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Article

Identification of Potential Migrants in Food Contact Materials Labeled as Bio-Based and/or Biodegradable by GC-MS

by
Emma López Sanvicente
1,
Letricia Barbosa-Pereira
1,2,
Raquel Sendón
1,2,
Ana Rodríguez Bernaldo de Quirós
1,2 and
Antía Lestido-Cardama
1,2,*
1
FoodChemPack Research Group, Department of Analytical Chemistry, Nutrition and Food Science, Faculty of Pharmacy, University of Santiago de Compostela, 15782 Santiago de Compostela, Spain
2
Instituto de Materiales (iMATUS), University of Santiago de Compostela, 15782 Santiago de Compostela, Spain
*
Author to whom correspondence should be addressed.
Coatings 2025, 15(7), 751; https://doi.org/10.3390/coatings15070751 (registering DOI)
Submission received: 3 June 2025 / Revised: 21 June 2025 / Accepted: 24 June 2025 / Published: 25 June 2025
(This article belongs to the Special Issue Bio-Based and Biodegradable Packaging Materials for Food Contact)
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Abstract

Bio-based and/or biodegradable food contact materials are being developed as alternatives to conventional petroleum-based materials. Like other food contact materials, these are subject to regulatory requirements. The characterization of these biomaterials enables the identification of chemical substances that could potentially migrate from these materials into food and may pose a risk to consumer health. In this work, commercial samples of food contact materials labeled as bio-based and/or biodegradable were analyzed. To tentatively identify compounds, two analytical methods were optimized: purge and trap (P&T) for volatile compounds and methanolic extract injection for the determination of semi-volatile compounds, both using gas chromatography coupled with mass spectrometry (GC-MS). Compound toxicity was estimated using an in silico methodology, namely Cramer’s rules. More than 200 compounds of different natures were tentatively identified, but only 29 are included in Regulation (EU) 10/2011 on plastic materials intended to come into contact with food, and 38 of them were classified as high-toxicity compounds.

Graphical Abstract

1. Introduction

Petroleum-based materials have a significant negative impact on the environment. Although their use as food contact materials (FCMs) is reducing, food packaging and products produced from non-renewable resources are still mainstream in the industry. This environmental concern has increased consumer interest and demand for more sustainable alternatives, such as bio-based and/or biodegradable materials [1,2].
There are two main groups of bioplastics according to the European Association of Bioplastics: plastics based on renewable resources (bio-based) and biodegradable plastics, which do not necessarily have to be biologically based [3].
Bio-based polymers can be defined as man-made or man-processed organic macromolecules synthesized or derived from renewable resources (plants and/or animals) or by microorganisms using a carbon source through fermentative processes. Occasionally, they can return to nature as carbon dioxide, water, inorganic compounds, and biomass through the composting process, leaving no distinguishable and/or toxic residues [4,5]. Their “bio” origin does not guarantee biodegradation; it depends on the chemical structure of the polymers.
Biodegradable plastics are those that easily biodegrade in nature through the action of microorganisms and other living organisms, reducing the molar masses of macromolecules. They can be composed of both natural and fossil sources [4,6,7].
Biodegradable and/or bio-based polymers can be classified into three main categories. The first group includes biodegradable and bio-based polymers, like cellulose, starch, polylactic acid (PLA), and polyhydroxyalkanoates (PHA) [4,8,9]. The second category comprises biodegradable but not bio-based polymers, which originate from petrochemicals, including polybutylene succinate (PBS) and poly(butylene adipate-co-terephthalate) (PBAT). Lastly are bio-based but not biodegradable polymers, which are synthesized similarly to petroleum-based plastics but originate from bio-based raw materials, such as bio-based polyethylene terephthalate (bio-PET) and bio-based polypropylene (bio-PP) [4].
Food contact bioplastics do not yet have specific regulations but must comply with Regulation (EC) No. 1935/2004 [10] on materials and articles intended to come into contact with food and must not transfer their constituents to food in quantities which could endanger human health. Regulation (EU) 10/2011 [11] on plastic food contact materials, which includes a list of substances that can migrate with their specific migration limits, should also be taken as a reference.
For these bioplastic materials to achieve properties similar to those of petroleum-based polymers (mechanical properties, permeability, etc.), it is common to incorporate additives such as plasticizers, antioxidants, and slip agents, among others. However, regarding food safety, the number of studies on the characterization of these bioplastic food contact materials is limited [12,13,14,15,16,17]. For example, Asensio et al. [17] analyzed natural biomaterials, identifying a total of 67 compounds used in manufacturing paper, adhesives, and food packaging. Migration tests in three liquid simulants revealed numerous compounds related to the food contact industry, such as decanal, nonanal, and phthalic anhydride, among others. In other study, Tsochatzis et al. [13] investigated the chemical safety of polysaccharide films made from pea starch, organocatalytic acetylated pea starch, and pectin using two official food simulants representing hydrophilic and lipophilic foods. Semi-volatile and non-volatile migrating compounds were identified and semi-quantified. Measurable migration levels of substances such as glycerol, monoacetylated maltose, and dibutyl phthalate were determined. These materials, like conventional plastics, can release substances and reach food. Potential migrants from food packaging include intentionally added substances (IAS), such as monomers and additives, and non-intentionally added substances (NIAS), such as reaction and/or degradation products, etc. Therefore, the characterization of these bioplastic materials is an imperative.
According to some authors [2,18], analytical methods currently used for the detection and identification of chemical compounds from petroleum-derived plastic FCMs, as well as migration assays, are expected to be suitable for bioplastic FCMs, for example, GC-MS methods for the determination of volatile and semi-volatile substances, liquid chromatography coupled to mass spectrometry (LC-MS) for the analysis of non-volatile compounds, etc. [4]. GC-MS is the most commonly used technique for identifying unknown volatile compounds due to its high reproducibility, robustness, and the availability of standardized commercial libraries [19].
In this work, the characterization of a set of commercial samples of food contact materials labeled as bio-based and/or biodegradable was carried out. First, Fourier-transform infrared spectroscopy with attenuated total reflection (FTIR-ATR) was used to identify the type of polymer in the samples. Once determined, two non-targeted methods for the tentative identification of both volatile and semi-volatile compounds were optimized: the P&T and GC-MS techniques allow the volatile compounds to become concentrated in a sorbent material, and the solvent extraction technique followed by GC-MS enables the detection of semi-volatile substances. Finally, for chemical compounds with no previous toxicity tests, their toxicity was estimated using an in silico methodology, i.e., Cramer’s rules.
This study aligns with the objectives of the proposed revision of the Packaging and Packaging Waste Regulation [20], which emphasizes not only the sustainability of packaging materials but also their chemical safety. The potential presence of potentially hazardous substances in bio-based and biodegradable food contact materials highlights the urgent need for standardized assessment frameworks.

2. Materials and Methods

2.1. Reagents and Analytical Standards

Methanol (MeOH) (CAS-No: 67-56-1) and n-hexane for gas chromatography (CAS-No: 110-54-3) were provided by Merck (Darmstadt, Germany).
Toluene-d8 (≥99%) (CAS-No: 2037-26-5), provided by Sigma-Aldrich (Schnelldorf, Germany), was used as the internal standard for the P&T method, while diethyl phthalate-3,4,5,6-d4 (DEP-d, 99,3%) (CAS-No: 93951-87-2), purchased from Fluka (Steinheim, Germany), was used as the internal standard for the determination of semi-volatile compounds.
Analytical standards with high purity (>99%) were used in this study for the confirmation of some of the compounds tentatively identified. Diethyl phthalate (CAS-No: 84-66-2), methenamine (CAS-No: 100-97-0), and diisobutyl phthalate (CAS-No: 84-69-5) were purchased from Sigma-Aldrich (Schnelldorf, Germany). Tributyl acetylcitrate (CAS-No: 77-90-7) was obtained from Fluka (Steinheim, Germany), and tetradecane (CAS-No: 629-59-4) was provided by Panreac (Barcelona, Spain). All standards were prepared using MeOH as a solvent, except for tetradecane which was dissolved in hexane.
Various preventive measures were performed to reduce possible contamination. To handle the samples, the use of plastic materials was avoided by using glass instead, previously washed with an organic solvent, muffled (to avoid contamination with ubiquitous compounds such as phthalates), and covered with aluminum foil until use.

2.2. Samples

A total of seven samples of commercial food contact materials labeled as bio-based and/or biodegradable were analyzed in this study. None of the samples had previously been in contact with foodstuffs. All of them were purchased from stores in Santiago de Compostela (Spain) and consisted of plastic materials, except for the pasta packaging (BSC) and the green paper straws (CBV), which were made of paper and cardboard. Sample information is detailed in Table 1.

2.3. Fourier-Transform Infrared Spectroscopy with Attenuated Total Reflectance (ATR-FTIR)

To identify the type of material, an ATR (attenuated total reflectance)-FTIR (Fourier-transform infrared) spectrometer (ATR-PRO ONE, FTIR 4700, Jasco, Tokyo, Japan) fitted with a diamond optical crystal and controlled by the Spectra Manager™ v.2 software (Jasco, Japan) was used.
Before the analysis, samples were cut, cleaned with an organic solvent, and dried. FTIR spectra were acquired in the region from 4000 to 650 cm−1, on the inside and outside surfaces of the material. For spectrum identification, KnowItAll 17.4.135.B software was used, comparing the recorded samples’ spectra with the infrared spectra available in the libraries of polymers and related compounds from Bio-Rad Laboratories, Inc. (Philadelphia, PA, USA). Only entries from the library with an impact quality index (HQI) greater than 80 were taken into account in the identification.

