Screening and Relative Quantification of Migration from Novel Thermoplastic Starch and PBAT Blend Packaging

Academic Editor: Ana Teresa Sanches-Silva Received: 19 May 2025 Revised: 10 June 2025 Accepted: 18 June 2025 Published: 21 June 2025 Citation: Wongphan, P.; Canellas, E.; Nerín, C.; Estremera, C.; Harnkarnsujarit, N.; Vera, P. Screening and Relative Quantification of Migration from Novel Thermoplastic Starch and PBAT Blend Packaging. Foods 2025,14, 2171. https://doi.org/ 10.3390/foods14132171 Copyright: © 2025 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/ licenses/by/4.0/). Article Screening and Relative Quantification of Migration from Novel Thermoplastic Starch and PBAT Blend Packaging Phanwipa Wongphan 1 , Elena Canellas 2 , Cristina Nerín 2 , Carlos Estremera 2 , Nathdanai Harnkarnsujarit 1,3, * and Paula Vera 2,* 1 Department of Packaging and Materials Technology, Faculty of Agro-Industry, Kasetsart University, 50 Ngam Wong Wan Rd., Latyao, Chatuchak, Bangkok 10900, Thailand; [email protected] 2GUIA Group, Department of Analytical Chemistry, University of Zaragoza, I3A, María de Luna, 3, 50018 Zaragoza, Spain; [email protected] (E.C.); [email protected] (C.N.); [email protected] (C.E.) 3 Center for Advanced Studies for Agriculture and Food, Kasetsart University, 50 Ngam Wong Wan Rd., Latyao, Chatuchak, Bangkok 10900, Thailand *Correspondence: [email protected] (N.H.); [email protected] (P.V.); Tel.: +66-2-562-5045 (N.H.); +34-978555049 (P.V.) Abstract A novel biodegradable food packaging material based on cassava thermoplastic starch (TPS) and polybutylene adipate terephthalate (PBAT) blends containing food preservatives was successfully developed using blown-film extrusion. This active packaging is designed to enhance the appearance, taste, and color of food products, while delaying quality deterioration. However, the incorporation of food preservatives directly influences consumer perception, as well as health and safety concerns. Therefore, this research aims to assess the risks associated with both intentionally added substances (IAS) and non-intentionally added substances (NIAS) present in the developed active packaging. The migration of both intentionally and non-intentionally added substances (IAS and NIAS) was evaluated using gas chromatography–mass spectrometry (GC-MS) and ultra-high-performance liquid chromatography coupled with quadrupole time-of-flight mass spectrometry (UHPLC-QTOF-MS). Fifteen different volatile compounds were detected, with the primary compound identified as 1,6-dioxacyclododecane-7,12-dione, originating from the PBAT component. This compound, along with others, resulted from the polymerization of adipic acid, terephthalic acid, and butanediol, forming linear and cyclic PBAT oligomers. Migration experiments were conducted using three food simulants—95% ethanol, 10% ethanol, and 3% acetic acid—over a period of 10 days at 60 ◦ C. No migration above the detection limits of the analytical methods was observed for 3% acetic acid and 10% ethanol. However, migration studies with 95% ethanol revealed the presence of new compounds formed through interactions between the simulant and PBAT monomers or oligomers, indicating the packaging’s sensitivity to high-polarity food simulants. Nevertheless, the levels of these migrated compounds remained below the regulatory migration limits. Keywords: migration; biodegradable; non-intentionally added substances; ultra-highpressure liquid chromatography coupled with quadrupole time-of-flight mass spectrometry; food packaging 1. Introduction The European Union has recently emphasized the significant potential of biobased and biodegradable products to foster more sustainable economies and reduce dependence Foods 2025,14, 2171 https://doi.org/10.3390/foods14132171 Foods 2025,14, 2171 2 of 16 on fossil fuels, presenting promising growth opportunities for the industry. Biomaterials, particularly bioplastics, are garnering increasing attention in the food industry for packaging applications. European