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Whenever free radicals are formed, independent of whether this occurs thermally, is induced by UV or ionizing irradiation, or takes place in redox reactions, they are converted rapidly into the corresponding peroxyl radicals in the presence of oxygen. Peroxyl radical reactions in aqueous environments are observed not only in aquatic systems (e.g., rivers, lakes and oceans) but also in the living cell and to a considerable degree even in the atmosphere (in water droplets). The peroxyl radical chemistry occurring in this medium is often very different from that observed in the gas phase or in organic solvents. In spite of the great importance of these reactions in medicine (for example in anti-cancer irradiation therapy and ischaemia) there have been comparatively few studies of peroxyl reactions in aqueous media. Radiation-chemical techniques such as pulse radiolysis offer the best means for carrying out such studies, so that it is not surprising that the majority of the information available in this area has been obtained with the help of radiation-chemical methods. The radiation chemistry of water can be controlled in such a manner that the main products are 'OH radicals (90 % yield), which react with substrate molecules to give substrate radicals and in the presence of oxygen to give substrate peroxyl radicals. The experimental conditions can also be varied in such a way that HO;/O;" radicals can be formed in 100 % yield and caused to react with substrates. We therefore have a simple access to these intermediates, which are extremely important in biological systems. A detailed product analysis, supported by kinetic studies carried out with the help of pulse radiolysis, has been used to clarify the chemistry of a series of peroxyl radicals, so that sufficient material is now available to justify a review of the variety of the peroxyl radical reactions studied by means of radiation-chemical methods. A more general survey of the physical properties of the peroxyl radicals and their unimolecular and bimolecular reactions will be followed by a discussion of selected examples of various classes of substance. Because of the great biological importance of radical-induced D N A damage this area will also be treated briefly.

Terephthalate and Fricke dosimetry have been carried out to determine the sonolytic energy yields of the OH free radical and of its recombination product H2O2 in aqueous solutions under various operating conditions (nature of operating gas, power, frequency, temperature). For example, in the sonolysis of Ar-saturated terephthalate solutions at room temperature, a frequency of 321 kHz, and a power of 170 W kg-1, the total yield [G(.OH) + 2 G(H2O2)], equals 16 x 10(-10) mol J-1. This represents the total of .OH that reach the liquid phase from gas phase of the cavitating bubble. The higher the solute concentration, the lower the H2O2 production as more of the OH free radicals are scavenged, in competition with their recombination. Fricke dosimetry, in the absence and presence of Cu2+ ions, shows that the yield of H atom reaching the liquid phase is much lower, with G(H.) of the order of 3 x 10(-10) mol J-1. These sonolytic yields are smaller in solutions that are at the point of gas saturation, and increase to an optimum as the initial sonication-induced degassing and effervescence subsides. The probing of the sonic field has shown that the rate of sonolytic free-radical formation may vary across the sonicated volume depending on frequency and power input.

In the ozonolysis of phenol in aqueous solution at pH 3, 7 and 10 the following products were quantified: catechol, hydroquinone, 1,4-benzoquinone, cis,cis-muconic acid, H2O2, 2,4-dihydroxybiphenyl and 4,4-dihydroxybiphenyl. At pH 10, material balance (products vs. phenol consumption) is obtained. Singlet dioxygen, O2(1 delta g), and .OH are formed as short-lived intermediates. The precursor of the latter, O3.-, and a phenoxyl radical is suggested to arise from electron transfer from phenol/phenolate to ozone. Addition of .OH to phenol gives rise to dihydroxycyclohexadienyl radicals which add dioxygen and eliminate HO2. thereby forming catechol/hydroquinone. In competition and catalysed by H+ and OH-, the dihydroxycyclohexadienyl radical eliminates water yielding a phenoxyl radical. At pH 10, they readily oxidize catechol and hydroquinone. This reforms phenol (accounting for the low phenol consumption) and yields higher-oxidised products, eventually 1,4-benzoquinone. cis,cis-Muconic acid can be accounted for by the Criegee mechanism, while O2(1 delta g) is released on the way to (some of the) catechol and hydroquinone. Similar reactions proceed with hydroquinone (products: 1,4-benzoquinone, 2-hydroxy-1,4-benzoquinone and H2O2, with high yields of O2(1 delta g) and .OH) and with catechol (products: 2-hydroxy-1,4-benzoquinone, cis,cis-muconic acid, H2O2 with high yields of O2(1 delta g) and .OH). Material balance is not obtained for these two systems. Pentachlorophenolate, pentabromophenolate and 2,4,6-triiodophenolate ions give rise to halide ions, O2(1 delta g) (58%/48%/10%) and .OH (27%/2%/0%). It is suggested that together with O2(1 delta g) the corresponding ortho- and para-quinones plus a halide ion are formed. Further halide ion is released upon the hydrolysis of these and other products. For pentachlorophenolate the material balance with respect to the short-lived intermediates is 85%. With the bromo- and iodophenolates the O2(1 delta g) yields are substantially lowered, most likely due to release of triplet (ground state) dioxygen induced by the heavy atom effect.