Food and beverage can coatings: a review on chemical analysis, migration, and risk assessment

Received: 8 January 2022 Revised: 24 March 2022 Accepted: 20 April 2022 DOI: 10.1111/1541-4337.12976 COMPREHENSIVE REVIEWS IN FOOD SCIENCE AND FOOD SAFETY Food and beverage can coatings: A review on chemical analysis, migration, and risk assessment Antía Lestido-Cardama1Raquel Sendón1Juana Bustos2María Teresa Nieto2 Perfecto Paseiro-Losada1Ana Rodríguez-Bernaldo de Quirós1 1Department of Analytical Chemistry, Nutrition and Food Science, Faculty of Pharmacy, University of Santiago de Compostela, Santiago de Compostela, Spain 2National Food Centre, Spanish Agency for Food Safety and Nutrition, Majadahonda, Spain Correspondence Ana Rodríguez-Bernaldo de Quirós, Department of Analytical Chemistry, Nutrition and Food Science, Faculty of Pharmacy, University of Santiago de Compostela, 15782 Santiago de Compostela, Spain. Email: [email protected] Funding information Ministerio de Ciencia, Innovación y Universidades; Fondo Europeo de Desarrollo Regional (FEDER); Agencia Estatal de Investigación, Grant/Award Number: PGC2018-094518-B-I00 Abstract The internal surface of food and beverage cans is generally covered with polymeric coatings to preserve food and protect metal substrate from corrosion. Coating materials are complex formulations that contain different starting substances (e.g., monomers, prepolymers, additives, etc.) and in addition during the manufacture of the material several compounds can be formed (e.g., reaction products, degradation products, etc.). These substances have the potential to migrate into the food. Many of them have not been identified and only some have been toxicologically evaluated. This article aims to provide a comprehensive review on the analytical methods used for the identification of potential migrants in can coatings. The migration and exposure to chemicals migrating from can coatings are also reviewed and discussed so far, which is essential for risk assessment. Moreover, a brief section on the current status of the legislation on varnishes and coatings for food contact in Europe is also presented. Liquid chromatography coupled to diode array and fluorescence detectors and particularly to mass spectrometry and gas chromatography–tandem mass spectrometry seem to be the techniques of choice for the identification of potential migrants in can coatings. Some studies have reported migration levels of BPA (bisphenol A) and BADGE (bisphenol A diglycidyl ether) and derivatives exceeding the specific migration limits set in the European legislation. On the whole, low dietary exposure to migrants from can coatings has been reported. However, it is interesting to highlight that in these studies the combined exposure to multiple chemicals has not been considered. KEYWORDS analytical techniques, exposure assessment, food metal cans, migration, polymeric coatings This is an open access article under the terms of the Creative Commons Attribution-NonCommercial-NoDerivs License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non-commercial and no modifications or adaptations are made. © 2022 The Authors. Comprehensive Reviews in Food Science and Food Safety published by Wiley Periodicals LLC on behalf of Institute of Food Technologists. 3558 wileyonlinelibrary.com/journal/crf3 Compr Rev Food Sci Food Saf. 2022;21:3558–3611. FOOD CONTACT COATINGS IN METAL CANS... 3559 1 INTRODUCTION Metal food packaging includes a wide variety of products such as cans, closures, lids, tubes, and aerosol containers among others. Cans are by far the most widespread, being canned foods and beverages an important part of the global food supply (LaKind, 2013; Oldring & Nehring, 2007). The canning of food and beverages is still an important process in food preservation since foods packed in metallic cans have a longer shelf life compared to food packed in other materials. Polymeric coatings are often applied in the inner surface of food metal cans acting as a barrier between food and the metal surface. They play an essential role in the preservation of food maintaining its quality as well as protecting the metal substrate from corrosion (Cooper & Tice, 2001; Driffield et al., 2018). Epoxy resins based on bisphenol A diglycidyl ether (BADGE) have been widely used for the inner coating of metal cans because of their excellent mechanical properties and chemical resistance. Although they are still being used, lately due to uncertainties about the potential effects on human health of the endocrine disrupting properties of bisphenol A (BPA), other coatings based on different chemistries are being employed (Driffield et al., 2018). Some examples of these types of resins include polyester, acrylic, and so on. During the coating manufacture, as a result of an incomplete polymerization process, residual prepolymers and monomers can remain in the final product and are able to migrate to the food. In addition to intentionally added substances, such as prepolymers, monomers, additives, catalysts, and so on, the final material may also contain the so-called nonintentionally added substances (NIAS), such as impurities, reaction products, degradation products, and so on. Thus, a large number of substances can be present in the final materials and have the potential to migrate into the foodstuffs (Aznar et al., 2015;Kato & Conte-Junior, 2021; Nerín et al., 2022). Migration is a mass transfer phenomenon where the substance transferredfromthepackaging tothe foodiscalled migrant. The potential migrants need to be identified to assure the safety of the material. Most of these compounds are unknown; therefore,theyhavenotbeen evaluatedtoxicologically, and some of them are highly reactive chemical species (Grob et al., 1999; Paseiro-Cerrato et al., 2017). The analysis of these potential migrants is an extremely difficult task for various reasons, being one the fact that frequently there is not enough information about the composition of the material. On the other hand, the manufacturing process is usually quite complex with several steps and, in many cases is not completely known (Hoppe et al., 2016). Liquid chromatography and gas chromatography coupled to mass spectrometry, particularly to high-resolution mass spectrometry (HRMS), have shown to be powerful tools to accomplish this challenging task (Canellas et al., 2019; Nerín et al., 2013). The strengths and limitations of the analytical techniques used in the analysis of migrants from food contact materials (FCMs) are summarized in a recent review (Nerín et al., 2022). Hence, to assess the safety of these materials, a number of issues need to be addressed, namely, the identification of potential migrants in the final materials, the determination of their migration in food and beverages, and the risk evaluations through food exposure assessments (Figure 1). The extent of migration and the specific toxicity of a given substance (s) are the two key factors that define the risk to human health that an FCM represents (Poças & Hogg, 2007). From a food legislation standpoint, varnishes and coatings are one example of a type of FCM for which there is currently no specific harmonized measure at European level; nevertheless, as it is the case for all FCMs, varnishes and coatings must meet the requirements of Article 3 of the Framework Regulation (EC) No. 1935/2004 (European Union, 2004) regarding the inertness criteria as well as the safety requirements for the consumer. On the other hand, national regulations should be followed and CoE (Council of Europe) resolution be used as reference. This review addresses different aspects of the coatings for food cans. First, a brief overview on the coatings used for food and beverages cans is presented. In the following sections, a compilation of the analytical methods for the identification of potential migrants in polymeric coatings is provided. Next, the migration of chemicals from the can coatings into food as well as the dietary exposure assessment are discussed. Finally, the regulatory aspects of coatings for food contact are commented on. 2COATINGS FOR FOOD AND BEVERAGE CANS Coatings can be applied in both the internal and external side of metal cans intended to contain food products and beverages. This review is limited to the coatings used on the food contact side. Coatings are formed by application of coating materials by different process, generally by either roller coating or spraying before the curing step. The coating application can be performed both on the metal sheet before forming the container and once the object is formed. In most cases, they have to be able to withstand mechanical deformations to which they are subjected. It is quite common to use 3560 FOOD CONTACT COATINGS IN METAL CANS... FIGURE 1 Schematic representation of an analytical approach for the chemical safety assessment of food-contact coatings more than one type of coating material or applying a coating material several times (Oldring & Nehring, 2007). The main components present in can coatings include resins, cross-linking agents, additives, and solvents; the latter are not always present (Oldring & Nehring, 2007). Some examples of compounds that can be present in polymeric can coatings are shown in Table 1. For food contact applications in metal cans, the most commonly resins used include epoxy, phenolic, polyester, acrylic, vinyl and oleoresins, and variations of them (LaKind,2013;Oldring&Nehring,2007).Thereisnosingle type of resin that serves for all foods, each one is suitable for a certain type of food. Thus, for example, epoxy acrylic resins cross-linked with an amino resin are commonly used for beverage cans; white aluminum-pigmented epoxy resinsaresuitedforfruits and vegetables;andphenolic and epoxy-phenolic blends containing aluminum pigment are widelyemployed forsulfur-bearing fish andmeat (LaKind, 2013; Robertson, 2012; Oldring & Nehring, 2007). A summary of the main chemical and mechanical properties, toxicity, and uses of the coatings used in metal cans is presented in Table 2. 2.1 Oleoresins Initially, before the introduction of synthetic resins, oleoresins were extensively used to coat the food contact surface of metal cans. These resins of natural origin are obtained from natural gums and rosins, and then are blended with drying oils such as linseed or tung oil. The oleoresinous-based coatings present a poor adhesion to metal surfaces and require long times of curing. With the exception of specific applications, particularly nonaggressive foods (e.g., dried beans), nowadays their use is very limited due to their poor resistance to corrosion. Besides, it FOOD CONTACT COATINGS IN METAL CANS... 3561 TABLE 1 Examples of compounds that could be present in polymeric can coatings (Continued) 3562 FOOD CONTACT COATINGS IN METAL CANS... TABLE 1 (Continued) *ChemDraw Professional. has been also reported that they may alter the organoleptic properties of food (LaKind, 2013; Oldring & Nehring, 2007; Robertson, 2012). 2.2 Epoxy-based coatings Epoxy resins are obtained through a condensation reaction between BPA and epichlorhydrin to yield BADGE. BADGE isthelowestmolecular weight resin.These resinsarecured with different curing agents mainly amino resins, phenolic resins, and anhydrides, to form a highly cross-linked threedimensional network in order to provide chemical and pack resistance necessary for the manufacture of food and beverage cans (Oldring & Nehring, 2007; Schaefer & Simat, 2004). Furthermore, BADGE can be also added as stabilizer for organosols acting as a scavenger for hydrochloric acid (El Moussawi et al., 2019; Schaefer & Simat, 2004). However, currently BADGE is not authorized as additive. Because of their good mechanical properties, high adhesiveness, and chemical resistance, these thermosetting resins are widely employed in internal coatings for metal cans for food and beverages. Moreover, they do not impart flavor to foods (LaKind, 2013). 2.3 Vinyl-based coatings The vinyl-based coatings are commonly mixed with other type of resins such as epoxy and phenolic in order to improve their properties. With the exception of vinyl organosol coatings, generally, they are not applied directly on the metal surface because of their limited adhesion to metal substrates (LaKind, 2013). Vinylic organosols are manufactured by mixing several types of resins including poly(vinyl chloride) (PVC), epoxy, and phenolic and epoxy-phenolic resins (Cottier et al., 1998). PVC is produced by polymerization of vinyl chloride monomer (PVM). The production of PVM involves the reaction between chlorine and ethylene to yield ethylene dichloride, then the dichloride is dehydrochlorinated togivethemonomer(Robertson,2012).Organosolspresent very good flexibility and pack resistance (Oldring & Nehring, 2007). They can be found in two-piece cans (e.g., canned fish) (LaKind, 2013). 