ABSTRACT
The common presence of glycidyl esters (GEs) in refined vegetable oils has been a concern for food safety. The present study aimed to investigate the inhibitory effects of three carotenoids derived from Haematococcus pluvialis microalga on GE formation in both rice oil and a chemical model during heating. The addition of astaxanthin (AS), lutein (LU), and ß-carotene (CA) at 0.6 mg/g in rice oil can reduce GE formation by 65.0%, 57.1%, and 57.5%, respectively, which are significantly higher than those achieved by common antioxidants such as l-ascorbyl palmitate (39.0%), α-tocopherol (18.5%), tert-butyl hydroquinone (42.7%), and quercetin (26.2%). UPLC-Q-TOF-MS/MS analysis showed that two new compounds, that is, propylene glycol monoester and diester of palmitic acid, were formed in the CA-added chemical model, which provided direct experimental evidence for the inhibition of antioxidants including AS, LU, and CA against GE formation not only by indirect antioxidative action but also by direct radical reactions to competitively prevent the formation of cyclic acyloxonium intermediates. Furthermore, it was interestingly found that only AS could react with the GEs. The adduct of AS with GEs, astaxanthin-3-O-propanetriol esters, was preliminarily identified using Q-TOF-MS/MS in the heated AS-GE model, suggesting that reacting with GEs might represent another distinct mechanism of AS to eliminate GEs.
Subject(s)
Carotenoids , Esters , Hot Temperature , Esters/chemistry , Esters/pharmacology , Carotenoids/chemistry , Plant Oils/chemistry , Plant Oils/pharmacology , Xanthophylls/chemistry , Xanthophylls/pharmacology , Tandem Mass Spectrometry , Epoxy Compounds/chemistry , Models, Chemical , Antioxidants/chemistry , Antioxidants/pharmacology , Lutein/chemistry , Lutein/pharmacology , Chlorophyceae/chemistry , Chlorophyta/chemistryABSTRACT
3-monochloropropane-1,2-diol esters (3-MCPDEs) and glycidyl esters (GEs) are food contaminants and have arisen continuous attention due to their toxicity, especially towards infants. Current risk assessment of these contaminants was mostly employing deterministic approaches, lacking quantitative characterization of the likelihood, incidence, or severity of the risks involved. Herein, 3-MCPDE and GE levels in 46 representative infant formulas (IFs) from Chinese market were determined by GC-MS/MS. Then, combining the occurrence data and consumption data from China National Food Consumption Survey, the Monte Carlo simulation-based probabilistic model for risk assessment of 3-MCPDEs and GEs in IFs from Chinese market was established. The results showed that all P90 (90th percentiles) hazard quotient values were below 1, demonstrating 3-MCPDEs didn't pose health risks to most populations aged 0-36 months old. However, for 0-12 months old groups, P10 (10th percentiles) margin of exposure values were all below 25000, indicating GEs may pose potential risks to 10% of this group. Uncertainty analysis revealed that the probabilistic model had considered uncertainties of model input and distribution, and realized refined assessment. This study is the first report on probabilistic assessment of 3-MCPDEs and GEs in IFs, which also provided references for the formulation of related regulatory limits in China.
Subject(s)
Food Contamination , alpha-Chlorohydrin , Infant , Humans , Infant, Newborn , Child, Preschool , Food Contamination/analysis , Infant Formula/analysis , Esters , Tandem Mass Spectrometry , Monte Carlo Method , alpha-Chlorohydrin/analysis , Risk AssessmentABSTRACT
High temperature is beneficial for the removal of polycyclic aromatic hydrocarbons (PAHs) from oil via steam, but leads to an increase in the content of 3-monochloropropane-1,2-diol esters (3-MCPDE) and glycidyl esters (GE). To inhibit the production of 3-MCPDE and GE during the removal of PAHs, rapeseed oil was deodorized using ethanol steam at low-temperature (140-220 °C) (L-ESD) and the content changes were studied for PAHs, 3-MCPDE and GE, and compared with conventional high-temperature water steam deodorization (H-WSD) (250 °C for 60 min). The removal rates of PAHs in L-ESD oil can be higher than those in conventional H-WSD oil, and the contents of 3-MCPDE and GE in L-ESD oil (140-180 °C for 60-100 min) ranged from 48.32 to 73.65 % and 50.49-69.90 %, respectively, in H-WSD oil due to the lower temperature of ethanol steam deodorization. These results indicate that L-ESD is beneficial in minimizing the contents of PAHs, 3-MCPDE and GE in vegetable oil.
