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Mayonnaise is a commonly used oil-in-water emulsion food product. Due to their toxicological properties/genotoxicity and carcinogenicity, chloropropanols' oral exposure has raised concerns over the past decade. The present study reports the occurrence level of free forms of 3-chloropropane-1,2-diol (3-MCPD) and 1,3-dichloro-2-propanol (1,3-DCP) in mayonnaise samples and the risk of oral exposure to these chemicals through consumption of the analyzed samples. Mayonnaise (low- and high-fat, from 6 brands, totally 120 samples) were analyzed for 1,3-DCP and 3-MCPD by gas chromatography-mass spectrometry. The mean level of chemicals was higher in the high-fat samples, with no significant difference among the brands. Generally, 1,3-DCP level was significantly lower in both high-fat and low-fat samples compared to 3-MCPD. Hazard Index (HI) values calculated for oral exposure to 3-MCPD for Iranian adults using probabilistic methods, were less than 1.0, reflecting no major risk. In the Margin of Exposure scenario, low- and high-fat mayonnaise samples were of de minimis health concern at the 50th, 80th, and 95th centiles. Nevertheless, in order to safeguard consumer interests, it is imperative to implement online real-time methodologies for monitoring reactions that result in generation of thermal process contaminants such as 3-MCPD and 1,3-DCP, and to innovate novel technologies to minimize the occurrence of such chemicals while preserving both safety and sensory attributes.

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What is already known about this topic?: Chloropropanols, along with their fatty acid esters and glycidyl fatty acid esters (GEs), are prevalent contaminants in a variety of processed foods, posing potential health risks to humans. What is added by this report?: In the Sixth China Total Diet Study (TDS), 3-monochloropropane-1,2-diol esters (3-MCPD esters) and GEs were identified as the predominant chloropropanols and their esters in composite food samples. Vegetables (47.0%) and cereals (15.4%) were the major contributors to exposure among the 12 food categories evaluated. What are the implications for public health practice?: The Sixth China TDS highlighted concerns regarding potential health risks associated with dietary exposure to GEs. This study underscores the need for further attention in devising practical strategies to mitigate dietary exposure to GEs.

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Chloropropanols, one of the major contaminants in food, and the corresponding esters or glycidyl esters (GEs) are of great concern in terms of product safety due to their potential carcinogenicity. During heat processing, glycerol, allyl alcohol, chloropropanol esters, sucralose, and carbohydrate in mixed foodstuffs are probable precursors of chloropropanol. The standard analytical techniques for chloropropanols or their esters are GC-MS or LC-MS following sample derivatization pretreatment. By comparing modern data against that five-year-old before, it appears that the levels of chloropropanols and their esters/GEs in food products have somewhat decreased. 3-MCPD esters or GEs may yet exceed the permitted intake set, however, especially in newborn formula which requires particularly stringent regulatory measures. Citespace (6.1. R2) software was employed in this study to examine the research focii of chloropropanols and their corresponding esters/GEs in the literature.

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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.

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Chloropropanols and their esters are a group of food contaminants that have various toxicities to the human body. Research and control to chloropropanols and their esters is important to food safety. Therefore, the sensitive, accurate, precise, and effective determination of chloropropanols and their esters is highly essential to study their concentration, formation, and mitigation. The indirect method, commonly applied in the determination of chloropropanols and their esters, is based on the cleavage of ester bond, extraction, and derivatization. The conventional indirect method will still be the mostly used method in the near future due to its good sensitivity and feasibility, although its parameters need to be chosen and optimized according to sample stuffs and chloropropanol concentrations. Meanwhile, direct method and other quantitative methods should also be developed for special applications, such as studying the profile of chloropropanol esters and rapid screening protocol. The challenges and future perspectives of these methods are discussed in this review. This review can provide a reference on the selection, designation, and modification of methods for determining chloropropanols and their esters.

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Electronic cigarettes (e-cigarettes) have gained increasing popularity in recent years, mostly because they are supposed to be less harmful than regular cigarettes. Therefore, it is highly imperative to investigate possible noxious effects to protect the consumers. E-liquids consist of propylene glycol, glycerol, aroma compounds and sweeteners. One of these sweeteners is a chlorinated version of sucrose, namely sucralose. The aim of this work was to investigate degradation products of sucralose in the presence of propylene glycol and glycerol at different temperatures of commercially available e-cigarettes. Chemical analysis and biological tests were simultaneously performed on e-liquid aerosol condensates. The results of the chemical analysis, which was executed by employing GC-MS/GC-FID, demonstrated high amounts of various chloropropanols. The most abundant one is extremely toxic, namely 3-chloropropane-1,2-diol, which can be detected at concentrations ranging up to 10,000 mg/kg. Furthermore, a cytotoxicity investigation of the condensates was performed on HUVEC/Tert2 cells in which metabolic activity was determined by means of resazurin assay. The cellular metabolic activity significantly decreased by treatment with e-liquid aerosol condensate. Due to the results of this study, we advise against the use of sucralose as sweetener in e-liquids.

