A mechanism by which La modifies the Fe-bearing intermetallics in a 6xxx series Al alloy is examined using calorimetry. Thermal events accompanying the formation of various phases are identified by establishing a correspondence between them and microstructures of as-cast alloys. It is concluded that a previously suggested surface adsorption mechanism is unlikely to be operative. During solidification, the addition of lanthanum results in the formation of the La(Al,Si)2 phase and the depletion of the remaining melt of Si. It is hypothesized that the decreased Si/Fe ratio in the melt caused by the presence of La favors the formation of the α-AlFeSi phase, which is less detrimental to the formability of the alloy than the β-AlFeSi phase.