Flake formation and composition in soda-lime-silica and borosilicate glasses.

Glass is a food contact material that has been used for a long time in food packaging because it is chemically durable and stable. However, when used for a long time in an aqueous solution or under certain conditions in which alteration may occur, solid flakes may be formed. The phenomenon could be observed when the process of boiling water in a glass kettle is repeated. Transparent and shiny needle-shaped glass fragments appear floating in the water, which may cause complaints from consumers. The purpose of this study is to investigate the conditions leading to the formation of flakes and to identify the components of the suspended flakes in glass container. In this study we investigated the formation of flakes at different temperatures (70-100 °C), initial pH values (3-11) and varying the solution composition (with Na+, K+, Ca2+, Mg2+ concentrations from 0.2 to 40 mg/L). Two types of glass materials, soda-lime-silica glass and borosilicate glass (heat-resistance glass) were examined. Results show that flakes were observed under the following conditions: 24 h at more than 90 °C, pH 8, and 20 mg/L Ca2+ for soda-lime-silica glass and more than 100 °C, pH 11 for borosilicate glass. The component of flakes was identified as a mixture of hydrates of magnesium, calcium, and aluminum silicate analyzed by X-ray fluorescence spectroscopy, inductively coupled plasma-optical emission spectroscopy, and X-ray diffraction.

LC-MS/MS analysis of BADGE, NOGEs, and their derivatives migrated from food and beverage metal cans.

A simple and novel method based on liquid chromatography-tandem mass spectrometry (LC-MS/MS) was developed and validated to determine the levels of 10 compounds (bisphenol A diglycidyl ether (BADGE), novolac-glycidyl ethers (NOGEs), and their related compounds) migrated from food and beverage cans into food simulants. Method validation showed acceptable linearity, precision, and accuracy. The detection limits ranged from 0.28 to 14.8 µg L-1, and the quantification limits ranged from 0.94 to 49.3 µg L-1. Water, 4% acetic acid, 50% ethanol, and n-heptane were employed as food simulants for the migration tests, and the developed LC-MS/MS method was applied to 104 epoxy-coated beverage and food metal cans. Only BADGE∙2H2O and BADGE were detected; the levels were below the specific migration limit. Based on the obtained migration results, the estimated daily intakes (EDIs) of BADGE∙2H2O and BADGE were calculated. Exposure assessments were conducted to compare the EDI with the tolerable daily intake (TDI), with a relatively low percentage of the TDI being reported. NOGE and its related compounds were not detected in the monitored cans. Long-term storage tests were also conducted at 60°C over 30 days. Only BADGE∙2H2O was detected in all food simulants, except for n-heptane, and the maximum amount detected was 114.6 µg L-1 in 50% ethanol.

HS-GC/MS method development and exposure assessment of volatile organic compounds from food packaging into food simulants.

A simultaneous headspace-gas chromatography/mass spectrometry (HS-GC/MS) method was developed and validated to determine the migration of 12 volatile organic compounds (methanol, acetone, methylethylketone, ethylacetate, isopropylalcohol, benzene, toluene, ethylbenzene, xylene, cumene, propylbenzene, and styrene) from food contact materials into food simulants (water, 4% acetic acid, 50% ethanol, and n-heptane). The limits of detection and quantification were 0.007-0.201 mg L-1 and 0.023-0.668 mg L-1, respectively. The method was applied to 205 samples of paper/paperboard, polyethylene, polypropylene, polystyrene, and polyethylene terephthalate. The estimated daily intake (EDI) was calculated using the migration results. Exposure assessments were carried out to compare the EDI to the tolerable daily intake (TDI); the results indicated that the EDI of styrene represented only a small percentage (8.0%) of the TDI. This analytical method will be a useful tool to examine levels of various volatile compounds migrating from food packaging to food simulants using HS-GC/MS method.

Migration of lead and arsenic from food contact paper into a food simulant and assessment of their consumer exposure safety.

Paper is one of the most commonly used food packaging materials. During the production of packaging paper, it is possible for trace amounts of heavy metals to be incorporated as contaminants. These could migrate into food when packaging paper (food contact paper) is used for cooking, storing and eating. The aim of this study was to determine the migration of lead (Pb) and arsenic (As) from food contact paper into a food simulant and then to assess human safety through the estimated daily intake (EDI) with consumption factor. Migration tests were conducted for 310 samples using 4% acetic acid as a food simulant at 25°C for 10 min and at 95°C for 30 min. Concentrations of Pb and As in a food simulant were quantified by inductively coupled plasma mass spectrometry. LODs for Pb and As were 0.002 and 0.005 µg L-1, respectively. The migration of Pb from food contact paper ranged from not detected (ND) to 17.5 µg L-1 at 25°C for 10 min and from 0.10 to 25.6 µg L-1 at 95°C for 30 min while As ranged from ND to 0.44 µg L-1 at 25°C for 10 min and from ND to 0.87 µg L-1 at 95°C for 30 min. The migration of Pb and As determined in this study confirm that the human exposure was within safe levels based on the EDI of food contact paper compared with the provisional tolerable weekly intake for Pb of 25 µg kg-1 bw and for As of 15 µg kg-1 bw.