2.4. Sample Preparation

Food contact materials were cut into small pieces of approximately 5 mm and stored in Petri glass dishes until analysis.
For the P&T GC-MS method, 1 g of the sample was weighed and introduced directly into EPA glass vials with a PTFE/silicone septum for this equipment, along with 50 µL of a 10 mg/L solution of toluene-d8 as an internal standard.
For the determination of semi-volatile compounds, solid–liquid extraction had previously been carried out. In each glass vial, the amount of optimized sample was weighed, and 5 mL of MeOH was added. Vials were left in the oven for 24 h at 70 °C. After this time, extracts were concentrated 15 times by evaporating to dryness with a stream of nitrogen at 40 °C (RapidVap Vertex Evaporator, Labconco, Kansas City, MO, USA) and subsequent reconstitution with MeOH, and 10 µL of a 10 mg/L solution of DEP-d was added as an internal standard. Then, the extract was filtered using a PTFE membrane filter of 0.45 µm (Membrane Solutions, Auburn, WA, USA) into a glass vial for its encapsulation and subsequent injection into the gas chromatograph. All tests were performed in triplicate.

2.5. P&T GC-MS Method for the Determination of Volatile Compounds

The P&T technique was used for the extraction of volatile compounds. The analysis was conducted in an ATOMX XYZ multi-matrix P&T system (Teledyne, CA, USA) operated with Atomx XYZ TekLink™ software. The purge temperature was 80 °C and the purge time was 20 min. The purge flow was 40 mL/min with helium as the purge gas, the desorption time was 2 min, and the temperature and desorption flow were 250 °C and 300 mL/min, respectively.
The GC-MS equipment used was a Trace 1300 Series GC gas chromatograph coupled to a Trace ISQ LT single-quadrupole mass spectrometer detector, both from Thermo Scientific (San José, CA, USA). For the separation of volatile compounds from the samples, a Rxi-624SilMS column from Restek® (Bellefonte, PA, USA) of 30 m length × 0.25 mm internal diameter and 1.40 µm film thickness was used.
The chromatographic conditions applied were the following: Helium (3× quality, from Nippon Gases, Madrid, Spain) was used as the carrier gas, at a constant flow of 1 mL/min. The initial oven temperature was set at 35 °C for 2 min, then increased at a rate of 9 °C/min until reaching 300 °C, holding this temperature for 10 min. The transfer line temperature and electron source temperature were set at 300 °C. Mass spectra were obtained with a mass-selective detector in which the ionization mode was electron impact (EI) at a voltage of 70 eV. To acquire the data, a full scan was performed with an m/z range of between 20 and 500. Xcalibur 2.0.7 software (Thermo Scientific Inc., San José, CA, USA) was used for acquisition and processing. For the tentative identification of the compounds, the commercial mass spectral libraries Wiley Registry™ 12th edition, with nearly one million mass spectra per EI, and NIST/EPA/NIH 11 version 2.0, with 30,898 mass spectra, were used.

2.6. GC-MS for the Determination of Semi-Volatile Compounds

The gas chromatograph and mass spectrometer equipment used was the same as indicated in Section 2.5, but with an AI 1310 automatic injector (Thermo Fischer Scientific, San José, CA, USA). For the separation of the semi-volatile compounds in the samples, an Rxi-5Sil MS column of 30 m length × 0.25 mm internal diameter and 0.25 µm film thickness from Restek® (Bellefonte, PA, USA) was used as the stationary phase.
For the screening analysis, 1.0 µL aliquots from the extracts of the samples were injected in splitless mode, with an injector temperature of 250 °C. Helium (3× quality, from Nippon Gases) was used as the carrier gas at a constant flow of 1 mL/min. An initial oven temperature of 40 °C was maintained for 2 min, subsequently increased following a temperature ramp of 9 °C/min until reaching 300 °C, and maintained at that temperature for 10 min. EI ionization was set at a voltage of 70 eV. Both the temperatures of the transfer line and the ion source were set at 300 °C. The acquisition of the chromatograms was carried out in full scan mode, over an m/z range of between 20 and 500. The same software and commercial mass spectral libraries were used as in Section 2.5.

2.7. Toxicity Estimation

Cramer’s decision tree (1978) is a tool used to carry out a first classification and ordering of substances according to the expected level of toxicity, based on their molecular structure, in order to estimate the toxicological risk of exposure to these compounds. For this purpose, the software Toxtree v3.1.0.1851 (Ideaconsult Ltd., Sofia, Bulgaria) [21] was used. This model classifies substances into three classes, according to their level of toxicity: class I (low toxicity), class II (intermediate toxicity), and class III (high toxicity). The Threshold of Toxicological Concern (TTC) values established were 1800 μg/person/day for Cramer class I, 540 μg/person/day for Cramer class II, and 90 μg/person/day for Cramer class III [22].

3. Results and Discussion

3.1. Characterization of the Materials by FTIR-ATR

The FTIR analysis allowed for the identification of the type of material used in the seven samples. The results are shown in Table 1. The two samples that corresponded to paper and cardboard are composed of cellulose (CBV and BSC samples); another two samples are based on PLA (VLT and CBX samples); one sample is composed of poly(lactic-co-glycolic) acid (PLGA), a copolymer formed by the polymerization of lactic acid (LA) and glycolic acid (GA) [23] (sample CFR); and two samples are composed of biodegradable polystyrene, a polymer mentioned by Pinaeva & Noskov (2024) (VCT and VBT samples) [24]. In all cases, the material of the internal surface matches the material of the external surface, except for the BSC sample, whose external surface could not be identified because it is probably a multilayered material or has coatings on the external surface, which makes its identification difficult by FTIR-ATR spectroscopy. All identifications presented an HQI greater than 87.
Figure 1 shows the IR spectrum of the VLT sample (blue) and the IR spectrum of the first entry in the IR spectral libraries (PLA, in red) overlapped. Characteristic bands of PLA [25] present in the spectrum of the VLT sample are indicated. The IR spectrum of the other sample can be seen in Figure S1 (Supplementary Materials).

3.2. Screening of Volatile Compounds by P&T GC-MS

3.2.1. P&T GC-MS Method Optimization

Several tests were carried out for the optimization of the method in the VCT sample, including the amount of sample to be analyzed (0.5, 1, or 2.5 g), the purge temperature (30, 60, or 80 °C), and the purge time (10, 20, or 30 min).
It was determined that 80 °C allowed a greater number of compounds to be identified than 60 °C or 30 °C. Regarding the time parameter, 20 min was chosen instead of 10 min or 30 min, since no significant differences were found between the number of compounds identified between 20 and 30 min, but better results were obtained when comparing 20 with 10 min. Finally, regarding the amount of sample used, 1 g of sample prevails over 0.5 g and 2.5 g, since the number of compounds that could be identified using 1 g was practically the same as using 2.5 g and greater than if 0.5 g was used.

