Effects of gamma- and electron-beam irradiation on semi-rigid amorphous polyethylene terephthalate copolymers.

Two semi-rigid amorphous polyethylene terephthalate copolymer materials (in both sheet and powder forms) containing 3% 1,4-cyclohexane dimethanol (CHDM) and 31% CHDM were irradiated at 5, 25 and 50 kGy at ambient temperature with a (60)Co radiator or an electron-beam accelerator. After irradiation, volatiles were determined using static headspace sampling with capillary gas chromatography and mass selective detection or flame ionization detection (HS/GC/MSD or FID). Non-volatiles were extracted with 10% aqueous ethanol and 100% n-heptane food-simulating solvents, maintained at 40 degrees C for up to 10 days. The non-volatiles in the materials and those migrating into the food-simulating solvents were determined by high-performance liquid chromatography (HPLC) with ultraviolet and/or photodiode array detection. The results obtained from the HS/GC/MSD suggest that no new chemicals were detected by either gamma- or e-beam irradiation when compared with non-irradiated specimens. The major volatiles in the copolymers were acetaldehyde and 2-methyl-1,3-dioxolane. The concentrations of acetaldehyde increased from 1.24-1.96 mg kg(-1) to 1.94-3.65, 3.52-7.23 and 5.45-15.37 mg kg(-1) after exposure to 5, 25 and 50 kGy doses, respectively. The concentrations of 2-methyl-1,3-dioxolane decreased from 2.49-5.26 mg kg(-1) to 2.07-3.13, 1.33-2.14 and 0.64-2.24 mg kg(-1) after exposure to 5, 25 and 50 kGy doses, respectively. The results of analysis of the copolymers for non-volatiles show that irradiation did not produce any new detectable non-volatile chemicals. A 5 kGy dose had no detectable effect on either copolymer. The 25 and 50 kGy doses had slightly different effects with respect to gamma- and e-beam irradiation on low MW oligomers. However, these increased doses did not significantly affect migration. The concentration of most low molecular weight oligomers migrating into 10% ethanol and 100% heptane was < or =2 ng g(-1) of each oligomer for both copolymers. The cyclic trimer migrating from the 3% CHDM copolymer was approximately 4 ng g(-1); it was 3 ng g(-1) for the 31% CHDM copolymer. The overall results suggest that irradiation significantly increased levels of acetaldehyde but had no effect on non-volatile compounds migrating into food simulants.

Evaluating the potential for recycling all PET bottles into new food packaging.

To evaluate the feasibility of recycling all PET bottles into food packaging, realistic estimates of the maximum concentration of contaminants that might be expected in the polymer are needed. To estimate the maximum concentration of a contaminant that might be in PET from the storage of non-food substances, sorption experiments into two types of PET were performed. These test materials were 0.8mm thick amorphous PET (a relative sink for contaminants) and commercial PET bottle wall. Using a commercial shampoo containing 1% lindane (C6H6Cl6), the test materials were stored in contact with the shampoo at 20 and 40 degrees C for 231 days. This commercial shampoo also represents an extreme case because it contains 7% acetone, a solvent which swells PET, further enhancing sorption of chemicals. Additional sorption experiments into PET were performed by preparing solutions of 10% toluene in Miglyol (a fractionated coconut oil), 10% benzophenone in Miglyol, 5% 2-butoxyethoxy ethanol (2-BE) in 50/50 water/ethanol, and 10% methyl stearate in heptane. Sorption data from the shampoo into PET illustrate Fickian behaviour. Specifically, the amount of sorption at room temperature is approximately40 times less than that at 40 degrees C. The amount of lindane sorbed into PET from the shampoo after 231 days was 0.1 and 3.7 mgdm(-2) at 20 and 40 degrees C respectively. These values correspond to 28 and 765 mg kg(-1) on a mass/mass basis. All sorptions are within the ranges measured and published by other authors using surrogate contamination testing schemes. Additionally, actual bottles from recycle bins were analysed for the amout of contamination. Results are discussed in terms of potential consumer exposure to non-food contaminants in food containers made of recycled PET and in relation to the surrogate testing methods recommended by the Food and Drug Administration (FDA) for determining the compatibility of a PET recycling process to produce containers suitable for food-contact use.

Volatile and non-volatile compounds in irradiated semi-rigid crystalline poly(ethylene terephthalate) polymers.

