Peroxide value , measurement

The peroxide value measurement is a general quantitative measure of peroxide/hydroperoxide intermediates produced during oxidative degradation. 

Peroxide value. Peroxide value (PV) is the most common measurement of lipid oxidation. Hydroperoxides have no flavor or odor of their own, but they are unstable and break down rapidly to other products such as aldehydes that have a strong, disagreeable flavor and odor. Peroxide value measures the mUiequivalents of oxygen... 

Peroxide value Measures peroxides (oxidation of Kl => I2) in fats/oils Cd 8-53 ... 

The Rancimat method has been used to measure the antioxidant activity of synthetic and natural antioxidants (2-/>2d) and has correlated well with oil stability measured by the Active Oxygen Method (27) and peroxide value measurement (28). Our study showed that using the Rancimat method to study the antiphotooxidative effect of carotenoids on the soybean oil was in agreement with the results using the headspace oxygen depletion method (16) and the peroxide value method (16,JT). 

At this point, the problem of measurement of rancidity would appear to be relatively simple, in that one would merely determine the peroxide value at arbitrary intervals, and at a given point the sample would be considered rancid. This paper points out some of the difficulties involved in such a procedure from the standpoint of obtaining useful data. 

The thiocyanate method involves measurement of the peroxide value using linoleic acid as substrate and has also been widely used to measure the antioxidant activity in plant-based foods such as ginger extracts (Kikuzaki and Nakatani 1993), fruit peels (Larrauri and others 1996 1997), extracts from vegetable by-products (Larrosa and others 2002 Llorach and others 2003 Abas and others 2006 Peschel and others 2006), blueberry juice, wines, and vinegars (Su and Chien 2007). 

Apart from specifications as to origin, e.g. palm kernel oil, fats are normally supplied on the basis of established parameters. One of these is the iodine value. This reflects the tendency of iodine to react with double bonds. Thus, the higher the iodine value the more saturated the fat is. An iodine value of 86 would approximate to one double bond per chain, while an iodine value of 172 approximates to two double bonds per chain. Another parameter is the peroxide value. This attempts to measure the susceptibility of the fat or oil to free radical oxidation. The test is applied on a freshly produced oil and measures the hydroperoxides present. These hydroperoxides are the first stage of the oxidation process. Obviously, this test would not give reliable results if applied on a stale sample. 

Peroxide value General quantitative measure of peroxides or hydroperoxides produced by oxidative degradation 0... 

Figure 3. Changes in concentration of O2, NO and Fe during cellular lipid peroxidation and its inhibition by NO. Shown ate the concentrations of NO and Fe at key time points. Peroxidation, as measured by O2 uptake, was initiated with 20 pM Fe. At 1 min after the addition of Fe 0.9 pM NO was introduced. NO was rapidly depleted and is below the limit of detection at about 4 min. At the time of NO depletion, rapid O2 uptake resumes. This reinitiation of O2 consumption is due to Fe that is still present at 7.2 pM or about 36% of its original value. (From Kelley, E.E., Wagner, BA., Buettner, G.R., and Bums, C.P., 1999, Arch. Biochem. Biophys. 370 97-104).

Classical low values for the mammalian enzyme that have appeared in the literature are the result of enzyme inactivation by hydrogen peroxide when measurements were carried out with peroxide levels in excess of 10 mM over time scales of 10 minutes or longer. The rapid sampling/titration method of Bonnichsen overcame the inactivation problem and permitted a satisfactory correlation of the overall catalytic measurements and Chance s observations on the intermediate complex (compound 1). Eventually, the introduction of the UV detector/spectrophotometer and the consequent assay based upon the UV absorbance of peroxide (35) further simplified the process by eliminating the discontinuous titrimetric assay. 

An important consideration for quality control in industry and commerce relates to the trend of developing faster analytical methods than those described in official sfandards the question in such cases is whether a proposed method is acceptable as replacement for the standard. This problem relates to the concepts fitness for purpose and measurement uncertainty, the latter serving for the estimation of the LOD and LOQ parameters of analytical quality. An example of this dilemma relating to the peroxide value is discussed in Section IV.B.5. 

Potentiometry biosensors, 664 fitness for purpose, 663 hydrogen peroxide determination, 650-1 iodine-iodide buffer, 699 measurement uncertainties, 663 peroxide value, 663-4 transition metal peroxides, 1069 POV see Peroxide value POZ see Primary ozonides Precipitation waters, hydrogen peroxide determination, 637... 

