Volatile acids, oxidation stability measurement

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. ... 

Gas Chromatographic Methods. Gas chromatographic methods may be used for measuring volatile oxidation products. Static headspace, dynamic headspace, or direct injection methods may be employed. Specific aldehydes may be measured as indicators for oxidative stability of oils and fats. Thus, propanal is an and as indicator for stability of omega-3 fatty acids, whereas hexanal is best for following the oxidative stability of omega-6 fatty acids. 

Metal oxide semiconductor chemical sensors in combination with MDA have been shown to be useful to estimate the oxidative stability of polypropylene during processing instead of traditional melt flow index analysis (50). An array of sensors was used to receive a detailed analysis of volatiles. At quality measurements of different poly(butylene adipate)s the use of indicator products has been proven better than analyses of the decrease in molecular weight or mass loss for early degradation detection. Adipic acid, quantified using gas chromatography, was then used as the indicator product [51]. 

AOCS has a recommended practice (Cg 3-91) for assessing oil quality and stability (AOCS, 2005) for measuring primary and secondary oxidation products either directly or indirectly. For example, peroxide value analysis (AOCS method Cd 8-53) (AOCS, 2005) determines the hydroperoxide content and is a good analysis of primary oxidation products. To determine secondary oxidation products, the procedure recommends p-anisidine value (AOCS Method Cd 18-90, 2005) volatile comlb by gas chromatography (AOCS Method Cg 4-94, 2005) and flavor evaluation. (AOCS Method Cg 2-83, 2005). The anisidine value method determines the amounts of aldehydes, principally 2-alkenals and 2, 4-dienals, in oils. The volatile compound analysis method measures secondary oxidation products formed during the decomposition of fatty acids. These comlb can be primarily responsible for the flavors in oils. The... 

In mixtures, 2-nonenal and 2,4-heptadienal are more rapidly oxidized than methyl linoleate and linolenate, and these fatty esters are more readily oxidized than nonanal. Therefore, during the more advanced stages of oxidation the saturated aldehydes accumulate and the unsaturated aldehydes are further oxidized to lower aldehydes and dialdehydes. At elevated temperatures, saturated aldehydes and dialdehydes are further oxidized into mono- and dibasic acids. The formation of low molecular weight volatile acids is used as a measure of thermal oxidation of fats, and is the basis for detection in some high temperature stability tests (Chapter 7). 

To evaluate oxidative stability, different methods are used to measure lipid oxidation after the sample is oxidized under standardized conditions to a suitable end-point. In Table 7.1, different lipid oxidation tests are ranked in decreasing order of usefulness in predicting Ae stability or shelf life of a food product. Methods for sensory evaluations, conjugated diene, gas chromatography of volatiles, peroxide values and thiobarbituric acid-reacting substances were discussed in Chapter 5. 

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. 

Rancidity measurements are taken by determining the concentration of either the intermediate compounds, or the more stable end products. Peroxide values (PV), thiobarbituric acid (TBA) test, fatty acid analysis, GC volatile analysis, active oxygen method (AOM), and sensory analysis are just some of the methods currently used for this purpose. Peroxide values and TBA tests are two very common rancidity tests however, the actual point of rancidity is discretionary. Determinations based on intermediate compounds (PV) are limited because the same value can represent two different points on the rancidity curve, thus making interpretations difficult. For example, a low PV can represent a sample just starting to become rancid, as well as a sample that has developed an extreme rancid characteristic. The TBA test has similar limitations, in that TBA values are typically quadratic with increasing oxidation. Due to the stability of some of the end-products, headspace GC is a fast and reliable method for oxidation measurement. Headspace techniques include static, dynamic and solid-phase microextraction (SPME) methods. Hexanal, which is the end-product formed from the oxidation of Q-6 unsaturated fatty acids (linoleate), is often found to be a major compound in the volatile profile of food products, and is often chosen as an indicator of oxidation in meals, especially during the early oxidative changes (Shahidi, 1994). 

Palaniappan and Narayana [168] studied the thermal stabilities of chemically prepared polyanilines in different acid media by isothermal heat treatments at 150°, 200°, 275° and 375°C in combination with EPR, electronic absorption and infra-red spectroscopic measurements. They also observed a three-step weight loss, the first step is attributed to the loss of water from the polymer salt starting at 110°C, the second, minor step is due to volatilization of acid ranging from 110°C to 275°C, and the polymer undergoes thermo-oxidative degradation of the polymer backbone in the third step above 275°C. The thermal stability was observed to be dependent on the doping counter-ion and no structural... 

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