Nitric and nitrous acid formation in plasma-treated water: Decisive role of nitrogen oxides (NO).

Nitrogen fixation using low-temperature plasma, particularly in relation to plasma-treated water (PTW) and its chemical and physical properties, has received a renewed research focus. Dissolving highly concentrated nitrogen oxides (NO) generated by air discharge into water results in the formation of two aqueous oxiacids (nitrous and nitric acids; HNO) and their conjugates (nitrate and nitrite ions; NO). Nonlinear formation of these species in PTW with respect to plasma conditions has been observed; however, the significance of the time-varying NO on this nonlinearity has not yet been thoroughly investigated. Here, we demonstrate real-time observations of HNO/NO as well as NO production in a surface dielectric barrier discharge reactor containing distilled water. Synchronized two optical absorption spectroscopy systems were employed to simultaneously measure gas-phase NO and liquid-phase HNO/NO in the plasma reactor operated under different oxygen contents of 5, 20, and 50%. Our results showed that reducing the oxygen content in the reactor accelerated the chemical transition from O and NO to NO, leading to a predominance of nitrite in PTW. Specifically, the NO-rich period was extended with increasing O content, resulting in the production of nitrate-dominant PTW at low pH levels. Our findings highlight the potential for the selective generation of HNO/NO in PTW through the active and passive control of NO in a plasma reactor. The direct, real-time observation of NO-HNO/NO conversion presented here has potential for improving the control and optimization of PTW, thereby enhancing its applicability.