Determination of chlordimeform and its metabolite residue in milk by gas chromatography-tandem mass spectrometry.

Herein, the determination of chlordimeform and its metabolite 4-chloro-2-methylaniline residue in milk was performed for the first time using gas chromatography-tandem mass spectrometry (GC-MS/MS). Samples were extracted using acetonitrile, and cleaned using a quick, easy, cheap, effective, rugged, and safe (QuEChERS) method. Separation was performed using the DB-17 MS column. It was detected in a selected reaction monitoring (SRM) mode and quantified using a matrix-matched isotope internal standard method. Under optimal conditions, a good linear relationship was observed in the concentration range of 10-200 µg/kg. The limit of quantitation was 10.0 µg/kg. The spiked recoveries for the target substance ranged from 84.5 % to 107.3 %, with relative standard deviations (RSD) of <7.2 %. The spiked samples were further confirmed by gas chromatography-quadrupole-Orbitrap high-resolution mass spectrometry (GC-Orbitrap HRMS). The combined method resulted in high accuracy and sensitivity and was suitable for the determination of chlordimeform and its metabolite 4-chloro-2-methylaniline residue in milk.

Determination of chloropropanol esters and glycidyl esters in nutritional foods by gas chromatography-tandem mass spectrometry based on acid hydrolysis and solid-phase extraction.

This study presents a method based on acid transesterification and the purification by solid-phase extraction (SPE) coupled with gas chromatography-tandem mass spectrometry for quantifying 3- and 2-monochloropropanediol esters (3-MCPDE, 2-MCPDE) and glycidyl esters (GE) in nutritional foods. The fat was extracted by liquid-liquid extraction with petroleum ether and diethyl ether after the sample was hydrolysed with ammonia. Then the extract was purified by a SPE cartridge filled with the aminopropyl sorbents. It was demonstrated that the optimal elution volume for 3-MCPDE, 2-MCPDE and GE greatly depended on the sample matrix and varied from 6 to 12 mL for four different kinds of food matrices. All three analytes in the sample solution could be fully collected in the first 10-12 mL of eluate. By this way, monoacylglycerols commonly present in the samples were fully removed. Therefore, the overestimation of GE quantification was effectively eliminated. The modified analytical procedure was fully validated in a single laboratory and has been recommended as a Chinese Food Safety National Standard. In addition, two derivatisation agents, heptafluorobutyrylimidazole and phenylboronic acid, were proved to be equivalent in method accuracy and precision for the quantification of three analytes.

Mitigation of 3-monochloropropane 1,2 diol ester and glycidyl ester in refined oil - A review.

The 3-Monochloropropane-1, 2-diol ester (3-MCPDE) and glycidyl ester (GE) are formed at high processing temperatures with the presence of respective precursors. Both are potentially harmful to humans, causing adverse health impacts including kidney damage, reproductive problems, and increased risk of cancer. The presence of 3-MCPDE and GE in palm oil is of particular concern because of its widespread use by the food industry. There are a variety of methods for reducing 3-MCPDE and GE. For example, water washing eliminates mostly inorganic chlorides that, in turn, reduce the formation of 3-MCPDE. 3-MCPDE has also been reduced by up to 99% using combinations of methods and replacing stripping steam with alcohol-based media. Activated carbon, clay, antioxidants, potassium-based salts, and other post-refining steps have positively lowered GE, ranging from 10 to 99%. Several approaches have been successful in reducing these process contaminants without affecting other quality metrics.

Food processing contaminants: Dietary exposure to 3-MCPD and glycidol and associated burden of disease for Italian consumers.

