Ionic charge, complexation equilibria, and acid-base equilibria can be measured at tracer concentrations by ion-exchange chromatography. To characterize better the principal components found in [99mTc]pyrophosphate preparations used for diagnostic bone and heart scanning, these were studied in two ion-exchange chromatographic systems: (A) DEAE-cellulose in pyrophosphate form at pH 6.0-7.5, and (B) DEAE-cellulose in perchlorate form at pH 3.7-4.8. The chromatographic retention times were measured as a function of pH and electrolyte concentration, and compared with those of trisoxalatochromium(III) complex, which was chosen as reference ion because of its similarity in charge and retention to the Tc-pyrophosphate complexes. The pyrophosphate complexes were even more sensitive to electrolyte concentration than was the triply negative reference ion: the calculated mean net charge in the mobile phase for the two principal Tc-pyrophosphate species were -4.5 +/- 0.5 and -4.9 +/- 0.5 at pH 4.3, and -11.2 +/- 1.3 and -10.1 +/- 1.0 at pH 7.0. It can be concluded that the two principal radioactive components in clinical Tc-pyrophosphate preparations both bear a high, pH-dependent negative charge.