CONCEPTUAL ALTERNATIVE MILLING FOR 3-MCPD MITIGATION

Effects of temperature and NaCl on the formation of 3-MCPD esters and glycidyl esters in refined, bleached and deodorized palm olein during deep-fat frying of potato chips.

Crude Palm Oil (CPO) is palm oil obtained from the extraction or compression process of oil palm fruit flesh and has not been purified. Palm oil is usually used for food, cosmetic industry, chemical industry, and animal feed industry. Increasingly open insight and increasing consumer awareness of the importance of food safety and quality assurance supported by technological developments and laboratory analysis methods, new types of contaminants in food products are also found. Currently, the Indonesian government is facing challenges regarding the issue of 3-monochloro-1,2-propanediol ester (3-MCPD Ester) and glycidyl ester (GE) in palm oil which can hamper Indonesia's palm oil trade in the future. The practice in the field affects the quality of CPO and the retrieval of low-quality CPO is mixed with high-quality CPO. And the length of time the process of pumping CPO from reclaimed tanks to VCT affects the quality of CPO. So this study aims to modify the pumping time and storage time of CPO from Reclaimed tanks to VCT by mixing samples from VCT (fresh CPO) and samples from Reclaimed tanks (lower quality CPO).

Approximately 900 tonne of crude palm oil (CPO) underwent washing using 5 to 10% hot water (90 to 95°C) at a palm oil mill. The aim of the CPO washing was to eliminate and/or reduce total chlorine content present in the conventional CPO, as it is known as the main precursor for the formation of 3-monochloropropane-1, 2-diol esters (3-MCPDE). By a simple hot water washing, more than 85% of the total chlorine was removed. However, washing did not have significant (p > 0.05) effect on other oil quality parameters such as the deterioration of bleachability index (DOBI), free fatty acid (FFA) content and diacylglycerol (DAG) content of the oil. The latter has been established as the main precursor for glycidyl esters (GE) formation. The treated CPO was then transported using tankers and further refined at a commercial refinery. Refining of washed CPO resulted in significantly (p < 0.05) lower formation of 3-MCPDE, but GE content remained slightly high. Post-treatment of refined oil significantly reduced the GE content (p < 0.05) to an acceptable level whilst almost maintaining the low 3-MCPDE level. The study has proven that water washing of CPO prior to refining and subsequent post-refining is so far the most effective way to produce good quality refined oil with considerably low 3-MCPDE and GE contents. Dry fractionation of refined palm oil showed these contaminants partitioned more into the liquid olein fraction compared to the stearin fraction.

In recent years, 3-monochloropropane-1,2-diol (3-MCPD) and glycidyl esters have drawn the attention of scientists and consumers worldwide. 3-MCPD esters and glycidyl esters are carcinogens that have been found in refined vegetables fats and oils especially in palm oil products. Many studies have been carried out by various research groups to investigate the effect of refining steps and heat processing on the formation of 3-MCPD and glycidyl esters and mitigate the formation of these processed contaminants in palm oil products. This chapter presents an overview on the formation and mitigation of 3-MCPD and glycidyl esters during palm oil refining processes. A comprehensive comparison between direct and indirect methods for the determination of 3-MCPD and glycidyl esters is also included in the chapter. As 3-MCPD and glycidyl esters are thermally induced contaminants during high-temperature processes, the effects of different frying systems and antioxidants on these processed contaminants are also reviewed.

This life cycle assessment (LCA) is a cradle-to-gate study of energy consumption and greenhouse gas (GHG) emissions in transportation of palm oil, palm olein and palm stearin along the palm oil supply chain. This includes the transportation of the oil palm pollinated bunches from the 'mother palm' to the seed laboratories, the germinated seeds to the nurseries, seedlings from nurseries to oil palm plantations, fresh fruit bunches (FFB) from plantations to mills, crude palm oil (CPO) from mills to refineries and refined, bleached and deodorised (RBD) palm oil (RBO PO) and its fractionated products namely RBD palm olein (RBD POo) and RBD palm stearin (RBO POs) from refineries/fractionation plants to ports and retailers. The objective of this study is to use the LCA approach to identify at which stage of the palm oil supply chain that transportation contributes the most to the environmental performance in terms of GHG emissions within the boundary of the study. The analysis of the LCI data for determining overall GHG emissions for the transportation along the oil palm supply chain, on the basis of the production of 1 t of the RBD PO, indicated that the transportation of FFB from plantation to mill and transportation of CPO from mill to refinery gave the highest GHG emissions. Based on the production of 1 t of the RBD PO, the GHG emissions during the transportation of FFB from plantation to mill and the transportation of CPO from mill to refinery were 21.94 kg CO 2 eq. and 20.86 kg CO 2 eq., respectively.