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Food contamination is a serious concern because of a high level of chemicals in food causes severe health issues. Safeguarding the public from the risk of adulterated foods has become a challenging mission. Chloropropanols are of importance to food safety and food security because they are common chemical food contaminants and believed to be carcinogenic to humans. In chemical sensing, chloropropanols are challenging analytes owing to the lacking diversity of functional groups and difficulty in targeting the hydroxyl group in aqueous environments. Moreover, because of their small molecular size, the compositions of chloropropanols remain challenging for achieving chromatographic determination. Herein, to simulate human smell and taste sensations, serum albumins, which are protein-based receptors, were introduced as low-selective receptors for differential sensing. Utilizing serum albumins, a fluorophore (PRODAN), and an additive (ascorbic acid), a differential-based optical biosensor array was developed to detect and differentiate chloropropanols. By integrating the sensor array with linear discriminant analysis (LDA), four chloropropanols were effectively differentiated based on their isomerism properties and the number of the hydroxyl groups, even at ultra-low concentration (5 nM). This concentration is far below the maximum tolerable level of 0.18 µM for chloropropanols. The sensing array was then employed for chloropropanols differentiation and quantification in the complex mixtures (e.g., synthetic soy and dark soy sauces). Leave-one-out cross-validation (LOOCV) analysis demonstrated 100% accurate classification for all tests. These results signify our differential sensing array as a practical and powerful tool to speedily identify, differentiate, and even quantify chloropropanols in food matrices.

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Sucralose is widely used as non-caloric intense artificial sweetener. It was previously considered to be thermally stable and safe. This was based on studies performed in the early 1990s. However, significant concerns have been raised more recently regarding the physicochemical stability of sucralose at high temperatures in the context of food processing. Over the last decades different independently performed studies indicated that sucralose is decomposed at high temperatures, e.g. through cooking. This - in turn - was considered to be associated with the formation of chlorinated potentially toxic compounds, such as chloropropanols and dioxins. In this review, the literature on thermal stability of sucralose and the generation of potentially toxic compounds was assessed and comparatively discussed. Considering the validity of published data, we conclude that sucralose can be degraded at high temperatures, e.g. during cooking or baking of sucralose-containing foods. As a consequence potentially toxic chlorinated compounds might be generated.

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2-monochloropropanediol (2-MCPD), 3-monochloropropanediol (3-MCPD) and their fatty acid esters have recently been identified as heat-induced contaminants in fat- and salt-containing foodstuff. Toxicity of 3-MCPD has been studied previously in some detail. Disturbance of glycolysis and cellular redox functions appear to be involved in 3-MCPD toxicity. By contrast, only very few toxicological data are available for 2-MCPD or 2-MCPD esters, especially at the molecular level. This study was therefore aimed to provide a comprehensive overview of proteomic alterations induced in rat kidney and liver by 2-MCPD and 2-MCPD dipalmitate, a representative 2-MCPD fatty acid ester. Sub-toxic doses of 10 mg/kg body weight 2-MCPD, or equimolar doses of 2-MCPD dipalmitate were applied in a 28-day in vivo gavage oral toxicity study in male rats. Two-dimensional gel electrophoresis and mass-spectrometric protein identification using material from 5 animals per treatment group were employed together with bioinformatic data mining to obtain information about the molecular basis of the observed proteomic alterations. Obtained data indicate toxic consequences of 2-MCPD exposure in the kidney and provide evidence that 2-MCPD exerts its cellular effects in rat kidney by mechanisms different from 3-MCPD.

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A new route to synthesize a covalent interaction-based molecularly imprinted polymer (MIP) material for 3-chloro-1,2-propanediol (3-MCPD) inside the nanopores of anodic alumina oxide (AAO) is presented. A series of adsorption experiments showed MIP had good extraction capacity and selectivity for 3-MCPD. In order to evaluate the usability of the MIP nanotubes membrane, a method combining AAO@MIP membrane extraction with gas chromatography - mass spectrometry (GC-MS) detection was developed for determination of chloropropanols. The limits of detection for the proposed method were 0.072 and 0.13 µg·L-1, respectively, for 3-MCPD and 1,3-DCP. The average recoveries of 3-MCPD and 1,3-DCP spiked oil samples at three concentrations (0.01, 0.05 and 0.1 mg·kg-1) were in the range of 75.6-101.0% with a RSD of 3.3-8.4%, indicating the method would be suitable for determination of chloropropanols in vegetable oils.

