Validation and application of an LC-MS/MS method for the determination of cyclic oligomers originating from polyamide 6 and polyamide 66 in food simulant

Polyamides (PAs) are used in the production of various food contact materials (FCMs) and articles such as kitchen utensils and packaging material. Cyclic oligomers have been identified as potential migrants from PA. This study describes the development, validation and application of a multi-oligomer analytical method based on LC-ESI-MS/MS for the identification and quantification of eight cyclic oligomers of PA 6 and four PA 66 migrating from FCMs into food simulant B (3% acetic acid) and beverages. It was proved that doubly charged precursor ions of the cyclic PA 6 and PA 66 oligomers above a mass of 500 Da are formed during the ionisation process of the electrospray technique used. Direct injection of a diluted food simulant into the LC-ESI-MS/MS system after migration makes the validated method a valuable tool for investigating migration of cyclic PA oligomers. The validation results demonstrate that the multi-oligomer method is applicable for the analysis of cyclic PA 6 and PA 66 oligomers in food simulant B. For all investigated cyclic PA oligomers, detection limits were in the range of 0.1–1.1 µg/l. Linearity (r² ≥ 0.99), trueness values between 91% and 122%, and intra-day (RSD_r < 10%) and inter-day precision (RSD_R < 19%) were determined and satisfied validation criteria set out by the European Reference Laboratory for FCMs. The method was extended to tap water and tea. Finally, the multi-oligomer method was successfully applied to determine cyclic PA oligomers in migration solutions originating from different PA FCMs. In all migration solutions, concentrations of cyclic PA oligomers were determined above the LOQ. A preliminary risk assessment based on in silico tools was performed. The results demonstrate the urgent need for toxicological data that would facilitate the evaluation of the health risk of cyclic PA oligomers.     

Migration of oligomers from PET: determination of diffusion coefficients and comparison of experimental versus modelled migration

ABSTRACT

Polyethylene terephthalate (PET) is increasingly used as food-contact material in, for example, containers for beverage such as bottles for soft drinks, mineral water, juices and beer. Mass transport of substances present in packaging materials into the packed food and beverages is monitored to verify the food law compliance of the materials. PET is known to contain or give rise to migrants that are oligomers derived from the polymeric material. Until now their actual migration potential has been investigated only poorly. A convenient way to determine their migration would be by using models. To verify existing models with experimental data, a migration kinetic study of PET oligomers was conducted. PET bottle material was submerged in 50% ethanol at 80°C for 15 h. The oligomer content in the migration solutions was determined every hour using LC-MS with the first-series cyclic PET trimer as standard. Diffusion coefficients of five PET oligomers (first-series dimer and trimer, second-series dimer and trimer, and third-series dimer) were calculated from the obtained data and compared with the calculated diffusion coefficients using the models of Welle and Piringer. This is the first study to provide diffusion characteristics of oligomers in PET other than the first-series cyclic trimer.     

Migration into food of polyethylene terephthalate (PET) cyclic oligomers from PET microwave susceptor packaging

A quantitative method has been developed to measure the migration of polyethylene terephthalate (PET) cyclic oligomers from aluminized PET susceptor film-type food packaging into several food types. Microwaveable French fries, popcorn, fish sticks, waffles and pizza sold in susceptor-type packaging were purchased in local markets, cooked according to package instructions and analysed for PET oligomers. Appropriate food blanks were cooked in glass containers. Quantities of PET oligomers found in the foods ranged from less than 0.012 micrograms/g to approximately 7 micrograms/g.     

Updated evaluation of the migration of styrene monomer and oligomers from polystyrene food contact materials to foods and food simulants

Due to the 2011 labelling of styrene monomer as “reasonably anticipated to be a human carcinogen” by the National Institutes of Health’s National Toxicology Program (NTP) and the controversy over whether styrene oligomers mimic the physiological effects of estrogen, an updated review of styrene monomer and oligomers in food and food contact materials (FCMs) was performed. The concentrations of styrene monomer and oligomers were determined in 24 polystyrene (PS) products and ranged from 9.3 to 3100 mg kg^–1 for the styrene monomer, 130–2900 mg kg^–1 for the sum of three styrene dimers, and 220–16,000 mg kg^–1 for the sum of six styrene trimers. Foods in contact with PS packaging had styrene monomer concentrations ranging from 2.6 to 163 ng g^–1; dimer concentrations from the limit of quantitation (LOQ) to 4.8 ng g^–1 and trimer concentrations were all below the LOQ (2 ng g^–1). Diffusion coefficients (D_p) and partition coefficients (K) were also calculated for styrene dimers and trimers. The results presented here indicate that styrene monomer concentrations in foods have not significantly changed since the 1980s and monomer concentrations in food packaging quantified in this study were all below USFDA limits. Although styrene dimers and trimers are present in higher concentrations in PS FCMs than the monomer, their migration to food is limited because of their high K values (4 × 10² to 2 × 10⁶) and their low diffusion coefficients in PS products. Additionally, diffusion coefficients calculated using USFDA-recommended food simulants and Arrhenius plots describing the temperature dependence of styrene dimers and trimers can be used in future calculations of dietary intake of the styrene oligomers.     

