2.1. Threshold between heterogeneous and homogeneous compositions as measured by EPMA
In order to find a criterion to exclude problematic analyses of amphibole and establish a threshold between homogeneous and heterogeneous compositional domains, we have performed multiple EPMA measurements (from 10 to 30 spot analyses) using a set of mineral and glass standards (Smithsonian Institution) and synthetic glasses with different composition, and calculated the average amount of element oxides (element oxide in wt%), the relative standard deviation (σ, in wt%) and its percentage value (σ% = σ x 100/ element oxide wt%;
Figure 1). Independently on the measured element oxide (i.e. SiO
2, TiO
2, Al
2O
3, Cr
2O
3, FeO
tot, MnO, MgO, CaO, Na
2O and K
2O), their averaged amount and EPMA setting (e.g., choice of analyzer crystals, current intensity and beam size) we found that σ% values decrease with the concentration of the measured element oxide (wt%) as follows:
This relationship basically represents the averaged precision based on 10 measured oxides characterizing the quality of EPMA and degree of homogeneity of the used samples.
Figure 1 also shows the pattern of a curve equal to (1) multiplied by a factor of 2 (red broken curve), i.e.:
It is worth to note that all measured homogeneous standards and glasses show σ% values ≤ to those calculated by equation (2) for all the measured element oxides. This relationship can then be used to distinguish homogeneous phases or intra-crystal domains from heterogeneous ones (see below).
In other words, homogeneous compositions should showσ% of all its element oxides lower than or equal to a threshold calculated by equation (2) whereas heterogeneous compositions are invariably characterized by higher uncertainties.
σ values calculated with (2) are 0.47 wt% at a level of measured element oxide of 70 wt%, 0.42 at 50wt%, 0.39 at 40 wt%, %, 0.31 wt% at 20 wt%, 0.24 wt% at 10 wt%, 0.19 wt% at 5 wt%, 0.14 wt% at 2 wt%, 0.11 wt% at 1 wt% and 0.05 wt% at 0.1 wt% levels. It is worth noting that (2) was recently used by [
1] to select the “high-quality” dataset of experimental amphiboles for refining his Amp-TB2 model.
2.2. Intra-crystal analysis of Amp composition and related physico-chemical parameters
Figure 2,
Figure 3,
Figure 4 and
Figure 5 shows back scattered electron (BSE) images and core-rim intra-crystal EPMA profiles of representative amphibole phenocrysts from different eruptive products of Bezymianny volcano (see section 4 and Supplementary Material for additional information). Core-rim variations of physico-chemical parameters (i.e. pressure, P; temperature, T; oxygen fugacity expressed as difference from the Ni-NiO buffer, ∆NNO; volatile content in the melt, H
2O
melt) are also shown in all figures. These conditions were calculated with Amp-TB2 that is attached to this work in a modified version, including eq. 2 and an intra-crystal compositional analyses of the Bezymianny Amp phenocrysts in
Figure 2,
Figure 3,
Figure 4 and
Figure 5. (i.e. Amp-TB2.1xlsx; Supplementary Material). Overall, the representative zoned phenocrysts show large compositional variations that are well above the homogeneity threshold provided by eq. 2. Nevertheless, in the core, mantle and rim zones of all phenocrysts, homogeneous intra-crystal domains (with σ%~≤ (2) for all measured element oxides) are found alternated to heterogeneous ones (with σ%> (2) for the main element oxides), indicating that Amp underwent stages of equilibrium (“steady-state”) crystallization alternated by disequilibrium (kinetic) modifications (Supplementary Material).
Figure 2 reports the intra-crystal analysis of a phenocryst in the Amp-bearing andesite sample from the Novy lava dome in central crater of Bezymianny volcano (extruded in 1990). The phenocrysts looks apparently homogeneous in BSE imaging. However, EPMA indicates three homogeneous domains (core, mantle and rim) describing normal zoning, i.e.where the amount of Al
2O
3 (that is reversely correlated to SiO
2) and Na
2O decreases from core to rim, along with P (487±23, 374±13, 230±16 MPa), T (937±10, 910±8, 852±03 °C) and H
2O
melt (7.2±0.3, 6.6±0.1, 6.3±0.3 wt%), indicative of periods of magma stagnation (“steady-state” equilibrium crystallization) at three different crustal levels. MgO and FeO
tot variations go along with relative oxygen fugacity (∆NNO, e.g. [
2,
27]) that is higher at the core (0.8±0.2 log units) and do not vary from mantle to rim (0.3±0.2 and 0.4±0.3 log units, respectively). In the heterogeneous zones, P, T and
fO
2 roughly follow the pattern shown by the normal domains suggesting magma ascent. Nevertheless, values σ for Al
2O
3 and FeO
tot are much higher than those calculated with (2) and thus the phyisico-chemical parameters cannot be quantitatively constrained (Supplementary Material). The breakdown corona indicate that the phenocryst was brought at conditions outside the Amp stability field during its ascent to the surface.