2.4 Polyester-based coatings Due to the uncertainties regarding the potential adverse effects associated to BPA, polyester-based coatings are being increasingly used as a promising alternative to epoxy resins. Polyesters are synthetized by a condensation reaction between polycarboxylic acids and polyols (Pietropaolo et al., 2018; Zhang et al., 2018; Ubeda et al., 2020). Different monomers are employed in their manufacture; some of the more widely used carboxylic acids include phthalic acid, terephthalic acid, isophthalic acid, adipic acid, and trimellitic acid; and among the polyols, some FOOD CONTACT COATINGS IN METAL CANS... 3563 TABLE 2 Coatings properties, toxicity uses, and applications Coating Chemical and mechanical properties Toxicity Uses and applications References Oleoresins Flexibility: good Adhesion to metal surfaces: poor Corrosion resistance: limited Limited information on toxicity is available. Studies have in general reported low toxicity of polymers obtained from natural oils. Limited uses. Fruits drinks, fruits, and vegetables. LaKind (2013) Geueke (2016) Sharma and Kundu (2006) Epoxy Flexibility: good Adhesion to metal surfaces: good Corrosion resistance: good BPA: endocrine disruptor; studies shown that it presents reproductive toxicity, genotoxicity, cytotoxicity, mutagenicity, and carcinogenicity. BADGEs: In vitro assays revealed that show endocrine disrupting properties and also exhibit genotoxicity and mutagenicity and cytotoxicity. In vivo assays have shown that BADGEs present adverse effects in the reproductive and endocrine systems. Wide range of foods and beverages (e.g., meats, fish, juices, etc.). LaKind (2013) Geueke (2016) Tarafdar et al. (2022) Wang et al. (2021) Vinyl based resins Vinyl Flexibility: very good Adhesion to metal surfaces: very poor Corrosion resistance: poor Vinyl organosol Flexibility: very good Adhesion to metal surfaces: good (higher than vinyl) Corrosion resistance: good (higher than vinyl) Organosol resins are manufactured mixing several types of resins including PVC, epoxy, and phenolic and epoxy-phenolic resins. The toxicity is related to the toxicity of epoxy resins (BPA, BADGE). Soft drinks (vinyl). Fish (vinyl organosol). LaKind (2013) Geueke (2016) Oldring and Nehring (2007) (Continues) 3564 FOOD CONTACT COATINGS IN METAL CANS... TABLE 2 (Continued) Coating Chemical and mechanical properties Toxicity Uses and applications References Polyester Flexibility: very good Adhesion to metal surfaces: good Corrosion resistance: poor Polyester can coatings extracts have been reported to present cytotoxicity. Nonacid foods. LaKind (2013) Geueke (2016) Oldring and Nehring (2007) Groh and Muncke (2017) Phenolic Flexibility: poor Adhesion to metal surfaces: poor Corrosion resistance: very good Components of resole have been reported to exhibit estrogenic activity. Phenolic resins are used as crosslinkers with other resins. Their main applications are canned fish and meat. LaKind (2013) Geueke (2016) Biedermann and Grob (2006b) Acrylic Flexibility: poor Adhesion to metal surfaces: good Corrosion resistance: suitable Studies have shown that the monomer ethylacrylate used in the manufacture of acrylic resins is nongenotoxic. Acrylic resins are commonly used as external coatings. When they are used in the food contact surface, the main applications are beverage cans. LaKind (2013) Geueke (2016) Forrest (2005) Bolognesi et al. (2017) FOOD CONTACT COATINGS IN METAL CANS... 3565 of the most frequent are ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 1,6-hexanediol, 2,2,4-trimethylpentane- 1,3-diol, trimethylolpropane, and cyclohexyldimethanol (Bradleyetal.,2009;Schaeferet al., 2004;Aznaretal.,2019; Ubeda,Aznar,Alfaroetal.,2019; Canellas et al., 2022). This type of resins can be cross-linked with amino resins, phenolic resins, or polyisocyanates (Oldring & Nehring, 2007). In past years, polyester-polyurethane coatings are being developed; these coatings contain in their formulations polyisocyanates to aid the cross-linking of the polymer network during the curing process, resulting in a more inert coatingwithlowermigrationcharacteristics(Bradleyetal., 2009). From the mechanical properties’ standpoint, polyester resins exhibit very good flexibility (Oldring & Nehring, 2007). In terms of food contact applications, the polyesterbased coatings are not suitable for aggressive and acidic foods since they are sensitive to hydrolytic attack of the ester bond under low-pH conditions (Oldring & Nehring, 2007;LaKind,2013). 2.5 Phenolic-based coatings Phenolic resins (called also resoles) are very complex mixtures derived from the reaction products of phenols (phenol, cresol, tert-butylphenol) with formaldehyde and low-molecular-weight aliphatic alcohols such as butanol. They are commonly used as cross-linker in combination with other resins such as epoxy resins (Biedermann & Grob, 2006a, 2006b; Oldring & Nehring, 2007). These coatings are often used in food cans and are resistant to aggressivefoodstuffs(Oldring& Nehring,2007).Theyhave good acid and sulfur resistance, but they impart flavor to some foods (Robertson, 2012). 2.6 Acrylic based coatings In FCMs, acrylic polymers have been used in different applications such as adhesives for food packaging (Nerín et al., 2009; Canellas et al., 2012; Canellas et al., 2017), kitchenware, and coatings on different substrates (Franz & Brandsch, 2013). These types of coatings result from the polymerization of acrylic acid and its derivatives (Piergiovanni & Limbo, 2016). The main monomer used for the production of acrylic resins is ethylacrylate. These coatings are commonly applied in the external surface (LaKind, 2013); however, these coatings also have applications in the easy open ends and bodies of cans intended to contain beverages (Forrest, 2005). These materials offer heat stability (Piergiovanni & Limbo, 2016). 3 ANALYTICAL METHODS FOR THE DETERMINATION OF MIGRANTS OF POLYMERIC COATINGS FOR FOOD CONTACT 3.1 Determination of migrants in polymeric coatings The polymeric coatings used in the inner surface of metal cans for food and beverages may contain in their formulations several components such as resins, cross-linking agents, additives including lubricants, wetting agents, and so on, and solvents. Besides these starting substances, other compounds such as oligomers, reaction products, or unreacted compounds resulting from an incomplete polymerizationprocessmay bepresentinthe finalproductand, therefore, have the potential to migrate from the can coating into the packed food (Bradley et al., 2008; El Moussawi et al., 2019). The identification and quantification of these potential migrants,many times newandunknown,canbe extremely difficult and challenging due, among other reasons, to the complexity of the formulations and the lack of commercial standards allowing confirmation. Chromatographic techniques coupled to different detectors and especially to mass spectrometers have been generally used to achieve this analytical task. Table 3contains a compilation of analytical methods with their main characteristics for the determination of starting substances, oligomers, and reaction products in polymeric coatings used in metal food and beverage cans. Some representative examples of analytical methods used for the determination of migrants from different coatings are given next. Both the earliest and the most recent methodologies are discussed. Conventional techniquessuch asHPLCandGC coupledtodifferentdetectors (UV, FLD, FID, etc.) have been commonly used in the analysis of the components of the coatings. Currently, MS technologies coupled to chromatographic techniques or the application of a battery of analytical techniques are the main approaches proposed to characterize the coatings. However, despite the powerful analytical techniques that are being used it is not possible to identify all detected compounds. The limited information about the formulation composition and the manufacturing process makes the identification of unknown migrants an extremely difficult task (Nerín et al., 2022; Hoppe et al., 2016; Bradley et al., 2008). 3566 FOOD CONTACT COATINGS IN METAL CANS... TABLE 3 Analytical methods used for the identification of potential migrants in polymeric can coatings Coatings Potential migrants Analytical technique detection system Chromatographic conditions Sensitivity/validation Reference Epoxy BADGE; BADGE⋅H2O; BADGE⋅2H2O; BADGE⋅HCl; BADGE⋅2HCl; BADGE⋅H2OHCl HPLC–FLD (λex 275 nm λem305 nm) DryLab R software Poroshell 120 SB-C18 (100 ×4.6 mm, 2.7 μm) column. Mobile phase: ACN and water. Elution mode: gradient Flow: 1.5 ml/min Injection vol.: 10 μl Column temp.: 30◦C Linearity: R2≥.9995 LOD: 0.01–020 ng/g LOQ: 0.03–0.66 ng/g Recovery: 91.65%–100.76% Reproducibility: RSD <7.02% Guo et al. (2020) Epoxy and phenoxy BADGE; BADGE⋅H2O; BADGE⋅2H2O; BADGE⋅HCl; BADGE⋅2HCl; BADGE⋅H2OHCl; CYDBADGE;BPA;BPB; BPC; BPE; BPF; BPG HPLC–FLD (λex 225 nm, λem 305 nm) Phenosphere 80 Å ODS (150 ×3.2 mm, 3μm) column. Mobile phase: water type I and a mixture of ACN:MeOH (50:50, v/v). Elution mode: gradient Flow: 0.5 ml/min Injection vol.: 10 μl Column temp.: 30◦C Linearity: R2≥.9994 LOD: 0.005 mg/L LOQ:0.0125 mg/L Within-day repeatability: RSD <5% Lestido- Cardama, Vázquez- Loureiro et al. (2021) Epoxy BADGE; BADGE⋅H2O; BADGE⋅2H2O; BADGE⋅HCl; BADGE⋅HCl⋅H2O; BFDGE; BFDGE⋅2HCl, BFDGE⋅2H2O; BADGE⋅2HCl LC–MS/MS (ESI+) Parent ion [M+NH4]+: BADGE 358.2; BADGE⋅H2O 376.2; BADGE⋅2H2O 394.2; BADGE⋅HCl 394.2; BADGE⋅HCl⋅H2O 412.1; BFDGE 330.2; BFDGE⋅2HCl 402.1; BFDGE⋅2H2O 366.2; BADGE⋅2HCl 430.1 Synergy MAX-RP (100 ×2.0 mm, 2.5 μm) column. Mobile phase: 0.01 M ammonium formate solution and MeOH. Elution mode: gradient Flow: 0.2 ml/min Column temp.: 40◦C Linearity: R2>.999 LOD: 0.5–3.1 μg/kg LOQ: 1.8–10.3 μg/kg Recovery: 89.92%–109.51% Intraday repeatability: RSD <9.5% Interday repeatability: RSD <12.0% Míguez et al. (2012) (Continues) FOOD CONTACT COATINGS IN METAL CANS... 3573 TABLE 3 (Continued) Coatings Potential migrants Analytical technique detection system Chromatographic conditions Sensitivity/validation Reference Epoxy BADGE⋅2H2O; BADGE⋅ H2O; BADGE⋅H2O⋅ BuEtOH; BADGE⋅H2O⋅Ph; BADGE⋅H2O⋅BPA; BADGE⋅BuEtOH; BADGE⋅Ph; Cyclo-DiBADGE; BADGE⋅BPA; BADGE⋅BPA⋅BuEtOH; BADGE (n=1)⋅BuEtOH; BADGE (n=1)⋅BPA; BADGE (n=1)⋅BPA⋅BuEtOH; BADGE (n=2); BADGE; BADGE⋅PrOH; BADGE⋅ 2BPA; BADGE (n=2)⋅H2O; BADGE (n=2) ⋅PrOH; BADGE⋅2BuEtOH; BADGE⋅ BuEtOH⋅BuOH; BADGE (n=1)⋅2BuEtOH; BADGE (n=1)⋅BuEtOH⋅BuOH HPLC–MS (ESI+)–UVD–FLD (UV (λ 275 nm) (FLD (λex 275 nm, λem 305 nm) Scan range m/z 80–1000. Protonated molecular ions (m/z)[M+H]+BADGE⋅ 2H2O377;BADGE⋅H2O359;BADGE⋅ H2O⋅BuEtOH 477; BADGE⋅H2O⋅Ph 453; BADGE⋅H2O⋅BPA587;BADGE⋅ BuEtOH 459; BADGE⋅Ph 435; Cyclo-DiBADGE 569; BADGE⋅BPA 569; BADGE⋅BPA⋅BuEtOH 687; BADGE (n=1)⋅BuEtOH 743; BADGE (n=1)⋅BPA 853; BADGE (n=1)⋅ BPA⋅BuEtOH 971; BADGE (n=2) 909; BADGE 341; BADGE⋅PrOH 401; BADGE⋅2BPA 797; BADGE (n=2) ⋅H2O927;BADGE(n=2) ⋅PrOH 969; BADGE⋅2BuEtOH 577; BADGE⋅ BuEtOH⋅BuOH 533; BADGE (n=1) ⋅2BuEtOH 861; BADGE (n=1) ⋅ BuEtOH⋅BuOH 817 Multospher R  100 5C18 column (250 ×3 mm). Mobile phase: 1 mM ammonium formate in water (pH 3) and can. Elution mode: gradient Flow: 0.5 ml/min Column temp.: 25◦C Reproducibility: RSD <11.50% LOD: 1.0 μg/L Schaefer and Simat (2004) (Continues) 3574 FOOD CONTACT COATINGS IN METAL CANS... TABLE 3 (Continued) Coatings Potential migrants Analytical technique detection system Chromatographic conditions Sensitivity/validation Reference Polyvinyl chloride ATBC; DEHA; OA; DBP; DiBP; BBP; DEHP; BGA; BGA-formaldehyde; ELSO UHPLC–HRMS (ESI+) (APCI+) Full scan m/z 75–1000; 87–1300 Protonated molecular ions (m/z)[M+H]+ATBC 403.2326; DEHA 371.3156; OA 282.2791; DBP 279.1591; DiBP 279.1591; BBP 313.1434; DEHP 391.2843; BGA 188.0935; BGA-formaldehyde 216.0880; ELSO (APCI) (C55H98O10 919.7233; C57H92O15 1017.6509; C57H96O13 989.6924; C57H98O12 975.7131; C57H100O11 961.7339; C57H102O10 947.7546) Acquity HSS T3 (100 ×2.1 mm,1.8 μm) analytical column. Mobile phase: 5 mM ammonium formate with 0.1% formic acid and MeOH containing 0.1% formic acid Elution mode: gradient Flow: 300 μl/min Injection vol.: 5 μl Column temp.: 40◦C Linearity: R2>.99 ESI: LOD: 1–5 ng/ml LOQ: 1–10 ng/ml APCI: LOD: 0.5–5 μg/ml LOQ: 1–25 μg/ml Repeatability: <12% Vaclavikova et al. (2016) Polyester Cis-endo-nadic acid; trans-endo,exo-nadic acid; cis-endo-nadic anhydride; cis-exo-nadic anhydride. PA and IPA. PUD Phthalic acids and nadic acids. LC–MS/MS (ESI–) Selected reaction monitoring (SRM) transitions cis-endo-nadic acid 181.1 >115.0; trans-endo,exo-nadic acid; 181.1 >163.0; Phthalic and isophthalic acid 165.0 >120.9 NAH (nadic anhydride) isomers. GC–TOF– MS Scan range m/z 30–400 exo-NAH and endo-NAH m/z 66.0470 for quantification and m/z 91.0548 for confirmation Oligomers LC–TOF–MS (ESI+) (ESI–) mass range m/z 100–1100 LC–MS/MS: Acquity UPLC HSS T3 (100 ×2.1 mm, 1.8 μm) column. Mobile phase: water with 0.1% acetic acid/0.1 mM ammonium fluoride and MeOH:ACN (1:1). Elution mode: gradient Flow: 0.4 ml/min Injection vol.: 1 μl Column temp.: 40◦C GC–TOF–MS: HP-5MS Ultra Inert column (30 m ×0.25 mm i.d., 0.25 μm) column. Temp. program: 40–290◦C. Carrier gas: Helium Flow: 1.1 ml/min LC–TOF–MS: Atlantis dC18 (150 ×2.1 mm, 3 μm) column. Mobile phase: 10 mM ammonium acetate in water and MeOH Elution mode: gradient Flow: 0.4 ml/min Injection vol.: 3 μl Column temp.: 30◦C LOD: 0.01–26 μg/kg Driffield et al. (2018) (Continues) FOOD CONTACT COATINGS IN METAL CANS... 3575 TABLE 3 (Continued) Coatings Potential migrants Analytical technique detection system Chromatographic conditions Sensitivity/validation Reference Polyesterpolyurethane Predicted oligomer combinations: Cyclic: 2NPG+2PA; 3NPG+3PA; 4NPG+4PA; NPG+HD+2PA; NPG+2HD+3PA; 2HD+2PA; NPG+3HD+4PA; 