In this study we assessed Italian consumers' dietary exposure to 3-MCPD and glycidol followed by risk characterization, potential cancer risk and the associated burden of disease. Consumption data was retrieved from the most recent Italian Food Consumption Survey (2017-2020), while contamination data was obtained from the European Food Safety Authority. The level of risk due to exposure to 3-MCPD was negligible, below the tolerable daily intake (TDI), except for high consumption of infant formulas. For infants, the intake level was higher than the TDI (139-141% of TDI), indicating a potential health risk. Exposure to glycidol indicated a health concern for infants, toddlers, other children, and adolescents consuming infant formulas, plain cakes, chocolate spreads, processed cereals, biscuits, rusks, and cookies (margin of exposure (MOE) < 25,000). The risk of cancer due to exposure to glycidol was estimated and the overall health impact was quantified in Disability-Adjusted Life Years (DALYs). The risk of cancer due to chronic dietary exposure to glycidol was estimated at 0.08-0.52 cancer cases/year/100,000 individuals depending on the life stage and dietary habits in Italy. The burden of disease quantified in DALYs varied from 0.7 to 5.37 DALYs/year/100,000 individuals. It is crucial to continuously gather consumption and occurrence data for glycidol over time to track patterns, assess potential health risks, identify exposure sources, and develop effective countermeasures, as long-term exposure to chemical contaminants can lead to an increased risk for human health. This data is critical for protecting public health and reducing the likelihood of cancer and other health issues related to glycidol exposure.

Association between dietary 3-monochloropropane-1,2-diol esters (3-MCPDE) and renal cancer in Peninsular Malaysia: exposure assessment and matched case-control study.

3-Monochloropropane-1,2-diol esters (3-MCPDE) are food contaminants commonly found in refined vegetable oils and fats, which have possible carcinogenic implications in humans. To investigate this clinically, we conducted an occurrence level analysis on eight categories of retail and cooked food commonly consumed in Malaysia. This was used to estimate the daily exposure level, through a questionnaire-based case-control study involving 77 subjects with renal cancer, with 80 matching controls. Adjusted Odds Ratio (AOR) was calculated using the multiple logistic regression model adjusted for confounding factors. A pooled estimate of total 3-MCPDE intake per day was compared between both groups, to assess exposure and disease outcome. Among the food categories analysed, vegetable fats and oils recorded the highest occurrence levels (mean: 1.91 ± 1.90 mg/kg), significantly more than all other food categories (p < .05). Risk estimation found the Chinese ethnic group to be five times more likely to develop renal cancer compared to Malays (AOR = 5.15, p = .001). However, an inverse association was observed as the 3-MCPDE exposure among the Malays (median: 0.162 ± 0.229 mg/day/person) were found to be significantly higher than the Chinese (p = .001). There was no significant difference (p = .405) in 3-MCPDE intake between the cases (median: 0.115 ± 0.137 mg/day/person) and controls (median: 0.105 ± 0.151 mg/day/person), with no association between high intake of 3-MCPDE and the development of renal cancer (OR = 1.41, 95% CI: 0.5091-2.5553). Thus, there was insufficient clinical evidence to suggest that this contaminant contributes to the development of renal malignancies in humans through dietary consumption. Further research is necessary to support these findings, which could have significant public health ramifications for the improvement of dietary practices and food safety measures.

3-MCPD as contaminant in processed foods: State of knowledge and remaining challenges.

3-Chloro-1,2-propanediol (3-MCPD) and its fatty acid esters (FE) are present as contaminants in different processed foods. Based on the available toxicological data the potential risk of 3-MCPD and its FE to human health was assessed by risk assessment authorities, including the European Food Safety Authority (EFSA). Considering the available data, EFSA concluded that 3-MCPD is a non-genotoxic compound exhibiting secondary carcinogenic effects in rodents. A tolerable daily intake of 2 µg/kg body weight and day was derived by EFSA for free and ester-bound 3-MCPD in 2018. However, there are still different pending issues that have remained unclear until now. Here, we summarize the current knowledge regarding 3-MCPD and its FE with a focus on pending issues regarding exposure assessment via biomarkers as well as the identification of (toxic) metabolites formed after exposure to FE of 3-MCPD and their modes of action.

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.

Ultrasound-assisted enzymatic indirect determination of total 3-monochloropropane-1,2-diol esters in canned fish oil fraction.

