Journal Pre-proof

Crustal melting and suprasolidus phase equilibria: From first

principles to the state-of-the-art

Tim Johnson, Chris Yakymchuk, Michael Brown

PII: S0012-8252(21)00279-8
DOI: https://doi.org/10.1016/j.earscirev.2021.103778
Reference: EARTH 103778

To appear in: Earth-Science Reviews

Received date: 25 January 2021

Revised date: 27 July 2021
Accepted date: 18 August 2021

Please cite this article as: T. Johnson, C. Yakymchuk and M. Brown, Crustal melting and
suprasolidus phase equilibria: From first principles to the state-of-the-art, Earth-Science
Reviews (2018), https://doi.org/10.1016/j.earscirev.2021.103778

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© 2018 © 2021 Published by Elsevier B.V.

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Crustal melting and suprasolidus phase equilibria: From first principles to the

state-of-the-art

Tim Johnsona,* tim.johnson@curtin.edu.au, Chris Yakymchukb, Michael Brownc

a
School of Earth and Planetary Sciences, The Institute for Geoscience Research, Curtin University, GPO Box

U1987, Perth, WA 6845, Australia

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b
Department of Earth and Environmental Sciences, University of Waterloo, Waterloo, ON, Canada N2L 3G1

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c
Laboratory for Crustal Petrology, Department of Geology, University of Maryland, College Park, Maryland

20742, USA
*
Corresponding author.
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Abstract
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Partial melting is the fundamental process by which juvenile crust was produced from the

mantle and subsequently reworked to become the stable, compositionally-differentiated

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continents on which we live and which host most of the elemental resources required by our
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modern technological society. Irreversible differentiation of the continental crust occurs

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principally through the production, segregation and migration of silica-rich (felsic) melts
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from deeper source rocks to shallower sinks where they erupt or, more commonly, crystallise

as granite sensu lato. Here we provide for both novices and professionals a comprehensive,

but accessible, account of the processes involved in crustal melting and suprasolidus phase

equilibria from first principles to the forefront of modern research. To begin we introduce the

tectono-metamorphic context for crustal melting before considering the evidence at outcrop

and in thin section for partial melting, and briefly reviewing melt extraction from crustal

rocks. As a prerequisite to understanding the physicochemical basis for crustal melting, we

summarize the essential thermodynamics that underpin calculated phase equilibria,

distinguish different types of melting reaction, and review the requirements for, methodology
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behind, and limitations of a phase equilibrium modelling approach based on equilibrium

thermodynamics. We explain the various types of phase diagram used to investigate partial

melting and assess open versus closed system processes, including internal and external

buffering of H2O. Those crustal sources that partially melt to produce granite are considered

in detail, namely basic rocks such as basalts and gabbros, clastic sedimentary rocks such as

greywackes, siltstones and mudstones (pelites), and granites themselves. We concentrate

mainly on intracrustal partial melting in convergent-margin settings, and on anatexis during

exhumation of deeply-subducted continental crust from mantle depths. We discuss the

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behaviour of trace elements and accessory minerals during melting, and consider the

implications for isotope geochemistry. To close we include a brief summary of some of the
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important points and offer a few suggestions for future lines of research on crustal melting.
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Keywords: Granite, Melting, Migmatite, Open vs closed systems, Suprasolidus phase

equilibria, including P–T–X pseudosections, Trace elements and accessory minerals

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1. Introduction
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In this article we review the current understanding of crustal melting (also known as
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anatexis) within the context of phase equilibria. Melting is the process of transforming a solid

substance into a liquid, usually, but not exclusively, by the addition of heat. Melting is

generally partial rather than complete, producing coexisting liquid (melt) and one or more

solids (minerals). Partial melting is the principal mechanism driving irreversible

differentiation of the crust, mostly through the production, segregation and migration of

silica-rich (felsic) melts from their source rocks to shallower levels, where they may erupt or,

more commonly, crystallise as granite sensu lato (hereafter simply granite). Thus, at one

extreme of scale, partial melting is responsible for the formation of the continents that we live
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on, and at the other, for the generation of rocks such as obsidian that our earliest ancestors

used for tools. Furthermore, partial melting and crustal differentiation has resulted in the

concentration of the many elements and compounds that have fundamentally shaped the

development of our society, from the discovery and smelting of tin and copper ores that

ushered in the Bronze Age to the present-day demand for the rare metals without which our

smart phones could not function.

Our intention is to provide a comprehensive but accessible reference for those who

wish to understand, or teach, a phase equilibrium approach to crustal melting from first

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principles to the state-of-the-art. Following this introduction, we provide a context for crustal

melting by briefly reviewing: (i) the realm of crustal metamorphism, particularly in relation
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to metamorphic facies, types of metamorphism in terms of varying thermobaric ratio (T/P),
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and sources of heat; (ii) the nomenclature and characteristics of partially-melted rocks at
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outcrop and under the microscope; and, (iii) the process of melt extraction from a partially

molten crustal source. For reasons of space, we restrict our review to those crustal rock types
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that, through partial melting, are responsible for the production of granitic rocks, which we
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subdivide into: (i) igneous protoliths, with an emphasis on metabasic rocks, and; (ii) clastic
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sedimentary protoliths, with an emphasis on metapelites and metagreywackes. Although their

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importance is undoubtedly underappreciated, we do not consider partial melting of

carbonates (Ferrero et al., 2016; Lentz, 1999), sulphides (Frost et al., 2002; Stevens et al.,

2005; Tomkins et al., 2007), or ultramafic rocks such as peridotites, pyroxenites and

komatiites.

We use 'fluid' or ‘aqueous fluid’ to refer to a H2O-dominated vapour phase, and ‘melt’ and

‘liquid’ interchangeably to mean a polymerised silicate melt phase. In the appendix we

provide a glossary of some of the more important terms used in section 2 that relate to crustal
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melting––key terms used elsewhere in the paper are explained in the main text. Phase

abbreviations follow Whitney and Evans (2010).

2. Metamorphism and crustal melting

2.1. Crustal metamorphism

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During prograde regional metamorphism, as temperature, T (and commonly

pressure, P), increase, the mineral assemblage in rocks generally equilibrates continuously
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as fluid or melt is generated. However, fluid and melt are less viscous and have a lower
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density than their metamorphic source rocks, so that as they become over pressured they
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generally segregate and migrate to higher crustal levels. Thus, during the retrograde

evolution, as T (and commonly P) decrease, mineral assemblages generally undergo much

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less change because fluid or melt is scarce or absent. An equilibrium mineral assemblage
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will tend to be preserved once fluid is lost (before or around the peak T of metamorphism) or
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as the last dregs of trapped melt crystallize (after the peak T, during cooling and crossing of
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the solidus), reflecting the P–T conditions at that point. This is the basic logic underlying the

concepts of the metamorphic peak and metamorphic facies.

Metamorphic facies are defined by commonly-occurring sets of mineral assemblages

developed in rocks of different compositions that recur in space and time (Eskola, 1920; Fyfe

et al., 1958); that is, metamorphic facies represent the overlapping stability fields in P–T

space for these sets of mineral assemblages. The common metamorphic facies, which are

shown in Fig. 1a, provide useful shorthand, for example in classifying the P–T ranges of

different sets of mineral assemblages and in a comparison of processes under different ranges
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of P–T conditions, such as anatexis under granulite facies versus eclogite facies conditions

(Fig. 1a). In addition, they form the basis for the metamorphic facies series and the

classification of metamorphic belts by Miyashiro (1961).

On the contemporary Earth, high-grade metamorphism and crustal melting are

predominantly associated with convergent plate boundary processes. Therefore, with the

increase in quantitative P–T data now available, it is convenient to use the thermobaric

ratios (T/P) retrieved from the peak metamorphic mineral assemblages, since these vary both

spatially and temporally during orogenesis. Using T/P, metamorphism has been classified

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into three types, each with tectonic significance (Fig. 1b; (Brown, 2007; Brown and Johnson,

2019b; Brown and Johnson, 2019c): high T/P metamorphism with thermobaric ratios >775
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°C/GPa, intermediate T/P metamorphism with thermobaric ratios between 775 and 375
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°C/GPa, and low T/P metamorphism with thermobaric ratios <375 °C/GPa. In a simple one-
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sided subduction-to-collision orogen, each type of metamorphism is typically associated with

a particular tectonic setting (Brown, 2010b). Low T/P metamorphism, which is characterised
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by blueschists, low-temperature (quartz) eclogites and ultrahigh pressure (coesite/diamond)

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eclogites, forms in subduction channels associated with accretionary orogens and during
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partial subduction of passive continental margins. Intermediate T/P metamorphism, which is

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characterised by high-pressure granulites and medium-to-high temperature eclogites, is

associated with mountain building, particularly during collision where continental crust is

thickened. High T/P metamorphism, which is characterised by upper amphibolite and

granulite facies rocks, and ultrahigh temperature (UHT) granulites, occurs in orogenic

hinterlands (backarcs and plateaus) and in regions of lithosphere extension (Cipar et al.,

2020).

In crustal rocks containing hydrous minerals or a pore fluid, melting takes place at

the solidus in the temperature range 650–700 °C and higher, conditions that may be achieved
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in all three types of metamorphism (Brown and Johnson, 2018, 2019a, b). Thus, we may refer

to subsolidus rocks, meaning protoliths that record peak P–T conditions below the solidus,

and suprasolidus rocks, referring to formerly melt-bearing lithologies that record peak P–T

conditions above the solidus.

The irreversible process of crustal differentiation by partial melting involves

feedback between heat flow, chemical reaction, melt flow and elastic–plastic deformation in

orogens (Brown, 2010c; Clark et al., 2011). In particular, partial melting requires high

temperatures and a large amount of energy due to the latent heat of fusion of crustal rocks

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(Bea, 2012; Moyen, 2020b; Schorn et al., 2018; Stüwe, 1995). Indeed, since the rates of melt

segregation, ascent and emplacement in the upper crust are all relatively fast, occurring in
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<<1 Myr, but the rate of prograde heating during regional metamorphism is generally
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relatively slow, taking >>1 Myr, it is heat flow that determines the overall rate of the crustal
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melting process (Brown, 2013; Harris et al., 2000).

During intermediate and high T/P metamorphism, regional-scale partial melting may
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be driven by thickening of continental crust, particularly if enhanced by a high concentration

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of heat producing elements (principally K, Th and U), as well as by magmatic underplating

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and by the upwelling of hot asthenosphere during lithospheric extension (Clark et al., 2011;
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Harley, 2016; Jamieson et al., 1998; Kelsey and Hand, 2015). At present, crustal melting is

occurring beneath orogenic plateaux associated with continental arcs, such the Andes (Yuan

et al., 2000), and in subduction-to-collision orogens and their hinterlands, in particular the

Himalaya and the Tibetan plateau (Nelson et al., 1996; Unsworth et al., 2005). During low

T/P metamorphism, regional-scale partial melting has been linked with the subduction and

exhumation of continental crust to and from mantle depths (ultrahigh-pressure

metamorphism) (Labrousse et al., 2011) (see section 8).

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At a more localized scale, partial melting may occur in contact metamorphic aureoles

associated with large mafic/ultramafic igneous complexes, such as the Bushveld (Johnson et

al., 2003b, 2010) and the Duluth (Ripley and Alawi, 1988) complexes, and around granite

plutons (Marchildon and Brown, 2002) and volcanic feeders (Holness, 1999). Melting may

also be associated with: (1) the influx of hydrous fluid into crust at temperatures above, but

close to, the H2O-saturated (wet) solidus (Collins et al., 2020b; Pourteau et al., 2020; Tafur

and Diener, 2020; Weinberg and Hasalová, 2015); (2) frictional heating (viscous dissipation)

associated with shear zones (Nabelek et al., 2010) and faults (Zhong et al., 2021); (3)

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subducting lithosphere younger than 25 Myr (Defant and Drummond, 1990); and, (4)

meteorite impacts (Gibson, 2002), particularly during the Hadean and Archean eons (Johnson

et al., 2018).
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2.2. Outcrop-scale features and nomenclature for partially-melted rocks

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If the temperature due to metamorphism becomes sufficiently high, most crustal rocks
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begin to melt (a process called partial melting or anatexis). Before partial melting occurs,
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source rocks are referred to as protoliths, some of which are more fertile than others,
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producing more melt at the same P–T conditions. Source rocks from which melt has drained

are referred to as residual. Criteria for the recognition of partial melting are discussed by

Sawyer (1999).

At outcrop, the presence of irregular patches, lenses and/or veins of

quartzofeldspathic material with a granitic composition and texture commonly (but not

always) provides evidence for partial melting (Brown et al., 1995; Sawyer, 1999; Sawyer,

2008; Sawyer and Barnes, 1988; Sawyer and Robin, 1986). Since melting is commonly

associated with deformation, these patches, lenses and veins routinely coalesce to form
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interconnected networks in response to the imposed stress field. Rocks that show such

features are called migmatites or are described as migmatitic. Commonly, migmatites

comprise two distinct components: the neosome—that portion affected by partial melting—

and the paleosome—that portion unaffected by partial melting (Sawyer, 2008). Compared to

the protolith or nearby paleosome, the neosome is generally coarser grained (Fig. 2a, b) and,

if not subsequently deformed in a solid state, lacks structural elements, particularly any pre-

anatectic foliation and/or lineation (Fig. 2b, e, f). These characteristics are especially helpful

in identifying partial melting in leucocratic protoliths, such as granites (Johnson et al., 2013;

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Sawyer, 2010).

Partial melting changes a rock into a two-phase material generally composed of a

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lower-viscosity, lower-density liquid (melt) and a higher-viscosity, higher-density solid
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residue (aka residuum), such that they may separate if there is sufficient driving force (Fig.
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2a). Thus, the residuum is the mostly solid part of the neosome from which melt drained. It is

commonly dominated by ferromagnesian minerals, such that it is darker coloured and

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sometimes called melanosome; for example, this term could be applied to the areas of
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residue in Fig. 2a. The complementary lighter-coloured part of the neosome, which represents
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material crystallized mostly from segregated melt, is called the leucosome. It is commonly
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dominated by quartz and feldspar, and it may or may not correspond to a liquid composition

according to whether fractionated melt was lost during partial crystallisation. In the case of

incongruent melting (discussed in detail below), melt and a peritectic mineral or minerals

are the liquid and solid products of the melting reaction, respectively; they are commonly co-

located, for example the garnet in leucosome in Fig. 2b.