3.2.2. Tentative Identification of Volatile Compounds

In this study, the optimized P&T GC-MS method was used to tentatively identify volatile compounds, which may be potential migrants.
Only compounds with a high spectral coincidence with the available libraries were considered, that is, those with an SI (search index) and RSI (reverse search index) greater than 700.
A total of 68 compounds of different natures were tentatively identified in the FCM samples analyzed (Table 2). The BSC sample was the one with the most volatile compounds, with a total of 29 compounds. Figure 2 shows the P&T GC-MS chromatogram of the CBV sample with some of the tentatively identified compounds.
Numerous compounds of different chemical nature (alkanes, aldehydes, ketones, alcohols, esters, etc.) were tentatively identified, related to the manufacture of FCM. Some of these compounds are IAS, such as monomers, additives, or other starting substances. Among the additives, phthalates, and other plasticizers, photoinitiators and slip agents were identified, among others. In addition, numerous NIAS were also detected in all seven samples, such as reaction and/or degradation products.
Within the IAS, numerous plasticizers were detected, like 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, in the CBV sample, which is a safer and environmentally friendly alternate non-phthalate plasticizer and ink solvent, included in Regulation (EU) 10/2011 with an SML of 5 mg/kg [11,62,70]. Regarding phthalate esters (PAEs), only one compound was tentatively identified, diisobutyl phthalate (DIBP) in the CBX sample, belonging to Cramer’s class I. PAEs are a group of compounds widely used as plasticizers to increase the durability and flexibility of products. Numerous studies classify them as endocrine disruptors [71].
Several compounds related to adhesives were found. For example, compound 1-hexanol-2-ethyl acetate (BSC sample), which is a Cramer’s class I compound, was previously found in adhesives [53,54]. The compound 1-hexanol-2-ethyl, identified in the BSC sample, is included in Regulation 10/2011 with an SML of 30 mg/kg, whose use is permitted as a monomer or another starting substance, and it has also been found in adhesives and paper manufacturing [11,17,47].
In the CBX and CFR samples (both based on PLA or derivatives), a PLA oligomer was identified, namely DL-lactide [28], which was classified as Cramer class I. Methyl lactate, a compound found in the VLT and CBX samples, is a degradation product of PLA belonging to Cramer’s class I [57].
Some characteristic compounds of cellulose and paper were found in the CBV and BSC samples. Many of the analyzed compounds originated from the degradation of a biopolymer chain such as alkanes and alkenes, which are considered NIAS of chain degradation [28]. Pentadecane and 3-methylpentadecane, which are both volatile organic compounds (VOCs) from recycled cellulose, were identified in both samples and belong to Cramer’s class I [53]. Propanoic acid, 2-methyl, 3-hydroxy-2,2,4-trimethylpentyl ester is a coalescent agent (a chemical additive that helps paint form a solid film) identified in the CBV samples, which belongs to Cramer’s class II [63]. 2-Ethylhexyl acrylate is an acrylic monomer used for solvent-free photopolymerizable paper coating, which was also found in the CBV sample, and it is included in Regulation (EU) 10/2011 with an SML of 0.05 mg/kg [11,58]. Propylene glycol is a softener additive used for cellulose regeneration found in the CBV sample, and it is included in Regulation (EU) 10/2011 with an SML of 60 mg/kg [11,34].
Compounds related to polystyrene were found in the VBT and VCT samples, like benzene, 1-methylpropyl [38] and benzene, 1-propenyl [40], both found in the VCT sample and belonging to Cramer’s class I. Benzene, 1,1′-(1,3-propanediyl)bis is an isomer of styrene dimers identified in the VCT sample, belonging to Cramer’s class III, which means high toxicity [67]. Benzene, 1,3-diethyl is an aromatic VOC of polystyrene found in the VBT sample (Cramer’s class I) [40].
Numerous compounds identified in the analyzed samples correspond to NIAS: 1-hexanol-2-ethyl, a product of the thermal decomposition or hydrolysis of plasticizers such as bis(2-ethylhexyl) phthalate (DEHP) or bis-(2-ethylhexyl) adipate (DEHA), was detected in the BSC sample [48]. Other highly abundant NIAS in the samples were polymerization by-products and degradation products of polystyrene, belonging to Cramer’s class I (decanal and propylbenzene, both in VCT and VBT [38]; 2-phenylpropenal in VCT [38]), as well as Cramer’s class III (2,4-diphenyl-1-butene in the VBT and VCT samples [38,68]), among others.
Some compounds related to printing ink were found in the analyzed samples, because the materials were analyzed on both sides, including the external side, which in some of the samples was printed or colored (BSC, CBV). Although this side is not in direct contact with food, it is interesting to take these substances into account due to possible contamination because of the set-off phenomenon, for example. Set-off occurs when, after printing, products are stacked without assembly, and part of the fresh ink may be stamped on the internal side of the adjacent product, which will be in contact with food [44]. In this study, some ink-related compounds were tentatively identified, such as 1,2,4-methenoazulene, decahydro-1,5,5,8A-tetramethyl (in the BSC sample, Cramer’s class I) [60,61] and benzaldehyde (VBT, CFR, and VLT samples, included in Regulation (EU) 10/2011 with an SML of 60 mg/kg) [11,35]. A compound that works as a photoinitiator for curing UV inks, methanone, (1-hydroxycyclohexyl)phenyl, which is also a component of some paints, coatings, and printing inks, was found in the VLT sample [44,69]. Other ink components were tentatively identified, such as α-pinene in the BSC sample, which is also used in adhesives, coatings, and adhesion agents [41]. This compound is listed in Regulation (EU) 10/2011 with a specific migration limit (SML) of 60 mg/kg [11]. Additionally, 1,2,3-trichlorobenzene was detected in the CBV, VBT, and VCT samples; this substance is used in lacquers, resins, and pigments and is classified as a Cramer class III compound [52].
This work shows the presence of numerous compounds that are not included in the list of substances allowed by Regulation (EU) 10/2011 [11]. Only 10 of the 68 compounds tentatively identified and grouped in Table 2 are included in it. In this context, Cramer’s method results in an adequate first step for estimating the toxicity of these potential migrants.

3.3. Screening of Semi-Volatile Compounds by GC-MS

3.3.1. GC-MS Method of Optimization

To carry out the extraction of compounds in the analyzed samples, the extraction solvent (MeOH), time, and temperature conditions were selected based on previous laboratory studies [32], with modifications. The amount of sample to be analyzed by this technique was optimized (0.5, 1 or 2.5 g). Finally, 1 g of sample was used since the results were significantly better than using 0.5 g, identifying a great number of chromatographic peaks (approximately 10), without major differences with respect to using 2.5 g. Subsequently, 5 mL of MeOH, the solvent chosen for both extraction and reconstitution, was added to each of the samples.

3.3.2. Tentative Identification of Semi-Volatile Compounds

In this work, the optimized GC-MS method was used for the tentative identification of semi-volatile compounds in the analyzed samples.
More than 100 compounds were tentatively identified in the samples, and the results are shown in Table 3. Five of the compounds were confirmed through the injection of the corresponding standard under the same conditions used for the sample analysis and their subsequent comparison regarding the mass spectrum and retention time. The remaining compounds were tentatively identified by comparing the obtained mass spectra with those available in the libraries. As with the P&T method, only compounds with an SI and RSI greater than 700 were considered.
Figure 3 shows the GC-MS chromatogram of the VCT sample, showing the tentative identification of several peaks. Only 19 of the total compounds tentatively identified are included in the list of substances allowed by Regulation (EU) 10/2011 [11].
Using the described technique, numerous compounds of different chemical natures (alkanes, aldehydes, alcohols, ketones, carboxylic acids, esters, etc.) related to the manufacturing of FCMs were tentatively identified as monomers and additives. Within the second group, numerous plasticizers (phthalates and others), antioxidants, solvents, stabilizers, slip agents, ultraviolet filters, photoinitiators, etc., were found.
Since the extraction was carried out by immersion, the material was extracted from both sides, and some ink-related components were identified in the samples, such as surfactants, which allow water-insoluble pigments to be compatible in aqueous-based inks. An example of an ink surfactant found in the CBV sample was 2,4,7,9-tetramethyl-5-decyn-4,7-diol, which was classified as a highly toxic chemical compound (Cramer class III) [82].
Numerous phthalates were detected in the samples, such as diethyl phthalate (DEP) (CBV, VBT, VLT, BSC, VCT), diisobutyl phthalate (DIBP) (BSC), bis(2-ethylhexyl)hexahydro phthalate (CFR), and bis(2-ethylhexyl) phthalate (DEHP) (CBV, VBT, VCT), which, in addition to their function as plasticizers, are often used in printing ink formulations and as solvents to maintain color [17,45,121]. DEHP is included in Regulation (EU) 10/2011 and authorized for use in plastic FCMs with an SML of 1.5 mg/kg, with restrictions of an SML of 60 mg/kg in terms of the sum of group substances [11], while DEP, bis(2-ethylhexyl)hexahydro phthalate, and DIBP are not included. DIBP and DEHP are classified as carcinogenic, endocrine-disrupting, and reproductively toxic substances by the European Chemical Agency (ECHA) [123]. For this reason, attempts have been made to replace them with other plasticizers. Some of the alternative plasticizers to phthalates found in the samples are bis(2-ethylhexyl) fumarate (DEHF) (BSC) [47]; 2,2,4-trimethyl-1,3-pentanediol (CBV) [76], which was classified as Cramer class II; and heptadecanol (CBV, CBX, CFR, VLT) [26,95]. 2,2,4-Trimethyl-1,3-pentanediol diisobutyrate (CBV) is a plasticizer and ink solvent [62] included in Regulation (EU) 10/2011, whose SML is 5 mg/kg [11]. This compound was also identified in the P&T analysis. Another class of alternative plasticizers to phthalates are citric acid esters, such as tributyl citrate (CFR) and tributyl acetylcitrate (ATBC) (VBT, CBX, CFR) [64]. ATBC is included in Regulation (EU) 10/2011 with restrictions of an SML of 60 mg/kg in terms of the sum of group substances [11]. Bis(2-ethylhexyl) hexanedioate (DEHA) is another plasticizer [47] included in Regulation (EU) 10/2011, with an SML of 18 mg/kg, also with restrictions of an SML of 60 mg/kg in terms of the sum of group substances [11]. Isopropyl myristate, found in the BSC sample, is a plasticizer used for cellulose, a pigment dispersant, and a binding agent [64]. Polyethylene glycol (PEG) is highly recommended as a plasticizer for PLA, which is why several compounds from the ethylene glycol family were identified in the PLA samples [84]. Recently, fatty acid methyl esters (FAMEs) have emerged as sustainable alternatives that can be used as greener plasticizers, such as 11-octadecenoic acid, methyl ester (BSC), which belongs to Cramer’s class I [98].
Some adhesive-related compounds, such as ethanol, 2-(2-ethoxyethoxy) (CBV, BSC), also used in paints, dyes, inks and surface coatings [72,73]; or 4-methylbenzenesulfonamide, in sample CFR (Cramer’s class III), have been identified [72]. Pentadecanoic acid and heptadecanoic acid, both found in the CBV sample, are two compounds related to adhesives used for the manufacturing of paper [17]. Polypropylene glycol and dodecanoic acid (BSC) [17,72] are two compounds used in adhesives, both authorized by Regulation (EU) 10/2011 for polymerization, with an SML of 60 mg/kg [11]. In addition to its use in adhesives, palmitic acid, a compound found in most samples (CBV, CBX, CFR, VLT, BSC), is used as a lubricant and slip agent in paper manufacturing [17,46,47,64].
Some compounds used as lubricants were detected in this study, such as 1-eicosanol (BSC) [74,102]. Oleic acid (CBV, BSC) and stearic acid (CBV, VLT) are two compounds included in Regulation (EU) 10/2011, with an SML of 60 mg/kg [11], and are used in the manufacturing of paper and adhesives, as well as lubricants [17,32,47].
Two compounds that function as UV filters, that is, protect the product by absorbing UV light, were identified in the BSC and CBV samples: 2-ethylhexyl salicylate and 2-propenoic acid, 3-(4-methoxyphenyl), 2-ethylhexyl ester, respectively [64,93]. Both compounds are classified as Cramer’s class I.
Numerous degradation products were found in the studied FCMs (NIAS) as antioxidant degradation products: 2,4-di-tert-butylphenol (CFR) [44,45,64] and 3-pentenoic acid, 4-phenyl (CBV) [44], both of low toxicity according to Cramer’s rules. The compounds benzene 1,1′-(1,2-cyclobutanediyl)bis, cis (VCT) [38,44] and 7,9-di-tert-butyl-1-oxaspiro(4,5)deca-6,9-diene-2,8-dione (CBV, CFR) [47], which are also degradation products of antioxidants, are classified as highly toxic according to Cramer’s decision tree. It should be noted that the slipping and anti-blocking agent N,N-diethyldodecanamide (CBV) has a chemical structure similar to the antistatic agent N,N-bis(2-hydroxyethyl)dodecanamide, which is subject to restriction [104].
It is interesting to note that, in the BSC sample, not only was the adhesive methyl dehydroabietate identified, but as was its degradation product, dehydroabietal [64,69,86]. While the adhesive belongs to Cramer’s class I, indicating low toxicity, its degradation product falls into a high-toxicity category.
Numerous compounds could be identified with both GC-MS techniques, such as 1-hexanol, 2-ethyl (BSC), included in Regulation (UE) 10/2011 with an SML of 30 mg/kg [11]; DL-lactide (CBX, CFR), Cramer’s class I; 2,2,4-trimethyl-1,3-pentanediol diisobutyr-ate (TXIB) (CBV), included in Regulation (EU) 10/2011 with an SML of 5 mg/kg [11]; 1,6-dioxacyclododecane-7,12-dione in the CFR sample; and benzene, 1,1′-(1,3-propanediyl)bis (VCT) and 2,4-diphenyl-1-butene (VBT, VCT), both belonging to Cramer’s class III. These results highlight the complementarity of the two techniques, which provide a complete screening analysis of the compounds present in the samples.

