The geochemistry of Hercynian basalts is reviewed with special reference to SW England. Hercynian basalts have the following chemical features: (1) relative enrichment in incompatible elements, (2) fractionated rare earth element (REE) patterns ranging from mild to strongly light-REE enriched, and (3) generally low large-ion-lithophile (LIL)/high field strength (HFS) element ratios. High and variable alkali contents and K/Rb ratios are indicative of low-grade alteration. Basalts are predominantly tholeiites, although alkali basalts may be developed on some trough margins. Basalts from different sedimentary troughs within the main Hercynian tectonic zones are characterized by specific incompatible element abundances and ratios. These variations are interpreted in terms of variable fractional crystallization, partial melting and mantle heterogeneity.

Hercynian volcanism was typically bimodal with basic and acid products characterizing the Rheno-Hercynian and Saxo-Thuringian zones. Activity in the Moldanubian zone was more variable with a high proportion of calc-alkali andesites. Two systematic chemical changes throughout the Devonian and Carboniferous have been recognized, with both light/heavy REE and LIL/HFS element ratios increasing with time. These features may relate to the introduction of LIL-enriched fluids derived by dehydration of subducted lithosphere that caused progressive metasomatism of the overlying mantle wedge.

Chemical discrimination of tectonic setting demonstrates that most of the basalts typify the continental intra-plate environment, although early Devonian basalts produced in the initial stages of continent rifting have some of the chemical features of incompatible element enriched oceanic basalts. An ensialic back-arc basin model underlain by a shallow northward-dipping subduction zone provides a possible explanation for the spatial and temporal variation in the Hercynian volcanic rocks.

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