macla nº 22. julio ‘17 revista de la sociedad española de mineralogía 119

Harmotome within Coatings of Basanitic Tephra from Cabeza Parda Volcano (Calatrava Volcanic Field) / FERNANDO SARRIONANDIA (1*), MANUEL CARRACEDO-SÁNCHEZ (2), JAVIER AROSTEGUI (2), JON ERRANDONEA- MARTIN (2), JOSÉ IGNACIO GIL-IBARGUCHI (2)

(1) Departamento de Geodinámica, Facultad de Farmacia, Universidad del País Vasco UPV/EHU, 01006 Vitoria, España (2) Departamento de Mineralogía y Petrología, Facultad de Ciencia y Tecnología, Universidad del País Vasco UPV/EHU, 48940 Leioa, España

INTRODUCTION 3º59’52.34’’). This is a scoria cone clinopyroxene and opaque minerals, essentially constituted by lapilli- to whereas the glass may vary from The Calatrava Volcanic Field (CVF) is bomb-sized pyroclasts, minor ash-tuffs, tachylitic to sideromelanic in the same located in the Ciudad Real province of and small lava flows, the latter clast. Sideromalene appears frequently Spain and includes more than 300 practically confined to the volcanic cone altered to palagonite. The lavic clasts volcanoes dispersed in an area of 5000 area. The volcanic edifice was built onto include quartzite xenoliths/xenocrystals. km2. The volcanic activity was effusive limestone deposits that fill the Tertiary and explosive with emission of alkali palustrine–lacustrine sedimentary basin The pyroclasts are coated as shown in basic and ultrabasic lavas (alkali basalt, of Cañada de Calatrava. The lava flows Figure 1 by a thin (≤ 1–2 mm) coat of an basanite, nephelinite, melilitite and consist of alkali basalts and basanites, isotrope, not coherent material with leucitite) between the Miocene (8.7–6.4 compositionally close to nephelinites. powdery aspect and reddish colour, Ma) and Plio-Quaternary (3.7–1.75 Ma; which appears speckled by microliths, e.g., Ancochea, 2004). Vesicles of the The reddish tephras of Cabeza Parda microphenocrystals and crystal volcanic deposits (lava flows, pyroclastic volcano fragments of clinopyroxene, olivine, and rocks, tephras, dykes and plugs) appear quartz. Also, among them, stand out often partially to totally filled by , At the top of the volcanic sequence and sparse, up to 200 µm in size, white sulfate minerals like ettringite and exposed in the quarry located south of coloured euhedral crystals that are thaumasite, and zeolites, particularly the Cabeza Parda volcanic cone, there nearly transparent to translucent, show , gonnardite, gismondine, and outcrop some reddish, massive lapilli a vitreous lustre and are often twinned. stilbite (e.g., Calvo et al., 2010). tephras. These lapilli show The optical characteristics of these white hyalocrystalline microporphyritic texture crystals, like habit, colour, relief, This contribution reports the first with a variable vesicular microlithic cleavage and twins, suggest that they evidence on the presence of a particular groundmass. The microphenocrystals may correspond to some type of zeolite. and rare zeolite, the harmotome, within and microliths are of olivine, Yet, their small crystal size required the the coatings of basanitic lapilli tephras that constitute part of the scoria cone of the Cabeza Parda volcano in the CVF.

Harmotome (e.g., Coombs et al., 1997) Pyroclast is an - and barium-bearing hydrated mineral that usually forms monoclinic crystals, frequently twinned; the proposed empirical formula is (Ba0.5,Ca0.5,K,Na)5(H2O)12[Al5Si11O32]. The harmotome defines a continuous series with calcic phillipsite (Ca0.5,Na,K)x(H2O)12[AlxSi16-xO32], where x Harmotome = 4.1–6.8. Harmotome has been Coating synthesized from gels with appropriate composition at atmospheric pressure and variable temperature between 95 and 250 ºC (Barrer and Marshall, 1964; Perrotta, 1976).

THE CABEZA PARDA VOLCANO 0.1 mm

The Cabeza Parda volcano is located 0.1 mm next to the Ciudad Real airport (Don

Quijote airport) in the central area of the fig. 1. Optical microscope image (crossed nichols) of the contact of a pyroclast and its coating. The inset CVF (longitude 38º52’46.79’’; latitude picture shows a detail of one harmotome crystal within the coating.

palabras clave: Harmotoma, Zeolita, Cabeza Parda, Calatrava. key words: Harmotome, Zeolite, Cabeza Parda, Calatrava. resumen SEM 2017 * corresponding author: [email protected]