Bioplastics defines bioplastics as materials either sourced from renewable or biological resources or as biodegradable plastics [ 1 , 2 ]. Additionally, the packaging industry is actively seeking more eco-friendly alternatives to conventional materials, driving researchers to focus on developing biodegradable and bioplastic-based food packaging. Common materials used in this area include thermoplastic starch (TPS), polybutylene adipate terephthalate (PBAT), polylactide (PLA), and polymer blends [3–5]. This work focuses on biodegradable films made from thermoplastic starch (TPS) blended with polybutylene adipate terephthalate (PBAT). PBAT is a random copolyester synthesized via a polycondensation reaction involving adipic acid, 1,4-butanediol, and dimethyl terephthalate. Although derived from petroleum-based raw materials, PBAT is biodegradable. It consists of two structural segments: (i) polybutylene adipate (PBA), an aliphatic component, and (ii) polybutylene terephthalate (PBT), an aromatic component, thereby incorporating both aliphatic and aromatic characteristics [ 6 , 7 ]. It is regarded as an excellent and highly inert material with excellent flexibility, thermal stability, and biodegradability, which are comparable to those of low-density polyethylene (LDPE) [ 8 – 10 ]. However, PBAT had limitations such as a high cost and slow and longer degradation cycle than other biodegradable plastics because of the butylene group. For TPS, as starch-based materials are highly hydrophilic, this leads to poor mechanical strength, formability, and stability [ 3 , 7 , 11 ]. Therefore, polyester/starch-based blends are among the most widely used biodegradable plastics for food packaging applications, particularly as food contact materials (FCMs) [ 4 , 5 , 12 ]. The development of new food packaging must prioritize safety by ensuring that no harmful compounds migrate from the packaging into the food [ 6 , 13 , 14 ]. The safety assessment and migration of substances from packaging needs to involve both intentionally added substances (IAS), such as plasticizers, slip agents, monomers, additives, and solvents, as well as non-intentionally added substances (NIAS), which include degradation products formed during or after manufacturing, impurities in raw materials, and interaction products between packaging components [ 15 , 16 ]. Therefore, the aim of this article is to assess the risk associated with IAS and NIAS present in the developed active packaging from our previous work [ 3 ]. Migration screening was conducted using gas chromatography coupled with mass spectrometry (GC-MS) and ultraperformance liquid chromatography quadrupole-time-of-fight mass spectrometry (UPLC-Q-TOF–MS) to analyze the migration from biodegradable TPS/PBAT samples intended for food packaging applications. 2. Materials and Methods 2.1. Chemicals and Reagents 1,4,7-Trioxacyclotridecane-8,13-dione (98% purity, CAS: 6607-37-7), 2,2,4-trimethyl1,3-pentanediol diisobutyrate ( ≥ 98.5%, CAS: 6846-50-0), and n-alkane standards (C7–C40) were purchased from Sigma–Aldrich (Madrid, Spain). Absolute ethanol (HPLC grade, CAS: 64-17-5), acetic acid, and dichloromethane were supplied by Scharlau (Setmenat, Spain). Hexane was obtained from Fisher Chemicals (Gothenburg, Sweden Loughborough, UK). Ultrapure water was produced using a Wasserlab Ultramatic GR system (Barbatáin, Spain). Solid-phase microextraction (SPME) fibers, including polydimethylsiloxane (100 µ m), polyacrylate (85 µ m), and divinylbenzene/Carboxen/polydimethylsiloxane (50/30 µ m), were supplied by Supelco (Madrid, Spain). Foods 2025,14, 2171 3 of 16 2.2. Sample Characteristics Neat PBAT film and PBAT/TPS blended film incorporated additives, namely sodium nitrite, sodium erythorbate, tetrasodium pyrophosphate, sodium tripolyphosphate, and sodium hexametaphosphate, which were produced via blown-film extrusion. The names and characteristics of the samples are shown in Table 1. The averaged thickness of all film was 0.04 mm. Table 1. Name and characteristics of neat PBAT and