Migmatites are heterogeneous at various scales (Fig. 2) with a morphology controlled

by the melt fraction formerly present in the rock and the amount of strain that accompanied

partial melting (Sawyer, 2008). A first-order classification of migmatites, based on the

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inferred former melt fraction in the rock (Sawyer, 2008), separates metatexite (lower former

melt fraction, pre-anatectic structures generally preserved) and diatexite (higher former melt

fraction, pre-anatectic structures disrupted) (Fig. 2c). Nonetheless, both metatexite and

diatexite may preserve coherent syn-anatectic and/or syn-crystallisation structural elements,

such as foliation and lineation (Solar and Brown, 2001a). The second-order classification of

migmatites relates to the amount of syn-anatectic strain, where various terms are used to

describe the geometry of the leucosome network in metatexites, such as patch (Fig. 2d),

stromatic (Fig. 2e), and net-structured (Fig. 2f), and the leucosome–residuum–paleosome

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relations in diatexites, such as raft, schollen (bottom-right of Fig. 2c) and schlieren (lower

half of Fig. 2c) (Johnson et al., 2001b; Sawyer, 2008). In source rocks with S > L fabrics,
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stromatic metatexite migmatites form in which the leucosome is generally planar and parallel
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to foliation, whereas in source rocks with L > S fabrics, the leucosome is generally spindle-
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shaped and parallel to lineation (Brown et al., 1999).

During partial melting, melt is more mobile than the residue, and the latter may be
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thought of as the part that largely remains in situ. Therefore, the location of the leucosome
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records whether the melt has remained in place or tracks the pathway(s) by which it drained
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from the source during the anatectic event.

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Thus, we may distinguish in situ leucosome, representing material remaining at its

source, in source leucosome, representing material that migrated away, but remained

confined within its source layer, and leucosome veins or dykes, representing material that

migrated out of its source layer, but which remained in the region affected by the anatectic

event (Sawyer, 2008). The hierarchy of leucosome types describes segments of the channel

network through which melt/magma migrates out of a migmatite (Brown, 2010a). In this

regard, an important concept to note is the melt connectivity transition (MCT), the melt

fraction (around 7 vol.% melt) above which the melt forms an interconnected network and
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the strength of a partially-molten rock drops by an order of magnitude or more (Rosenberg

and Handy, 2005). If the melt volume produced during reaction was below the MCT (i.e. <7

vol.%) then, in the absence of significant syn-anatectic deformation, melt may be retained.

For further information about migmatites, particularly field descriptions and the

associated (evolving) nomenclature, the reader is referred to the books by Mehnert (1968),

Ashworth (1985), Ashworth and Brown (1990), Brown and Rushmer (2006a) and Sawyer

(2008).

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2.3. Thin section-scale features

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2.3.1. Microstructural features of partially-melted rocks
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Recognition of partial melting at the grain scale may not always be clear cut because

the microstructures associated with prograde melting and retrograde melt crystallization are
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commonly modified during exhumation and/or cooling. For example, if melt is retained at
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the grain scale, retrograde reaction between melt and the peritectic products may
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progressively destroy any prograde reaction microstructures (Brown, 2002). Fortunately, melt
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drainage limits such retrograde effects (Brown, 2002; White and Powell, 2002b) and allows

inferences about melting to be made. After the metamorphic peak, microstructures in an

anatectic rock evolve during cooling to reduce the internal energy, as discussed in detail by

Holness and Sawyer (2008), Holness et al. (2011) and Vernon (2018).

Notwithstanding the potential limitations imposed by modifications during cooling, at

the grain scale, the former presence of melt may be inferred based on various

microstructures, in particular pseudomorphs of melt pores and grain boundary melt films.

Furthermore, in rocks that record P–T conditions consistent with partial melting, the presence
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of mineral assemblages that correspond to a melt-producing (or, during cooling, a melt-

consuming) reaction is sufficient to demonstrate anatexis.

To illustrate these principles in a simple way, we refer to the experimental melting of

a natural rock—a quartz–muscovite schist—under H2O-saturated conditions at 0.1 GPa

(Rubie and Brearley, 1990). In this experiment (Fig. 3a), quartz and muscovite react to

produce a layer of melt along the quartz–muscovite grain boundary, together with the

localised nucleation of the solid reaction product mullite (due to excess Al2O3). This is an

example of a fluid-present incongruent melting reaction. For comparison, a natural example

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of muscovite and quartz breakdown to form a film of melt, now pseudomorphed by K-

feldspar, along the common grain boundary is shown in Fig. 3b.

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More mineralogically complex, but otherwise similar microstructures are produced by
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fluid-absent incongruent melting reactions involving, for example, the breakdown of biotite
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and sillimanite/kyanite in metapelites to produce peritectic garnet and/or cordierite with melt

(Fig. 3c). In these cases, it is common to find inclusions of relict reactant minerals, such as
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biotite and sillimanite, in the peritectic product that itself is surrounded by leucosome, as
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shown in Figs 2b, d and 3c, and discussed by Jones and Brown (1990) and White et al.
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(2005). Drainage of melt may leave behind a compacted residue in which trapped melt
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pockets (in 3D) may now be pseudomorphed by quartz or feldspar patches (in 2D) that have

cuspate edges with low dihedral angles against host minerals (Fig. 3c; Johnson et al.,

2003b). In some cases, prograde melting reactions may be inferred from the modal

proportions and/or microstructural relations between reactant and product phases (Guernina

and Sawyer, 2003; discussed further below). By contrast, fluid-present congruent melting

reactions, for example between quartz and feldspars, that produce only melt are better

identified using diagnostic microstructures related to either partial melting, such as corroded

relict grains of reactant minerals, or resulting from crystallisation of retained melt pockets,
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such as pseudomorphs of quartz or feldspar after melt in pores and along grain boundaries.

Overall, a wide variety of microstructures related to partial melting and melt crystallisation is

commonly preserved in residual (migmatitic) source rocks, many of which are illustrated in

section F of the Atlas of Migmatites (Sawyer, 2008).

Microstructures related to the beginning of melt segregation in migmatites in orogenic

belts are rarely preserved due to the effects of syn-anatectic deformation and melt flow.

However, the grain-scale process of melt segregation into micro-leucosomes has been studied

in metatexites from the contact aureole of the Duluth complex in Minnesota (Sawyer, 2014b).

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The leucosomes are small and display a systematic progression in morphology from equant

micropores to elliptical micro-leucosomes (~1 mm in length), to en echelon arrays of

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elliptical micro-leucosomes, to zigzag-shaped micro-leucosomes (~4 mm in length), and, as
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the zigzag arrays connect, to high aspect ratio micro-leucosomes up to 19 mm in length. This
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process is reminiscent of the way ductile fractures grow, and consistent with earlier

observations and interpretations at outcrop scale (Brown, 2004).

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One microstructural feature largely ignored until relatively recently is the presence in
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migmatites and residual granulites of tiny glass or nanogranite inclusions in peritectic

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minerals, most commonly garnet. These features have been interpreted as aliquots of
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anatectic melt that were captured during growth of the peritectic mineral (Cesare et al., 2015).

Melt inclusions are particularly important because, although difficult to measure accurately,

they provide some of the best natural examples of largely unmodified anatectic melt

compositions from a wide range of P–T conditions (Bartoli et al., 2016; Cesare et al., 2011;

Ferrero et al., 2019).

2.3.2. Inference of melting reactions

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To illustrate the methodology by which we may infer melting reactions, we briefly

review two examples from the literature. In the first example, a residual granulite terrane,

although most of the melt had drained from the rocks, the melting reaction and volume of

melt produced can be estimated from the mode of peritectic orthopyroxene in the granulites.

The second study concerns an eclogite sample in which the melt produced during exhumation

mostly crystallised in situ within the reaction microstructure itself.

In the case of the residual granulites, the prograde melting reaction was deduced from

the decrease in modal biotite and quartz and the increase in orthopyroxene and plagioclase

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contents, together with microstructures that indicated melting through breakdown of biotite +

quartz + plagioclase to melt + orthopyroxene + Fe–Ti oxides (Guernina and Sawyer, 2003).
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Based on the proportion of melt to peritectic orthopyroxene in experimental studies of this
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reaction, Guernina and Sawyer (2003) estimated the volume of melt produced on average to
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have been ~30 vol.%. However, only 1–3 vol.% melt was retained in the melt-depleted

granulites, largely as quartz, plagioclase and K-feldspar pseudomorphs along what were once
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melt-filled grain boundaries, leading to the conclusion that melt drainage in this case was
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highly efficient. The counterintuitive relative increase in plagioclase in the mode of the
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residual granulites, despite it being a reactant phase, was due to breakdown of dominantly
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biotite and quartz during melting, and efficient loss of melt, which was the dominant product

of the reaction relative to orthopyroxene.

In circumstances where the melt volume produced is low, for example below the

MCT, it may crystallise in situ preserving the reaction microstructure. Such an example has

been described by Feng et al. (2021) from eclogite; representative microstructures from their

study are shown in Fig. 4. Here the evidence for incongruent partial melting is clear. First,

there are optically continuous networks of plagioclase that span the width of the field of view

in Fig. 4a, b and are interpreted as pseudomorphs of former melt films along grain
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boundaries. The plagioclase has low relief and is colourless in Fig. 4a but is pale orange (due

to the use of the 1 plate to emphasise continuity) in Fig. 4b. Second, this network of

plagioclase is associated with patches that show reaction microstructures, as seen on the left-

hand side and at the bottom right in Fig. 4a and b. Similarly, in the centre of Fig. 4c and d

there is a large (1000–1500 m) grain of Na–Al-rich pyroxene (omphacite) that is partially

replaced by optically-continuous plagioclase, which has pseudomorphed former melt. This is

a two-dimensional cut through a small pocket of leucosome that is a typical feature formed

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during the early stage of crustal anatexis (Sawyer, 2008). Small grains of peritectic omphacite

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within the leucosome pockets have lower concentrations of the Na–Al pyroxene (jadeite)

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component than the large rock-forming grains. Phengite shows some evidence for minor

corrosion, but zoisite appears to be largely stable together with garnet. Major and trace
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element compositions of minerals support the microstructural interpretation that the melting
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reaction in this case involved mostly omphacite with only minor contributions from phengite

+ zoisite + quartz to produce melt and the small grains of less sodic omphacite. Subsequently,
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the melt has crystallised to plagioclase, which now pseudomorphs the former melt, both in
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pockets and along grain boundaries, together with subhedral-to-euhedral amphibole grains in
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the leucosome pockets (Feng et al., 2021).

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2.4. Melt extraction from a melting crustal source

Crustal melting and segregation, ascent and emplacement of melt are complex

processes. Melt is generated as micrometre-scale droplets at multiple grain boundaries in a

deep crustal source, but ultimately accumulates to form plutons in the upper crust that

comprise on the order of 103 to 104 km3 of magma aggregated from countless smaller batches

of melt (each perhaps 10–1 to 102 km3) (Brown, 2010a; Brown, 2010c). Examples of this style
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of magma emplacement from different tectonic settings include the Manaslu granite in the

Himalayas (Deniel et al., 1987), the Phillips pluton in Maine (Pressley and Brown, 1999), and

the Tuolumne intrusive suite in California (Coleman et al., 2004). Thus, in the extreme case

of a lower crustal source and an upper crustal sink, melt extraction is a process with a length

scale that spans more than seven orders of magnitude or a volume concentration factor that

exceeds 1021 (Brown, 2010a; Brown, 2010c). The mechanisms by which this might have

been achieved, from the inception and growth of leucosomes to the formation of plutons,

have been addressed in many articles (e.g. Brown, 2013; Clemens and Stevens, 2016;

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Sawyer, 2014a; Soesoo and Bons, 2015; Weinberg et al., 2013), and we provide only a

succinct summary here.

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In residual migmatites and granulites, evidence of melt-extraction pathways at
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outcrop scale is recorded by crystallized products of melt (leucosome) and residual material
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from which melt has drained (melanosome). These features form networks or arrays that

potentially demonstrate the temporal and spatial relations between deformation and melting.
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Multiple studies have shown that syn-anatectic shear-enhanced compaction drove melt from
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dynamically created porosity, recorded by pseudomorphs after melt along grain boundaries,
ur

into melt-induced deformation-band networks, represented by leucosome-filled veins, and

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from these to granite-filled ascent conduits, evidenced by anastomosing ductile or brittle

dykes (Brown, 2004, 2005; Etheridge et al., 2020; Weinberg and Regenauer-Lieb, 2010;

Weinberg et al., 2015). In these cases, melt may have accumulated locally, forming a

connected microfracture network (Etheridge et al., 2020), until the volume reached then

exceeded the MCT throughout a large volume of the source (Rosenberg and Handy, 2005).

This multi-scale connectivity allowed the melt to drain down hydraulic potential gradients to

crack-like, ductile opening-mode fractures propagating from dilation or shear bands during

one or several melt extraction events (Brown, 2013). Thus, any outcrop surface though a
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migmatite terrain likely represents a level of melt generation, but also records evidence of

influx of melt, mostly from deeper in the crust, and drainage of melt to shallower crustal

levels (Fig. 5). In these circumstances, the volume of leucosome frozen in the anatectic crust

may exceed that produced at that level, even though some of the melt produced locally has

migrated (Marchildon and Brown, 2003; Yakymchuk et al., 2013).

In granulite facies migmatite terrains where syn-anatectic deformation drove efficient

melt drainage, for example along the foliation, even though the melt volume remained below

the MCT (Guernina and Sawyer, 2003), melt flow may have been continuous for as long as

f
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melt was generated or fluxed through the anatectic crust. If a sufficient volume of melt

accumulates in the anatectic crust, diatexite magma may form, which may lead to multiple
pr
phases of partial crystallization and melt extraction under amphibolite and granulite facies
e-
conditions (Sawyer, 2020; Solar and Brown, 2001b). Deep crustal migmatite complexes may
Pr

link to shallower granite plutons (Brown et al., 2016; Brown and Solar, 1999; Johnson et al.,

2001b) or they may give way upwards to injection complexes that include sheeted plutons
al

(Morfin et al., 2013, 2014).

n

Leucosomes in metatexite migmatites have thickness and spacing distributions

ur

generally consistent with being sampled from power-law (scale-invariant) distributions

Jo

(Bonamici and Duebendorfer, 2010; Brown, 2003; Marchildon and Brown, 2003; Saukko et

al., 2020; Tanner, 1999; Yakymchuk et al., 2013). Furthermore, the spatial distribution of

ascent conduits in residual crustal sources and intrusive complexes at higher structural levels

indicates that these features are also scale-invariant (Brown, 2005; Cruden, 2006; Cruden and

McCaffrey, 2001; Hall and Kisters, 2012; Koukouvelas et al., 2006; McCaffrey and Petford,

1997). These conclusions from outcrop and map measurements are supported by numerical

modelling of stepwise accumulation and transport of batches of melt by propagation of

hydrofractures (Bons et al., 2004). In this study, Bons et al. (2004) showed that the model
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system developed spontaneously into a self-organised critical state, in which the melt

distribution was organised in a self-similar way that allowed melt drainage above a system-

determined volume threshold. In nature, in the absence of significant deformation, this

threshold could be the MCT, but during regional-scale crustal anatexis, deformation will

lower the threshold below the MCT allowing smaller melt batches to migrate. Thus, it is

likely that anatectic systems in the crust are strongly self-organized at a range of scales from

the bottom up, becoming more ordered by decreasing the number and increasing the width of

melt-bearing conduits from the anatectic zone through the overlying subsolidus crust to the

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ductile-to-brittle transition zone, where melt accumulates in plutons (Brown, 2010c).

pr
e-
3. The thermodynamic basis of calculated phase equilibria
Pr

Any quantitative treatment of crustal melting is founded on equilibrium

al

thermodynamics. As the name implies, thermodynamics is the branch of physics concerned

n

with the relationship between heat and work, and how heat relates to other forms of energy
ur

and the properties of matter. As a serious scientific discipline, thermodynamics emerged from
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the industrial revolution, principally through a desire to understand, and thereby increase the

efficiency of, steam engines (Carnot, 1824). Formalisation of the principles and equations

governing thermodynamics involved some of the best-known names in science, including

Ludwig Boltzmann, Robert Boyle, Rudolf Clausius, Robert Hooke, James Clerk Maxwell,

Max Planck, William Rankine and William Thomson (Lord Kelvin). To this (non-exhaustive)

list can be added the name of J. Willard Gibbs, who elegantly showed how thermodynamic

processes could be visualised graphically in terms of changing pressure, temperature, volume

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and other thermodynamic variables (Gibbs, 1879), an approach that forms the foundation of

much of what follows.