Polyphenylsulfone (PPSU) for baby bottles: a comprehensive assessment on polymer-related non-intentionally added substances (NIAS)

Polyphenylsulfone (PPSU) is a new material for the production of baby bottles. PPSU is a polyether plastic formally composed of bisphenol S (BPS) and 4,4?-dihydroxybiphenyl (DHBP), which both have slight endocrine activities in in vitro tests. So far, little is known about the presence and the release of potentially hazardous substances from PPSU baby bottles. In this study, we present a three-step approach for the analysis of PPSU starting with polymer characterisation in terms of chemical structure, total oligomer content and hydrolytic stability. Second is the determination of extractables focussing on monomers, monomer derivatives, linear and cyclic oligomers below 1000 Da and residual solvent. Third is a risk assessment on migration-related substances in accordance to European Union plastics regulation no. 10/2011 based on triplicate consecutive migration experiments using official milk simulant 50% ethanol. We analysed five types of PPSU baby bottles from different brands as well as corresponding raw materials from different manufacturers by various analytical techniques (high-performance liquid chromatography (HPLC)-diode array detector /fluorescence detector/Corona/electrospray ionisation-MS, HPLC-size exclusion chromatography, gas chromatography-mass spectrometry (GC-MS), ¹H-NMR). We found significant variations of PPSU materials from different producers with regard to polymer and oligomer chain end groups (methoxylation, chlorination), while total oligomer content below 1000 Da was similar (mean about 0.48%). BPS was not detected above 0.3 mg/kg polymer in any PPSU sample. Residual DHBP content ranged between 1.7 and 15.5 mg/kg polymer. The most common oligomer in all PPSU samples was the cyclic tetramer (about 1200 mg/kg polymer), which is the only cyclic compound below 1000 Da. Residual solvent, sulfolane, was determined to a maximum of 1300 mg/kg polymer. In migration tests, we detected exceedances of neither specific migration limits for listed substances nor of thresholds of toxicological concern for non-listed substances (monomer derivatives, oligomers). Based on our analytical results, no concerns exist regarding migration of polymer-related substances from PPSU baby bottles.     

Migration of lactic acid,lactide and oligomers from polylactide food-contact materials

Polylactide (PLA) is used for manufacturing lunch boxes and for packaging fresh food in Japan. PLA can be hydrolysed relatively easily to produce lactic acid, lactide and oligomers. Different types of PLA sheet were subjected to migration tests under various conditions and the lactic acid, lactide and oligomers contents of the migration solutions were determined using liquid chromatography/mass spectrometry (LC/MS). Furthermore, the change in molecular weight was determined by a migration test. PLA was stable at 40°C for 180 days; the total of lactic acid, lactide and oligomers migration levels were 0.28–15.00 µg cm^?2. PLA decomposed clearly at 60°C for only 10 days, the total migration levels were increased to 0.73–2840 µg cm^?2. PLA sheets with a high D-lactic acid content decomposed particularly rapidly. The amounts of alkali decomposition products, based on the conversion of lactide and oligomers to lactic acid by alkali hydrolysis, corresponded with the total migration levels.     

Potential for short-term migration of mineral oil hydrocarbons from coated and uncoated food contact paper and board into a fatty food simulant

