Rancimat™, oxidation stability measurement

IV, CCR and oxidation stability are three strictly co-related parameters. As a general rale, the reduction of IV (on the same feedstock) dramatically improves the oxidation stability. On the contrary the distillation step removes the main part of naturally occurring antioxidants. For this reason, even after hydrogenation the Rancimat induction time (as measured according to the EN 14112 standard) of the hydrogenated sample does not fulfill the EN 14214 requirement for oxidation stabihty (6 hours at 110°C), 4 hours being the measured induction period. 

Rancimat is an accelerated method to assess oxidative stability of fats and oils. In this test, the sample is subjected to an accelerated oxidative process (by heat in presence of oxygen), where short-chain volatile acids are produced. The acids formed are measured by conductivity. 

A widespread method for determining the induction period for autoxidation of oils and fats consists of passing a continuous stream of air through the heated sample and collecting the volatile acids evolved in a water trap, where they are determined on a real time basis. The time plot usually presents a flat appearance for a certain period and then takes off in an accelerated manner. This test is the basis of several national and international standards (e.g. AOCS Cd 12b-92—oil stability index" ISO 6886—accelerated oxidation test for oxidative stability of fats and oils ) and the design of the Rancimat equipment, where the end determination is based on conductivity measurements . In addition to oxidation stability as determined by the Rancimat method and POV, which negatively affects virgin olive oil stability, other nonstandard properties were proposed for better assessment of the quality of this oil, namely LC determination of Vitamin E (21), colorimetric determination of total polar phenols and UVD of total chlorophyll. ... 

NOTE This method relies on either of two commercially available instruments that consist of a means of controlling sample temperature (maintained at 0.1 °C), an air distribution system, conductivity tubes, stoppers and probes, and electronics or software for measuring conductivity and determining induction period. The following steps are generally applicable to both the Rancimat and the Oxidative Stability Instrument however, some variations exist due to differences in hardware and models available. Consult the manufacturer s instructions for additional detail. 

The Biodiesel Stability (BIOSTAB) project, supported by the European Commission, was initiated in 2001 to establish clear criteria and analytical methods for the monitoring biodiesel fuel stability (Various, 2003 Prankl, 2002). The resulting unified method, EN 14112 (Anon., 2003c) established a means for measuring oxidative stability utilizing the Rancimat or oxidation stability instruments. This test method was essentially developed from standards employed in the fats and oils industry to measure isothermally the induction period for oxidation of fatty derivatives. At present, both biodiesel fuel standards ASTM D 6751 (Anon., 2007a) and EN 14214 (Anon., 2003b) include an oxidative stability specification based on measurement by method EN 14112. 

An earlier study (Stavinoha and Howell, 2000) examined the effects of TBHQ and a-tocopherol on oxidative stability of SME from four different sources by non-isothermal P-DSC in static (zero air-purge) mode. P-DSC curves were analyzed by measuring the OT where P = 2000 kPa, initial temperature = 25 °C, and (S = 5°C/min. Results for two of the SME samples showed that addition of 2000 ppm a-tocopherol increased OT by -20 °C while addition of 2000 ppm TBHQ increased OT by -30 °C. Addition of the same concentration of a-tocopherol and TBHQ to the other two SME samples increased OT by -30 °C and -40 °C, respectively. Interpretation of these results suggested TBHQ was more effective at increasing relative resistance to oxidation of SME than a-tocopherol, a conclusion that was in accordance with those by Mittelbach and Schober (2003) for the isothermal Rancimat method. 

Oa StabUity Index. Two conductivity instruments, Rancimat and The Oxidative Stability Instmment, have been developed as alternatives to AOM Stability analysis. These instruments measure the increase in deionized water conductivity resulting from trapped volatile oxidation products produced when the oU product is heated under a stream of air. The conductivity increase is related to the oxidative stabihty of the products. These instruments provide a more reproducible measurement of oxidation stability with less technician time and attention. 

