X-ray spectra of n = 2 to 1 transitions in hydrogen-like Ca19 +, helium-like Ca18 + and nearby satellites have been obtained from Alcator C-Mod tokamak plasmas using a spatially imaging high resolution x-ray spectrometer system. For Ca19 +, the intensity ratio of Ly 2(1s1S1/2-2p 2P1/2) to Ly1 (1s 1S1/2-2p 2P3/2) was found to be ∼0.531 ± 0.005 over a range of plasma parameters, which is somewhat greater than the ratio of the statistical weights of the upper n = 2 levels, 1/2. This difference is mainly due to interaction with the 2S1/2 fine structure sub-level. Experimental results are compared to calculations from COLRAD, a collisional-radiative modelling code, and good agreement is shown. For Ca18 +, the intensity ratio of the dielectronic satellite k (1s22p2P1/2-1s2p 22D3/2) to the resonance line w (1s 21S0-1s2p 1P1) is sensitive only to the electron temperature. The observed brightness ratio scaling with Te is in good agreement with the calculated ratio of the respective dielectronic recombination to the collisional excitation rates. © 2014 IOP Publishing Ltd.