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Objective To establish an isotope dilution gas chromatography-mass spectrometry(GC-MS)for the determination of chloropropanol esters in fried foods.Methods A total of 88 fried food samples were collected from supermarket,breakfast shop and street breakfast,stalls,the fried food sample with no chloropropanols esters detected was used as the blank sample. Samples were extracted using a solvent extraction method,followed by ester-bond cleavage reaction with sodium methylate-methanol and purification by diatomite solid-supported liquid-liquid extraction column. The derivatives in purified solution was detected by GC-MS after being derivatived with heptafluoro butyrylimidazole. The concentration of chloropropanols esters was quantified by using deuterium isotopes as internal standards. The accuracy of the method for evaluating recovery rate of blank samples was adopted,and the relative standard deviation(RSD)of the recovery rate represents the precision of the method.Results The 3-MCPD ester and 2-MCPD ester had good linear relationship in the concentration range of 25-1000 g/L(r>0.9995). The detection limits of 3-MCPD ester and 2-MCPD ester were 20μg/kg. The recovery rate of fat extracts from blank samples at 25,50,100,and 200μg/kg levels ranged from 89.7% to 103.7%,and RSD<8.4%. The detection rates of 3-MCPD ester and 2-MCPD ester in 88 samples were 81.82% and 70.45% respectively,and the content ranges from not-detected(ND) to 1.65mg/kg and to 0.93 mg/kg respectively.Conclusion The method is simple,accurate and reliable. It is suitable for the determination of chloropropanol esters in fried foods. There is a certain degree of contamination of chloropropanol esters in fried foods,and this comtamination is quite common.

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A method was established for the simultaneous determination of the total fatty acid esters of chloropropanols in edible oils by gas chromatography-mass spectrometry combined with isotope dilution technology. The samples were hydrolyzed with sodium methylate-methanol, and then purified by diatomite cartridge. After being derivatized with heptafluorobutyrylimidazole ( HFBI ), the target analytes were determined by GC-MS with the deuteriumchloropropanols esters as the internal standards. An excellent linear correlation in the range of 0. 050-2. 000 mg / L was acquired for 3-monochloropropane-1,2-diol (3-MCPD) esters, 2-MCPD esters, dichloropropan-2-ol (1,3-DCP) esters and 2,3-dichloropropan-1-ol (2,3-DCP) esters, with all the correlation coefficients (r) higher than 0. 9995. The limits of detection (LODs) for 3-MCPD esters, 2-MCPD esters, 1,3-DCP esters and 2,3-DCP esters were 0. 015, 0. 015, 0. 030, and 0. 030 mg / kg, respectively, and the limits of quantitation (LOQ) were 0. 050, 0. 050, 0. 100, and 0. 100 mg / kg, respectively. The average spike recoveries of the four kinds of chloropropanols esters in blank extra virgin olive oil matrix were typically in a range of 87. 0% -110. 5% with the relative standard deviations (RSDs) less than 10. 1% . The detection rates of 3-MCPD esters, 2-MCPD esters, 1,3-DCP esters and 2,3-DCP esters in 74 edible oil samples were 94. 6% , 63. 5% , 5. 4% , and 0% , respectively. The contamination levels of 3-MCPD esters, 2-MCPD esters and 1,3-DCP esters were in the range of not detected (ND) to 10. 646 mg / kg, ND to 3. 617 mg / kg and ND to 0. 089 mg / kg, respectively. This method is accurate and rugged for the simultaneous determination of total fatty acid esters of chloropropanols in edible vegetable oils.

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Chloropropanols are processing toxicants with a potential risk to human health due to the increased intake of processed foods. A rapid and efficient method for the determination of three chloropropanols in human plasma was developed using ultrasound-assisted dispersive liquid-liquid microextraction. The method involved derivatization and extraction in one step followed by gas chromatography with tandem mass spectrometry analysis. Parameters affecting extraction, such as sample pH, ionic strength, type and volume of dispersive and extraction solvents were optimized by response surface methodology using a pentagonal design. The linear range of the method was 5-200 ng/mL for 1,3-dichloro-2-propanol, 10-200 ng/mL for 2,3-dichloro-2-propanol and 10-400 ng/mL for 3-chloropropane-1,2-diol with the determination coefficients between 0.9989 and 0.9997. The limits of detection were in the range of 0.3-3.2 ng/mL. The precision varied from 1.9 to 10% relative standard deviation (n = 9). The recovery of the method was between 91 and 101%. Advantages such as low consumption of organic solvents and short time of analysis make the method suitable for the biomonitoring of chloropropanols.