In this study two different semi-rigid crystalline and oriented polyethylene terephthalate materials were used and were irradiated at 25-kGy dose at room temperature by using a caesium137 radiator. Volatile and non-volatile compounds present in the irradiated materials were identified and quantified. The qualitative results obtained from HS/GC/TCD/FID analysis at room temperature showed volatiles could not be identified. The HS/GC/MSD analysis performed at 106 degrees C showed that the irradiation generated 668-742 micrograms/kg formic acid, 868-922 micrograms/kg acetic acid, 17-32 micrograms/kg 1,3-dioxolane, and 47-71 micrograms/kg 2-methyl-1, 3-dioxolane based on PET weight. The results obtained from the thermal desorption and GC/MSD performed at 200 degrees C showed that 10-12 mg/kg acetaldehyde, 479-975 micrograms/kg 1,3-dioxolane, and 6.6-11.2 mg/kg methyl-1, 3-dioxolane were detected after irradiation. The concentrations of the two dioxolanes found from thermal desorption were much higher than those observed in the HS, although formic and acetic acids were not detected. It is possible that the formic and acetic acids produced by irradiation underwent further reactions with ethylene glycol during thermal desorption to form the dioxolanes. The soluble solid extracted from various PET specimens before and after irradiation were in a range of 0.67-0.78%. PET cyclic trimer is the major component and is present at 0.41-0.50%, accounting for more than 50% of the percent total solid in PET. Statistically, irradiation did not increase the soluble solid and cyclic trimer. The overall results suggest that 25-kGy irradiation had a significant effect on increasing the volatile but not the non-volatile compounds detected in the PET specimens.

Determination of the diglycidyl ether of bisphenol A and its derivatives in canned foods.

Migration of the diglycidyl ether of bisphenol A (DGEBA) to food from can enamels and can pull-top seals is reported. Derivatives of DGEBA are also determined in some foods. Levels of DGEBA in the foods surveyed in this study range from nondetected (<0.3 ppb) to 50 mg/kg as determined by liquid-liquid extraction or solid-phase extraction coupled with high-pressure liquid chromatography using fluorescence detection. Confirmation of the analytes is by gas and/or liquid chromatography with mass spectral analysis. Fourier transform infrared spectroscopy with 30 degrees specular reflectance/transmittance is used to characterize the coated food contact surfaces. Stability studies with DGEBA in water, acid, and saline solutions show conversion to the hydrolysis products and chloro adducts occurs readily. The presence of DGEBA derivatives in food demonstrates that analysis for DGEBA migration alone is not a good indicator of total migration from can coatings to foods.

Searching for conscientiousness on the MMPI-2.

It has been argued that the revised Minnesota Multiphasic Personality Inventory (MMPI-2) fails to measure the Big Five dimension of conscientiousness (C) an assertion supported by the research finding that none of the factors underlying the MMPI correlate substantially with the C factor of the NEO Personality Inventory (NEO-PI)-a popular operationalization of the Big Five model. In this study we reconsidered the relationship between the MMPI-2 item pool and the C factor of the NEO-PI-R (Form S). Collections of MMPI-2 C markers did not correlate much higher than .5 with the NEO-PI-R factor scale in cross-validation hold-out samples. Most pervasive, however, was the finding that MMPI-2 item markers of C were also strongly (in many cases, more highly) related to the NEO-PI-R factor of neuroticism (N). Efforts to purify collections of MMPI-2 C markers, first by careful item selection and then by suppression of N variance, were met with limited success. Intercorrelations among NEO-PI-R scales suggest that the difficulty in finding markers that discriminate between N and C extends beyond any shortcomings of the MMPI-2 item pool.

Survey of trihalomethanes and other volatile chemical contaminants in processed foods by purge-and-trap capillary gas chromatography with mass selective detection.

A limited number of soft drinks, juices, beers, and waters from processed vegetables were analyzed for trihalomethanes (THMs), benzene, and toluene by a modified Environmental Protection Agency (EPA) Method 524.2. The THMs, which include chloroform, bromodichloromethane, dibromochloromethane, and bromoform, are reaction by-products of water disinfection by chlorination. EPA Method 524.2 is a purge-and-trap capillary gas chromatographic method based on mass spectrometric detection which identifies and simultaneously measures purgeable volatile organic compounds in drinking water. Chloroform was present at concentrations ranging from none detected to 94 ng/g in the 44 foods analyzed. Bromoform was not found in any of the products at a detection limit of 0.1 ng/g. Residue levels of the other THMs ranged from none detected to highs of 12 and 2 ng/g for bromodichloromethane and dibromochloromethane, respectively. Benzene residues were typically < 5 ng/g, except for 7 and 9 ng/g in 2 foods. Toluene residues were typically < or = 3 ng/g except for 23, 29, and 75 ng/g in 3 canned foods.

Survey of benzene in foods by using headspace concentration techniques and capillary gas chromatography.