Before considering melt-bearing (suprasolidus) phase equilibria, we will discuss those

aspects of equilibrium thermodynamics that are a pre-requisite for understanding what is to

follow, with reference to some straightforward examples involving simple minerals (solids).

For those seeking a deeper understanding, the HPx-eos and THERMOCALC

(https://hpxeosandthermocalc.org/) and Science Education Resource Center at Carleton

College (https://serc.carleton.edu/research_education/equilibria/index.html) websites are

f
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good places to start. For a comprehensive treatment of the application of equilibrium

thermodynamics to petrological problems, a number of excellent books are available,

pr
including those by Wood and Fraser (1976), Powell (1978), Spear (1995) and Ganguly
e-
(2008).
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3.1. Some simple definitions

n al

A system is that part of the universe that we wish to consider. In many cases that
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system might be an individual rock sample or a thin section. However, it might be an entire
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planet or a single atomic nucleus. A system may be completely isolated, meaning it cannot

exchange energy or matter with its surroundings, closed, such that it can exchange energy but

not matter with its surroundings, or open, meaning it can exchange both energy and matter. In

nature, crustal rocks undergoing metamorphism are open systems, in which the heat sources

may be internal (e.g. radioactive decay or viscous dissipation) or external (e.g. mantle heat,

heat from nearby plutons), and fluids (principally H2O and/or CO2) and/or melt may be

produced and lost. However, when modelling phase equilibria, we commonly make the

(simplistic but necessary) assumption that the system is closed, as discussed later in this
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section. A more comprehensive treatment of closed versus open behaviour in partially melted

systems is given in section 5.

Of fundamental importance to calculated phase equilibria is the bulk chemical

composition (hereafter bulk composition) of a system. The bulk composition consists of

variable quantities of the different independent chemical components that comprise the

system. Crustal rocks mostly consist of the elements oxygen, silicon, aluminium, iron,

calcium, sodium, magnesium, potassium and titanium, which together account for ~99% of

the crust by mass (Goldschmidt, 1954; Hofmann, 1988; Rudnick and Gao, 2003). By

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oo
convention, concentrations of these major elements, along with some minor elements such as

hydrogen, phosphorus, manganese and chromium, are generally expressed as the weight
pr
percent of their oxides (SiO2, Al2O3, FeO/Fe2O3, CaO, Na2O, MgO, K2O, TiO2, H2O, P2O5,
e-
MnO, Cr2O3), whereas concentrations of the remaining trace elements are reported as weight
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fractions in parts per million (ppm; equivalent to grams per tonne and more formally as

mg.kg–1). As we shall see, petrological experiments and phase equilibria are mostly founded
al

on systems considering the major element oxides as the components. However, how the trace
n

elements behave is key to deciphering the petrogenesis of many rocks (see section 9), in
ur

constraining the behaviour of accessory minerals (section 10) and in understanding the
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formation of many key mineral deposits.

A phase is a part of the system within which all physical and chemical properties are

essentially uniform, and which is (commonly) mechanically separable. For our purposes,

phases are the different minerals (solid phases) that coexist with a melt (liquid phase) and/or

fluid (liquid or gas phase). Importantly, the number of components in a system is the

minimum required to define the compositions of all the phases within that system. For

example, when considering reactions between the minerals quartz (SiO2), corundum (Al2O3)

and sillimanite (Al2SiO5), two components (SiO2 and Al2O3) are required to define the
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system. However, when considering reactions between the aluminosilicate polymorphs

sillimanite, andalusite and kyanite, only one component (Al2SiO5) is required.

The changeable physicochemical properties of a system can be subdivided into

intensive and extensive variables. An intensive variable is one that is independent of the size

of that system, or the amount of matter within it. By definition, at equilibrium (from the Latin

aequi = equal and libra = balance), the state at which the energy of the system is minimised,

the values of the intensive variables are identical everywhere within the system. For our

purposes, the main intensive variables are temperature (T; in ºC or K) and pressure (P; in

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kbar or GPa), but also include chemical potential (). In response to changes in these

pr
variables, the system will attempt to equilibrate through conduction/convection (for T),

deformation (for P) and diffusion (for ). By contrast, extensive variables do depend on the
e-
size of the system and the quantity of matter within it. These include entropy (S), volume (V),
Pr

and chemical composition (X), which can be considered as the conjugate pairs to T, P and ,

respectively, as discussed in detail by Powell et al. (2005). We will return to many of these
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terms later.
n
ur

3.2. Gibbs’ phase rule

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Stemming from his seminal paper (Gibbs, 1879), Gibbs derived the phase rule that

bears his name and which, in a system at equilibrium, relates the number of components (C)

and phases (P) to the degrees of freedom (F; also known as variance), the number of

intensive variables that can be changed independently. The Gibbs phase rule is F = C – P + 2,

and is explained with reference to a simple example, the aluminosilicate phase diagram (Fig.

6).
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As discussed previously, the stability of the aluminosilicate polymorphs can be

described in the one-component (C = 1) chemical system Al2SiO5. Let us consider a P–T

condition, for example a point at 0.8 GPa and 550 ºC, where a rock (the system) with a

composition of pure Al2SiO5 contains grains of only one phase, kyanite. With P = 1, the

Gibbs phase rule tells us that F = 2 (1 – 1 + 2), meaning that, within limits, we are free to

change pressure (to a’) or temperature (to a’’) or both (to a’’’) without ‘upsetting’ the system

(changing the stable assemblage). With two degrees of freedom, the primary phase field of

kyanite (or sillimanite or andalusite) is divariant. Now consider a P–T condition at which the

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rock contains two phases, for example point b, where both kyanite and sillimanite are stable

(i.e. P = 2) at ~0.65 GPa, 645 ºC. Here, F = 1 (2 – 1 + 2), meaning that if we change one of
pr
the intensive variables, the other must change in a dependent way. For example, we can
e-
change the pressure (e.g. to Pb’) but, if we are to maintain the same assemblage (kyanite +
Pr

sillimanite), the temperature must change to Tb’. Similarly, we may change the temperature

(to Tb’’), but then pressure must also change (to Pb’’). The lines along which F = 1 are
al

univariant equilibria. Finally, point c is the unique P–T condition (~0.42 GPa, 540 ºC) at
n

which all three polymorphs may stably coexist, the so-called aluminosilicate triple point.
ur

Here, P = 3, so F = 0 (3 – 1 + 2)––we can change neither P nor T without changing the

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assemblage. The triple point is an example of an invariant equilibrium.

3.3. Reactions, heat and temperature

Heat is the thermal energy supplied to (or extracted from) a system. The addition or

subtraction of heat may lead to a reaction, the process by which a phase or combination of

phases transforms into a different phase or combination of phases. A change in the supply of

heat can lead to a change in temperature, which is a measure of the average vibrational
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energy of particles within the system, but in some cases does not. Let us return to the triple

point (Fig. 6, point c), where the rock contains coexisting kyanite, sillimanite and andalusite.

If heat is supplied to the system at constant pressure, the tendency is for the system to move

into the primary phase field of sillimanite at higher temperature. However, it cannot do so

until all the kyanite and andalusite have been consumed. Initially, the additional heat (energy)

does the work of transforming the kyanite and andalusite to sillimanite, during which the

temperature remains at a fixed value (that of the triple point). Only when all kyanite and

andalusite have been consumed, and the rock consists only of sillimanite, does heating lead to

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a rise in temperature. The transformation described here is a reaction of the form:

pr
kyanite + andalusite → sillimanite. (1)
e-
Pr

On the left-hand-side of this reaction (kyanite + andalusite) are the reactants (the phase or

phases that are consumed in the reaction), whereas on the right-hand-side (sillimanite) are the
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products (the phase or phases produced by the reaction).

n
ur

3.4. Gibbs’ free energy

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The stability fields shown in Fig. 6 are a manifestation of a key thermodynamic

property that also derives its name from J. Willard Gibbs, the Gibbs free energy (G) of the

three aluminosilicate polymorphs as a function of pressure and temperature. By definition, in

a system at equilibrium, G is minimised. At points a, a’, a’’ and a’’’ in Fig. 6, the Gibbs free

energy of kyanite (GKy) is less than that of sillimanite or andalusite, or of any combination of

the three minerals. At points b, b’ and b’’’, the Gibbs free energies of kyanite and sillimanite
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are equal, and both are lower than that of andalusite (GKy = GSill < GAnd). At the triple point,

the Gibbs free energy of all phases is the same (GKy = GSill = GAnd).

The Gibbs free energy of a substance, which changes with pressure and temperature,

can be broken down into its component parts that include some of the variables we

introduced earlier:

G = E + PV – TS, (2)

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where E is the internal energy of the phase, V is the volume and S is the entropy. The internal

energy can be thought of as the total energy a substance possesses, whereas entropy is a
pr
measure of the randomness or disorder of a substance, which increases with increasing
e-
temperature. By definition, at absolute zero (0 K or –273.15 °C), entropy is also zero,
Pr

meaning the atoms within a substance are perfectly stationary such that it is perfectly ordered.

As heat is supplied, so the vibrational energy (temperature) and entropy both increase.
al

An undoubtedly simplistic but potentially useful way to think about how the different
n

terms in equation 2 relate to each other is as follows: the Gibbs free energy, G, can be
ur

thought of as the amount of energy a substance possesses that is available (free) for it to react
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with other substances. This free energy is not simply the total energy (E) the substance

possesses, but must account for the energy that the substance requires to maintain its

coherence. This comprises an entropy contribution that increases with temperature and which

must be subtracted from the energy available for reaction (G)––temperature makes the

substance vibrate more vigorously and become less ordered (S), such that it needs to use

more energy to maintain its coherence––and a volume term (V) that is pressure dependent,

but which is added to the energy available for reaction––a higher pressure helps the substance

maintain its coherence. The first two terms on the right-hand-side of equation 2 together
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define another thermodynamic variable, enthalpy (H = E + PV), the amount of energy

consumed or released when a substance expands or contracts. This leads to an alternative

definition of the Gibbs free energy of a substance:

G = H – TS. (3)

When thinking about reactions between substances, equations 2 and 3 need to be

recast in terms of the difference in the energies of the reactants and products, such that:

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G = E + PV – TS

and
pr (4)
e-
G = H – TS, (5)
Pr

in which the delta () notation refers to the total energy of the products minus the total
al

energy of the reactants. If G > 0, the products have a higher Gibbs free energy than, and are
n

unstable with respect to, the reactants. Conversely, if G < 0 the products are more stable
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than the reactants. If G = 0, the products and reactants are in stable coexistence and the
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system is at equilibrium.

In detail, the entropy change (S) of a system includes for each phase of interest a

heat capacity (Cp) term, and the volume change (V) includes terms accounting for thermal

expansivity () and compressibility (), all of which have a dependence on temperature

and/or pressure. Those wishing to delve deeper might begin with the web pages and books

cited in the introductory paragraph of this section.

3.5. Reactions and the equilibrium relationship

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Thus far we have considered only the thermodynamic properties of pure phases with

a fixed chemical composition, such as kyanite, sillimanite and andalusite. However, most

phases in rocks are solid solutions, whose composition is a mixture of two or more end

members. For example, olivine is a solid solution mineral that consists essentially of a

mixture of the end members forsterite (Mg2SiO4) and fayalite (Fe2SiO4), in which

composition changes by the substitution of Mg for Fe2+. The energetics of mixing in these

impure phases must be accounted for, which brings us to the fundamental equation

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underlying phase diagram calculations.

For a system at equilibrium:

pr
e-
G = –RT ln K, (6)
Pr

where R is the gas constant (= 8.314 J.K–1.mol–1). We have already discussed the left-hand-
al

side of this equation (G, but added a degree sign to remind us that it refers to the pure end
n

members), which can be broken down into a combination of the end-member thermodynamic
ur

variables given in equations 4 and 5. However, the right-hand-side of equation 6 includes a

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new term, the equilibrium constant (K), which permits consideration of the energies

associated with impure (solid solution) phases.

