Migration of photoinitiators, phthalates and plasticizers from paper and cardboard materials into different simulants and foodstuffs.

The migration of photoinitiators, phthalates and plasticizers from two paper and cardboard materials into food simulants (50% and 95% EtOH and Tenax) and foodstuffs (rice, cereals and milk powder) was studied. In the case of liquid simulants migration was observed to reach the equilibrium after 60 min and depended on the material type and the physicochemical parameters of the migrants, whereas the temperature (room temperature and 60 °C) did not show significant effects. The study of migration of the compounds from a baking paper to Tenax at high temperatures (150 and 250 °C) evidenced an increment of migration when increasing temperature, except for the most volatile analytes. Finally, the migration to foodstuffs was studied using fully validated analytical protocols. Overall, the comparison of the migration rates demonstrated that Tenax was adequate for the simulation of the migration to rice and cereals, but underestimated the migration to infant milk powder, for which 95% EtOH resulted a more suitable simulant.

Target and suspect screening of substances liable to migrate from food contact paper and cardboard materials using liquid chromatography-high resolution tandem mass spectrometry.

This work describes the analysis of both target and non-target compounds in paper and cardboard materials together with the characterization of their migration to Tenax® by means of liquid chromatography coupled to both low (LC-QqQ) and high resolution tandem mass spectrometry (LC-q-Orbitrap), respectively. To this aim, an entire analytical procedure was fully developed and validated for both matrices: paper/cardboard and Tenax®. A total of 97 chemicals, including photoinitiators, phthalates, biocides, antioxidants, etc., listed by the European Regulation, were found in the materials under study together with other substances not included in this list. Moreover, the majority of annotated substances were present in the simulant, giving evidence of their migration capacity. Migration percentages of 10 photoinitiators, 4 phthalates, bisphenol A, bis-(2-ethylhexyl) adipate, acetyltributyl citrate and caprolactam to Tenax® were quantified. Despite not exceeding the established specific migration limit (SML) in any case, benzophenone, 4-phenylbenzophenone and bisphenol A concentrations in some paper and cardboard materials were very close to the SML values established by the EU legislation.

Perfluorinated alkyl substances (PFASs) in northern Spain municipal solid waste landfill leachates.

Landfill leachates have been recognized as significant secondary sources of poly- and perfluoroalkyl substances (PFASs). This study presents data on the occurrence and concentration of 11 perfluoroalkyl carboxylates (PFCAs) and 5 perfluoroalkyl sulfonates (PFSAs) in leachates from 4 municipal solid waste landfill sites located across northern Spain. To the best of our knowledge, this is the first report of the presence of PFASs in Spanish landfill leachates. Two of the landfill sites applied on-site treatment using membrane bioreactors (MBR), and its effect on PFASs occurrence is also reported. Total PFASs (∑PFASs) in raw leachates reached 1378.9 ng/L, while in treated samples ∑PFASs was approximately two-fold (3162.3 ng/L). PFCAs accounted for the majority of the detected PFASs and perfluorooctanoic acid (PFOA) was the dominant compound in raw leachates (42.6%), followed by shorter chain PFHxA (30.1%), PFPeA and PFBA. The age of the sites might explain the PFASs pattern found in raw leachates as all of them were stabilized leachates. However, PFASs profile was different in treated samples where the most abundant compound was PFHxA (26.5%), followed by linear perfluorobutane sulfonate (L-PFBS) (18.7%) and PFOA (17.7%). The overall increase of the PFASs content as well as the change in the PFASs profile after the MBR treatment, could be explained by the possible degradation of PFASs precursors such as fluorotelomer alcohols or fluorotelomer sulfonates. Using the volume of leachates generated in the landfill sites, that served 1.8 million people, the discharge of 16 ∑PFASs contained in the landfill leachates was estimated as 1209 g/year.

Current theories in the calculation of activity coefficients-II. Specific interaction theories applied to some equilibria studies in solution chemistry.

The adequation of the current theories for calculating activity coefficients has been studied for a series of ionic equilibria in analytical chemistry: the water ionic product as well as two reactions of complex formation and oxidation-reduction. In all the cases, the specific interaction theory (SIT) has proved to be adequate and simple to apply in a restricted interval (0.5-3M), whereas Pitzer's theory is outstanding for its high precision in reproducing experimental behaviour and to correlate values of equilibrium constants for different conditions and media.