4. Conclusions

In this work, two GC-MS methods were used for the tentative identification of a wide range of potential migrant compounds, both volatile and semi-volatile, present in commercial FCM samples labeled as bio-based and/or biodegradable. This screening approach allowed for the tentative identification of over 200 compounds of different natures, including intentionally added substances (IAS), such as plasticizers, lubricants, UV filters, antioxidants, or photoinitiators, as well as non-intentionally added substances (NIAS), such as antioxidant or plasticizer degradation products, among others. Currently, there is no specific legislation for these bio-based and/or biodegradable FCMs, and only 29 of the identified compounds are included in Regulation (EU) 10/2011.
The toxicity of these tentatively identified migrant compounds was assessed using an in silico method, specifically Cramer’s decision tree. The results classified most of the compounds in class I. Overall, approximately 12% of the tentatively identified compounds were categorized as high toxicity (class III), highlighting the importance of further toxicological evaluation.
Consequently, it is important to highlight that the results demonstrate that even alternative materials marketed as biodegradable and/or bio-based are not exempt from chemical complexity. The presence of potentially hazardous substances among the tentatively identified migrants reinforces the idea that these materials should not be assumed to be inherently safer than conventional fossil plastics. This underscores the need for a more comprehensive assessment framework that includes both chemical characterization and toxicological analysis, in accordance with current and future regulatory requirements.
Therefore, it is necessary to highlight the need to carry out further studies for the characterization and quantification of these new food contact materials, since their use is expected to increase in the coming years, progressively replacing petrochemical-derived FCMs. A deeper understanding of their potential risks to consumer health is essential to ensure their safety and to guide future regulatory developments.

Supplementary Materials

The following supporting information can be downloaded a: https://www.mdpi.com/article/10.3390/coatings15070751/s1, Figure S1. ATR-FTIR spectra of the inner side of the samples, CBV (a), VBT (b), CBX (c), CFR (d), BSC (e), and VCT (f) (blue), and the IR spectrum of the first entry on the IR spectra libraries (red) overlapped.

Author Contributions

Conceptualization, A.L.-C. and A.R.B.d.Q.; methodology, A.L.-C. and E.L.S.; software, E.L.S.; validation, E.L.S.; formal analysis, E.L.S.; investigation, E.L.S.; data curation, A.L.-C.; writing—original draft preparation, E.L.S.; writing—review and editing, A.L.-C., L.B.-P., A.R.B.d.Q., R.S.; supervision, A.L.-C., L.B.-P., A.R.B.d.Q.; project administration, A.R.B.d.Q.; funding acquisition, A.R.B.d.Q. All authors have read and agreed to the published version of the manuscript.

Funding

This research was funded by the Ministerio de Ciencia e Innovación, Agencia Estatal de Investigación, and by Fondo Europeo de Desarrollo Regional (FEDER). Ref. No. PID2021-124729NB- I00 “MIGRABIOQUANT” (MCIN/AEI/10.13039/501100011033/FEDER, UE).

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

The data presented in this study are available in [Identification of potential migrants in food contact materials labeled as bio-based and/or biodegradable by GC-MS].

Conflicts of Interest

The authors declare no conflicts of interest.