A novel, fast, and cost-effective indirect enzymatic method was successfully developed to assess the total 3-monochloropropane-1,2-diol (3-MCPD) in canned food's oil fraction by the action of Burkholderia cepacia lipase. The total 3-MCPD were derivatized with n-Heptafluorobutyrylimidazole (HFBI) for GC-MS analysis during dispersive liquid-liquid microextraction (DLLME). An asymmetrical 2213//8 screening design was used to study the influence of critical factors on the method's effectiveness. The analytical features of the proposed method were assessed following Food and Drug Administration (FDA) guidelines using extra virgin olive oil (EVOO) as a blank sample. Outstanding results were achieved in terms of linearity (r2 = 0.9995), sensitivity, precision (2.1 % to 10.4 % RSD), and accuracy (98.7 % ≤ recovery ≤ 101.9 %). Method efficacy was tested by comparing the results of 10 edible oils for total 3-MCPD with those reported in previous works. A total of 41 samples were analyzed. The lowest 3-MCPD content was found in samples of albacore canned in EVOO oil, while the highest amounts were found in albacore, mackerel, and Atlantic saury samples, all preserved in refined sunflower oil.

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.

In-syringe cotton fiber-supported liquid extraction coupled with gas chromatography-tandem mass spectrometry for the determination of free 3-mono-chloropropane-1,2-diol in edible oils.

In the current study, natural cotton fiber was served as the supporter of water, and the water acted as an extractant for liquid-phase microextraction of polar components in low-polar edible oils. An in-syringe extraction device was constructed to facilitate the extraction process by simply loading a certain amount of cotton fibers between the syringe needle and the plastic syringe tube. Then, the extraction process can be conveniently conducted by pull-push the syringe plunger. It can be regarded as a new type of dynamic liquid-phase microextraction method while operated more convent. For the feasibility study, the novel in-syringe cotton fiber-supported liquid extraction (CF-SLECF-SLE) pretreatment method was applied to extract free 3-mono-chloropropane-1,2-diol (3-MCPD) in edible oils. Specifically, the cotton fibers supported a certain amount of water by successfully pulling-pushing 1 mL of water and 1 mL of HEX in/out twice, respectively. Then, 2.0 mL of diluted oil sample (containing 0.4 g oil) was loaded in and out four times for extraction, during which process 3-MCPD was extracted into the supported water. The extracted 3-MCPD was desorbed with 1 mL of ethyl acetate (EA), derivatized with trimethyl silane imidazole (TMSI), and analyzed by gas chromatography-tandem mass spectrometry (GC-MS/MS). For three different spiked edible oils, the internal standard normalized matrix effect (IS-normalized ME) values were in ranges of 96.3-104.8% with RSD being 4.3%, benefiting the accurate quantitative analysis. The limit of quantification (LOQ) was calculated to be 2 ng/g, which met the regular determination requirement of 3-MCPD in edible oils. Satisfied linearity was obtained in 2-500 ng/g, with correlation coefficients (R2) being 0.998. The relative recoveries were in the ranges of 96.9-110.5%. The intra-/inter-day RSDs were less than 8.2% and 10.2%, respectively. The proposed method provides an efficient, simple, low-cost, and easy to automate strategy for determining free 3-MCPD in edible oils.

Urinary non-targeted toxicokinetics and metabolic fingerprinting of exposure to 3-monochloropropane-1,2-diol and glycidol from refined edible oils.

The widespread presence of 3-monochloropropane-1,2-diol (3-MCPD) and glycidol in refined edible oils have raised food industrial and public health concerns, but their specific biomarkers of exposure and urinary metabolic pathways indicating nephrotoxicity remain largely unknown. Here, we unraveled the in vivo biotransformation of these two contaminants and revealed how they affect metabolic pathways in rats. Urine metabolomes in rats administered with glycidol or 3-MCPD were investigated using ultra-high performance liquid chromatography combined with a quadrupole-orbitrap high-resolution mass spectrometry. Compared to the currently acknowledged metabolite which is only 2,3-dihydroxypropyl mercapturic acid, we identified 8 and 4 new specific exposure biomarkers of glycidol and 3-MCPD, respectively, via mapping the glyceryl polymerization and glutathione and sulfur conjugation. The changes of metabolites in the surrounding metabolic network were investigated to further gain insight into their metabolic fates. Exposure to glycidol up-regulated citrate, isocitrate, ketoglutarate, malate, and pyruvate in the tricarboxylic acid cycle and glycolysis pathways, while 3-MCPD intake down-regulated these signal molecules in both pathways. Nonetheless, L-cysteine, proline, and arginine were significantly decreased by the effect of either glycidol or 3-MCPD. Our findings first map the urinary metabolomics of both contaminants from edible oils and advance the omics-level recognition for their observational health hazards.

