Perfluorochemicals are widely used in the manufacturing and processing of a vast array of consumer goods, including electrical wiring, clothing, household and automotive products. Furthermore, relatively small quantities of perfluorochemicals are also used in the manufacturing of food-contact substances that represent potential sources of oral exposure to these chemicals. The most recognizable products to consumers are the uses of perfluorochemicals in non-stick coatings (polytetrafluoroethylene (PTFE)) for cookware and also their use in paper coatings for oil and moisture resistance. Recent epidemiology studies have demonstrated the presence of two particular perfluorochemicals, perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) in human serum at very low part per billion levels. These perfluorochemicals are biopersistent and are the subject of numerous studies investigating the many possible sources of human exposure. Among the various uses of these two chemicals, PFOS is a residual impurity in some paper coatings used for food contact and PFOA is a processing aid in the manufacture of PTFE used for many purposes including non-stick cookware. Little information is available on the types of perfluorochemicals that have the potential to migrate from perfluoro coatings into food. One obstacle to studying migration is the difficulty in measuring perfluorochemicals by routine conventional analytical techniques such as GC/MS or LC-UV. Many perfluorochemicals used in food-contact substances are not detectable by these conventional methods. As liquid chromatography-mass spectrometry (LC/MS) develops into a routine analytical technique, potential migrants from perfluoro coatings can be more easily characterized. In this paper, data will be presented on the types of perfluoro chemicals that are used in food packaging and cookware. Additionally, research will be presented on the migration or potential for migration of these chemicals into foods or food simulating liquids. Results from migration tests show mg kg À1 amounts of perfluoro paper additives/coatings transfer to food oil. Analysis of PTFE cookware shows residual amounts of PFOA in the low mg kg À1 range. PFOA is present in microwave popcorn bag paper at amounts as high as 300 mg kg À1.

Materials and articles intended to come into contact with food must be shown to be safe because they might interact with food during processing, storage and the transportation of foodstuffs. Framework Directive 89/109/EEC and its related specific Directives provide this safety basis for the protection of the consumer against inadmissible chemical contamination from food-contact materials. Recently, the European Commission charged an international group of experts to demonstrate that migration modelling can be regarded as a valid and reliable tool to calculate 'reasonable worst-case' migration rates from the most important food-contact plastics into the European Union official food simulants. The paper summarizes the main steps followed to build up and validate a migration estimation model that can be used, for a series of plastic food-contact materials and migrants, for regulatory purposes. Analytical solutions of the diffusion equation in conjunction with an 'upper limit' equation for the migrant diffusion coefficient, D P , and the use of 'worst case' partitioning coefficients K P,F were used in the migration model. The results obtained were then validated, at a confidence level of 95%, by comparison with the available experimental evidence. The successful accomplishment of the goals of this project is reflected by the fact that in Directive 2002/72/EC, the European Commission included the mathematical modelling as an alternative tool to determine migration rates for compliance purposes.

Fluorochemical-treated paper was tested to determine the amount of migration that occurs into foods and food-simulating liquids and the characteristics of the migration. Migration characteristics of fluorochemicals from paper were examined in Miglyol, butter, water, vinegar, water-ethanol solutions, emulsions and pure oil containing small amounts of emulsifiers. Additionally, microwave popcorn and chocolate spread were used to investigate migration. Results indicate that fluorochemicals paper additives do migrate to food during actual package use. For example, we found that microwave popcorn contained 3.2 fluorochemical mg kg(-1) popcorn after popping and butter contained 0.1 mg kg(-1) after 40 days at 4 degrees C. Tests also indicate that common food-simulating liquids for migration testing and package material evaluation might not provide an accurate indication of the amount of fluorochemical that actually migrates to food. Tests show that oil containing small amounts of an emulsifier can significantly enhance migration of a fluorochemical from paper.

Bisphenol-A (BPA) is a principal reactant in the preparation of polycarbonate (PC) plastics and has been shown in in vitro cell proliferation studies to exhibit estrogen-like characteristics. Reusable baby bottles, water carboys, and other housewares are often made of PC. A high-pressure liquid chromatographic (HPLC) protocol was used to determine residual BPA in PC and BPA migrated to food simulants in contact with PC under controlled time/temperature conditions. Confirmation of BPA was performed by gas chromatography/mass spectrometry (GC−MS). Residual amounts of BPA found in PC food contact articles ranged from 7 to 58 μg/g. In migration tests the plastic was exposed to water, ethanol/water mixtures, and Miglyol (a food oil simulant) in sealed vials at a constant temperature of 65 °C, for up to 10 days. BPA in food simulants ranged from 13 to 368% of BPA available to migrate from the polymer. GC−MS methods were applied to the analysis of water stored in reusable PC 5-gal water carboys. The amount of BPA found in the water ranged from ND to 5 ppb. Keywords: Bisphenol-A; polycarbonate; migration; baby bottles; hydrolysis