ABSTRACT

Mineral oil hydrocarbons (MOH) are widely used in the food industry for applications such as printing inks, additives, adhesives, and processing aids for food additives. Recently, the migration of MOH from food contact paper and board into foods has raised public health concerns. In this study, a total of 110 food contact paper and board samples, including baking and cooking paper (23), baking cups (28), food packaging bags (22), lunch boxes (8), party plates (26), and straws (3) were evaluated to quantify the content and short-term migration levels of MOH. The MOH were separated into mineral oil saturated hydrocarbons (MOSH)/polyolefin oligomeric saturated hydrocarbons (POSH) and mineral oil aromatic hydrocarbons (MOAH) via a validated on-line liquid chromatography?gas chromatography?flame ionisation detection (LC–GC–FID) technique. The coating materials of the sample products comprised polyethylene, polypropylene, polyethylene terephthalate, and silicone. The effects of the coating materials on the content and migration of MOH/POSH were evaluated. Quantitative analysis of the MOH in the samples showed that the MOSH/POSH and MOAH content varied widely, ranging from 16 to 5626 mg kg^?1 for MOH, regardless of the coating materials. Short-term migration of MOSH/POSH was observed only in samples with polyolefinic coatings, such as polyethylene and polypropylene, in experiments conducted at 25 °C for 10 min, although the extent of MOAH migration for all samples was at the trace level. The migration of MOSH/POSH was detected within the range of 0.93 to 62.3 μg L^?1 in 22 samples, and the migration of MOAH was detected within the range of 0.80 to 2.6 μg L^?1 in only 4 samples. These results demonstrate that although the short-term migration potential of MOH is generally negligible, the migration of MOSH/POSH into wet fatty foods can be accelerated by polyolefinic coatings, even within a very short time.     

Migration of Ti from nano-TiO2-polyethylene composite packaging into food simulants

An analytical method based on ICP-MS was developed for the determination of Ti in food simulants (3% (w/v) aqueous acetic acid and 50% (v/v) aqueous ethanol). The method was used to determine the migration of Ti from nano-TiO₂-PE films used for food packaging into food simulants under different temperature and migration time conditions. The maximum migration amounts into 3% (w/v) aqueous acetic acid were 1.4 ± 0.02, 6.3 ± 0.5 and 12.1 ± 0.2 μg kg^?1 at 25, 70 and 100°C, respectively, while into 50% (v/v) aqueous ethanol, the maximum migration amounts were 0.5 ± 0.1, 0.6 ± 0.03 and 2.1 ± 0.1 μg kg^?1 at 25, 70 and 100°C, respectively. Increasing the additive content in the film promoted migration of nanoparticles. The results indicated that the migration of nanoparticles might occur via dissolution from the surface and cut edges of the solid phase (film) into the liquid phase (food simulant).     

Antimony Assessment in PET Bottles for Soft Drink

The aim of this work was to develop a method for the determination of antimony (Sb) in polyethylene terephthalate (PET) bottles and to evaluate its migration into soft drink and simulant. In this context, a new procedure for PET sample preparation, using a high pressure asher (HPA), is presented for the determination of Sb by inductively coupled plasma optical emission spectrometry (ICP-OES). The concentration of Sb in PET bottles ranged between 272 and 650 mg kg^?1. The migration of Sb into soft drink after 180 days at 35 °C was below the LOQ, 20 μg L^?1. The specific migration of Sb from the bottle into simulant 3% of acetic acid after the contact per 10 days at 40 °C was less than the LOQ, 23.5 μg L^?1. The results showed that all packaging evaluated contained Sb, but the maximum permissible migration value for Sb, 40 μg L^?1, established by Anvisa and EU, was never exceeded.     

发泡餐盒中苯乙烯单体和低聚物的测定及迁移风险评估

目的建立聚苯乙烯发泡餐盒中苯乙烯单体和低聚物的检测方法,并对其向食品的迁移进行风险评估。方法采用二氯甲烷溶解-甲醇沉淀法提取餐盒中的苯乙烯单体和低聚物,采用气相色谱-质谱联用法测定目标物向水、酒精和脂肪食品模拟物的迁移量,通过比较各物质的估计日摄入量和毒理学安全阈值评估迁移风险。结果苯乙烯单体和低聚物在0.02~1.00 μg/mL范围内线性良好（R均大于0.99）,在餐盒及食品模拟物中的加标回收率为80.5%~101.2%,相对标准偏差为1.6%~10.5%;在5%显著性水平下各物质向脂肪食品模拟物的迁移量明显大于向水和酒精食品模拟物的迁移量 ,扩散系数为1.3×10-15~1.4×10-9 cm2/s,迁移活化能为33.5~53.3 kJ/mol;目标分析物的估计日摄入量均未超过毒理学关注阈值。结论该方法简单、可靠, 可用于测定发泡餐盒中苯乙烯单体和低聚物的含量。聚苯乙烯发泡餐盒不适合在高温条件下盛放脂肪食品。     

Preparation and characterization of carbon black/polybutylene terephthalate/polyethylene terephthalate antistatic fiber with sheath–core structure