PBAT/TPS film samples, which incorporated additives, namely sodium nitrite, sodium erythorbate, tetrasodium pyrophosphate, sodium tripolyphosphate and sodium hexametaphosphate, produced via blown-film extrusion. Sample Name Sample Code Film Properties Oxygen Permeability (cm3·mm/m2·day·atm) Water Vapor Permeability (g·mm/m2·day·KPa) Tensile Strength (MPa) Elongation at Break (%) PBAT Resins R - - - - PBAT Films F - - - - PBAT/TPS C 16.69 ±0.08 4.20 ±0.14 14.43 ±0.51 656.11 ±11.50 PBAT/TPS + Sodium Nitrite N 4.65 ±0.26 4.51 ±0.18 11.64 ±0.66 794.62 ±17.45 PBAT/TPS + Sodium Erythorbate E 5.26 ±0.18 3.54 ±0.18 12.82 ±0.58 651.94 ±18.46 PBAT/TPS + Sodium Tripolyphosphate T 21.42 ±0.73 4.01 ±0.06 10.60 ±0.24 571.37 ±16.18 PBAT/TPS + Sodium Hexametaphosphate H 11.22 ±1.89 3.11 ±0.14 10.42 ±8.78 595.95 ±8.78 PBAT/TPS + Tetrasodium Pyrophosphate P 29.07 ±3.81 4.30 ±0.20 9.31 ±0.31 521.30 ±6.19 2.3. Sample Extraction All films were cut into small pieces, and 0.5 g of each sample was extracted three times with 3 mL of solvent in an ultrasonic bath (frequency applied: 40 Hz, Branson Ultrasonics TM 3510, Emerson Electric Co., St. Louis, MO, USA) at 40 ◦ C for 1 h to enhance solvent penetration and disrupt the matrix, improving compound release. Dichloromethane and ethanol were used as extraction solvents to dissolve non-polar and polar volatile compounds, respectively. The extraction solution (total volume of 9 mL) was concentrated to 2 mL under nitrogen flow using a nitrogen evaporator (TECHNE sample concentrator, Cole-Parmer Ltd., Eaton Socon, UK) at 60–65 ◦ C before injection. Each sample and solvent blank were analyzed in duplicate with blank extractions performed every two sample extractions to monitor contamination. In addition, PBAT resin and PBAT film were used as positive controls by controlling the weight of resin and film in the extraction to control the concentration of the extracted amount. Samples were analyzed using GC-MS with liquid injection. 2.4. Migration Assays Migration analysis was carried out by total immersion of the film samples in three different food simulants: 10% ethanol (simulant A), 3% acetic acid (simulant B), and 95% ethanol (simulant D2), following the specifications of Regulation (EU) No. 10/2011. The films were cut into strips measuring 1 × 4 cm 2 for simulant D2 and 1 × 5 cm 2 for simulants A and B, ensuring the appropriate surface area-to-volume ratio. Each sample was placed in 20 mL glass vials and 18 mL of the corresponding simulant was added under gravimetric control. All samples were incubated in the oven at 60 ◦ C for 10 days. Blank samples were prepared and treated under identical conditions. Migration tests were conducted in triplicate, with blank extractions performed after every three test samples. The Foods 2025,14, 2171 4 of 16 simulant samples were analyzed using and UPLC-Q-TOF–MS to determine the migrated compounds from film samples. This offered a high-resolution mass analysis suitable for non-targeted and semi-targeted screening of migrants (e.g., additives, degradation products, and monomers). 2.5. Instrument Conditions 2.5.1. GC-MS Samples subjected to migration testing via liquid injection were analyzed using a 6890N gas chromatograph with a 5977D mass spectrometry detector (Agilent Technilogies, Santa Clara, CA, USA). Separation was performed on an HP-5MS capillary column ( 30 m ×0.25 mm i.d. × 0.25 µ m film thickness) obtained from Agilent Technologies (Madrid, Spain). A total of 1 µ L of migration extract was injected in the splitless mode. High-purity helium (99.99%) was used as the carrier gas at a constant flow rate of 1.0 mL/min. The GC oven temperature program was as follows: an initial temperature of 50 ◦ C was held for 5 min, followed by an increase to 300 ◦ C at a ramp rate of 10 ◦ C/min. A solvent delay of 5 min was applied. Data acquisition was performed in the SCAN mode. Volatile compounds were identified by comparing the acquired mass spectra with those in the National Institute of Standards and Technology (NIST) Chemistry WebBook spectral library integrated into the instrument software. The minimum requirement of mass spectrum match to consider a volatile compound by NIST was 80%. The standard of the compounds was analyzed for confirmation and quantitation using calibration curves from an external standard compound in ethanol, based on the same time period and having a chemical structure similar or close to that of the obtained substance. 