Water and magmas: application of the Gibbs-Duhem equation

Burnham (1975a, b) has shown that in several alumino-silicate systems Henry's law constant is independent of silicate melt composition up to X^melt_H2O = 0.5. He has used this fact to conclude that such silicate melts behave ideally over a wide range of compositions based on the application of the Gibbs-Duhem relation. Unless Henry's law is valid up to X^melt_H2O = 1.0, the application of the Gibbs—Duhem relation to three component systems only shows that if one component obeys Henry's law, the other two components follow the two component Gibbs-Duhem equation. There is no thermodynamic requirement of ideality.     

Water and magmas: clarification of a controversy on applications of the Gibbs-Duhem equation

It is shown mathematically that if the activity coefficient of water in ternary water-magma (aluminosilicate) systems is constant or varies only with the mole fraction of water, it is not necessary that the binary magmas form ideal solutions contrary to the claims by Burnham et al. (1978, Geochim. Cosmochim. Acta42, 275–276). A molecular viewpoint is presented to support this argument. The properties of analytical equations capable of representing the activity coefficients of usual and unusual systems are discussed. The correct form of the Gibbs-Dunhem equation for dissociative dissolution processes is presented to disprove the claims by Burnham (1975, Fortschr. Mineral.52, 101–118; 1975, Geochim. Cosmochim. Acta39, 1077–1084), and by Burnhamet al. (1978, Geochim. Cosmochim. Acta42, 275–276).     

Water and magmas; a mixing model

A model for the mixing of H₂O and silicate melts has been derived from the experimentally determined effects of H₂O on the viscosity (fluidity), volumes, electrical conductivities, and especially the thermodynamic properties of hydrous aluminosilicate melts. It involves primarily the reaction of H₂O with those O^?2 ions of the melt that are shared (bridging) between adjacent (Al, Si)O₄ tetrahedra to produce OH^? ions. However, in those melts that contain trivalent ions in tetrahedral coordination, such as the Al³⁺ ion in feldspathic melts, the model further involves exchange of a proton from H₂O with a non-tetrahedrally coordinated cation that must be present to balance the net charge on the AlO₄ group. This cation exchange reaction, which goes essentially to completion, results in dissociation of the H₂O and is limited only by the availability of H₂O and the number of exchangeable cations per mole of aluminosilicate.In the system NaAlSi₃O₈-H₂O, upon which this thermodynamic model is based, there is 1 mole of exchangeable cations (Na⁺) per mole (GFW) of NaAlSi₃O₈, consequently ion exchange occurs for H₂O contents up to a 1:1 mole ratio (X^m_w = mole fraction H₂O = 0.5). For mole fractions of H₂O greater than 0.5, no further exchange can occur and the reaction with additional bridging oxygens of the melt produces 2 moles of associated OH^? ions per mole of H₂O dissolved. These reactions lead to a linear dependence of the thermodynamic activity of H₂O (a^m_w) on the square of its mole fraction (X^m_w) for values of X^m_w, up to 0.5 and an exponential dependence on X^m_w at higher H₂O contents. Thus, for values of $\text{X}{}^{\mathrm{m}}{}_{\mathrm{w}}\text{? 0.5, a}{}^{\mathrm{m}}{}_{\mathrm{w}}\text{= k(X}{}^{\mathrm{m}}{}_{\mathrm{w}}\text{)}{}^2$, where k is a Henry's law constant for the dissociated solute.Extension of the thermodynamic model for NaAlSi₃O₈-H₂O to predict H₂O solubilities and other behavior of compositionally more complex aluminosilicate melts (magmas) requires placing these melts on an equimolal basis with NaAlSi₃O₈. This is readily accomplished using chemical analyses of quenched glasses by normalizing to the stoichiometric requirements of NaAlSi₃O₈, first in terms of equal numbers of exchangeable cations for mole fractions of H₂O up to 0.5 and secondly in terms of 8 moles of oxygen for higher H₂O contents. Chemical analyses of three igneous-rock glasses, ranging in composition from tholeiitic basalt to lithium-rich pegmatite, were thus recast and the experimental H₂O solubilities were computed on this equimolal basis. The resulting equimolal solubilities are all the same, within experimental error, as the solubility of H₂O in NaAlSi₃O₈ melt calculated from the thermodynamic relations.The equivalence of equimolal solubilities implies that the Henry's law constant (k), which is a function of temperature and pressure, is independent of aluminosilicate composition over a wide range. Moreover, as a consequence of the Gibbs-Duhem relation and the properties of exact differentials, it is clear that the silicate components of the melt, properly defined, mix ideally. Thus, a relatively simple mixing model for H₂O in silicate melts has led to a quantitative thermodynamic model for magmas that has far-reaching consequences in igneous petrogenesis.     

