Simultaneous Analysis of 3-MCPD and 1,3-DCP in Asian Style Sauces Using QuEChERS Extraction and Gas Chromatography-Triple Quadrupole Mass Spectrometry.

Acid hydrolyzed vegetable protein (aHVP) is used for flavoring a wide variety of foods and also in the production of nonfermented soy sauce. During the production of aHVP, chloropropanols including 3-monochloropropane-1,2-diol (3-MCPD) and 1,3 dichloropropane-2-ol (1,3-DCP) can be formed through the reaction of the hydrochloric acid catalyst and residual fat and the reaction of 3-MCPD with acetic acid, respectively. 3-MCPD is a carcinogen, and 1,3-DCP has been classified as a genotoxic carcinogen. The European Union (EU) has set a maximum concentration of 0.02 mg/kg of 3-MCPD in aHVP, and the Food and Drug Administration (FDA) set a guidance limit of 1 mg/kg of 3-MCPD in aHVP. 1,3-DCP is not an approved food additive, and the Joint FAO/WHO Expert Committee on Food Additives (JEFCA) has set a limit at 0.005 mg/kg, which is close to the estimated method detection limit. Currently there are few analytical methods for the simultaneous determination of 3-MCPD and 1,3-DCP without derivatization due to differences in their physical chemical properties and reactivity. A new method was developed using QuEChERS (quick, easy, cheap, effective, rugged, and safe) with direct analysis of the extract without derivatization using gas chromatography-triple quadrupole mass spectrometry (GC-QQQ). Additionally, a market sampling of 60 soy sauce samples was performed in 2015 to determine if concentrations have changed since the FDA limit was set in 2008. The sampling results were compared between the new QuEChERS method and a method using phenylboronic acid (PBA) as a derivatizing agent for 3-MCPD analysis. The concentrations of 3-MCPD detected in soy sauce samples collected in 2015 (

Single-laboratory validation of a method for the determination of select volatile organic compounds in foods by using vacuum distillation with gas chromatography/mass spectrometry.

Recent studies showed that headspace and purge and trap methods have limitations when used to determine volatile organic compounds (VOCs) in foods, including matrix effects and artifact formation from precursors present in the sample matrix or from thermal decomposition. U.S. Environmental Protection Agency Method 8261A liberates VOCs from the sample matrix by using vacuum distillation at room temperature. The method was modified and validated for the determination of furan, chloroform, benzene, trichloroethene, toluene, and sytrene in infant formula, canned tuna (in water), peanut butter, and an orange beverage (orange-flavored noncarbonated beverage). The validation studies showed that the LOQ values ranged from 0.05 ng/g toluene in infant formula to 5.10 ng/g toluene in peanut butter. Fortified recoveries were determined at the first, second, and third standard additions, and concentrations ranged from 0.07 to 6.9 ng/g. When quantified by the method of standard additions, the recoveries ranged from 56 to 218% at the first standard addition and 89 to 117% at the third. The validated method was used to conduct a survey of the targeted VOCs in 18 foods. The amounts found ranged from none detected to 73.8 ng/g furan in sweet potato baby food.

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 (Dp) 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 × 10(2) to 2 × 10(6)) 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.

Evaluation of accelerated UV and thermal testing for benzene formation in beverages containing benzoate and ascorbic acid.

Under certain conditions, benzene can form in beverages containing benzoic and ascorbic acids. The American Beverage Assn. (ABA) has published guidelines to help manufacturers mitigate benzene formation in beverages. These guidelines recommend accelerated testing conditions to test product formulations, because exposure to ultraviolet (UV) light and elevated temperature over the shelf life of the beverage may result in benzene formation in products containing benzoic and ascorbic acids. In this study, the effects of UVA exposure on benzene formation were determined. Benzene formation was examined for samples contained in UV stabilized and non-UV stabilized packaging. Additionally, the usefulness of accelerated thermal testing to simulate end of shelf-life benzene formation was evaluated for samples containing either benzoic or ascorbic acid, or both. The 24 h studies showed that under intense UVA light benzene levels increased by as much as 53% in model solutions stored in non-UV stabilized bottles, whereas the use of UV stabilized polyethylene terephthalate bottles reduced benzene formation by about 13% relative to the non-UV stabilized bottles. Similar trends were observed for the 7 d study. Retail beverages and positive and negative controls were used to study the accelerated thermal testing conditions. The amount of benzene found in the positive controls and cranberry juice suggests that testing at 40 degrees C for 14 d may more reliably simulate end of shelf-life benzene formation in beverages. Except for cranberry juice, retail beverages were not found to contain detectable amounts of benzene (<0.05 ng/g) at the end of their shelf lives.

