A glow discharge optical emission spectroscopy (GD-OES) source that operates at atmospheric pressure is described. This device utilizes an electrolytic solution containing the analyte specimen as one of the discharge electrodes. The passage of electrical current (either electrons or positive ions) across the solution/gas phase interface causes local heating and the volatilization of the analyte species. Collisions in the discharge region immediately above the solution surface result in optical emission that is characteristic of the analyte elements. Operation of this device with the analyte solution acting as either the cathode or anode is demonstrated. Current-voltage (i-V) plots reveal abnormal glow discharge characteristics, with operating parameters being dependent on the electrolyte concentration (i.e., solution conductivity) and the gap between the solution surface and the counterelectrode. Typical conditions include discharge currents of 30-60 mA, and potentials of 500-900 V. Electrolyte solutions having pH, pNa, or pLi values of 0.5-2 and interelectrode gaps of 0.5-3 mm produce stable plasmas in which the analyte solutions flow at rates of up to 3.0 mL/min. Preliminary limits of detection are determined for the elements Na, Fe, and Pb to be in the range of 11-14 ppm (approximately 60 ng) for 5-microL sample volumes.