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Coatings 15 00751 g001
Figure 1. IR spectrum of the VLT sample (blue line) and the first entry of the IR spectral libraries that corresponds to PLA (red line). Characteristic bands are indicated by arrows. In the lower left part of the image, the molecular structure of PLA is shown.
Figure 1. IR spectrum of the VLT sample (blue line) and the first entry of the IR spectral libraries that corresponds to PLA (red line). Characteristic bands are indicated by arrows. In the lower left part of the image, the molecular structure of PLA is shown.
Coatings 15 00751 g001
Coatings 15 00751 g002
Figure 2. P&T GC-MS chromatogram of the CBV sample as an example with some of the tentatively identified compounds indicated by arrows.
Figure 2. P&T GC-MS chromatogram of the CBV sample as an example with some of the tentatively identified compounds indicated by arrows.
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Coatings 15 00751 g003
Figure 3. GC-MS chromatogram of the VCT sample with some of the tentatively identified compounds indicated by arrows.
Figure 3. GC-MS chromatogram of the VCT sample with some of the tentatively identified compounds indicated by arrows.
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Table 1. Information on food contact materials analyzed in this study.
Table 1. Information on food contact materials analyzed in this study.
CodingSample DescriptionType of Material
Internal SideExternal Side
CBVGreen paper strawsCelluloseCellulose
VBTTransparent low glassPSPS
CBXIce cream spoonPLA-basedPLA-based
CFRColored plastic strawsPLGA-basedPLGA-based
VLTTransparent long glassPLAPLA
BSCPasta packagingCellulose-
VCTTransparent small glassPSPS
PS: polystyrene; PLA: polylactic acid; PLGA (poly(lactic-co-glycolic) acid).
Table 2. Volatile compounds tentatively identified using P&T GC-MS in the studied FCM.
Table 2. Volatile compounds tentatively identified using P&T GC-MS in the studied FCM.
RT (min)m/zCompoundIUPAC NameFormulaCAS NoApplicationsSIRSITCSML (mg/kg)Samples
CBVVBTCBXCFRVLTBSCVCT
5.1441, 43, 56, 57HexaneHexaneC6H14110-54-3Ink-related compound; degradation product [26,27]942957INI X
5.2541, 43, 56, 57Alkane NIAS of chain degradation [28]747859 X
5.4941, 43, 57, 86Alkane NIAS of chain degradation [28]759840 X
7.3443, 45, 60Acetic acidAcetic acidC2H4O264-19-7Product of PLA degradation [29]895946 ** X
8.6043, 71, 74Methyl butyrateMethyl butanoateC5H10O2623-42-7Resins; adhesives in FCMs [30]753882INIX X
9.5198, 100Toluene-d8 C7D82037-26-5Internal standard (IS)940940 XXXXXXX
9.5791, 92Benzene, methylTolueneC7H8108-88-3Solvent [31] 988989INI X
10.3341, 43, 57, 71, 85Heptane, 2,4-dimethyl2,4-DimethylheptaneC9H20 2213-23-2Detected in PLA [32]853921INI X
10.6544, 56, 57HexanalHexanalC6H12O66-25-1VOCs in food contact paperboard [33] 712904INI X XX
10.6843, 45Propylene glycolPropane-1,2-diolC3H8O257-55-6Softener additive for cellulose regeneration [34]947954 **X
11.2643, 57, 71, 85Octane, 4-methyl4-MethyloctaneC9H202216-34-4VOC [32,35]731952INI X XX
11.7591, 106EthylbenzeneEthylbenzeneC8H10100-41-4Precursor of styrene and PS, VOC [36,37,38,39]811956INI X X
11.9440, 91, 106p-Xylene1,4-XyleneC8H10106-42-3Aromatic compound in PS [40]749914INI X X
12.0443, 57, 85NonaneNonaneC9H20111-84-2NIAS of chain degradation [28]716852INI X
13.10105, 120Benzene, (1-methylethyl)CumeneC9H1298-82-8Aromatic compound in PS; oxidized product of aliphatic hydrocarbon [38,40]813915INI X X
13.1039, 77, 91, 93, 105, 120Alpha-pinene2,6,6-Trimethylbicyclo[3.1.1]hept-2-eneC10H16 80-56-8Formation of terpene resins for adhesives, printing ink compound, coatings, and adhesion agents; monomer [41]765835 ** X
13.4841, 55, 69, 832,2-Dimethyl-3-heptene trans(E)-2,2-Dimethylhept-3-eneC9H1819550-75-5Identified in mixtures of wood biomass and polypropylene [42]712804INI X
13.7343, 57, 704-Methylhexanal4-MethylhexanalC7H14O41065-97-8Aldehyde found in paper and board products [43]759818INIX
13.7591, 120Benzene, propylPropylbenzeneC9H12103-65-1Styrene polymerization by-product [38]954969INI X X
14.0541, 55, 56, 69, 70, 83, 971-DeceneDec-1-eneC10H20872-05-9Degradation of biopolymer chain [28]819923 0.05 X
14.3081, 82, 138Furan, 2-penthyl2-PentylfuranC9H14O3777-69-3Cellulose degradation product [17]766950IIINI X X
14.3977, 78, 115, 117, 118Alpha-methylstyreneProp-1-en-2-ylbenzeneC9H1098-83-9Oxidized products of aliphatic hydrocarbon [38]940961 0.05 XX
14.6051, 77, 105, 106BenzaldehydeBenzaldehydeC7H6O100-52-7Ink-related compound; styrene oxidation product [35,38,44,45]953968 ** X XX
14.91105, 134Benzene, 1-methylpropylButan-2-ylbenzeneC10H14135-98-8Found in PS [38]872934INI X
15.0043, 56, 84OctanalOctanalC8H16O124-13-0Odorant compound [46]848944INI X X X
15.42115, 117, 118Benzene, 1-propenyl[(E)-Prop-1-enyl]benzeneC9H10873-66-5VOC in PS [40]743925INI X
15.5641, 43, 57, 70, 841-Hexanol, 2-ethyl2-Ethylhexan-1-olC8H18O104-76-7Adhesives; by-product of plasticizers; paper manufacturing [17,47,48]740866 30 X
15.78105, 119, 134Benzene, 1,3-diethyl1,3-DiethylbenzeneC10H14141-93-5Aromatic VOC of PS [40]786873INI X
15.79111, 146, 148, 1501,4-Dichlorobenzene1,4-DichlorobenzeneC6H4Cl2106-46-7Additive in FCM [49]726834 12 X
15.9741, 55, 69, 83, 84, 974-Undecene, 4-methyl4-Methylundec-4-eneC12H2461142-40-3NIAS of chain degradation [28]732793INI X
16.1343, 57, 71, 84, 85Decane, 5,6-dimethyl5,6-DimethyldecaneC12H261636-43-7NIAS of chain degradation [28]746805INI X
16.2865, 91, 92, 120Benzeneacetaldehyde2-PhenylacetaldehydeC8H8O 122-78-1Styrene-oxidized products [38]801922INI X X
16.2941, 55, 69, 70, 83, 843-Decene, 2,2-dimethyl(E)-2,2-Dimethyldec-3-eneC12H2455499-02-0NIAS of chain degradation [28]789814INI X
16.5255, 70, 832-Decene, 2,4-dimethyl2,4-Dimethyldec-2-eneC12H24 74421-03-7NIAS of chain degradation [28]704770INI X
16.7377, 105, 120Acetophenone1-PhenylethanoneC8H8O98-86-2Monomer; styrene degradation product [38,44,50]867928INI X X
16.8255, 69, 83, 1685-Undecene, 5-methyl5-Methylundec-5-eneC12H2431613-73-7NIAS of chain degradation [28]764805INI X
17.05119, 1341,2,4,5-Tetramethylbenzene1,2,4,5-TetramethylbenzeneC10H1495-93-2VOC in food contact cardboard [51]830932INIX
17.39180, 1821,2,3-Trichlorobenzene1,2,3-TrichlorobenzeneC6H3Cl387-61-6Printing inks, lacquers, resin, and pigments [52]858951IIINIXX X
17.4343, 55, 70, 831-Hexanol, 2-ethyl, acetate2-Ethylhexyl acetateC10H20O2103-09-3Adhesives used in FCM [53,54]871927INI X
17.56117, 1321-Allyl-2-methylbenzene1-Methyl-2-prop-2-enylbenzeneC10H121587-04-8Found in wood [55]717818INIX
17.6059, 100, 101, 129Pentanedioic acid, dimethyl ester (dimethyl glutarate)Dimethyl pentanedioateC7H12O41119-40-0Used in polyester paints, varnishes, lacquers, solvents, resins, and plasticizers [56]749915INI X
17.6145, 88, 89Propanoic acid, 2-hydroxy-methyl ester (methyl lactate)Methyl 2-hydroxypropanoateC4H8O3547-64-8PLA degradation product [57]724732INI X X
17.8843, 57, 71, 85DodecaneDodecaneC12H26112-40-3NIAS from chain degradation [28]895935INI X X
18.4051, 77, 103, 104, 1322-Phenylpropenal2-Phenylprop-2-enalC9H8O4432-63-7Styrene oxidation product [38]749931INI X
18.7441, 57, 70, 82DecanalDecanalC10H20O112-31-2Aliphatic hydrocarbons oxidation product in PS [38]832911INI X X
18.83127, 128, 130NaphthaleneNaphthaleneC10H8 91-20-3Plastic manufacturing [17]750910IIINI X
18.8555, 57, 702-Ethylhexyl acrylate2-Ethylhexyl prop-2-enoateC11H20O2103-11-7Acrylic monomer for solvent-free photopolymerizable paper coating [58]761796 0.05X
19.6845, 561,4-Dioxane-2,5-dione, 3,6-dimethyl (DL-Lactide)3,6-Dimethyl-1,4-dioxane-2,5-dioneC6H8O4 95-96-5PLA oligomer [28]943950INI XXX
21.1543, 57, 71, 85TetradecaneTetradecaneC14H30 629-59-4Alkane; possible lubricant [14,34,38,59]751915INI X XX
21.6091, 94, 105, 119, 133, 161, 189Longicyclene(2S,9S)-2,6,6,9-Tetramethyltetracyclo[5.4.0.02,9.08,10]undecaneC15H241137-12-8“Set-off” ink migration in carboard cups and water-borne coating paper [60,61]818878INI X
21.7742, 56, 70, 83, 89, 982,2,4-Trimethyl-1,3-pentanediol diisobutyrate (TXIB)[2,2,4-Trimethyl-3-(2-methylpropanoyloxy)pentyl] 2-methylpropanoateC16H30O4 6846-50-0Plasticizer and ink solvent [62]843846 5X
22.0042, 56, 70, 89Propanoic acid, 2-methyl, 3-hydroxy-2,2,4-trimethylpentyl ester(3-Hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoateC12H24O377-68-9Coalescent agent [63]917918IINIX
22.1143, 57, 71, 85EicosaneIcosaneC20H42112-95-8VOC found in recycled cellulose [34]861917INI X
22.6443, 57, 71, 85PentadecanePentadecaneC15H32629-62-9VOC found in recycled cellulose [34]860939INIX X
23.2443, 57, 71, 85Alkane NIAS of chain degradation [28]790865 X
23.5443, 57, 712-Methylpentadecane2-MethylpentadecaneC16H34 1560-93-6VOC found in recycled cellulose [34]810850INIX
23.6641, 55, 57, 71, 83, 853-Methylpentadecane3-MethylpentadecaneC16H342882-96-4VOC found in recycled cellulose [34]754807INIX X
24.0441, 43, 57, 71HexadecaneHexadecaneC16H34544-76-3NIAS of chain degradation [17,28,64]877937INIX X
24.8954, 55, 84, 100, 1291,6-Dioxacyclododecane-7,12-dione1,6-Dioxacyclododecane-7,12-dioneC10H16O4 777-95-7VOC found in biomaterials; degradation product in resins [46,65,66]738828INI X
25.3743, 57, 71, 85Alkane NIAS of chain degradation [28]902933 X X
25.8091, 92, 105, 196Benzene, 1,1′-(1,3-propanediyl)bis3-PhenylpropylbenzeneC15H16 1081-75-0Isomer of the styrene dimers [67]820893IIINI X