Consider a univariant (F = 1) reaction in the three-component (C = 3) CAS (CaO–

Al2O3–SiO2) system involving the mineral end members anorthite (CaAl2Si2O8), grossular

garnet (Ca3Al2Si3O12), kyanite (Al2SiO5) and quartz (SiO2) (P = 4). In this and any chemical

reaction, mass is conserved, requiring that the reaction be balanced. This mass balance is

achieved by adding stoichiometric coefficients, the number of atoms or molecules of each

reactant and product phase involved in a reaction. In the example given, three moles of
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reactant anorthite are consumed to produce one mole each of grossular and quartz and two of

kyanite (if a single mole is involved, the ‘1’ is by convention omitted):

3 anorthite → grossular + 2 kyanite + quartz (7)

3 CaAl2Si2O8 → Ca3Al2Si3O12 + 2 Al2SiO5 + SiO2

In natural rocks in which these minerals occur, such as metapelites, both kyanite and quartz

may be considered as effectively pure phases with a fixed composition, but plagioclase and

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garnet are seldom (or ever) pure anorthite and grossular. In particular, plagioclase

incorporates variable amounts of Na (as the albite component) and garnet commonly contains
pr
significant quantities of Fe2+, Mg and Mn (as the almandine, pyrope and spessartine
e-
components, respectively). These ‘diluting’ species reduce the energetic contribution of the
Pr

Ca end members. This contribution is K, which consists of the product of the activity (a) of

each new phase (product) raised to the power of its respective stoichiometric coefficient,
al

divided by the product of the activity of each reactant phase raised to the power of its
n

respective stoichiometric coefficient. In the example given:

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K = aGr. aKy2. aQtz / aAn3. (8)

The activity can be thought of as the ‘effective concentration’ of an end member within the

solid solution mineral in question. In essence, the energy associated with the end member is

not simply a linear function of the concentration (or mole fraction, X) of that end member,

which we can easily measure using an electron probe microanalyser, but involves additional

energy related to how different atoms (or ions) within the substance interact, which we can

estimate based on theory and/or experiments. In pure phases, a = 1, but in solid solution
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phases (including melts and supercritical fluids), a < 1. Thus, in equation 7, if we consider

quartz and kyanite to be pure, the associated terms can be disregarded to leave aAn3, the

activity of anorthite in plagioclase raised to the power of three (there are three moles of

plagioclase in the balanced reaction 8) and aGr, the activity of the grossular component in

garnet, of which only one mole participates in the reaction. Thus, equation 8 reduces to K =

aGr / aAn3, which forms the basis for the so-called GASP (garnet–aluminosilicate–quartz

(silica)–plagioclase) barometer (Ghent, 1976; Holdaway, 2001).

Therefore, to perform quantitative calculations to constrain the (P, T) conditions of

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equilibration of a system comprising a mixture of pure and impure phases (i.e. a rock), we

pr
must solve both sides of equation 6. Solving the left-hand-side (G) requires a knowledge of

the thermodynamic properties of the pure end members, whereas solving the right-hand-side
e-
–RT ln K) requires a knowledge of the energies associated with mixing (the interaction
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energy, W) between the various end members of solid solution phases, collectively termed

activity–composition (a–X) relationships (also known as solution models) for the phases of
al

interest. Providing, expanding and refining these data represents a very significant proportion
n

of the progress that has been made in quantitative petrology over the past few decades. We
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will address the various sources of thermodynamic data and existing a–X models required to
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solve equation 6, and the different types of software that are most commonly used, after

describing the types of suprasolidus phase diagrams a user might encounter or want to

calculate.

3.6. Slopes of reactions

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The Clapeyron equation (also called the Clausius–Clapeyron equation or relationship)

relates the slope of a reaction line in P–T space (P/T) to the entropy and volume terms,

such that:

P/T = S/V. (9)

As we will see, this relationship is useful in qualitatively orienting reaction lines in P–T space

f
and in establishing which phases occur on which side of the reaction, in particular when

oo
constructing petrogenetic grids (see section 4.2). For example, reaction 7 involves only solid

pr
phases (minerals), for which the differences in the degree of disorder (S) between the

products and reactants is small, and the energetics of the reaction relate mainly to changes in
e-
volume (V). Consequently, the slope of the reaction 7 is shallow (small P/T) in P–T
Pr

space, such that it provides a useful means of constraining pressure in rocks of an appropriate

composition (i.e. it is a good (geo)barometer).

al

Of particular importance here is that, during heating, most crustal rocks first undergo
n

dehydration reactions then, as the solidus is crossed, melting reactions. As the products
ur

include H2O and melt, respectively, both types of reactions involve a positive volume change
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and a very significant increase in the disorder of the system associated with solid to fluid

and/or liquid transitions. Consequently, dehydration and melting reactions generally have

steep positive slopes in P–T space, with H2O or melt on the high T (high S) side of the

reaction, as intuition tells us.

3.7. Equilibrium volume

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To end, an important but difficult variable to consider is the equilibrium (or

equilibration) volume, that is, the volume of a system that is considered to have attained

(chemical/diffusive) equilibrium (Powell et al., 2005, 2019). In high-grade crustal rocks, such

as migmatites and granulites, equilibrium is generally assumed to have been attained on a

hand-specimen or larger scale, although in many cases this may not be justified. For example,

where mineral grains preserve compositional zonation, such as Ca in garnet, the core of those

grains cannot be in equilibrium with garnet rims or the matrix of the rock. In addition, in

crustal rocks that reached the highest metamorphic temperatures (900–1000 °C), reaction

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microstructures such as symplectites and coronae are common, indicating gradients in

chemical potential and that equilibrium was attained at a grain scale or smaller (Mitchell et
pr
al., 2020; Powell et al., 2019; White and Powell, 2011; White et al., 2008). The development
e-
of strongly-domainal equilibrium volumes generally reflects the absence of melt and/or fluid,
Pr

inhibiting diffusion, which in the case of high-T migmatites and granulites requires effective

melt loss (Johnson et al., 2010; Mitchell et al., 2020).

al

In nature, constraining a single equilibration volume is impossible for several reasons,

n

including that different elements diffuse at different rates that are dependent on changes in P
ur

and T, the minerals involved and whether any melt or fluid was present at equilibrium, and
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many other factors (Powell et al., 2019). However, in practice, an appropriate equilibrium

volume can generally be estimated, at least for the major elements, that is constrained by the

slowest diffusing species, commonly thought to be Al (Carmichael, 1969).

4. Suprasolidus phase equilibria

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As described briefly in the introduction, melting is the process by which a solid or

solids are transformed into a liquid, usually by the addition of heat. By assuming that liquid is

not allowed to migrate, this case can be considered as closed system behaviour and modelled

as such. However, melting of rocks may also occur due to a reduction in pressure

(decompression melting, which also can be modelled as a closed system) or the addition of a

fluid, generally H2O (H2O- or fluid-fluxed melting), which is an example of open system

behaviour. To begin this section, we summarise some key aspects of melting experiments

using various starting compositions. Then we describe the fundamentals of suprasolidus

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phase equilibria and associated terminology with reference to the simple case by which heat

is supplied to a closed and compositionally simple system. We examine open system

pr
behaviour, including fluid-fluxed melting, in section 5.
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Pr

4.1. Experiments
al

Experimental petrology fundamentally underpins the thermodynamic data on which

n

quantitative phase equilibrium calculations depend. For example, the end-member data used
ur

in the construction of many of the calculated phase diagrams that follow (Holland and Powell
Jo

(2011) come from >650 articles, most of which report experimental studies (although not

necessarily partial melting experiments). We cannot do justice to the numerous melting

experiments that have been undertaken, but we provide some background information for

context. Detailed summaries are provided elsewhere (Castro, 2013; Gao et al., 2016b;

Johannes and Holtz, 1996; Patiño Douce, 1999). In particular, table 1 in the paper by Gao et

al. (2016b) provides a synthesis of many of the experimental studies that have considered

partial melting of a broad range of crustal rocks or their synthetic analogues, including both

(meta)igneous and (meta)sedimentary compositions, over a wide range of P–T conditions.

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Table 1. Bulk compositions (mol.% normalised to 100%) used in the construction of

pseudosections.

SiO Ti Al2 Fe Mg Ca Na2 K2 H2 Mn XM Xferr K/N

Figure Sample 2 O2 O3 OT O O O O O O O g ic a
64.3 3.1 0.4
9 Taylor exp. 3 – 9.35 5.51 4.54 – 3.22 8 9.87 – – 5 – 0.99
54.9 1.2 11.4 0.3 0.5 0.3 0.1
12 C-F2 3 7 8.91 9 6.22 8.56 2.95 6 4.73 – 8 8 0 0.12
50.0 1.0 12.1 11.6 0.2 0.4 0.6 0.1
14a N-MORB 9 1 8.69 7.78 5 7 2.50 2 5.44 – 7 4 2 0.09
49.1 0.5 17.1 0.1 0.4 0.6 0.1
14b Isua basalt 5 5 6.11 9.55 8 9.95 1.49 8 5.37 – 8 7 0 0.12
15a and X = 0 in 53.4 1.0 11.9 0.6 1.1 0.5 0.3
15b 87S35a 8 1 0 7.68 6.80 9.47 4.33 8 3.48 – 6 6 0 0.16
45.1 0.8 10.0 0.5 18.5 0.9 0.5 0.3
X = 1 on 15b 87S35a 2 6 3 6.48 5.74 7.99 3.66 7 8 – 8 6 0 0.16
60.5 0.8 12.8 2.7 0.6 0.4 0.1

f
20 Metapelite 5 5 0 7.52 5.18 1.49 1.88 6 6.24 0.16 0 5 6 1.47

oo
Metagreywa 75.3 0.5 1.2 0.3 0.5 0.1
22 cke 5 1 7.96 4.09 3.74 1.12 2.77 2 2.61 0.34 1 2 5 0.44

4.1.1. Felsic (meta)igneous rocks pr

The long history of experimental studies of granitic rocks is documented in detail in
e-
the book by Johannes and Holtz (1996), so we highlight only a few key aspects here. The first
Pr

(fluid-absent) experiments melting a granite, by Hall (1805), date back almost to the

beginnings of geology as a scientific discipline, and were undertaken with the direct purpose
al

of testing Hutton’s postulate of an origin of granite through crystallisation of magma (Hutton,

n

1788). However, it was Norman L Bowen who established experimental petrology as a

ur

serious subdiscipline within geology. With Oliver Tuttle, he published the first detailed
Jo

investigations on melting in the synthetic haplogranite system (Ab–Or–Qz–H2O) (Tuttle and

Bowen, 1958) that resolved the granite controversy (Read, 1957), in which it was established

that granites may form at T < 700 °C. In the same study, these authors also performed

experiments on two natural plagioclase-bearing granites from the USA, the two-mica (‘S-

type’) Westerly granite, subsequently used in several key experimental studies, and an

amphibole-bearing (‘I-type’) granite from Quincy (the I–S typology of granites is discussed

in section 6).
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Noting the close correspondence between the onset of melting in the synthetic and

natural systems, Tuttle and Bowen (1958) constrained the location in P–T space of the H2O-

saturated (‘wet’) solidus (the locus of P–T conditions at which, with increasing T, an H2O-

saturated composition will begin to melt) in quartz- and feldspar-bearing rocks that is

fundamental to understanding suprasolidus phase equilibria in common crustal lithologies.

The H2O-saturated solidus has a shallow negative slope in P–T space (P/T) at pressures

below a few tenths of a GPa, but steepens at higher P. Subsequently, this study was extended

f
to pressures from 0.4 to 1.0 GPa (Luth et al., 1964) and to investigate the influence of CO2

oo
(Wyllie and Tuttle, 1959), which was found to be much less soluble than H2O in granitic

pr
melt. These last authors went on to show the effects of other volatile species, notably that the

addition of Li and F reduced the temperature of the wet solidus by 50–90 °C (Wyllie and
e-
Tuttle, 1964; Wyllie and Tuttle, 1961).
Pr

Experiments considering the effects of H2O, ranging from anhydrous to H2O-

saturated, were key to understanding the processes of H2O-undersaturated (fluid-absent)

al

partial melting and the fundamental controls of H2O-content and temperature in the genesis
n

of granite (Clemens and Wall, 1981; Maaløe and Wyllie, 1975; Robertson and Wyllie, 1971a,
ur

b; Whitney, 1988; Wyllie, 1971). Experiments extending to much higher pressures (up to ~3–
Jo

4 GPa) showed that the H2O-saturated solidus had a positive P/T above ~2 GPa and that

aqueous solutions at high-P are significantly enriched in solute (Boettcher and Wyllie, 1968;

Huang and Wyllie, 1975; Stern and Wyllie, 1981). Although most of the melting experiments

on felsic igneous rocks have concentrated on ‘S-type’ (muscovite- and/or biotite-bearing)

granites, there have been detailed studies on tonalite (Patiño Douce, 1997, 2005; Singh and

Johannes, 1996a, b; Watkins et al., 2007) and trondhjemite (van der Laan and Wyllie, 1992)

starting compositions. These rocks are compositionally and mineralogically similar to

greywackes, and behave in an analogous manner (see below and section 7).
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The compositions of melt derived from felsic igneous protoliths are highly variable,

and a function of P, T, aH2O and source composition. As a generalisation, muscovite-bearing

(‘S-type’) granites produce high K/Na peraluminous melts ((ASI = Al2O3/(Al2O3 – 3.33P2O5

+ Na2O + K2O) > 1; (Frost et al., 2001; Shand, 1943), biotite-bearing (‘S-type') granites

produce peraluminous to weakly metaluminous melts (ASI < 1), and rocks with lower K/Na

ratios and hornblende-bearing (‘I-type’) granites produce mostly metaluminous sodic melts

(Johannes and Holtz, 1996; Whitney, 1988). These compositions and the peritectic minerals

that form with melt correspond to those produced by partial melting of common

f
oo
metasedimentary (in the case of ‘S-type’) and metabasic (in the case of ‘I-type’) protoliths, as

detailed in the next two subsections and in sections 6 and 7. However, granites generally are
pr
less fertile under higher T fluid-absent conditions due to a lower abundance of hydrous
e-
reactant minerals. Nevertheless, as we show later, a wide variety of melt compositions may
Pr

be generated from a single source composition depending mostly on the P, T and aH2O

conditions of melting (Conrad et al., 1988; Holtz and Johannes, 1991).

n al

4.1.2. Basic (meta)igneous rocks

ur

The first detailed experiments on the anatexis of a hydrated basaltic composition

Jo

(amphibolite) were undertaken by Yoder and Tilley (1962), who noted that the addition of

H2O to basalt led to a drastic drop in the temperature of the solidus such that the onset of

melting closely corresponded with that of granite. They also noted the ‘anorthositic’ (likely

tonalitic or trondhjemitic) composition of the melts so formed. Building on this and later

studies, in particular that of Burnham (1979), many of the key experiments on the partial

melting of amphibolite, including both fluid-absent and fluid-present conditions, were

undertaken in the period from 1989 to 1995 (Beard and Lofgren, 1989, 1991; Patiño Douce

and Beard, 1995; Rapp and Watson, 1995; Rapp et al., 1991; Rushmer, 1991; Sen and Dunn,
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1994; Wolf and Wyllie, 1994, 1995; Wyllie and Wolf, 1993). The results are generally

consistent, allowing some general statements to be made regarding the appropriate variables

and phase equilibria.