Subject(s)
Polycyclic Aromatic Hydrocarbons , alpha-Chlorohydrin , Temperature , Rapeseed Oil , Steam , Palm Oil , Ethanol , Distillation , Esters , Plant Oils , WaterABSTRACT
The presence of 3-monochloropropanediol esters (3-MCPDE), 2-monochloropropanediol esters (2-MCPDE) and glycidyl esters (GE) in infant formula products has raised serious concerns. They incorporate vegetable oils, particularly palm-based oils, which are well-known to contain large amounts of these process contaminants. An analysis was conducted on infant formula samples (n = 16) obtained from the Malaysian market to determine the levels of 3-MCPDE, 2-MCPDE and GE using gas chromatography-mass spectrometry (GC-MS). The method was validated, with a limit of quantification (LOQ) on instrument of 0.10 µg/g for all analytes. The median concentrations of 3-MCPDE, 2-MCPDE and GE in infant formula in this study were 0.008 µg/g, 0.003 µg/g and 0.002 µg/g respectively. The estimated dietary intakes calculated from consumption of infant formula show higher exposures to infants within the age group of 0 to 5 months, highest for GE (1.61 µg/kg bw/day), followed by 3-MCPDE (0.68 µg/kg bw/day) and 2-MCPDE (0.41 µg/kg bw/day) compared to the age group of 6 to 12 months. Only one sample, relating to GE exposure is a potential risk for both age groups with MOE value below 25,000.
Subject(s)
Infant Formula , alpha-Chlorohydrin , Infant , Humans , Infant, Newborn , Infant Formula/analysis , Esters/analysis , Malaysia , alpha-Chlorohydrin/analysis , Plant Oils/analysis , Glycerol/analysis , Food Contamination/analysis , Risk AssessmentABSTRACT
Herein, a modified indirect method was established for the determination of 3-monochloropropane-1,2-diol esters (3-MCPDEs) and glycidyl esters (GEs), employing magnetic solid phase extraction by boronic acid-functionalized magnetic nanoparticles to replace the traditional clean-up procedure. Compared with routine methods, it has been proved to be more sensitive with limits of detection in the range of 0.02-1.5 µg/kg and less susceptible to contamination of phenylboronic acid derivatives and fatty acid methyl esters. The proposed method was applied to analyze 42 samples covering the entire infant formula (IF) production chain. Results revealed that homogenization process contributed 79-91 % of the total growth of the contaminants due to the vegetable oil addition, while the following evaporation and spray-drying processes contributed 9-21 % of the total growth owing to involved heat treatment. The GE levels in final IF products exceeded the maximum level set by EU regulation 2020/1322, indicating quality safety concerns in the production chain.
Subject(s)
Esters , alpha-Chlorohydrin , Esters/analysis , Fatty Acids/analysis , Food Contamination/analysis , Humans , Infant , Infant Formula/analysis , Magnetic Phenomena , Solid Phase Extraction , alpha-Chlorohydrin/analogs & derivatives , alpha-Chlorohydrin/analysisABSTRACT
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.