26.6391, 104, 130, 2082,4-Diphenyl-1-butene3-Phenylbut-3-enylbenzeneC16H16 16606-47-6By-product of styrene polymerization [38,68]736938IIINI X X
26.9055, 77, 81, 99, 105Methanone, (1-hydroxycyclohexyl)phenyl (Irgacure 184)(1-Hydroxycyclohexyl)-phenylmethanoneC13H16O2947-19-3Photoinitiators for curing UV inks [44,69]780927INI X
27.06104Benzene, 1, 1′-(1,2-cyclobutanediyl)bis, trans[(1R,2R)-2-Phenylcyclobutyl]benzeneC16H1620071-09-4By-product of styrene polymerization [38]906920IIINI X X
27.36130, 180, 207, 2081-Phenyl-1,2,3,4-tetrahydronaphthalene1-Phenyl-1,2,3,4-tetrahydronaphthaleneC16H16 3018-20-0Co-monomer [44,45]818897IIINIX
28.46149, 150, 223Diisobutyl phtalate (DIBP)Bis(2-methylpropyl) benzene-1,2-dicarboxylateC16H22O484-69-5Plasticizer; printing inks; solvent to maintain color [45]787931INI X
28.4774, 87, 149Hexadecanoic acid, methyl esterMethyl hexadecanoateC17H34O2112-39-0Intermediary for emulsifiers, stabilizers, resins, and plasticizers [17,64]820927INI X
RT: retention time; SI: search index; RSI: reverse search index; CT: Cramer toxicity; NI: not included in Regulation (EU) 10/2011; SML: specific migration limit; **: specific migration limit of 60 mg/kg (substances for which there is no specific migration limit or other restrictions in Annex I of Regulation (EU) 10/2011); VOC: volatile organic compound; NIAS: substances not intentionally added.
Table 3. Semi-volatile compounds tentatively identified using GC/MS in the studied FCM.
Table 3. Semi-volatile compounds tentatively identified using GC/MS in the studied FCM.
RT (min)m/zCompoundIUPAC NameFormulaCAS NoApplicationsSIRSITCSML (mg/kg)Samples
CBVVBTCBXCFRVLTBSCVCT
8.5445, 59, 72Diethylene glycol monoethyl ether2-(2-Ethoxyethoxy)ethanolC6H14O3111-90-0Adhesives, paints, dyes, inks, and surface coatings [72,73]918925INIX X
8.9742, 45, 59, 892-Propanol, 1,1′-oxybis1-(2-Hydroxypropoxy)propan-2-olC6H14O3110-98-5Additive; monomer [74]799862 ** X
9.0441, 43, 55, 57, 70, 831-Hexanol, 2-ethyl2-Ethylhexan-1-olC8H18O 104-76-7Adhesives; degradation product of plasticizers; paper manufacturing [17,47,48]947965 30 X
9.2841, 45, 59, 103Polypropylene glycol1-(1-Butoxypropan-2-yloxy)propan-2-olC6H14O325322-69-4Adhesives; coating [54,72,75]735797 ** X
10.6545, 88, 89Methyl lactateMethyl 2-hydroxypropanoateC4H8O3547-64-8PLA degradation product [57]785790INI XX
11.2543, 56, 571,3-Pentanediol, 2,2,4-trimethyl2,2,4-Trimethylpentane-1,3-diolC8H18O2144-19-4Metabolite for the plasticizer TXIB [76]901924IINIX
11.6643, 45, 561,4-Dioxane-2,5-dione, 3,6-dimethyl (DL-Lactide)3,6-Dimethyl-1,4-dioxane-2,5-dioneC6H8O495-96-5PLA oligomer [28]956956INI XXX
11.7545, 74Lactic acid2-Hydroxypropanoic acidC3H6O3 50-21-5Production of PLA [77]707820 ** X
11.8141, 45, 572-(2-Butoxyethoxy)Ethanol2-(2-Butoxyethoxy)ethanolC8H18O3112-34-5Solvents; lacquers; inks [48,69]893908INI XX
12.3777, 94, 138Ethanol, 2-phenoxy2-PhenoxyethanolC8H10O2122-99-6Solvent for cellulose acetate, dyes, inks, resins, and in the synthesis of plasticizers [78]869907INI X
12.7242, 140Methenamine *1,3,5,7-Tetrazatricyclo[3.3.1.13,7]decaneC6H12N4100-97-0Pesticides; catalytic agents; cross-linking agents [79]853915 15X
13.0843, 60, 115Nonanoic acidNonanoic acidC9H18O2112-05-0Adhesive FCMs [17]748861INIX X
14.1945, 57, 71Methoxyacetic acid, 2-ethylhexyl ester2-Ethylhexyl 2-methoxyacetateC11H22O3NA 859860IIINI X
14.4243, 71, 83(1-Hydroxy-2,4,4-trimethylpentan-3-yl) 2-methylpropanoate(1-Hydroxy-2,4,4-trimethylpentan-3-yl) 2-methylpropanoateC12H24O374367-33-2Ink plasticizer [44]721864INI X
14.4343, 71, 83, 89, 982,2,4-Trimethyl-1,3-pentanediol diisobutyrate (TXIB)[2,2,4-Trimethyl-3-(2-methylpropanoyloxy)pentyl] 2-methylpropanoateC16H30O46846-50-0Plasticizer; ink solvent [80]901902 5X
14.5941, 60, 73N-decanoic acidDecanoic acidC10H20O2334-48-5Additive; monomer [11]811860 ** X
14.7741, 43, 56, 71, 89Propanoic acid, 2-methyl, 3-hydroxy-2,2,4-trimethylpentyl ester(3-Hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoateC12H24O377-68-9PLA coating for paper and cardboard [81]923923IINIX X
15.1341, 43, 57, 71, 85Tetradecane *TetradecaneC14H30629-59-4Lubricant [14,59]955966INI X
15.2543, 109, 1512,4,7,9-Tetramethyl-5-decyn-4,7-diol2,4,7,9-Tetramethyldec-5-yne-4,7-diolC14H26O2126-86-3Surfactant in water-based printing inks [82]866882IIINIX
16.1943, 55, 691-DodecanolDodecan-1-olC12H26O112-53-8Paper manufacturing [17]874941INIX X
16.6345, 89Tetraethylene glycol2-[2-[2-(2-Hydroxyethoxy)ethoxy]ethoxy]ethanolC8H18O5112-60-7Solvent; oligomer of the plasticizer polyethylene glycol (PEG) [44,83,84]942942 ** XX
16.6657, 191, 2062,4-Di-tert-butylphenol2,4-Ditert-butylphenolC14H22O96-76-4Antioxidant degradation product [44,64,65]889906INI X
17.2741, 54, 551,6-Dioxacyclododecane-7,12-dione1,6-Dioxacyclododecane-7,12-dioneC10H16O4 777-95-7PBAT (polybutylene adipate-co-terephthalate) cyclic oligomer [85]913913INI X
17.3741, 60, 73Dodecanoic acidDodecanoic acidC12H24O2143-07-7Additive; monomer; antimicrobial agent; adhesive [11,17,44]822860 ** X
17.74153, 181Diethyl phthalate-3,4,5,6-d4 C12H10D4O493952-12-6Internal standard (IS)878933 XXXXXXX
17.75149, 177Diethyl phtalate (DEP) *Diethyl benzene-1,2-dicarboxylateC12H14O484-66-2Plasticizer; printing ink; solvent to maintain color [45,64,86]857950INIXX XXX
17.9041, 43, 57, 71, 85HexadecaneHexadecaneC16H34544-76-3NIAS from chain degradation [28]935935INI X
17.9191, 131, 1763-Pentenoic acid, 4-phenyl(E)-4-Phenylpent-3-enoic acidC11H12O253774-19-9Antioxidant degradation product [44]756888INIX
18.0041, 43, 45, 57Methoxyacetic acid, decyl esterDecyl 2-methoxyacetateC13H26O3259141-02-1 807821IIINI X
18.16146, 160, 2352,6-Diisopropylphenylcarbamic acid methyl esterMethyl N-[2,6-di(propan-2-yl)phenyl]carbamateC14H21NO239076-23-8Additive [87]834836INI X
18.6991, 92, 105Benzene, 1,1′-(1,3-propanediyl)bis3-PhenylpropylbenzeneC15H161081-75-0Isomer of the styrene dimers [67]831934IIINI X X
18.7443, 95, 121Alpha-cadinol(1R,4S,4aR,8aR)-1,6-Dimethyl-4-propan-2-yl-3,4,4a,7,8,8a-hexahydro-2H-naphthalen-1-olC15H26O481-34-5Adhesives; printing inks; coatings; adhering agents [88]851885IIINI X
18.8365, 91, 155, 171p-Toluenesulfonamide4-MethylbenzenesulfonamideC7H9NO2S70-55-3Adhesives [72]906927IIINI X
18.8843, 55, 69, 831-TetradecanolTetradecan-1-olC14H30O112-72-1Resin monomers; precursors; raw materials [26,89]898935INI X
18.8943, 55, 57, 691-TridecanolTridecan-1-olC13H28O26248-42-0Lubricant; precursor of surfactants; plasticizers [90]860935INI X
18.9345, 57, 71, 74, 89Methoxyacetic acid family 772790 X
19.1977, 81, 991-Hydroxycyclohexyl phenyl ketone(1-Hydroxycyclohexyl)-phenylmethanoneC13H16O2947-19-3Photoinitiator; paints; printing inks [44,69]926949INI X
19.278, 104Benzene, 1,1′-(1,2-cyclobutanediyl)bis, cis[(1S,2R)-2-Phenylcyclobutyl]benzeneC16H167694-30-6Antioxidant degradation product; by-products of styrene polymerization [38,44]733855IIINI X
19.4674, 87, 143, 199Methyl tetradecanoateMethyl tetradecanoate C15H30O2124-10-7Slip agent [64]921953INI X
19.5091, 104, 1302,4-Diphenyl-1-butene3-Phenylbut-3-enylbenzeneC16H16 16606-47-6By-product of styrene polymerization [38,68]738951IIINI X X
19.65107, 135, 147, 178Coniferyl aldehyde(E)-3-(4-Hydroxy-3-methoxyphenyl)prop-2-enalC10H10O3 458-36-6Lignin precursor [91,92]754793INI X
19.6991, 124, 137, 180Coniferyl alcohol4-[(E)-3-Hydroxyprop-1-enyl]-2-methoxyphenolC10H12O3458-35-5Lignin precursor [91]850945INI X
19.8778, 103, 104Benzene, 1,1′-(1,2-cyclobutanediyl)bis trans[(1R,2R)-2-Phenylcyclobutyl]benzeneC16H1620071-09-4Monomer by-product [44]919923IIINI X X
19.8943, 55, 73, 129, 185Myristic acidTetradecanoic acidC14H28O2544-63-8Lubricant; adhesive; paper manufacturing [17,32,64]879907 **X XXXX
20.0443, 45, 57, 71, 853-Methylheptadecane3-MethylheptadecaneC18H386418-44-6Lubricant [44]824884INI X
20.12130, 179, 208Naphthalene, 1,2,3,4-tetrahydro-1-phenyl1-Phenyl-1,2,3,4-tetrahydronaphthaleneC16H163018-20-0Co-monomer [44,45]841913IIINIXX X
20.1545, 89Pentaethylene glycol2-[2-[2-[2-(2-Hydroxyethoxy)ethoxy]ethoxy]ethoxy]ethanolC10H22O64792-15-8Polyester resin; PEG oligomer; plasticizer [32,83,84]957957INI X
20.3843, 57, 71, 85Alkane NIAS of chain degradation [28]787903INIX X X
20.4191, 128, 206Naphthalene, 1,2-dihydro-4-phenyl4-Phenyl-1,2-dihydronaphthaleneC16H147469-40-1Residue of polymerization in recycled PS [68]799897IIINI X X
20.49120, 121, 1382-Ethylhexyl salicylate2-Ethylhexyl 2-hydroxybenzoateC15H22O3118-60-5Photoinitiator; UV filter [64,93]793916INI X
20.6543, 55, 57, 102Isopropyl myristatePropan-2-yl tetradecanoateC17H34O2110-27-0Cellulose plasticizer, pigment dispersant, and binding agent [60,64]759814INI X
21.0541, 43, 55, 60, 73Pentadecanoic acidPentadecanoic acidC15H30O21002-84-2Adhesives; paper/board packaging manufacturing [34]812830INIX
21.0941, 57, 149Diisobutyl phthalate (DIBP) *Bis(2-methylpropyl) benzene-1,2-dicarboxylateC16H22O484-69-5Plasticizer; printing inks; solvent to maintain color [17,45]858913INI X X
21.3143, 55, 57, 831-HexadecanolHexadecan-1-olC16H34O36653-82-4Adhesives; plasticizer; ionic surfactant; foam stabilizer [26,61,94]862928 **X XX X
21.5343, 57, 71Alkane NIAS of chain degradation [28]701855 X
21.6257, 175, 205, 2177,9-Di-tert-butyl-1-oxaspiro(4,5)deca-6,9-diene-2,8-dione7,9-Ditert-butyl-1-oxaspiro[4.5]deca-6,9-diene-2,8-dioneC17H24O382304-66-3Antioxidant Irganox 1010 degradation product [47]842879IIINIX X