Migration study of caprolactam from polyamide 6 sheets into food simulants.

Caprolactam, used in manufacturing polyamide (PA) 6, may threaten human health. Here, PA 6 sheets were produced by using a twin-screw extruder to evaluate its safety. Caprolactam migration concentrations from the PA 6 sheets into food simulants were evaluated according to the standard migration test conditions under the Korean Food Standards Codex (KFSC). Concentrations were investigated under various food simulants (distilled water, 4% acetic acid, 20 and 50% ethanol, and heptane) and storage conditions (at 25, 60, and 95 °C). Caprolactam migration concentrations into food simulants were determined as follows: 4% acetic acid (0.982 mg/L), distilled water (0.851 mg/L), 50% ethanol (0.624 mg/L), 20% ethanol (0.328 mg/L), and n-heptane (not detected). Migrations were determined to be under the regulatory concentration (15 mg/L) according to the KFSC test conditions. Taken together, these results verified that the standard migration test conditions by KFSC were reliable to evaluate the safety of PA 6.

Release of N-nitrosamines and N-nitrosatable substances from baby bottle teats and rubber kitchen tools in Korea.

Ensuring the safety of baby bottle teats and kitchen tools made from rubber is critical. Therefore, the migration of N-nitrosamines and N-nitrosatable substances from 30 teats and 45 kitchen tools to artificial saliva was analyzed by liquid chromatography-tandem mass spectrometry. The method was validated by assessing the limits of detection (0.46-3.87 µg/kg), limits of quantification (1.38-11.73 µg/kg), and recoveries (86.3-108.6%) of seven compounds. Nitrosodimethylamine (NDMA), N-nitrosopiperidine, and N-nitrosomorpholine (NMOR) migrated from baby bottle teats at concentrations of not detected (ND) to 3.67 µg/kg. NDMA and NMOR concentrations ranged from ND to 1.72 µg/kg after migration from 45 rubber kitchen tools. N-nitrosatable substances ranged from ND to 42.16 µg/kg after migration from baby bottle teats but did not migrate from rubber kitchen tools. All tested products were considered safe for use, as N-nitrosamine and N-nitrosatable substance levels did not exceed the permitted management specifications.

Simultaneous analysis and exposure assessment of migrated bisphenol analogues, phenol, and p-tert-butylphenol from food contact materials.

A simple, rapid, and novel liquid chromatography tandem-mass spectrometry (LC-MS/MS) method was developed and validated to determine levels of eight bisphenol analogues (A, S, F, B, P, AF, AP, and Z), phenol, and p-tert-butylphenol migrated from food contact material (FCM) into food simulants. Method validation showed acceptable values in terms of linearity, precision, and accuracy. The limits of detection and quantification were 0.53-29.6 and 1.77-29.6 µg L-1, respectively. Water, 4% acetic acid, 50% ethanol, and n-heptane were employed as food simulants for the migration tests, and the proposed method was applied to 234 articles of 11 FCMs including polycarbonate, polyethersulfone, polypropylene, and polyethyleneterephthalate, obtained from domestic markets and manufacturers in Korea. Only phenol was found in the FCMs poly(cyclophexane-1,4-dimethylene terephthalate), polylactide, and thermoplastic polyurethane. Eight bisphenol analogues and p-tert-butyl phenol were not found in any samples. Using the obtained migration results, the estimated daily intake (EDI) of phenol was calculated. Exposure assessments were carried out to compare the EDI with the tolerable daily intake (TDI), showing a low percentage (0.18%) of the TDI reported. This is the first study to examine eight bisphenol analogues and two phenols simultaneously in FCMs using the LC-MS/MS.

Perfluorinated compounds in food simulants after migration from fluorocarbon resin-coated frying pans, baking utensils, and non-stick baking papers on the Korean market.

Perfluorinated compounds (PFCs) are used in manufacturing food contact materials, including non-stick cookware coatings and oil- and moisture-resistant paper coatings. The chemical stability of PFCs poses an issue for human safety, as they do not degrade well naturally and hence may accumulate in the body. In terms of food safety, since dietary intake is thought to be a major source of exposure to PFCs, it is necessary to assess the migration of PFCs from food packaging articles to food under typical cooking and storage conditions. An analytical method was developed for assessing the migration of 16 PFCs from food contact materials to food simulants using liquid chromatography-tandem mass spectrometry. The applicability of the method for regular inspection was assessed by monitoring 312 samples. Based on the results of the exposure assessment, all food contact materials deemed to be safe for use, which evaluated migrated concentrations and dietary food intake.