2NPG+2HD+4PA; 2NPG+HD+3PA; 3HD+3PA; 4HD+4PA; 3NPG+HD+4PA; DEG+NPG+2PA; 2DEG+2PA; EG+DEG+2PA; EG+2NPG+3PA; DEG+2NPG+3PA; EG+DEG+NPG+3PA; 2DEG+NPG+3PA; DEG+3NPG+4PA; EG+3NPG+4PA; EG+2DEG+3PA; EG+DEG+2NPG+4PA; EG+NPG+2PA; 2EG+NPG+3PA; 2EG+2NPG+4PA Linear: 2HD+PA; NPG+HD+PA LC–HRMS (HESI+) Full-scan mode m/z 155–1200. Mean measured [M+NH4]+m/z Cyclic: 2NPG+2PA 486.21289; 3NPG+3PA 720.30192; 4NPG+4PA 954.39106; NPG+HD+2PA 500.22849; NPG+2HD+3PA 748.33313; 2HD+2PA 514.24422; NPG+3HD+4PA 996.43788; 2NPG+2HD+4PA 982.42209; 2NPG+HD+3PA 734.31758; 3HD+3PA 762.34875; 4HD+4PA 1010.45361; 3NPG+HD+4PA 968.40703, DEG+NPG+2PA 488.19216; 2DEG+2PA 490.17139; EG+DEG+2PA 446.14514; EG+2NPG+3PA 678.25511; DEG+2NPG+3PA 722.28122; EG+DEG+NPG+3PA 680.23438; 2DEG+NPG+3PA Hypersil Gold (100 ×2.1 mm, 1.9 μm) analytical column. Mobile phase: 10 mM ammonium acetate in water and 10 mM ammonium acetate in ACN. Elution mode: gradient Flow: 0.4 ml/min Injection vol.: 10 μl Column temp.: 40◦C Omer et al. (2018) (Continues) 3576 FOOD CONTACT COATINGS IN METAL CANS... TABLE 3 (Continued) Coatings Potential migrants Analytical technique detection system Chromatographic conditions Sensitivity/validation Reference Unpredicted compounds: Cyclic: Caprolactam dimer; Caprolactam trimer; Caprolactam tetramer; EG+NPG+PA+SA; EG+DEG+PA+SA; EG+DEG+2SA; 2NPG+PA+SA; DEG+NPG+PA+SA; 2DEG+PA+SA; NPG+TEG+2PA; DEG+TEG+2PA; EG+2NPG+2PA+SA; EG+NPG+DEG+2PA+SA; 3NPG+2PA+SA; DEG+2NPG+2PA+SA; C12H24O2+NPG+HD+3PA; C12H24O2+2HD+3PA; 4NPG+3PA+SA 724.26048; DEG+3NPG+4PA 956.37058; EG+3NPG+4PA 912.34420; EG+2DEG+3PA 682.21360; EG+DEG+2NPG+4PA914.32351; EG+NPG+2PA 444.16589; 2EG+NPG+3PA 636.20833; 2EG+2NPG+4PA 870.29726 Linear: 2HD+PA 384.23855; NPG+HD+PA 370.22284 Unpredicted compounds: Cyclic: Caprolactam dimer 227.17565 [M+H]+; Caprolactam trimer 340.25993 [M+H]+; Caprolactam tetramer 453.34406 [M+H]+; EG+NPG+PA+SA 480.25989 [M+NH4]+;EG+DEG+PA+SA 482.23913 [M+NH4]+;EG+DEG+2SA 518.33325 [M+NH4]+;2NPG+PA+SA 522.30681 [M+NH4]+; DEG+NPG+PA+SA 524.28620 [M+NH4]+;2DEG+PA+SA 526.26544 [M+NH4]+;NPG+TEG+2PA 532.21841 [M+NH4]+;DEG+TEG+2PA 534.19774 [M+NH4]+;EG+2NPG+2PA+SA 714.34891 [M+NH4]+; EG+NPG+DEG+2PA+SA 716.32826 [M+NH4]+;3NPG+2PA+SA 756.39567 [M+NH4]+;DEG+2NPG+2PA+SA 758.37498 [M+NH4]+; C12H24O2+NPG+HD+3PA 830.41152 [M+NH4]+;C 12H24O2+2HD+3PA 844.42731 [M+NH4]+; 4NPG+3PA+SA 990.48536 [M+NH4]+ (Continues) FOOD CONTACT COATINGS IN METAL CANS... 3577 TABLE 3 (Continued) Coatings Potential migrants Analytical technique detection system Chromatographic conditions Sensitivity/validation Reference Polyesterpolyurethane 2EG+2PA; 2EG+PA+SA; EG+NPG+2PA; EG+DEG+2PA; EG+NPG+PA+SA; EG+DEG+PA+SA; 2NPG+2PA; NPG+DEG+2PA; 2DEG+2PA; NPG+HD+2PA; 2HD+2PA; EG+DEG+2SA; 2NPG+PA+SA; NPG+DEG+PA+SA; 2DEG+PA+SA; NPG+TEG+2PA; DEG+TEG+2PA; IPDI; DPMDI GC–MS (GC–(EI)qMS; GC–(EI)Orbitrap; GC–(APCI)TOFHRMS) Full-scan mode m/z 50–750; m/z 50–1200. Molecular mass: 2EG+2PA 384.08452; 2EG+PA+SA 420.17842; EG+NPG+2PA 426.13147; EG+DEG+2PA 428.11074; EG+NPG+PA+SA 462.22537; EG+DEG+PA+SA 464.20464; 2NPG+2PA 468.17842; NPG+DEG+2PA 470.15769; 2DEG+2PA 472.13695; NPG+HD+2PA 482.19407; 2HD+2PA 496.20972; EG+DEG+2SA 500.29854; 2NPG+PA+SA 504.27232; NPG+DEG+PA+SA 506.25159; 2DEG+PA+SA 508.23085; NPG+TEG+2PA 514.18390; DEG+TEG+2PA 516.16317 DB-5MS capillary column (30 m ×0.25 mm i.d., 0.25 μm). Temp. program: 120–310◦C Injector: 250◦C Carrier gas: Helium Flow: 1 ml/min (1.7 ml/min) Injection mode: Splitless Injection vol.: 1 μl Omer et al. (2019) Polyesterpolyurethane IPDI; MEKO; 2-Ethylhexanoic acid; Oligomers: 2 PA+2EG; 2PA+EG+NPG; 2PA+EG+DEG; 2PA+CHDM+EG; 2PA+ 2NPG; 2PA+CHDM+NPG; 3PA+2EG+NPG or 3PA+3PG; 3PA+EG+2NPG; 3PA+CHDM+EG+NPG; 3PA+3NPG; 3PA+CHDM+2PG; 3PA+CHDM+2NPG; 3PA+2CHDM+NPG MEKO-blocked IPDI. LC–MS/MS (ESI+) m/z928.7 [M+H]+(quantification) and m/z950.68 [M+Na]+ (confirmation). 2-Ethylhexanoic acid. GC–MS m/z88 and 116. Oligomers. LC–TOF–MS, mass: 2PA+2EG (Cyclic) 384.0845; 2PA+EG+NPG (Cyclic) 426.1315; 2PA+EG+DEG (Cyclic) 428.1107; 2PA+CHDM+EG (Cyclic) 466.1630; 2PA+2NPG (Cyclic) 468.1784; 2PA+CHDM+NPG (Cyclic) 508.2114; 3PA+2EG+NPG or 3PA+3(PG) (Cyclic) 618.1737; 3PA+EG+2NPG (Cyclic) 660.2238; 3PA+CHDM+EG+NPG (Cyclic) 700.2520; 3PA+3NPG 702.2703; 3PA+CHDM+2PG (Linear) 704.2469; 3PA+CHDM+2NPG (Cyclic) 742.3003; 3PA+2CHDM+NPG (Cyclic) 782.3330 IPDI trimer: Waters Sunfire (C18) column (150 ×2.1 mm, 3.5 μm). Mobile phase: 0.05% formic acid in ACN. Flow: 0.2 ml/min Injection vol.: 20 μl Column temp.: 30◦C MEKO-blocked IPDI LOD: 0.01 μg/dm2 2-Ethylhexanoic acid LOD: 0.1 μg/dm2 IPDI trimer LOD: 0.02 μg/dm2 Bradley et al. (2009) (Continues) 3578 FOOD CONTACT COATINGS IN METAL CANS... TABLE 3 (Continued) Coatings Potential migrants Analytical technique detection system Chromatographic conditions Sensitivity/validation Reference Polyester-phenol TPA,IPA,TMA,ADA,EG, DEG, NPG, MPD, BD, TCDDM. Polyester oligomers: 2TPA+2BD; 2TPA+1BD+1TCDDM; 2TPA+2TCDDM; 3TPA+3BD; 3TPA+2BD+1TCDDM; 3TPA+2TCDDM+1BD; 3TPA+3TCDDM; 2PA+2EG; 2PA+1NPG+1EG; 2PA+2NPG; 3PA+3EG; 3PA+2EG+1NPG; 3PA+2NPG+1EG; 3PA+3NPG; 4PA+4EG; 4PA+3EG+1NPG; 4PA+2EG+2NPG; 4PA+3NPG+1EG; 4PA+4NPG; 2PA+2EG; 2PA+2MPD; 2PA+1MPD+1DEG; 2PA+2DEG; 3PA+3MPD; 3PA+2MPD+1DEG; 3PA+2DEG+1MPD; 3PA+3DEG Polyester acids. HPLC–DAD (scan 200–400 nm) λ210, 220, 240, 275 nm. Polyester polyols GC–MSD (scan m/z 30–150) Polyester oligomers RP-HPLC–DAD–MS (ESI+) (λ232 nm) Precursor ions [M+H]+2TPA+2BD 441.5; 2TPA+1BD+1TCDDM 547.7; 2TPA+2TCDDM 653.8; 3TPA+3BD 661.8; 3TPA+2BD+1TCDDM 767.9; TPA+2TCDDM+1BD 874.1; 3TPA+3TCDDM 980.3; 2PA+2EG 385.2; 2PA+1NPG+1EG 427.4; 2PA+2NPG 469.5; 3PA+3EG 577.3; 3PA+2EG+1NPG 618.5; 3PA+2NPG+1EG 661.6; 3PA+3NPG 703.8; 4PA+4EG 769.4; 4PA+3EG+1NPG 811.6; 4PA+2EG+2NPG 853.7; 4PA+3NPG+1EG 895.9; 4PA+4NPG 938.0; 2PA+2EG 385.2; 2PA+2MPD 441.4; 2PA+1MPD+1DEG 457.3; 2PA+2DEG 473.2; 3PA+3MPD 661.6; 3PA+2MPD+1DEG 677.5; 3PA+2DEG+1MPD 693.4; 3PA+3DEG 709.3 HPLC–DAD Polaris R C18-Ether column. Mobile phase: 0.1% (v/v) trifluoroacetic acid in distilled water and ACN. Elution mode: gradient Flow: 0.5 ml/min Injection vol.: 10 μl Column temp.: 30◦C GC–MSD WAXplus R capillary column (30 m ×0.25 mm i.d., 0.5 μm) Temp. program: 60–260◦C. Injector temp.: 260◦CTransferline: 260◦C Carrier gas: Helium Injection mode: Splitless RP-HPLC–DAD–MS Multospher 120 RP18 HP column (250 ×3 mm, 5 μm). Mobile phase: 0.015% (v/v) formic acid in water and 2-propanol. Elution mode: gradient Flow: 0.4 mL/min Injection vol.: 10 μl Column temp.: 60◦C Multohigh 100 Phenyl column (250 ×3 mm, 5 μm) Mobile phase: 0.015% (v/v) formic acid in water and ACN. Elution mode: gradient Flow: 0.3 ml/min Injection vol.: 10 μl Column temp.: 35◦C Recovery: 80%–120% Eckardt et al. (2020) (Continues) FOOD CONTACT COATINGS IN METAL CANS... 3579 TABLE 3 (Continued) Coatings Potential migrants Analytical technique detection system Chromatographic conditions Sensitivity/validation Reference Polyesterpolyurethane IPDI trimer LC–MS/MS (ESI+) IPDI trimer derivatized with dibutylamine. Precursor ion m/z 1078 [M+Na]+ Waters Sunfire (C18) column (150 ×2.1 mm, 3.5 μm). Mobile phase: 0.05% formic acid in ACN. Flow: 0.2 ml/min Injection vol.: 20 μl Column temp.: 30◦C Linearity: R2>.9979 for the quantification channel 1078 >819 and R2>.9906 for the confirmation channel 1078 >949 LOD: 0.02 μg/100 cm2 Recovery: 87%–106% Repeatability: RSD <24% Driffield et al. (2007) (Continues) 3580 FOOD CONTACT COATINGS IN METAL CANS... TABLE 3 (Continued) Coatings Potential migrants Analytical technique detection system Chromatographic conditions Sensitivity/validation Reference Polyester-urethane and polyester-phenolic ADA; IPA; PA; TPA; TMA; dimethyl isophthalate; BHET;1,3-BD;EG;HD; NPG; 1,2-PG; 1,3-PG; 2,2,4-trimethylpentane- 1,3-diol; COH; MPD; Cyclic oligoesters: CYCLO DA (dicarboxylic acid) PO (polyols) (2DA 2PO-1); CYCLO (2DA 1PO-1 1PO-2); CYCLO (2DA 2PO-2); CYCLO (3DA 1PO-1 2PO-2); CYCLO (2DA 2PO-2 1PO-3); CYCLO (3DA 3PO-2); CYCLO (4DA 1PO-1 3PO-2); CYCLO (3DA 2PO-2 1PO-3); CYCLO (4DA 4PO-3); CYCLO (3DA 3PO-1); CYCLO (2DA 1PO-1 1PO-4); CYCLO (3DA 2PO-1 1PO-4); CYCLO (2DA 2PO-4); CYCLO (3DA 1PO-1 2PO 4); CYCLO (2DA 1PO-5 1PO-6); CYCLO (2DA 2PO-5); CYCLO (2DA 1PO-3 1PO-5); CYCLO (3DA 1PO-3 2PO-5) Polyols (PO): GC–FID; dicarboxylic acids (DA): HPLC–MS–UV (ESI+); cyclic oligoesters: HPLC–MS–UV (ESI+)and HPLC–ELSD–UV (UV λ232 nm) (Mass range m/z 80–1000) GC–FID: CP-Pora-Plot Q-HT, capillary column (12.5 m ×0.32 mm i.d., 10 μm). Temp. program: 160–270◦C Carrier gas: Nitrogen Injector temp.: 280◦C Detector temp.: 280◦C HPLC–MS–UV (ESI+)and HPLC–ELSD–UV: For dicarboxylic acids Aqua 125 5C18, column (250 ×3 mm). Mobile phase: 5 mM ammonium formate in water (pH 3.9) and ACN. Elution mode: gradient Flow: 0.5 ml/min Column temp.: 30◦C For cyclic oligoesters Multospher R  100 5C18, column (250 ×3mm). Mobile phase: 1 mM ammonium formate in water (pH 3) for MS or bidistilled water for ELS detection and ACN. Elution mode: gradient Flow: 0.5 ml/min Column temp.: 25◦C LOQ: 0.01 mg/dm2Schaefer et al. (2004) (Continues) FOOD CONTACT COATINGS IN METAL CANS... 3581 TABLE 3 (Continued) Coatings Potential migrants Analytical technique detection system Chromatographic conditions Sensitivity/validation Reference Polyester Linear oligomers: NA+2EG; PA+MBO; NA+COH; PA+2MBO; PA+COH; 2PA+MBO; NA+COH+MBO; PA+MBO+COH; NA+PA+2MBO; 2PA+2MBO; NA+PA+COH; NA+2COH; 2PA+COH; NA+PA+3MBO; PA+NA+COH+MBO; PA+tBuPh+COH; 2PA+MBO+COH; 2PA+2MBO+COH; 2PA+2COH; 3PA+2COH+MBO; 3PA+2MBO+COH; 2PA+2COH+MBO. Cyclic oligomers: 3PA+3MBOc; 2NA+MBO+COHc; 3PA+2MBO+COHc; 2PA+COH+MBOc; 2NA+PA+3MBOc; PA+NA+COH+MBOc; NA+PA+2COHc HPLC–DAD/MS (ESI+)(ESI–)(λ 200–400 nm, 225, 254, 280, 288, and 330 nm) Full-scan mode m/z 100–1000 HPLC–DAD/CAD UHPLC–HRMS (ESI+,ESI–) Full-scan m/z 100–800 (ESI+) Full-scan m/z 100–1000 (ESI–) Exact mass (m/z): Linear oligomers: NA+2EG 293.0999 [M+Na]+; PA+MBO 237.0771[M–H]–;NA+COH 331.1519 [M+Na]+;PA+2MBO 333.1212 [M+Na]+;PA+COH 291.1242 [M–H]–; 2PA+MBO 385.0935 [M–H]–; NA+COH+MBO 403.2095[M+Na]+; PA+MBO+COH 387.1781[M+Na]+; NA+PA+2MBO 497.1790 [M+Na]+; 2PA+2MBO 457.1511[M–H]–; NA+PA+COH 474.2126 [M+NH4]+; NA+2COH 457.2566 [M+Na]+; 2PA+COH 463.1363 [M+Na]+; NA+PA+3MBO 569.2364 [M+Na]+; PA+NA+COH+MBO 551.2259 [M+Na]+;PA+tBuPh+COH 425.2302 [M+H]+;2PA+MBO+COH 511.1979 [M–H]–;2PA+2MBO+COH 607.2521[M+Na]+;2PA+2COH 565.2450 [M–H]–;3PA+2COH+MBO 787.3306 [M+H]+;3PA+2MBO+COH 750.3124 [M+NH4]+; 2PA+2COH+MBO 639.3170 [M+H]+. Cyclic oligomers: 3PA+3MBOc 678.2500[M+NH4]+; 2NA+MBO+COHc 544.2913[M+NH4]+; 3PA+2MBO+COHc 715.2726 [M+H]+; 2PA+COH+MBOc 517.1840 [M+Na]+; 2NA+PA+3MBOc 710.3172 [M+NH4]+; PA+NA+COH+MBOc 511.2331[M+H]+;NA+PA+2COHc 565.2804[M+H]+ HPLC–DAD/MS Agilent Polaris 3 (C18) column (150 × 2.0 mm). Mobile phase: water 0.1% formic acid and ACN 0.1% formic acid. Elution mode: gradient Flow: 0.3 ml/min Injection vol.: 10 μl Column temp.: 25◦C HPLC–DAD/CAD Agilent Zorbax Extend C18 column 80 Å (2.1 ×150 mm, 3 μm). Mobile phase: water and ACN. Elution mode: gradient Flow: 0.3 ml/min Injection vol.: 10 μl Column temp.: 25◦C UHPLC–HRMS Acquity UPLC BEH C18 column (150 ×2.1 mm, 1.7 μm). Mobile phase: 5% ACN in water 0.1% formic acid and 5% water in ACN 0.1% formic acid Elution mode: gradient Flow: 0.2 ml/min Injection vol.: 1 μl Paseiro- Cerrato, MacMahon et al. (2016) (Continues) 3582 FOOD CONTACT COATINGS IN METAL CANS... TABLE 3 (Continued) Coatings Potential migrants Analytical technique detection system Chromatographic conditions Sensitivity/validation Reference Polyester Linear oligomers: IPA+2 HD; IPA+2NPG; IPA+2MPD; TPA+2HD. Cyclic oligomers: 2TPA+2HD; 2IPA+2HD; 2IPA+2MPD; 2TPA+2MPD; IPA+TPA+2NPG; 2IPA+HD+MPD; 2IPA+HD+NPG; 3IPA+3HD 2DPA+2HD; (internal standard) HPLC–MS (ESI+) Precursor ion m/z [M+H]+ IPA+2NPG 339.2; TPA+2HD 367.2; IPA+2HD 367.2; IPA+2MPD 311.1; 2TPA+2HD 497.2; 2IPA+2HD 497.2; 2IPA+2MPD 441.2; 2TPA+2MPD 441.2; IPA+TPA+2NPG 469.2; 2IPA+HD+MPD 469.2; 2IPA+HD+NPG 483.2; 3IPA+3HD 745.3; 2DPA+2HD 499.2 Quantification: micro-HPLC–HRMS/MS HPLC–MS: Atlantis T3 C18 column (150 mm ×4.6 mm, 5 μm). Mobile phase: ultrapure water with 0.1% trifluoroacetic acid and MeOH. Elution mode: gradient Flow: 1.0 ml/min HPLC–HRMS/MS: Halo C18 column (100 ×0.5 mm, 2.7 μm). Mobile phase: ammonium acetate (1.0 mM) in water and ammonium acetate (1.0 mM) in MeOH. Elution mode: gradient Flow: 15.0 μl/min Injection vol.: 300 nl Column temp.: 45◦C Linearity: R2>.996 LOD: 0.003–0.30 ng/ml LOQ: 0.010–1.00 ng/ml Intraday: RSD <8.2% Interday: RSD <13.3% Recovery: 55.1–68.4% Pietropaolo et al. (2018) Acrylic resins MMA; EMA; BMA; iBMA GC–FID DB VRX column (30 m ×0.32 mm i.d., 1.8 μm) and DB 624 column (30 m ×0.32 mm i.d., 1.8 μm). Temp. program: 35–260◦C Transferline: 150◦C Detector: 260◦C Linearity: R2>.996 LOD (Water): 20–80 pg/ml LOD (Tenax): 0.25 μg/ml LOD (Miglyol 840): 0.2–1.5 ng/ml Recovery (Water): 88%–104% Recovery (Tenax): 87%–100% Recovery (Miglyol 840): 91%–99% Franz and Brandsch (2013) (Continues) FOOD CONTACT COATINGS IN METAL CANS... 3589 study, the authors determined acrylic acid methyl ester, methacrylic acid ethyl ester, methacrylic acid butyl ester, and methacrylic acid isobutyl ester in four acrylic resins. Samples were analyzed by multiple headspace extraction sampling with six sequential extractions before the GC–FID determination. Quantification was performed by the external standard method and appropriate linearity (R2>.998) was reported. The release of the monomers in different food simulants was also investigated and, in general, low diffusion coefficients were obtained compared with other polymers. More recently, Paseiro-Cerrato et al. (2017) investigated potential migrants from an acrylic–phenolic coating using HPLC coupled to different detectors, for example, DAD, CAD, MS, and HRMS. Several migrants including BPA, BADGE⋅2H2O, and BGA (benzoguanamine) and seven unknown compounds that showed good response with DAD were detected in ACN extracts of acrylic–phenolic can coating as well as in food simulants (aqueous food simulants, 50% ethanol [v/v]). However, the authors indicated that it was not possible to identify acrylic–phenolic derivatives. Mainly, higher concentrations of migrants in food simulants than in ACN extracts were found. 