2.5.2. SPME-GC-MS Samples were extracted using a divinylbenzene/Carboxen/polydimethylsiloxane (DVB/CAR/PDMS) solid-phase microextraction (SPME) fiber (50/30 µ m). DVB/CAR/PDMS fiber (50/30 µ m) is well-suited for a broad range of volatile and semi-volatile compounds due to its mixed sorbent phases, combining polarity, porosity, and surface area. Preliminary extractions were performed at 80 ◦ C for 30 min to enhance analyte partitioning into the headspace without compromising thermal stability. The SPME analysis was conducted in a 20 mL glass vial, fully filled with simulants, under the same conditions used for GC-MS analysis. 2.5.3. UHPLC-Q-TOF-MS Analysis The samples were analyzed using Acquity TM UHPLC chromatography system coupled to a Xevo G2 QTOF mass spectrometer (Waters, Manchester, UK). The mass spectrometer was equipped with an atmospheric pressure ionization (API) source operating with an electrospray ionization (ESI) interface. The detector configuration includes a hexapole, a quadrupole, a collision cell, and a time of flight as analyzer (QTOF). Chromatographic separation was performed using an ACQUITY UPLC ® BEH C18 column (2.1 × 100 mm, 1.7 µ m particle size, Agilent Technologies Spain, S.L., Madrid, Spain) at a flow rate of 0.3 mL/min. The gradient elution was performed using ultrapure water with 0.1% formic acid as mobile phase A and methanol with 0.1% formic acid as mobile phase B. The gradient started at 5% phase B and increased linearly to 100% phase B over 15 min, followed by a 2 min re-equilibration to the initial conditions. The injection volume was 10 µ L. Electrospray ionization (ESI) was operated in positive mode (ESI+), and data were acquired in the sensitivity mode with a capillary voltage of 1 kV and a sampling cone voltage of 30 V. Leucine-enkephalin [M+H] + ,m/z556.2766, was used as the lock-mass compound for real-time mass correction. Data acquisition was performed in the data-independent acquisition (DIA) mode using high-definition MSE, which simultaneously collects data at a Foods 2025,14, 2171 5 of 16 low collision energy (6 eV) and elevated collision energy (ramped from 20 to 40 eV). Argon was employed as the collision gas, while nitrogen served as the ion mobility separation (IMS) gas. The IMS gas flow rate was set at 25 mL/min, with a wave velocity of 250 m/s and an IMS pulse height of 45 V. Following the completion of the migration assays, the simulant samples were extracted and analyzed using UPLC-IMS-QTOF. Calibration curves for quantitation were prepared using standard solutions in ethanol. The structural identification of the detected peaks was achieved through UPLC-Q-TOF-MS analysis, utilizing accurate mass measurements. Molecular structures were determined using the ChemSpider chemical database (Royal Society of Chemistry 2025) by comparing the experimentally obtained accurate masses. 3. Results and Discussion 3.1. Identification of Volatile and Semi-Volatile Compounds by GC-MS The optimization of PBAT and TPS/PBAT sample extraction was achieved through solvent extraction using ethanol and dichloromethane. This method was chosen because it detects a greater number of highly volatile compounds with a lower expansion volume [17–20] . Compound identification was analyzed via GC-MS using liquid injection. Figure 1shows a chromatogram of the dissolved PBAT and TPS/PBAT films obtained through solvent extraction, facilitating the identification of unknown migrants in food contact materials. Table 2lists 13 identified compounds with library matching scores ≥80% compared to NIST library. A total of 15 different volatile