Petrography and geochemistry of achnelithic tephra from Las Herrerías Volcano (Calatrava volcanic field, Spain): Formation of nephelinitic achneliths and post-depositional glass alteration

We present the results of a petrographic and geochemical study carried out on a layer of achnelithic tephra outcropping at the base of the volcanic cone of Las Herrerías (Miocene-Quaternary volcanic region of Campo de Calatrava, Spain). The tephra, with a composition of nephelinite and ash (< 1 mm) to coarse lapilli (ca. 1 cm) in size, is made of intact isolated achneliths (mostly elongated and spheroidal, including Pele's tears), achnelith fragments and rare welded achneliths. The achneliths at Las Herrerías were generated in a gas-rich fire fountain that fragmented the magma into micro- to nanometre particles. The low viscosity of the nephelinitic blebs (< 1235 Pa.s) inside the hottest (ca. 900 °C), inner zone of the fountain allowed the development of the characteristic fluidal shapes of these pyroclasts and their welding above the glass transition temperature (533-669 °C). The sideromelane glass of the achneliths, also nephelinitic in composition, is variably altered to palagonite. The palagonitization was isovolumetric and took place in a near closed system at the achnelith scale. Palagonitization involved depletion in the concentration (g/cm3) of all major elements and notable increase in H2O content. The elements liberated by this process formed smectite with an average structural formula comprised between those of beidellite and nontronite end terms: (Na0.01K0.03Ca0.18) (Mg0.22Fe0.16)2 + (Fe0.48Al1.02)3 + (Ti0.18)4 + (Si3.58Al0.42) O10(OH)2. The degree of palagonitization in each achnelith was likely related to the amount of water incorporated by individual clasts at the moment of their deposition in a volcanic maar lake. Afterwards, there was no more water circulation through the achnelithic tephra, which was sealed from water by overlying hydrovolcanic tuff deposits. It was this isolation that made possible the preservation of glass to the present day.