In this study, antistatic sheath–core composite fibers with the core composed of polyethylene terephthalate (PET) polymer and a sheath composed of carbon black/polybutylene terephthalate (CB/PBT) polymer were fabricated using a conjugate spinning process. CB powders of various particle sizes were compounded with PBT polymers to prepare the antistatic CB/PBT pellets, and their electrical resistivities strongly depended on the intrinsic properties and dispersion of CB powders. The CB/PBT/PET fibers consisted of well-mixed CB powders within the polymer matrix showed an outstanding antistatic function, and they were employed to manufacture an antistatic glove with commercial acrylic yarns for practical applications. The antistatic glove with a reliable washing fastness is capable of being used on capacitive touch panels of smart phones, tablets, and other wearable electronic devices. This approach offers new possibilities for a variety of textile applications requiring antistatic properties.     

Antioxidant power,bacteriostatic activity,and characterization of white grape pomace extracts by HPLC–ESI–MS

Polyphenolic fractions obtained from white grape pomace by aqueous extraction were analyzed to determine their antioxidant power (DPPH and TBARS methods), bacteriostatic activity, the effect of particle size on total extractable polyphenols (expressed as gallic acid equivalents (GAE)), and to characterize by HPLC–ESI–MS. The extraction of polyphenols from Albariño variety grape pomace was performed both on lab-scale and on pilot-plant scale using particles sizes of <1 mm, 3–5 mm and entire particle. Lab-scale assays showed that the lower the particle size the higher the raw extract (RE) percentage (%w/w), which values were 21.3 ± 0.37% (SD), 12.6 ± 0.38%, and 6.6 ± 0.44%, respectively. Several fractions were obtained from RE, either as result of applying liquid–liquid partition or gel permeation chromatography. The antiradical activities of the fractions were lower than that of gallic acid (17.8 ± 0.1 mg GAE/mol DPPH) but similar to that of catechin or procyanidin B₂ (46.0 ± 2.3 mg GAE/mol DPPH and 52.3 ± 6.3 mg GAE/mol DPPH). Several fractions showed bacteriostatic activity both at 50 and at 100 mg/L. Total aerobic bacterial enumeration (TABE, log UFC/cm²) of treated samples revealed a significant lower TABE than that for control. HPLC–ESI–MS studies demonstrated that fractions V and VI included monomers, dimers, and trimers of procyanidins, few of them galloylated. Fraction VII contained several oligomers and galloylated procyanidins.     

Migration from plasticized films into foods. 5. Identification of individual species in a polymeric plasticizer and their migration into foods.

To assess the significance of migration of polymeric plasticizers into foods, chemical characterization and quantification of individual oligomeric species is required. This paper reports the identification of seven individual oligomers isolated from a poly(butylene adipate) plasticizer. Based on mass spectrometry, NMR and chemical degradation, the oligomers were identified as a series of diol-terminated units ranging from a trimer up to an 11-monomer unit, along with a cyclic tetramer, all in the molecular weight range of 300-1100. A study of the migration of polymeric plasticizer from PVC film into olive oil indicated preferential migration of low molecular weight species. These oligomers which comprised 24% of the parent plasticizer contributed more than 90% of the plasticizer migration with the smallest oligomers migrating 90-fold more readily than the bulk of the plasticizer. From a knowledge of total polymeric plasticizer migration from PVC films under actual conditions of food-use, the abundance of individual oligomers in the foods has been estimated.     

Determination of biogenic amines in traditional Chinese fermented foods by reversed-phase high-performance liquid chromatography (RP-HPLC)

A survey of biogenic amine content of traditional Chinese fermented foods (douchi, sufu, fermented sausage, yulu, and shrimp paste) was carried out. Eight major biogenic amines including putrescine, cadaverine, histamine, phenylethylamine, tyramine, spermine, spermidine and tryptamine were separated by reversed-phase HPLC-DAD on Inertsil ODS-SP column after pre-column derivatisation with dansyl chloride. The results showed that spermine (1.65–3.96 mg 100 g^?1), putrescine (0.20–10.89 mg 100 g^?1), cadaverine (3.60–12.14 mg 100 g^?1), and histamine (0.57–20.24 mg 100 g^?1) were the most represented amines. All amines were detected in yulu, while sufu showed a much higher content of most amines. Shrimp paste showed the lowest level of total biogenic amines. Moreover, the composition and content of eight biogenic amines in the selected samples varied among different food types, origins and batches. Although the average content for each amine is within the range that may elicit direct adverse reactions, consumers should be aware of the potential synergistic effect among different amines and limit their consumption at each meal.     

