Occurrence of glycidyl esters in infant formula products on the Canadian market between 2015 and 2019.

Glycidyl fatty acid esters (GEs) are processing contaminants formed during refining steps of vegetable oils. 'In vivo' hydrolysis of GEs releases potentially carcinogenic and genotoxic glycidol (2,3-epoxy-1-propanol). Occurrence of GEs in vegetable oils used for infant formula manufacturing may pose a potential health concern for formula-fed infants. Refined oils are commonly used as the main fat ingredient in formula manufacturing. For this study, different infant formula products (powders, concentrates and ready-to-feed formula products) were purchased and analysed in 2015 (35 samples) and 2019 (33 samples). Seven individual GEs were analysed by LC-MS/MS via direct approach by stable isotope dilution analysis, and total bound glycidol concentrations were calculated. Concentrations of bound glycidol in reconstituted formula reached maxima of 40.3 ng/g in the 2015 samples and 31.5 ng/g in the samples collected in 2019, with respective means of 8.7 ng/g and 6.7 ng/g. The analysed bound glycidol concentrations are comparable with concentration ranges from other studies, but are higher than observed in studies from the European market. Temporal trend data show a reduction of bound glycidol concentrations in 2019. GE concentrations were compared across different manufacturers.

Occurrence of 2- and 3-monochloropropanediol esters (MCPDE) in infant formula products on the Canadian market between 2015 and 2019.

2- and 3-monochloropropanediol esters (MCPDEs) are most commonly formed as process-induced contaminants during the refinement of vegetable oils used for food production. 'In vivo' hydrolysis of 3-MCPDEs releases the potential carcinogen 3-monochloropropanediol (3-MCPD). Levels of MCPDEs in infant formula are of particular concern, as refined oils are commonly used as main fat ingredients. For this study, infant formula samples (powders, liquid concentrates and ready-to-feed infant formula samples) from the Canadian market were purchased and analysed in 2015 (35 samples) and 2019 (33 samples). MCPDE concentrations (expressed as free MCPD equivalents) were examined through an indirect analytical approach, applying acid-catalysed ester cleavage and using cyclohexanone as derivatising agent. Labelled diesters were used as internal standards. 2015 Survey data were analysed by gas chromatography-mass spectrometry (GC-MS) in selected ion monitoring mode (SIM). 2019 Survey data were analysed with an updated method using GC-MS/MS in multiple reaction monitoring modes (MRM). In 2015, levels in reconstituted formula ranging from 3.7 ng/g to 111 ng/g for 3-MCPD and 2.2 ng/g to 56.2 ng/g for 2-MCPD were found. In 2019, levels ranging from 3.9 ng/g to 74.8 ng/g for 3-MCPD and 1.0 ng/g to 33.9 ng/g for 2-MCPD were found. A significantly reduced mean of combined MCPDEs was observed between 2015 and 2019 data (64.5 ng/g, standard deviation (SD) 8.6 ng/g in 2015 to 31.8 ng/g, SD 5.6 ng/g in 2019, p-value = 0.024). For the majority of manufacturers, the data comparison among brand products over time shows decreased levels of MCPDEs. Occurrence data of MCPDEs, including data from previously published surveys (2012/2013), were also compared and a temporal trend was established.

An investigation of presence of 2- and 3-monochloropropanediol fatty acid esters in Canadian human milk samples.

Occurrence of 2- and 3-monochloropropanediol fatty acid esters (MCPDEs) in 199 human milk samples collected from Canadian women was examined in this study. MCPDEs were determined via indirect analytical approach by using acidic hydrolysis/transesterification and derivatization with cyclohexanone using a fluorinated sulfonic acid resin as a catalyst followed by GC-MS analysis. Analyses were done by a stable isotope dilution assay (SIDA) using 3-monochloropropanediol-d5 dipalmitate and 2-monochloropropanediol-d5 distearate as internal standards. In all samples 2-MCPD esters were not detected, at LOD = 1 ng/g for 2-MCPD equivalent. 3-MCPD esters were not detected, at LOD = 2 ng/g for 3-MCPD equivalent, in 193 samples. Six samples had the apparent concentration of 3-MCPD equivalent in the range of 2.0-5.1 ng/g, which was likely caused by accidental contamination during processing of samples. For selected samples, these findings were confirmed by direct analysis via LC-MS/MS analysis based on SIDA for 3-MCPD dipalmitate and 2-MCPD distearate. To our best knowledge, this is the first study to analyze human milk samples for 2-MCPD esters.

