Ultra-high-performance liquid chromatography-atmospheric pressure ionization-tandem mass spectrometry method for the migration studies of primary aromatic amines from food contact materials.

This work describes the development of an ultra-high-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) method for the determination of 23 primary aromatic amines (PAAs) that can potentially migrate from food contact materials. The chromatographic separation was performed in a pentafluorophenylpropyl (PFPP) column achieving the separation of all PAAs in less than 6.5 min using water to acetonitrile (0.1% acetic acid in both solvents) as mobile phase and a gradient elution. The feasibility of atmospheric pressure chemical ionization (APCI) and atmospheric pressure photoionization (APPI) was evaluated as alternative to electrospray ionization (ESI) for the analysis of PAAs. Results showed that for most of the compounds, better responses were obtained with APCI, which shows the advantage of being less susceptible to matrix effects. Tandem mass spectrometry (MS/MS) fragmentation studies of [M + H]+ allowed for the selection of the two most characteristic and abundant product ions of the 23 PAAs which led to the development of a selective and sensitive UHPLC-APCI-MS/MS method with limits of detection ranging from 0.2 to 2 µg kg-1. Moreover, intra-day and inter-day precisions of the method in terms of relative standard deviation (RSD%) were lower than 10% and 15%, while trueness as relative error was <15% for most of the compounds. The UHPLC-APCI-MS/MS method was applied to the analysis of twenty black Nylon kitchenware samples that were submitted to migration tests using food simulant B (3% acetic acid, w/v), and the presence of PAAs were detected in eighteen samples at concentrations above the legislated limit (2 µg kg-1 of food or food simulants).

Integrated sample-pretreatment strategy for separation and enrichment of microplastics and primary aromatic amines in the migration of teabag.

In this work, an integrated sample-pretreatment strategy for the separation and enrichment of microplastics and primary aromatic amines from the migration of teabag was developed. The migration solution of teabag was passed through a homemade device. The microplastics were firstly captured by a silver membrane, and then the primary aromatic amines were enriched by a solid-phase extraction column. The microplastics migrated from teabag were detected by attenuated total reflection-Fourier transform infrared spectrometer and Raman spectroscopy. The data showed the character, the number of particles, area ratio, and morphology of microplastics migrated from the teabag. Subsequently, after the enrichment procedure, a sensitive analytical method for primary aromatic amines was established followed by ultra-high performance liquid chromatography-tandem mass spectrometry. The method showed wide linear ranges with R2 greater than 0.9915, low limits of detection (2-18 ng/L), and low limits of quantification (8-50 ng/L). The developed method was adopted to analyze microplastics and primary aromatic amines migrated from nylon and polyethylene terephthalate teabag under different temperatures and times. The integrated sample-pretreatment strategy displayed promising potentials in the one-step preparation of the microplastics and hazardous molecules in the sample of environment and food security.

Primary aromatic amines in kitchenware: Determination by liquid chromatography-tandem mass spectrometry.

The aim of this paper is to develop and validate a methodology with potential for routine analysis that allows a fast and easy quantification of 19 primary aromatic amines (PAAs) in acid simulant (3% (w/v) acetic acid aqueous) in food contact materials (FCM). The main reason for studying these amines was the fact that some of them have a carcinogenic factor according to toxicological studies. To validate the method, the parameters linearity, limit of detection (LOD) and limit of quantification (LOQ), precision and accuracy using an UPLC-MS/MS were evaluated. This study also analyzed 36 samples of kitchenware obtained from retail markets: 16 were made of polyamide (PA), one was made of polypropylene (PP) and 19 were made of silicone. The origins of samples were Brazil, China and Turkey. Eleven samples had levels of 4,4´-diaminodiphenylmethane higher than permitted by legislation and five samples showed values of aniline above the limit. Considering the Mood test for polyamides, there were significant differences between the samples from Brazil and China, as well as between the colors in the silicone samples. Regarding the polyamides, the Chinese samples showed higher amounts of PAAs than the Brazilian ones, being above that allowed by legislation. Three Chinese silicone samples presented values above the legislation limit. These were all from the same importer.

Target analysis of primary aromatic amines combined with a comprehensive screening of migrating substances in kitchen utensils by liquid chromatography-high resolution mass spectrometry.

An analytical strategy including both the quantitative target analysis of 8 regulated primary aromatic amines (PAAs), as well as a comprehensive post-run target screening of 77 migrating substances, was developed for nylon utensils, using liquid chromatography-orbitrap-high resolution mass spectrometry (LC-HRMS) operating in full scan mode. The accurate mass data were acquired with a resolving power of 50,000 FWHM (scan speed, 2 Hz), and by alternating two acquisition events, ESI+ with and without fragmentation. The target method was validated after statistical optimization of the main ionization and fragmentation parameters. The quantitative method presented appropriate performance to be used in official monitoring with recoveries ranging from 78% to 112%, precision in terms of Relative Standard Deviation (RSD) was less than 15%, and the limits of quantification were between 2 and 2.5 µg kg(-1). For post-target screening, a customized theoretical database was built for food contact material migrants, including bisphenols, phthalates, and other amines. For identification purposes, accurate exact mass (<5 ppm) and some diagnostic ions including fragments were used. The strategy was applied to 10 real samples collected from different retailers in the Valencian Region (Spain) during 2014. Six out of eight target PAAs were detected in at least one sample in the target analysis. The most frequently detected compounds were 4,4'-methylenedianiline and aniline, with concentrations ranging from 2.4 to 19,715 µg kg(-1) and 2.5 to 283 µg kg(-1), respectively. Two phthalates were identified and confirmed in the post-run target screening analysis.