Fat oxidative stability is measured by the active oxygen method (AOM, AOCS Method Cd 12-57). Oil or fat is held at 97.8°C while air is bubbled through it. The time required to develop a peroxide concentration of 100 meq/kg is the AOM stability of the sample. A closely related method, the oil stability index (OSI, AOCS Method Cd 12b-92), also bubbles air through hot oil. One of the breakdown products is formic acid, which is trapped in a water cell. The machine continuously monitors conductivity of the water, and records the time when it rises sharply. Rancimat times obtained at 110°C are 40-45% of the AOM times, so an OSI stability of 4 h is equal to an AOM stabihty of 10 h. 

The active oxygen method (AOM) is the most common analytical method used to measure oxidative stability of fats and oils products. AOM employs heat and aeration to accelerate oxidation of the oil by continuously bubbling air through a heated sample. Periodic peroxide values are measured to determine the time required for the oil to oxidize to a predetermined peroxide value under the AOM conditions. This method requires close attention to detail to produce reproducible results and even then the variation between laboratories is 25 for a 100 h AOM sample. Conductivity instruments such as the Rancimat and the Oxidative Stability Instrument have been developed as alternatives to AOM stability analysis. These instruments measure the increase in the conductivity of deionized water resulting from trapped volatile oxidation products produced when the oil product is heated under a stream of air. The conductivity increase is related to the oxidative stability of the products. These instruments provide a more reproducible measurement of oxidation stability with less technician time and attention. 

The Oil Stability Index (OSI) is another method to measure oil stability that can be conducted using AOCS Method Cd 12b-92 (AOCS, 2005) with a Rancimat instrument or an Oxidative Stability Instrument. The OSI may be run at temperatures of 100, 100, 120, 130, and 140°C. Although oil processors and food manufacturers are interested in rapid measurements of oxidation, the high temperature at which the procedure is conducted may not be relevant to ambient temperatures used for most oil storage. Frankel (1993) suggested that the variation in results at 110°C with the rapid analysis and ambient temperature storage may be because of differences in the oxidation mechanisms at the two temperatures. 

Matthaus, B. W. 1996. Determination of the oxidative stability of vegetable oils by Rancimat and conductivity and chemiluminescence measurements. J. Am. Oil Chem. Soc. 73 1039-1043. 

The oxidative stability of oils and fats is an important parameter for the analysis of their quality. It is performed using the Rancimat test equipment or the Omnlon Instrument to measure the changes in the electrical conductivity in water caused by the formation and release of volatile oxidation compounds [13]. 

In addition to sensory evaluation, some other parameters are suitable to describe the quality of cold-pressed oils. Such characteristic features are oxidative stability (Rancimat test), tocopherol content and composition, amount of trans-fatty acids or stigmastadiene, showing a heat treatment during production, as weU as content of chlorophyll, as a measure not only for the maturity of the raw material, but also as an indicator of improper pressing conditions. 

The most common method used to determine the oxidative stability of fatty compounds is Rancimat (EN14214) also called OSl (Oxidation Stability Index). This test method consists in bubbling air through a sample maintained at llO C. This air is then passed through deionized water while the conductivity is measured. The sudden increase in water conductivity is due to soluble secondary oxidation products (volatile organic acids). The time at which the conductivity drastically increases is the induction time. 

Other indices measure a secondary stage of oxidation, such as the anisidine value (ANV), pointing to formation of carbonyl compounds, capable of undergoing condensation reactions with p-anisidine, and the thiobarbituric acid reactive substance (TBARS) pointing to the presence of malondialdehyde (MDA) in particular. In biological systems, TBARS is of widespread use as a measure for the extent of oxidation damage. Another test for stability of oils to oxidation is based on the development of acidity as secondary product, for example, standards using the Rancimat equipment or a similar setup. 

Lipid oxidation is also estimated by instrumental analyses such as by Rancimat test method and used for accelerated stability study [6]. Electron spin resonance can measure radical formation in many types of food matrices [7]. Analysis of volatiles with dynamic headspace/GC-MS is highly sensitive and can provide lot of information with regard to volatile lipid oxidation products and other volatiles with sensory impact in food samples. This type of data can also give information on possible reaction pathways of food deterioration [8]. Front-face fluorescence spectroscopy... 

---