The Thor lake deposit is a world class resource of rare earth (REE) metals and minerals in Canada. Development work to optimize a REE mineral recovery process flow sheet is underway, however, given the ore mineralogy; the developed reagent scheme is relatively complex. As part of a research project, micro-flotation tests were conducted on a feed sample in order to examine factors affecting stream partitioning. SEM–EDX was performed to evaluate variability in grain composition between streams (concentrate and tails) and TOF-SIMS surface analysis was used to determine statistically significant differences in surface species particularly related to potential activation (or depression) of the examined mineral phases. SEM–EDX analysis reveal that the concentrate has a significantly higher proportion of REE bearing grains (carbonates and phosphates) relative to the tail (almost none were identified). Spectral fingerprinting by TOF-SIMS has allowed for the identification of all reagent species investigated. Reagent signal intensity discrimination on test stream mineral surfaces was observed by the TOF-SIMS analysis using reagents at plant concentration levels. TOF-SIMS analysis confirmed that REE bearing grains reporting to the concentrate are doing so in response to collector attachment whereas grains reporting to the tail are doing so in response to a lack of collector and/or in combination with the presence of the depressant. The surface analysis of gangue phases reveal a similar reagent discrimination; the signal intensity of collector species was significantly higher on the concentrate samples relative to the tails while depressant species were significantly enriched on the surface of the gangue phases in the tail samples. A detailed evaluation of the surface species representing the various reagents used in flotation scheme revealed a distinct competitive relationship between two of the reagents. The surface analysis identified that when used in concurrently, there appears to be a negative feedback resulting in a significant reduction in loading for several of the collectors on grains reporting to the concentrate. An evaluation of the effect of reagents on REE mineral in pilot plant is currently under way.