The liquid electrode dielectric barrier discharge (LE-DBD) is a miniaturized atmospheric pressure plasma as emission excitation source for elemental determination with pulsed behavior. Metals dissolved in liquids are detectable in flow systems with low flow rates of 20 μL min(-1) by means of optical emission spectrometry using a simple portable spectrometer. Time-resolved determination of the hydrogen excitation temperature Tαβ indicates that the LE-DBD does not reach a stable state during a burning phase, whereat the maximum and minimum Tαβ is independent of the flow rate. Adding dissolved metals to the liquid electrode does not influence the minimum Tαβ at the end of a burning phase. With the help of measured doubly charged lanthanum lines and spatially resolved measurements, the mechanism of the liquid transfer into the plasma will be clarified. Emissions from metal oxides indicate a thermal evaporation transfer mechanism, but only an additional electrospray-like transfer mechanism can explain the observed La III emissions and nonhomogeneous spatial distribution of exited species. The reaction pathways for electrosprayed hydrated metal ions are discussed for triply and doubly charged ions. The analytical performance is evaluated for 23 elements from the categories of alkali, alkaline earth, transition, and poor metals. The achieved detection limits are between 0.016 mg L(-1) for Li and 41 mg L(-1) for Bi.