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The discovery of fatty acid esters of monochloropropanediol (MCPD) and glycidol generated during the refinement process in vegetable fats and oils caused concerns about possible adverse health effects. As these fats are components of infant formula, the current investigation of the MCPD and glycidyl ester contents in infant formula was necessary to update the data for risk assessment purposes. For the analysis of 3-MCPD, 2-MCPD and glycidyl esters in infant formula, an existing method for fats and oils had to be modified and validated. The fat fraction containing MCPD and glycidyl esters was extracted from infant formula by accelerated solvent extraction (ASE). The extracted fat was then analysed according to an established method for fats and oils. Glycidyl esters are converted to monobrompropanediol (3-MBPD) esters, MCPD and 3-MBPD esters hydrolysed subsequently and after derivatisation detected by GC-MS. Seven different products of infant formula, covering two types and five lots each, altogether 70 samples, were bought in retail markets and analysed. In all samples, 3-MCPD and glycidyl esters could be detected. Both 3-MCPD and glycidyl esters' concentration levels were found to be lower in comparison with earlier investigations described in the literature. The occurrence of 2-MCPD esters in infant formula was investigated for the first time and revealed concentrations about half of 3-MCPD ester concentrations.

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Sodium chloride has been shown to promote chlorination of glycerol during thermal processing. However, the detailed mechanism of this reaction is not well understood. Preliminary experiments have indicated that the reaction mixture should contain an amino acid and it should be dissolved thoroughly in water in order to induce chlorination. These observations are consistent with the process of dissociation of sodium chloride and its re-association with amino acid and eventual formation of the chlorinating agent in the form of the hydrochloride salt. Release of HCl from this salt can be manifested in chlorination and hydrolytic reactions occurring during thermal processing. The generation of HCl at room temperature from a mixture of sodium chloride and glycine was confirmed through spectrophotometric monitoring of the pH. Hydrolytic and chlorination reactions were demonstrated through monitoring of formation of HMF and chlorinated products under pyrolytic conditions using glucose or sucrose and amino acid mixtures.

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Substantial progress has been recently made in the development and optimisation of analytical methods for the quantification of 2-MCPD, 3-MCPD and glycidyl esters in oils and fats, and there are a few methods currently available that allow a reliable quantification of these contaminants in bulk oils and fats. On the other hand, no standard method for the analysis of foodstuffs has yet been established. The aim of this study was the development and validation of a new method for the simultaneous quantification of 2-MCPD, 3-MCPD and glycidyl esters in oil-based food products. The developed protocol includes a first step of liquid-liquid extraction and purification of the lipophilic substances of the sample, followed by the application of a previously developed procedure based on acid transesterification, for the indirect quantification of these contaminants in oils and fats. The method validation was carried out on food products (fat-based spreads, creams, margarine, mayonnaise) manufactured in-house, in order to control the manufacturing process and account for any food matrix-analyte interactions (the sample spiking was carried out on the single components used for the formulations rather than the final products). The method showed good accuracy (the recoveries ranged from 97% to 106% for bound 3-MCPD and 2-MCPD and from 88% to 115% for bound glycidol) and sensitivity (the LOD was 0.04 and 0.05 mg kg(-1) for bound MCPD and glycidol, respectively). Repeatability and reproducibility were satisfactory (RSD below 2% and 5%, respectively) for all analytes. The levels of salts and surface-active compounds in the formulation were found to have no impact on the accuracy and the other parameters of the method.

