diPAPs) with recoveries between 72–110 %. Method limits of quantification for food samples were in the sub to low picogram per gram range. For quantitative analysis of PAPs, compound-specific labeled internal standards showed to be essential as sorption and matrix effects were observed. Mono-, di-, and/or triPAPs were detected in all food packaging materials obtained from the Swedish market. Up to nine diPAPs were detected in the food samples, with the 6:2/6:2 and 6:2/8:2 diPAPs as the dominant compounds. DiPAP concentrations in the food samples ranged from 0.9 to 36 pg/g, which was comparable to individual PFCA concentrations in the same samples. Consumption of food packed in PAP-containing materials could be an indirect source of human exposure to PFCAs.     

Spatial variability and temporal changes in the heavy metal content of soils with a deep furrow-and-ridge microrelief formed by an afforestation plowing

An appropriate sampling method that provides for the representation of the collected material and the reliability of results plays a crucial role in environmental monitoring. This is especially important in soil quality investigations on sites with a differentiated surface microrelief, as in the case of afforested post-arable soils that have a specific, deep furrow-and-ridge microrelief. The present research was carried out on three sites afforested with pine (4-, 8-, and 15-year-old stands) located near a large tailings pond collecting the wastes from copper ore enrichment. Soils were sampled at depths of 0–10 and 0–30 cm, separately in the furrows and ridges. The “wide-furrow plow” contributed to the spatial variation in soil properties, including higher pH, organic carbon, and Cu content in soils of the ridges. The difference in Cu content in the ridges and furrows initially reached 300 %, and decreased with the decline of the furrow-and-ridge microrelief to 60 % at 15 years after the plowing. Observed rate of the furrow shallowing allows for an estimation of the time necessary for the complete disappearance of the furrow-and-ridge microrelief and associated variability in soil properties to at least 30–40 years after the plowing. Afforestation plowing had little impact on the Zn variability which was not influenced by the emissions from the tailings pond. Soil sampling in contaminated sites with furrow-and-ridge microrelief must collect equal quantities of soil samples from both furrows and ridges to allow a reliable estimation of the mean trace elements’ concentration.     

Geometrical Factors and Metapopulation Dynamics of the Bush Cricket, Metrioptera bicolor Philippi (Orthoptera: Tettigoniidae)

This paper presents a metapopulation study of the bush cricket, Metrioptera bicolor , living in a recently fragmented landscape. The species inhabits grass and heathland patches of varying area and isolation. Analyses are made of how these geometrical factors affect local population size and density, distribution pattern, and the probability of local extinction and colonization. The proportion of available patches occupied varied between 72 and 79% during 1985–1990. Unoccupied patches were smaller and more isolated than those that were occupied. Patches where populations became extinct during this period were smaller than those with persisting populations. Since local population size was well correlated with patch area, it was clear that stochastic extinctions only occurred in small populations. Critical patch size for population extinction was approximately half a hectare. Colonized patches were less isolated than those that had not been colonized. Critical inter-patch distance for colonization was about 100 meters. The turnover was restricted to an identifiable share of the available patches. Only 33% of the patches were so small that extinction due to stochastic causes could be considered highly probable. This metapopulation will therefore most likely persist over a considerable period in its present spatial structure. There are apparent threats of further fragmentation, however, and nothing is known about the likelihood of large-scale extinctions resulting from extremely unfavorable weather conditions. Nevertheless, our results show that it is appropriate to include geometrical factors in metapopulation models.