Migration of mineral oil,photoinitiators and plasticisers from recycled paperboard into dry foods: a study under controlled conditions

Migration from recycled paperboard was monitored after 2, 4 and 9 months of storage for six test foods industrially packed in five configurations, four with internal plastic films. After 9 months, the migration of mineral oil saturated hydrocarbons into foods directly packed in the paperboard amounted to 30–52 mg/kg, which corresponded to 65%–80% of those of a volatility up to that of the n-alkane C₂₄ in the paperboard. The concentration of the migrated aromatic hydrocarbons in the foods ranged from 5.5 to 9.4 mg/kg. More than half of this migration occurred in the first 2 months. Differences between the foods amounted to mostly less than a factor of 2 and seemed to be related to porosity or permeability more than fat content. Nine photoinitiators were detected in the paperboard, of which eight migrated into the packed food at up to 24%. Several plasticisers were present in the recycled paperboard, but only butyl phthalates showed significant migration. After 9 months, up to 40% of diisobutyl phthalate and 20% of dibutyl phthalate migrated into the food with direct contact. The internal polyethylene film hardly slowed migration, but the film and the tray absorbed approximately three times more mineral oil than the food, despite constituting merely 4% of the mass of the pack. Oriented polypropylene strongly slowed migration: The highest migration of saturated hydrocarbons measured after 9 months (2.3 mg/kg) corresponded to only 3% of the content in the paperboard and included migrated polyolefin oligomeric saturated hydrocarbons. Coating of polypropylene with an acrylate further slowed the migration, but the migration from the paperboard was still detectable in four of the six samples. Polyethylene terephthalate was a tight barrier.     

Simultaneous Determination of Ten Ginsenosides in American Ginseng Functional Foods and Ginseng Raw Plant Materials by Liquid Chromatography Tandem Mass Spectrometry

A method was established for simultaneous determination of ten ginsenosides (ginsenosides Rg1, Re, Rb1, Rf, Rb3, 20(S)-F1, 20(S)-F2, Rg3, 20(S)-Rh2, and pseudoginsenoside F11) in American ginseng functional foods and ginseng raw plant materials by high-performance liquid chromatography with electrospray ionization tandem mass spectrometry. After samples were ultrasonically extracted with 60 % (v/v) methanol aqueous solution, centrifuged, and filtered, the analytes in sample solution were separated by a Hypersil Gold column (2.1?×?150 mm, 5 μm) at 25 °C with a programmed gradient elution. Mobile phases consisting of 0.01 % (v/v) formic acid aqueous solution and methanol were used for elution with a flow rate of 250 μL/min. Qualitative determination was completed by comparison with characteristic ion pairs and retention time of the targeted compounds using selective reaction monitoring mode. Digoxin was used as internal standard in positive ionization mode. The internal standard curves were used for quantification. The limits of detection of the method were from 1.0 to 5.0 mg/kg. The linear dynamic ranges covered from 10 to 5,000 μg/L (R ²?≥?0.99). Principal component analysis was used for distinguishing ginseng sources of the functional foods. Thirty-seven samples, including 11 American ginseng raw plants, 12 labeled American ginseng functional foods, 5 notoginsengs, 5 Asian ginsengs, and 4 red ginsengs, were analyzed by this method. The results showed that five labeled American ginseng functional foods might have quality defects and six functional foods might be adulterated. This method can be applied to quality control and ginseng source assessment of American ginseng functional foods.     

Simulation of the migration of mineral oil from recycled paperboard into dry foods by Tenax®?

Conventional migration testing for long-term storage at ambient temperature with Tenax^® was applied to a recycled paperboard as well as to the same paperboard with a polyethylene or polypropylene film in between. Test conditions were from the European Union plastic Regulation 10/2011, that is, 10 days at 60°C, but previous standard conditions of 10 days at 40°C were also applied. The results were compared with the migration into real packs made of the same packaging material containing six test foods and stored over 9 months. For the direct contact, simulation at 60°C overestimated the maximum migration of the saturated hydrocarbons in the real packs by 73%. Simulation reflected hardly any effect by the plastic films and resulted in an overestimation of the maximum migration into the real packs by a factor of 5.1 and 27 for the polyethylene and the polypropylene film, respectively. Analogous simulation was performed with polenta (corn semolina) instead of Tenax^®. Three main causes for this deviation were identified: (i) at 60°C, migration reached beyond n-C₃₅, whereas it ends at about n-C₂₄ in reality. (ii) Tenax^® is a far stronger adsorbent than foods, resulting in almost complete extraction. (iii) The significant barrier effect of polypropylene films at ambient temperature is lost at increased temperature. The suitability of such simulation for the prediction of long-term migration is questioned.     

