Solutions of the strong complexing agent ethylenediaminetetraacetic acid (EDTA) and Cu, Pb, Cd, Al, and Fe(III) were examined by electrospray mass spectrometry (ES/MS). Uncomplexed EDTA and metal-EDTA complexes survive the electrospray process intact and can be detected simultaneously by mass spectrometry. Best sensitivity was achieved in the positive ion mode in which EDTA and EDTA-metal complexes (present in solution as anions) were detected as protonated species with a single positive charge, Except for the protonation, the aqueous metal-EDTA complexes are preserved and neither fragmentation of complexes nor formation of clusters with more than one metal or ligand were observed in the mass spectra, Detection limits are between approximately 1 to 2 mu M for uncomplexed EDTA and for the Cu-EDTA and Pb-EDTA complexes, with a linear range up to 10(-4) ill. Calibrations based on solutions with equimolar concentrations of EDTA and Cu or Pb ran be used to quantify EDTA-metal complexes in solutions with excess EDTA or metal, and in solutions with more than one metal present. Isotopic signatures of metals in the metal-ligand complexes are preserved, allowing the identification of the metal in a metal-ligand complex. Isotopic signatures of metals ran therefore aid in the identification of metal-ligand complexes in unknown samples.