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A novel approach involving ultrasound-assisted dispersive liquid-liquid microextraction (UA-DLLME) and derivatization combined with gas chromatography-mass spectrometry was developed for the determination of chloropropanols in water and beverages. UA-DLLME was optimized as less solvent-consuming and cost-effective extraction method for water, fruit juice, milk and soy milk samples. The effect of parameters such as the type and volume of extraction solvent, the type and volume of dispersive solvent, amount of derivatization agent, temperature, pH of sample and ionic strength was investigated and optimized for each specimen, using experimental designs. By adding acetonitrile as dispersive solvent, N-heptafluorobutyrylimizadole (HFBI) as derivatization agent and chloroform as extraction solvent, the extraction-derivatization and preconcentration were simultaneously performed. The analytical concentration range was investigated in detail for each analyte in the different samples, obtaining linearity with R(2) ranging between 0.9990 and 0.9999. The method detection limits were in the range of 0.2-1.8µgL(-1) (water), 0.5-15µgL(-1) (fruit juices) and 0.9-3.6µgkg(-1) (milk) and 0.1-1.0µgkg(-1) (soy milk). The method was applied to the analysis of a variety of specimens, with recoveries of 98-101% from water, 97-102% from juices, 99-103% from milk and 97-105% from soy beverage. The relative standard deviation (precision, n=6) varied between 1.3 and 4.9%RSD in water, 2.3 and 5.8%RSD in juices, 1.0 and 5.7%RSD in milk and 3.9 and 9.3%RSD in soy milk. The proposed method was applied to analysis of twenty-eight samples. 1,3-Dichloro-2-propanol was found in an influent water sample from urban wastewater treatment plant (WWTP) (2.1±0.04mgL(-1)) but no chloropropanols were found in the corresponding effluent water sample. This result suggests that the purification system used in the WWTP has been effective for this compound. Moreover, the results revealed the presence of 3-chloropropane-1,2-diol (3-MCPD) and 2,3-dicloro-2-propanol (2,3-DCP) in soy milk at concentrations within the ranges 19.2-95.0µgkg(-1) and 3.0-14.3µgkg(-1), respectively. The method is suitable for the determination of target contaminants in liquid samples, particularly for environmental and safety food control fields.

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This study aimed to establish a novel robust method for the simultaneous determination of total fatty acid esters of 4 chloropropanols including fatty acid esters of 3-monochloropropane-1,2-diol (3-MCPD esters), 2-monochloropropane-1,3-diol (2-MCPD esters), 1,3-dichloropropan-2-ol (1,3-DCP esters) and 2,3-dichloropropan-1-ol (2,3-DCP esters) in edible oils. In this method, sodium methylate in methanol was used as the reagent for the ester cleavage reaction of chloropropanols esters. The reaction products were extracted by a sodium sulfate solution, and then purified by solid-supported liquid-liquid extraction (SLE) using diatomaceous earth (Hydromatrix™) as the sorbent. Finally, the extracts were derivatized with heptafluorobutyrylim idazole (HFBI) and analyzed by gas chromatography-mass spectrometry (GC-MS). Quantification was achieved using deuterated chloropropanols as their respective internal standards, including 3-MCPD-d5, 2-MCPD-d5, 1,3-DCP-d5 and 2,3-DCP-d5. A good linear relationship between peak area and concentrations was obtained within the range of 0.025-2.000mgL(-1) with a correlation coefficients not less than 0.999 for all the chloropropanols esters. The limits of detection (LODs) of esters of 3-MCPD, 2-MCPD, 1,3-DCP and 2,3-DCP (calculated as corresponding chloropropanols) were 30, 30, 100 and 30µgkg(-1), respectively. The average recoveries of the 3-MCPD esters and the 4 chloropropanols spiked at 0.1, 0.5 and 2mgkg(-1) into blank oil matrix were typically in a range from 70.7% to 113.3%. The robust method validation data including calibration, LOD/LOQ, accuracy and repeatability and proficiency test results (Z-score: -0.5) of the official Food Analysis Performance Assessment Scheme (FAPAS) indicated that the present quantitative method could be successfully applied to the determination of total chloropropanols esters in various edible oils.

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This paper reports levels of 3-monochloropropan-1,2-diol (3-MCPD) and 1,3-dichloro-2-propanol (1,3-DCP) in a wide range of food items and estimates their dietary exposure for secondary school students in Hong Kong. Dietary exposure to chloropropanols was estimated using local food consumption data obtained from secondary school students in 2000 and the concentrations of 3-MCPD and 1,3-DCP in food samples taken from the local market. The dietary exposure to 3-MCPD for an average secondary school student consumer was estimated to be 0.063-0.150 µg kg(-1) body weight (bw) day(-1), whilst that for the high consumer was 0.152-0.300 µg kg(-1) bw day(-1). Both estimates fell below the provisional maximum tolerable daily intake of 2 µg kg(-1) bw established by the Joint Expert Committee on Food Additives (JECFA) and amounted to less than 20% of this safety reference value. The dietary exposure to 1,3-DCP for an average secondary school student consumer was estimated to be 0.003-0.019 µg kg(-1) bw day(-1), whilst that for the high consumer was 0.009-0.040 µg kg(-1) bw day(-1). The resulting margins of exposures were of low concern for human health. It could be concluded that both the average and high secondary school student consumers were unlikely to experience major toxicological effects of 3-MCPD and 1,3-DCP.

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