We present the results of a series of experiments designed to probe the interactions between Al and the amorphous silica surface as a function of thermodynamic driving forces. The results from 27Al single pulse magic angle spinning (SP/MAS) and 27Al{1H} rotational echo double resonance (REDOR) allow us to identify the reaction products and constrain their structure. In all cases, despite low Al and Si concentrations we observe the formation of metastable aluminosilicates. Results from low temperature experiments indicate that despite thermodynamic driving forces for the formation of gibbsite we observe the precipitation of separate octahedrally coordinated Al (Al[6]) and tetrahedrally coordinated Al (Al[4]) silicate phases. At higher temperatures the Al[4] silicate phase dominates the speciation. Structural models derived from the NMR data are also proposed, and the results are discussed as they relate to previous work on Al/Si cycling.