3.1.4 Analysis of phenolic resins components Phenolic resins or resoles are complex mixtures commonly employed as a cross-linkers for other resins. Due to the complexity of its nature, they are difficult to characterize, and it is to be expected that different techniques will be needed to address the study of their composition. An analytical methodology that involves the use of a battery of instrumental techniques, including GC–MS, comprehensive two-dimensional GC (GC×GC), normalphase high-performance liquid chromatography (NPLC), and size exclusion chromatography (SEC), for the determination of resole components has been proposed by Biedermann and Grob (2006a). Thus, GC–MS was used as a very useful tool in terms of identification of chromatographic peaks; GC×GC provided additional information, an improved resolution, and also allowed to group peaks belonging to the same type of compounds. NPLC was used as a complementary technique, namely, as a preseparation step of samples before GC analysis, and SEC provided information about the distribution of the molecular weight of the compounds in the mixture. The method was applied to characterize a commercial resole based on phenol. Samples were trimethyl silylated before the GC analysis. Monophenolic, bisphenols, and polyphenols resole components were identified. The authors highlighted the valuable information provided by each technique for a complete analysis. In the second part of the work (Biedermann & Grob, 2006b), the methodology was applied to two resoles based on cresol/phenol mixtures and a resole manufactured from tert-butylphenol. Resole components including mono-cresols, mono-tert-butylphenols, cresolphenols, bis-cresols, bis-tert-butylphenols, and three-ring compounds were identified. The resole obtained from tertbutylphenol was mainly composed by components with one to three rings. 3.2 Determination of migrants transferred from coatings in foods The analysis of the migrants in the foodstuff usually involves the extraction of the analytes from the matrix prior to the chromatographic analysis. Several sample preparation treatments have been used for bisphenols, BADGE, and derivatives, as reported in Table 4; solvent extraction and solid-phase extraction (SPE) are the most predominant. Other extraction techniques including solid-phase microextraction (SPME), online SPE, supramolecular solvent-based microextraction (SUPRASs), Quick, Easy, Cheap, Effective, Rugged, & Safe (QuEChERS), and molecularly imprinted polymers, among others, have been also applied. The SUPRAS-based microextraction has demonstrated to be a suitable technique to extract bisphenols and BADGEs from a diversity of canned foods including vegetables, fish, and meat products. Several variables, namely, solvent composition and volume, pH, and time, were tested during the optimization of SUPRAS extraction. Tetradecanol-based SUPRAS was reported to be the most suitable and a good extraction efficiency for the target analytes was achieved (Alabi et al., 2014). An interesting alternative to the conventional SPE is the molecularly imprinted polymers-solid phase extraction (MISPE). Due to its inherent selectivity, it generally provides greater effectiveness. MISPE cartridges have been successfully applied for the purification of bisphenols and BADGEs from canned beers and energy drinks (Cirillo et al., 2019; Gallo et al., 2017). A new single-step extraction and clean-up method based on alkylcarboxylate-coated magnetic nanoparticles to extract BPA from soft drinks has been proposed by Yazdinezhad et al. (2013). The authors highlighted that the method was rapid and simple and showed lower solvent consumption compared to other conventional procedures. In the case of polyester monomers and oligomers, there are very few examples in the literature. The extraction procedures reported comprise a solvent extraction followed by a clean-up step with SPE or QuEChERS (Paseiro-Cerrato et al., 2019a;Driffield et al., 2018). 3590 FOOD CONTACT COATINGS IN METAL CANS... TABLE 4 Migration values of chemical components from can coatings into food Coating Migrant Food Extraction procedure Analytical technique Migration results (Restrictions) Reference Polyester coating TA, IPA, NA, and oligomers (PA+2MPD, PA+CHDM+MPD) Chicken noodle soup, chicken cream, sauerkraut, mushrooms, green beans, tomatoes, pumpkins, coconut milk, and chicken rice no salt Solvent extraction (ACN with 0.1% formic acid) and SPE UFLC–MS/MS for monomers, and LC–DAD for oligomers UHPLC–HRMS for confirmation aIPA: 5.1–69 μg/kg; TA: nd–61 μg/kg; NA: <LOD–21 μg/kg; PA+2MPD: nd–324 μg/kg; PA+CHDM+MPD: nd–454 μg/kg Paseiro-Cerrato et al. (2019a) Polyester can coatings based on NAH PA, IPA, NA isomers (cis-endo-NA, trans-endo-exo-NA), NAH isomers (endo-NAH, exo-NAH), and oligomers <1000 Da Green beans, tomato sauce, diced tomatoes, wax beans, peas, whole kernel corn, crema style corn, corn, spilt pea and ham soup, chicken broth, pumpkin, refried beans, potatoes, pork and beans, black beans, ketchup, and jalapeno peppers Solvent extraction (ACN) (oligomers) and QuEChERS (monomers) LC–MS/MS for monomers, GC–TOF–MS for NAHs, and LC–TOF–MS for oligomers aIPA: <20 μg/kg; PA: <20 μg/kg; cis-endo-NA: <0.01–17 μg/kg; trans-endo-exo-NA: <0.02–2.2 μg/kg; dendo-NAH: <0.77–42 μg/kg; dexo-NAH: <0.78–4.6 μg/kg; oligomers (<1000 Da): <LOD–943 μg/kg Driffield et al. (2018) Epoxy resin BPA, BPF, BPE, BPB, BPS Soft drinks (soda, beer, cola, tea, and energy drinks) On-line SPE LC–MS/MS aBPA: nd–607 ng/L; BPF: nd–218 ng/L; BPS, BPE, BPB: nd Gallart-Ayala et al. (2011b) (Continues) FOOD CONTACT COATINGS IN METAL CANS... 3591 TABLE 4 (Continued) Coating Migrant Food Extraction procedure Analytical technique Migration results (Restrictions) Reference Epoxy resin BADGE.2H2O, BPF, BPE, BPA, BADGE.H2O.HCl, BADGE.H2O, BPB, BADGE.2HCl, BADGE.HCl, BADGE, BFDGE, BFDGE.2HCl Vegetables (mushroom, red pepper, olive, green beans, asparagus), legumes (chickpeas, lentils), fruits (pineapple, peach), fish and other seafood (mackerel, mussels, tuna, cockles), meat products (tripe, meat ball), and grains (sweet corn) Microextraction with a SUPRASs made up of inverse aggregates of tetradecanol HPLC–FLD bBADGE.2H2O: nd–959 μg/kg; BPF, BPE: nd; aBPA: nd–241 μg/kg; BADGE.H2O.HCl: nd–533 μg/kg; BADGE.H2O: nd–179 μg/kg; BPB: nd–40 μg/kg; BADGE.2HCl: nd–215 μg/kg; BADGE.HCl: nd–21 μg/kg; BADGE: nd–7.1 μg/kg; BFDGE: nd–314 μg/kg; BFDGE.2HCl: nd–120 μg/kg Alabi et al. (2014) Epoxy resin BPA, BPB Vegetables (maize, green beans, peas, mushroom, soybean, tomato, spinach, and carrot) and fruits (pineapple, peaches, lychees, pears, mango, papaya, passion, and fruit salad) QuEChERS and DLLME using ACN as dispersive solvent, tetrachloroethylene as extractive solvent, and anhydride acetic as derivatizing reagent GC–MS Fruits aBPA: nd–10.2 μg/kg BPB: nd–3.4 μg/kg Vegetables BPA: nd–265.6 μg/kg BPB: nd–3 μg/kg Cunha and Fernandes (2013) Epoxy resin BPA, BPB, BPF, BADGE, and BFDGE Energy drinks MIP (Affinimip R BPA SPE cartridge) UPLC–FLD aBPA: <LOQ–3.3 ng/ml; BPB: <LOQ; BPF: <LOQ–1.3 ng/ml; bBADGE: <LOQ–19.4 ng/ml; BFDGE: <LOQ–0.6 ng/ml Gallo et al. (2017) (Continues) 3592 FOOD CONTACT COATINGS IN METAL CANS... TABLE 4 (Continued) Coating Migrant Food Extraction procedure Analytical technique Migration results (Restrictions) Reference BPA-based epoxy resin BPA, BPF, BADGE, BADGE.2H2O, BADGE.H2O, BADGE.HCl.H2O, BADGE.2HCl, and BADGE.HCl Beer (Pilsner, wheat beer, black beer, and others) LLE LC–MS/MS aBPA: <0.1–2.54 μg/L; BPF: nd–0.3 μg/L; bBADGE: nd–<0.05 μg/L; BADGE.2H2O: <0.5–14.3 μg/L; BADGE.H2O: nd; BADGE.HCl.H2O: nd–0.65 μg/L; BADGE.2HCl: nd–0.55 μg/L; BADGE.HCl: nd–<0.1 μg/L Zech et al. (2015) Epoxy resin BADGE, BADGE.H2O, BADGE.2H2O, BADGE.HCl, BADGE.2HCl, BADGE.HCl.H2O, BFDGE, BFDGE.2HCl and BFDGE.2H2O Fish products (mussels, European anchovy, sardines, mackerels, and tuna) Solvent extraction (1:1, ACN-hexane) LC–MS/MS bBADGE, BADGE.HCl, BADGE.2HCl, BFDGE, BFDGE.2HCl, BFDGE.2H2O: nd; BADGE.H2O: nd–120 μg/kg; BADGE.2H2O: nd–625 μg/kg; BADGE.HCl.H2O: nd–87 μg/kg Míguez et al. (2012) Amino-based cross-linking resins Melamine Three food types (acidic, fatty, and fish/meat) Solvent extraction (ACN and water) LC–MS/MS cMelamine: <23–152 μg/kg Bradley et al. (2011) Epoxy resin BPA Beverages, fruits, vegetables, and fat-containing foodstuffs Sol–gel immunoaffinity chromatography HPLC–FLD aBPA: nd–43 ng/g in tuna Braunrath et al. (2005) Epoxy resin BPA Pineapple, tuna, and mushrooms MAE and MISPE LC–ESI/MS aBPA:7.3 ng/g in pineapple to 42.3 ng/g in tuna Maragou et al. (2020) (Continues) FOOD CONTACT COATINGS IN METAL CANS... 3593 TABLE 4 (Continued) Coating Migrant Food Extraction procedure Analytical technique Migration results (Restrictions) Reference Epoxy-phenolic and organosol coatings BADGE and BFDGE Seafood products (sardines, tuna, mackerel, mussels, cod) and covering sauces Solvent extraction: n-heptane and ACN 90% HPLC–FLD The highest values were 0.34 mg/kg for bBADGE and 0.74 mg/kg for BFDGE in mackerel with red pepper sauce Cabado et al. (2008) Epoxy lacquers BPA, BPF, BPZ, and BP Beverages and filling liquids of canned vegetables Derivatization and SBSE TD–GC–MS Soft drinks: aBPA: nd–0.68 μg/L; BPF: nd–0.26 μg/L; BPZ: nd–0.09 μg/L; BP: nd Filling liquids: BPA: nd–13.98 μg/L; BPF: nd–7.07 μg/L; BPZ: nd–0.92 μg/L; BP: nd–0.58 μg/L Cacho et al. (2012) Epoxy resin BADGE, BADGE.H2O, BADGE.2H2O, BADGE.HCl, BADGE.2HCl, BADGE.HCl.H2O, BFDGE, BFDGE.2H2O, and BFDGE.2HCl Soft drinks and aqueous-based canned foods (fruits and vegetables) Soft drinks: SPE; canned food: ethyl acetate LC–MS/MS bBADGE, BFDGE, BFDGE.2H2O, BFDGE.2HCl: nd; BADGE.H2O: nd–53 μg/kg; BADGE.2H2O: 2.1–675 μg/kg; BADGE.HCl: nd–11 μg/kg; BADGE.2HCl: nd–2.8 μg/kg; BADGE.HCl.H2O: nd–274 μg/kg Gallart-Ayala et al. (2011a) Organosol and epoxy can coatings BPA Tuna fish Solvent extraction (MeOH, hexane and ACN) RP-HPLC–FLD aBPA: <LOQ to 102.7 μg/kg Munguía-López et al. (2005) (Continues) 3594 FOOD CONTACT COATINGS IN METAL CANS... TABLE 4 (Continued) Coating Migrant Food Extraction procedure Analytical technique Migration results (Restrictions) Reference PVC organosol BADGE.2HCl, BFDGE.2HCl, BADGE.2H2O, BFDGE.2H2O, BADGE.HCl.H2O, and BFDGE.HCl.H2O Ready-to-drink canned coffee and canned vegetables (corn, tomatoes, and others) Solvent extraction (15% DCM/pentane) HPLC–FLD and GC–MS for confirmation bBADGE.2HCl: <0.02–0.14 mg/kg; BFDGE.2HCl: <0.04–0.42 mg/kg; BADGE.2H2O: nd–4.03 mg/kg; BFDGE.2H2O: nd–0.7 mg/kg; BADGE.HCl.H2O: nd–0.48 mg/kg; BFDGE.HCl.H2O: nd–1.08 mg/kg Uematsu et al. (2001) Epoxy phenolic coating BPA Canned foods (green beans, tomatoes, peas, pineapple, ravioli, chili, fish, soups, etc.) separating the solid food from the liquid supernatant Solvent extraction (ACN) HPLC–MS/MS aBPA: <2–790 ng/g, showing that BPA concentrations are higher in the solid food Noonan et al. (2011) Epoxy resins, organosol, and polyester coatings Cyclo-di-BADGE 2010: canned fish 2012: canned fish in oil and meat, chocolate cream, soup Solvent extraction (EtOH and hexane) HPLC–FLD CYDBADGE: (2010) <25–1980 μg/kg (2012) <25–2600 μg/kg Biedermann et al. (2013) Epoxy-based lacquers BPA Vegetables, fruit, fish, soup and sauces, meat, spaghetti and baked beans, infant foods, beverages, and miscellaneous Solvent extraction (ACN or ACN- trimethylpentane for samples with >1% fat) and derivatization (acetic anhydride) GC–MS aBPA: <10–192 μg/kg Thomson and Grounds (2005) (Continues) FOOD CONTACT COATINGS IN METAL CANS... 3595 TABLE 4 (Continued) Coating Migrant Food Extraction procedure Analytical technique Migration results (Restrictions) Reference Epoxy-based coating BPA Canned tomatoes (peeled, cherry, and concentrated paste) SPE HPLC–DAD– FLD aBPA: Mean concentrations range: 0.31–3.80 μg/kg in peeled tomatoes, 0.90–2.21 μg/kg in cherry tomatoes, 0.39–1.82 μg/kg in concentrated tomato paste Errico et al. (2014) Epoxy can coatings BPA Jalapeño peppers Solvent extraction (MeOH) HPLC–FLD and confirmation by GC–MS aBPA: <LOQ–5.59 μg/kg Munguía-López et al. (2002) Epoxy resin BFDGE Fish in oil (sardine, tuna, anchovy, mackerel, mussel, oyster, etc.) LLE (hexane and ACN) HPLC–FLD and confirmation by GC–MS bBFDGE: nd–4.2 mg/kg Theobald et al. (2000) Epoxy-phenolic coating BPA, BPF, BADGE, BADGE.2H2O, BADGE.2HCl, BFDGE, BFDGE.2H2O, and BFDGE.2HCl Vegetables including fava beans, red beans, chickpeas, and okra Solvent extraction (MeOH) and SPE UHPLC–FLD and UHPLC– TOF–MS for