21.7943, 74, 87Hexadecanoic acid, methyl esterMethyl hexadecanoateC17H34O2112-39-0Intermediary for emulsifiers, stabilizers, resins, and plasticizers [64]934944INIX XX
22.2143, 55, 60, 73, 129Palmitic acidHexadecanoic acidC16H32O257-10-3Varnishes; slip agent; adhesives; lubricant in paper manufacturing [17,46,47,64]925930 **X XXXX
22.5543, 45, 57, 71Diethylene glycol monododecyl ether2-(2-Dodecoxyethoxy)ethanolC16H34O33055-93-4Adhesives [72]794844INIX
22.6443, 57, 71, 85Alkane NIAS of chain degradation [28]921927 X
22.8657, 79, 107, 134JuvabioneMethyl (4R)-4-[(2R)-6-methyl-4-oxoheptan-2-yl]cyclohexene-1-carboxylateC16H26O3 17904-27-7Natural compound in some kinds of wood [84]836844INI X
23.2641, 43, 57, 73, 129Heptadecanoic acidHeptadecanoic acidC17H34O2506-12-7Adhesives; paper manufacturing [17]737894INIX
23.2845, 89Ethylene glycol family Plasticizer for PLA [84]936936 X
23.3769, 81, 95, 13713-Epimanool(3S)-5-[(1S,4aS,8aS)-5,5,8a-Trimethyl-2-methylidene-3,4,4a,6,7,8-hexahydro-1H-naphthalen-1-yl]-3-methylpent-1-en-3-olC20H34O 1438-62-6Natural component in wood and bark [86]902910IIINI X
23.5241, 43, 55, 69, 83, 97HeptadecanolHeptadecan-1-olC17H36O1454-85-9Plasticizer [26,95]923957INIX XXX
23.6367, 81, 95Methyl linolelaidateMethyl (9E,12E)-octadeca-9,12-dienoateC19H34O2 2566-97-4Fatty acid methyl esters (FAMEs) [96]789808INI X
23.7541, 55, 69, 83, 97, 26411-Octadecenoic acid, methyl esterMethyl (E)-octadec-11-enoateC19H36O252380-33-3FAMEs plasticizers [97,98]935938INI X
23.9443, 74, 87Methyl stearateMethyl octadecanoateC19H38O2 112-61-8Solvent; defoamers; slip agent [44,50,99]914917INIX XX
24.0541; 55; 69Oleic acid(Z)-Octadec-9-enoic acidC18H34O2112-80-1Lubricant; paper manufacturing; adhesives [17,47]800811 **X X
24.29112, 156, 158Tributyl aconitateTributyl (Z)-prop-1-ene-1,2,3-tricarboxylateC18H30O67568-58-3Plasticizer by-product [100]920939INI X
24.3041, 43, 57, 60, 73Stearic acidOctadecanoic acidC18H36O257-11-4Lubricant; slip agent in adhesives [32]916925 **X X
24.5041, 57, 129, 185Tributyl citrateTributyl 2-hydroxypropane-1,2,3-tricarboxylateC18H32O777-94-1Plasticizer [64]906920IIINI X
24.7043, 57, 71, 85N-docosaneDocosaneC22H46629-97-0Adhesives [54]867924INI X
24.9555, 57, 70, 112Bis(2-ethylhexyl) fumarate (DEHF)Bis(2-ethylhexyl) (E)-but-2-enedioateC20H36O4141-02-6Plasticizer [86]906906INI X
25.13129, 185, 259Tributyl acetylcitrate (ATBC) *Tributyl 2-acetyloxypropane-1,2,3-tricarboxylateC20H34O877-90-7Plasticizer [64,84]920933 60 expressed as the sum of group substances XXX
25.2045, 72, 87, 100DimethylpalmitamideN,N-DimethylhexadecanamideC18H37NO3886-91-7Polyamide blend films [31]897900IIINIX
25.3343, 45, 57, 71, 89Triethylene glycol monododecyl ether2-[2-(2-Dodecoxyethoxy)ethoxy]ethanolC18H38O4 3055-94-5Ink [101]776815INIX
25.51159, 173, 185, 269, 284Dehydroabietal(1R,4aS,10aR)-1,4a-Dimethyl-7-propan-2-yl-2,3,4,9,10,10a-hexahydrophenanthrene-1-carbaldehydeC20H28O13601-88-2Degradation product of adhesives [86]892897IIINI X
25.5643, 55, 57, 69, 831-OctadecanolOctadecan-1-olC18H38O112-92-5Adhesives; paper manufacturing; lubricant; ink solvent [17,26,102]899916INI X
25.6443, 57, 71, 85Alkane NIAS of chain degradation [28]771915 X
25.85161, 1782-Propenoic acid, 3-(4-methoxyphenyl), 2-ethylhexyl ester2-Ethylhexyl (E)-3-(4-methoxyphenyl)prop-2-enoateC18H26O3 5466-77-3UV filter [64]914927INIX
25.9143, 55, 74, 87Eicosanoic acid, methyl esterMethyl icosanoateC21H42O21120-28-1FAME [103]812855INI X
25.9391, 105, 129, 207R-methyl phenyl sulfoxide Possible degradation product of PS [104]702753 X X
26.0445, 89Ethylene glycol family Possible plasticizer for PLA [84]951951 X
26.13239, 240, 241Methyl dehydroabietateMethyl (1R,4aS,10aR)-1,4a-dimethyl-7-propan-2-yl-2,3,4,9,10,10a-hexahydrophenanthrene-1-carboxylateC21H30O21235-74-1Cellulose derivative, varnishes, printing inks, and adhesives [64,69,86]886893INI X
26.1558, 100, 115Dodecanamide, N,N-diethylN,N-DiethyldodecanamideC16H33NO 3352-87-2Slipping and anti-blocking agent [105]841909IIINIX
26.2241, 55, 59, 729-Octadecenamide, (Z)(Z)-Octadec-9-enamideC18H35NO301-02-0Slip agent [46,50]770818 ** X
26.4657, 70, 71, 129Hexanedioic acid, dioctyl ester (dioctyl adipate)Dioctyl hexanedioateC22H42O4123-79-5Plasticizer [69]721925INI X
26.4755, 57, 70, 129Hexanedioic acid, bis(2-ethylhexyl) ester (DEHA)Bis(2-ethylhexyl) hexanedioateC22H42O4103-23-1Plasticizer [106]708924 18 (60 expressed as the sum of group substances) X
26.5843, 57, 71, 85TetracosaneTetracosaneC24H50646-31-1Lubricant [87]859872INI X
26.6245, 57, 85, 125Ethanol, 2-butoxy, phosphateTris(2-butoxyethyl) phosphateC18H39O7P78-51-3Flame retardant, lacquer, paint, and plasticizer [107,108,109]877885IIINI X
26.69149, 161, 164, 177Phenol, 2,2′-methylenebis[6-(1,1-dimethylethyl)-4-methyl (Antioxidant 2246)2-Tert-butyl-6-[(3-tert-butyl-2-hydroxy-5-methylphenyl)methyl]-4-methylphenolC23H32O2119-47-1Antioxidant [110]907918 1.5 expressed as the sum of group substancesXX X
26.7445, 89Ethylene glycol family Plasticizer for PLA [84]821887 X
26.9045, 57, 90Methoxyacetic acid, octadecyl ester family 784824 X
27.0491, 117Cyclohexane, 1,3,5-triphenyl(3,5-Diphenylcyclohexyl)benzeneC24H2428336-57-4PS by-product [111]711823IIINI X X
27.2057, 145Hexanoic acid, 2-ethyl, hexadecyl esterHexadecyl 2-ethylhexanoateC24H48O259130-69-7Emollient agent [112]823877INIX
27.2843, 57, 71, 155Bis(2-ethylhexyl)hexahydro phthalateBis(2-ethylhexyl) cyclohexane-1,2-dicarboxylateC24H44O484-71-9Plasticizer [113]809826INI X
27.2977, 105, 149Diethylene glycol dibenzoate2-(2-Benzoyloxyethoxy)ethyl benzoateC18H18O5 120-55-8Plasticizer [64,86]966968INIX
27.4643, 57, 71, 85PentacosanePentacosaneC25H52629-99-2Adhesives; lubricant [87,114]751917INIXX X
27.6143, 57, 98, 134, 2392-Palmitoylglycerol1,3-Dihydroxypropan-2-yl hexadecanoateC19H38O423470-00-0Slip agent [96,115]835862INI X
27.74149, 167Di(2-ethylhexyl) phthalate (DEHP)Bis(2-ethylhexyl) benzene-1,2-dicarboxylateC24H38O4117-81-7Plasticizer; printing inks; solvent [45,86]802913 0.6 (60 expressed as the sum of group substances)XX X
27.8443, 59, 255, 31515-Hydroxydehydroabietic acid, methyl esterMethyl (1R,4aS,10aR)-7-(2-hydroxypropan-2-yl)-1,4a-dimethyl-2,3,4,9,10,10a-hexahydrophenanthrene-1-carboxylateC21H30O329461-23-2Oxidation product of Pinaceae resin [116]805822INI X
27.8691, 129, 207R-methyl phenyl sulfoxide Degradation product of PS [104,117]812822 X X
27.9991, 129, 207(2,3-Diphenylcyclopropyl)methyl phenyl sulfoxide[2-(Benzenesulfinylmethyl)-3-phenylcyclopropyl]benzeneC22H20OS131758-71-9Degradation product of PS [117,118]809813IIINI X X
28.0143, 45, 55, 57, 91Methoxyacetic acid, hexadecyl esterHexadecyl 2-methoxyacetateC19H38O3NA 732835IIINI X
28.0591, 129, 207R-methyl phenyl sulfoxide Degradation product of PS [104,117]803809 X X
28.1491, 129, 207R-methyl phenyl sulfoxide Degradation product of PS [104,117]813819 X X
28.3543, 57, 71, 85Alkane NIAS of chain degradation [28]917943 X
28.5145, 89, 134Ethyleneglycol family Plasticizer for PLA [84]894896 X
28.7457, 71, 127, 155Cyclohexanedicarboxylic acid family Found in PLGA [119,120]715718 X
28.9391, 129, 207R-methyl phenyl sulfoxide Degradation product of PS [104,117]724794 X X
28.9543, 57, 71, 85, 127, 155Cyclohexanedicarboxylic acid family Monomer [121]743759 X
29.1145, 89Ethylene glycol family Plasticizer for PLA [84]814851 X
29.1291, 129, 207R-methyl phenyl sulfoxide Degradation product of PS [104,117]701784 X
29.1355, 57, 69, 83, 971-EicosanolIcosan-1-olC20H42O 629-96-9Lubricant [74,102]857908INI X
29.1443, 57, 71, 85HeptacosaneHeptacosaneC27H56 593-49-7Alkane in paper-based food packaging [86]751808INIX
29.16-29.6385, 127, 156Cyclohexanedicarboxylic acid family Monomer [121]807833 X
29.6543, 45, 47Methoxyacetic acid, octadecyl esterOctadecyl 2-methoxyacetateC21H42O3NA 756801IIINI X
29.78-30.0685, 127, 157Cyclohexanedicarboxylic acid family Monomer [121]809835 X
30.0769, 81Squalene(6E,10E,14E,18E)-2,6,10,15,19,23-Hexamethyltetracosa-2,6,10,14,18,22-hexaeneC30H50111-02-4Plasticizer; oxygen scavenger [45,59,64]836866INIX X
30.18-30.3981, 126, 155Cyclohexanedicarboxylic acid family Monomer [121]809853 X
31.2243, 57, 229Myristyl myristateTetradecyl tetradecanoateC28H56O2 3234-85-3Ester formed by the reaction between fatty acids used as lubricants and alcohols [96]850856INI X
31.2745, 89Ethyleneglycol family Plasticizer for PLA [84]806813 X
33.0043, 57, 229Tetradecanoic acid, hexadecyl esterHexadecyl tetradecanoateC30H60O2 2599-01-1Ester formed by the reaction between fatty acids used as lubricants and alcohols [96]822847INI X
34.3457, 71, 239PalmitoneHentriacontan-16-oneC31H62O502-73-8NIAS of sizing agents in paper and cardboard [86,122]818845IINIX
35.4043, 55, 57, 257Hexadecanoic acid, octadecyl esterOctadecyl hexadecanoateC34H68O22598-99-4Ester formed by the reaction between fatty acids used as lubricants and alcohols [96]802912INI X
37.3743, 57, 71, 239Dialkyl ketone family NIAS of sizing agents in paper and cardboard [122]719782 X
RT: retention time; * confirmed with standard; SI: search index; RSI: reverse search index; CT: Cramer toxicity; NI: not included in Regulation (EU) 10/2011; SML: specific migration limit; **: specific migration limit of 60 mg/kg (substances for which there is no specific migration limit or other restrictions in Annex I of Regulation (EU) 10/2011); VOC: volatile organic compound; NIAS: substances not intentionally added.
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MDPI and ACS Style

