Elsevier

Talanta

Volume 208, 1 February 2020, 120394
Talanta

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

https://doi.org/10.1016/j.talanta.2019.120394Get rights and content

Highlights

  • Target and non-target analysis was performed on paper and cardboard (P/B) materials.

  • LC-QqQ and LC-q-Orbitrap were used for target and non-target analysis, respectively.

  • Tenax was used for migration experiments simulating long-term storage of dry foods.

  • 97 compounds were annotated in the studied FCMs being most of them present in Tenax.

  • This work highlights the necessity of a specific regulation for P/B FCMs.

Abstract

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.

Introduction

Social and scientific concern on food contamination has increased within the past decades. Food contact materials (FCMs) are one of the main important sources of food contamination. While FCMs are intended for food protection and preservation, their direct or indirect contact with food can induce the migration of different contaminants such as additives, including stabilizers, antioxidants or slipping agents, among others, commonly added to these materials [1]. Besides, the migration of non-intentionally added substances (NIASs) [2] coming from a variety of sources (i.e., degradation, reaction or presence in raw materials) should not be underestimated.

Recycled paper and board (P/B) can contain many chemical substances originally present in the waste paper that might eventually be present in the final recycled material. They can contain many additives such as fillers, biocides, etc. Moreover, printed paper contains printing inks, pigments, photoinitiators, adhesives, plasticizers, mineral oils, etc., apart from other contaminants coming from the waste paper treatment [3]. According to EU Regulation [4], FCMs “shall be manufactured in compliance with good manufacturing practice, so that, under normal or foreseeable conditions of use, they do not transfer their constituents to food in quantities which could endanger human health or bring about an unacceptable change in the composition of the food or a deterioration in the organoleptic characteristics thereof”. This regulation covers all FCMs. However, in contrast to the case of plastic FCMs [5], there is no specific regulation to be applied to paper and board [6] and, consequently, the plastic regulation is often used.

The main factors involved in the migration of FCM constituents are related with the physicochemical properties of the migrant, the characteristics of the foodstuffs or food simulants and the temperature [7]. In order to estimate migration from food packaging materials, experiments can be either performed with food or food simulants. Food simulants are often preferred to food due to the simpler analytical procedures required [8]. Modified polyphenylene oxide (MPPO), Tenax®, is the recommended simulant for dry foods, for plastics and P/B FCMs [5].

For decades, the analysis of substances present in FCMs has been carried out using target approaches, which require a previous selection of the compounds of interest. Liquid chromatography coupled to low-resolution mass spectrometry (LC-MS) has been widely chosen for the analysis of additives with low volatility and low thermal stability present in FCMs [9]. However, the development of high resolution efficiency (>50,000 FWHM) analytical techniques such as high-resolution mass spectrometry (HRMS) coupled to separation techniques has provided the tools to tackle this problem using a non-target analysis approach [10,11]. In non-target HRMS analysis, full scan acquisition modes give the opportunity of screening expected and unexpected compounds. While target analysis requires the use of reference standards, non-target analysis requires neither prior information nor reference standards. In between, suspect screening allows analysing the samples based on prior information on the expected/suspected compounds but with no need of reference standards [12]. Data-dependent acquisition modes in tandem HRMS provide accurate mass (1–5 ppm) and isotope information, as well as fragmentation, being possible the tentative identification of the suspect compounds [12]. Application of suspect/non-target approaches for the analysis of additives, printing inks and NIASs in plastic FCMs has increased in the last years but few applications to P/B are found [[13], [14], [15], [16], [17], [18]]. However, HRMS should be considered as a powerful technique in the P/B FCM field, since the nature of all the migrating substances in those materials cannot be predicted in advance because many of those compounds correspond to unknown by-products or the real composition of the FCMs is unknown, especially in the case of recycled P/B FCMs.

Within this context, the aim of the present work was to perform a quantitative target analysis of contaminants (10 photoinitiators, 4 phthalates, bisphenol A (BPA), bis(2-ethylhexyl)adipate (BEA), acetyltributyl citrate and caprolactam) in several P/B samples together with the screening of the substances liable to migrate from the FCMs by means of LC-HRMS (LC-qOrbitrap). For this purpose, the analytical procedure was fully validated and applied to P/B FCMs such as packaging cardboard, pizza boxes and baking paper collected in local markets and restaurants from the Basque Country (North of Spain). Migration tests were performed using Tenax® in order to simulate long-term storage of dry foods at room temperature. To our knowledge, this is the first time that both identification and migration of target and non-target analytes are performed in the aforementioned P/B FCMs.

Section snippets

Reagents and materials

Laboratory material was carefully cleaned with pure water (<0.2 μS/cm, Millipore, USA) and without using detergent to avoid possible contamination produced by detergent residues. The glass material was sonicated under clean acetone (Panreac Química, Barcelona, Spain) for an hour, rinsed with ultrapure water (<0.057 μS/cm, Milli-Q purification system model 185; Millipore, Bedford, MA, USA) and dried in an oven at 400 °C for 4 h.

Photoinitiators were acquired from different suppliers: benzophenone

Method validation

Prior to analysis of samples, method validation was performed in terms of linearity, procedural limits of detection (LODproc), absolute recoveries and precision calculated at three concentration levels (20 ng/g, 200 ng/g and 2000 ng/g) using P/B and Tenax® matrices (see Table 2). Chromatograms obtained by means of LC-QqQ analysis (section 2.5) at the lowest spiked level for both P/B materials and Tenax® can be observed in Fig. S2.

Calibration curves were built with standard solutions in MeOH in

Conclusions

The current work presents the target and non-target identification of compounds from P/B materials, together with the study of their migration ability to dry foodstuffs during long-term storage using Tenax® as simulant. In this sense, up to 97 substances belonging to a wide range of families (photoinitiators, phthalates, biocides, antioxidants, etc.) were annotated in 8 different P/B materials. Moreover, when standard references were available, quantification was also performed, concluding that

Acknowledgements

This work has been financially supported by the Basque Government through the Project PA18/02. Itsaso Zabaleta is grateful to the University of the Basque Country (UPV/EHU) for her post-doctoral fellowship (DOKBERRI 2018-I).

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