Figure 3 shows the intra-crystal analysis of a twin phenocryst coming from another sample of the same lava dome extrusion. The BSE image shows evident zoning for the left side of the crystal with brightness progressively increasing towards the rim. Two homogeneous domains (core and rim) are easily distinguishable indicating different conditions (706±60 MPa, 971±13 °C, ∆NNO+2.2±0.4, 8.0±0.3 wt% H
2O
melt vs. 246±16 MPa, 874±7°C, ∆NNO+0.8±0.2 log units, 5.8±0.2wt% H
2O
melt) suggesting the ascent of the magma through the crust. Magma ascent is also suggested by the heterogeneous domain where the composition and phyisico-chemical parameters gradually vary from core to rim. However, σ% values calculated for this zone are much higher than (2) for Al
2O
3,FeO
tot and MgO, and P and log
fO
2 standard deviations (20% and 0.9 log units) are well above those predicted by Amp-TB2 (12% and 0.4 log units, respectively; Supplementary Material). The gradual-diffusive compositional variation from core to rim could be due to a re-equilibration process in the crust by the contact with a more silicic melt, e.g. [
28,
29,
30,
31], or a constant-speed magma ascent where the Amp grew in contact with a melt gradually cooling down and evolving to silicic compositions.
Figure 4 shows an Amp phenocryst from the historical products of Bezymianny (1–1.35 kys BP, Lochmaty lava dome) with a very complex zoning. However, 4 homogeneous domains can be identified with the application of eq. 2 (core, mantle 1, mantle 2 and rim). Despite its complexity, Al
2O
3, TiO
2 and Na
2O do not show large variations from core to mantle 2 with calculated P-T-H
2O
melt conditions (543–603 MPa, 950–970°C, 7.2–7.3 wt%) varying well within the uncertainties of Amp-TB2. At the homogeneous rim zone slight decreases of P (498±26 MPa) and T (925±9 °C) come along with an increase of H
2O
melt (8.1±0.5 wt%). The main compositional variations are due to MgO and FeO
tot correlated with large
fO
2 variations (core = -9.4±0.3, mantle 1 = -8.7±0.2, - mantle 2= 9.3±0.3, rim = 10.1±0.2 log units) (Supplementary Material). It is worth to note that the phenocryst does not show any breakdown rim and the calculated P goes down to 380 MPa at its rim (
Figure 4). All of this suggests that the phenocryst grew in a magma zone at 400–600 MPa where its process of crystallization was affected by hot fluids/melts coming from deeper zones, and was finally rapidly ejected to the surface.
Figure 5 shows another Amp phenocryst characterized by complex zoning and no breakdown corona from the old historical products of Bezymianny (3.3–5.5 kys BP, lava dome Expeditsii). It is characterized by three homogeneous domains where Al
2O
3 increases reversely from core to rim 1 and decrease (normal zoning) from rim 1 to 2. This variation is accompanied by an increase of equilibrium P from 307±9 MPa (core) to 459±22 MPa (rim 1) followed by a decrease of ~100 MPa (rim 2 P = 379±13 MPa). [
6] cautiously suggested to avoid the application of Amp thermobarometry to reverse zonings. However, this suggestion was due to the lack in their database of enough detailed core-rim EMP profiles. Reverse zonings are common in the recent and old products of Bezymianny and consistent with depth and size of the magma chambers obtained by seismic tomography (see [
23] and section 4). A similar pattern is observed for H
2O
melt (core = 5.5, rim 1 = 7.2, rim 2 = 5.5±0.3 wt%). From core to rim 1, T follows the same pattern of P (894±7 and 936±9 °C, respectively) but do not show substantial variations at rim 2 (943±8 °C). ∆NNO shows a reverse relationship with P (core = 1.6±0.4, rim 1 = 1.2±0.2, rim 2 = 1.6±0.2 log units) (Supplementary Material;
Figure 5). Al
2O
3 decreases at the heterogeneous domain to increase again towards rim 1. This patter suggest a process of interdiffusion of aluminium and should be not considered for thermobarometric constraints. All of this recalls for a period of convective cycling of the magma within a crust chamber in between 460 and 310 MPa, followed by a rapid ejection to surface of the magma (as inferred by the absence of breakdown corona at the Amp phenocryst rim).