López Sanvicente, E.; Barbosa-Pereira, L.; Sendón, R.; Rodríguez Bernaldo de Quirós, A.; Lestido-Cardama, A. Identification of Potential Migrants in Food Contact Materials Labeled as Bio-Based and/or Biodegradable by GC-MS. Coatings 2025, 15, 751. https://doi.org/10.3390/coatings15070751

AMA Style

López Sanvicente E, Barbosa-Pereira L, Sendón R, Rodríguez Bernaldo de Quirós A, Lestido-Cardama A. Identification of Potential Migrants in Food Contact Materials Labeled as Bio-Based and/or Biodegradable by GC-MS. Coatings. 2025; 15(7):751. https://doi.org/10.3390/coatings15070751

Chicago/Turabian Style

López Sanvicente, Emma, Letricia Barbosa-Pereira, Raquel Sendón, Ana Rodríguez Bernaldo de Quirós, and Antía Lestido-Cardama. 2025. "Identification of Potential Migrants in Food Contact Materials Labeled as Bio-Based and/or Biodegradable by GC-MS" Coatings 15, no. 7: 751. https://doi.org/10.3390/coatings15070751

APA Style

López Sanvicente, E., Barbosa-Pereira, L., Sendón, R., Rodríguez Bernaldo de Quirós, A., & Lestido-Cardama, A. (2025). Identification of Potential Migrants in Food Contact Materials Labeled as Bio-Based and/or Biodegradable by GC-MS. Coatings, 15(7), 751. https://doi.org/10.3390/coatings15070751

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