Xenoliths of plutonic rocks sporadically torn off by erupting magmas are known to carry valuable information about volcano plumbing systems and the lithosphere in which they are emplaced. One of the main steps in the interpretation of such information is to quantify the pressure and temperature conditions at which the xenolith mineral assemblages last equilibrated. This chapter discusses some aspects of geothermobarometry of mafic and ultramafic rocks using the xenolith populations of the Hualalai and Mauna Kea volcanoes, Hawaii, as case studies. Multipleâreaction geobarometry, recently revisited for olivine + clinopyroxene + plagioclase ± spinel assemblages, provides the most precise pressure estimates (uncertainties as low as 1.0 kbar). An example is shown that integrates these estimates with the calculated seismic velocities of the xenoliths and the available data from seismic tomography. The results make it possible to better constrain some kilometerâscale horizontal and vertical heterogeneities in the magmatic system beneath Hawaii. Ultramafic xenoliths at Hualalai are the residuals of magma crystallization at 16â21 km depth, below the preâHawaiian oceanic crust. The few available gabbronorites and diorites record instead lower pressures and likely represent conduits or small magma reservoirs crystallized at 0â8 km depth. At Mauna Kea, on the other hand, a significant portion of the xenolith record is composed of olivineâgabbros, which crystallized almost over the entire crustal thickness (3â18 km). Ultramafic xenoliths are less abundant and might represent the bottom of the same magma reservoirs that crystallized in the deeper portion of the magmatic systems (11â18 km). Some unresolved issues remain in the geothermometry of mafic and ultramafic rocks representing portions of magma reservoirs that cooled and recrystallized under subsolidus conditions. This suggests that further experimental and theoretical work is needed to better constrain the thermodynamics and kinetics of peridotitic and basaltic systems at low (<1000°C) temperatures.
1.1. INTRODUCTION
The geothermobarometry of magmatic rocks is well known to be one of the key tools used to interpret the processes within volcanic systems. This is why much effort has been put in since the first pioneering studies in petrology (e.g., Bowen, 1928; Green & Ringwood, 1967; Tuttle & Bowen, 1958; Wells, 1977) to perform experimental and theoretical work constraining the relationships between the mineralogy and chemistry of magmatic rocks and the temperatures and pressures at which their constituent phases formed. It was clear since then that the complexity of volcanic processes and the compositional variability of the erupted magmas and their lithic fragments make it difficult to develop geothermobarometers that are both accurate and precise for any sample, but considerable progress has been made in the last three decades. Considering only published work on magmatic systems relevant for crustal processes, more than 6,000 phase equilibrium laboratory experiments have been performed so far (based on the LEPR database at http://lepr.ofmâresearch.org and additional literature). These experiments led to the development of geothermobarometers and forward thermodynamic simulations (e.g., Ghiorso & Sack, 1995; Gualda et al., 2012; Jennings & Holland, 2015; Masotta et al., 2013; Mollo et al., 2018; Putirka, 2008, 2016; Ziberna et al., 2017) that can now be used to model the differentiation paths of magmas.
The most common inverseâmodeling approach to estimating the pressure (P) and temperature (T) of volcanic systems is geothermobarometry based on mineralâliquid equilibria (see Putirka, 2008, for an exhaustive discussion). It is usually applied to porphyric lava samples, using wholeârock chemical analyses (as representative of liquid compositions) in combination with the chemistry of phenocrysts. As a rule, measured partition coefficients [e.g., KD(FeâMg)mineralâliquid] is compared to experimental values to demonstrate equilibrium (e.g., Putirka, 2008). For basaltic to andesitic and trachytic rocks, clinopyroxeneâliquid geothermometry and geobarometry proved to be the most precise methods when tested against experimental data, producing model errors as small as 28 °C and 1.4 kbar (Masotta et al., 2013; Neave & Putirka, 2017; Putirka, 2008). The success of such methods lies in the large entropy and volume change of the reactions used as geothermometers and geobarometers, respectively (Putirka, 2008), and in the ubiquity of clinopyroxene in many basaltic systems. Other common methods are plagioclaseâliquid geothermometry (e.g., Lange et al., 2009; Putirka, 2008), amphiboleâliquid geothermometry and geobarometry (Molina et al., 2015; Putirka, 2016), and mineralâmineral equilibria like twoâpyroxene geothermometers and geobarometers (e.g., Lindsley, 198...