Carbonate is a somewhat enigmatic anion in static secondary ion mass spectrometry (SIMS) because abundant ions containing intact CO32− are not detected when analyzing alkaline-earth carbonate minerals common to the geochemical environment. In contrast, carbonate can be observed as an adduct ion when it is bound with alkali cations. In this study, carbonate was detected as the adduct Na2CO3·Na+ in the spectra of sodium carbonate, bicarbonate, hydroxide, oxalate, formate and nitrite and to a lesser extent nitrate. The appearance of the adduct Na2CO3·Na+ on hydroxide, oxalate, formate and nitrite surfaces was interpreted in terms of these basic surfaces fixing CO2 from the ambient atmosphere. The low abundance of Na2CO3·Na+ in the static SIMS spectrum of sodium nitrate, compared with a significantly higher abundance in salts having stronger conjugate bases, suggested that the basicity of the conjugate anions correlated with aggressive CO2 fixation; however, the appearance of Na2CO3·Na+ could not be explained simply in terms of solution basicity constants. The oxide molecular ion Na2O+ and adducts NaOH·Na+ and Na2O·Na+ also constituted part of the carbonate spectral signature, and were observed in spectra from all the salts studied. In addition to the carbonate and oxide ions, a low-abundance oxalate ion series was observed that had the general formula Na2−xHxC2O4·Na+, where 0 < x < 2. Oxalate adsorption from the laboratory atmosphere was demonstrated but the oxalate ion series also was likely to be formed from reductive coupling occurring during the static SIMS bombardment event. The remarkable spectral similarity observed when comparing the sodium salts indicated that their surfaces shared common chemical speciation and that the chemistry of the surfaces was very different from the bulk of the particle. Copyright © 2003 John Wiley & Sons, Ltd.