Bulk ion toroidal rotation plays a critical role in controlling microturbulence and MHD stability as well as yielding important insight into angular momentum transport and the investigation of intrinsic rotation. So far, our understanding of bulk plasma flow in hydrogenic plasmas has been inferred from impurity ion velocity measurements and neoclassical theoretical calculations. However, the validity of these inferences has not been tested rigorously through direct measurement of the main-ion rotation in deuterium plasmas, particularly in regions of the plasma with steep pressure gradients where very large differences can be expected between bulk ion and impurity rotation. New advances in the analysis of wavelength-resolved D α emission on the DIII-D tokamak [J. L. Luxon et al., Fusion Sci. Technol. 48, 807 (2002)] have enabled accurate measurements of the main-ion (deuteron) temperature and toroidal rotation. The Dα emission spectrum is accurately fit using a model that incorporates thermal deuterium charge exchange, beam emission, and fast ion Dα (FIDA) emission spectra. Simultaneous spectral measurements of counter current injected and co current injected neutral beams permit a direct determination of the deuterium toroidal velocity. Time-dependent collisional radiative modeling of the photoemission process is in quantitative agreement with measured spectral characteristics. L-mode discharges with low beam ion densities and broad thermal pressure profiles exhibit deuteron temperature and toroidal rotation velocities similar to carbon. However, intrinsic rotation H-mode conditions and plasmas with internal transport barriers exhibit differences between core deuteron and carbon rotation which are inconsistent with the sign and magnitude of the neoclassical predictions. © 2012 American Institute of Physics.