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Contaminants formed during food processing are of increasing concern to public and food safety experts, as well as international risk assessment organizations. The emergence of 'omic' technologies (e.g. genomics and transcriptomics) have greatly increased the mechanistic knowledge of the toxicity associated with these compounds, and consequently have provided a better understanding of their potential adverse effects. Of note, microRNAs (miRNAs) have emerged as being of key importance during the development of cancer as well as being associated with food-processing contaminants. MiRNAs have been demonstrated to trigger toxic processes in hepatic and renal tissues due to exposure to toxic compounds such as furan and 3-monochloropropane-1,2-diol (3-MCPD), respectively. In this review, we consider the roles of miRNAs in the toxicity process and the challenges that lay ahead in order to translate this knowledge to the benefit of industrial food processing.

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Esters of 3-monochloropropane-1,2-diol (3-MCPD) and glycidol are reported vegetable fats and oils contaminants formed during processing. During digestion, esterified forms are hydrolyzed making the free forms, with high toxicity to human health, possibly available in the digestive system, which could depend, among other factors, on the phase condition stablished in the gastrointestinal tract between contaminants and lipids. Therefore, this work was aimed at evaluating the solid-liquid equilibrium (SLE) of binary and pseudobinary mixtures of fatty acids (palmitic, oleic and stearic), triacylglycerols (tripalmitin, triolein and tristearin) and a partial acylglycerols, with 3-MCPD and glycidol, by differential scanning calorimetry (DSC) and thermodynamic modeling with Margules 2 and 3 suffixes, UNIFAC and ideal models. Melting properties of the contaminants were determined by DSC thermograms, with microstructure micrographs and compared to some predictive group contribution models (GC). 14 complete SLE phase diagrams could be determined. Results showed that the lipid compounds had high affinity with the free contaminants with probably the formation of liquid crystalline structures and/or solid solutions. The Margules 3 suffixes model showed the best fit with the lowest average relative deviations, no higher than 1%, although the parameters probably incorporated the non-ideality promoted by the crystalline phase behavior. The formation of mesophases and/or solid solutions with very high melting temperature probably means a difficulty of separating the contaminants from the lipid matrix in which, on the other hand, could avoid separation process or affect (probably decreasing) their absorption during digestion.

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Palm oil is a type of vegetable oil which presents a variety of applications including food, energy, and international trading. However, one of the major concerns associated with palm oil uses as a food ingredient is the significant amount of processing contaminants, such as monochloropropanediol esters (MCPDE) and glycidyl esters (GE) which are formed during the refining process. These contaminants may pose a health risk to consumers due to their carcinogenicity. Thus, mitigation strategies have been studied to reduce these substances in palm oil. In this study, we investigated the effect of the application of an aqueous washing step, as a mitigation strategy, prior to deodorization in three different palm oil cultivation systems: organic, conventional and certified palm oil by the Roundtable on Sustainable Palm Oil (RSPO). In addition, we evaluated the quality parameters after the application of the washing step. For the organic, conventional and RSPO palm oil samples, the aqueous washing step reduced approximately 41%, 34% and 36% of the 3-MCPDE, respectively. The levels of 2-MCPDE for the organic, conventional and RSPO palm oil presented a reduction of 55%, 41% and 32%, respectively. The GE levels are considerably low for all the deodorized palm oils, and presented no statistically significant difference (p > 0.05). Besides, the quality parameters such as free fatty acids, color, and OSI met the recommended limits. Therefore, the aqueous washing could be used as a supplementary strategy to reduce these contaminants from palm oil.

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This study verified the formation profile of esters of 3-monochloropropane-1,2-diol (3-MCPDE), 2-monochloropropane-1,2-diol (2-MCPDE), and glycidol (GE), and evaluated the physicochemical changes (free-fatty acid, acylglycerols, and colour) that occurred during the deodorization of palm oil in different conditions of time (30, 60, 90, and 120 min) and temperature (210, 230, 250, and 270 °C). Levels of 3-MCPD and 2-MCPD esters ranged from 1.91 to 2.70 mg/kg and 0.68 to 1.44 mg/kg, respectively, and were formed at the mildest tested condition (210 °C, 30 min). No correlation was observed between these contaminants and physicochemical changes. GE levels varied from 0.12 to 8.51 mg/kg and showed correlation with color and diacylglycerol content. While the temperature had little influence on the formation of esters of 3-MCPD and 2-MCPD, the content of GE considerably raised above 250 °C.

