Determination of several PFAS groups in food packaging material from fast-food restaurants in France.

Per- and polyfluoroalkylated substances (PFAS) are a large group of toxic compounds which have been widely used in industrial and consumer applications, from where they can migrate into the environment. They can pose a risk to human health because they have been associated with several diseases. To obtain more information on the risk of PFAS in fast food packaging materials, several PFAS (perfluorocarboxylic acids or PFCAs (n = 16), perfluorosulfonic acids or PFSAs (n = 14), and a miscellaneous group constituted by sulfonamides (n = 5) and fluorotelomer phosphate esters or PAPs (n = 5)) were quantified in food contact materials (FCMs) from fast-food restaurants in France. Perfluorohexanoic acid (PFHxA), 6:2 fluorotelomer sulfonic acid (6:2 FTS) and 6:2/6:2 fluorotelomer phosphate diester (6:2/6:2 diPAP) were detected in all samples. PFCAs with shorter chain lengths (C4-C6) showed the highest concentrations compared to median (C7-C10) and longer chain length PFCAs (C11-C18). However, they had lower detection frequencies (DFs) (except for PFHxA, DF = 100%) with values of 36 and 34% for C4 and C5 PFCAs, respectively. The DF of longer chain length PFCAs was higher, especially those of the median chain length PFCAs (C8-C10, with DF = 79-98%). Analytes from the PFSA group with high DFs (70-98%) were perfluorobutane sulfonic acid (PFBS), perfluorohexane sulfonic acid (PFHxS), perfluorooctane sulfonic acid (PFOS, linear and branched) and 10:2 fluorotelomer sulfonic acid (10:2 FTS), with concentrations similar to some analytes from the PFCA group. 4:2 Fluorotelomer phosphate monoester (4:2 mPAP), 8:2 fluorotelomer phosphate monoester (8:2 mPAP) and 8:2/8:2 fluorotelomer phosphate diester (8:2/8:2 diPAP) were found with the highest concentrations (<0.006-42.7 ng g-1, <0.001-2.7 ng g-1 and <0.001-287 ng g-1, respectively) and the highest DFs (ranged 68-94%). Some correlations between analytes were found, indicating similar degradation routes or a common origin.

Supramolecular solvent extraction and ambient mass spectrometry for the determination of organic contaminants in food packaging material.

A rapid method based on a fast sample treatment with supramolecular solvents (SUPRASs) and ambient mass spectrometry (AMS) analysis was developed for the screening and quantification of organic contaminants in food packaging materials (FCMs). The suitability of SUPRASs made up of medium chain alcohols in ethanol:water mixtures was investigated, given their low toxicity, proven capacity for multi-residue analysis (since they provide a wide variety of interactions and multiple binding sites) and restricted access properties for simultaneous sample extraction and clean-up. Two families of emerging organic pollutants, bisphenols and organophosphate flame retardants, were targeted as representative compounds. The methodology was applied to 40 FCMs. Target compounds were quantitated using ASAP (atmospheric solids analysis probe)-low resolution MS and a broad-spectrum screening of contaminants was performed through spectral library search using direct injection probe (DIP) and high resolution MS (HRMS). The results showed the ubiquity of bisphenols and of some flame retardants, as well as the presence of other additives and unknown compounds in about half of the analyzed samples, which highlight the complex composition of FCMs and the possible associated health risks.

Supramolecular solvent-based microextraction probe for fast detection of bisphenols by ambient mass spectrometry.

In this study, we investigated for the first time the suitability of supramolecular solvent (SUPRAS)-based microextraction probe for the development of generic and fast sample treatment prior to qualitative analysis by ambient mass spectrometry (AMS) based on ASAP (atmospheric solids analysis probe). SUPRAS are nanostructured liquids formed by the self-assembly of amphiphilic aggregates with multiple binding sites and microenvironments of different polarity for the efficient extraction of multiple compounds. Different types of SUPRAS were evaluated as a simple and single step sample treatment for ASAP. The method was applied to the screening of bisphenol A and structural analogues in thermal paper. Optimal results were achieved with SUPRAS synthesized with 1-decanol in mixtures of ethanol:water. SUPRAS (1.1-2 µL) were loaded onto glass probes and placed in contact with samples for 10 s before ASAP analysis. AMS signal peaks (width: 0.2-0.5 min) were easily integrated and normalized with internal standards (RSD: 2-25%). The method was applied to 62 samples of thermal paper. BPA and BPS were the most widely used, this highlighting the progressive industrial replacement of BPA by BPS.

Supramolecular solvent-based microextraction of aryl-phosphate flame retardants in indoor dust from houses and education buildings in Spain.

Aryl-phosphate flame retardants (aryl-OPFRs) are flame retardants or plasticizers (among other functions) that can be found in a wide variety of products, from furniture and textiles to cars and electronic equipment. There is an increasing concern about the human exposure to these contaminants due to their ubiquity (as additives they can be easily released from the product to the environment) and potential toxicity. In this study, we investigated the presence of six representative aryl-OPFRs, two well-known aryl-OPFRs (triphenyl phosphate, TPHP and 2-ethylhexyl diphenyl phosphate, EHDPP), two novel aryl-OPFRs (cresyl diphenyl phosphate, CDP and isodecyl diphenyl phosphate, IDPP) and two oligomeric aryl-OPFRs [bisphenol A bis(diphenyl phosphate), BDP and resorcinol bis(diphenyl phosphate, RDP] in indoor dust from houses and education buildings from Spain. Sample treatment was carried out by a novel and simple procedure based on supramolecular solvents (SUPRAS) prior to LC-MS/MS analysis. The median Σaryl-OPFRs was two times higher in classrooms than in houses, being particularly high at University classrooms. The most abundant aryl-OPFR in houses was TPHP (median 497 ng·g-1) while EHDPP (median 407 ng·g-1) and IDPP (median 403 ng·g-1) were dominant in classrooms. This is the first study reporting IDPP, BDP and RDP in different education buildings.

Supramolecular solvent-based microextraction of emerging bisphenol A replacements (colour developers) in indoor dust from public environments.

Bisphenol A (BPA) is present in a wide variety of materials and it is a well-known endocrine disruptor that is widespread in indoor and outdoor environments. For this reason, industry has introduced a variety of replacements, such as Bisphenol S (BPS) or Bisphenol F (BPF), and other less known structural analogs, such as BPS-MAE, D-8 or TGSA. These emerging potential contaminants have been identified in thermal paper products, according to recent studies, but their potential toxic effects and their migration into the environment remain unclear. In this study, we report for the first time the presence of emerging BPA replacements in indoor dust from public environments (shops, restaurants, etc.). For this purpose, we optimized a novel supramolecular solvent (SUPRAS)-based microextraction method. SUPRAS are multi-target solvents made up of self-assembled amphiphiles. They offer multiple extraction interactions (dispersion, polar, hydrophobic, etc.) and they constitute excellent candidates to develop generic and fast sample treatment procedures at low cost. By this method, emerging BPA replacements (BPS-MAE, D-8 and TGSA) were detected in dust at median concentrations in the range 6-22 ng g-1 (around ten times lower than BPS) with detection frequencies in the range 50-90%. These results constitute a first insight into the migration of emerging BPA replacements into the environment via indoor dust, which is a common route of human exposure to contaminants.