Subject(s)
Infant Formula , alpha-Chlorohydrin , Infant , Humans , Chromatography, Liquid , Infant Formula/analysis , Tandem Mass Spectrometry , Esters/analysis , Food Contamination/analysis , Canada , Epoxy Compounds/analysis , Plant Oils/analysis , alpha-Chlorohydrin/analysisABSTRACT
This study investigated the prevalence and occurrence of 3-monochloropropanediol esters (3-MCPDEs) and glycidyl esters (GEs) in domestically and commercially prepared food in Singapore and assessed the total dietary exposure for the Singaporean population. Minimal impact on the formation of 3-MCPDEs and GEs was observed from the domestic cooking methods commonly practiced in Singapore such as deep frying and stir frying. The estimated total dietary exposure to 3-MCPDEs for the Singaporean population (aged 15 to 92) was 0.982 µg/kg bw/day for general consumers and 2.212 µg/kg bw/day for high consumers (95th percentile), which accounted for 49.1% and 110.6% of the tolerable dietary intake (TDI) at 2 µg/kg bw/day by the European Food Safety Authority (EFSA). The calculated margins of exposure (MOE) for GEs based on the dietary exposure for general consumers at 0.882 µg/kg bw/day and 2.209 µg/kg bw/day for high consumers were below 10,000, indicating a potential health concern. Our study showed that the occurrence of 3-MCPDEs and GEs varied among vegetable oils, and domestic cooking methods did not significantly impact the levels of 3-MCPDEs and GEs in prepared food. The critical factor influencing the prevalence and occurrence of 3-MCPDEs and GEs was the choice of oil used for cooking, which absorbed into the cooked food. It is essential to encourage the food industry to continue its innovation on mitigation measures to control and reduce 3-MCPDEs and GEs in vegetable oil production. Consumers are advised to make informed choices on food consumption and cooking oil for food preparation to reduce their exposure to 3-MCPDEs and GEs.
ABSTRACT
OBJECTIVE: To explore the contamination characteristics of chloropropanol esters and glycidyl esters in infant formulas sold in Beijing in 2021, and to evaluate the exposure risk of chloropropanol esters and glycidyl esters for infants and toldders aged 0-36 months old. METHODS: The contents of chloropropanol esters and glycidyl esters in infant formula samples were determined using gas chromatography-mass spectrometry with deuterated internal standards. Combined with the recommended consumption of infant formulas, the exposure level of chloropropanol esters and glycidyl esters in infants and toddlers aged 0-36 months was calculated. RESULTS: The detection rate of 3-chloropropane-1, 2-diol esters(3-MCPDE), 2-chloropropane-1, 3-diol esters(2-MCPDE) and glycidyl esters in infant formulas were 98.6%, 97.1% and 95.7%, respectively. The average contents of 3-MCPDE, 2-MCPDE and glycidyl esters were 44.54, 15.65 and 12.65 µg/kg. For infant of each age groups, the daily intakes of 3-MCPDE via infant formulas by each infant groups were 0.28-0.90 µg/(kg BW), which were all lower than the tolerable daily intake(TDI, 2 µg/(kg BW));the daily intakes of 2-MCPDE via infant formulas by each infant groups were 0.10-0.29 µg/(kg BW);the exposure levels of glycidyl were 0.08-0.22 µg/(kg BW), and the margin of exposure(MOE) values were all higher than 25 000. CONCLUSION: Chloropropanol esters and glycidyl esters in infant formulas sold in Beijing from 2021 were less polluted and their intake was within the safe range.