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use of additional analytical techniques microscope), crystals and crystal coatings of reddish tephra clasts from for a proper determination. fragments of olivine, clinopyroxene and the Cabeza Parda volcano of the CVF. quartz dispersed into this aggregate, Harmotome appears as euhedral RESULTS AND DISCUSSION and, notably, euhedral crystals up to crystals, generally twined, dispersed into 200 µm long, with monoclinic symmetry an aggregate of glassy silicate micro- to Harmotome determination and commonly twinned, whose crystal nano-spherules that cover the pyroclasts shape and twin features are of the tephra. Precise mineral identification of the characteristic of the harmotome– suspected zeolite has been carried out phillipsite series (Fig. 2). Element Crystal by applying common techniques in this kind of studies, namely: (1) X–ray SEM–EDX data for the isotrope micro- to Weight % #1 #2 #3 powder diffraction (XRD), and (2) nano-spheres indicate that they have an Mg 0.2 0.58 0.53 Scanning Electron Microscopy (SEM) Al-rich silicate composition with minor Al 11.10 8.43 8.00 combined with spot chemical analysis amounts of Mg, K, Ca, Ti, Mn and Fe. by means of SEM–EDX methods. These Si 28.70 20.30 24.32 determinations where carried out at the Euhedral crystals of the presumed K 2.29 3.32 3.92 SGIker-facility of the University of the zeolites analized by SEM–EDX indicate Ca 3.19 6.99 5.34 Basque Country UPV-EHU. that they are also Al-rich but with K, Ca, Ba and some Mg, while Ba 9.01 23.20 17.73 XRD was performed on material displaying marked variations in Ca, K O 45.50 37.18 40.16 obtained through ultrasonic immersion and Ba contents (Table 1). The chemical Table 1. SEM-EDX analyses of harmotome within and scratching of the surface of coatings data suggest that these zeolite crystals coatings of reddish tephra from the Cabeza Parda developed in the lapilli clasts. The are compositionally intermediate volcano. results obtained indicate that besides between end member terms the orthomagmatic phases typical of harmotome (Ba) and phillipsite (Ca, K). ACKNOWLEDGEMENTS this kind of lavas, i.e., pyroxene, olivine, Yet, Ba contents markedly higher than K and glass, and the quartz present as and Ca would imply that they might Grants GIU15/05 (UPV/EHU) and xenolith/xenocryst, in the pyroclasts, effectively be regarded as harmotome CGL2015-63530-P (MINECO), there exists a mineral of the rather than Ba-bearing phillipsite (e.g., scholarship UPV/EHU (2016) to JEM, harmotome–phillipsite series; some Passaglia and Sheppard, 2001). technical and human (Drs. Sangüesa smectite was also found as an accessory and Fernández Armas) support of the phase. CONCLUSIONS SGIker facility (UPV/EHU), MICINN, GV/EJ, FEDER and FSE. SEM images of the surface coating of X–Ray diffraction data, SEM imagery, the lapilli clasts (Fig. 2) reveal that it is and semi-quantitative SEM–EDX REFERENCES constituted by an aggregate of micro-, to chemical analysis have allowed us to nano-spheres (isotrope under optical identify harmotome zeolite in the Ancochea, E. (2004): La región volcánica del Campo de Calatrava. In: “Geología de España”, J.A. Vera, ed. SGE-IGME, Madrid, 676-677. Barrell, R.M. & Marshall, D.J. (1964): Hydrothermal chemistry of silicates. Part XIII. Synthetic barium aluminosilicates J. Chem. Soc., 2296-2305. Calvo, M., Calvo Sevillano, G., Viñals, J., Sanz, A. (2010): Presencia de Ettringita y Thaumasita en Vacuolas de los Basaltos del Campos de Calatrava (Ciudad Real). Macla, 13, 53-54. Coombs, D.S., Alberti, A., Armbruster, T., Artioli, G., Colella, C., Galli, E., Grice, J.D., Liebau, F., Mandarino, J.A., Minato, H., Nickel, E.H., Passaglia, E., Peacor, D.R., Harmotome Quartieri, S., Rinaldi, R., Ross, M., Sheppard, R.A., Tillmanns, E., Vezzalini, G. (1997): Recommended nomenclature for zeolite minerals: Report of the subcommittee on zeolites of the international mineralogical association, commission on new minerals and mineral names. Can. Mineral., 35, 1571-1606. Passaglia, E. & Sheppard, R.A. (2001): The crystal chemistry of zeolites. Rev. Mineral. Geochem., 54, 654-656. Perrotta, A.J. (1976): A low-temperature synthesis of a harmotome-type zeolite. Am. Mineral., 61, 495-496. fig. 2. SEM image of the coating of the reddish tephra pyroclasts. Harmotome crystals appear immersed in an isotrope aggregate of aluminosilicate micro-, nano-spherules. Inset picture: euhedral shape of one harmotome crystal.