Nickel content of basaltic magmas: identification of primary magmas and a measure of the degree of olivine fractionation

Available NiO analyses of olivine in peridotites of probable mantle origin are consistent in giving values around 0.40 weight per cent. Assuming that basaltic magma forming from the mantle was in equilibrium with such peridotitic olivine, the NiO content of primary basaltic magmas is estimated to be about 0.030–0.050 weight per cent. The fractionation behaviour of nickel in basaltic magma due to the crystallization of olivine has been calculated using constant NiMg and FeMg exchange partition coefficients between olivine and magma. It is shown that the NiO content of both magma and olivine decreases by 50 per cent after fractional crystallization of 6–12 per cent of olivine. The nickel distribution in some basaltic rocks and olivines is examined in the light of these results, and it is suggested that basaltic magmas, such as some of the ocean-floor basalt and the Hawaiian tholeiite and alkali basalts, represent primary magmas from mantle peridotites.     

Limestone assimilation by basaltic magmas: an experimental re-assessment and application to Italian volcanoes

The results of an experimental study of limestone assimilation by hydrated basaltic magmas in the range 1,050–1,150°C, 0.1–500 MPa are reported. Alkali basalts doped with up to 19 wt% of Ca, Mg-carbonates were equilibrated in internally heated pressure vessels and the resulting phase relationships are described. The major effects of carbonate incorporation are: (1) generation of CO₂-rich fluid phases; (2) change in liquidus phase equilibria; the crystallization of Ca-rich clinopyroxene is favored and the other phases (e.g. olivine, plagioclase), present in the absence of carbonate assimilation, are consumed. As a consequence of the massive clinopyroxene crystallization, the residual melt is strongly silica-depleted and becomes nepheline-normative. Compositional and mineralogical evolutions observed in Mt. Vesuvius eruptive products match those documented in our experiments with added carbonates, suggesting the possibility that carbonate assimilation increased during the last 25 ka of activity. In Central-Southern Italy, carbonate assimilation at shallow levels probably superimposes on deeper source heterogeneities.     

Magnetite scavenging and the buoyancy of bubbles in magmas. Part 2: Energetics of crystal-bubble attachment in magmas

The fate of pre-eruptive bubbles depends largely on their buoyancy, which can be strongly modified by the presence of crystals attached to the bubble–melt interface. We define the attachment energy and attachment force as those resulting from the attachment of a crystal to a bubble. The attachment energy is such that (1) attachment of crystals to bubbles is always favored energetically, and (2) oxide minerals attach to bubbles much more strongly than silicates, because the attachment energy is a strong function of the wetting angle. Attaching crystals to bubbles can cause bubble–crystal pairs to become neutrally buoyant. There is a critical bubble radius below which the attachment force will be strong enough to keep the pair together; we show that crystals as large as 1 mm in diameter can form neutrally buoyant pairs. For early erupted Bishop magma, if all magnetite forms neutrally buoyant pairs with gas bubbles, ca. 0.1–0.2 vol% gas can be stored in the magma; 2–3 vol% of gas can be accounted for if all minerals form neutrally buoyant aggregates. These values are an order of magnitude lower than what is inferred from melt inclusions. Hence, both magnetite-free and magnetite-rich bubbles might have existed, but only a very small fraction of them could have been neutrally buoyant. Importantly, an intrinsic association between magnetite crystals and bubbles is expected. However, most magnetite crystals in the early erupted Bishop are free of bubbles; the puzzling conclusion is that nucleation away from crystals is favored over heterogeneous nucleation on crystal substrates. Electronic Supplementary Material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Crystallization conditions of leucite-bearing magmas and their implications on the magmatological evolution of ultrapotassic magmas: the Vico Volcano, Central Italy