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RESUMO

The formation of toxic compounds, potentially carcinogenic, during food processing has been considered an important food safety issue. Among them, particular attention has been given to 3-monochloropropane-1,2-diol esters (3-MCPDE), 2-monochloropropane-1,3-diol esters (2-MCPDE) and glycidyl esters (GE), which can be formed during vegetable oil refining, especially palm oil. These substances may pose a health risk to humans due to their toxicity and carcinogenicity. The aim of this study was to investigate the effect of washing bleached palm oil (BPO) with different solvents, and evaluate the reduction of 3-MCPDE, 2-MCPDE and GE as well as assess the quality parameters of the final product. For this purpose, we used two types of washing with different solvents. A single washing was carried out in one step and a double washing in two steps using a solvent gradient. Single washing had a limited reduction in the levels of 3-MCPDE and 2-MCPDE and resulted in an increased level of GE, whereas double washing slightly reduced 3-MCPDE and 2-MCPDE and resulted in a significant reduction of GE levels. The reduction achieved in this study was up to 17.1% for 3-MCPDE, 56.4% for 2-MCPDE and 76.9% for GE levels. The reduction of 3-MCPDE and 2-MCPDE might be due to the removal of part of the ethanol-soluble chlorinated precursors from the oil which suggests that highly lipophilic forms of these substances are present in BPO. The substantial reduction on GE levels might be associated with the removal of the precursors present in the oil such as diacylglycerols. Thus, the washing treatment could be used as a supplementary strategy to reduce processing contaminants from palm oil, especially GEs.

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Cloropropanóis são um grupo conhecido de contaminantes relacionados ao processamento de alimentos. Eles são formados na reação entre lipídeos e cloretos quando submetidos ao tratamento térmico, e podem ser encontrados na forma livre ou ligada. O 3-monocloro-1,2-propanediol (3-MCPD), é classificado pela IARC como possível carcinógeno humano (grupo 2B). O glicidol (e seus ésteres), é classificado também pela IARC como uma substância provavelmente carcinogênica para seres humanos (grupo 2A), e, recentemente, vem sendo encontrado em alimentos. O objetivo deste trabalho foi avaliar a presença do 3-MCPD e do glicidol em óleos vegetais comestíveis utilizando a cromatografia gasosa com detector de massa triplo quadrupolo MS/MS. A técnica utilizada foi a preconizada pela AOCS Cd 29c-13, sendo uma análise indireta, e foi possível adaptá-la visando as determinações do 3-MCPD e glicidol através da construção de curvas de calibração e análises de amostras de referência. O método foi validado e os resultados indicaram o limite de detecção do composto 3-MCPD, de 42,4 µg/kg e o limite de quantificação de 50 µg/kg, e para o Glicidol indicaram o limite de detecção de 43,5 µg/kg e limite de quantificação de 50 µg/kg. Os resultados para 3-MCPD obtidos nos ensaios da curva de calibração e linearidade demonstraram que o método foi capaz de expressar resultados com boa linearidade (0 - 10 mg/kg , r2, = 0.9991). Os resultados obtidos nos ensaios de exatidão obedeceram aos critérios de 70 a 120% de recuperação, e ±20% de variação entre os resultados de acordo com SANTE (2017). O método em questão demonstrou ser seletivo, uma vez que não foram observados picos interferentes nos tempos de retenção dos compostos estudados. Os ensaios de precisão nos níveis baixos, médio e alto e robustez demonstraram que o método é robusto e preciso, portanto a validação foi considerada adequada ao uso pretendido. Foram analisadas 368 amostras de óleos vegetais (76 amostras de óleo de canola, 48 amostras de óleo de milho, 69 amostras de óleo de algodão, 33 amostras de óleo de palma, 10 amostras de óleo de palmiste, 50 amostras de oleína de palma, 30 amostras de óleo de soja e 51 amostras de óleo de girassol). As concentrações das amostras analisadas apresentaram resultados para 3-MCPD com valores médios entre 203 a 1205 µg/kg. Para o Glicidol os valores foram de 2 a 1198 µg/kg, com elevado o desvio padrão entre os resultados analíticos, onde o óleo de palma apresentou a maior variação de 1600 a 5260 µg/kg. Através da avaliação do risco realizada para o composto 3-MCPD foi possível detectar, utilizando o critério do pior cenário de exposição e resultados analíticos, os valores diários de consumo de óleo de algodão de 0,044 µg/kg p.c., de óleo de girassol 0,045 µg/kg p.c., óleo de canola 0,18 µg/kg p.c., óleo de palma de 0,28 µg/p.c, óleo de milho de 0,0462 µg/kg p.c., e o óleo de soja, de maior consumo no Brasil (72%) apresentou o valor de 0,27 µg/kg p.c. O consumo de todos estes óleos, pela a população brasileira, pode ser considerado seguro ao comparar com o valor de TDI Ingestão Diária Tolerável - de 2µg/kg p.c.. Através da avaliação do risco realizada também utilizando o critério de pior cenário de exposição e e resultados analíticos para o composto glicidol foi possível verificar que os valores diários de consumo de óleo de algodão de 0,061 µg/kg p.c., de óleo de girassol 0,03 µg/kg p.c., óleo de canola 0,13 µg/kg p.c. e de óleo de palma de 0,57 µg/p.c, de óleo de milho de 0,11 µg/kg p.c, e o óleo de soja de maior consumo no Brasil (72%) não ultrapassam o valor de 0,288 µg/kg p.c indicando consumo seguro destes óleos para a população brasileira baseado na TDI de 1000µg/kg p.c