Subject(s)
alpha-Chlorohydrin , Beijing , Child, Preschool , Esters/analysis , Food Contamination/analysis , Humans , Infant , Infant Formula/analysis , Infant, Newborn , Risk Assessment , alpha-Chlorohydrin/analogs & derivatives , alpha-Chlorohydrin/analysisABSTRACT
A comprehensive analytical method based on gas chromatography-mass spectrometry (GC-MS) was developed for the determination of 3-monochloropropanediol esters, 2-monochloropropanediol esters, and glycidyl esters in vegetable oils. Different parameters, such as bromination reaction temperature, bromination reaction time, derivatization reagent dosage, and derivative reaction time, were studied. The optimal conditions were as follows: 0.25 g of oil was weighed in a 10-mL glass tube, followed by the addition of 2 mL tetrahydrofuran, 25 µL of internal working standard solutions, and 30 µL of acid aqueous solution of NaBr, homogenized, and the mixture was incubated at 50 â for 15 min. The reaction was stopped by the addition of 3 mL of an aqueous solution of sodium hydrogen carbonate. To separate the oil from the water phase, n-heptane was added, and the upper layer was transferred to an empty test tube and evaporated to dryness under a nitrogen stream. The residue was dissolved in 1 mL of tetrahydrofuran. 1.8 mL of sulfuric acid solution in methanol was added to the sample, and the resulting mixture was incubated at 40 â for 16 h. The reaction was stopped by the addition of 0.5 mL of an aqueous solution of sodium hydrogen carbonate. After purification by n-hexane and derivatization of phenylboric acid, the derivatives were extracted with n-hexane. After nitrogen blowing, the residue was dissolved in 1 mL of n-hexane, and then filtered through a 0.45-µm membrane filter unit prior to GC-MS analysis. Temperature programming was applied at an initial temperature of 80 â. After 0.5 min, the temperature was raised to 180 â at a rate of 20 â/min, held for 0.5 min, raised to 200 â at a rate of 5 â/min for 4 min, and finally raised to 300 â at a rate of 40 â/min for 4 min. The target compounds were separated on a DB-5MS column (30 m×0.25 mm×1 µm). Identification and quantification were achieved using an electron impact (EI) ion source in the positive ion mode with the selected ion monitoring mode. The internal standard method was used to quantify the 3-chloropropanediol esters, 2-chloropropanediol esters, and glycidyl esters. Under the optimal conditions, the correlation coefficients of the standard calibration curves were greater than 0.999 in the mass concentration range of 0.01-0.80 mg/L. The limits of detection were 25, 25, and 20 µg/kg (S/N=3), and the limits of quantification were 75, 75, 60 µg/kg (S/N=10). Four samples of different matrix types were selected for scaling experiments. At spiked levels of 250, 500, and 750 µg/kg, the recoveries of 3-chloropropanediol esters, 2-chloropropanediol esters, and glycidyl esters in spiked samples ranged from 89.0% to 98.7%, with relative standard deviations between 2.05% and 7.81% (n=6). This method was used to determine 112 commercially available vegetable oil samples, among which 84 samples were detected with 3-chloropropanediol esters, 2-chloropropanediol esters, or glycidyl esters. The method developed in this study was remarkably different from the standard method, which are mentioned in the national standard method (GB 5009.191-2016) and industry standard method (SN/T 5220-2019), especially in the pretreatment step that involved acidic transesterification. Use of the acidic transesterification method can avoid side reactions, such as the conversion of 3-chloropropanediol, 2-chloropropanediol, and 3-bromopropanediol to free glycidol under alkaline conditions. The method developed in this study was more efficient, and the results were more accurate and reproducible. It has theoretical and practical significance for the control of 3-chloropropanediol esters, 2-chloropropanediol esters, and glycidyl esters residues in vegetable oils, establishment of detection standards, and optimization of the production process.
Subject(s)
Esters , alpha-Chlorohydrin , Esters/analysis , Gas Chromatography-Mass Spectrometry , Plant Oils , Tandem Mass SpectrometryABSTRACT
3-monochloropropane-1,2-diol esters (3-MCPDE) and glycidyl esters (GE) are processed-developed contaminants presence in vegetable oils after undergo refining process under excessive heat. Refined oils are extensively used in various frying applications, nevertheless, the reservation against their quality and safety aspects are of major concern to consumers and food industry. Realizing the importance to address these issues, this article deliberates an overview of published studies on the manifestation of 3-MCPDE and GE when vegetable oils undergo for frying process. With the modest number of published frying research associated to 3-MCPDE and GE, we confined our review from the perspectives of frying conditions, product properties, antioxidants and additives, pre-frying treatments and frying oil management. Simplicity of the frying process is often denied by the complexity of reactions occurred between oil and food which led to the development of unwanted contaminants. The behavior of 3-MCPDE and GE is closely related to physico-chemical characteristics of oils during frying. As such, relationships between 3-MCPDE and/or GE with frying quality indices - i.e. acidity in term of free fatty acid or acid value); secondary oxidation in term of p-anisidine value, total polar compounds and its fractions, and refractive index - were also discussed when oils were subjected under intermittent and continuous frying conditions.