2- and 3-Monochloropropanediols in paper products and their transfer to foods.

The occurrence of 2- and 3-monochloropropanediol (MCPDs) in selected paper products sold on the Canadian market and the transfer of 3-MCPD from those products to beverages was probed. Products included coffee filters, tea bags, disposable paper hot beverage cups and milk packaged in paperboard containers. The occurrence MCPDs in coffee and tea filters on the German market was investigated as well. Furthermore, the presence of MCPDs in paper towels on the German market was also investigated. Analytes were determined by stable isotope dilution analysis GC-MS in SIM mode. 3-MCPD was detected in most paper products with levels ranging from a few nanograms in tea bags to a few micrograms in white coffee filters. Milk containers' paperboard contained 3-MCPD at about 500-1500 ng g(-1); however, 3-MCPD was detected in milk only in smaller containers, 237-500 ml (likely due to a lower volume/surface ratio) at levels of about 1 ng g(-1). Out of three disposable hot beverage paper cups tested (of 237-473 ml capacity), paperboard of two contained 3-MCPD at 632-792 ng g(-1), and 3-MCPD was detected in leachate from those paper cups at levels of about 16 ng per cup. 3-MCPD was detected in all paper towels at levels of 42-2466 ng g(-1). 2-MCPD was detected in many paper products (from Canadian and German sources) and in all the towels tested at levels varying from about 0.5-10% of that of 3-MCPD.

Cohort profile: the maternal-infant research on environmental chemicals research platform.

BACKGROUND: The Maternal-Infant Research on Environmental Chemicals (MIREC) Study was established to obtain Canadian biomonitoring data for pregnant women and their infants, and to examine potential adverse health effects of prenatal exposure to priority environmental chemicals on pregnancy and infant health. METHODS: Women were recruited during the first trimester from 10 sites across Canada and were followed through delivery. Questionnaires were administered during pregnancy and post-delivery to collect information on demographics, occupation, life style, medical history, environmental exposures and diet. Information on the pregnancy and the infant was abstracted from medical charts. Maternal blood, urine, hair and breast milk, as well as cord blood and infant meconium, were collected and analysed for an extensive list of environmental biomarkers and nutrients. Additional biospecimens were stored in the study's Biobank. The MIREC Research Platform encompasses the main cohort study, the Biobank and follow-up studies. RESULTS: Of the 8716 women approached at early prenatal clinics, 5108 were eligible and 2001 agreed to participate (39%). MIREC participants tended to smoke less (5.9% vs. 10.5%), be older (mean 32.2 vs. 29.4 years) and have a higher education (62.3% vs. 35.1% with a university degree) than women giving birth in Canada. CONCLUSIONS: The MIREC Study, while smaller in number of participants than several of the international cohort studies, has one of the most comprehensive datasets on prenatal exposure to multiple environmental chemicals. The biomonitoring data and biological specimen bank will make this research platform a significant resource for examining potential adverse health effects of prenatal exposure to environmental chemicals.

Dietary exposure to acrylamide in adolescents from a Canadian urban center.

The distribution of acrylamide in food items frequently consumed by Canadian adolescents was determined along with estimates of their contribution to the overall dietary intake of acrylamide. A total of 196 non-smoking adolescents (10-17 years old) were recruited in Montreal Island population, Canada. Participants were invited to fill out a 2-day food diary and a food frequency questionnaire over the last month. 146 samples of foods most frequently consumed by participants were analyzed for acrylamide contents. The highest acrylamide contents were measured in deep-fried french fries and potato chips (mean ± SD: 1053 ± 657 and 524 ± 276 ng/g respectively). On the basis of the 2-day food diary, median total daily intake of acrylamide was estimated at 0.29 µg/kg bw/d, as compared to 0.17 µg/kg bw/d on the basis of the food frequency questionnaire. These values are similar to those reported in comparable populations. Deep-fried french fries consumption contributed the most to daily acrylamide intake (50%) followed by potato chips (10%), oven-baked french fries (8%) and breakfast cereals (8%). Margins of exposure based on genotoxic benchmark dose limits were estimated to be low (≈<100) in high-consumer adolescents, indicating the need to continue efforts to reduce dietary acrylamide exposure.