Fluid-absent melting of amphibolites proceeds by incongruent reactions mainly

consuming hornblende, along with any biotite and quartz; although some plagioclase may be

consumed, in most fluid-absent experiments it is not a major reactant (Beard and Lofgren,

1989, 1991; Patiño Douce and Beard, 1995). The onset of fluid-absent partial melting is

dependent on the starting bulk composition and hornblende (i.e. structurally-bound H2O)

f
oo
content, and for a fully-saturated amphibolite at plausible crustal pressures (~0.5–1.5 GPa)

the (wet) solidus occurs at temperatures of 600–700 °C (see summary in (Wyllie and Wolf,

1993).
pr
e-
The melt produced in fluid-absent experiments ranges in composition from
Pr

granodiorite to tonalite, but most commonly is low-K metaluminous (ASI < 1) to weakly

peraluminous (ASI > 1) and trondhjemitic to tonalitic (i.e. sodic); melt volumes show a
al

broadly linear increase with temperature, and are around 40–50 vol.% at 1000 °C, with melt
n

compositions becoming increasingly sodic (higher Na2O/K2O) and magnesian, and depleted
ur

in Si and Al (Beard and Lofgren, 1989, 1991; Patiño Douce and Beard, 1995; Rapp and
Jo

Watson, 1995; Rapp et al., 1991; Rushmer, 1991; Sen and Dunn, 1994; Wolf and Wyllie,

1994, 1995; Wyllie and Wolf, 1993). The main solid products are clinopyroxene with or

without orthopyroxene at lower pressures and include garnet (with or without epidote) at

higher pressures, with plagioclase generally remaining stable to temperatures in excess of

1000 °C (López and Castro, 2001; Patiño Douce and Beard, 1995; Wyllie and Wolf, 1993);

see section 6). The lower limit of suprasolidus garnet stability, which has a shallow P/T, is

strongly dependent on bulk composition, in particular XMg, and garnet may be stable at

pressures as low as ~0.7 GPa (Johnson et al., 2017; Wyllie and Wolf, 1993).
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Importantly, the experiments predict total consumption of hornblende at temperatures

of around 1000 °C at ~1.0 GPa, but at lower temperatures at both lower and higher pressures,

and hornblende is not stable with melt at pressures much in excess of 2 GPa (Beard and

Lofgren, 1991; Burnham, 1979; Rushmer, 1991; Wyllie and Wolf, 1993). This has important

consequences for the partial melting of eclogite. Although experiments at P > or >> 2.0 GPa

predict the formation of large volumes of melt (Rapp and Watson, 1995; Rapp et al., 1991),

the starting materials used in these experiments contain ~1 vol.% H2O. As almost all of this

H2O must exist as a free fluid in natural rocks, it is likely to have been lost during burial,

f
oo
questioning the importance of high-pressure melting of eclogite in nature (see also section 8).

Partial melting of amphibolite in experiments with excess H2O produces results that
pr
differ significantly from fluid-absent experiments (Beard and Lofgren, 1989, 1991). As the
e-
H2O required for melting is already present, fluid-present melting proceeds by reactions
Pr

consuming plagioclase and any quartz along with the H2O. Although peritectic phases are

predicted in some of the experiments, melt is the major product, and hornblende is predicted
al

to remain stable in the residuum until very high temperature. Importantly, experimental H2O-
n

present melting produces melts that are generally low-K but may be strongly peraluminous
ur

(Beard and Lofgren, 1989, 1991).

Jo

4.1.3. Metasedimentary rocks

The majority of partial melting experiments on metasedimentary lithologies have used

(meta)pelitic or (meta)greywacke starting compositions, and thereby considered fluid-absent

melting by incongruent reactions consuming mica (Gao et al., 2016b; Johannes and Holtz,

1996). However, early experiments on compositions varying from greywacke to calcareous

pelite were H2O-saturated and showed that large melt volumes may be generated at near-

solidus conditions producing melts that range in composition from tonalite to granite
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(Winkler, 1957; Winkler and Von Platen, 1958, 1960; Winkler and von Platen, 1961).

Experiments by Wyart and Sabatier (1959) at low P (~0.2 GPa) and 800 °C produced

cordierite and spinel as solid (peritectic) biproducts. Importantly, these authors recognised the

fundamental role of partial melting and melt drainage in the creation of the large-scale

differentiation of the crust into granitic upper and residual granulitic lower portions (Wyart

and Sabatier, 1959).

Due to their high fertility and sensitivity to metamorphic conditions, numerous

experimental studies have been undertaken to investigate the fluid-absent partial melting of

f
oo
metapelitic compositions across a wide range of P–T–X conditions (Carrington and Harley,

1995; Gardien et al., 1995; Grant, 2004; Le Breton and Thompson, 1988; Nair and Chacko,
pr
2002; Patiño Douce and Harris, 1998; Patiño Douce and Johnston, 1991; Pickering and
e-
Johnston, 1998; Spicer et al., 2004; Stevens et al., 1997; Vielzeuf and Holloway, 1988). At
Pr

pressures above 0.4–0.5 GPa, fluid-absent melting initially occurs by reactions consuming

mainly muscovite plus quartz to produce sillimanite (or kyanite), K-feldspar, minor biotite
al

and melt, the latter with strongly peraluminous compositions that show a close
n

correspondence with Himalayan leucogranites (Le Breton and Thompson, 1988; Patiño
ur

Douce and Harris, 1998; Vielzeuf and Holloway, 1988; see section 7). At higher temperature,
Jo

or at lower pressure, major melting occurs by the fluid-absent breakdown of biotite,

aluminosilicate and quartz to produce K-feldspar, melt and cordierite at low P and/or garnet

at higher P; orthopyroxene and/or aluminous spinel generally form at higher T depending on

pressure and bulk composition, in particularly XMg and XAl (= molar Al2O3/(Al2O3 + FeO +

MgO)) (Carrington and Harley, 1995; Gardien et al., 1995; Grant, 2004; Le Breton and

Thompson, 1988; Nair and Chacko, 2002; Patiño Douce and Harris, 1998; Patiño Douce and

Johnston, 1991; Pickering and Johnston, 1998; Spicer et al., 2004; Stevens et al., 1997;

Vielzeuf and Holloway, 1988; see section 7). The melts produced are mostly peraluminous.
 Journal Pre-proof

Experimental studies on greywacke starting compositions have concentrated on

peraluminous (mostly continental-arc-derived) rather than metaluminous (mostly oceanic-

arc-derived) variants. Conrad et al. (1988) undertook H2O-saturated and -undersaturated

experiments at 1.0 GPa on a peraluminous greywacke and compared these with those on a

metaluminous dacite, both from the Taupo Volcanic Zone in New Zealand. Fluid-absent

melting of the greywacke consumed biotite, quartz and plagioclase to produce melt with

gedrite (orthoamphibole), garnet and/or orthopyroxene depending on temperature. Fluid-

present melting of the same composition preceded mostly through consumption of H2O,

f
oo
plagioclase and quartz. Experiments investigating the fluid-absent melting of greywacke over

a wide range of temperatures and pressures up to 2 GPa showed that reactions preceded by
pr
breakdown of biotite, plagioclase and quartz to produce mainly orthopyroxene with or
e-
without cordierite, spinel or garnet depending on composition (in particular XMg) and pressure
Pr

(Montel and Vielzeuf, 1997; Patiño Douce and Beard, 1996; Vielzeuf and Montel, 1994; see

section 7). Melt compositions evolved to lower K2O/Na2O and higher FeO + MgO + TiO2
al

contents with increasing P and lower ASI with increasing T (Montel and Vielzeuf, 1997;
n

Patiño Douce and Beard, 1996).

ur
Jo

4.2. Melting in unary (C = 1) and binary (C = 2) systems

At any given pressure in a one-component system, the reaction by which a pure solid

may melt (i.e. break down) to produce a liquid of the same composition is univariant (C = 1,

P = 2) and occurs at a fixed temperature known as the melting point. For example, at

atmospheric pressure (P = 0.1 MPa or 1 bar), solid H2O starts to breaks down (react) to liquid

H2O at 0 C, the melting point of ice. Adding heat drives the melting reaction, but the two-

component system (ice + water) remains at 0 C until all of the ice has been consumed (C =
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1), after which temperature may rise. However, in multicomponent systems, such as rocks,

the transformation of the system from 100% solid to 100% liquid occurs over a range of

temperatures, the melting interval. The melting interval extends from the temperature at

which melt first forms, termed the solidus, to the temperature at which the system is entirely

molten, called the liquidus.

These different features are illustrated with reference to Fig. 7a, which shows phase

relations in a simple fictive binary system (C = 2) at fixed pressure. This is an example of a

T–X phase diagram, in which temperature increases vertically upwards and composition (X)

f
oo
changes along the horizontal axis between two end-member compositions, in this case A and

B. Melting relations for the pure phase A in the one-component system (C = 1 and X = A) are
pr
shown along the left-hand-edge of Fig. 7a. For example, at temperature TSS the system is
e-
entirely solid and consists of the pure phase A. On heating, T increases until the melting point
Pr

of A is reached (MPA), where the addition of heat leads to the breakdown of solid phase A to

a liquid with composition A by the univariant reaction A → Liq, which occurs at fixed T until
al

all solid A is consumed. A similar behaviour is shown for the one-component system with the
n

bulk composition B, although the melting point of B (MPB) is at higher T.

ur

Now consider an intermediate bulk composition, X1, in the two-component system A–

Jo

B. At temperature TSS, the system consists of two solid phases, A and B, whose proportions

are given by the lever rule. The proportion of A is the distance between X1 and B (= a0)

divided by the distance between A and B (AB), and the proportion of B is bo/AB, so the

subsolidus assemblage consists of 60% A and 40% B. With an increase in heat, temperature

rises and the assemblage and proportion of A and B remain the same until the solidus is

encountered at temperature TS. At this point, melt with a composition half way between A

and B (XE) begins to form at the eutectic point, EP, by the univariant reaction:
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A + B → Liquid (10)

This first-formed melt is known as the eutectic melt or minimum melt. In reaction 10, the

solid reactants (A + B) form a melt of the same composition (AB), and the reaction is said to

be congruent. This reaction continues at fixed temperature, TE (meaning it is a discontinuous

reaction), until all B is consumed, at which point the assemblage consists of 20% A and 80%

melt ((a1/(a1 + l1) and l1/(a1 + l1), respectively) and temperature may rise again within the

field A + Liq. As temperature rises, the proportion of A decreases, and of melt increases by

f
oo
the divariant congruent reaction A → Liq, until all A is consumed at the liquidus at

temperature TL. As this reaction occurs over a range of temperatures, it is said to be a

pr
continuous reaction. In almost all cases, rocks melt via continuous (F > 1) reactions.
e-
For any intermediate bulk compositions more enriched in B than the composition of
Pr

XE (i.e. to the right of XE), for example X2, reaction 10 consumes all A, and melting continues

by the reaction B → Liq until the liquidus is reached. Although all intermediate compositions
al

begin to melt at the same temperature, that of the eutectic point, the temperature of the
n

liquidus, and consequently the melting interval, are a function of composition. For the unique
ur

bulk composition XE, the solidus and liquidus coincide.

Jo

Now consider a two-component system that includes an intermediate phase, AB (Fig.

7b). In Fig. 7b, the three phases, A, AB and B, each melt congruently, but at different melting

points (MPAB > MPA > MPB). The solidus and eutectic point (LE1) for intermediate

compositions in the subsystem A–AB (TE1) are at higher T than those in the subsystem AB–B

(TE2). Otherwise, this T–X diagram can be considered as two modified versions of Fig. 7a

joined together.

Another binary phase diagram with an intermediate phase AB is shown in Fig. 7c.

However, rather than melting congruently to a liquid of the composition of AB at fixed T, as

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in Fig. 7b, the pure solid with composition AB (X1) melts over a temperature interval. As it

heats up it reaches the solidus at TS1 and begins to melt via the univariant reaction:

AB → A + Liquid, (11)

remaining at temperature TS1 until all AB is consumed. Temperature then rises and melt

forms by the congruent continuous reaction A → Liquid until the liquidus is reached. A

melting reaction such as reaction 11, by which a solid phase (or phases; here just AB) breaks

f
oo
down to form melt plus a different solid (or solids; here just A) is an example of incongruent

melting. The composition of the melt (here XP) formed by the incongruent reaction is
pr
governed by the location of the peritectic point, P, and the solid phase that is produced with
e-
the melt (here A) is called a peritectic mineral.
Pr

Examination of Fig. 7c shows that all intermediate bulk compositions to the left of XP

undergo incongruent melting. For those to the left of AB, for example X2, the subsolidus
al

assemblage A + AB first melts by reaction 10 at TS1, then by the reaction A → Liquid. For
n

those intermediate compositions between X1 and XP, for example X3, a subsolidus assemblage
ur

of AB + B melts first by the congruent discontinuous reaction AB + B → Liquid at TS2, then

Jo

by reaction 11, then by the reaction A → Liquid until the liquidus is reached. Bulk

compositions more enriched in B than XP only undergo congruent melting.

For the interested reader, phase equilibria in simple (binary, ternary and quaternary)

melt-bearing systems are described elegantly and in detail by Cox et al. (1979). Although

these are described mostly from the perspective of igneous petrology (i.e. heat out driving

crystallisation), those describing equilibrium crystallisation are the inverse of equilibrium

melting described above.

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4.3. Types of phase diagram

4.3.1. Compatibility diagrams and petrogenetic grids

We have already discussed a simple P–T phase diagram in the unary system Al2SiO5

(Fig. 6). This diagram shows three univariant (discontinuous) reactions emanating from an

invariant point––otherwise called a reaction bundle––for the aluminosilicate minerals. More

complex diagrams in larger chemical systems, known as petrogenetic grids, involve multiple

invariant points and reaction bundles, the latter of which are sometimes termed

f
oo
Schreinemakers’ bundles after the Dutch physical chemist Franciscus Schreinemakers, who

developed the rules governing their geometry (Schreinemakers, 1915; Zen, 1966).
pr
We illustrate the logic behind deciphering reactions and the graphical construction of
e-
reaction bundles and petrogenetic grids in P–T space using a simple example in the four-
Pr

component KASH (K2O–Al2O3–SiO2–H2O) subsystem (Fig. 8). Figure 8a is a ternary

compatibility diagram showing the compositions of the phases muscovite, K-feldspar,

al

sillimanite, melt (L) and H2O projected from quartz (the SiO2 apex). Projecting from quartz
n

allows us to easily establish graphically (i.e. on a piece of paper or a screen) what the
ur

univariant reactions are, but only those involving quartz––in other words, quartz is
Jo

considered to be in excess. Note that in this simple example, the only solid solution phase is

melt, which can contain variable quantities of H2O (it lies on a straight line whose extension

intersects the H2O apex).

In this four-component system, and considering six phases, the phase rule tells us

there is only one invariant equilibrium where all phases coexist at a single P–T point. Each

univariant reaction line stemming from the invariant point involves five phases, meaning

there are six reactions in total, each one excluding one of the six phases. Considering quartz
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to be in excess leaves five univariant reactions, which by convention are labelled with the

absent phase in square brackets.