During high-temperature refining of vegetable oils, 3-monochloropropanediol (3-MCPD) esters, possible carcinogens, are formed from acylglycerol in the presence of a chlorine source. To investigate organochlorine compounds in vegetable oils as possible precursors for 3-MCPD esters, we tested crude palm, soybean, rapeseed, sunflower, corn, coconut, and olive oils for the presence of organochlorine compounds. Having found them in all vegetable oils tested, we focused subsequent study on oil palm products. Analysis of the chlorine isotope mass pattern exhibited in high-resolution mass spectrometry enabled organochlorine compound identification in crude palm oils as constituents of wax esters, fatty acid, diacylglycerols, and sphingolipids, which are produced endogenously in oil palm mesocarp throughout ripening. Analysis of thermal decomposition and changes during refining suggested that these naturally present organochlorine compounds in palm oils and perhaps in other vegetable oils are precursors of 3-MCPD esters. Enrichment and dose-response showed a linear relationship to 3-MCPD ester formation and indicated that the sphingolipid-based organochlorine compounds are the most active precursors of 3-MCPD esters.

Alkaline neutralization is a classical method for removal of free fatty acids (FFA) in crude oil. It is generally accompanied by neutral oil loss. Thus, reduction of refining losses associated with alkaline neutralization is very desirable. Refined, bleached and deodorized (RBD) palm oils with different FFA contents were used as oil models in this study. FFA in the oil models were neutralized with sodium hydroxide in polyhydric alcohols as neutralization media. Glycerol, propylene glycol and ethylene glycol in water were effective neutralization media. FFA in the oil models were totally removed in one step of neutralization, while percentages of refining losses were different. The losses were increased in the order of water &gt; propylene glycol &gt; ethylene glycol &gt; glycerol used as neutralization media. Also, a higher concentration of polyhydric alcohol in the neutralizing media significantly reduced the percentage of refining loss (p &lt; 0.05). Glycerol (90% in water) was the most effective neutralization media (p &lt; 0.05). When neutralization was carried out on crude palm oil (containing 7.53% FFA), refining loss was reduced from 36.1% (in water) to 20.0% (in 90% glycerol in water).

Palm oil is the vegetable oil refined and modified in the largest amount. In this study, we present the effect of wet fractionation and hydrogenation of RBD palm oil on the removal of 3-MCPD and glycidyl esters. Fractionated palmstearins had significantly decreased contents of 3-MCPD esters (71–74%) and glycidyl esters (21–26%), whereas top olein contained the highest levels of processing-induced contaminants accompanied by polar compounds. Exhaustive hydrogenation conditions caused rapid degradation of 3-MCPD esters (51–70%) in high melting palm oil products. Reduction of glycidyl esters (1–42%) was dependent on the type of nickel catalyst. The effect of iodine value drop on the contaminant degradation was shown to be linear. The combined action of dry-reduced, supported, 22% Ni and Raney nickel catalysts was found to be an optimal. Adsorptive bleaching and deodorization of hydrogenated palm stearin impacted particularly repeated formation of glycidyl esters up to 1.01–1.76 mg/kg, while 3-MCPD esters remained under the input RBD palm oil level. The mechanism of the catalyst action was investigated with glycidyl-d5 palmitate, 3-MCPD-d5-1,2-dipalmitate. They were transformed into non-carcinogenic and non-genotoxic products by hydrogenolysis and deoxygenation reactions.

Discrepancies in the analysis of 3‐chloropropane‐1,2‐diol (3‐MCPD) esters can be explained by the hypothesis that in some refined oils significant amounts of fatty acid esters of glycidol (glycidyl esters) are present in addition to 3‐MCPD esters. Glycidyl esters were separated from triacylglycerols by gel permeation chromatography (GPC) and detected by gas chromatography‐mass spectrometry (GC‐MS). Six samples of palm oil and palm oil‐based fats were analyzed by GPC and GC‐MS. In chromatograms of all samples, significant peaks, retention time and mass spectra in conformity with self‐synthesized glycidyl palmitate and glycidyl oleate were detectable. Quantification of individual glycidyl esters was not possible because of a lack of pure standards. Concentration of ester‐bound glycidol in different samples of fats and oils was estimated using an indirect difference method. Glycidyl esters could be detected only in refined, but not in crude or native, fats and oils. The highest concentrations were detected in palm oil and palm oil‐based fats. In a palm oil sample, glycidyl ester concentration varied according to different deodorization parameters, temperature, and time, while 3‐MCPD ester concentration was relatively constant, indicating that mitigation of glycidyl esters possibly may be achieved by optimizing refining parameters.

