A stable direct current atmospheric pressure glow microdischarge (dc-μAPGD) was generated between a miniature Ar flow microjet and a small sized flowing liquid cathode. The microdischarge was operated in the open to air atmosphere. High energy species, including OH, NH, NO, N2, H, O and Ar were identified in the emission spectra of this microdischarge. Additionally, atomic lines of metals dissolved in water solutions were easily excited. The near cathode and the near anode zones of the microdischarge were investigated as a function of an Ar flow rate up to 300 sccm. The spectroscopic parameters, i.e., the excitation, the vibrational and the rotational temperatures as well as the electron number density, were determined in the near cathode and the near anode regions of the microdischarge. In the near cathode region, the rotational temperatures obtained for OH (2000–2600 K) and N2 bands (1600–1950 K) were significantly lower than the excitation temperatures of Ar (7400 K–7800 K) and H (11 000–15 500 K) atoms. Vibrational temperatures of N2, OH and NO varied from 3400 to 4000 K, from 2900 to 3400 K and from 2700 to 3000 K, respectively. In the near anode region, rotational temperatures of OH (350–1750 K) and N2 (400–1350 K) and excitation temperatures of Ar (5200–5500 K) and H (3600–12 600 K) atoms were lower than those measured in the near cathode region. The effect of the introduction of a liquid sample on the microdischarge radiation and spectroscopic parameters was also investigated in the near cathode zone. The electron number density was calculated from the Stark broadening of the Hβ line and equals to (0.25–1.1) × 1015 cm− 3 and (0.68–1.2) × 1015 cm− 3 in the near cathode and the near anode zones, respectively. The intensity of the Na I emission line and the signal to background ratio (SBR) of this line were investigated in both zones to evaluate the excitation properties of the developed excitation microsource. The limit of detection for Na was determined at the level of 3 ng mL− 1.