Diffusion behaviour of the acetaldehyde scavenger 2-aminobenzamide in polyethylene terephthalate for beverage bottles

Polyethylene terephthalate (PET) bottles are widely used as packaging material for natural mineral water. However, trace levels of acetaldehyde can migrate into natural mineral water during the shelf life and might influence the taste of the PET bottled water. 2-Aminobenzamide is widely used during PET bottle production as a scavenging agent for acetaldehyde. The aim of this study was the determination of the migration kinetics of 2-aminobenzamide into natural mineral water as well as into 20% ethanol. From the migration kinetics, the diffusion coefficients of 2-aminobenzamide in PET at 23 and 40°C were determined to be 4.2 × 10^?16 and 4.2 × 10^?15 cm² s^–1, respectively. The diffusion coefficient for 20% ethanol at 40°C was determined to be 7.7 × 10^?15 cm² s^–1, which indicates that 20% ethanol is causing swelling of the PET polymer. From a comparison of migration values between 23 and 40°C, acceleration factors of 9.7 when using water as contact medium and 18.1 for 20% ethanol as simulant can be derived for definition of appropriate accelerated test conditions at 40°C. The European Union regulatory acceleration test based on 80 kJ mol^–1 as conservative activation energy overestimates the experimentally determined acceleration rates by a factor of 1.6 and 3.1, respectively.     

Analysis of isophthalaldehyde in migration samples from polyethylene terephthalate packaging

In the present work, different pre-concentration strategies were evaluated for the analysis of isophthalaldehyde in migration samples from food packaging materials. This compound is a potential migrant in several copolymers used for food packaging, and since it is considered a non-intentionally added substance, its concentration in migration samples must be determined. Derivatisation was the first sample treatment evaluated. o-(2,3,4,5,6-Pentafluorobenzyl)hydroxylamine was tested as derivatisation agent, but no satisfactory results were obtained. Then, hollow-fibre liquid-phase microextraction (HF-LPME) and solid-phase microextraction were optimised. The HF-LPME method showed the highest sensitivity, achieving an enrichment factor of 60-fold. The limit of detection of the method was 10 ng g^?1, the limit of quantification was 30 ng g^?1 and the relative standard deviation was 6.1%. Finally, the method was applied to migration studies to evaluate the safety in use of a poly(ethylene terephthalate) packaging material. The content of isophthalaldehyde was determined in two aqueous food simulants: 10% ethanol (v/v) and 3% acetic acid (w/v). Different migration conditions were tested. The results obtained showed a considerable rise in the concentration of isophthalaldehyde when increasing the time and temperature of the migration experiment.     

Silver migration from nanosilver and a commercially available zeolite filler polyethylene composites to food simulants

Polyethylene composites containing Agion^TM commercial silver ion filler at three different percentage fill rates (0.5, 1.0 and 2% w/w) and polyethylene composites containing laboratory produced silver nanoparticles (Agnps) at two different percentage fill rates (0.1 and 0.5% w/w) underwent migration tests according to Commission Regulation (EU) No. 10/2011. Migrated silver in the two simulants (acidified water with 3% acetic acid and distilled water) was quantified using two techniques: inductively coupled atomic emission spectroscopy (ICPAES) and Hach Lange spectroscopy. The former had higher sensitivity with mean silver migration from Agion composites (n = 12) ranging from < 0.001 to 1.50 × 10^?2 mg l^–1. Mean silver migration from Agnps composites ranged from 4.65 × 10^?2 to 0.38 mg l^–1 and 8.92 × 10^?2 and 5.15 × 10^?2 mg l^–1 for Hach Lange spectrophotometry and ICPAES, respectively. Both percentage fill rate in the composite and the simulant type, as factors, were found to be significant in both silver migration from Agion (p < 0.0001 and < 0.01, respectively) and Agnps (p < 0.05 and < 0.01, respectively). Transmission electron microscopy (TEM) imagery showed differences in size distributions and morphology of particles (shape and degree of agglomeration) before and after migration. PE composites containing 0.5% Agion, simulating contact with non-acidic foods, was the only scenario that did not exceed the permitted migration level of non-authorised substances given in EU 10/2011. This study illustrates the need for careful engineering of the composite filler system to conform to limits with cognisance of food pH and percentage fill rate.