confirmation BPF, BADGE, BADGE.2HCl, BFDGE; BADGE.2HCl, BFDGE.2H2O, and BFDGE.2HCl: nd aBPA: 12.8–54.6 μg/kg and BADGE⋅2H2O: 101–146 μg/kg were confirmed by MS El Moussawi et al. (2019) Gold epoxy-phenolic lacquer or BADGE enamel BPA, BPB, BADGE, BFDGE Tuna fish (in oil or aqueous medium) Tuna: solvent extraction (n-hexane/ACN) Oil: solvent extraction (n-hexane) and SPE Aqueous medium: directly LC–FLD and confirmation by LC–MS/MS Tuna aBPA: nd–187 ng/g; BPB: nd–145.9 ng/g; bBADGE: nd–91.1 ng/g; BFDGE: nd–38.5 ng/g Medium BPA: nd–16.2 ng/ml; BADGE: nd–66.9 ng/ml; BPB, BFDGE: nd Fattore et al. (2015) (Continues) 3596 FOOD CONTACT COATINGS IN METAL CANS... TABLE 4 (Continued) Coating Migrant Food Extraction procedure Analytical technique Migration results (Restrictions) Reference Epoxy-based coating BPA Canned foodstuffs (peas, rice pudding, toffee pudding, beans, spaghetti Bolognese, etc.) Solvent extraction (n-heptane and ACN) and derivatization GC–MS aBPA: 8.6–129.5 μg/kg Goodson et al. (2004) Epoxy lacquers BPA, BPS, and BP Peas, peas with carrots, sweet corn, artichoke, mushroom, bean shoot, and mixed vegetables SPME and derivatization (acetic anhydride or BSTFA) GC–MS Food aBPA: nd–77.7 ng/g; BPS: nd–36.1 ng/g; BP: nd–40.1 ng/g Supernatant BPA: 11.7–321 ng/ml; BPS: nd–175 ng/ml; BP: 17.2–365 ng/ml Viñas et al. (2010) Epoxy-phenolic and organosol coatings BADGE Tuna, sardines, anchovies, mackerel, corned beef, ham/chopped ham and pork, pork luncheon meat, spreads, milk, infant formulae Solvent extraction (DCM, hexane and ACN) and SPE HPLC–FLD and confirmation by GC–MS bBADGE <0.02–62 mg/kg Summerfield et al. (1998) Epoxy resin BPA and BADGE Fish, meats, fruits and vegetables, soups and sauces, coconut milk Solvent extraction (ACN, water) and SPE LC/ECD or LC/MS, LC/MS/MS for confirmation aBPA: nd–842 ng/g; BADGE: nd Sajiki et al. (2007) Epoxy resin BPA, BPB, BPF, BADGE, and BFDGE Beers SPE (MIPs) UPLC–FLD aBPA: <LOQ–0.8 ng/ml; BPF: <LOQ–2.5 ng/ml; BADGE: <LOQ–1.2 ng/ml; BPB and BFDGE: <LOQ Cirillo et al. (2019) (Continues) FOOD CONTACT COATINGS IN METAL CANS... 3597 TABLE 4 (Continued) Coating Migrant Food Extraction procedure Analytical technique Migration results (Restrictions) Reference Organosol (PVC type), epoxy lacquers BADGE, BADGE.H2O, BADGE.2H2O, BADGE.HCl, BADGE.2HCl Fish in oil, in tomato/dill sauce, or in vinegar, vegetables, pasties, and meat sauce Solvent extraction (ACN:hexane and ethyl acetate) HPLC–FLD bBADGE was found in concentrations up to 5.1 mg/kg, BADGE.2H2Oupto 2.6 mg/kg, BADGE.H2O was not detected, BADGE.HCl up to 2.4 mg/kg and BADGE.2HCl up to 8.3 mg/kg Hammarling et al. (2000) Epoxy resin BPA Soft drinks Hemimicellar magnetic SPE LC–MS/MS aBPA: 0.066–1.08 ng/ml Yazdinezhad et al. (2013) Abbreviations: ACN, acetonitrile; BADGE, bisphenol A diglycidyl ether; BADGE⋅H2O, bisphenol A (2,3-dihydroxypropyl) glycidyl ether; BADGE⋅2H2O, bisphenol A bis(2,3-dihydroxypropyl) ether; BADGE⋅HCl, bisphenol A (3-chloro-2-hydroxypropyl) glycidyl ether; BADGE⋅2HCl, bisphenol A bis(3-chloro-2-hydroxypropyl) ether; BADGE⋅H2OHCl, bisphenol A (3-chloro-2-hydroxypropyl) (2,3-dihydroxypropyl) ether; BFDGE, bisphenol F diglycidyl ether; BFDGE⋅2HCl:bisphenol F bis [3 chloro-2 hydroxypropyl] ether; BFDGE⋅2H2O, bisphenol F bis [2, 3 dihydroxypropyl] ether; BFDGE⋅H2O⋅HCl, p,p bisphenol F (3-chloro-2-hydroxypropyl) (2,3-dihydroxypropyl) ether; BP, bisphenol; BPA, bisphenol A; BPB, bisphenol B; BPE, bisphenol E; BPF, bisphenol F; BPS, bisphenol S; BPZ, bisphenol Z; BSTFA, N,O-bis(trimethylsilyl)trifluoroacetamide; CHDM, 1,4- cyclohexanedimethanol; CYDBADGE, cyclo-di-BADGE; DLLME, dispersive liquid–liquid microextraction; ECD, electrochemical detection; ESI, electrospray ionization; GC–MS, gas chromatography–mass spectrometry; GC–TOF–MS, gas chromatography–time of flight–mass spectrometry; HPLC–FLD, high-performance liquid chromatography–fluorescence detector; IPA, isophthalic acid; MISPE, molecularly imprinted polymer-solid- phase extraction; LC–DAD, liquid chromatography–diode array detector; LC–MS/MS, liquid chromatography–tandem mass spectrometry; LC–TOF–MS, liquid chromatography–time of flight–mass spectrometry; LLE, liquid–liquid extraction; LOD, limit of detection; LOQ, limit of quantification; MAE, microwave assisted extraction; MIP, molecularly imprinted polymer; MPD, 2-methyl-1,3-propanediol; NA, nadic acid; NAH, nadic anhydride; nd, not detect; PA, phthalic acid; PVC, polyvinyl chloride; QuEChERS, Quick, Easy, Cheap, Effective, Rugged, & Safe; SBSE, stir bar sorptive extraction; SPE, solid-phase extraction; SPME, solid-phase microextraction; SUPRAS, supramolecular solvent; TA, terephthalic acid; TD–GC–MS, thermal desorption–gas chromatography–mass spectrometry; UFLC–MS/MS, ultrafast liquid chromatography–tandem mass spectrometry; UHPLC-HRMS, ultrahigh-performance liquid chromatography–high-resolution mass spectrometry. aRegulation (EU) No. 10/2011 Specific Migration Limit (SML) in plastic materials; SML BPA 0.6 mg/kg; SML BPS 0.05 mg/kg; SML IPA 5 mg/kg; SML TA 7.5 mg/kg; SML melamine 30 mg/kg. Regulation (EU) 2018/213 SML BPA 0.05 mg/kg. bRegulation (EC) No. 1895/2005 Sum of the migrations of BADGE+BADGE⋅H2O+BADGE⋅2H2O 9 mg/kg; BADGE⋅HCl+BADGE⋅2HCl+BADGE⋅H2O⋅HCl 1 mg/kg. BFDGE “The use and/or presence in the manufacture of materials and articles are prohibited.” Commission Directive 2002/16/EC: Sum of the migration levels of BADGE+BADGE⋅H2O+BADGE⋅HCl+BADGE⋅2HCl+BADGE⋅H2O⋅HCl 1 mg/kg. Sum of the migration levels of BFDGE+BFDGE⋅H2O+BFDGE⋅HCl+BFDGE⋅2HCl+BFDGE⋅H2O⋅HCl 1 mg/kg. No longer in force, date of end of validity: December 31, 2005. cCommission Regulation (EU) No. 1282/2011 SML melamine 2.5 mg/kg. dEFSA CEF Panel (EFSA Panel on Food Contact Materials, Enzymes, Flavorings, and Processing Aids), 2014. Scientific Opinion on the safety assessment of the substance, 5-norbornene-2,3-dicarboxylic anhydride, CAS No 826-62-0, for use in food contact materials. Migration of 5-norbornene-2,3-dicarboxylic anhydride and its hydrolysis products should in total not exceed 50 μg/kg food. 3598 FOOD CONTACT COATINGS IN METAL CANS... 4 MIGRATION OF CHEMICALS FROM CAN COATINGS Components of the can coatings can migrate into the food and may adversely affect its quality and safety. In order to assess the safety of the coatings and to estimate the exposure to substances migrating into the food, migration tests into foodstuffs or food simulants should be performed. The migration is a predictable phenomenon that usually obeys Fick’s laws of diffusion. The key parameters that define the migration kinetics are the partition coefficientandthe diffusioncoefficient.The partitioncoefficient (KP/F) indicates the relative solubility of the migrant between the polymer and the food when the equilibrium is reached, and thus KP/F >1 indicates that the migrant is found in higher concentrations in the polymer than in the food. And the diffusion coefficient describes the kinetics of the migration process (Tehrany & Desobry, 2004; Castle, 2007;Maiaetal.,2016; Nerín, 2016; Canellas et al., 2010; Rodríguez-Bernaldo de Quirós et al., 2019). Migration of chemicals from food packaging materials is affected by several factors. The migrant (size/shape), the thickness of the film, the degree of cross-linking, the time of exposure, and, most crucial, the temperature are someofthefactorsreportedbyWagneretal.(2018) that influence the migration from an epoxy-phenolic can coating. The results of the study showed that the apparent diffusion coefficients decreased as the cross-link density increased, whereas they increased as the film thickness increased. Other important factors that also affect the migration are the nature of food or food simulant as well as the type of contact (Castle, 2007). Some of these parameters have been evaluated in different studies. For example, Cabado et al. (2008) studied the migration of BADGE and BFDGE in canned seafood with various coveringsauces andmanufacturedunder differentconditions, that is, different sterilization conditions (115◦C/45 min; 121◦C/30 min) and different time and temperature storage conditions. It was found, on one hand, that the migration of BADGE and BFDGE depended on the specie of the seafood and the composition of the sauce; thus, migration occurs to a greater extent in fatty foods. The highest values of BADGE and BFDGE were found in mackerel-red pepper sauce, which was the highest fat content. However, it was not affected by the sterilization conditions. On the other hand, the BFDGE migration also depended on the storage time; the migration levels after 12 and 18 months of storage were significantly different than those found at 6 months. Munguía-Lópezetal.(2005)reportedamarked effect ofthe heating process on the migration of BPA into a fatty food simulant. However, in a previous study, the same authors found a minimal effect of heat treatment on BPA migration into an acidic food simulant. In another work, Errico et al. (2014)reportedanincreaseinthemigrationofBPA in canned tomatoes with the storage temperature and also observed higher migration levels in damaged cans compared to intact ones. In the opposite way, Goodson et al. (2004) found no appreciable effect on BPA migration in damaged cans. The authors also investigated the effect of storage and concluded that about 80%–100% of the BPA present in the coating migrated during the can processing stage and this level was not increased during the storage (9 months). In a series of studies reported in the literature, longterm migration tests were evaluated. Paseiro-Cerrato, Noonan et al. (2016) investigated the migration of polyester monomersandoligomersfrompolyestercoatingsintofood simulants at 40◦C for 515 days. The authors reported an increase in the concentration of the monitored migrants during the assay, particularly in ethanol simulants, and also concluded that 3% acetic acid (w/v) is not an appropriate simulant because of rusting. In a later work, the same authors evaluated the migration from two different coatings, an epoxy and an acrylic–phenolic resin, and several migrants such as BPA, BADGE, BADGE derivatives, and so on were monitored. For water, no variation in concentration during the test was observed; in the case of 50% ethanol (v/v), an increase in concentration was observed until equilibrium was reached (90–305 days). This increase occurred after 10 days, which is the time conventionally used in migration tests (Paseiro-Cerrato et al., 2017). Subsequently, the authors carried out the tests under accelerated conditions, and concluded that the migration tests performed at 60◦C in short periods of time (4 h to 30 days) may simulate migration tests performed at 40◦C over long periods of time (1.5 years) (Paseiro-Cerrato et al., 2019b). In order to reduce the migration from polymeric coatings, newer materials are being developed. Polyesterbased coatings are growing continuously. In this context, polyester-polyurethane coatings are a promising alternative. These coatings present lower migration properties due to the formation of urethane linkages by reacting with polyisocyanate (Driffield et al., 2018; Bradley et al., 2009). Migration levels in canned food and beverages are discussed next and summarized in Table 4.ForBPA, the concentrations detected ranged from not detected to 842 ng/g. The highest concentrations have been reported in brown sauce with 842 ng/g (Sajiki et al., 2007); refried beans with 790 ng/g (Noonan et al., 2011); mushroom slices with 265 μg/kg (Cunha & Fernandes, 2013); and red pepper with 241 μg/kg (Alabi et al., 2014). The samples of brown sauce and refried beans exceeded the previous established SML of 0.6 mg/kg (Commission Regulation [EU] No. 10/2011 [European Union, 2011]), and the FOOD CONTACT COATINGS IN METAL CANS... 3605 2004), whereby they must fulfill the general requirements (Article 3) for all FCMs. Varnishes and coatings are included in Annex I of the aforementioned regulation, which specified the list of groups of materials and articles for which specific measures may be established. On the other hand, there is a resolution of the Council of Europe (CoE, 2004) on coatings intended to come into contact with foodstuffs that includes general guidelines and a list of substances used in the manufacture of coatings intended to come into contact with foodstuffs. Notwithstanding the above, the Regulation (EC) No. 1895/2005 (European Union, 2005) restricts the use of certain epoxy derivatives in materials and articles intended to come into contact with food. Specifically, it establishes a maximum SML of 9 mg/kg for the sum of BADGE and their hydrolyzed derivatives, that is, BADGE⋅H2Oand BADGE⋅2H2O, and also an SML of 1 mg/kg for the sum of their hydrochloric derivatives, that is, BADGE⋅HCl, BADGE⋅2HCl, and BADGE⋅H2O⋅HCl. Moreover, the use or presence of BFDGE and NOGE (novolac glycidyl ether) in the manufacture of materials is prohibited. And, with respect to the use of BPA in varnishes and coatings intended to come into contact with food, Regulation (EU) No. 2018/213 (European Union, 2018), an amendment of Regulation (EU) No. 10/2011 (European Union, 2011) regarding the use of that substance in plastic FCM, set the SML of BPA at 0.05 mg/kg. Hence, varnishes and coatings should be in compliance with these substancespecific measures, and with the Framework Regulation (EC) No. 1935/2004 (European Union, 2004), and furthermore, they must also comply with national legislations when available. 