Subject(s)
alpha-Chlorohydrin , Esters , Hot Temperature , Plant Oils/chemistry , alpha-Chlorohydrin/analogs & derivatives , alpha-Chlorohydrin/chemistryABSTRACT
The scientific literature is rich in investigations on the presence of various contaminants in biscuits, and of articles aimed at proposing innovative solutions for their control and prevention. However, the relevant information remains fragmented. Therefore, the objective of this work was to review the current state of the scientific literature on the possible contaminants of biscuits, considering physical, chemical, and biological hazards, and making a critical analysis of the solutions to reduce such contaminations. The raw materials are primary contributors of a wide series of contaminants. The successive processing steps and machinery must be monitored as well, because if they cannot improve the initial safety condition, they could worsen it. The most effective mitigation strategies involve product reformulation, and the use of alternative baking technologies to minimize the thermal load. Low oxygen permeable packaging materials (avoiding direct contact with recycled ones), and reformulation are effective for limiting the increase of contaminations during biscuit storage. Continuous monitoring of raw materials, intermediates, finished products, and processing conditions are therefore essential not only to meet current regulatory restrictions but also to achieve the aim of banning dietary contaminants and coping with related diseases.
ABSTRACT
Fatty acid esters of 3-monochloropropane-1,2-diol (3-MCPD), 2-monochloropropanediol-1,3-diol (2-MCPD), and glycidol are heat-induced processing contaminants formed during the deodorisation step of edible oil refining. Because these compounds are potentially carcinogenic and/or genotoxic, their presence in refined oils and fats and foods containing these oils/fats poses possible health concerns. In particular, formula-fed infants may be exposed to these compounds due to their presence in commercial infant formulas. For this reason, in 2018, the European Union established maximum limits for glycidyl esters in oils/fats and infant formulas and recently, as of January 2021, implemented regulations for the sum of free 3-MCPD and 3-MCPD fatty acid esters as well. This work involved the analysis of 3-MCPD and glycidyl ester contents in 45 infant formula products purchased from German supermarkets in 2019. The data produced in this study showed that average contaminant concentrations across all manufacturers were exceptionally low, with 100% of the products analysed falling below the current EU regulation for glycidyl esters in powdered formulas and 96% of the products analysed meeting the recently implemented regulation for the sum of free and bound 3-MCPD. In addition, a comparison of the 2019 data set to occurrence data collected for German formulas purchased in 2015 showed that average bound 3-MCPD and glycidol concentrations have decreased (from 0.094 to 0.054 µg g-1 and from 0.010 to 0.006 µg g-1, respectively), likely indicating that additional/improved mitigation measures for reducing contaminant concentrations in infant formulas have been implemented over the 4-year period. The data collected in this occurrence study are suitable for estimating levels of exposure to these compounds for German infants.Abbreviations: 2-MCPD: 2-monochloropropane-1,3-diol; 3-MCPD: 3-monochloropropane-1,2-diol; ARA: arachidonic acid; CE: collision energy; CXP: collision cell exit potential; DHA: docosahexaenoic acid; DP: declustering potential; EP: entrance potential; EPA: eicosapentaenoic acid; EtOAc: ethyl acetate; IPA: isopropanol; LC-MS/MS: liquid chromatography-tandem mass spectrometry; MeOH: methanol; MTBE: methyl tert-butyl ether; SPE: solid-phase extraction.
