Factors impacting the formation of monochloropropanediol (MCPD) fatty acid diesters during palm (Elaeis guineensis) oil production

Recently, organic and inorganic chlorinated compounds were detected in crude and commercially refined palm oils. Further, the predominant formation mechanism of monochloropropanediol (MCPD) diesters at high temperatures (>170-180°C) was revealed. The present study involved the development and comparison of solutions to mitigate MCPD diester levels in oils from various stages of palm oil production. Partially refined palm oil samples and oil extracted from fresh palm fruits were submitted to bench-top deodorisation experiments. Application of glycerol and ethanol as refining aids during the deodorisation of refined-bleached palm oil proved to be moderately effective; about 25%-35% reduction of MCPD diester levels was achieved. Washing crude palm oil with ethanol-water (1:1) prior to deodorisation was also an effective strategy yielding an ～30% reduction of MCPD diester contents. Washing palm fruit pulp before oil extraction, however, was most impactful, resulting in a 95% reduction of MCPD diesters when compared to the deodorised control oil. This suggests that intervention upstream in the process chain is most efficient in reducing levels of these contaminants in refined oils. Following the study, a root-cause analysis was performed in order to map the parameters potentially responsible for the occurrence of MCPD diesters in refined palm oil and related fractions.     

Formation mechanisms of monochloropropanediol (MCPD) fatty acid diesters in refined palm (Elaeis guineensis) oil and related fractions

Monochloropropanediol (MCPD) fatty acid esters are process contaminants generated during the deodorisation of edible oils. In particular, MCPD diesters are found in higher abundance in refined palm oil than other edible oils. In the present study, a series of model reactions mimicking palm oil deodorisation has been conducted with pure acylglycerols in the presence or absence of either organic or inorganic chlorine-containing compounds. Results showed that the bulk of MCPD diesters are formed above 200°C through the reaction of organochlorines with triacylglycerols (TAG). Additional experiments confirmed that this reaction can be initiated during palm oil deodorisation by hydrogen chloride (HCl) gas evolved through the thermal degradation of organochlorines present in the oil. Therein, the majority of the ultimately produced MCPD diesters are the result of HCl reacting with TAG, via protonation, followed by the elimination of a fatty acid residue. Two possible MCPD diester formation mechanisms are highlighted, both of which involve acyloxonium ion reactive intermediates. Investigations with pure TAG regio-isomers showed that MCPD ester formation is regioselective and the sn-1(3) position of the glycerol backbone is favoured.     

The effects of physical refining on the formation of 3-monochloropropane-1,2-diol esters in relation to palm oil minor components

The formation of 3-monochloropropane-1,2-diol (3-MCPD) esters in refined palm oil during deodorisation is attributed to the intrinsic composition of crude palm oil. Utilising D-optimal design, the effects of the degumming and bleaching processes on the reduction in 3-MCPD ester formation in refined palm oil from poor-quality crude palm oil were studied relative to the palm oil minor components that are likely to be their precursors. Water degumming remarkably reduced 3-MCPD ester formation by up to 84%, from 9.79 mg/kg to 1.55 mg/kg. Bleaching with synthetic magnesium silicate caused a further 10% reduction, to 0.487 mg/kg. The reduction in 3-MCPD ester formation could be due to the removal of related precursors prior to the deodorisation step. The phosphorus content of bleached palm oil showed a significant correlation with 3-MCPD ester formation.     

Glycidyl esters in refined palm (Elaeis guineensis) oil and related fractions. Part I: Formation mechanism

Glycidyl esters (GE) are process contaminants generated during the deodorisation step of edible oil refining. In particular, GE are found in high abundance in refined palm oil. Palm oil is unique in that it contains a high amount of diacylglycerols (DAG, 4-12%). In the present study, a series of model reactions mimicking palm oil deodorisation has been conducted with pure tri-, di- and mono-acylglycerols (MAG). Results showed that GE are formed from DAG and MAG, but not from TAG, at temperatures (T) above 200 °C. Our observations suggest that GE are formed predominantly by intramolecular elimination of a fatty acid from DAG. In addition, isomers of GE, formed from DAG heated at T > 140 °C, were identified as oxopropyl esters. These new isomers were found to represent approximately 10% of GE levels in refined palm oil. Based on these considerations, the final GE content of palm oil could be limited by reducing DAG levels before oil processing and minimising deodorisation temperatures.     

