Six samples of virgin olive oil obtained from several varieties of olive fruits (Picual, Manzanilla, Lechín, and Arbequina) were submitted to an accelerated oxidation process during a 63-h period under the conditions of the oil stability index (OSI), as measured by a Rancimat (100ºC) apparatus. Spectra were measured every 3 h, and chlorophyll and carotenoid indexes and CIELAB color ordinates were calculated. As oxidation time increased, remarkable changes in the spectral characteristics and color ordinates were observed. Oxidation provoked less vivid colors (lower values for chroma, C* ab ) in all the samples; however, only some varieties became darker (lower values for lightness, L*). The pigment loss calculated for oxidized oils was 67% for the carotenoid index and 58% for the chlorophyll index. Mathematical models are offered to predict color changes with time of storage at 20ºC.

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Visible-light photo-irradiation of the commercial phenolic antioxidants (PhAs) butylated hydroxyanisole (BHA) and butylated hydroxytoluene (BHT), in the presence of vitamin B2 (riboflavin, Rf), in methanolic solutions and under aerobic conditions, results in the photo-oxidation of the PhAs. The synthetic dye photosensitiser Rose Bengal was also employed for auxiliary experiments. With concentrations of riboflavin and PhAs of ca. 0.02 mM and < 1 mM, respectively, the excited triplet state of the vitamin (3Rf*) is quenched by BHT in a competitive fashion with dissolved ground state triplet oxygen. From the quenching of 3Rf*, the semireduced form of the pigment is generated through an electron transfer process from BHT, with the subsequent production of superoxide anion radical (O2*-) by reaction with dissolved molecular oxygen. In parallel, the species singlet molecular oxygen, O2(1delta(g)), is also generated. Both reactive oxygen species produce the photodegradation of BHT. In the case of BHA, the lack of any effect exerted by superoxide dismutase drives out a significant participation of a O2(*-)-mediated mechanism. BHA mainly interacts with O2(1delta(g)) and exhibits a desirable property as an antioxidant--a relatively high capacity for O2(1delta(g)) de-activation and a low photodegradation efficiency by the oxidative species. Electrochemical determinations support the proposed photodegradative mechanism.

Square wave voltammetry (SWV) on carbon disk ultramicroelectrodes (UME) was used to determine antioxidants tert-butylhydroxyanisole (BHA) and tert-butylhydroxytoluene (BHT) in vegetable oils. Direct determinations were accomplished in benzene/ethanol/H 2 SO 4 solutions or in acetonitrile (ACN) after an extractive procedure. Much better recovery percentages were obtained in ACN extracts. By comparing with high-performance liquid chromatography (HPLC) results, BHA has a slightly lower recovery percentage by the SWV technique on ACN extracts. On the other hand, BHT shows a greater recovery percentage using the methodology proposed here. The analysis time through SWV is less than an hour for a duplicated analysis while the HPLC technique needs a greater time, besides the overnight stored time required by the current methodology. The present work tends to show that SWV on carbon disk UME allows sensitive, reproducible, and faster determination of BHA, BHT, or antioxidant mixtures in oil-solvent solutions or after a simple extractive procedure with the advantage of a higher recovery percentage. This validates the methodology as an analytical alternative for antioxidant quantification.Paper no. J9364 in JAOCS 77, 731-735 (July 2000).KEY WORDS: Antioxidant electroanalytical determination, BHA, BHT, carbon disk ultramicroelectrode, nonaqueous solvents, square-wave voltammetry, standard addition method, synthetic antioxidants, vegetable oils.During recent years, many articles claim the advantage of the use of electrochemistry in food process or analysis (1-5). In the analytical field, electrochemical techniques were used to determine and quantify phenolic compounds used as antioxidants (6-10). tert-Butylhydroxyanisole (BHA) and/or tert-butylhydroxytoluene (BHT) are the most common antioxidants used in the lipid industry to improve stability and prevent rancidity in their products (11-13). Thus, the identification and quantification of antioxidants play an important role in the quality assignment of lipid compounds.Both the AOAC (14) and AOCS Official Methods and Recommended Practices (15) include the determination of several antioxidants with acetonitrile (ACN) extraction step followed by high-performance liquid chromatography (HPLC) separation with ultraviolet (UV) detection at 280 nm.Electrochemistry on ultramicroelectrodes (UME) appears as a good alternative for electroanalysis, particularly for the quantification of synthetic antioxidants (16-21).On the other hand, pulse voltammetric techniques, especially square-wave voltammetry (SWV), have been proposed as alternative methods to decrease the time needed for analytical purposes (7,22). Thus, it is also possible to combine disk UME with SWV (23) to obtain highly reproducible signals, to minimize the cleaning difficulties of the UME and to improve both speed and sensitivity compared with other voltammetric methods (7,18,24).In this work, direct measurements of antioxidants on vegetable oil solutions as well as determinations after extraction steps followed by SWV detect...

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