We first consider the reaction that excludes melt, i.e. [L]. With quartz in excess and

excluding melt, the compatibility diagram for the remaining phases (inset to Fig. 8b) has

muscovite at its centre and K-feldspar, sillimanite and H2O at each apex. As muscovite is

located entirely within the area bounded by the other three phases, we deduce the reaction to

be: Ms → Sil + Kfs + H2O. Petrographic observations (and alternative graphical projections)

show that quartz is consumed along with muscovite, such that the full subsolidus dehydration

f
oo
reaction is:

pr
Ms (+ Qz) → Sil + Kfs + H2O [L]. (12)
e-
Pr

This is a terminal reaction in KASH, at temperatures above which muscovite is no longer

stable (in quartz-bearing rocks). The Clapeyron equation discussed earlier predicts that
al

reaction 12 has a positive slope with H2O on the high-T side. Figure 8b shows reaction 12
n

plotted (qualitatively) in P–T space extending from lower to higher T. However, common
ur

sense tells us that, as we increase temperature (and P) along this univariant line, at some
Jo

point the assemblage will begin to melt. With the addition of melt (L), the assemblage

becomes invariant (and [L] terminates at the invariant point IP in Fig. 8b). We may draw

reaction 12 continuing through IP to higher T but, as H2O is no longer stable with respect to

melt, it is termed the metastable extension of this reaction (and is dashed). With one reaction

plotted, we complete the reaction bundle simply by following Schreinemakers’ metastable

rule: “The metastable extension of the [phase-absent] reaction must fall in the sector in

which that phase is stable in all possible assemblages” (Spear, 1995).

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Next consider the H2O-absent reaction [H2O]. With quartz in excess and excluding

H2O, muscovite is located within the triangle joining sillimanite, K-feldspar and melt, and the

full reaction is:

Ms (+ Qz) → Sil + Kfs + L [H2O]. (13)

The Clapeyron equation predicts that this fluid-absent incongruent melting reaction has a

positive slope with melt on the high-T side, and must also must emanate from IP. However,

f
oo
Schreinemakers’ rule tells us that the metastable extension of reaction 12 ([L]) must be on the

same side as melt in reaction 13 [H2O], and that the metastable extension of reaction 13 must
pr
be on the same side of the line as H2O in reaction 12, giving us the topology shown in Fig.
e-
8c.
Pr

Following the same logic allows us to deduce the muscovite-absent and sillimanite-

absent reactions to be:

n al

Sil + Kfs + H2O (+ Qz) → L [Ms] and (14)

ur

Ms + Kfs + H2O (+ Qz) → L [Sil], (15)

Jo

respectively. These fluid-present congruent melting reactions lie on the low-P (Fig. 8d) and

high-P (Fig. 8e) sides of the metastable extensions of reactions 12 and 13, respectively, and

together define the H2O-saturated (‘wet’) solidus. Again, with quartz in excess these are

terminal (albeit in the retrograde sense) reactions as, by definition, melt cannot be stable at

temperatures below the solidus. Melt, as the sole product, lies on the high-T (and high S) side

of reactions 14 and 15, but with H2O as a reactant, these equilibria are associated with a

negative volume change, and consequently have a steep negative P/T. Importantly, as the
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solubility of H2O in melt is positively correlated with P (Hamilton et al., 1964; Holtz et al.,

2001), the slope of the H2O-saturated solidus becomes shallower with decreasing pressure.

The final reaction is that excluding K-feldspar (Fig. 8f). In the compatibility diagram,

rather than forming a triangle surrounding one phase, the four phases participating in the

reaction define a quadrilateral with muscovite and H2O defining one pair of opposing

corners, and sillimanite and melt the other. The crossed tie-lines from each pair of corners

define the reaction:

f
oo
Ms + H2O (+ Qz) → Sil + L [Kfs]. (16)

pr
This reaction is not a terminal reaction, as either muscovite or H2O can be consumed
e-
depending on their relative abundance, which is a function of the bulk composition. A
Pr

petrogenetic grid in the enlarged KFMASH system appropriate to metapelitic rocks is shown

and discussed in section 7.

al

It is important to note that petrogenetic grids show all of the possible univariant
n

reactions a system might encounter (or ‘see’), projected into the pressure–temperature plane
ur

of interest, hence their alternative name of P–T projections. However, specific bulk
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compositions may see only a portion of any reaction, or none of it. In addition, petrogenetic

grids require that the system includes only a relatively small number of components such that

univariant equilibria can be calculated. Although this is possible for metapelites via the

simplified KFMASH system (Carrington and Harley, 1995; Grant, 1985; Thompson, 1982;

White et al., 2001, 2014a), based on the pioneering work of J. B. Thompson (Thompson Jr,

1957), equilibria governing the partial melting of metabasic rocks in plausible chemical

systems (e.g. NCFMASH) are of higher variance and this approach is unsuitable. Thus, while

petrogenetic grids are extremely useful, for example in illustrating qualitatively which phases
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might appear or disappear during melting along a specified P–T trajectory, and are key to

understanding the underlying topology of phase diagrams, they generally do not provide

useful quantitative constraints on the behaviour of natural rocks during anatexis (White et al.,

2007).

4.3.2. P–T–X pseudosections

Within the context of petrology, the term pseudosection owes its origin to Roger

Powell (Powell, 1978) to describe equilibrium phase diagrams depicting stable multivariant

f
oo
assemblage fields for specified bulk rock compositions (Powell et al., 1998), although such

diagrams were in use in the early 1970s (Hensen, 1971). Pseudosections are two-dimensional
pr
(Cartesian) diagrams mostly constructed in P–T–X space, such that the three main types are
e-
P–T, T–X and P–X pseudosections. Although others prefer the terms phase-diagram sections
Pr

(Connolly and Petrini, 2002; Tinkham and Ghent, 2005a), equilibrium assemblage diagrams

(Capitani and Petrakakis, 2010) or, in the case of P–T pseudosections, isochemical phase
al

diagrams, the ‘pseudo’ prefix is intended to indicate that the compositions of the phases
n

predicted to be stable generally do not plot within the compositional plane of interest (i.e.
ur

‘pseudo’ as in ‘almost’ or ‘similar to’ rather than ‘false’ or ‘spurious’). Notwithstanding, over
Jo

the past few decades calculated pseudosections have become the tool of choice in providing

quantitative constraints on the (evolving) P–T (and other) conditions during metamorphism

and partial melting. Much of what follows in this review regarding the behaviour of crustal

rocks during anatexis is illustrated with reference to pseudosections.

The most commonly used diagrams are P–T pseudosections that are constructed for a

fixed bulk composition (X), where the bulk composition most commonly was measured via

XRF analysis of a whole-rock powder or estimated based on the abundance (through image

analysis) and composition (through electron probe microanalysis (EPMA)) of the constituent
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minerals. P–T pseudosections are essentially maps showing the equilibrium assemblages that

are predicted to be stable for a specified rock composition in a P–T window of interest. An

example is shown in Fig. 9a, a P–T pseudosection drawn for a synthetic composition in the

six-component NKFMASH system (the compositions used to calculate this and all other

pseudosections in subsequent figures in terms of mol.% oxides normalised to 100% are

provided in Table 1), as used in the discussion of the experiments of Taylor et al. (2015b),

and calculated for the P–T range from 0.5 and 1.5 GPa, and from 750 to 1200 C.

f
The logic behind these diagrams and reading them is straightforward. The diagram is

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clearly subdivided by the depth of colour into different assemblage fields, which are labelled

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with the stable phases, and are adjacent to fields that are either paler or darker in shade. By

convention, the depth of shading of the assemblage fields reflects increasing variance (F).
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Crossing into a paler field requires the production of a new phase (decreasing variance by 1),
Pr

whereas moving into a darker field indicates that a phase is consumed (increasing variance by

1). For example, for the experimental composition used, at 750 C and 1.0 GPa (point A in
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Fig. 9a) the equilibrium assemblage should be kyanite–garnet–biotite–alkali feldspar–quartz–

n

liquid, a trivariant (F = 3) assemblage in the modelled system. Heating at fixed P thereafter

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first predicts the consumption of kyanite at ~755 C, associated with moving into the darker
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quadrivariant (F = 4) field containing garnet–biotite–alkali feldspar–quartz–liquid. Further

heating leads to the appearance of orthopyroxene then the consumption of biotite over a

narrow temperature interval (~3 C) at ~810 C across the paler narrow trivariant field

containing garnet–orthopyroxene–biotite–alkali feldspar–quartz–liquid. With further heating,

first orthopyroxene then quartz is consumed until at 1000 C, 1.0 GPa (point B in Fig. 9a) the

composition should contain just garnet and melt (F = 7). Isothermal decompression from

point B predicts the reappearance of orthopyroxene then spinel, and then exhaustion of garnet

at 0.65 GPa.
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Inspection of Fig. 9a shows that many of the lines bounding the assemblage fields

meet at points, from which exactly four lines emanate. The reason for this is self-evident

when examining phase relations within the dashed black box in Fig. 9a (see inset). This

region essentially comprises the intersection between two lines across which a mineral

disappears––one with a steep positive P/T that, when crossing to higher T, leads to the

disappearance of alkali feldspar, and the other with a shallower negative P/T that, on

crossing to higher P, leads to the disappearance of orthopyroxene. Thus, there is a pale low-

f
variance field (F = 5; Grt–Opx–Fsp–L) that is bounded by two F = 6 fields, one lacking alkali

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feldspar and another lacking orthopyroxene, and which lies opposite an F = 7 field that lacks

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both minerals. With the exception of univariant lines, this logic holds for all pseudosections–

–i.e. at an intersection, the lowest-variance field with variance n is bounded on either side by
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fields of variance n + 1 and lies opposite a field of variance n + 2.
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In addition to the assemblage field boundaries, which correspond to the conditions at

which the abundance (‘mode’) of a phase becomes zero, pseudosections can also be
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contoured for the mode and composition of phases, termed mode isopleths (or isomodes) and
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compositional isopleths, respectively. As an example, the mode isopleths for biotite at 6, 4,

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and 2 mol.% are shown (dotted red lines in Fig. 9a; note that THERMOCALC, which was used
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to calculate Fig. 9, outputs the abundance of phases as mol.% based on one-oxide molar

proportions such that they approximate vol.%). These provide additional and useful

information, in particular in illustrating the rate of change (consumption or growth) of a

phase within the P–T window of interest. For example, at point A, a little more than 6 vol.%

biotite is predicted in the modelled composition. Heating thereafter causes biotite to be

consumed (i.e. biotite is a reactant) at a more-or-less steady rate until, as the path intersects

the narrow trivariant field in which orthopyroxene appears, there is a little more than 2 vol.%

remaining. Thus, over a temperature interval of ~60 C (750 to 810 C), ~4 vol.% biotite has
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been consumed at a rate of 1 vol.% every ~15 C. However, the trivariant field containing

coexisting biotite and orthopyroxene is very narrow, and the remaining 2 vol.% biotite is all

consumed over ~3 C, representing a reaction rate (here taken to mean the rate of change of

the abundance (mode) of a reactant or product as a function of changing T and/or P) an order

of magnitude or so faster.

This illustrates an important point, that most of the (re)action in pseudosections

occurs within the lowest-variance fields, as shown by the closely-spaced mode isopleths of

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biotite in the divariant (F = 2) field in the bottom left corner where the assemblage

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cordierite–garnet–orthopyroxene–biotite–alkali feldspar–quartz–liquid is stable. Across this

field >6 vol.% biotite is consumed (with quartz) over ~3 C by a fluid-absent incongruent
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hydrate-breakdown reaction producing mostly melt and peritectic orthopyroxene.
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In an ideal world, Fig. 9a should replicate the assemblages that the experimentalist
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might expect at any P–T of interest. For example, to examine Fe–Mg exchange between

garnet, orthopyroxene and melt without the complication of the presence of any other solid
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phases, the experimentalist should be able to do so by performing an experiment at 0.7 GPa

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and 950 C (the star in Fig. 9a). However, in constructing the pseudosection, some of the
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end-member thermodynamic data or a–X models (or solution models) describing the
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energetics of mixing in the solid solution minerals may be poorly constrained, perhaps due to

a lack of suitable experiments that underpin these models. In addition, it is almost inevitable

that experimental charges will undergo some oxidation (converting some FeO to Fe2O3), and

possible or even likely that some minerals will have difficulty nucleating or dissolving over

the timescale of an experiment, such that equilibrium in may not be attained in part or all of

the experimental charge (for more details see White et al., 2011).

Now let us assume that the experimental petrologist wishes to know whether it is

possible to grow cordierite but no garnet in an experiment at 0.9 GPa (the dashed white line
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in Fig. 9a) simply by adjusting the XMg (molar MgO/(MgO + FeO)) of the original

composition (in which XMg = 4.54/10.05 = 0.45). To address this problem, the experimentalist

can construct a T–X pseudosection at a fixed pressure of 0.9 GPa between two end-member

compositions in which XMg ranges, for example, from 0.1 to 0.9 by adjusting the FeO and

MgO contents accordingly (to 9.04 mol.% FeO and 1.01 mol.% MgO and 1.01 mol.% FeO

and 9.04 mol.% MgO, respectively). The result is shown in Fig. 9b, an isobaric T–X

pseudosection that can be read exactly as described earlier, but in which T increases upwards

in the y-direction and bulk composition (X in terms of XMg) varies in the x-direction. The

f
oo
vertical dashed white line in Fig. 9b represents the original composition used (Fig. 9a), such

that the phase equilibria calculated from left to right along the white dashed line in Fig. 9a are
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identical to those calculated from bottom to top along the equivalent line in Fig. 9b.
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Inspection of Fig. 9b indicates that cordierite is stable only in compositions with XMg
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greater than ~0.7 and at temperatures between ~800 and 950 C (in the region bounded by the

thick black line). Only in compositions with XMg greater than 0.83 (to the right of the dashed
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thick black line) is cordierite but no garnet predicted. Thus, the experimentalist might run a
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charge on a composition with, for example, XMg = 0.9 at 920 C and 0.9 GPa (the white star
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in Fig. 9b).
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Hopefully, the logic behind constructing a P–X pseudosection (not shown) for

variable XMg at fixed T, for example, should be clear. For this example, with XMg = 0.45, the

resulting phase equilibria correspond to a vertical line at the appropriate T in Fig. 9a.