基于傅里叶变换红外光谱的大豆原油掺伪定量 分析模型研究

目的应用傅里叶变换红外光谱(FTIR)结合最小偏二乘法(PLS)建立大豆原油-棕榈油二元掺伪体系的定量分析模型。方法以42个大豆原油、21个精炼油、88个掺伪油的FIIR谱图为模型样本,预处理方法选用标准正态变量(SNV),在此基础上应用主成分分析(PCA)提取特征变量,随机选取60个掺伪油样组成校正集,28个掺伪油样组成验证集,以PLS方法建立大豆原油的掺伪定量模型。结果 PCA可将大豆原油及精炼油分成独立的2类。经PCA分析,大豆原油中掺入棕榈油的掺伪检测限为5%。PLS校正模型的判定系数R2为0.9926,校正误差均方根RMSEC为1.8121。预测模型的R2为0.9823,交叉验证误差均方根RMSECV为2.8189。同时得到的预测结果的偏差在1.3909%~3.1019%之间,差异不显著,说明此模型可行。结论 FTIR-PLS模型能够实现大豆原油的掺伪定量分析,分析速度快,能够满足大豆原油入库要求,是一种可行的大豆原油掺伪分析方法。     

Removal of organochlorines from vegetable oils and its benefits in preventing formation of monochloropropanediol diesters

This paper reports the first results on depleting certain organochlorines from vegetable oils without the use of any solvent in order to mitigate monochloropropanediol diesters (MCDPE). The concept is based on separating the organochlorines from the bulk oil by using trapping agents (e.g. monoacylglycerols) that can be easily separated from the oil. The process starts by mixing and homogenizing crude vegetable oils with the trapping agent and subsequently separating the trapping agent from the oil bulk via crystallization. The proof-of-concept of the approach is demonstrated on a spiked sunflower model system, solvent extracted crude sunflower oil, industrially produced crude soybean and corn oils. The depletion of organochlorines in the crude oils and its beneficial effect on the MCPDE content in the heat treated samples is measured by LC-MS. The depletion efficacy of the monitored organochlorines was estimated to be in the 60–95 % range. Both the melting point and polarity of the trapping agents affected the depletion efficacy of the organochlorines. Trapping agents with higher melting point and polarity, such as monostearin were more effective in comparison to high melting point but less polar agents such as palm stearin or agents rich in polar but low melting point monolinolein/monoolein. The effect of organochlorine depletion on the subsequent MPCDE levels in heat treated oil was in the range of 60–90 % reduction depending on the type of the studied oil.     

Mass-defect filtering of isotope signatures to reveal the source of chlorinated palm oil contaminants

This paper reports new insights at the molecular level into the route of a worldwide problem of the food industry: the occurrence of monochloro-propanediol (MCPD) esters. The application of mass defect-driven workflows is described to generate a hypothesis on the identity and occurrence of those thermally labile, chlorinated contaminant precursors that may act as chlorine donors during the formation of MCPD esters. For the first time, holistic mass-defect filtering of isotope signatures is used to pinpoint completely unknown and unexpected chlorine-containing substances naturally present in various extracts of palm fruit and partially and fully refined oils. Supervised multivariate analysis showed the effective classification of samples from various stages of industrial processing, suggesting that these steps strongly impact a complex and dynamic pool of chlorinated substances. In-vitro experiments confirmed that several of these naturally occurring chlorinated plant constituents decompose upon heat treatment, thus potentially being a source of chlorine for further reactions with palm oil lipids in a subsequent chlorination cascade. It is hypothesised that during oil refining the organochlorines naturally present in palm fruits act as a ‘chlorine source’ for the generation MCPD diesters. This discovery implies that industrial efforts targeting the mitigation of chlorinated substances must intervene at the earliest possible production stage or preferably even prior to oil processing. Current performance and limitations of mass-defect filtering are discussed and future developments are outlined.     

Influence of chemical refining process and oil type on bound 3-chloro-1,2-propanediol contents in palm oil and rapeseed oil

The formation of bound 3-chloro-1,2-propanediol (3-MCPD-ester) in oils during chemical refining process was investigated for two palm oils and one rapeseed oil. Additionally, contents of mono- and diglycerides as well as total chlorine and chloride were determined. For all oils the deodorisation step representing one part of the refining process had the main impact on formation of 3-MCPD-esters whereas a direct effect of the other process steps could be neglected. 3-MCPD values in the range of 4–5 ppm for palm oil and 1 ppm for rapeseed oil were found. The chloride content was below detection limit. However, measurable amounts of total chlorine were found in palm oil with the highest 3-MCPD-ester contents. A considerable part of this total chlorine in the refined palm oil was embedded in the 3-MCPD-esters. On the other hand, content of diglycerides as the other potential pre-cursor was between 1% and 10% exceeding the 3-MCPD-ester contents by up to five magnitudes.     