Challenges and trends in the determination of selected chemical contaminants and allergens in food.

This article covers challenges and trends in the determination of some major food chemical contaminants and allergens, which-among others-are being monitored by Health Canada's Food Directorate and for which background levels in food and human exposure are being analyzed and calculated. Eleven different contaminants/contaminant groups and allergens have been selected for detailed discussion in this paper. They occur in foods as a result of: use as a food additive or ingredient; processing-induced reactions; food packaging migration; deliberate adulteration; and/or presence as a chemical contaminant or natural toxin in the environment. Examples include acrylamide as a food-processing-induced contaminant, bisphenol A as a food packaging-derived chemical, melamine and related compounds as food adulterants and persistent organic pollutants, and perchlorate as an environmental contaminant. Ochratoxin A, fumonisins, and paralytic shellfish poisoning toxins are examples of naturally occurring toxins whereas sulfites, peanuts, and milk exemplify common allergenic food additives/ingredients. To deal with the increasing number of sample matrices and analytes of interest, two analytical approaches have become increasingly prevalent. The first has been the development of rapid screening methods for a variety of analytes based on immunochemical techniques, utilizing ELISA or surface plasmon resonance technology. The second is the development of highly sophisticated multi-analyte methods based on liquid chromatography coupled with multiple-stage mass spectrometry for identification and simultaneous quantification of a wide range of contaminants, often with much less requirement for tedious cleanup procedures. Whereas rapid screening methods enable testing of large numbers of samples, the multi analyte mass spectrometric methods enable full quantification with confirmation of the analytes of interest. Both approaches are useful when gathering surveillance data to determine occurrence and background levels of both recognized and newly identified contaminants in foods in order to estimate human daily intake for health risk assessment.

Determination of iodoacetic acid using liquid chromatography/electrospray tandem mass spectrometry.

A rapid analytical method based on liquid chromatography/tandem mass spectrometry (LC/MS/MS) using electrospray ionization in negative ion detection mode was developed for the analysis of underivatized iodoacetic acid in water. The method was applied to model reaction mixtures in the study of the formation of iodoacetic acid after chlorinated tap water was boiled in the presence of potassium iodide or iodized table salt. Samples can be directly analyzed by the LC/MS/MS system without extraction or chemical derivatization. Limit of detection was determined to be 0.3 microg/L (or 0.3 ng/mL) and limit of quantitation was about 1 microg/L (1 ng/mL).

Determination of benzene in soft drinks and other beverages by isotope dilution headspace gas chromatography/mass spectrometry.

An automated, simple, and reproducible method was developed for the determination of benzene in soft drinks, based on isotope dilution headspace gas chromatography/mass spectrometry in the selected-ion monitoring mode. The method was used to assess benzene levels in samples of 124 soft drinks and beverages. Benzene was not detected in 60% of the 124 products. The average benzene levels in 6 products exceeded the Canadian maximum acceptable concentration of 5 microg/L for benzene in drinking water, and 2 of the 6 products had benzene levels above the World Health Organization guideline of 10 microg/L. The highest level of benzene, 23 microg/L, was found in a soft drink product specifically marketed to children.

Furan precursors in food: a model study and development of a simple headspace method for determination of furan.

Furan was previously detected in foods that had undergone thermal treatment. Because furan is now classified as a possible human carcinogen, a model system was developed to investigate the origins of furan. Also, a simple, rapid isotope dilution (d4-furan) headspace method was developed to measure furan. Two pathways of furan formation have been identified in the model systems tested so far. The first is the oxidation of polyunsaturated fatty acids at elevated temperatures, and the second is linked to the decomposition of ascorbic acid derivatives. The analytical procedure, based on the use of a 50 microL injection (from the headspace of a 1.5 mL vial containing 0.5 mL water) into the split/splitless injection port of a gas chromatograph/mass spectrometer (electron ionization, selected-ion monitoring), showed linearity in the 10-1000 ng/g range with a limit of detection of 1 ng/g.