Chloropropanols are a known group of contaminants related to food processing. They are formed during the reaction process between lipids and chlorides when submitted to heat treatment and can be found in free or bound form. The 3-monochloro-1,2-propanediol (3-MCPD), is classified by IARC as a possible human carcinogen (group 2B). Glycidol (and its esters), also classified by IARC as a substance likely to be carcinogenic to humans (group 2A), has recently been found in food. The present study aims to evaluate the presence of 3-MCPD and glycidol in edible vegetable oils using gas chromatography with triple quadrupole MS/MS mass detector. The technique applied is recommended by AOCS, guide Cd 29c-13, an indirect analysis, and allows quantification of 3-MCPD and glycidol by building the calibration curves and analysis of reference samples. The method was validated and the detection limit of the contaminant 3-MCPD of 42,4 µg/kg and the quantification limit of 50 µg/kg was established. For Glycidol the detection limit of was 43,5 µg/kg and quantification limit was 50 µg/kg. The results obtained in the calibration and linearity curves demonstrated that the method could express results with good linearity (0 10 mg/kg, r2, = 0.9991). The results obtained in the trueness trials agreed to the criteria of 70 to 120% of recovery, and ± 20% of variation between the results according to what is preconized by SANTE (2017). The method showed to be selective, since no interfering peaks were observed in the retention times of the studied compounds. The tests performed on low, medium and high values demonstrated the robustness and precision of the method, so the validation was considered completed and suitable for the purpose. A total of 368 vegetable oil samples were analyzed (76 samples of canola oil, 48 samples of corn oil, 69 samples of cottonseed oil, 33 samples of palm oil, 10 samples of kern palm oil, 50 samples of palm olein, 30 samples of soybean oil and 51 samples of sunflower oil). The results found in samples for 3-MCPD were within mean values between 203 and 1205 µg/kg. The results found in samples for glycidol were within mean values between 2 to 1198 µg/kg where palm oil presented the highest variation for glycidol from 1600 to 5260 µg/kg. Through the risk assessment for the contaminant 3-MCPD it was possible to detect the values based on exposed worst case scenario and analytical results. The results for cottom oil were 0,044 µg/kg bw, sunflower 0,045 µg/kg bw, canola 0,18 µg/kg bw and palm oil 0,28 µg/kg bw, corn oil 0,0462 µg/kg bw, and for soybean, which is the most consumed oil in Brazil (72%) the value of 0,27 µg/kg bw. These results indicates safe consumption for these oils based in the Theoretical Daily Ingestion - TDI of 2µg/kg bw. The risk assessment for the glycidol based on exposure worst case scenario and analytical results presented for cottom oil the value of 0,061 µg/kg bw, sunflower 0,03 µg/kg bw, canola oil 0,13 µg/kg bw , palm oil 0,57 µg/kg bw, corn oil 0,11 µg/kg bw and for soybean, which is the most consumed in Brazil - 72% the value of 0,27 µg/kg bw. These results indicates safe consumption for these oils based in the TDI of 1000µg/kg bw

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Levels of 3-monochloropropane-1,2-diol (3-MCPD) fatty acid esters were evaluated in commercial deep-fat fried foods from the Brazilian market using a GC-MS method preceded by acid-catalysed methanolysis. A limit of detection of 0.04 mg kg(-1), a limit of quantitation of 0.08 mg kg(-1), mean recoveries varying from 82% to 92%, and coefficients of variation ranging from 2.5% to 5.0% for repeatability and from 3.6% to 6.5% for within-laboratory reproducibility were obtained during in-house validation. The levels of the compounds in the evaluated samples, expressed as free 3-MCPD equivalent, ranged from not detected to 0.99 mg kg(-)(1), and the highest concentrations were observed in samples of chopped onion and garlic. A preliminary estimation of 3-MCPD intake using these occurrence data suggested low risks to human health, but a potential concern may arise in particular cases of consumers of fried food.

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An in-house validated GC-MS method preceded by acid-catalysed methanolysis was applied to 97 samples of vegetable oils and fats marketed in Brazil. The levels of the compounds ranged from not detected (limit of detection = 0.05 mg kg(-1)) to 5.09 mg kg(-1), and the highest concentrations were observed in samples containing olive pomace oil and in products used for industrial applications, such as palm oil and its fractions (olein and stearin). The content of diesters and monoesters was also investigated by employing solid-phase extraction on silica cartridges, indicating that the majority of the compounds were present as diesters. This study provides the first occurrence data on these contaminants in Brazil and the results are comparable with those reported in other countries.

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