Investigation of factors influencing the release of chloropropanols (3-MCPD and 1,3-DCP) from food contact paper.

Chloropropanols such as 3-monochloropropane-1,2-diol (3-MCPD) and 1,3-dichloro-2-propanol (1,3-DCP) have drawn increasing attention due to their release from food contact paper and their potential carcinogenic effects. In this study, the effects were investigated of water extraction conditions on release of chloropropanols from food contact paper, and the extraction efficiencies of chloropropanols by water extract and migration method were compared. Cold water was found to be more severe than hot water for extraction of chloropropanols, with the highest water extraction value obtained at 23°C. Two hours of extraction was sufficient as the chloropropanols can be fully extracted from food contact paper within a short period of time. Increase of temperature in the range of 10°C-60°C had little impact on release of chloropropanols, however, the extraction of chloropropanols decreased when high temperatures (80°C or above) were applied due to volatilisation losses. Hence, attention should be paid when choosing extract conditions representing the worst-case scenario. The water extraction value using EN 645 method gives higher results compared to migration test described in GB 31604.1 and GB 5009.156, suggesting that the water extract method was probably more severe. For migration test, aqueous-based simulants were found to be more conservative than oil-based simulants, suggesting the conventional experiment conditions applicable for compliance test of chloropropanols migration can be simplified and optimised.

Chloropropanols (3-MCPD, 1,3-DCP) from food contact materials: GC-MS method improvement, market survey and investigations on the effect of hot water extraction.

The chloropropanols, monochloropropane-1,2-diol (3-MCPD) and 1,3-dichloro-2-propanol (1,3-DCP) are potential contaminants that may be found in food contact materials (FCM) from paper and paperboard that have been treated with certain wet-strength resins. They can migrate from the paper matrix to aqueous food and beverages and, due to their potentially carcinogenic properties, are of increasing interest in quality assurance or official controls of paper-based FCM. We hereby describe an improved method for the analysis of 3-MCPD and 1,3-DCP in water extracts of FCM making use of 1-chloro-3-methoxy-2-propanol (CMP) as a novel internal standard. The LOD and LOQ were determined to be 0.4 µg/L and 1.2 µg/L for both analytes, making the method appropriate for the quantification of 3-MCPD and 1,3-DCP below the current legal limits. The method was applied to an extensive market survey of food contact articles made from paper and paperboard including 674 samples. The survey revealed that a high percentage of the products available on the market (e.g., up to 55% of the analysed drinking straws) exceed the BfR limits with values of up to 327 µg/L 3-MCPD and 20 µg/L 1,3-DCP detected in the cold water extract. Remarkable differences were observed concerning the release of 3-MCPD and 1,3-DCP from different kinds of paper-based FCM products, with drinking straws, cupcake cases, bagasse bowls and kitchen rolls showing particularly high rates (>10%) of non-conformity with the legal limits. A number of samples with especially high concentrations were additionally analysed by hot water extraction, which surprisingly yielded considerably lower results for the release of 3-MCPD and 1,3-DCP than cold water extraction. The results indicate that cold water extraction is the most sensitive method to detect the migration and control the risk of exposure to 3-MCPD and 1,3-DCP.

Determination of 3-monochloropropanediol esters and glycidyl esters in fatty matrices by ultra-high performance liquid chromatography-tandem mass spectrometry.

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.

Chloride reduction by water washing of crude palm oil to assist in 3-monochloropropane-1, 2 diol ester (3-MCPDE) mitigation.