Determination of acrylamide in various food matrices: evaluation of LC and GC mass spectrometric methods.

Recent concerns surrounding the presence of acrylamide in many types of thermally processed food have brought about the need for the development of analytical methods suitable for determination of acrylamide in diverse matrices with the goals of improving overall confidence in analytical results and better understanding of method capabilities. Consequently, the results are presented of acrylamide testing in commercially available food products--potato fries, potato chips, crispbread, instant coffee, coffee beans, cocoa, chocolate and peanut butter, obtained by using the same sample extract. The results obtained by using LC-MS/MS, GC/MS (El), GC/HRMS (El)--with or without derivatization--and the use of different analytical columns, are discussed and compared with respect to matrix borne interferences, detection limits and method complexities.

Semicarbazide formation in azodicarbonamide-treated flour: a model study.

Semicarbazide was previously found in foods that were in contact with rubber gaskets foamed at high temperatures with a blowing agent azodicarbonamide. Because azodicarbonamide is an approved flour additive in certain countries, we set out to ascertain if semicarbazide is formed during the baking process from flours containing that additive. The levels of semicarbazide in baking flour treated with azodicarbonamide and bread baked from such flours were determined by isotope dilution (13C15N2-semicarbazide) liquid chromatography electrospray tandem mass spectrometry (LC-MS/MS). The samples were homogenized with HCl, extracted with n-pentane, derivatized with 2-nitrobenzaldehyde, and the derivative was extracted with ethyl acetate. After solvent exchange to 10% acetonitrile in water containing 0.1% acetic acid, the samples were analyzed using a 2.1 mm x 150 mm C18 column eluted with 2 mM ammonium formate in water/methanol (40:60). Semicarbazide was formed during the dry heating of commercial azodicarbonamide-containing flours at temperatures of 150-200 degrees C reaching levels of 0.2 mg/kg. Similar levels of semicarbazide were found in the crusts of breads made from azodicarbonamide-treated flour.

Acrylamide in French fries: influence of free amino acids and sugars.

The free amino acid profile and sugar (fructose, glucose, and sucrose) composition were determined in potato samples selected to give a large range of variation (a total of 66 samples). From these samples French fries were produced in a laboratory-scale simulation of an industrial process followed by a finish fry at 180 degrees C for 3.5 min using a restaurant fryer. The final product was blast frozen and analyzed for acrylamide. Acrylamide was detected in all samples, but its concentration varied significantly from 50 to 1800 ng/g. For isotope dilution (13C3) acrylamide analysis, samples were extracted with water, cleaned up on HLB Oasis polymeric and Accucat mixed mode anion and cation exchange SPE columns, and analyzed by LC-MS/MS. Statistical analysis of the data indicates that the effect of sugars and asparagine on the concentration of acrylamide in French fries is positive and significant (p < 0.001). It appears that one of the ways acrylamide formation in French fries can be effectively controlled is by the use of raw products with low sugar (and to a lesser degree, asparagine) content.

Acrylamide in foods: occurrence, sources, and modeling.

Acrylamide in food products-chiefly in commercially available potato chips, potato fries, cereals, and bread-was determined by liquid chromatography-tandem mass spectrometry (LC-MS/MS). Samples were homogenized with water/dichloromethane, centrifuged, and filtered through a 5 kDa filter. The filtrate was cleaned up on mixed mode, anion and cation exchange (Oasis MAX and MCX) and carbon (Envirocarb) cartridges. Analysis was done by isotope dilution ([D(3)]- or [(13)C(3)]acrylamide) electrospray LC-MS/MS using a 2 x 150 mm (or 2 x 100 mm) Thermo HyperCarb column eluted with 1 mM ammonium formate in 15% (or 10% for the 2 x 100 mm column) methanol. Thirty samples of foods were analyzed. Concentrations of acrylamide varied from 14 ng/g (bread) to 3700 ng/g (potato chips). Acrylamide was formed during model reactions involving heating of mixtures of amino acids and glucose in ratios similar to those found in potatoes. In model reactions between amino acids and glucose, asparagine was found to be the main precursor of acrylamide. Thus, in the reaction between nitrogen-15 (amido)-labeled asparagine and glucose, corresponding (15)N-labeled acrylamide was formed. The yield of the model reaction is approximately 0.1%.