7 CONCLUSIONS The inner surface of food metal cans is usually coated with a polymeric coating. Currently, coatings based on different chemistries such as epoxy, polyester, acrylic, and so on are being applied. The polymeric coatings are very complex formulations that contain not only starting substances (e.g., monomers, prepolymers, additives, etc.) but also unknown compounds (e.g., degradation and reaction products, oligomers, etc.). These substances can migrate into the food and may constitute a risk for the consumers’ health; therefore, it is necessary to analyze them properly. Sample preparation previous to instrumental analyses usually comprises solvent extraction followed by a cleanup step. SPE and QuEChERS are the most commonly used sample pretreatment methods. For complex matrix, molecularly imprinted polymers cartridges instead of the conventional SPE cartridges have been used due to their high selectivity. For separation and detection, liquid chromatography and gas chromatography coupled to different detectors and particularly to mass spectrometry are the techniques of choice to accomplish this task. For the unknown compounds, HRMS has demonstrated to be a powerful tool that provides accurate mass measurements. Recent applications have shown DART–HRMS as a complementary and efficient analytical tool that allows to complete the analysis in few minutes. Canned food can be an important source of exposure to different chemicals, for example, bisphenols, BADGEs, and so on; therefore, the study of the migration and dietary exposure is required for the risk assessment and the successive establishment of legislation. Although a considerable number of studies on the migration from metal cans have been reported in the literature, most of them are focused on the migration of monomers and other starting substances; however, information about oligomers and other NIAS is limited. Hence, more studies are needed to identify and evaluate the migration of these substances to ensure the safety of the canned food. As an essential step in the risk assessment, the exposure to chemicals migrating from coatings is assessed, but up to now scarce data are available and much effort is still needed to investigate human exposure to these migrants. Future works should consider the combined exposure to multiple chemicals. From the regulatory perspective, at present there is not a harmonized legislation in the European Union for varnishes and coatings for food contact; they must comply with the Framework Regulation No. 1935/2004 (European Union, 2004) applicable to all FCMs. It would be of value to have an harmonized European legislation for varnishes and coatings in order to support the safety of this group of FCMs. ACKNOWLEDGMENTS This study was funded by the Ministerio de Ciencia, Innovación y Universidades, Fondo Europeo de Desarrollo Regional (FEDER), and Agencia Estatal de Investigación (Ref. no. PGC2018-094518-B-I00 “MIGRACOATING” [MICIU/FEDER, UE]). AUTHOR CONTRIBUTIONS Antía Lestido-Cardama: Conceptualization; Investigation; Methodology; Writing—original draft. Raquel Sendón: Conceptualization; Methodology; Project administration; Supervision; Writing—review & editing. Juana Bustos: Conceptualization; Methodology; Supervision; Writing—review & editing. María Teresa Nieto: Methodology; Writing—review & editing. Perfecto Paseiro-Losada: Conceptualization; Methodology; Supervision; Writing—review & editing. Ana Rodríguez- Bernaldo de Quirós: Conceptualization; Funding acquisition; Investigation; Methodology; Supervision; Writing—original draft. 3606 FOOD CONTACT COATINGS IN METAL CANS... CONFLICTS OF INTEREST The authors declare no conflicts of interest. ORCID AnaRodríguez-Bernaldo de Quirós https://orcid.org/ 0000-0002-7551-2727 REFERENCES Alabi, A., Caballero-Casero, N., & Rubio, S. (2014). Quick and simple sample treatment for multiresidue analysis of bisphenols, bisphenol diglycidyl ethers and their derivatives in canned food prior to liquid chromatography and fluorescence detection. Journal of Chromatography A,1336,23–33.https://doi.org/10.1016/j.chroma. 2014.02.008 Aznar, M., Domeño, C., Nerín, C., & Bosetti, O. (2015). Set-off of non volatile compounds from printing inks in food packaging materials and the role of lacquers to avoid migration. Dyes and Pigments, 114,85–92.https://doi.org/10.1016/j.dyepig.2014.10.019 Aznar, M., Ubeda, S., Dreolin, N., & Nerín, C. (2019). Determinationof non-volatile componentsof abiodegradablefood packaging material based on polyester and polylactic acid (PLA) and its migration to food simulants. Journal of Chromatography A,1583, 1–8. https://doi.org/10.1016/j.chroma.2018.10.055 Bemrah, N., Jean, J., Rivière, G., Sanaa, M., Leconte, S., Bachelot, M., Deceuninck, Y., Le Bizec, B., Dauchy, X., Roudot, A. C., Camel, V., Grob, K., Feidt, C., Picard-Hagen, N., Badot, P. M., Foures, F., & Leblanc, J. C. (2014). Assessment of dietary exposure to bisphenol A in the French population with a special focus on risk characterizationfor pregnantFrenchwomen.Food and Chemical Toxicology, 72, 90–97. https://doi.org/10.1016/j.fct.2014.07.005 Biedermann, M., & Grob, K. (1998). Food contamination from epoxy resins and organosols used as can coatings: Analysis by gradient NPLC. Food Additives & Contaminants,15(5), 609–618. https://doi. org/10.1080/02652039809374688 Biedermann,M., &Grob,K. (2006a).Phenolic resinsfor cancoatings: I. Phenol-based resole analysed by GC-MS, GC x GC, NPLC-GC and SEC. LWT Food Science and Technology,39,633–646.https:// doi.org/10.1016/j.lwt.2005.04.008 Biedermann,M., &Grob,K. (2006b).Phenolicresinsfor cancoatings: II. Resoles based on cresol/phenol mixtures or tert. butyl phenol. LWT Food Science and Technology,39,647–659.https://doi.org/10. 1016/j.lwt.2005.04.007 Biedermann, S., Zurfluh, M., Grob, K., Vedani, A., & Brüschweiler, B. J. (2013). Migration of cyclo-diBA from coatings into canned food: Method of analysis, concentration determined in a survey and in silico hazard profiling. Food and Chemical Toxicology,58,107–115. https://doi.org/10.1016/j.fct.2013.04.004 Bradley, E. L., Driffield, M., Harmer, N., Oldring, P. K. T., & Castle, L. (2008). Identification of potential migrants in epoxy phenolic can coatings. International Journal of Polymer Analysis and Characterization,13, 200–223. https://doi.org/10.1080/ 10236660802070512 Bolognesi, C., Castoldi, A. F., Crebelli, R., Barthélémy, E., Maurici, D., Wölfle, D., Volk, K., & Castle, L. (2017). Genotoxicity testing approaches for the safety assessment of substances used in food contact materials prior to their authorization in the European Union. Environmental and Molecular Mutagenesis,58,361–374. Bradley, E. M., Driffield, M., Guthrie, J., Harmer, N., Oldring, P. K. T., & Castle, L. (2009). Analytical approaches to identify potential migrantsinpolyester–polyurethanecancoatings.Food Additives & Contaminants: Part A,26(12), 1602–1610. https://doi.org/10.1080/ 19440040903252256 Bradley, E. L., Castle, L., Day, J. S., & Leak, J. (2011). Migration of melamine from can coatings cross-linked with melamine-based resins, into food simulants and foods. Food Additives & Contaminants,28(2), 243–250. https://doi.org/10.1080/19440049.2010. 536167 Braunrath, R., Podlipna, D., Padlesak, S., & Cichna-Markl, M. (2005). Determination of bisphenol A in canned foods by immunoaffinity chromatography, HPLC, and fluorescence detection. Journal of Agricultural and Food Chemistry,53(23), 8911–8917. https://doi. org/10.1021/jf051525j Cabado, A. G., Aldea, S., Porro, C., Ojea, G., Lago, J., Sobrado, C., & Vieites, J. M. (2008). Migration of BADGE (bisphenol A diglycidyl-ether) and BFDGE (bisphenol F diglycidyl-ether) in canned seafood. Food and Chemical Toxicology,46(5), 1674–1680. https://doi.org/10.1016/j.fct.2008.01.006 Cacho, J. I., Campillo, N., Viñas, P., & Hernández-Córdoba, M. (2012).Stirbarsorptiveextractioncoupledtogaschromatography– mass spectrometry for the determination of bisphenols in canned beverages and filling liquids of canned vegetables. Journal of Chromatography A,1247,146–153.https://doi.org/10.1016/j.chroma. 2012.05.064 Canellas, E., Aznar, M., Neríın, C., & Mercea, P. (2010). Partition and diffusion of volatile compounds from acrylic adhesives used for food packaging multilayers manufacturing. Journal of Materials Chemistry,20, 5100–5109. Canellas, E., Vera, P., Domeño, C., Alfaro, P., & Nerín, C. (2012). Atmospheric pressure gas chromatography coupled to quadrupole-time of flight mass spectrometry as a powerful tool for identification of non intentionally added substances in acrylic adhesivesused infood packagingmaterials.Journal of Chromatography A,1235,141–148.https://doi.org/10.1016/j.chroma.2012.02. 039 Canellas, E., Vera, P., & Nerín, C. (2017). Migration assessment and the ‘threshold of toxicological concern’ applied to the safe design of an acrylic adhesive for food-contact laminates. Food Additives & Contaminants: Part A,34(10), 1721–1729. https://doi.org/10.1080/ 19440049.2017.1308017 Canellas, E., Vera, P., & Nerín, C. (2019). Ion mobility quadrupole time-of-flight mass spectrometry for the identification of nonintentionally added substances in UV varnishes applied on food contact materials. A safety by design study. Talanta,205,120103. https://doi.org/10.1016/j.talanta.2019.06.103 Canellas, E., Vera, P., Nerín, C., Dreolin, N., & Goshawk, J. (2022). The detection and elucidation of oligomers migrating from biodegradable multilayer teacups using liquid chromatography coupled to ion mobility time-of-flight mass spectrometry and gas chromatography–mass spectrometry. Food Chemistry,374, 131777. https://doi.org/10.1016/j.foodchem.2021.131777 Cao, X. L., Dufresne, G., Clement, G., Blisle, S., Robichaud, A., & Beraldin, F. (2009). Levels of bisphenol A diglycidyl ether (BADGE) and bisphenol F diglycidyl ether (BFDGE) in canned liquid infant formula products in Canada and dietary intake estimates. Journal of AOAC International,92(6), 1780–1789. FOOD CONTACT COATINGS IN METAL CANS... 3607 Castle, L. (2007). Chemical migration into food: An overview. In K. A. Barnes, C. R. Sinclair, & D. H. Watson (Eds.), Chemical migration and food contact materials (pp 1–13). Woodhead Publishing Limited. Chen, M. Y., Ike, M., & Fujita, M. (2002). Acute toxicity, mutagenicity, and estrogenicity of bisphenol-A and other bisphenols. Environmental Toxicology,17,80–86.https://doi.org/10.1002/tox. 10035 Cirillo, T., Esposito, F., Fasano, E., Scognamiglio, G., Di Marco Pisciottano, I., Mita, G. D., & Gallo, P. (2019). BPA, BPB, BPF, BADGEand BFDGEincannedbeers fromtheItalianmarket.Food Additives & Contaminants: Part B,12(4), 268–274. https://doi.org/ 10.1080/19393210.2019.1650835 Council of Europe (CoE). (2004). Policy statement concerning coatings intended to come into contact with foodstuffs.Author. Cooper, I., & Tice, P. (2001). Food contact coatings- European legislation and future predictions. Surface Coatings International Part B: Coatings Transactions,84(B2), 105–112. Cottier, S., Riquet, A. M., Felgenbaum, A., Pollet, B., Lapierre, C., & Mortreuil, P. (1997). Identification of potential migrants from a vinylic organosol varnish by gas chromatography-mass spectrometry and liquid chromatography-mass spectrometry. Journal of Chromatography A,771, 366–373. Cottier, S., Feigenbaum, A., Mortreuil, P., Reynier, A., Dole, P., & Riquet, A. M. (1998). Interaction of a vinylic organosol used as can coating with solvents and food simulants. Journal of Agricultural and Food Chemistry,46,5254–5261. Cunha, S. C., & Fernandes, J. O. (2013). Assessment of bisphenol A and bisphenol B in canned vegetables and fruits by gas chromatography–mass spectrometry after QuEChERS and dispersive liquid–liquid microextraction. Food Control,33(2), 549–555. https://doi.org/10.1016/j.foodcont.2013.03.028 Driffield, M., Bradley, E. L., & Castle, L. (2007). A method of test for residual isophorone diisocyanate trimer in new polyesterpolyurethane coatings on light metal packaging using liquid chromatography with tandem mass spectrometric detection. Journal of Chromatography A,1141, 61–66. https://doi.org/10.1016/j. chroma.2006.12.005 Driffield, M., Garcia-Lopez, M., Christy, J., Lloyd, A. S., Tarbin, J. A., Hough,P.,Bradley,E.L.,&Oldring,P.K.T.(2018).Thedetermination of monomers and oligomers from polyester-based can coatings into foodstuffs over extended storage periods. Food Additives & Contaminants: Part A,35(6), 1200–1213. https://doi.org/10. 1080/19440049.2018.1440643 Duffy, E., Hearty, A. P., Mccarthy, S., & Gibney, M. J. (2007). Estimation of exposure to food packaging materials. 3: Development of consumption factors and food-type distribution factors from datacollected onIrish children.Food Additives and Contaminants, 24(1), 63–74. Eckardt, M., Hetzel, L., Brenz, F., & Simat, T. J. (2020). Release and migration of cyclic polyester oligomers from bisphenol A non-intent polyester–phenol-coatings into food simulants and infant food – A comprehensive study. Food Additives & Contaminants: Part A,37(4), 681–703. https://doi.org/10.1080/19440049. 