The physical processes and chemical reactions that take place inside different temperature plasma zones in water are only partially understood. The present study uses the emission spectroscopy and hydrogen peroxide measurements as indicators of the processes that take place on the gas-liquid boundary and inside plasma. Based on the hydrogen peroxide measurements with negative and positive high-voltage polarities as a function of solution conductivity, it was concluded that the main difference between positive polarity plasma and negative polarity plasma lies in the active radical concentration inside plasma. Data suggested that in the positive polarity electrical discharge the hydrogen peroxide concentration depends on the solution pH, whereas in the negative polarity discharge, it depends on the solution conductivity. Also, only in the negative polarity discharge do some of the electrons that are emitted from the high voltage electrode diffuse into the bulk where they react with the solutes.