Effect of high pressure processing on migration characteristics of polypropylene used in food contact materials.

The migration of small molecular mass organic compounds from polypropylene (PP) copolymer films into food simulants during and after high pressure processing (HPP) was studied. An overlapping temperature profile was developed to isolate the pressure effect of HPP (700 MPa, 71°C, 5 min) from equivalent thermal processing (TP) at atmospheric pressure (0.1 MPa). Chloroform, toluene, methyl salicylate, and phenylcyclohexane were chosen as surrogate compounds, and were spiked into test polymer films at concentrations of 762-1152 mg kg-1 by a solvent soaking technique. Migration (w/w) of surrogate compounds from loaded PP films into Miglyol 812 (a medium-chain triglyceride mixture) and 10% ethanol was quantified by headspace GC/MS during HPP and TP, and subsequent storage at 25°C for up to 10 days. HPP significantly delayed migration of the surrogates from PP into both food simulants relative to TP. The average migrations into Miglyol after TP and HPP were 92.2-109% and 16-60.6%, respectively. Diffusion coefficients estimated by migration modelling showed a reduction of more than two orders of magnitude for all surrogate compounds under high pressure at 700 MPa (AP' = 8.0) relative to equivalent TP at 0.1 MPa (AP' = 13.1). The relative Tg increase of PP copolymer under compression at 700 MPa was estimated as Tg+94°C. For 10% ethanol, average migrations after TP and HPP were 9.3-50.9% and 8.6-22.8%, respectively. During extended storage, migration into both simulants from HPP-treated samples was initially slower than that from untreated or TP-treated films. However, after 8-24 hours of storage, the differences in percent migration of selected surrogates were not significant (p > .05) among the treated PP films. Therefore, the physical changes of PP films that occur during HPP appear to be reversible with a return to their original dimensions and diffusion properties after decompression.

Arsenic speciation in rice cereals for infants.

The aim of this study was to conduct a survey of arsenic (As) content in rice cereals for infants. The analysis was based on the FDA Elemental Analysis Manual (EAM 4.11). An inductively coupled plasma mass spectrometer (ICP-MS) was used to determine total As. Due to the different toxicities of the chemical forms of arsenic, the ICP-MS coupled to a high-performance liquid chromatograph (HPLC) was used to perform As speciation. The total and speciated arsenic was determined in 31 different infant rice cereals sold in U.S. supermarkets. The mass fraction of total inorganic As (iAs; sum of arsenite As(III) and arsenate As(V)) concentrations ranged between 55.5 ± 1.3 and 158.0 ± 6.0 µg/kg. The average total arsenic and iAs concentrations in infant rice cereal were 174.4 and 101.4 µg/kg, respectively. There was no substantial difference in iAs levels between organic and conventional rice cereals. The mixed-grain rice cereal contained the least total (105 µg/kg) and inorganic arsenic (63 µg/kg). The major detected organoarsenical species was dimethylarsinic acid (DMA). Monomethylarsonic acid (MMA) was not detected, or only trace levels were found. Spiked sample percent recoveries for iAs, DMA, and MMA ranged from a low of 97.3% for iAs to a high of 115.0% for DMA. Results for speciated and total As in the National Institute of Standards and Technology standard reference material rice flour (NIST SRM 1568) were in good agreement with certified values. In the NIST SRM 1568 sample (n = 5) repeatability (%RSD) was 2.8% for iAs, 1.7% for DMA and species sum, and 5.3% for the total arsenic by As total method. The average percent mass balance was 99.9 ± 6.3% for the NIST SRM 1568 sample. This study provides new and much needed information on arsenic levels in rice-based infant cereals.

Static liquid permeation cell method for determining the migration parameters of low molecular weight organic compounds in polyethylene terephthalate.

The migration of low molecular weight organic compounds through polyethylene terephthalate (PET) films was determined by using a custom permeation cell assembly. Fatty food simulant (Miglyol 812) was added to the receptor chamber, while the donor chamber was filled with 1% and 10% (v/v) migrant compounds spiked in simulant. The permeation cell was maintained at 40°C, 66°C, 100°C or 121°C for up to 25 days of polymer film exposure time. Migrants in Miglyol were directly quantified without a liquid-liquid extraction step by headspace-GC-MS analysis. Experimental diffusion coefficients (DP) of toluene, benzyl alcohol, ethyl butyrate and methyl salicylate through PET film were determined. Results from Limm's diffusion model showed that the predicted DP values for PET were all greater than the experimental values. DP values predicted by Piringer's diffusion model were also greater than those determined experimentally at 66°C, 100°C and 121°C. However, Piringer's model led to the underestimation of benzyl alcohol (Áp = 3.7) and methyl salicylate (Áp = 4.0) diffusion at 40°C with its revised "upper-bound" Áp value of 3.1 at temperatures below the glass transition temperature (Tg) of PET (<70°C). This implies that input parameters of Piringer's model may need to be revised to ensure a margin of safety for consumers. On the other hand, at temperatures greater than the Tg, both models appear too conservative and unrealistic. The highest estimated Áp value from Piringer's model was 2.6 for methyl salicylate, which was much lower than the "upper-bound" Áp value of 6.4 for PET. Therefore, it may be necessary further to refine "upper-bound" Áp values for PET such that Piringer's model does not significantly underestimate or overestimate the migration of organic compounds dependent upon the temperature condition of the food contact material.