2019.1616831 EFSA. (2004). Opinion of the scientific panel AFC related to bisphenol A diglycidyl ether (BADGE). The EFSA Journal,86,1–40. EFSA. (2013). International frameworks dealing with human risk assessment of combined exposure to multiple chemicals. EFSA Journal,11(7), 1–69. https://doi.org/10.2903/j.efsa.2013.3313 EFSA. (2015). Scientific opinion on the risks to public health related to the presence of bisphenol A (BPA) in foodstuffs. EFSA Journal, 13(1), 3978. https://doi.org/10.2903/j.efsa.2015.3978 EFSA (2019). Evaluation of materials intended for varnishes and coatings on food contact materials. Report of EFSA Task force on varnishes and coatings for food contact materials. https://zenodo. org/record/3583381#.Ybsk8WjMK70 El-Kosasy, A. M., Abdel-Aziz, O., Ayad, M. F., & Mabrouk, O. M. (2018). HPLC Method for simultaneous determination of Bisphenol-A-Diglycidyl ether and some of its reaction products in canned foods using photodiode array detector. Journal of Chromatographic Science,56(10), 920–932. https://doi.org/10. 1093/chromsci/bmy069 El Moussawi, S. N., Ouaini, R., Matta, J., Chébib, H., Cladière, M., & Camel, V. (2019). Simultaneous migration of bisphenol compounds and trace metals in canned vegetable food. Food Chemistry,288,228–238.https://doi.org/10.1016/j.foodchem.2019. 02.116 Errico, S., Bianco, M., Mita, L., Migliaccio, M., Rossi, S., Nicolucci, C., Menale, C., Portaccio, M., Gallo, P., Mita, D. G., & Diano, N. (2014). Migration of bisphenol A into canned tomatoes produced in Italy: Dependence on temperature and storage conditions. Food Chemistry,160,157–164.https://doi.org/10.1016/j.foodchem.2014. 03.085 European Union. (2004). Regulation (EC) No. 1935/2004. Official Journal of the European Union,L338,4–17. European Union. (2005). Regulation (EC) No. 1895/2005. Official Journal of the European Union,L302,28–32. European Union. (2011). Regulation (EU) No. 10/2011. Official Journal of the European Union,L12,1–89. European Union. (2018). Regulation (EU) No. 2018/213. Official Journal of the European Union,L41,6–12. Fattore, M., Russo, G., Barbato, F., Grumetto, L., & Albrizio, S. (2015). Monitoring of bisphenols in canned tuna from Italian markets. Food and Chemical Toxicology,83,68–75.https://doi.org/10.1016/ j.fct.2015.05.010 FDA. (2007). Guidance for industry: Preparation of premarket submissions for food contact substances (chemistry recommendations).https://www.fda.gov/regulatory-information/search-fda- guidance-documents/guidance-industry-preparation-premarket- submissions-food-contact-substances-chemistry Forrest, M. J. (2005). Coatings and inks for food contact materials. Rapra Review Reports,16(6), 1–142. Franz, R., & Brandsch, R. (2013). Migration of acrylic monomers from methacrylate polymers – Establishing parameters for migration modelling. Packaging Technology and Science,26,435–451. https://doi.org/10.1002/pts.1995 Gallart-Ayala, H., Moyano, E., & Galceran, M. T. (2010). Multiplestage mass spectrometry analysis of bisphenol A diglycidyl ether, bisphenol F diglycidyl ether and their derivatives. Rapid Communications in Mass Spectrometry,24,3469–3477. Gallart-Ayala, H., Moyano, E., & Galceran, M. T. (2011a). Fast liquid chromatography–tandem mass spectrometry for the analysis of bisphenol A-diglycidyl ether, bisphenol F-diglycidyl ether and 3608 FOOD CONTACT COATINGS IN METAL CANS... their derivatives in canned food and beverages. Journal of Chromatography A,1218,1603–1610.https://doi.org/10.1016/j.chroma. 2011.01.026 Gallart-Ayala, H., Moyano, E., & Galceran, M. T. (2011b). Analysis of bisphenols in soft drinks by on-line solid phase extraction fast liquid chromatography–tandem mass spectrometry. Analytica Chimica Acta,683(2), 227–233. https://doi.org/10.1016/j.aca.2010. 10.034 Gallo, P., Pisciottano, I. D. M., Esposito, F., Fasano, E., Scognamiglio, G., Mita, G. D., & Cirillo, T. (2017). Determination of BPA, BPB, BPF, BADGE and BFDGE in canned energy drinks by molecularly imprinted polymer cleaning up and UPLC with fluorescence detection. Food Chemistry,220, 406–412. https://doi.org/10.1016/j. foodchem.2016.10.005 Geens, T., Apelbaum, T. Z., Goeyens, L., Neels, H., & Covaci, A. (2010). Intake of bisphenol A from canned beverages and foods on the Belgian market. Food Additives and Contaminants,27(11), 1627–1637. https://doi.org/10.1080/19440049.2010.508183 Geueke, B. (2016). FPF Dossier: Can coatings. Food Packaging Forum. https://doi.org/10.5281/zenodo.200633 Goodson, A., Robin, H., Summerfield, W., & Cooper, I. (2004). Migration of bisphenol A from can coatings—Effects of damage, storage conditions and heating. Food Additives and Contaminants,21(10), 1015–1026. https://doi.org/10.1080/02652030400011387 Grob, K., Spinner, C., Brunner, M., & Etter, R. (1999). The migration from the internal coatings of food cans; summary of the findings and call for more effective regulation of polymers in contact with foods:A review.Food Additives and Contaminants,16(12),579–590. https://doi.org/10.1080/026520399283722 Groh, K. J., & Muncke, J. (2017). In vitro toxicity testing of food contact materials: State-of-the-art and future challenges. Comprehensive Reviews in Food Science and Food Safety,16,1123–1150. Guo, M., He, M., Zhong, J., He, Q., Ismail, B. B., Chen, G., & Liu, D. (2020). High-performance liquid chromatography(HPLC)- fluorescence method for determination of bisphenol A diglycidyl ether (BADGE) and its derivatives in canned foods. Science of the Total Environment,710,134975.https://doi.org/10.1016/j.scitotenv. 2019.134975 Hammarling, L., Gustavsson, H., Svensson, K., & Oskarsson, A. (2000). Migration of bisphenol-A diglycidyl ether (BADGE) and its reaction products in canned foods. Food Additives & Contaminants,17(11), 937–943. https://doi.org/10.1080/ 026520300750038126 Holmes, M. J., Hart, A., Northing, P., Oldring, P. K. T., Castle, L., Stott, D., Smith, G., & Wardman, O. (2005). Dietary exposure to chemical migrants from food contact materials: A probabilistic approach. Food Additives & Contaminants,22(10), 907–919. https://doi.org/ 10.1080/02652030500307172 Hoppe, M., de Voogt, P., & Franz, R. (2016). Identification and quantification of oligomers as potential migrants in plastics food contact materials with a focus in polycondensates – A review. Trends in Food Science & Technology,50,118–130.https://doi.org/ 10.1016/j.tifs.2016.01.018 Huang, M., Liu, S., Fu, L., Jiang, X., & Yang, M. (2020). Bisphenol A and its analogues bisphenol S, bisphenol F and bisphenol AF induce oxidative stress and biomacromolecular damage in human granulosa KGN cells. Chemosphere,253,126707. Hwang, J. B., Lee, S., Lee, J. E., Choi, J. C., Park, S. J., & Kang, Y. (2020). LC-MS/MS analysis of BADGE, NOGEs, and their derivatives migrated from food and beverage metal cans. Food Additives & Contaminants: Part A,37(11),1974–1984. https://doi.org/10.1080/ 19440049.2020.1791974 Jordáková, I., Dobiás,J.,Voldrich, M., & Poustka, J. (2003). Determination of Bisphenol A, bisphenol F, bisphenol A diglycidyl ether and bisphenol F diglycidyl ether migrated from food cans using gas chromatography-mass spectrometry. Czech Journal of Food Sciences,21(3), 85–90. Kato, L. S., & Conte-Junior, C. A. (2021). Safety of plastic food packaging: The challenges about non-intentionally added substances (NIAS) discovery, identification and risk assessment. Polymers,13(13), 2077. https://doi.org/10.3390/polym1313 2077 LaKind, J. S. (2013). Can coatings for foods and beverages: Issues and options. International Journal of Technology, Policy and Management,13(1), 80–95. Lestido-Cardama, A., Sendón, R., Bustos, J., Santillana, M. I., Paseiro- Losada, P., & Rodríguez-Bernaldo de Quirós, A. (2019). GC-MS Screening for the identification of potential migrants present in polymeric coatings of food cans. Polymers,11(12), 2086. https://doi. org/10.3390/polym11122086 Lestido-Cardama, A., Vázquez-Loureiro, P., Sendón, R., Paseiro- Losada, P., & Rodríguez-Bernaldo de Quirós, A. (2021). Application of chromatographic analysis for detecting components from polymeric can coatings and further determination in beverage samples. Journal of Chromatography A,1638, 461886. https://doi. org/10.1016/j.chroma.2021.461886 Lestido-Cardama, A., Sendón, R., Bustos, J., Santillana, M. I., Paseiro-Losada, P., & Rodríguez-Bernaldo de Quirós, A. (2021). Multi-analyte method for the quantification of bisphenol related compounds in canned food samples and exposure assessment of the Spanish adult population. Food Packaging & Shelf Life,28, 100671. https://doi.org/10.1016/j.fpsl.2021.100671 Lestido-Cardama, A., Vázquez-Loureiro, P., Sendón, R., Bustos, J., Santillana, M. I., Paseiro-Losada, P., & Rodríguez-Bernaldo de Quirós, A. (2022). Characterization of polyester coatings intended for food contact by different analytical techniques and migration testing by LC-MSn. Polymers,14(3), 487. https://doi.org/10.3390/ polym14030487 Liao, C., & Kannan, K. (2013). Concentrations and profiles of bisphenol A and other bisphenol analogues in foodstuffs from the United States and their implications for human exposure. Journal of Agricultural and Food Chemistry,61(19), 4655–4662. https://doi.org/10. 1021/jf400445n Lorber, M., Schecter, A., Paepke, O., Shropshire, W., Christensen, K., & Birnbaum, L. (2015). Exposure assessment of adult intake of bisphenol A (BPA) with emphasis on canned food dietary exposures. Environment International,77,55–62.https://doi.org/ 10.1016/j.envint.2015.01.008 Maćczak, A., Cyrkler, M., Bukowska, B., & Michałowicz, J. (2017). Bisphenol A, bisphenol S, bisphenol F and bisphenol AF induce different oxidative stress and damage in human red blood cells (in vitro study). Toxicology in Vitro,41, 143–149. https://doi.org/10. 1016/j.tiv.2017.02.018 Maia, J., Rodríguez-Bernaldo de Quirós, A., Sendón, R., Cruz, J. M., Seiler,A., Franz,R., Simoneau,C.,Castle,L.,Driffield,M., Mercea, P., Oldring, P., Tosa, V., & Paseiro, P. (2016). Determination of key diffusionandpartitionparametersand theirusein migration modelling of benzophenone from low-density polyethylene (LDPE) FOOD CONTACT COATINGS IN METAL CANS... 3609 into different foodstuffs. Food Additives & Contaminants: Part A, 33(4), 715–724. https://doi.org/10.1080/19440049.2016.1156165 Maragou, N. C., Thomaidis, N. S., Theodoridis, G. A., Lampi, E. N., & Koupparis, M. A. (2020). Determination of bisphenol A in canned food by microwave assisted extraction, molecularly imprinted polymer-solid phase extraction and liquid chromatography-mass spectrometry. Journal of Chromatography B,1137,121938.https:// doi.org/10.1016/j.jchromb.2019.121938 Marqueño, A., Pérez-Albaladejo, E., Flores, C., Moyano, E., & Porte, C. (2019). Toxic effects of bisphenol A diglycidyl ether and derivatives in human placental cells. Environmental Pollution,244, 513–521. https://doi.org/10.1016/j.envpol.2018.10.045 Míguez, J., Herrero, C., Quintás, I., Rodríguez, C., Gigosos, P. G., & Mariz, O. C. (2012). A LC-MS/MS method for the determination of BADGE-related and BFDGE-related compounds in canned fish food samples based on the formation of [M +NH4]+ aducts. Food Chemistry,135, 1310–1315. https://doi.org/10.1016/j. foodchem.2012.05.099 Munguía-López, E. M., Peralta, E., González-León, A., Vargas- Requena, C., & Soto-Valdez, H. (2002). Migration of bisphenol A (BPA) from epoxy can coatings to jalapeno peppers and an acid food simulant. Journal of Agricultural and Food Chemistry,50(25), 7299–7302. https://doi.org/10.1021/jf0257502 Munguía-López, E. M., Gerardo-Lugo, S., Peralta, E., Bolumen, S., & Soto-Valdez, H. (2005). Migration of bisphenol A (BPA) from can coatings into a fatty-food simulant and tuna fish. Food Additives and Contaminants,22(9), 892–898. https://doi.org/10.1080/ 02652030500163674 Nerín, C., Philo, M. R., Salafranca, J., & Castle, L. (2002). Determination of bisphenol-type contaminants from food packaging materials in aqueous foods by solid-phase microextraction–highperformance liquid chromatography. Journal of Chromatography A,963,375–380. Nerín, C., Canellas, E., Aznar, M., & Silcock, P. (2009). Analytical methods for the screening of potential volatile migrants from acrylic-base adhesives used in food-contact materials. Food Additives and Contaminants,26(12), 1592–1601. https://doi.org/10.1080/ 02652030903161572 Nerín, C., Alfaro, P., Aznar, M., & Domeño, C. (2013). The challenge of identifying non-intentionally added substances from food packagingmaterials:Areview.Analytica Chimica Acta,775,14–24. https://doi.org/10.1016/j.aca.2013.02.028 Nerín, C., Ubeda, J. L., Alfaro, P., Dahmani, Y., Aznar, M., Canellas, E., & Ausejo, R. (2014). Compounds from multilayer plastic bags cause reproductive failures in artificial insemination. Scientific Reports,4,4913.https://doi.org/10.1038/srep04913 Nerín, C. (2016). Migration analysis of compounds in food packaging. In M. P. M. Garcia, M. C. Gómez-Guillén, M. E. López-Caballero, & G. V. Barbosa-Cánovas (Eds.) Edible films and coatings (pp. 489– 495). CRC Press. Nerín, C., Bourdoux, S., Faust, B., Gude, T., Lesueur, C., Simat, T., Stoermer, A., Van Hoekh, E., & Oldring, P. (2022). Guidance in selecting analytical techniques for identification and quantification of non-intentionally added substances (NIAS) in food contact materials (FCMS). Food Additives & Contaminants: Part A,39(3), 620–643. https://doi.org/10.1080/19440049.2021.2012599 Noonan,G.O., Ackerman,L. K.,& Begley,T.H.