Palm oil is one of the major oils and fats produced and traded worldwide. The value of palm oil products is mainly influenced by their quality. According to ISO 17025:2005, accredited laboratories require a quality control procedure with respect to monitoring the validity of tests for determination of quality parameters. This includes the regular use of internal quality control using secondary reference materials. Unfortunately, palm oil reference materials are not currently available. To establish internal quality control samples, the stability of quality parameters needs to be evaluated. In the present study, the stability of quality parameters for palm oil products was examined over 10 months at low temperature storage (6 ± 2 °C). The palm oil products tested included crude palm oil (CPO); refined, bleached and deodorized (RBD) palm oil (RBDPO); RBD palm olein (RBDPOo); and RBD palm stearin (RBDPS). The quality parameters of the oils [i.e. moisture content, free fatty acid content (FFA), iodine value (IV), fatty acids composition (FAC) and slip melting point (SMP)] were determined prior to and throughout the storage period. The moisture, FFA, IV, FAC and SMP for palm oil products changed significantly (P < 0.05), whereas the moisture content for CPO, IV for RBDPO and RBDPOo, stearic acid composition for CPO and linolenic acid composition for CPO, RBDPO, RBDPOo and RBDPS did not (P > 0.05). The stability study indicated that the quality of the palm oil products was stable within the specified limits throughout the storage period at low temperature. The storage conditions preserved the quality of palm oil products throughout the storage period. These findings qualify the use of the palm oil products CPO, RBDPO, RBDPOo and RBDPS as control samples in the validation of test results. © 2017 Society of Chemical Industry.

Effects of natural and synthetic antioxidants on changes in 3-MCPD esters and glycidyl ester in palm olein during deep-fat frying

Quality and food safety are of paramount importance to the palm oil industry. In this work, we investigated the practicability of ethylene gas exogenous application on post‐harvested oil palm fruit bunches to improve the crude palm oil (CPO) quality. The bunches were first exposed to ethylene gas for 24 hr to induce abscission of palm fruits from bunches. The detached fruits were then subjected to heat treatment, mechanical extraction, clarification and drying to produce CPO. Critical quality parameters of CPO produced, that is free fatty acid, deterioration of the bleachability index and triacylglycerol showed improvement with ethylene gas treatment. Contaminant content that is phosphorus, chloride, iron, and copper also showed a reduction in the CPO derived from ethylene‐treated bunches. These findings corresponded with low levels of contaminants such as 3‐monochloropropane‐1,2‐diol esters and glycidyl esters in refined oil. The implementation strategy and practicability of this method is herein proposed and discussed. Ethylene application not only improves the CPO quality, but could potentially enhance the process sustainability of palm oil mills.

Palm oil used as a food product is usually produced from palm oil as well as from palm kernel oil through fractionation, refinement and hydrogenation. PT.X produces the main product, namely cooking oil (olein). The cooking oil in the manufacturing process comes from CPO (Crude Palm Oil) which undergoes a degumming, bleaching, filtration process using a Niagara filter and deodorization at the Refining Plant with the resulting product being RBDPO (Refined, Bleached, and Deodorized Palm Oil). This research aims to determine the levels Free Fatty Acids (ALB) in CPO and RPO as well as knowing the color levels in CPO and RPO according to standards at PT. X. From the results of the analysis carried out in the PT. The free fatty acid content in crude palm oil (CPO) and refined palm oil (RPO) obtained an average value of 3.29% and 0.042%. Meanwhile, the color content results for crude palm oil (CPO) and refined palm oil (RPO) obtained an average of 22R and 1.7R. Based on the results of analysis of free fatty acids (ALB) and color in crude palm oil (CPO) and refined palm oil (RPO) in the PT. Key words: palm oil, free fatty acids, color, CPO, and RPO.

Comparison assessment between SIM and MRM mode in the analysis of 3-MCPD ester, 2-MCPD ester and glycidyl ester

Mills produce Crude Palm Oil (CPO) from procurement channels of their plantation, plasma farm, and independent smallholders’ farm. The mill manufactures Fruit Fresh Bunch FFB from all channels and sells CPO with low Free Fatty Acid (FFA) CPO for foods and CPO for industrial. CPO with low FFA for export consists of premium-grade CPO with FFA level < 2% and super-grade CPO with FFA level <3.5%. This Low FFA CPO is exported for food to developed countries. The food industry as a CPO customer needs a lot of information about the origin of the CPO commodity and information about sustainable oil palm agriculture governance. The challenges of building low FFA CPO traceability system raw material of CPO come from three-channel of FFB procurement and produce the various quality of CPO. This study aims to map the FFB supply at PT. RSI from Roundtable on Sustainability Palm Oil (RSPO) certificate farm in independent smallholders groups channel in the Hyperledger Fabric blockchain network and smart contract. The interaction of entities with smart contracts is described in the ERD diagram, and the form of collaboration between entities is illustrated in the sequence diagram. The design of blockchain network of FFB supply and traceability of FFB from independent smallholders group procurement channel was based on CPO sales data from the exporter. The contribution of independent smallholders group channels to produce low FFA CPO was calculated. By presenting the CPO supply system on a map, independent smallholders’ farms’ source of low FFA CPO can be identified. Finally, various sustainable information in the farms can be shared.