The reaction of benzene with exchangeable Cu(II) and Fe(III) in hectorite clay films was studied by electron paramagnetic resonance (EPR). The reaction when carried out in a sealed tube between 60° and 100°C produced a variety of organic radical products. The nature of these products depended on the concentration of water in the reaction medium and the reaction time. The free radicals were accompanied by a reduction in the oxidation state of the metal ions; this process had a zero-order dependence on the metal ion concentration. The activation energies determined from the zero-order rate constants are 67 ± 11 kJ/mole (Cu(II)) and 46 ± 6 kJ/mole (Fe(III)). The free radicals initially formed under anhydrous conditions appeared to populate sites in the interlayer region; the activation energies determined for this first order process are 57 ± 9 kJ/mole (Cu(II)) and 42 ± 3 kJ/mole (Fe(III)). These activation energies are within experimental error of those determined from the metal ion kinetics. The EPR signal due to organic radicals showed little temperature dependence; thus, exchange processes involving organic free radicals were probably not important in determining EPR lineshapes.

The effects of low and high frequency ultrasound on the production of volatile compounds along with their derivation and corresponding off-flavours in milk and milk products are discussed in this review. The review will simultaneously discuss possible mechanisms of applied ultrasound and their respective chemical and physical effects on milk components in relation to the production of volatile compounds. Ultrasound offers potential benefits in dairy applications over conventional heat treatment processes. Physical effects enhance the positive alteration of the physicochemical properties of milk proteins and fat. However, chemical effects propagated by free radical generation cause redox oxidations which in turn produce undesirable volatile compounds such as aldehydes, ketones, acids, esters, alcohols and sulphur, producing off-flavours. The extent of volatile compounds produced depends on ultrasonic processing conditions such as sonication time, temperature and frequency. Low frequency ultrasound limits free radical formation and results in few volatile compounds, while high ultrasonic frequency induces greater level of free radical formation. Furthermore, the compositional variations in terms of milk proteins and fat within the milk systems influence the production of volatile compounds. These factors could be controlled and optimized to reduce the production of undesirable volatiles, eliminate off-flavours, and promote the application of ultrasound technology in the dairy field.

Electron paramagnetic resonance (EPR) spectra of different particle size fractions of four kaolins from diverse sources in North America, Europe and Asia have been investigated in order to characterize their paramagnetic properties and heterogeneity. There were major differences in the sources of the EPR signals from transition metals; V and Mn were structural, Fe was both structural and as associated oxides, and Cu was in the form of an adsorbed ion. The radiation-induced free radical signals commonly known as the A- and B-centres were observed in three of the deposits; however, in addition to the previously reported 27Al hyperfine structure associated with the B-centre, we also observed much smaller 27Al hyperfine structure on the g┴ feature of the A-centre. The other kaolin sample produced four free radical signals that have not previously been reported in kaolins. Each had substantial 1H hyperfine splitting; three are interpreted as corresponding to defect centres associated with Si-OH groups, and the other to a Si hole surrounded by protonated O atoms. The EPR spectra changed progressively with particle size, and measurements on the Asian specimens after grinding showed major differences in the Fe3+ signals from the same particle size fractions separated from the natural samples, thus supporting previous reports that grinding results in major structural changes in the minerals.

The EPR spectrum of a previously unreported paramagnetic centre formed in kaolin minerals by exposure to γ radiation is described. This centre, which is referred to here as the ‘C-centre’, was seen initially during an investigation of the radiation dose response of the EPR signal in the natural Lampang kaolin from northern Thailand, and its EPR properties are now presented for a purified sample from this material. They suggest a paramagnetic centre with rhombic symmetry based on O− associated with a single 27Al atom. Computer simulations suggest spin Hamiltonian parameters of g1 = 1.976, g3 = 2.0417 and A(27Al) = 2.10 mT, with g2 ≈ 2.01. This C-centre was also seen as a minor radiationinduced component in both crude and purified Ranong kaolin samples, along with a stronger signal from the B-centre radical. It seems to be associated with the kaolinite component, but was lost on annealing to 300°C after which only the signal from the A-centre was visible.