Subject(s)
Food Contamination , Infant Formula/chemistry , alpha-Chlorohydrin/chemistry , Epoxy Compounds/chemistry , Esters , Food Handling , Germany , Hot Temperature , Humans , Infant , Propanols/chemistryABSTRACT
The potentially carcinogenic process contaminant 3- and 2-monochloropropanediol esters (2-MCPD and 3-MCPD esters) and glycidyl esters (GEs) are under study in refined oils and foodstuffs. Legislation set recommended total daily intake (TDI) for 3-MCPD of 0.8 µg/kg and as low as reasonably achievable (ALARA) for glycidol. Usually, the so far adopted method for the determination of these contaminants relay on numerous and time-consuming steps for sample preparation (AOCS methods) and on GC-MS detection. The obtained sensitivities and the number of processable samples are thus limited. In this optic, new reliable methods that allow for the fast and sensitive determination of these contaminants in edible oils may be considered an improvement of the overall strategy of tackling the problem. In this paper a new automated method for sample preparation and detection by GC-MS/MS is presented and validated. Data on sensitivity (LOD at 1.5, 2.2 and 3 ng/g for 3-MCPD, 2-MCPD, 3-MBPD (deriving from glycidol), respectively), linearity across low and high calibration ranges and precision showed to be fit-for-purposes. Finally, the methodology was applied to ten extra virgin oil samples and one sample of sunflower seeds oil.
Subject(s)
Esters , Food Analysis , Gas Chromatography-Mass Spectrometry , Plant Oils , Carcinogens/analysis , Epoxy Compounds/chemistry , Esters/analysis , Esters/chemistry , Food Analysis/methods , Food Contamination/analysis , Glycerol/analogs & derivatives , Glycerol/chemistry , Olive Oil/chemistry , Plant Oils/chemistry , Propanols/chemistry , Propylene Glycols/chemistry , Sunflower Oil/chemistry , Tandem Mass Spectrometry/methodsABSTRACT
The U.S. Food and Drug Administration's (FDA's) Center for Veterinary Medicine (CVM) has been investigating reports of pets becoming ill after consuming jerky pet treats since 2007. Renal failure accounted for 30% of reported cases. Jerky pet treats contain glycerin, which can be made from vegetable oil or as a byproduct of biodiesel production. Glycidyl esters (GEs) and 3-monochloropropanediol esters (3-MCPDEs) are food contaminants that can form in glycerin during the refining process. 3-MCPDEs and GEs pose food safety concerns, as they can release free 3-MCPD and glycidol in vivo. Evidence from studies in animals shows that 3-MCPDEs are potential toxins with kidneys as their main target. As renal failure accounted for 30% of reported pet illnesses after the consumption of jerky pet treats containing glycerin, there is a need to develop a screening method to detect 3-MCPDEs and GEs in glycerin. We describe the development of an ultra-high-pressure liquid chromatography/quadrupole time-of-flight (UHPLC/Q-TOF) method for screening glycerin for MCPDEs and GEs. Glycerin was extracted and directly analyzed without a solid-phase extraction procedure. An exact mass database, developed in-house, of MCPDEs and GEs formed with common fatty acids was used in the screening.
Subject(s)
Chromatography, High Pressure Liquid , Epoxy Compounds/analysis , Food Contamination , Glycerol/analysis , Glycerol/chemistry , Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization , alpha-Chlorohydrin/analysis , Animals , Esters , Food AnalysisABSTRACT
3-Monochloropropanediol esters (3-MCPDEs) and glycidyl esters (GEs) with high toxicity have drawn global concerns due to their widespread occurrence in refined oils and oil-based foods. The effect mechanisms of organic chlorine compound lindane, inorganic chlorine compounds tetra-n-butylammonium chloride (TBAC) and sodium chloride (NaCl) on the formation of 3-MCPDEs and GEs were investigated in model oils and chemical models at 240 °C. Results showed that 3-MCPDEs contents increased with the addition of lindane and TBAC, whereas, surprisingly, GEs presented the same tendency as the results of 3-MCPDEs. This suggested that although chlorine compounds were not involved in the formation reaction of GEs, they could also promote GEs formation. Chemical model experiments confirmed that the presence of chlorine compounds led to the transformation of GEs to 3-MCPDEs and conversely 3-MCPDEs could also transform to GEs. The latter transformation rate from 3-MCPDEs to GEs was higher than the former, which might account for the fact that chlorine compounds promoted GEs formation. Additionally, it was also observed that solid NaCl did not induce the increase of 3-MCPDEs and GEs levels in chemical models, suggesting that the chlorine in NaCl, different from lindane and TBAC, was not available for 3-MCPDEs formation. The present findings give novel insights into the interactions between 3-MCPDEs and GEs formation mechanisms, which offer the theoretical basis for efficient and simultaneous inhibition of 3-MCPDEs and GEs.