Metal food and drink cans are commonly coated with epoxy films made from phenolic polymers produced from bisphenol A (BPA). It is well established that residual BPA monomer migrates into can contents during processing and storage. While a number of studies have reported BPA concentrations in foods from foreign markets and specialty foods on the U.S. market, very few peer-reviewed data for the BPA concentrations in canned food from the U.S. market were available. This study quantified BPA concentrations in 78 canned and two frozen food products from the U.S. market using an adaptation of a previously reported liquid chromatography-tandem mass spectrometry method. The tested products represented 16 different food types that are from the can food classifications that constitute approximately 65% of U.S. canned food sales and canned food consumption. BPA was detected in 71 of the 78 canned food samples but was not detected in either of the two frozen food samples. Detectable BPA concentrations across all foods ranged from 2.6 to 730 ng/g. Large variations in BPA concentrations were found between different products of the same food type and between different lots of the same product. Given the large concentration ranges, the only distinguishable trend was that fruits and tuna showed the lowest BPA concentrations. Experiments with fortified frozen vegetables and brine solutions, as well as higher BPA concentrations in canned food solids over liquid portions, clearly indicated that BPA partitions into the solid portion of foods.

Investigations into the biodegradation potential of perfluorooctane sulfonate (PFOS)-precursor candidates have focused on low molecular weight substances (e.g., N-ethyl perfluorooctane sulfonamido ethanol (EtFOSE)) in wastewater treatment plant sludge. Few data are available on PFOS-precursor biodegradation in other environmental compartments, and nothing is known about the stability of high-molecular-weight perfluorooctane sulfonamide-based substances such as the EtFOSE-based phosphate diester (SAmPAP diester) in any environmental compartment. In the present work, the biodegradation potential of SAmPAP diester and EtFOSE by bacteria in marine sediments was evaluated over 120 days at 4 and 25 °C. At both temperatures, EtFOSE was transformed to a suite of products, including N-ethyl perfluorooctane sulfonamidoacetate, perfluorooctane sulfonamidoacetate, N-ethyl perfluorooctane sulfonamide, perfluorooctane sulfonamide, and perfluorooctane sulfonate. Transformation was significantly more rapid at 25 °C (t(1/2) = 44 ± 3.4 days; error represents standard error of the mean (SEM)) compared to 4 °C (t(1/2) = 160 ± 17 days), but much longer than previous biodegradation studies involving EtFOSE in sludge (t(1/2) ∼0.7-4.2 days). In contrast, SAmPAP diester was highly recalcitrant to microbial degradation, with negligible loss and/or associated product formation observed after 120 days at both temperatures, and an estimated half-life of >380 days at 25 °C (estimated using the lower bounds 95% confidence interval of the slope). We hypothesize that the hydrophobicity of SAmPAP diester reduces its bioavailability, thus limiting biotransformation by bacteria in sediments. The lengthy biodegradation half-life of EtFOSE and recalcitrant nature of SAmPAP diester in part explains the elevated concentrations of PFOS-precursors observed in urban marine sediments from Canada, Japan, and the U.S, over a decade after phase-out of their production and commercial application in these countries.

Migration of bisphenol A (BPA) from epoxy-coated can surfaces to infant formula concentrates is reported. Levels of BPA in the undiluted concentrates surveyed in this study range from 0.1 to 13 parts per billion (ppb) as determined by solid phase extraction/high-pressure liquid chromatography with fluorescence detection and confirmation by gas chromatography with mass selective detection. Fourier transform infrared spectroscopy with 30° specular reflectance/transmittance was used to screen formula cans for epoxy coatings. Keywords: Bisphenol A; epoxy; can coating; migration; infant formula

Fatty acid esters of 3-monochloropropanediol (3-MCPD) and glycidol are processing contaminants found in a wide range of edible oils. While both 3 MCPD and glycidol have toxicological properties that at present has concerns for food safety, the published occurrence data are limited. Occurrence information is presented for the concentrations of 3-MCPD and glycidyl esters in 116 retail and/or industrial edible oils and fats using LC-MS/MS analysis of intact esters. The concentrations for bound 3-MCPD ranged from below the limit of quantitation (