Chloride reduction in crude palm oil (CPO) of greater than 80% was achieved with water washing conducted at 90°C. Inorganic chloride content in CPO was largely removed through washing, with no significant reduction in the organic chloride. Phosphorous content of CPO reduced by 20%, while trace elements such as calcium, magnesium and iron were also reduced in the washing operation. The 3-MCPDE formed in the refined, bleached and deodorised palm oil displayed (RBDPO) a linear relationship with the chloride level in washed CPO, which could be represented by the equation y = 0.91x, where y is 3-MCPDE and x represents the chloride in RBDPO refined from washed CPO. In plant scale trials using 5% water at 90°C, mild acidification of the wash water at 0.05% reduced chloride by average 76% in washed CPO. Utilising selected bleaching earths, controlled wash water temperature and wash water volume produced low chloride levels in RBDPO. Chloride content less than 1.4 mg kg-1 in plant RBDPO production was achieved, through physical refining of washed CPO containing less than 2 mg kg-1 chloride and would correspond to 3-MCPDE levels of 1.25 mg kg-1 in RBDPO. The 3-MCPDE reduced further to 1.1 mg kg-1 as the chloride level of washed CPO decreased below 1.8 mg kg-1. Chloride has been shown to facilitate the 3-MCPDE formation and its removal in lab scale washing study has yielded lower 3-MCPDE levels formed in RBDPO. In actual plant operations using washed CPO, 3-MCPDE levels below 1.25 mg kg-1 were achieved consistently in RBDPO.

Determination of glycidyl esters and 3-MCPD esters in edible oils by sample pretreatment with the combination of lipase hydrolysis and modified QuEChERS for GC-MS analysis.

Glycidyl esters (GEs) and 3-chloroprapane-1,2-diol esters (3-MCPDEs) are processing contaminants in refined edible oils that have raised concerns globally owing to their potentially carcinogenic properties. Official analytical methods for GEs and 3-MCPDEs, such as AOCS Cd 29a-13 and AOCS Cd 29b-13, require up to 16 h for chemical hydrolysis. Also, parallel experiments should be conducted to correct for the conversion of analytes during hydrolysis in AOCS Cd 29b-13. For AOCS Cd 29c-13 with the shortest operating time, the reaction time (3.5-5.5 min) and temperature of alkaline hydrolysis should be carefully controlled, implying the accuracy may be influenced by human errors. Here, we propose a novel method based on Candida rugosa lipase hydrolysis and direct detection of free form GEs, glycidol, which was achieved by sample preparation with modified QuEChERS, to prevent side reactions in previous approaches, and also to shorten the overall sample preparation time. Glycidol was directly analyzed without halogenation and derivatization, whereas 3-MCPD required derivatization for analysis by GC-MS. Our method showed good accuracy and precision in terms of repeatability, intermediate precision, and reproducibility (inter-laboratory precision). The limit of detection (LOD) and limit of quantification (LOQ) for glycidol were 0.02 and 0.1 mg/kg, which is sufficient for practical applications. The proposed method was further compared with AOCS Cd 29c-13 by determination of GEs content in commercial oil samples and spiked samples. Our method with a streamlined procedure seems to possess potential advantage of reduced errors from operational factors. This proposed method based on direct detection of glycidol may serve as a simplified alternative for routine analysis of GEs and 3-MCPDEs in edible oils.

Simple and rapid detection of free 3-monochloropropane-1,2-diol based on cysteine modified silver nanoparticles.

A rapid colorimetric method using cysteine-modified silver nanoparticles (Cys-AgNPs) is applied for the detection of 3-monochloropropane-1,2-diol (3-MCPD). Indeed, in the presence of 3-MCPD, the color of Cys-AgNPs solution changes from yellow to pink within five minutes at 100 °C and pH 9.3. This change is mainly attributed to the ability of amino group of cysteine to react with 3-MCPD to form N-(2,3-dihydroxypropyl)-amino acid grafted on AgNPs (3-MCPD-Cys-AgNPs) in alkaline medium. This color change makes 3-MCPD to be clearly detectable by unassisted visual means even at 0.1 µg⋅mL-1. Besides, using UV-Vis spectroscopic technique, a linear range from 0.1 µg⋅mL-1 to 1.25 µg⋅mL-1 for 3-MCPD detection is obtained, with a calculated detection limit of 0.084 µg⋅mL-1. These results suggest that this sensing technique is sensitive to 3-MCPD and may have a substantial application in the rapid detection of food contaminants particularly, where quality and safety of food products are paramount concern.

