We report the first measurements of Ca+ made from the Arecibo Observatory achieved by using a frequency-agile resonance fluorescence lidar. Simultaneous observations of the electron concentration of the lower ionosphere using the Arecibo incoherent scatter radar were also made, as well as K lidar observations of the mesospause region. We find excellent agreement in the distribution of ions observed between the lidar and radar for both the thin tidal ion layers and for broader formations of ionization that occasionally occur near 90 km altitude. The concentration of Ca+ within ion layers was found to be slightly less than the relative fraction of calcium in meteors, and generally consistent with previous lidar, rocket, and twilight airglow measurements.