(2011).Concentration of bisphenol A in highly consumed canned foods on the US market. Journal of Agricultural and Food Chemistry,59(13), 7178–7185. https://doi.org/10.1021/jf201076f Oldring, P. K. T., Castle, L., Hart, A., & Holmes, M. J. (2006). Migrants from food cans revisted–application of a stochastic model for a more realistic assessment of exposure to bisphenol A diglycidyl ether (BADGE). Packaging Technology and Science,19(3), 121–137. https://doi.org/10.1002/pts.715 Oldring, P. K. T., & Nehring, U. (2007). Packaging materials 7. Metal packaging for foodstuffs. ILSI Europe. Oldring, P. K. T., O’Mahony, C., Dixon, J., Vints, M., Mehegan, J., Dequatre, C., & Castle, L. (2014). Development of a new modelling tool (FACET) to assess exposure to chemical migrants from food packaging. Food Additives & Contaminants: Part A,31(3), 444–465. https://doi.org/10.1080/19440049.2013.862348 Omer, E., Cariou, R., Remaud, G., Guitton, Y., Germon, H., Hill, P., Dervilly-Pinel, G., & Le Bizec, B. (2018). Elucidation of non-intentionally added substances migrating from polyesterpolyurethane lacquers using automated LC-HRMS data processing. Analytical and Bioanalytical Chemistry,410,5391–5403. https://doi.org/10.1007/s00216-018-0968-z Omer, E., Bichon, E., Hutinet, S., Royer, A. L., Monteau, F., Germon, H., Hill, P., Remaud, G., Dervilly-Pinel, G., Cariou, R., & Le Bizec, B. (2019). Toward the characterization of non-intentionally added substances migrating from polyester-polyurethane lacquers by comprehensive gas chromatography-mass spectrometry technologies. Journal of Chromatography A,1601,327–334.https://doi.org/ 10.1016/j.chroma.2019.05.024 Paseiro-Cerrato, R., MacMahon, S., Ridge, C. D., Noonan, G. O., & Begley, T. H. (2016). Identification of unknown compounds from polyester cans coatingsthat may potentially migrate into food or food simulants. Journal of Chromatography A,1444, 106–113. https://doi.org/10.1016/j.chroma.2016.03.038 Paseiro-Cerrato, R., Noonan, G. O., & Begley, T. H. (2016). Evaluation of long-term migration testing from can coatings into food simulants: Polyester coatings. Journal of Agricultural and Food Chemistry,64,2377–2385.https://doi.org/10.1021/acs.jafc.5b05880 Paseiro-Cerrato, R., DeVries, J., & Begley, T. H. (2017). Evaluation of Short-term and long-term migration testing from can coatings into food simulants: Epoxy and acrylic−phenolic coatings. Journal of Agricultural and Food Chemistry,65,2594–2602.https://doi.org/ 10.1021/acs.jafc.7b00081 Paseiro-Cerrato, R., DeJager, L., & Begley, T. H. (2019a). Determining the migration of nadic acid, terephthalic acid, isophthalic acid and twooligomers frompolyesterfood cansinto foodin theUS market. Food Control,101,69–76.https://doi.org/10.1016/j.foodcont.2019. 02.033 Paseiro-Cerrato, R., DeJager, L., & Begley, T. H. (2019b). Assessment of the impact of accelerated migration testing for coated food cans using food simulants. Molecules,24(17), 3123. https://doi.org/10. 3390/molecules24173123 Paseiro-Losada, P., Paz-Abuín, S., Vázquez-Odériz, L., Simal- Lozano, J., & Simal-Gándara, J. (1991). Quality control of cured epoxy resins. Determination of residual free monomers (mxilylenediamnine and bisphenol A diglycidyl ether) in the finished product. Journal of Chromatograph,585,75–81. Paseiro-Losada, P., Pérez-Lamela, C., López-Fabal, M. F., San Martin- Fenollera, P., & Simal-Lozano, J. (1997). Two RP-HPLC sensitive methods to quantify and identify bisphenol a diglycidyl ether 3610 FOOD CONTACT COATINGS IN METAL CANS... and its hydrolysis products. 1. European Union aqueous food simulants. Journal of Agriculture and Food Chemistry,45,3493– 3500. Piergiovanni, L., & Limbo, S. (2016). Metal packaging materials. In L. Piergiovanni & S. Limbo (Eds.), Food packaging materials (1st ed., pp. 13–22). Springer. Pietropaolo, E., Albenga, R., Gosetti, F., Toson, V., Koster, S., Marin- Kuan, M., Veyrand, J., Patin, A., Schilter, B., Pistone, A., & Tei, L. (2018). Synthesis, identification and quantification of oligomers from polyester coatings for metal packaging. JournalofChromatography A,1578,15–27.https://doi.org/10.1016/j.chroma.2018. 10.002 Poças, M. F., & Hogg, T. (2007). Exposure assessment of chemicals from packaging materials in foods: A review. Trends in Food Science & Technology,18,219–230.https://doi.org/10.1016/j.tifs.2006. 12.008 Rauter, W., Dickinger, G.-, Zihlarz, R., & Lintschinger, J. (1999). Determination of Bisphenol A diglycidyl ether (BADGE) and its hydrolysis products in canned oily foods from the Austrian market. Zeitschrift für Lebensmitteluntersuchung und -Forschung A, 208,208–211. Robertson, G. L. (2012). Metal packaging materials. In G. L. Robertson (Ed.), Food packaging: Principles and practice (3rd ed., pp. 189–228). CRC Press (Chapter 7). Rodríguez-Bernaldo de Quirós, A., Lestido-Cardama, A., Sendón, R., & García-Ibarra, V. (2019). Food contamination by packaging (1st ed.). De Gruyter. Safta, M., Limam, I., Bouajina, A., Ousji, B., Jomaa, G., Turki, E., Belgaied, S., Driss, M. R., & Kalfat, R. (2018). Characterization of the migration of bisphenol A and F diglycidyl ethers from epoxycoated containers to food simulants. Analytical Letters,51(3), 296–311. https://doi.org/10.1080/00032719.2017.1331353 Sajiki, J., Miyamoto, F., Fukata, H., Mori, C., Yonekubo, J., & Hayakawa, K. (2007). Bisphenol A (BPA) and its source in foods in Japanese markets. Food Additives and Contaminants,24(1), 103–112. https://doi.org/10.1080/02652030600936383 Schaefer, A., Ohm, V. A., & Simat, T. J. (2004). Migration from can coatings: Part 2. Identification and quantification of migrating cyclic oligoesters. Food Additives & Contaminants,21(4), 377–389. https://doi.org/10.1080/02652030310001637939 Schaefer, A., & Simat, T. J. (2004). Migration from can coatings: Part 3. Synthesis, identification and quantification of migrating epoxybased substances below 1000 Da. Food Additives & Contaminants, 21(4), 390–405. https://doi.org/10.1080/02652030310001657388 Sendón García, R., & Paseiro-Losada, P. (2004). Determination of bisphenol A diglycidyl ether and its hydrolysis and chlorohydroxy derivatives by liquid chromatography–mass spectrometry. Journal of Chromatography A,1032, 37–43. https://doi.org/10.1016/j. chroma.2003.10.039 Sharma, V., & Kundu, P. P. (2006). Addition polymers from natural oils—A review. Progress in Polymer Science,31, 983–1008. https:// doi.org/10.1016/j.progpolymsci.2006.09.003 Simoneau, C., Theobald, A., Wiltschko, D., & Anklam, E. (1999). Estimation of intake of bisphenol-A-diglycidyl-ether (BADGE) from canned fish consumption in Europe and migration survey. Food Additives & Contaminants,16(11), 457–463. https://doi.org/ 10.1080/026520399283740 Simoneau, C., Raffael, B., Garbin, S., Hoekstra, E., Mieth, A., Lopes, J. A., & Reina, V. (2016). Non-harmonised food contact materials in the EU: Regulatory and market situation. JRC Science for Policy report. JRC. Summerfield, W., Goodson, A., & Cooper, I. (1998). Survey of bisphenol a diglycidyl ether (BADGE) in canned foods. Food Additives & Contaminants,15(7), 818–830. https://doi.org/10.1080/ 02652039809374716 Tarafdar, A., Sirohib, R., Balakumaranc, P. A., Reshmyd, R., Madhavan, A., Sindhu, R., Binod, P., Kumar, Y., Kumar, D., & Sim, S. J. (2022). The hazardous threat of Bisphenol A: Toxicity, detection and remediation. Journal of Hazardous Materials,423,127097. https://doi.org/10.1016/j.jhazmat.2021.127097 Tehrany, E. A., & Desobry, S. (2004). Partition coefficients in food/packaging systems: A review. Food Additives & Contaminants,21(12), 1186–1202. https://doi.org/10.1080/ 02652030400019380 Theobald, A., Simoneau, C., Hannaert, P., Roncari, P., Roncari, A., Rudolph, T., & Anklam, E. (2000). Occurrence of bisphenol- F-diglycidyl ether (BFDGE) in fish canned in oil. Food Additives & Contaminants,17(10), 881–887. https://doi.org/10.1080/ 026520300420475 Theobald, A., Simoneau, C., Roncari, A., & Anklam, E. (2002). Identification of epoxy containing migrants from can coatings in edible oil: A model study on reaction products of Bisphenol-A- Diglycidyl-Ether (BADGE) with solvents for coating production. Deutsche Lebensmittel-Rundschau,98, 249–256. Thomson, B. M., & Grounds, P. R. (2005). Bisphenol A in canned foods in New Zealand: An exposure assessment. Food Additives & Contaminants,22(1), 65–72. https://doi.org/10.1080/ 02652030400027920 Úbeda, S., Aznar, M., Vera, P., Nerín, C., Henríquez, L., Taborda, L., & Restrepo, C. (2017). Overall and specific migration from multilayer high barrier food contact materials – Kinetic study of cyclic polyester oligomers migration. Food Additives & Contaminants: Part A,34(10), 1784–1794. https://doi.org/10.1080/19440049.2017. 1346390 Ubeda, S., Aznar, M., Alfaro, P., & Nerín, C. (2019). Migration of oligomers from a food contact biopolymer based on polylactic acid (PLA) and polyester. Analytical and Bioanalytical Chemistry,411, 3521–3532. https://doi.org/10.1007/s00216-019-01831-0 Ubeda, S., Aznar, M., & Nerín, C. (2019). Determination of volatile compounds and their sensory impact in a T biopolymer based on polylactic acid (PLA) and polyester. Food Chemistry,294,171–178. https://doi.org/10.1016/j.foodchem.2019.05.069 Ubeda, S., Aznar, M., Rosenmai, A. K., Vinggaard, A. M., & Nerín, C. (2020). Migration studies and toxicity evaluation of cyclic polyesters oligomers from food packaging adhesives. Food Chemistry,311,125918.https://doi.org/10.1016/j.foodchem.2019.125918 Uematsu, Y., Hirata, K., Suzuki, K., Iida, K., & Saito, K. (2001). Chlorohydrins of bisphenol A diglycidyl ether (BADGE) and of bisphenol F diglycidyl ether (BFDGE) in canned foods and ready-to-drink coffees from the Japanese market. Food Additives & Contaminants,18(2), 177–185. https://doi.org/10.1080/ 02652030010005501 U.S. Environmental Protection Agency (U.S. EPA). (1988). Bisphenol A. Integrated Risk Information System (IRIS). https://iris.epa.gov/ ChemicalLanding/&substance_nmbr=356 Vaclavikova, M., Paseiro-Cerrato, R., Vaclavik, L., Noonan, G. O., DeVries, J., & Begley, T. H. (2016). Target and non-target analysis of migrants from PVC-coated cans using UHPLC-Q-Orbitrap FOOD CONTACT COATINGS IN METAL CANS... 3611 MS: Evaluation of long-term migration testing. Food Additives & Contaminants: Part A,33(2), 352–363. https://doi.org/10.1080/ 19440049.2015.1128564 Viñas,P.,Campillo, N., Martínez-Castillo, N., &Hernández-Córdoba, M. (2010). Comparison of two derivatization-based methods for solid-phase microextraction–gas chromatography–mass spectrometric determination of bisphenol A, bisphenol S and biphenol migrated from food cans. Analytical and Bioanalytical Chemistry,397(1), 115–125. https://doi.org/10.1007/s00216-010-3 464-7 Von Goetz, N., Pirow, R., Hart, A., Bradley, E., Poças, F., Arcella, D., Lillegard, I. T. L., Simoneau, C., van Engelen, J., Husoy, T., Theobald, A., & Leclercq, C. (2017). Including non-dietary sources into an exposure assessment of the European Food Safety Authority: The challenge of multi-sector chemicals such as bisphenol A. Regulatory Toxicology and Pharmacology,85,70–78.https://doi. org/10.1016/j.yrtph.2017.02.004 Wagner, J., Castle, L., Oldring, P. T. K., Moschakis, T., & Wedzicha, B. L. (2018). Factors affecting migration kinetics from a generic epoxy-phenolic food can coating system. Food Research International,106,183–192.https://doi.org/10.1016/j.foodres.2017.12.059 Wang, D., Zhao, H., Fei, X., Synder, S. A., Fang, M., & Liu, M. (2021). A comprehensive review on the analytical method, occurrence, transformation and toxicity of a reactive pollutant: BADGE. Environment International,155,106701. Yazdinezhad, S. R., Ballesteros-Gómez, A., Lunar, L., & Rubio, S. (2013). Single-step extraction and cleanup of bisphenol A in soft drinks by hemimicellar magnetic solid phase extraction prior to liquid chromatography/tandem mass spectrometry. Analytica Chimica Acta,778,31–37.https://doi.org/10.1016/j.aca.2013.03. 025 Zech, J., Manowski, A., Malchow, S., Rettberg, N., & Garbe, L. A. (2015). Determination of bisphenols, bisphenol A diglycidyl ether (BADGE), BADGE chloro-hydrins and hydrates from canned beer by high-performance liquid chromatographytandem mass spectrometry. Brewing Science,68,102–109. Zhang, N., Kenion, G., Bankmann, D., Mezouari, S., & Hartman, T. G. (2018). Migration studies and chemical characterization of low molecular weight cyclic polyester oligomers from food packaging lamination adhesives. Packaging Technology and Science,31,197– 211. https://doi.org/10.1002/pts.2367 Zhang, N., Scarsella, J. B., & Hartman, T. G. (2020). Identification and quantitation studies of migrants from BPA alternative food-contact metal can coatings. Polymers,12(12), 2846. Zhou, J., Chen, X. H., Pan, S. D., Wang, J. L., Zheng, Y. B., Xu, J. J., Zhao, Y. G., Cai, Z. X., & Jin, M. C. (2019). Contamination status of bisphenol A and its analogues (bisphenol S, F and B) in foodstuffs and the implications for dietary exposure on adult residents in Zhejiang Province. Food Chemistry,294, 160–170. https://doi. org/10.1016/j.foodchem.2019.05.022 How to cite this article: Lestido-Cardama, A., Sendón, R., Bustos, J., Nieto, M. T., Losada, P. P., & Rodríguez-Bernaldo de Quirós, A. (2022). Food and beverage can coatings: A review on chemical analysis, migration, and risk assessment. Comprehensive Reviews in Food Science and Food Safety,21, 3558–3611. https://doi.org/10.1111/1541-4337.12976