To examine the extent that cage and entropy had on the original data, activation parameters for the reduction of di-ferf-butyl peroxide were measured from a temperature study using a series of donors. These values are compared with those predicted by the model that accounts for cage and entropy effects and are summarized in Table 5. Examination of the two series of AG appears to account for the original discrepancy in the ET rate... 

Several methods have been introduced which express the degree of oxidation deterioration in terms of hydroperoxides per unit weight of fat. The modified Stamm method (Hamm et at 1965), the most sensitive of the peroxide determinations, is based on the reaction of oxidized fat and 1,5-diphenyl-carbohydrazide to yield a red color. The Lea method (American Oil Chemists Society 1971) depends on the liberation of iodine from potassium iodide, wherein the amount of iodine liberated by the hydroperoxides is used as the measure of the extent of oxidative deterioration. The colorimetric ferric thiocyanate procedure adapted to dairy products by Loftus Hills and Thiel (1946), with modifications by various workers (Pont 1955 Stine et at 1954), involves conversion of the ferrous ion to the ferric state in the presence of ammonium thiocyanate, presumably by the hydroperoxides present, to yield the red pigment ferric thiocyanate. Newstead and Headifen (1981), who reexamined this method, recommend that the extraction of the fat from whole milk powder be carried out in complete darkness to avoid elevated peroxide values. Hamm and Hammond (1967) have shown that the results of these three methods can be interrelated by the use of the proper correction factors. However, those methods based on the direct or indirect determination of hydroperoxides which do not consider previous dismutations of these primary reaction products are not necessarily indicative of the extent of the reaction, nor do they correlate well with the degree of off-flavors in the product (Kliman et at. 1962). 

Alternate Protocol Determination of Peroxide Value by Measurement... 

ALTERNATE PROTOCOL DETERMINATION OF PEROXIDE VALUE BY MEASUREMENT OF IRON OXIDATION The ferrous oxidation/xylenol orange (FOX) method is based on the ability of lipid peroxides to oxidize ferrous ions at low pH. The resulting oxidation is quantitated by using a dye that complexes with the generated ferric ions to produce a color that can be measured spectrophotometrically. Peroxide values (PVs) as low as 0.1 meq active oxygen/kg sample can be determined with this method, providing a distinct advantage over iodometric titration. 

Oishi, M., Onishi, K Nishijima, M., Nakagomi, K.. and Nakazawa, H. 1992. Rapid and simple cou-lometric measurements of peroxide value in edible oils and fats. J. AOAC Int. 75 507-510. 

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). 

The OSI replaced the Active Oxygen method (AOM), which is no longer recommended by the American Oil Chemists Society. The AOM required frequent measurement of peroxide value. Not only was this laborious, but determining peroxide value resulted in a... 

The oils of ajowan show excellent antioxidant effects (better than those of the synthetic antioxidant and butylated hydroxytoluene Gurdip et al., 1998). Mehta et al. (1994) demonstrated ajowan as a source of natural lipid antioxidant. Soybean oil treated with meth-anolic extracts has been subjected to storage and heating tests, which showed a marked decrease in oxidation of the oil as measured using peroxide values, conjugated diene... 

The maximum shelf-life of bulk packaged WMP containing 3% moisture is about 6 months at 30°C (Kjaergaard Jensen, 1988). The oxidation of WMP, as measured by peroxide value, is dependent on the moisture content of the powder, van Mil and Jans (1991) reported that under similar storage conditions, the peroxide value of WMP increases more rapidly for powder containing 3% moisture than in powder containing 2.4% moisture. The water activity (aw) range for WMP is usually 0.13 0.20, with a typical value from 0.16 to 0.18 (Wewala, 1990). Stapelfeldt et al. (1997) found that the quality of WMP is maintained best at aw between 0.11 and 0.23, whereas the quality of the powder decreases when stored at aw of 0.31 at 45°C. However, the critical aw for improved oxidative stability of WMP stored at 40°C for one year is 0.21 0.24 at a moisture level of 3.4% (Wewala, 1990). 

Peroxide Value, Fats and Oils (PV) (Cd 8-53) determines all substances, in terms of milliequivalents of peroxide per 1000 g of sample, that oxidize potassium iodide (KI). These substances generally are assumed to be peroxides or products of fat oxidation. Phosphorus in Oils (Ca 13-55) estimates the phospholipid content of crude, degummed, and refined vegetable oils in terms of phosphorus. Refineries often use induction coupled plasma (ICP) spectrographs to analyze divalent cations rapidly in aspirated crude oil. The calcium and magnesium measured are mainly responsible for nonhydratable phosphatides (NHP) and are determined directly. An AOCS method for analysis by ICP is being developed. 

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