Fast and simple determination and exposure assessment of bisphenol A, phenol, p-tert-butylphenol, and diphenylcarbonate transferred from polycarbonate food-contact materials to food simulants.

Polycarbonate (PC) plastics find extensive use in baby bottles, food storage containers, and various kitchen items. Possibly hazardous chemicals, bisphenol A (BPA), phenol, p-tert-butylphenol (TBP), and diphenylcarbonate (DPC), are source materials or by-products from PC production. Therefore, a fast and simple analytical method was developed to determine and assess the exposure of BPA, phenol, TBP, and DPC transferred from PC food-contact materials to four different food simulants (water, 4% acetic acid, 50% ethanol, and n-heptane) at different temperatures. The method was validated in terms of limit of detection (LOD) and quantification (LOQ), recovery, and precision for the detection of BPA, phenol, and TBP using HPLC-FLD and of DPC using HPLC-UV. BPA, phenol, TBP, and DPC concentrations transferred from 200 PC samples to food simulants were determined. The highest migration levels of BPA (54.3 µg L-1) and phenol (43.8 µg L-1) were found in 50% ethanol at 70 °C. TBP did not migrate to any simulant. DPC did not show any migration from PC samples into water and only migrated from a cup to 4% acetic acid at 70 °C and 100 °C, whereas migration occurred from several cups, ladles, spoons, and tongs to 50% ethanol and to n-heptane at 25 °C. Food simulants and temperature were the crucial factors for the migration of BPA and phenol from PC samples. Estimated daily intakes (EDIs), based on food consumption and food-type distribution factors, for BPA, phenol, and DPC were calculated to be 0.007, 0.001, and 2.5 × 10-4 µg kg-1 bw day-1, respectively.

Migration Study of Butylated Hydroxytoluene and Irganox 1010 from Polypropylene Treated with Severe Processing Conditions.

Safety concerns have emerged over the increased use of polypropylene (PP) in food-packaging markets. Some antioxidants in PP can migrate to foods and cause undesirable effects in humans. In this study, migration behaviors of butylated hydroxytoluene (BHT) and Irganox 1010 (I-1010) in PP sheets were determined according to the US FDA migration test conditions. In particular, we tested the effects of severe conditions of food processing and storage, such as autoclave heating (sterilization at about 121 °C), microwave radiation (700 W), and deep freezing (-30 °C) on migration of antioxidants. Migrant concentrations were higher in 95% ethanol as lipid food simulant, because of the hydrophobic nature of both PP and antioxidants. Autoclave heating treatment increased migrant concentrations compared with other processing conditions. Moreover, increased migrant concentrations by deep freezing condition were attributed to the brittleness of PP at freezing temperature. Regardless of processing conditions, BHT which has a lower molecular weight, migrated faster than I-1010. PRACTICAL APPLICATION: The antioxidants with hydrophobic nature such as butylated hydroxytoluene (BHT) and Irganox 1010 (I-1010) in polypropylene sheets would be migrated to foods, which is an important issue for industrial production food packaging materials. Migration behavior was promoted by severe processing conditions such as autoclave heating, microwave radiation, freezing, and especially autoclave heating treatment led the highest migration among them. Therefore, control of chemical additive migration from polypropylene food packaging is needed for safe food processing.

Potential silver nanoparticles migration from commercially available polymeric baby products into food simulants.

In recent years, silver nanoparticles (AgNPs) have been extensively employed in food packaging systems as a potential antibacterial agent. Although proven to be highly effective, the increased number of AgNP-containing products raises concerns among consumers regarding the migration of AgNPs from the packaging material into foods, which may exert toxic effects. To address this, five baby products were chosen (baby bottle A, baby bottle B, pacifier A, pacifier B and breastmilk storage bag) to investigate AgNPs migration into three food simulants (deionised water, 4% acetic acid (w/v) and 50% ethanol (v/v)) using inductively coupled plasma mass spectrometry (ICP-MS). As a result, the highest level of migrated Ag was observed for 4% acetic acid in the case of baby bottle B, pacifier A, pacifier B and the breastmilk storage bag, with the detection amount ranging from 1.05-2.25 ng/mL. On the other hand, baby bottle A showed the maximum migration for 50% ethanol due to the polymer nature. Finally, a centrifugal ultrafiltration experiment was conducted to determine the fraction of dissolved Ag in acidic simulant and it was found that migrated Ag was predominantly in Ag+ form, with a small fraction of non-ionic AgNPs. Thus, it has been found that the amount of migrated Ag in baby products was low; however, the migration was dependent on the type of food simulant and polymer nature.