Summary Mineral compositions in leucite-bearing and leucite-free rocks from Vico volcano are reported. FeO/MgO partitioning (Kd_ol/liq) between olivine and latite (0.14–0.22), and between olivine and trachyte (0.06–0.10) indicates a lack of equilibrium between mineral and host rock. This suggests that mingling and/or mixing between magmas was a leading process during magmatic differentiation. In addition, a phono-tephrite olivine population with high (0.84) and equilibrium (0.23–0.29) Kd_ol/liq values has been produced by the interaction of differently evolved magmas. Zoning in clinopyroxene and plagioclase from these rocks recorded the same processes. In addition, resorbed quartz xenocrysts with coronas of clinopyroxene microlites indicate that digestion of crustal rocks occurred during the residence of magma in a shallow level reservoir. Increasing Fe coupled with decreasing Ca in diopside crystals from some phonolites, together with the petrographic and trace element data, indicate that polybaric fractional crystallisation also may be involved in the genesis of magmas of the second period of Vico activity. Leucite-free trachybasalts erupted in a late stage contain highly forsteritic olivine phenocrysts (forsterite 84–88 mol.%) in-equilibrium (Kd_ol/liq = 0.24–0.35) with the host rock, which indicate that they did not suffer chemical modification at low pressure. Received November 28, 2000; revised version accepted September 27, 2001     

Oceanic potassic magmas: An example of the Atlantic Ocean

Statistical study of volcanic rocks from oceanic islands and seamounts in the Atlantic Ocean based on approximately 6000 analyses (data from the authors’ databank) makes it possible to recognize rocks close to the parental melts (approximately 2000 analyses). This set is demonstrated to include a unique group of high-potassium (K₂O/Na₂O > 1) rocks, whose K₂O/Na₂O ratio is several times higher than in the mantle and calls for the explanation of the mechanism that increased the K₂O concentration during the melting of the mantle and for the identification of an additional K₂O source in the mantle and a process responsible for K and Na differentiation. A new model is proposed to account for the genesis of high-potassium melts-fluids, whose ascent brings about extensive mantle metasomatism. The genesis of high-potassium fluid is related to solid-state reactions at deep mantle levels.     

Major element evolution of basaltic magmas: a comparison of the information in CMAS and ALFE projections

Basalt petrologists disagree as to whether the commonly used projection, forsterite-diopside-silica, in the system CMAS (CaO-MgO-Al₂O₃-SiO₂), can adequately resolve differences in basaltic glass compositions for purposes of petrogenetic modelling. Here, we suggest than an analogous plot, the aluminium-factor diagram (ALFE) of Nesbitt and Cramer (1981), has greater diagnostic value than Fo-Di-Sil. A plot of molar (Al₂O₂-CaO-Na₂O-K₂O)/(FeO + MgO) vs FeO/(FeO + MgO), it produces more coherent patterns both for experimental basalt glasses, and for natural lavas. It is, like Fo-Di-Sil, a projection through plagioclase, but has the advantage that it monitors changes in Fe/(Fe + Mg) in melts and associated crystalline phases, and is particularly useful in assessing the timing of clinopyroxene crystallization in a suite of lavas. The diagram owes its greater resolving power to the fact that the computation of its coordinates is less sensitive to analytical uncertainty than for Fo-Di-Sil. In the latter diagram, normative quartz is calculated as a residual and thus manifests the uncertainties in all the major elements.     

Ultrabasic magmas and high-degree melting of the mantle

As the degree of melting of mantle peridotite increases, the liquids that are formed become more basic and less viscous, and the spacing between residual crystals increases. The settling velocities of residual crystals in partial melts consequently will increase by several orders of magnitude, from 9.4 × 10^–4 cm/s to 4.3 × 10^–1 cm/s for a 1 cm olivine grain, as the proportion of liquid increases from 15 to 60%.To produce an ultrabasic komatiitic magma from a source with commonly assumed mantle composition requires 50 to 80% melting. Before this degree of melting can be reached, a highly fluid picritic magma produced by 30 to 50% melting will segregate from the source. Ultrabasic magmas probably form by a sequential melting process and are derived from a residuum composed of refractory minerals and trapped liquid left by previous episodes of partial melting and magma extraction. Trace element concentrations in ultrabasic komatiite lavas are consistent with this theory.     

Origins of co-existing diverse magmas in a felsic pluton: the Lysterfield Granodiorite,Australia

Numerous batches of initially heterogeneous magma aggregated to form the I-type Lysterfield Granodiorite, with four geochemically distinct series of granodioritic rocks, emplaced in the shallow crust. The compositional heterogeneities originated through variations in the stoichiometries of melting reactions in the protolith terrane and variable degrees of peritectic assemblage entrainment. The high-K series contains igneous, microgranular enclaves that most probably formed through deep-level hybridisation of enriched mantle magmas with crustal melts. In the model presented here, this heterogeneous collection of magmas ascended to form a thin, sheet-like intrusion, quenched against cold wall rocks. Later, laccolithic inflation, through ingress of voluminous more felsic magmas, arched the pluton roof and fragmented the initial sheet, pieces of which fell back into the Granodiorite to become enclaves, some of which were further hybridised by plastic deformation and mechanical incorporation of host-derived crystals. This may be a common mechanism for the formation of such enclave suites.     

