Magma recharge

Plagioclase textures and chemistry have proven useful to trace recharge in magma reservoirs (e.g. Cashman and Blundy, 2013; Humphreys et al., 2006; Davidson and Tepley, 1998; Singer et al., 1995). The An content in plagioclase varies as function of temperature, PH2O and melt

composition (Cashman and Blundy, 2013), and the combination of major, minor and trace elements measurements can be used to disentangle these effects (Ruprecht and Wörner, 2007).

Minor and trace element partitioning are typically mainly dependent on melt composition and to a lesser extent on variables such as temperature or PH2O (Dohmen and Blundy, 2014; Bindeman et al., 1998). Previous work on plagioclase from the UTP eruption (Smith et al., 2009) has revealed late stage sudden increases in An content (> 10 mol. %) for many crystals coupled with

plagioclase crystals especially in their outer portions. Chemical profiles in plagioclase from Plinian eruptions show good correspondence between abrupt changes in An content and elements such as Fe, Mg, Ti and Sr (dashed lines in chemical profiles of Figure 4.7). These correlations, together with the large abundance of reverse zoning and stepped saw-tooth textures point towards an open magmatic system that undergoes differentiation and repeated recharge cycles that eventually trigger an eruption.

An alternative hypothesis is that the magma was initially H2O under-saturated and that late stage volatile saturation triggered the eruptions, as gas volume expansion can be expected to create large overpressures in magmatic reservoirs (Tait et al., 1989). Plagioclase-liquid

hygrometry shows that pre-eruptive H2O contents for the three eruptions are likely between 5 and 6 wt. %, which when compared to the 2±1 kbar (UTP, MTP) 2.8±1 kbar (LTP) constrained by amphibole barometry, and experimental phase equilibria (Arce et al., 2013; 2006), indicate that the Toluca magmas could have been close to or beyond volatile saturation. In either case, a key observation is that the ubiquitous resorption and overgrowth textures found in plagioclase and orthopyroxene are corresponding to chemical changes that are not easily explained by changes in H2O content (Fig. 4.3b; Fig. 4.7). Thus, we suggest that compositional mixing rather than changes in volatile content are recorded by mineral chemistry in the period immediately preceding eruption.

Similarities and differences in the pre-eruptive record of magmatic processes for the three Plinian eruptions are evident from the systematics of FeOt and An (Fig. 4.3b). Fe partitioning in plagioclase is a function of melt composition and to a much lesser extent temperature (Bindeman et al., 1998). As Fe occurs in two oxidation states in most crustal

magmas (Carmichael, 1991), a strong dependence of Fe partitioning on oxygen fugacity has been shown experimentally (Wilke and Behrens, 1999). The partition coefficient of Fe in plagioclase increases from 0.08 to 0.55 from reducing to oxidizing conditions in the range of log fO2 = -15.78 to -7.27 (Wilke and Behrens, 1999), showing that Fe is mostly incorporated into

plagioclase by the substitution of Al³⁺ by Fe³⁺ (Hofmeister and Rossman, 1984). Likewise, the partition coefficient of Eu in plagioclase increases from 0.095 to 1.81 in the same fO2 range (Wilke and Behrens, 1999). This implies that if changes in fO2 drive chemical variation in plagioclase, correlation between redox sensitive elements should be observed. Fe contents in the plagioclase from Plinian eruptions correlate well with Ti and Mg and not obviously with fO2

dependent Eu (Fig. S4.5), which indicates that Fe content in plagioclase from the three Plinian eruptions is mainly controlled by melt composition rather than oxygen fugacity.

Figure 4.7. Back scattered electron (BSE) images with corresponding major (An and FeOt) and trace element (Sr, Mg, Ti, La and Ba) profiles through Nevado de Toluca plagioclase. White line in BSE images marks the position of the analytical traverse through the crystal. All profiles were drawn from rim to core. Dashed vertical lines indicate prominent changes in the zonation

pattern between different elements. a) and b) UTP. c) and d) MTP. e) and f) LTP plagioclase.

Plagioclase core and mantle compositions from the three Plinian eruptions typically show a weak positive An-FeO correlation mostly between 28 and 55 mol. % An and 0.1 to 0.2 wt. % FeO (Fig. 4.3d-f). Individual crystals record cycles of both increasing and decreasing An content, frequently linked to prominent resorption textures, which is inconsistent with simple cooling, but points towards an open dynamic system in which crystals experience repeated changes in intensive parameters. The relatively low slope in FeO content indicates that these changes are not controlled by interaction with a significantly more mafic melt, but can rather be explained by changes in temperature or volatile content (Ginibre et al., 2002; Ruprecht and Wörner, 2007). Petrological experiments at 200 MPa on similar compositions show that changes in An content of the same order of magnitude as those observed in our study can be translated into temperature changes of 60°C or changes in xH2O^fluid between 1 and 0.25 (Riker et al., 2015;

Rutherford and Devine, 2008). The presence of similar groups of plagioclase showing An-FeO correlation in cores from the studied eruptions indicates that the magmatic systems of Nevado de Toluca was in a similar background state of activity prior to these Plinian events. Plagioclase crystallization occurred within a reservoir of rather evolved melt, likely highly crystallized, that was repeatedly disturbed by thermal perturbations and/or invasion of CO2 rich fluids (Caricchi et al., 2018), resulting in the oscillating An and Fe contents in crystal cores.

The An-FeO systematics reveals a further magmatic pattern prior to each Plinian eruption. Plagioclase mantles and outermost crystal rim compositions show elevated FeO contents after prominent resorption zones with steep increase of FeO at relatively high An content (Fig. 4.3d-f). Such pattern are consistent with injection of more mafic magma into a dacitic magma reservoir (Ruprecht and Wörner, 2007), as also testified by opx chemistry.

Interestingly, the distributions of An and FeO of the outermost plagioclase rims differ for the three eruptions. UTP and LTP rims are characterized by relatively homogeneous An content and a bimodal distribution of FeO content (Fig. 4.6 b, f). The difference in An and FeO for these two groups of rim compositions are not consistent with contamination by micro-inclusions of glass or Fe-Ti oxides (Figs. S4.5, S4.11). Such distributions can be interpreted as resulting from magma homogenization prior to eruption with differing fractions of crystals that were in close proximity to the recharge magma,or reflect plagioclase growth from the different magmatic endmembers that are evident at least in case of the LTP deposit, which is zoned from andesite to dacite (Arce et al., 2013). In contrast to these two eruptions, plagioclases from MTP show more

heterogeneous An and FeO, which could reflect incomplete hybridization of potentially smaller mafic magma input into a heterogeneous reservoir at lower temperature.