Mass-defect filtering of isotope signatures to reveal the source of chlorinated palm oil contaminants

This paper reports new insights at the molecular level into the route of a worldwide problem of the food industry: the occurrence of monochloro-propanediol (MCPD) esters. The application of mass defect-driven workflows is described to generate a hypothesis on the identity and occurrence of those thermally labile, chlorinated contaminant precursors that may act as chlorine donors during the formation of MCPD esters. For the first time, holistic mass-defect filtering of isotope signatures is used to pinpoint completely unknown and unexpected chlorine-containing substances naturally present in various extracts of palm fruit and partially and fully refined oils. Supervised multivariate analysis showed the effective classification of samples from various stages of industrial processing, suggesting that these steps strongly impact a complex and dynamic pool of chlorinated substances. In-vitro experiments confirmed that several of these naturally occurring chlorinated plant constituents decompose upon heat treatment, thus potentially being a source of chlorine for further reactions with palm oil lipids in a subsequent chlorination cascade. It is hypothesised that during oil refining the organochlorines naturally present in palm fruits act as a 'chlorine source' for the generation MCPD diesters. This discovery implies that industrial efforts targeting the mitigation of chlorinated substances must intervene at the earliest possible production stage or preferably even prior to oil processing. Current performance and limitations of mass-defect filtering are discussed and future developments are outlined.     

Glycidyl esters in refined palm (Elaeis guineensis) oil and related fractions. Part II: Practical recommendations for effective mitigation

In a previous work, it was shown that at high temperatures (up to 280 °C) glycidyl esters (GE) are formed from diacylglycerols (DAG) via elimination of free fatty acid (FFA). In the present study, the impact of DAG content and temperature on the formation of GE using a model vacuum system mimicking industrial edible oil deodorization is investigated. These deodorization experiments confirmed that the formation of GE from DAG is extensive at temperatures above 230-240 °C, and therefore, this value should be considered as an upper limit for refining operations. Furthermore, experimental data suggest that the formation of GE accelerates in particular when the DAG levels in refined oils exceed 3-4% of total lipids. Analysis of the lipid composition of crude palm oil (CPO) samples allowed the estimation that this critical DAG content corresponds to about 1.9-2.5% of FFA, which is the conventional quality marker of CPO. Moreover, high levels (>100 ppm) of GE were also found in palm fatty acid distillate samples, which may indicate that the level of GE in fully refined palm oils also depends on the elimination rate of GE into the fatty acid distillate.     

Effects of Different Pretreatments to Fresh Fruit on Chemical and Thermal Characteristics of Crude Palm Oil

This study selected 5 methods, including boiling, hot air drying, high‐pressurized steam, freezing, and microwave radiation to pretreat fresh oil palm fruit before solvent extraction of the oil. Using fresh fruit as a control, the pretreatment methods were compared for the effects on the activity of the 2 main enzymes in the fruit and some physicochemical properties of the crude palm oil. The results indicated, although all the 5 pretreatments could inactivate lipase and peroxidase in the treated flesh significantly (P < 0.05), the high‐pressurized steam was the most effective. There were also differences in the unsaturated fatty acid contents of the 6 oils. The crude oil from frozen fruit contained significantly more vitamin E (37829.33 ppm) than previously reported. Microwave radiation was shown to significantly decrease the free fatty acid content and the peroxide value, while increasing the oxidative stability index. Thermal behaviors of the oils were significantly different to each other with the exception a few parameters (P < 0.05).     

Mitigation Strategies for the Reduction of 2‐ and 3‐MCPD Esters and Glycidyl Esters in the Vegetable Oil Processing Industry