compounds were reported in the literature, with 7 found in PBAT resin and 9 in PBAT film. Both PBAT resin and film samples exhibited identical compounds when analyzed by GC–MS. Cyclopentanecarboxylic acid, 2-oxo-, ethyl ester is a degradation by-product of PBAT resins, as reported by Capolupo et al. [ 21 ] and Lin et al. [ 7 ]. Additionally, 1,6-Dioxacyclododecane-7,12-dione is a cyclic molecule formed during PBAT polymerization via polyester condensation involving the monomers 1,4-butanediol and adipic acid. It was found in both the resin and film and is classified as a non-intentionally added substance (NIAS) as noted by Lin et al. [ 7 ], Canellas et al. [ 22 ], Ubeda et al. [ 23 ]. Other compounds present at lower intensities in both PBAT resin and film included cyclopentanone, tetraethyl silicate, butylated hydroxytoluene (BHT), 2-ethylhexyl salicylate, methyl stearate, and ethyl stearate [ 19 , 24 ]. Cyclopentanone is formed by a radical reaction between aldehydes and ketones occurring in PBAT resin. The intensity of this peak slightly decreased in film samples, likely due to the high temperature during film manufacturing, as previously detected by Ubeda et al. [ 23 ] and Capolupo et al. [ 21 ]. Tetraethyl silicate, a silane compound, is a common additive used as a coupling agents in resins, adhesives, and inks to improve their chemical and thermal resistance [ 25 ]. BHT, used as an antioxidant or plastic stabilizer, is approved for food contact applications under EU regulation [ 26 ] and was previously detected by Ibarra et al. [ 6 ] and Pack et al. [ 27 ]. However, BHT has been scrutinized for its potential endocrine-disrupting properties and long-term safety at higher exposure levels [ 28 ]. 2-Ethylhexyl salicylate, used as a UV-filter additive, is generally regarded as safe but may contribute to cumulative exposure risks depending on its concentration and frequency of ingestion [ 29 ]. Stearate compounds were detected and are derived from fatty acids from, though they are also commonly found as contaminants in packaging materials. Additionally, an unknown compound with a retention time of 26.00 min was also detected. Based on the bibliographic information and mass spectrum several key fragments were observed: m/z54.0 likely represents a small alkyl chain breakage associated with the molecule’s fragmentation, while m/z104.0 could correspond to a larger fragment, indicating more complex molecular breakage possibly involving part of the cyclic structure. The mid-range m/zvalues of 132.0 and 149.0 may represent fragments of the dioxacyclododecane core, reflecting partial structures of the compound. Foods 2025,14, 2171 6 of 16 Finally, m/z369.1 represents the molecular ion peak (M+), which corresponds to the entire molecule and is characteristic of the molecular mass of 1,6-Dioxacyclododecane-7,12-dione. Given this fragmentation pattern, the compound is likely an oligomer formed during the PBAT polymerization process via polyester condensation, which involves the monomers 1,4-butanediol and adipic acid. This suggests that the compound is a larger oligomer than 1,6-Dioxacyclododecane-7,12-dione, which also has a similar fragmentation pattern. The presence of these specific m/zvalues indicates that the compound retains the core cyclic structure of 1,6-Dioxacyclododecane-7,12-dione but with additional polymerization units, resulting in a more complex molecular structure. (a) (b) Figure 1. Chromatogram of (a) PBAT film and (b) TPS/PBAT blended film using GC-MS. Foods 2025,14, 2171 7 of 16 Table 2. Volatile and semi-volatile compounds were identified in total ethanol extracts of PBAT resin, PBAT film, and TPS/PBAT films—with and without incorporated food preservatives (sodium nitrite [N], sodium erythorbate [E], sodium tripolyphosphate [T], sodium hexametaphosphate [H], and tetrasodium pyrophosphate [P])—using GC–MS. The retention time (Rt) and relative intensity (I) of each compound were recorded, with intensity categorized by relative abundance as follows: I = 1 (0–5%), I = 2 (5–20%), I = 3 (20–50%), and I = 4 (50–100%). No. Rt Candidate CAS Number Molecular Formular Mass Cramer Class Samples Remark R F C N E T H P 1 5.35 Cyclopentanone 120-92-3 C5H8O 84.06 II 1 1 1 1 1 1 nd nd Surfactant 2 7.73 Butyrolactone 96-48-0 C4H6O286.04 I nd nd nd 1 1 nd nd nd By product 3 8.86 1,4-Butanediol 110-63-4 C4H10O290.07 I nd nd nd 1 1 1 nd nd Monomer 4 9.10 ni nd nd 1 1 1 1 1 1 Fragments; 61.0/75.0/108.0/117.0/133.0 5 9.28 Tetraethyl silicate 78-10-4 C8H20O4Si 208.11 III 1 1 nd nd nd nd nd nd Processing aids 6 12.85 Cyclopentanecarboxylic acid, 2-oxo-, ethyl ester 611-10-9 C8H12O3156.18 - nd 1 nd 1 nd nd nd nd By product 7 16.38 Glycerin 56-81-5 C3H8O392.05 I nd nd 4 4 4 4 4 4 Plasticizer 8 17.16 Butylated Hydroxytoluene 128-37-0 C15H24O 220.18 II 1 1 1 1 1 1 1 1 Antioxidants 9 17.55 1,6-Dioxacyclododecane7,12-dione 777-95-7 C10H16O4200.10 - 4 4 1 1 1 1 1 1 Oligomer 10 17.99 1,4-Benzenedicarboxylic acid, ethyl methyl ester 22163-52-6 C11H12O4208.07 - nd nd nd 1 1 1 nd nd By product 11 20.66 2-Ethylhexyl salicylate 118-60-5 C15H22O3250.16 I 1 1 nd nd nd 1 1 nd Processing aids 12 21.99 Palmitic acid 57-10-3 C16H32O2256.24 I nd nd 1 nd nd 1 1 1 FDA Inventory of Effective Food Contact Substance Notifications 13 23.50 Methyl stearate 112-61-8 C19H38O2298.29 I 1 1 1 nd 1 nd nd nd By product 14 24.09 Ethyl stearate 111-61-5 C20H40O2312.30 I 1 1 1 nd 1 1 nd nd By product 15 26.00 ni nd 1 1 1 1 1 1 1 Fragments; 54.0/104.0/132.0/149.0/369.1 nd: not detected, ni: not identified. Foods 2025,14, 2171 8 of 16 For TPS/PBAT films, both with and without food preservatives, the compound with the highest intensity identified was glycerol (CAS 56-81-5), which serves as an internal additive substance (IAS) and plasticizer for forming TPS via extrusion. Glycerol is also listed in the EU regulation No. 10/2011 [ 26 ] for food contact applications, either as an additive, a monomer, or for use in polymer production. Additionally, the results revealed five compounds not previously detected, including butyrolactone, 1,4-butanediol, 1,4benzenedicarboxylic acid ethyl methyl ester, palmitic acid, and an unknown compound at a retention time of 9.10 min (fragments: m/z61.0, 75.0, 108.0, 117.0, and 133.0). Palmitic acid is an additive used as a slip agent and it is also an approved additive and monomer for food contact material in the EU regulation [ 26 ]. The other compounds are likely degradation products formed during film manufacturing through reactions between ketones, aldehydes, and ethers. Compounds such as 1,6-dioxacyclododecane-7,12-dione and other cyclic esters have been previously reported in polyester-based materials and may lack comprehensive toxicological data [ 27 , 30 – 32 ]. Although substances such as glycerol and BHT are listed as approved additives under EU Regulation No. 10/2011, their migration levels must remain below specific limits to avoid potential endocrine-disrupting or cytotoxic effects [ 28 , 29 ]. The detection of palmitic acid and 2-ethylhexyl salicylate also warrants attention, as these may originate from additives or external contamination and contribute to cumulative dietary exposure. The incorporation of food preservatives to enhance the functionality of TPS/PBAT films also influenced the chemical structure of starch, PBAT, and TPS/PBAT matrix by acting as hydrolysis agents, plasticizers, and compatibilizers [ 3 , 12 , 33 ]. This structural modification may have promoted the breakdown of polymer chains and the formation of monomers and by-products. 