Stepwise accumulation and ascent of magmas

One of the currently popular theories on magma ascent is that it mainly occurs by propagating hydrofractures (dykes) and that magma viscosity is the primary rate‐controlling factor. This theory is based on mathematical models for single hydrofractures under idealised conditions. We simulated magma ascent with air ascending through gelatine and observed that the air ascended in batches, following paths made by their predecessors. Multiple batches accumulate at obstacles along the path. Although magma viscosity may control ascent rate during movement, obstacles ultimately control the size and average ascent velocity of ascending batches. We propose that step‐wise movement of magma batches is the mechanism of primary accumulation and ascent from the partially molten source rock of a magma to its first emplacement site and therefore the main ascent mechanism for granitic magmas. ‘Classical’ dyking is the mechanism for secondary ascent from a magma chamber.     

The fluid regime of crystallization of water-saturated granitic and pegmatitic magmas: a physicochemical analysis

Miarolitic granite pegmatites are a unique natural object that makes it possible to study magmatic processes that lead to the formation of ore-forming media and systems. This paper summarizes modern views on phase transformations in aqueous silicate systems at parameters close to those of the transition from magmatic to hydrothermal crystallization. Comparison of phase diagrams and the results of study of pegmatite-forming media permits making conclusions about the crystallization of the water-saturated magmas of miarolitic granite pegmatites. The fluid regime of aqueous granite systems of simple composition, not enriched in fluxing components, is determined mainly by magma degassing or the supply of volatiles with flows of transmagmatic fluids. These processes cause the separation of essentially carbon dioxide or essentially hydrous fluid. During the evolution of such magmas, crystallization from silicate melt is separated in PT-space and, possibly, in time from the crystallization from aqueous or mixed carbon dioxide-aqueous super- and subcritical solutions. The evolution of chambers of water-saturated granitic and pegmatitic magma enriched in F, B, and alkali metals presupposes the formation of a heterogeneous mineral-forming medium in which crystallization occurs in the magmatic melt at high-temperature stages; as temperature decreases, crystallization can proceed in hydrous fluid, hydrosilicate, and/or hydrosaline liquids simultaneously. Hydrothermal crystallization can also take place in a heterogeneous medium consisting of aqueous solutions of different salinities and vapor or vapor-carbon dioxide gas mixture. The relationship between different fluid regimes during the evolution of volatile-saturated granitic and pegmatitic magmas determines the variety of postmagmatic rocks accompanying granite massifs.     

Parental magmas of the Nain Plutonic Suite anorthosites and mafic cumulates: a trace element modelling approach

Equilibrium melt trace element contents are calculated from Proterozoic Nain Plutonic Suite (NPS) mafic and anorthositic cumulates, and from plagioclase and orthopyroxene megacrysts. Assumed trapped melt fractions (TMF) <20% generally eliminate all minor phases in most mafic cumulate rocks, reducing them to mixtures of feldspar, pyroxene and olivine, which would represent the high-temperature cumulus assemblage. In anorthosites, TMF <15% generally reduce the mode to a feldspar-only assemblage. All model melts have trace element profiles enriched in highly incompatible elements relative to normal mid-ocean ridge basalt (NMORB); commonly with negative Nb and Th anomalies. Most mafic cumulates yield similar profiles with constant incompatible element ratios, and can be linked through fractional crystallization. High K-La subtypes probably represent crust-contaminated facies. Mafic cumulates are inferred to belong to a tholeiitic differentiation series, variably contaminated by upper and lower crustal components, and probably related to coeval tholeiitic basaltic dyke swarms and lavas in Labrador. Model melts from anorthosites and megacrysts have normalized trace element profiles with steeper slopes than those calculated from mafic cumulates, indicating that mafic cumulates and anorthosites did not crystallize from the same melts. Orthopyroxene megacrysts yield model melts that are more enriched than typical anorthositic model melts, precluding an origin from parental melts. Jotunites have lower K-Rb-Ba-Y-Yb and higher La-Ce than model residues from fractionation of anorthositic model melts, suggesting they are not cosanguineous with them, but provide reasonable fits to evolved mafic cumulate model melts. Incompatible element profiles of anorthositic model melts closely resemble those of crustal melts such as tonalites, with steep Y-Yb-Lu segments that suggest residual garnet in the source. Inversion models yield protoliths similar to depleted lower crustal granulite xenoliths with aluminous compositions, suggesting that the incompatible trace element budget of the anorthosites are derived from remobilization of the lower crust. The similarity of the highly incompatible trace elements and LILE between anorthositic and mafic cumulate model melts suggests that the basalts parental to the mafic cumulates locally assimilated considerable quantities of the same crust that yielded the anorthosites. The reaction between underplating basalt and aluminous lower crust would have forced crystallization of abundant plagioclase, and remobilization of these hybrid plagioclase-rich mushes then produced the anorthosite massifs.     