Subject(s)
Esters , Plant Oils , Chlorides , Chlorine , Esters/analysis , Fatty Acids/analysis , Food Contamination/analysis , Models, ChemicalABSTRACT
The development and validation of a method for the analysis of traces of 3-monochloropropanediol (3-MCPD) esters (19) and glycidyl esters (7) of fatty acids in vegetable oils, margarine, biscuits and croissants was performed. An extraction method based on the use of solvents (tertbutyl methyl ether (20% ethyl acetate, v/v)) was carried out and cleaning of the extract with a mixture of sorbents (Si-SAX, PSA and Z-sep+) was optimized for the elimination of fatty interferents. The analysis of the targeted compounds was carried out by ultra-high-performance liquid chromatography coupled to tandem mass spectrometry, using a triple quadrupole analyzer (UHPLC-MS/MS-QqQ). The validation of the method provided trueness values between 72 and 118% and precision lower than 20%. The limits of quantification ranged from 0.01 to 0.1 mg kg-1, which were below the current legal limits. Twenty samples of vegetable oils as well of 4 samples of margarine, biscuits and croissants were analyzed. Six out of the 24 samples (25%) exceeded the limits set by European legislation, and a maximum contamination of 3-MCPD esters at 2.52 mg kg-1 was obtained in a sample of corn oil (being 1-myristoyl-3-MCPD the compound detected at the highest concentration). A maximum concentration of glycidyl esters at 7.84 mg kg-1 was determined in a soybean oil sample (glycidyl linoleate as the main compound). Only one sample of olive oil exceeded the maximum allowable limit for 3-MCPD esters with a value of 1.72 mg kg-1, expressed as 3-MCPD.
Subject(s)
Chromatography, High Pressure Liquid/methods , Esters/analysis , Tandem Mass Spectrometry/methods , alpha-Chlorohydrin/analysis , Epoxy Compounds/analysis , Fatty Acids/analysis , Food Contamination/analysis , Limit of Detection , Margarine/analysis , Olive Oil/analysis , Propanols/analysis , Reference Standards , Reproducibility of Results , Soybean Oil/analysisABSTRACT
The dietary exposures to fatty esters of 3- and 2-monochloropropanediol (MCPD) and glycidol were estimated for children aged 2- to 3-year-old from two areas of China using duplicate diet collection method. The 24-h daily duplicate diet samples over three consecutive days were collected from 40 healthy children aged between 26 and 36 months. The analysis of these contaminates in food samples was measured by an indirect method that entails MCPD/glycidol cleavage from their esterified forms for GC-MS analysis. Over 71% of the mixed diet and dairy products samples were found to be contaminated with 3-MCPD and glycidyl esters. The estimated daily exposure to bound 3-MCPD (mean: 0.48-0.49 µg kg-1 bw day-1; P95: 1.00-1.11 µg kg-1 bw day-1) were well below the health guidance values and were considered of low safety concern. The daily exposure to bound 2-MCPD was estimated to be 0.031-0.038 µg kg-1 bw day-1 on average and 0.12-0.14 µg kg-1 bw day-1 for the P95 exposure. However, it was not possible to assess its risk due to the lack of health guidance value of 2-MCPD. The margin of exposure (MOE) estimates for the mean exposure to bound glycidol (0.10-0.12 µg kg-1 bw day-1) were far above 10000 and were considered of low safety concern. However, the margin of exposure estimates for the P95 bound glycidol exposure (0.41-0.45 µg kg-1 bw day-1) were below 10000 and indicated a health concern. Our data indicated that the mixed diet accounted for nearly 76% to 91% of bound MCPD and glycidol exposure. In addition, the follow-on formula was also an important source for the children aged 2-3 years.
