Primitive, mantle-derived magmas provide important clues about the formation and equilibration conditions of magmas at depth. In subduction zones, it is uncommon for primitive magmas to ascend through the shallow mantle and crust without undergoing chemical modification. Instead, magmas commonly differentiate through fractional crystallization, crustal assimilation, or magma mixing. Those rare primitive lavas that do erupt along a volcanic arc are useful for elucidating subduction-related processes within the mantle wedge (~30–80 km depth) and are the focus of this research. I used piston-cylinder apparatuses to investigate the high-pressure, high-temperature, H2O-undersaturated phase equilibria for several primitive compositions that have erupted at volcanic arcs. I aimed to reveal the permissible residual mantle mineralogy, as well as the P-T- H2O conditions over which the putative mantle melts last equilibrated before erupting. My work focuses on the Trans-Mexican Volcanic Belt (TMVB), where primitive compositions span a range of SiO2, total alkalies (K2O+Na2O), magmatic H2O, and incompatible trace element enrichments. Variations among these components are presumed to result from melting heterogeneous mantle that has been affected, to varying degrees, by a subduction component. Chapter III focuses on the phase equilibria of a Mexican basaltic andesite and an Aleutian basalt. Results show that hydrous basaltic andesite equilibrated with harzburgite in the shallow mantle, whereas the basalt equilibrated with lherzolite. The former appears more common in continental arcs and the latter in intraoceanic arcs. Chapter IV focuses on two alkaline lavas of varying K2O content from the TMVB that are transitional between potassic, hydrous minette and H2O-poor intraplate alkali basalt. Experimental phase relations and trace element modeling reveals that melting and/or mixing of peridotite and clinopyroxene-rich veins are likely involved in producing these transitional lava types. These experimental data are integrated with other petrologic and geophysical data to provide an along-arc perspective of mantle-melt equilibration in the TMVB. Primitive melts appear to commonly equilibrate with chemically heterogeneous mantle at depths above the "hot nose" of the mantle wedge. It is apparent that the shallow mantle wedge is a key component for understanding the geochemical complexities of subduction zone magmas. This dissertation includes previously published and unpublished co-authored material.