Structure of volcanic glasses from the NMR-EPR perspective: a preliminary application to the Neapolitan Yellow Tuff

Glass samples from alkali-trachytic pumice of the Lower Member (LM, level LM1) and Upper Member (UM) of the Neapolitan Yellow Tuff at Campi Flegrei Caldera were studied by nuclear magnetic resonance (NMR) and electron paramagnetic resonance (EPR) spectroscopy. The EPR data show that the relative occupancy of the different iron sites varies in samples from the Lower Member LM1 and Upper Member of the eruptive sequence. The LM1 glasses are characterized by a more homogeneous distribution of the cationic site population of iron compared with UM and by a different Fe3+/Al3+ substitution in the C2v symmetrical sites of the silicate framework. 29Si MAS NMR spectra on glasses indicate that LM1 glasses are more depolymerized than UM glasses, indicating the existence of structurally distinct magma batches. 27Al MAS NMR spectra indicate the occurrence in UM glasses of aluminum in both tetrahedral and octahedral coordination; the observed AlVI is believed to be a primary feature of the glass, since 27Al CP-MAS NMR experiments do not reveal detectable esa-hydrated Al. The Al in sixfold coordination could be ascribed either to the more abundant alkali–OH terminations in UM, in which alkalies would be extracted from their charge-balance role for Al, thus altering its fourfold structural position, or to permanent compaction during fast cooling and decompression of high-pressure melts. 23Na CP-MAS NMR experiments indicate the existence of Na–OH groups in both LM1 and UM glasses, relatively more abundant in the latter. Although preliminary, the results indicate the possible application of atomic-scale studies to variables that determine the regimes of explosive volcanism.