3.2. Identification of Non-Volatile Compounds by UHPLC-Q-TOF-MS The chromatograms of the TPS/PBAT film sample extraction, conducted as described in Section 2.3 and obtained using UHPLC-Q-TOF-MS, are presented in Figure 2. Structural elucidation of the detected peaks was performed using UPLC-Q-TOF-MS analysis by examining the mass spectra of each peak to determine their molecular composition. High-resolution mass measurements allowed for precise identification through the analysis of fragmentation patterns and isotopic distributions. The experimentally obtained masses were compared against entries in the ChemSpider chemical database to propose potential molecular structures [ 19 ]. Additionally, the mass spectra were cross-validated with previously reported data in the literature from Isella et al. [ 32 ], Aznar et al. [ 34 ] to confirm consistency with known compounds. Table 3lists the non-volatile compounds identified in the total dissolution of PBAT resin, PBAT film, and TPS/PBAT with and without food preservatives, namely sodium nitrite (N), sodium erythorbate (E), sodium tripolyphisphate (T), sodium hexametaphosphate (H), and tetrasodium pyrophosphate (P). Most of the ten detected compounds, classified as NIAS, were cyclic compounds derived from adipic acid (AA), 1,4-butanediol (BD), and terephthalic acid (TPA) [ 19 , 22 , 34 , 35 ]. These are PBAT-derived oligomers, some of which were also identified via GC-MS, which likely originate as by-products from raw PBAT resin, formed during the polycondensation process of polyester synthesis. This is supported by the higher mass intensities observed in PBAT samples compared to TPS/PBAT, as shown in Figure 3. The intensities of these compounds decreased progressively throughout the manufacturing process, likely due to degradation caused by thermal processing during blown-film extrusion. PBAT film are subjected to a single extrusion step, whereas TPS/PBAT film undergo three heating stages—two during pellet preparation and one during film blowing—resulting in a more pronounced reduction in compound intensity [ 3 , 22 , 33 , 35 ]. Additionally, the incorporation of food preservatives introduced new compounds, including methyl phenylglyoxylate Foods 2025,14, 2171 9 of 16 (4.69_165.0552), triacetin (5.13_203.0919), and resorcinol (6.08_111.0446), which function as curing agents, surface modifiers, and linking agents, respectively. These findings indicate that both thermal processing and the incorporation of preservatives significantly alter the chemical composition of TPS/PBAT films, potentially impacting their functionality and safety [ 36 ]. A thorough understanding of these changes is essential for optimizing film performance and ensuring their compliance with food packaging safety requirements, particularly in terms of chemical stability and migration behavior. Figure 2. Chromatogram obtained by UHPLC-Q-TOF-MS analysis of TPS/PBAT film. Figure 3. Intensity of the non-volatile components of PBAT resin, PBAT film, and TPS/PBAT with and without food preservatives, namely sodium nitrite, sodium erythorbate, sodium tripolyphisphate, sodium hexametaphosphate, and tetrasodium pyrophosphate films. Significant differences are indicated by different letters. Foods 2025,14, 2171 16 of 16 22. Canellas, E.; Vera, P.; Nerín, C. UPLC–ESI-Q-TOF-MS E and GC–MS identification and quantification of non-intentionally added substances coming from biodegradable food packaging. Anal. Bioanal. Chem. 2015,407, 6781–6790. [CrossRef] 23. Ubeda, S.; Aznar, M.; Nerín, C. Determination of volatile compounds and their sensory impact in a biopolymer based on polylactic acid (PLA) and polyester. Food Chem. 2019,294, 171–178. [CrossRef] 24. Brocca, D.; Arvin, E.; Mosbæk, H. Identification of organic compounds migrating from polyethylene pipelines into drinking water. Water Res. 2002,36, 3675–3680. [CrossRef] 25. Felix, J.S.; Isella, F.; Bosetti, O.; Nerin, C. Analytical tools for identification of non-intentionally added substances (NIAS) coming from polyurethane adhesives in multilayer packaging materials and their migration into food simulants. Anal. Bioanal. Chem. 2012,403, 2869–2882. [CrossRef] [PubMed] 26. Commission, E. Commission Regulation (EU) No 10/2011 of 14 January 2011 on plastic materials and articles intended to come into contact with food. Off. J. Eur. Union 2011,OJ L 12, 1–89. 