The refining of vegetable oils leads to the formation of 2‐ and 3‐monochloropropane‐1,2‐diol esters (2‐ and 3‐MCPD‐E), and glycidyl esters (Gly‐E). A literature review was performed aiming to provide up‐to‐date knowledge on mitigation strategies during oil refining that can reduce the formation of these three processing contaminants. The review used the database Scopus and covered the period from 2009 to 2017. Most of the 18 papers dealt with palm oil and two papers with vegetable oil. Most studies focused on 3‐MCPD‐E, some on Gly‐E, and none on 2‐MCPD‐E. Water degumming was able to reduce the concentrations of 3‐MCPD‐E by 84% and Gly‐E by 26%. Neutralization of the oil reduced concentrations of 3‐MCPD‐E by 81% and Gly‐E by 84%. Bleaching with synthetic magnesium silicate reduced the 3‐MCPD‐E concentration by 67%. For the deodorization step, several mitigation strategies, such as double‐deodorization, the addition of various antioxidants, or a longer deodorization time, can reduce the formations of 3‐MCPD‐E by 82% and Gly‐E by 78%. Postrefining mitigation, including the use of absorbents, enzymes, or rebleaching of the oil, has also been reported to produce desirable contaminant reduction. Postrefining treatment with calcinated zeolite was able to reduce the 3‐MCPD‐E concentration by 19% and the Gly‐E concentration by 77%. Applying combined mitigation strategies to multiple steps of oil refining is likely crucial in order to adequately reduce levels of 3‐MCPD‐E and Gly‐E.     

Relationship between laser-induced fluorescence intensity and crude palm oil quality

Crude palm oil quality is an important consideration in the production of refined palm oil of consistent high quality. The quality of crude palm oil is determined by the analysis of oxidative and hydrolytic parameters such as peroxide value, anis dine value, free fatty acid content and moisture and impurities, all very time consuming and counter-productive for both crude palm oil mills and refineries to carry out. This study shows that laser-induced fluorescence (LIF) analysis can be used as an alternative to analysing all the common oxidative and hydrolytic parameters mentioned. LIF at 673 nm was indicative of the oxidative quality of crude palm oil. There was also positive correlation between fluorescence intensity and the carotene and the deterioration of bleach ability index of crude palm oil, and the Rancimat induction time of the final refined product.     

棕榈油和大豆油在油条煎炸过程中品质变化研究

以不同熔点棕榈油和棕榈油―大豆油混合油为原料,以大豆油作对照,通过比较油条外观、口感,筛选出适于煎炸油条的棕榈油,再进一步通过测定油条煎炸过程中油脂样品游离脂肪酸(FFA)、过氧化值(PV)、色泽、极性值(PC)、羰基价(COV)等指标,研究两种油在油条煎炸过程中品质变化情况。研究结果表明,熔点14℃棕榈液油和大豆油都适于煎炸油条,且棕榈液油在煎炸过程中具有比大豆油更好氧化稳定性,仅是其游离脂肪酸(FFA)和色泽上升速率快于大豆油。总的来说,两种油在满足煎炸油质量要求前提下,同等数量棕榈油可比大豆油煎炸更多油条。     

Fatty acid esters of 3-chloropropane-1,2-diol in edible oils.

A series of 25 virgin and refined edible oils, obtained from retailers, was analyzed for levels of free 3-chloropropane-1,2-diol (3-MCPD) and 3-MCPD released from esters with higher fatty acids (bound 3-MCPD). Oils containing free 3-MCPD ranging from <3 microg kg-1 (LOD) to 24 microg kg-1. Surprisingly, bound 3-MCPD levels were much higher and varied between <100 (LOD) and 2462 microg kg-1. On average, virgin oils had relatively low levels of bound 3-MCPD, ranging from <100 (LOD) to <300 microg kg-1 (LOQ). Higher levels of bound 3-MCPD were found in oils from roasted oilseeds (337 microg kg-1) and in the majority of refined oils (<300-2462 microg kg-1), including refined olive oils. In general, it appears that the formation of bound 3-MCPD in oils is linked to preliminary heat treatment of oilseeds and to the process of oil refining. Analysis of unrefined, de-gummed, bleached, and deodorized rapeseed oil showed that the level of bound MCPD decreased during the refining process. However, additional heating of seed oils for 30 min at temperatures ranging from 100 to 280 degrees C, and heating at 230 degrees C (260 degrees C) for up to 8 h, led to an increase in bound 3-MCPD levels. On the other hand, heating of olive oil resulted in a decrease in bound 3-MCPD levels. For comparison, fat isolated from salami was analyzed for intact fatty acid esters of 3-MCPD. This fat contained bound 3-MCPD at a level of 1670 microg kg-1 and the fatty acid esters of 3-MCPD mainly consisted of 3-MCPD diesters; monoesters of 3-MCPD were present in smaller amounts. The major types of 3-MCPD diesters (about 85%) were mixed diesters of palmitic acid with C18 fatty acids (stearic, oleic, linoleic acids). These diesters were followed by 3-MCPD distearate (11%) and 3-MCPD dipalmitate (4%). Generally, very little 3-MCPD existed as the free compound (31 microg kg-1).     