Validation of a rapid lateral flow test for the simultaneous determination of ß-lactam drugs and flunixin in raw milk.

ß-Lactam antibiotics are the most commonly used drugs on dairy farms. ß-Lactam residues in milk are kept out of the human milk supply with good agricultural practices and mandatory truck screening performed by the dairy industry under Appendix N of the Pasteurized Milk Ordinance. Flunixin, a nonsteroidal and anti-inflammatory drug, appears in dairy cattle tissue residues with a frequency similar to the occurrence of penicillin G. This creates concern that flunixin residues could be in milk and would go undetected under current milk screening programs. A single test that combines mandatory ß-lactam screening with voluntary flunixin screening is an economical approach for monitoring and controlling for potential flunixin or 5-hydroxyflunixin, the primary flunixin metabolite marker in milk. The objective of this study was to validate a ß-lactam and flunixin rapid lateral flow test (LFT) and compare the results obtained with a liquid chromatography-triple quadrupole tandem mass spectrometry (LC-MS/MS) method for the simultaneous determination of flunixin and 5-hydroxyflunixin in raw milk with a limit of detection of , 1 ppb, equivalent to 1 ng/ml. Using the LFT, three combined manufactured lots of test strips detected penicillin G at 2.0 ppb, ampicillin at 6.8 ppb, amoxicillin at 5.9 ppb, cephapirin at 13.4 ppb, ceftiofur (total metabolites) at 63 ppb, and 5-hydroxyflunixin at 1.9 ppb at least 90% of the time with 95% confidence. The LFT also detected incurred flunixin milk samples that were analyzed with the LC-MS/MS and diluted to tolerance in raw milk. The detection levels for the LFT are lower than the U.S. safe levels or tolerances and qualify the test to be used in compliance with U.S. milk screening programs.

Multiresidue pesticide analysis of dried botanical dietary supplements using an automated dispersive SPE cleanup for QuEChERS and high-performance liquid chromatography-tandem mass spectrometry.

An automated dispersive solid phase extraction (dSPE) cleanup procedure as part of the Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) method, coupled with liquid chromatography-tandem mass spectrometry using electrospray ionization in positive mode, was used for the simultaneous analysis of 236 pesticides in three dried powdered botanical dietary supplements (ginseng, saw palmetto, and gingko biloba). The procedure involved extraction of the dried powdered botanical samples with salt-out acetonitrile/water extraction using anhydrous magnesium sulfate and sodium chloride, followed by an automated dSPE cleanup using a mixture of octadodecyl- (C18) and primary-secondary amine (PSA)-linked silica sorbents and anhydrous MgSO4 and online LC-MS/MS analysis. Dynamic multiple-reaction monitoring (DMRM) based on the collection of two precursor-to-product ion transitions with their retention time windows was used for all of the targeted pesticides and the internal standard. Matrix-matched calibration standards were used for quantitation, and standard calibration curves showed linearity (r(2) > 0.99) across a concentration range of 0.2-400 ng/mL for the majority of the 236 pesticides evaluated in the three botanical matrices. Mean recoveries (average %RSD, n = 4) were 91 (6), 93 (4), 96 (3), and 99 (3)% for ginseng, 101 (9), 98 (6), 99 (4), and 102 (3)% for gingko biloba, and 100 (9), 98 (6), 96 (4), and 96 (3)% for saw palmetto at fortification concentrations of 25, 100, 250, and 500 µg/kg, respectively. The geometric mean matrix-dependent instrument detection limits were 0.17, 0.09, and 0.14 µg/kg on the basis of the studies of 236 pesticides tested in ginseng roots, gingko biloba leaves, and saw palmetto berries, respectively. The method was used to analyze incurred ginseng samples that contained thermally labile pesticides with a concentration range of 2-200 µg/kg, indicating different classes of pesticides are being applied to these botanicals other than the traditional pesticides that are commonly used and analyzed by gas chromatography techniques. The method demonstrates the use of an automated cleanup procedure and the LC-MS/MS detection of multiple pesticide residues in dried, powdered botanical dietary supplements.