Influence of dough composition on the formation of processing contaminants in yeast-leavened wheat toasted bread.

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.

In-house validation of accelerated solvent extraction-gas chromatography-mass spectrometry for the determination of bound 3- and 2-monochloropropanediols (MCPD) and glycidol in food products.

The study aimed to establish the detection method for bound 3-, 2-MCPD, and glycidol using accelerated solvent extraction (ASE) and gas chromatography mass spectrometry (GC-MS). The ASE was modified for reduced solvent volume and process time to extract lipid from the chocolate spread, infant formula, potato chips, and sweetened creamer. The solvent selected for ASE was a mixture of iso-hexane and acetone at 100°C with the lipid and analyte recovery ranging from 96.9% to 98.6% and 84.1% to 107.5%, respectively. The derivatisation of analytes was adopted from the AOCS method Cd29a-13 for GC-MS analysis. The results showed that the coefficient of determination (R2) of all analytes was >0.99. The limit of detection (LOD) was 0.1 mg kg-1 expressed in lipid basis for both bound 3- and 2-MCPD and 0.2 mg kg-1 expressed in lipid basis for bound glycidol. The limit of quantitation (LOQ) was 0.3 mg kg-1 expressed in lipid basis for both bound 3- and 2-MCPD and 0.6 mg kg-1 expressed in lipid basis for bound glycidol. A blank spiked with 3-monochloropropanediols fatty acid esters (MCPDE) and 2-MCPDE (0.3, 2.1, and 7.2 mg kg-1) and glycidol esters (0.6, 4.7, and 16.6 mg kg-1) were chosen for accuracy and precision tests. The recoveries were 91.7% to 105.9%. Both repeatability and within-laboratory reproducibility of the analysis were within the acceptable level of precision ranging from 1.7% to 16%. This is the first time that a full validation procedure extending to both accuracy and precision tests has been carried out for sweetened creamer and chocolate spread. Overall, the combined protocol of ASE and AOCS Cd29a-13 was successfully validated for both solid and liquid food samples with lipid content from 10% to 30%.

Dietary exposure of general Chinese population to fatty acid esters of 3-monochloropropane-1, 2-diol (3-MCPD) from edible oils and oil-containing foods.

Edible oils and oil-containing foods have been regarded as the main source of 3-monochloropropane-1, 2-diol (3-MCPD) esters. A total of 3,847 individual food samples were collected in China to carry out 3-MCPD fatty acid esters analysis. The samples comprising edible oils, fried foods and bakery foods from 31 Chinese provinces, municipalities and autonomous regions were obtained from the national food contaminant information system during 2015-2017. The dietary exposure and potential risks associated with the consumption of 3-MPCD esters from edible oils and oil-containing foods were estimated using a semi-probabilistic assessment model. Concentrations of 3-MCPD fatty acid esters in food samples were detected by gas chromatography-mass spectrometry (GC-MS). The mean levels of 3-MCPD fatty acid esters in edible oils, fried foods and bakery foods were 0.862, 0.249 and 0.145 mg/kg, respectively. The range of mean dietary intakes of 3-MCPD esters in different subpopulation groups (classified by gender and age) was from 0.586 to 1.539 µg/kg bw/day, which were all lower than 2 µg/kg bw/day - the tolerable daily intake (TDI) established by the European Food Safety Authority (EFSA). The range of dietary intake of 3-MCPD esters in high consumers (95th percentile) in each group was from 1.511 to 4.027 µg/kg bw/day, which accounted for 75.6% to 201.4% of the TDI. The 3-MCPD esters exposure level of 3.5% of the total Chinese population exceeded the TDI. The findings indicate that the potential health risks caused by dietary 3-MCPD esters from edible oils and oil-containing foods were of low concern for most of the Chinese population. However, the exposure risk of the consumers with excessive edible oil consumption calls for attention.