Quantitative changes in some unsaponifiable components of soya bean oil due to refining

The effects were studied of the processes of degumming, neutralisation, bleaching and deodorisation on the content and composition of the various fractions of unsaponifiables in soya bean oil. The effect of each of the various technological steps on the decrement of the investigated unsaponifiables in the processed oils was different. When compared with the crude oil, the refined soya bean oil contained less tocopherols (by 31 to 47%), sterols (by 25 to 32%) and squalene (by 15 to 37%). No significant differences were observed in the compositions of the sterol and tocopherol fractions of the crude and refined soya bean oils.     

Rapid determination of chlorophylls in vegetable oils by laser-based fluorometry

The presence of chlorophylls in vegetable oils is considered undesirable due to their adverse effects on oxidative deterioration, bleachability and hydrogenation. The usual methods for determination of chlorophylls in vegetable oils are absorption spectrophotometry, fluorometry and liquid chromatography using fluorescence detectors. This paper outlines a fluorometric method using a laser as the excitation source. The chlorophylls in crude palm oil, rapeseed oil, soya bean oil and olive oil were determined directly by laser-based fluorometry using (a) a helium-neon laser (632-8 nm, 5 mW) as the excitation source and an optical-multichannel analyser (OMA) with an intensified diode array as the detector, and (b) a helium-neon laser and a photomultiplier tube as the detector. The method is especially suitable for the detection of chlorophylls in crude palm oil since no pre-extraction step is required. The levels of chlorophylls measured in vegetable oils using the laser technique was also compared against values obtained by conventional spectrophotometric methods. The simplicity and rapid quantification of laser based fluorometry suggest that this technique can be readily applied to the detection or a wide variety of fluorescing species in vegetable oils.     

Functionality of Palm Oil as a Stabilizer in Peanut Butter

ABSTRACT: Studies have shown that palm oil is an effective stabilizer in peanut butter. The objective of our investigation was to better define the role of palm oil as a stabilizer. Peanut butters without and with palm oil added at concentrations of 1.5, 2.0, and 2.5% (w/w of peanuts), and Fix-X™ (hydrogenated rapeseed and cottonseed oils as commercial control) were stored at 0, 21, 30, and 45 °C for 23 wk. Palm oil improved the oil holding capacity (OHC) of peanut butters, but had no effect on their adhesiveness and hardness characteristics. The unstabilized and palm oil-stabilized peanut butters were not as good as the Fix-X™ stabilized peanut butters with regard to their OHC, hardness, and adhesiveness characteristics.     

Pan-frying of French fries in three different edible oils enriched with olive leaf extract: Oxidative stability and fate of microconstituents

Sunflower oil, olive oil, and refined palm oil were enriched with an extract - rich in polyphenols - obtained from olive tree (Olea europaea) leaves at levels of 120 and 240 mg total polyphenols per kg oil. Potatoes were pan-fried in both the enriched and the non-supplemented oils under domestic frying conditions. Total polyphenols were estimated by Folin-Ciocalteu and antioxidant capacity was assessed by the DPPH radical scavenging assay. Tocopherols' content was determined by HPLC analysis, phytosterols and squalene by GC, and oxidative stability by Rancimat. Supplemented frying oils had higher total polyphenols and tocopherols' content, oxidative stability, and antioxidant capacity, while phytosterols and squalene content were not affected by the supplementation. French fries prepared in supplemented oils had higher total polyphenols, tocopherols, phytosterols, and squalene content and exhibited higher antioxidant capacity than those fried in non-supplemented oils. By consuming French fries pan-fried in enriched oils, up to 1.4-, 2.2-, and 1.5-fold increase of tocopherols, phytosterols, and squalene intake could be achieved as compared to those prepared in the non-supplemented oils.     

A high performance liquid chromatography method for determination of furfural in crude palm oil

A modified steam distillation method was developed to extract furfural from crude palm oil (CPO). The collected distillates were analysed using high performance liquid chromatography (HPLC) coupled with an ultraviolet diode detector at 284 nm. The HPLC method allowed identification and quantification of furfural in CPO. The unique thermal extraction of CPO whereby the fresh fruit bunches (FFB) are first subjected to steam treatment, distinguishes itself from other solvent-extracted or cold-pressed vegetable oils. The presence of furfural was also determined in the fresh palm oil from FFB (without undergoing the normal extraction process), palm olein, palm stearin, olive oil, coconut oil, sunflower oil, soya oil and corn oil. The chromatograms of the extracts were compared to that of standard furfural. Furfural was only detected in CPO. The CPO consignments obtained from four mills were shown to contain 7.54 to 20.60 mg/kg furfural.