Mafic magmas typically erupt non-explosively, but although rare, we observe explosive mafic deposits in Earth’s rock record. Recent work suggests that the rapid rising of the magma through the crust to eruption leads to an explosive eruption of the mafic magma and informs our understanding of how these mafic magmas erupt explosively. However, it is unknown what conditions of the magmatic system and the evolution of the magma lead to these particular magmas rapidly rising through the crust, leaving the why undefined. Here, we use small volume chemical characterization of samples from an explosive mafic eruption of an active Chilean volcano (Llaima) and machine-learning methods to build a picture of hidden small-scale changes in the magma and magmatic system prior to the explosive eruption. By targeting small volumes of samples, we find previously unseen variations in the erupted compositions and can relate them to differences in the initial generation of the magma and the minerals crystallizing from the magma prior to eruption. With this information, we can understand how magma evolution and the mixing of different magmas can drive explosive eruptions at Llaima volcano.