Sonochemical formation of peroxynitrite in water: Impact of ultrasonic frequency and power

There is a lack of literature on peroxynitrite formation due to sonolysis of aerated water. In this work, the impact of sonication parameters, frequency and power, on ultrasonic peroxynitrite production in aerated alkaline water was investigated. Peroxynitrite formation was clearly established with undeniable evidence at all the tested frequencies in the range of 516-1140 kHz with a typical G-value (energy-specific yield) of 0.777 × 10^-10, 0.627 × 10^-10, 0.425 × 10^-10 and 0.194 × 10^-10 mol/J at 516, 558, 860 and 1140 kHz, respectively. The ultrasonication frequency has a direct impact on the sonochemical peroxynitrite production. Increasing the ultrasonication frequency in the interval 321-1140 kHz reduces peroxynitrite formation. The most practical sonochemistry dosimetries, including hydrogen peroxide production, triiodide dosimetry, Fricke dosimetry, and 4-nitrocatechol formation, were compared with the sonochemical efficiency of the reactors used to produce peroxynitrite. The G-value, energy specific yield, for the tested dosimetries was higher than that for peroxynitrite formation, regardless of frequency. For all chemical dosimetries investigated, the same trend of frequency dependence was found as for peroxynitrite generation. The influence of ultrasonication power on peroxynitrite formation by sonication at diverse frequencies in the interval 585-1140 kHz was studied. No peroxynitrite was formed at lower acoustic power levels, regardless of frequency. As the frequency increases, more power is required for peroxynitrite formation. The production of peroxynitrite increased as the acoustic power increased, despite the frequency of ultrasonic waves. Ultrasonic power is a key factor in the production of peroxynitrite by sonolysis. Since peroxynitrite is uniformly distributed in the bulk solution, peroxynitrite-sensitive solutes can be transformed both in the bulk of the solution and in the surfacial region (shell) of the cavitation bubble. The formation of peroxynitrite should be taken into account in sonochemistry, especially at higher pH values. Ultrasonic peroxynitrite formation in alkaline solution (pH 12) can be considered as a kind of chemical dosimetry in sonochemistry.