Recently, the combination of sodium or potassium benzoate with ascorbic acid was shown to produce low levels (ng/g) of benzene in fruit-flavored soft drinks. The presence of benzene also was reported in butter, eggs, meat, and certain fruits; levels of these findings ranged from 0.5 ng/g in butter to 500-1900 ng/g in eggs. Because benzoates are widely used as food preservatives, a limited survey of other foods containing added benzoate salts was conducted to investigate the potential for benzene formation. Selected foods that did not contain added benzoates but were previously reported to contain benzene were analyzed for comparison. More than 50 foods were analyzed by purge-and-trap or static headspace concentration and capillary gas chromatography. Benzene was quantitated by using the method of standard additions, and its identity was confirmed by mass selective detection. Results of this limited survey show that foods without added benzoates (including eggs) contained benzene at levels equal to or less than 2 ng/g. Slightly higher levels were present in some foods and beverages containing both ascorbic acid and sodium benzoate.

Determination of volatile chemicals released from microwave-heat-susceptor food packaging.

Microwave heat susceptors that convert electromagnetic energy to heat attain high temperatures that make it possible to cook some foods to golden crispness in a microwave oven. Susceptors are typically packaged with foods intended for microwave use, e.g., waffles, pizzas, and french fries. The high temperatures > 302 degrees F used to cook some foods release trace levels of volatile chemicals from metalized polyester film, adhesive, and paper packaging materials; these volatile chemicals may be absorbed by the food. We simulated microwave susceptor cooking conditions and developed protocols by using headspace concentration capillary gas chromatography and mass spectrometry to identify volatile chemicals released from heated susceptors. We purchased a limited, cross-sectional sample of local retail microwave food products packaged with susceptors and used our protocol to analyze 10 different susceptor products. Although more than 140 unique chromatographic peaks were tabulated, only 44 volatile chemicals were identified, including 1,1,1-trichloroethane, benzene, and 2-(2-butoxyethoxy)ethanol, which were derived primarily from the paper and adhesive susceptor components. No one susceptor contained all the identified substances. The standard additions technique was the preferred method for quantitation. Trichloroethane and 2-(2-butoxyethoxy)ethanol were present in several products at 75-122 micrograms/in.2 of susceptor surface area. Benzene was found in 3 susceptors at < or = 0.22 microgram/in.2 levels. Examination indicates that adhesives used in more recent susceptor products were reformulated to remove even this trace level of benzene.

Quantitative multiresidue analyses for volatile organics in water and milk, using a fused silica open-tubular wide-bore capillary column and automated headspace gas chromatography.

A modified multiresidue capillary gas chromatographic (GC) procedure has been developed using automated headspace sampling and a wide-bore fused silica open-tubular (FSOT) capillary column for the determination of volatiles in water and milk. Compounds are quantitated by the method of standard additions. An IBM System 9000 computer with the CAPMC3 chromatographic applications package and a BASIC linear regression program are used for data reduction. Data are presented for solutions prepared by fortifying water and milk with volatile solvents such as acetone, methyl ethyl ketone, benzene, methylene chloride, and chloroform, which are commonly used in the manufacture of packaging materials and adhesives. The wide-bore FSOT capillary columns showed dramatically improved detection for certain compounds, compared with normal-bore capillary GC columns. Data presented for various chemicals demonstrate the improved limits of detection from the use of automated headspace gas chromatography with wide-bore capillary columns and flame ionization detection.

Headspace gas chromatographic determination of residual 1,3-butadiene in rubber-modified plastics and its migration from plastic containers into selected foods.

A headspace gas chromatographic procedure has been developed for the determination of 1,3-butadiene in rubber-modified plastics and in some foods. Polymer solutions or foods are equilibrated in sealed vials at 90 degrees C, and headspace samples are injected into a gas chromatograph. 1,3-Butadiene residues are measured using a flame ionization detector and are quantitated by the method of standard additions or an external calibration curve. Refrigerator tubs, vegetable oil bottles, chewing gum, and foods in contact with this type of packaging were analyzed. Limits of quantitation varied with the matrix, ranging from 2 ng/g (ppb) in chewing gum to 20 ng/g in polymers. 1,3-Butadiene was found in one polymer at 53 ng/g with an 8% coefficient of variation. The procedure yields "apparent" trace levels of 1,3-butadiene, and confirmation by a complementary technique is required.

Gas-solid chromatographic procedures for determining acrylonitrile monomer in acrylonitrile-containing polymers and food simulating solvents.

A gas chromatographic method is described for acrylonitrile monometer (AN), using a nitrogen/phosphorus detector. Procedure for the analysis of AN in 5 food simulants (water, 3% acetic acid, heptane, 50% ethanol, and 8% ethanol) as well as in the polymer matrix are included. The quantitation limit for direct injection of AN/food simulant solution is 0.04 ng AN/microliter. AN-based polymers are dissolved in N,N-dimethylacetamide and injected directly. Residual AN in the polymer can be quantitated at the 0.5 ng/microliter level. Results of migration studies are also presented.