27. Pack, E.C.; Lee, K.Y.; Jung, J.S.; Jang, D.Y.; Kim, H.S.; Koo, Y.J.; Lee, H.G.; Kim, Y.S.; Lim, K.M.; Lee, S.H.; et al. Determination of the migration of plastic additives and non-intentionally added substances into food simulants and the assessment of health risks from convenience food packaging. Food Packag. Shelf Life 2021,30, 100736. [CrossRef] 28. Koch, H.M.; Calafat, A.M. Human body burdens of chemicals used in plastic manufacture. Philos. Trans. R. Soc. B Biol. Sci. 2009, 364, 2063–2078. [CrossRef] [PubMed] 29. Muncke, J. Endocrine disrupting chemicals and other substances of concern in food contact materials: An updated review of exposure, effect and risk assessment. J. Steroid Biochem. Mol. Biol. 2011,127, 118–127. [CrossRef] [PubMed] 30. Groh, K.J.; Backhaus, T.; Carney-Almroth, B.; Geueke, B.; Inostroza, P.A.; Lennquist, A.; Leslie, H.A.; Maffini, M.; Slunge, D.; Trasande, L. Overview of known plastic packaging-associated chemicals and their hazards. Sci. Total Environ. 2019,651, 3253–3268. [CrossRef] 31. Groh, K.J.; Geueke, B.; Martin, O.; Maffini, M.; Muncke, J. Overview of intentionally used food contact chemicals and their hazards. Environ. Int. 2021,150, 106225. [CrossRef] 32. Isella, F.; Canellas, E.; Bosetti, O.; Nerin, C. Migration of non intentionally added substances from adhesives by UPLC-Q-TOF/MS and the role of EVOH to avoid migration in multilayer packaging materials. J. Mass. Spectrom. 2013,48, 430–437. [CrossRef] 33. Garcia, P.S.; Baron, A.M.; Yamashita, F.; Mali, S.; Eiras, D.; Grossmann, M.V.E. Compatibilization of starch/poly (butylene adipate-co-terephthalate) blown films using itaconic acid and sodium hypophosphite. J. Appl. Polym. Sci. 2018,135, 46629. [CrossRef] 34. Aznar, M.; Ubeda, S.; Dreolin, N.; Nerín, C. Determination of non-volatile components of a biodegradable food packaging material based on polyester and polylactic acid (PLA) and its migration to food simulants. J. Chromatogr. A 2019,1583, 1–8. [CrossRef] [PubMed] 35. Zhang, H.; Su, Q.Z.; Shang, G.Q.; Weng, Y.X.; Zhu, L. Elucidation of Non-Intentionally Added Substances from Plant Fiber/Plastic Composites by UPLC-QTOF/MS. Foods 2023,12, 678. [CrossRef] 36. Riboni, N.; Bianchi, F.; Cavazza, A.; Piergiovanni, M.; Mattarozzi, M.; Careri, M. Mass spectrometry-based techniques for the detection of non-intentionally added substances in bioplastics. Separations 2023,10, 222. [CrossRef] 37. Osorio, J.; Aznar, M.; Nerín, C.; Elliott, C.; Chevallier, O. Comparison of LC-ESI, DART, and ASAP for the analysis of oligomers migration from biopolymer food packaging materials in food (simulants). Anal. Bioanal. Chem. 2022,414, 1335–1345. [CrossRef] 38. Argyri, A.A.; Mallouchos, A.; Panagou, E.Z.; Nychas, G.J. The dynamics of the HS/SPME-GC/MS as a tool to assess the spoilage of minced beef stored under different packaging and temperature conditions. Int. J. Food Microbiol. 2015,193, 51–58. [CrossRef] 39. Committee, E.S.; More, S.J.; Bampidis, V.; Benford, D.; Bragard, C.; Halldorsson, T.I.; Hernández-Jerez, A.F.; Hougaard Bennekou, S.; Koutsoumanis, K.P.; Machera, K. Guidance on the use of the Threshold of Toxicological Concern approach in food safety assessment. EFSA J. 2019,17, e05708. 40. Vera, P.; Canellas, E.; Barknowitz, G.; Goshawk, J.; Nerin, C. Ion-Mobility Quadrupole Time-of-Flight Mass Spectrometry: A Novel Technique Applied to Migration of Nonintentionally Added Substances from Polyethylene Films Intended for Use as Food Packaging. Anal. Chem. 2019,91, 12741–12751. [CrossRef] 41. Diamantidou, D.; Tsochatzis, E.; Kalogiannis, S.; Alberto Lopes, J.; Theodoridis, G.; Gika, H. Analysis of Migrant Cyclic PET Oligomers in Olive Oil and Food Simulants Using UHPLC-qTOF-MS. Foods 2023,12, 2739. [CrossRef] 42. Hoppe, M.; Fornari, R.; de Voogt, P.; Franz, R. Migration of oligomers from PET: Determination of diffusion coefficients and comparison of experimental versus modelled migration. Food Addit. Contam. Part A 2017,34, 1251–1260. [CrossRef] Disclaimer/Publisher’s Note: The statements, opinions and data contained in all publications are solely those of the individual author(s) and contributor(s) and not of MDPI and/or the editor(s). 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