Formation and ascent of granitic magmas

New results obtained by the investigation of liquidus and solidus phase relationships in the haplogranite system Qz-Ab-Or are used to discuss the evolution of magmas during their ascent in the crust. It is assumed that the magmas are formed at 720°C, 820°C, 920°C and at a depth corresponding to a pressure of 8 kbar. The starting composition of the magma is taken as 50% melt plus 50% quartz and feldspars. In case of a closed system (no heat exchange and no transfer of elements) the melt fraction of magmas, the water activity and the viscosity increase with decreasing pressure. The temperature slightly decreases. At 700°C the viscosity is approximatively 2 orders of magnitude lower than at 900°C. This is related to the higher amount of water in the (H₂O-undersaturated) melt at low T. It is also shown that dehydration melting is only realistic at high T (900°C). At lower temperatures water has to be added from outside to obtain an intrusive magma with approximatively 50% melt.

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Zusammenfassung Neue Ergebnisse, erzielt durch Untersuchungen von Liquidus und Solidus Phasenbeziehungen des Granitsystems Qz-Ab-Or, werden benutzt, um die Entwicklung eines granitoiden Magmas während seines Aufstiegs zu diskutieren. Es wird vorausgesetzt, daß die Magmen bei Temperaturen von 720°C, 820°C und 920°C gebildet werden, sowie in einer Tiefe die einem Druck von 8 kbar entspricht. Die anfängliche Zusammensetzung des Magmas wird mit einem Verhältnis von 50% Schmelze sowie 50% Quarz und Feldspäten angenommen. Im Falle eines geschlossenen Systems (kein Austausch von Wärme und Elementen) steigt die Teilschmelzbildung von Magmen, die Aktivität des Wassers und die Viskosität bei abnehmenden Druck; hierbei sinkt die Temperatur leicht. Bei 700°C ist die Viskosität um ca. 2 Größenordnungen geringer als bei 900°C. Dies wird bedingt durch den höheren Gehalt an Wasser in der (H₂O-untersättigten) Schmelze bei tieferen Temperaturen. Es wird außerdem gezeigt, daß Magmenbildung durch Dehydratation nur bei hohen Temperaturen realistisch ist (900°C). Bei tieferen Temperaturen muß Wasser von außen zugeführt werden um ein intrusives Magma zu erhalten, das ungefähr 50% Schmelze besitzt.

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Résumé L'évolution des magmas granitiques au cours de leur ascension dans la croûte est discutée à la lumière de données nouvelles relatives aux relations entre phases liquides et solides dans le système Q-Ab-Or. On suppose que les magmas se forment à des températures de 720°C, 820°C, 920°C et à une profondeur correspondant à une pression de 8 Kb. On admet pour leur composition initiale un mélange de 50% de liquide et 50% de quartz + feldspaths. Dans le cas d'un système fermé (pas d'échange de chaleur ni de matière), la fraction liquide du magma, l'activité de l'eau et la viscosité augmentent quand la pression diminue; en même temps, la température décroît légèrement. A 700°C, la viscosité est d'environ 2 ordres de grandeur plus basse qu'à 900°C. Cette propriété est en relation avec la teneur en eau plus élevée dans le liquide (sous-saturé en eau) à basse température. On peut également montrer qu'une fusion déshydratante n'est vraisemblable qu'à haute température (900°C). Aux températures plus basses, de l'eau doit être apportée de l'extérieur pour l'obtention d'un magma à 50% de liquide.