Single-laboratory validation of a method for the determination of furan in foods by using headspace gas chromatography/ mass spectrometry, part 2--low-moisture snack foods.

In 2004, a quantitative headspace (HS) gas chromatographic/mass spectrometric method was developed and used to determine furan in approximately 300 foods. This method was modified and validated for the determination of furan in low-moisture snack foods. The modifications include a smaller test portion size and lower HS oven temperature. The limits of detection ranged from 0.4 ng/g in graham crackers to 4.4 ng/g in pretzels. Recoveries from samples fortified at 0.5, 1,2, and 3 times the levels of incurred furan found in the samples ranged from 96 to 102%, and HorRat values showed that the recovery data met the criteria for repeatability. The modified method was shown to be reliable for the determination of furan in foods when test portions were equilibrated for 30 min in a 60 degrees C HS oven. The modified method was used to conduct a survey of furan in 22 low-moisture snack foods. All of the samples were found to contain furan ranging from 3.7 ng/g in graham crackers to 60 ng/g in corn chips. Results from the survey were consistent with results obtained for similar snack foods analyzed by a U.S. Food and Drug Administration field laboratory.

Survey of furan in heat processed foods by headspace gas chromatography/mass spectrometry and estimated adult exposure.

Furan is a suspected human carcinogen that is formed in some processed foods at low ng per g levels. Recent improvements in analytical methodology and scientific instrumentation have made it possible to accurately measure the amount of furan in a wide variety of foods. Results from analysis of more than 300 processed foods are presented. Furan was found at levels ranging from non-detectable (LOD, 0.2-0.9 ng g(-1)) to over 100 ng g(-1). Exposure estimates for several adult food types were calculated, with brewed coffee being the major source of furan in the adult diet (0.15 microg kg(-1) body weight day(-1)). Estimates of mean exposure to furan for different subpopulations were calculated. For consumers 2 years and older, the intake is estimated to be about 0.2 microg kg(-1) body weight day(-1).

Survey results of benzene in soft drinks and other beverages by headspace gas chromatography/mass spectrometry.

Benzene, a carcinogen that can cause cancer in humans, may form at nanogram per gram levels in some beverages containing both benzoate salts and ascorbic or erythorbic acids. Through a series of reactions, a hydroxyl radical forms that can decarboxylate benzoate to form benzene. Elevated temperatures and light stimulate these reactions, while sugar and ethylenediaminetetraacetic acid (EDTA) can inhibit them. A headspace gas chromatography/mass spectrometry method for the determination of benzene in beverages was developed and validated. The method was used to conduct a survey of 199 soft drinks and other beverages. The vast majority of beverages sampled contained either no detectable benzene or levels below the U.S. Environmental Protection Agency's drinking water limit of 5 ng/g. Beverages found to contain 5 ng/g benzene or more were reformulated by the manufacturers. The amount of benzene found in the reformulated beverages ranged from none detected to 1.1 ng/g.

Single-laboratory validation of a method for the determination of furan in foods by using static headspace sampling and gas chromatography/mass spectrometry.

A headspace gas chromatography/mass spectrometry method was developed and validated in-house for the determination of furan in foods. The method of standard additions with d4-furan as the internal standard was used to quantitate furan. The limit of detection and limit of quantitation (LOQ) values ranged from 0.2 and 0.6 nglg, respectively, in apple juice to 0.9 and 2.9 ng/g, respectively, in peanut butter. Recoveries were obtained at 0.5, 1, 2, and 3 times the LOQ. At 1, 2, and 3 times the LOQ, the recoveries ranged from 89.4 to 108%, and the relative standard deviations ranged from 3.3 to 17.3% for all the matrixes. For apple juice, chicken broth, and infant formula, the averaged coefficients of determination from the linear regression analyses were >0.99 with each food fortified at 0.5, 1, 2, and 3 times the LOQ. The coefficients of determination were >0.99 for green beans and 0.96 for peanut butter with the foods fortified at 1, 2, and 3 times the LOQ. Within-laboratory precision was determined by comparing the amounts of furan found in 18 samples by 2 analysts on different days with different instruments. For most of the foods, the difference between the amounts found by each analyst was <18%. The method was used to conduct a survey of >300 foods. The furan levels found ranged from none detected to 174 ng/g.