4.3.3. Other phase diagrams

Although most calculated reactions, grids and pseudosections in the petrological

literature are P–T or T–X and P–X diagrams, other diagrams can be used to investigate

multiple compositional parameters at a fixed P–T condition (e.g. X–X diagrams; (Riesco et
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al., 2005; White et al., 2003). Furthermore, other thermodynamic variables might be chosen

as the axes of choice, for example volume, entropy or activity (Powell et al., 2005). Although

such diagrams are generally less intuitive, they can be used to illustrate critically important

processes, including adiabatic or isentropic (constant S) melting of upwelling mantle

(Asimow et al., 1997; Iwamori et al., 1995; McKenzie and Bickle, 1988), and thermal

buffering of the crust due to strongly-endothermic partial melting reactions (Bea, 2012;

Schorn et al., 2018; Stüwe, 1995). Diagrams using chemical potential () as one or both axes

f
are particularly useful in understanding the spatial organisation of minerals in reaction

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textures, such as partial pseudomorphs, coronae and/or symplectites, which are particularly

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common in formerly melt-bearing granulites, including UHT rocks (Doukkari et al., 2018;

Gallien et al., 2012; Mictchell et al., 2020; Powell et al., 2019; White and Powell, 2011;
e-
White et al., 2008). However, the assumptions and simplifications required in their
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construction mean that chemical potential diagrams are of limited use in providing

quantitative constraints on the processes of partial melting.

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Of particular use in modelling partial melting are plots of molar proportion versus
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temperature or pressure (Yakymchuk and Brown, 2014b), or along specified thermobaric

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ratios (Johnson et al., 2017), now colloquially called ‘modebox’ diagrams (Holland et al.,
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2013). They are important in visualising how the abundance (mode) of phases with a system

(or rock) are expected to evolve during melting along a specified path (Johnson et al., 2008;

Yakymchuk et al., 2017). An example is given in Fig. 9c, which shows the changing

abundances of phases predicted along the isobaric (1.0 GPa) path from 750 to 1000 C (point

A to point B) on Fig. 9a. Along this path, the proportion of melt increases from ~0.3 to ~0.8

(30 to 80 vol.%), largely by the breakdown of biotite, quartz and alkali feldspar. A small

amount of peritectic orthopyroxene is produced by biotite breakdown, then consumed at

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higher T. The abundance of garnet changes little with increasing T, indicating that garnet is

neither a major reactant nor product of melting along the chosen heating path.

4.4. Calculating phase diagrams

Having outlined the thermodynamic basis of phase equilibria, and the types of phase

diagrams most commonly drawn to constrain the conditions and processes of partial melting,

in particular pseudosections, we now outline the requirements and practicalities behind their

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oo
calculation. Clearly, solving the equilibrium relationship (equation 6) is key, which requires

end-member thermodynamic data, a–X models describing the energetics of mixing in solid-

solution phases and appropriate software.

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e-
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4.4.1. End-member data

Values for the thermodynamic properties of end members (to satisfy the left-hand-
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side of equation 5) that describe most of the common rock-forming minerals, and more
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recently fluid, melt and aqueous species, have existed for more than four decades (Berman,
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1988; Ghiorso and Sack, 1995; Gottschalk, 1996; Helgeson et al., 1978; Holland and Powell,
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1985, 1990, 1998a, 2011; Miron et al., 2016; Naumov et al., 1974; Saxena et al., 2012). The

data sets most widely used currently, at least in the metamorphic community, are those of

Holland and Powell (1998a) and Holland and Powell (2011). These data sets represent a

collation of a large body of thermodynamic data including experimentally-determined phase

equilibria in simple and more complex chemical systems, calorimetric measurements on pure

end members and, increasingly, natural data from coexisting phases in rocks inferred to have

attained equilibrium. Importantly, the absolute values and uncertainties on the various

thermodynamic properties, which include the standard enthalpy of formation (ΔfH), entropy
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(S), heat capacity (CP), and volume (V) as a function of temperature and pressure (the

coefficients of thermal expansion, and compressibility, ) are optimised to provide the best

statistical fit to the disparate sources of data, such that the full data set provides an internally

consistent thermodynamic framework for calculations. The different approaches used in the

derivation of the internally consistent data are summarised by Gottschalk (1996).

4.4.2. Activity–composition (solution) models

f
The energies associated with mixing between end members in variably complex solid

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solution phases (to satisfy the right-hand-side of equation 5) are themselves complex.

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Whereas some data are relatively well-constrained experimentally, for example the

interaction energies (Ws) relating to Fe2+–Mg substitution in minerals such as olivine,

e-
clinopyroxene, garnet and biotite (Bhattacharya et al., 1992; Ellis and Green, 1979; O'Neill
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and Wood, 1979; von Seckendorff and O'Neill, 1993), in many other cases there is little or no

data, and the associated energetics of mixing must be estimated. This is achieved largely
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using a heuristic approach–– we fix those things for which data exist and/or we understand
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well, then make educated guesses to fit those parameters for which there is little or no data
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and/or that we do not understand well (Powell et al., 2014).

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For example, based on existing experimental data on specific ferromagnesian

minerals, we may be able to make some general assumptions regarding the energetics of

mixing between Fe2+ and Mg in all ferromagnesian minerals, and solve for other

compositional variables. In essence, adjusting the interaction energies (Ws) within limits that

we think are sensible is a means of ‘tweaking’ or ‘tuning’ the a–X models such that they

behave as we think they should. For instance, many decades of experience tells us the order

of appearance of new minerals we might expect in a sequence of pelitic rocks undergoing

progressive prograde regional metamorphism (Barrow, 1893; Read, 1952), and the relative
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XMg (Mg/(Mg + Fe2+)) of coexisting ferromagnesian minerals (Droop and Harte, 1995; Harte

and Hudson, 1979). If the sequence of isograds or composition of coexisting phases predicted

by calculations using the relevant a–X models is inconsistent with these observations, one or

more may need to be adjusted (Cesare et al., 2003; Johnson et al., 2003a; Pattison et al.,

2002). The a–X models, also known as solution models, are many and varied in their

applicability and complexity (see for example:

http://www.perplex.ethz.ch/perplex/datafiles/solution_model.dat), and many different models

may exist for particular minerals, such as garnet.

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4.4.3. Software
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Several software programs exist for calculating phase equilibria to address
e-
petrological problems (Asimow and Ghiorso, 1998; Connolly, 1990, 2005; de Capitani and
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Petrakakis, 2010; Ghiorso et al., 2002; Gualda et al., 2019; Powell et al., 1998; Powell and

Holland, 1988; Spear and Menard, 1989). Increasingly, applications are being developed that
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automate or refine particular aspects of the process, such that calculating phase diagrams is
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becoming ever more ‘user friendly’ (Duesterhoeft and de Capitani, 2013; Mayne et al.,
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2020b; Pearce et al., 2015; Xiang, 2020; Xiang and Connolly, 2021). Here we briefly review
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the three computer programs (or rather families of programs) most commonly used to

calculate subsolidus and suprasolidus phase equilibria in metamorphic studies, viz.

THERMOCALC (Powell and Holland, 1988), Perple_X (Connolly, 1990, 2005) and THERIAK-

DOMINO (de Capitani and Petrakakis, 2010). By metamorphic studies we mean scenarios

mostly involving the addition of heat to solid-dominated systems, of which partial melting is

the most important. We do not discuss the MELTS family of software, which is mainly

designed to investigate crystallising and fractionating melts and magmas (liquid-dominated

systems), representing systems from which heat is being removed, and which might be
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considered closer to the realm of igneous studies if such classifications are useful (Asimow

and Ghiorso, 1998; Ghiorso et al., 2002; Ghiorso and Sack, 1995; Gualda et al., 2019).

Each of the three main software packages discussed here has benefits and limitations

that may/will change as the user gains experience and/or based on the problem being

addressed. In constructing pseudosections, Perple_X and THERIAK-DOMINO adopt a

method of Gibbs energy minimisation and are (at least superficially) rather easy to use. In

essence, the user selects the end member thermodynamic dataset to use, provides the bulk

composition or bulk compositional range in terms of the components (usually major oxides)

f
oo
of interest, defines the P–T window of interest, and selects the solution models for all the

phases they think might be stable within that window. The software then calculates the
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Gibbs’ free energy for all possible combinations of the chosen phases at regular spacings
e-
within the P–T window of interest (i.e. on a grid), for which the combination with the lowest
Pr

Gibbs energy is taken to be the equilibrium assemblage. After some time, which may be

seconds or many days depending on the complexity of the calculation, a pseudosection is (or
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can be) plotted automatically using the output data. Provided the user has correctly included
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solution models for all of the appropriate phases, the output diagram should correspond to the
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stable (lowest G) configuration.

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THERMOCALC uses a different approach to calculate phase diagrams involving solid

solutions, which involves solving sets of non‐linear equations. In the construction of

pseudosections, using a bulk composition or bulk compositional range specified by the user,

THERMOCALC reads the end-member thermodynamic data and solution models to solve

statements of equality of chemical potential (i.e. equilibrium) among the end-members of a

specific combination of phases (assemblage) that the user thinks might be stable. If it is able

to find solutions, it outputs the equilibrium compositions and abundance of those phases at

the user-specified (generally P–T–X) conditions. However, the chosen combination of phases
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need not be the most stable (lowest G) assemblage. Consequently, the user should have some

confidence that they are calculating a stable rather than metastable equilibrium based on

experience or on examination of a phase diagram for a similar bulk composition under

similar P–T–X conditions. In THERMOCALC, pseudosections are built up manually, line by

line and point by point, following the logical rules set out earlier in this section.

Results calculated using any one of these programs are no better or worse that those

generated using the others––for a given database of end-member thermodynamic data,

solution models and user-defined P–T–X constraints, they should produce identical phase

f
oo
diagrams. However, there are pros and cons, and perils and pitfalls, pertaining to the usability

and functionality of each. As stated previously, Perple_X and THERIAK-DOMINO are very
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easy to run, and a user with almost no experience can generate a pseudosection with minimal
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effort. However, both programs have a large library of solution models available, meaning it
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is easy for users with less experience to pick inappropriate or incompatible models for one or

more phases, such that the resulting diagrams, whilst appearing perfectly reasonable, might
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have little bearing on the problem at hand (see Gervais and Trapy, 2021) for a comparison of
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different end-member data and a–X models). However, once a diagram is calculated,
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Perple_X and THERIAK-DOMINO have far more flexibility, for example in easily
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extracting other data related to the chosen system or its component phases, such as V, S, a,

density (), and P- and S-wave velocities.

A limitation of THERMOCALC is that it only works with those solution models that

were calibrated specifically against one or more of the Holland and Powell end-member

thermodynamic databases (Holland and Powell, 1990, 2011), now collectively termed ‘HPx-

eos’ (Green et al., 2016; Holland et al., 2018; White et al., 2014a, b). It is more difficult to get

started on phase diagram calculations using THERMOCALC, but doing so arguably leads to a

deeper understanding of phase equilibria than other programs as the diagrams have to be
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constructed from scratch. In terms of functionality, it is more difficult to extract other useful

data from the THERMOCALC output, although a great deal of progress has been made recently

and is ongoing.

Ultimately, the fundamentally different way in which THERMOCALC solves the

equilibrium relationship coupled with advances in the complexity of solution models and

expansion of the compositional systems that can be modelled mean it will probably outlast its

Gibbs energy minimiser competitors. To quote (or paraphrase) Jamie Connolly (ETH Zürich)

in response to a user who wished to undertake calculations using the complex new solution

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models of Holland et al. (2018): “…Perple_X has been teetering on the edge of dimensional

oblivion for a decade… the root(s) of the problem are polymorphic solutions, such as the
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pyroxenes and amphiboles… if worse comes to worst and it turns out that it is too
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(computationally) costly to resolve the composition space of solutions such as the Green et
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al. (2016) amphibole model, then Perple_X will not be robust (its only virtue) and in that

case one might as well rely on expertise-based, non-linear, optimization which is both faster
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and more precise” (see: https://groups.io/g/PerpleX/message/2201).

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4.5. Getting started – perils and pitfalls

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We end this section by discussing some of practicalities that should be considered

before embarking on the construction of a pseudosection for a natural sample about which

little is known, along with some of the assumptions and limitations involved. While many of

these should be self-evident, it is worthwhile to clarify them.

4.5.1. Sample selection and petrographic characterisation

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A first-order consideration is the question of which sample(s) to model. The first

assumption is that the sample under consideration has attained equilibrium on some scale.

Having identified an equilibration volume, which may be an entire hand-specimen and/or thin

section, and assuming the purpose is to constrain peak P–T conditions or the P–T path, it is

almost always preferable to attempt to identify samples with the lowest variance assemblage

(i.e. those containing the most minerals), as these generally occupy smaller (more tightly

constrained) assemblage fields than higher variance assemblages (see Fig. 9a, b and later

sections). In many cases, low-variance assemblages occur in rocks containing one or more

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conspicuous porphyroblasts. At a particular location (outcrop) and for a particular generalised

protolith (e.g. metabasite or metapelite), changes in variance reflect variations in bulk

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composition, which can be subtle such that porphyroblasts may only occur rarely in some
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layers. Where possible, it is best to collect several samples covering a range in bulk
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compositions from any locality, as P–T conditions will generally be more tightly constrained

using the intersection of several calculated assemblage fields.

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Once suitable samples have been collected, the next logical step is to make thin
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sections and examine these under the petrological microscope or via other imaging
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techniques, for example those that are commonly available on a scanning electron
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microscope (SEM). Petrographic study of the samples serves multiple purposes, including: (i)

assessing the degree of alteration (it is more difficult to accurately estimate the original

(high–T) concentrations of volatile phases in moderately- to heavily-altered samples, and

minerals present at or near the metamorphic peak may have been replaced); (ii) determining

whether one or more minerals shows significant compositional variation (zoning), which

leads to complexities in estimating an appropriate bulk composition for phase equilibrium

modelling and in constraining mineral compositions at the metamorphic peak; (iii)

categorising any inclusions within high-T minerals, identify the peak metamorphic
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assemblage and document any high-T reaction microstructures, which may constrain the

prograde, peak and high-T retrograde path, respectively; and, (iv) identifying dateable

accessory or rock-forming minerals and their microstructural context that, along with analysis

of minerals separates, might provide temporal constraints on the metamorphic evolution of

the sample.

4.5.2. Bulk composition, including ferric iron and H2O

Once those samples to be modelled have been selected, their bulk major oxide

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compositions need to be determined. If the intention is to quantitatively constrain P–T (and

other) conditions, the modelled bulk compositions should be in the largest system available
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(currently MnO–Na2O–CaO–K2O–FeO– MgO–Al2O3–SiO2–H2O–TiO2–O
e-
(MnNCFMASHTO) for pelite/greywacke/granite compositions, and including Cr2O3 for
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(ultra)basic compositions) such that it most closely approximates natural rock compositions.

Bulk compositions are most commonly measured using X-ray fluorescence (XRF),
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but may also be determined by dissolution inductively-coupled mass spectrometry (ICP–MS).

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In such cases, the (normally sawn) portion of the sampled rock to be analysed should be free
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of weathered portions and in most cases as compositionally homogeneous as possible.