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Phase relations governing the derivation of alkaline basaltic magmas from primary magmas at high pressures

A comparison between the variation trend of alkaline basaltic magmas within the CaO-MgO-Al₂O₃-SiO₂ system and experimentally estimated phase relations for this system at high pressures, suggests an olivine reaction relationship, which may explain the transition from primary magmas in equilibrium with olivine to alkaline basaltic magmas in which olivine does not form at high pressures. This reaction relationship is considered to be due to a transition from positive to negative crystallization with respect to olivine along the four phase curve where olivine, diopside, pyrope garnet and liquid are initially in equilibrium. The bimineralic, eclogitic character of alkaline basaltic compositions at high pressures is interpreted as being due to the presence of a thermal minimum on the three phase surface, where dioside and pyrope garnet are in equilibrium with liquid.     

Deep seated magmas and their mantle roots: Introduction

<正>In the last decade there has been a considerable effort to better understand the joint evolution of mafic and ultramafic magmatic systems and their deep mantle roots,through integrated petrological and thermo-barometric studies.Magma generation is regarded as the result of complex processes including melting,creation of channels for melt transfer,and interaction with the wall-rocks.Complexities in magmatic systems involve metasomatism and the creation of metasomatic fronts,branching and splitting of magma volumes during their evolution,and vat-     

Stability and chemical equilibrium of amphibole in calc-alkaline magmas: an overview, new thermobarometric formulations and application to subduction-related volcanoes

This work focuses on a rigorous analysis of the physical–chemical, compositional and textural relationships of amphibole stability and the development of new thermobarometric formulations for amphibole-bearing calc-alkaline products of subduction-related systems. Literature experimental results (550–1,120°C, <1,200 MPa, −1 ≤ ΔNNO ≤ +5), H₂O–CO₂ solubility models, a multitude of amphibole-bearing calc-alkaline products (whole-rocks and glasses, representing 38 volcanoes worldwide), crustal and high-P (1–3 GPa) mantle amphibole compositions have been used. Calcic amphiboles of basalt-rhyolite volcanic products display tschermakitic pargasite (37%), magnesiohastingsite (32%) and magnesiohornblende (31%) compositions with aluminium number (i.e. Al# = ^[6]Al/Al_T) ≤ 0.21. A few volcanic amphiboles (~1%) show high Al# (>0.21) and are inferred to represent xenocrysts of crustal or mantle materials. Most experimental results on calc-alkaline suites have been found to be unsuitable for using in thermobarometric calibrations due to the high Al# (>0.21) of amphiboles and high Al₂O₃/SiO₂ ratios of the coexisting melts. The pre-eruptive crystallization of consistent amphiboles is confined to relatively narrow physical–chemical ranges, next to their dehydration curves. The widespread occurrence of amphiboles with dehydration (breakdown) rims made of anhydrous phases and/or glass, related to sub-volcanic processes such as magma mixing and/or slow ascent during extrusion, confirms that crystal destabilization occurs with relatively low T–P shifts. At the stability curves, the variance of the system decreases so that amphibole composition and physical–chemical conditions are strictly linked to each other. This allowed us to retrieve some empirical thermobarometric formulations which work independently with different compositional components (i.e. Si^*, Al_T, Mg^*, ^[6]Al^*) of a single phase (amphibole), and are therefore easily applicable to all types of calc-alkaline volcanic products (including hybrid andesites). The Si^*-sensitive thermometer and the fO₂–Mg^* equation account for accuracies of ±22°C (σ_est) and 0.4 log units (maximum error), respectively. The uncertainties of the Al_T-sensitive barometer increase with pressure and decrease with temperature. Near the P–T stability curve, the error is <11% whereas for crystal-rich (porphyritic index i.e. PI > 35%) and lower-T magmas, the uncertainty increases up to 24%, consistent with depth uncertainties of 0.4 km, at 90 MPa (~3.4 km), and 7.9 km, at 800 MPa (~30 km), respectively. For magnesiohornblendes, the ^[6]Al^*-sensitive hygrometer has an accuracy of 0.4 wt% (σ_est) whereas for magnesiohastingsite and tschermakitic pargasite species, H₂O_melt uncertainties can be as high as 15% relative. The thermobarometric results obtained with the application of these equations to calc-alkaline amphibole-bearing products were finally, and successfully, crosschecked on several subduction-related volcanoes, through complementary methodologies such as pre-eruptive seismicity (volcano-tectonic earthquake locations and frequency), seismic tomography, Fe–Ti oxides, amphibole–plagioclase, plagioclase–liquid equilibria thermobarometry and melt inclusion studies. A user-friendly spreadsheet (i.e. AMP-TB.xls) to calculate the physical–chemical conditions of amphibole crystallization is also provided.