Subject(s)
Dietary Exposure/analysis , Epoxy Compounds/analysis , Food Contamination/analysis , Glycerol/analogs & derivatives , Propanols/analysis , Schools, Nursery , alpha-Chlorohydrin/analysis , Child, Preschool , China , Esters/analysis , Fatty Acids/analysis , Female , Food Analysis , Glycerol/analysis , Humans , MaleABSTRACT
The influence of dough composition on acrylamide, 3-monochloropropane-1,2-diol (3-MCPD) esters, and glycidyl esters (GE) formation during bread toasting was investigated. The doughs differed in added amounts of soy lecithin, salt, and reducing agents (l-cysteine and glutathione). The toasting of bread for 2.5 min considerably enhanced the formation of acrylamide and 3-MCPD esters. The addition of lecithin (1%, w/w) resulted in four times higher content of 3-MCPD esters in toasted bread slices. No distinct relationship between dough composition and GE formation in untoasted and toasted bread was found. The addition of reducing agents (0.05%, w/w) mitigated during toasting not only the formation of 3-MCPD esters (more than six times) but also the extent of Maillard reaction that resulted in three times lower amounts of acrylamide and predominant formation of alcohol-like compounds. Toasted bread without reducing agents contained typical Maillard reaction compounds such as aldehydes, alkyl pyrazines, and derivatives of furan.
Subject(s)
Bread/analysis , Cooking/methods , Saccharomyces cerevisiae/metabolism , Triticum/chemistry , Acrylamide/analysis , Esters/analysis , Gas Chromatography-Mass Spectrometry , Glutathione/chemistry , Lecithins/chemistry , Maillard Reaction , Solid Phase Microextraction , Triticum/metabolism , Volatile Organic Compounds/analysis , Volatile Organic Compounds/isolation & purification , alpha-Chlorohydrin/analysisABSTRACT
BACKGROUND: Glycidyl esters (GEs) have attracted worldwide attention for their potential harm to human health. The GEs in edible oils mainly form during the deodorization of the oil refining processes. We used sesamol and sesamolin to inhibit the formation of GEs in model corn oil (MCO), model palm oil (MPO) and model rice bran oil (MRO) during a deodorization process. RESULTS: The results showed that, in the three model oils, the total GE content was in the following order from highest to lowest: MRO (1437.98 µg kg-1 ) > MPO (388.64 µg kg-1 ) > MCO (314.81 µg kg-1 ). The inhibitory effect of the three antioxidants on the formation of GEs in the MCO was in the following order from strongest to weakest: tert-butylhydroquinone (TBHQ) > sesamol > sesamolin. CONCLUSION: When the mass percentage of sesamol was 0.05%, its inhibition percentage on GEs was close to the inhibition percentage of 0.02% added TBHQ. The present study provides a foundation for understanding how to inhibit the formation of GEs in oils by adding sesamol during the deodorization process.
Subject(s)
Benzodioxoles/analysis , Dioxoles/analysis , Epoxy Compounds/chemistry , Phenols/analysis , Plant Oils/chemistry , Antioxidants/analysis , Color , Food Additives/chemistry , Food Handling , Hot Temperature , Oxidation-Reduction , Palm Oil/chemistryABSTRACT
This study aimed to develop a mitigation strategy for the formation of 2-monochloropropane-1,3-diol esters (2-MCPDE), 3-monochloropropane-1,2-diol esters (3-MCPDE), and glycidol fatty acid esters (GE) during palm oil refining. Single physical refining was the starting point (the control) for this study. Experimental treatments including a double refining repeating the entire single refining process (T1), double refining with a high-low deodorization temperature (T2), and double deodorization (T3) with similar temperature settings as T2 were performed. Compared with the control experiment, T2 successfully reduced the formation of GE by 87%; in particular, the second degumming and bleaching were crucial for eliminating GE. Both 2- and 3-MCPDE were formed prior to the deodorization process in all treatments. MCPDE concentrations remained stable throughout the refining process and, hence, they require a different mitigation approach as compared to GE. These results provide useful insights which can directly be implemented by the oil industry.