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Increasingly, metamorphic P–T(–t) studies use the composition of the constituent minerals

(measured by EPMA or through energy-dispersive spectroscopy (EDS) on an SEM) and their

modal abundance (estimated using image analysis or SEM/EPMA mapping, including

automated mineral liberation analysis) within polished thin sections to calculate a

composition (Clarke et al., 2001; Godet et al., 2020a, b; Johnson et al., 2004; Lanari et al.,

2013; Lasalle and Indares, 2014; Mitchell et al., 2019; Tinkham and Ghent, 2005b).

However, where minerals are zoned, it may be necessary to ‘remove’ core compositions from

the bulk composition to be modelled to account for those portions of the rock considered not
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to be in communication (equilibrium) with the matrix (Evans, 2004; Marmo et al., 2002;

Tinkham and Ghent, 2005a; Vance and Mahar, 1998; Zuluaga et al., 2005).

Regardless of the method used, uncertainties on the measured concentrations of most

major oxides are generally small (< or << 10% relative), and probably within the

uncertainties associated with phase equilibrium modelling (see below). However, the most

commonly used methods for estimating bulk composition are unable to distinguish the

valency of relevant elements, of which, for our purposes, Fe is the most important (Boger et

al., 2012; Diener and Powell, 2010). Iron exists in many phases in its relatively reduced

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divalent form (Fe2+) and/or its more oxidised trivalent form (Fe3+), which form ferrous oxide

(FeO) and ferric oxide (Fe2O3), respectively. For example, pure magnetite (Fe3O4) comprises
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one mole each of FeO and Fe2O3, whereas pure hematite, which is more oxidised, contains
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only Fe2O3. The proportions of ferrous and ferric iron can be measured directly through a
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redox titration of a sample powder, but these measurements are rather imprecise and involve

working with aggressive chemicals. In any case, relative to the redox conditions under which
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they formed, high-T rocks can only become more oxidised on their return to, and residence
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on, the surface, and subsequently during sample preparation. As such, Xferric values (Fe3+/Fe)
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measured using titrations should be regarded as maxima. In most high-T rocks, values for
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Xferric between 0.1 (commonly used for Archean rocks; Berry et al., 2008) and 0.2 (commonly

used for Phanerozoic rocks) give reasonable results, although T–Xferric (or P–Xferric) diagrams

can be used where P (or T) and H2O contents are constrained (Boger et al., 2012; Diener and

Powell, 2010; Korhonen et al., 2012).

Potentially a more significant problem lies in constraining the abundance of H2O in

modelled bulk rock compositions, as it exerts a first-order control on melt compositions and

fertility, as discussed in section 5. The H2O contents are most commonly estimated based of

the loss on ignition (LOI), measured as part of a standard XRF analysis. However, LOI
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values do not discriminate among the numerous volatile species that might be present (e.g.

H2O, CO2, CH4, N2, F, Cl, S, etc.), and consequently provide only a maximum constraint for

the H2O content of the analyte. Any alteration, which can be very fine-grained, for example

within feldspars, will also increase the H2O content of the rock compared to its original high-

T state. Alternatively, H2O contents can be estimated based on the measured abundance of

hydrous minerals inferred to have been present at the metamorphic peak in combination with

their measured or estimated OH contents. Similar to Xferric, H2O contents can be estimated

using T–XH2O pseudosections if other variables are reasonably well constrained (Johnson et

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al., 2003b; Korhonen et al., 2012; White et al., 2001). From a more theoretical standpoint, if

the purpose is to model partial melting of protolith composition that is minimally saturated in
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H2O as it crossed the solidus at a particular pressure, the H2O content can be adjusted
e-
manually such that < or <<1% H2O-saturated melt is produced at the solidus (Johnson and
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Brown, 2004; Mayne et al., 2020b; White et al., 2001), which is the case for many of the

pseudosections that follow. Alternatively, in situations where H2O is considered to be present

al

as a free phase, its abundance can effectively be set to be infinite.

n

Finally, some consideration should be given to minor components that cannot

ur

(currently) be modelled. This can be done either using the measured or estimated mode and
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composition of the minerals in which these components occur, or using the abundance of the

minor element. For example, in many crustal rocks, phosphorous, which currently cannot be

modelled as a component, is mostly concentrated in apatite (Ca5(PO4)3(OH, F, Cl)). In such

cases, as each mole of P2O5 in (end member) apatite is associated with 3.33 moles of CaO,

this amount can be removed from the bulk composition before any phase equilibrium

calculations (Johnson et al., 2003a). However, in many high-grade metapelitic rocks, most

phosphorous resides in monazite, and P2O5 can simply be ignored. Although MnO can be

modelled in metapelitic systems (White et al., 2014b), it is commonly ignored when

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modelling high-T phase equilibria as Mn only plays a significant role in expanding the

stability field of garnet in greenschist facies rocks. If analysed, the concentrations of sulphur

can be used to subtract an appropriate quantity of Fe associated with any pyrite/pyrrhotite.

4.5.3. Uncertainties and realities

Searching the titles, abstracts and keywords of peer-reviewed articles reveals almost

1000 papers in the petrological literature that include the word ‘pseudosection’, with an

average of around one per year in the 1970s and ‘80s, growing to more than 50 per year since

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2011. Many such papers propose P–T constraints with a degree of accuracy and precision that

is both unreasonable and unjustified. Like all modelling, phase equilibrium calculations are
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associated with uncertainties, some of which are quantifiable and some of which are not
e-
(Palin et al., 2016a). These uncertainties can be subdivided into ‘thermodynamic’,
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‘analytical’ and ‘interpretive’, some of which are intertwined.

For example, it is possible to calculate uncertainties on the end-member

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thermodynamic data that can be propagated through calculations (Powell and Holland, 2008),
n

but less easy (or impossible) to calculate or estimate uncertainties on the a–X models.
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Analytical errors include those associated with measuring or estimating the bulk rock
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composition to be modelled, and the composition and abundance of minerals, including

estimating Xferric in relevant minerals (Droop, 1987; Schumacher, 1991). In relation to

compositions of rocks and minerals, there are inevitable differences between natural systems

and modelled systems related to the omission of elements that cannot (yet) be included in the

modelling, particularly, for example, in relation to crustal melting, the halogens in hydrous

minerals (Bartoli, 2021; Johnson et al., 2008). Interpretive uncertainties might involve

petrographic observations, including the incorrect identification of the peak assemblage or

misinterpretation of reactions between minerals.

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A more thorough treatment of the uncertainties involved in the method are provided

elsewhere (Palin et al., 2016a; Powell and Holland, 2008). Regardless of what is output by

the various computer programs used in calculations, for example a stability field for the peak

assemblage that is a few degrees and/or a few hundredths of a GPa in extent, in reality the 2

uncertainties of ± 50 °C and ± 0.1 GPa estimated (heuristically) for conventional

thermobarometry (Powell and Holland, 2008) are probably sensible minima for most P–T

constraints derived from pseudosections.

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5. Open vs closed systems
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e-
5.1 Definitions
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Definitions of isolated, closed and open systems are provided in section 3.1. Here, we
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introduce two end-member variants on the terminology for open systems: conditionally open,
n

which indicates that the system becomes episodically open to some infiltration or exfiltration
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of fluid or melt (Handy et al., 2001b), but is otherwise closed; and, unconditionally open,
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where the system is always open. Whether natural anatectic systems are open or closed is

partly a matter of scale. At a kilometre scale, suprasolidus crust is generally considered to be

unconditionally open, because it is a source for granites emplaced at higher levels (Brown et

al., 2016; Handy et al., 2001b; Sawyer et al., 2011), even as it accumulates melt from deeper

in the suprasolidus crust (Brown, 2004; Carvalho et al., 2016; Diener and Fagereng, 2014;

Hall and Kisters, 2012; Marchildon and Brown, 2003; Morfin et al., 2013; Nyman et al.,

1995; Schwindinger and Weinberg, 2017; Yakymchuk et al., 2013). However, at the scale of

a thin section or hand sample, a system may remain closed (Yakymchuk, 2021). Outcrops

may comprise layered sequences of different compositions, some of which remained closed
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systems (e.g. refractory metabasite boudins) whereas others were open (e.g. melt-rich

metapelites). As a consequence, phase equilibrium modelling of open system behaviour is

similarly scale-dependent, with implications for the methodology and applicability of the

results.

In studies of crustal melting, the treatment of open-system behaviour is generally

restricted to the gain or loss of fluid (H2O and, less commonly, CO2) and melt. However,

natural systems are inevitably more complex. For example, as melt migrates, batches may

blend with each other and/or entrain residual or peritectic minerals from the source (Clemens

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et al., 2011; Stevens et al., 2007) or xenocrysts and xenoliths from the host rocks, and

migrating aqueous fluids contain dissolved cations and minor quantities of other volatile

species.
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5.2. Internally vs externally buffered H2O

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The activity of H2O in a metamorphic system may be internally or externally

n

buffered. Closed systems, where the proportion of any fluid is generally low, are internally
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buffered. For suprasolidus rocks, the activity of H2O decreases as temperature increases, and
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melting reactions at temperatures well above the solidus do not include a free fluid phase (i.e.

the system is H2O-undersaturated, with aH2O < 1). Such reactions commonly generate

anhydrous peritectic minerals through hydrate-breakdown (section 2.3), and the volume of

melt produced is limited by the volume of the hydrous reactant mineral present (Sawyer,

2010; Slagstad et al., 2005).

The ingress of an externally-derived fluid into a system above its wet solidus will

cause fluid-present (or fluid-fluxed) melting. In the case of H2O, providing the quantity of

fluid supplied is sufficiently large, the melt may become H2O saturated (aH2O = 1) and remain
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so as long as the supply of H2O is maintained. As fluid is being supplied to the system, none

is required from hydrate breakdown, and H2O-fluxed melting proceeds by consuming

feldspars (plagioclase and/or alkali feldspar) and quartz by the generalised congruent

reaction:

Qtz + Fsp + H2O = L. (17)

The volume of melt produced by H2O-fluxed melting is limited by the supply of H2O or,

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where fluid:rock ratios are high, the abundance of one or more of the solid reactants.

These principles are well illustrated by migmatites developed in the contact aureole of
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the Ballachulish igneous complex in the west-central Scottish Highlands (Pattison and Harte,
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1988, 1997). The metasedimentary rocks in the lower-temperature western sector of the
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contact zone of the aureole (i.e. above the 'melt-in' isograd) produced the largest volume of

melt, which led locally to the formation of schollen diatexite migmatites in the ‘Chaotic
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Zone’, where the greatest fluid-fluxing occurred. By contrast, in the higher-temperature

n

eastern sector of the contact zone, fluid-absent partial melting led to the formation of net-
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structured metatexite migmatites, reflecting the lower volume of melt produced in these
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rocks. In the case of fluid-present melting, heat is mainly consumed by melting rather than

increasing the temperature, whereas in the absence of a free fluid, heat is used to increase the

temperature until a major fluid-absent melting reaction is encountered.

A thorough review of the evidence for and role of fluid-present melting has been

provided by Weinberg and Hasalová (2015). Although fluid-present melting reactions

generally are congruent (Johannes, 1985; Stevens and Clemens, 1993), some may be

incongruent, producing peritectic minerals including hornblende (Slagstad et al., 2005),

garnet (Patiño Douce and Harris, 1998) and cordierite (Yardley and Barber, 1991). In
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general, a role for fluid-present melting may be indicated if in situ melt fractions inferred

from the volume of leucosome in a migmatite complex are higher than can reasonably be

accounted for through fluid-absent melting at peak metamorphic conditions (Brown, 2013;

Pourteau et al., 2020), although care is required since melt may have infiltrated from deeper

levels in the crust. The trace element composition of granites can also be used to infer the

behaviour of plagioclase and micas during partial melting to estimate if H2O was a reactant

and if fluid-present melting occurred (Gao et al., 2017a; Inger and Harris, 1993).

The relative importance of fluid-present and fluid-absent partial melting in the

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generation of granites is debated (Clemens et al., 2016, 2020; Weinberg and Hasalová, 2015).

Fluid-fluxed melting has been argued to be important for the growth of continental crust at
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subduction zones (Collins et al., 2020b), but in orogenic belts the limited permeability of the
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deep crust at steady-state conditions (Yardley and Valley, 1997) may prohibit pervasive fluid
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movement and restrict widespread fluid-present partial melting. However, shear zones that

develop during deformation may provide permeable conduits to allow ingress of hydrous
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fluids and induce significant melting (Carvalho et al., 2016; Johnson et al., 2001c; Mogk,
n

1992; Sawyer, 2010; Weinberg and Hasalová, 2015). Although the efficacy and extent of
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fluid-present melting in the continental crust is debated, there is commonly a genetic link
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between migmatites that formed through fluid-present melting and syn-anatectic deformation.

One of the biggest challenges in the petrogenesis of migmatites generated through

fluid-present partial melting is determining the source of H2O. To do so usually requires a

detailed understanding of the tectonic, metamorphic and magmatic history of a terrane

coupled with geochronology and stable isotope analysis of both the migmatites and the

inferred fluid sources. Fluids can be locally sourced or be derived far from the site of

anatexis. For example, H2O may readily be derived from sedimentary rocks beneath large

intrusions, such as the Bushveld Complex, in which dehydration reactions at depth may flux
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melting of rocks closer to the basal contact (Johnson et al., 2003b). In regional metamorphic

terranes, two commonly inferred sources of H2O are: (1) underthrust or underplated

sedimentary rocks that undergo dehydration reactions without melting (Berger et al., 2008;

White et al., 2005); and, (2) fluids exsolved from the crystallization of hydrous granite

(Finger and Clemens, 1995) or basalt magmas (Annen and Sparks, 2002; Collins et al., 2016,

2020b; Pourteau et al., 2020). Diffusion of H2O from a magmatic source into rocks at

temperatures close to the wet solidus is a viable mechanism to produce granite melts, but it is

unlikely to generate a significant volume of magma (Tafur and Diener, 2020). Although fluid

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sources may be cryptic, oxygen isotope analysis can be used to differentiate alternative

sources, whether using whole-rock samples (Holk and Taylor, 2000; Johnson et al., 2003b;
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Sawyer, 2020; Taylor Jr, 1978; Yakymchuk et al., 2019b) or in situ analysis of minerals
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(Gordon et al., 2009; Higashino et al., 2019; Smithies et al., 2021).
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5.3. Phase equilibrium modelling approaches to open system melting

n al

A first-order consequence of melt drainage is an increase in the density and strength

ur

of the residual crust (Diener and Fagereng, 2014; Yakymchuk and Brown, 2014b). Although
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the effect of continuous melt loss on crustal rheology has not been quantified, accumulation

of melt up to the MCT (or a lower threshold, as discussed in section 2.4) allows episodic melt

drainage, leading to transient periods of strengthening and weakening in the source (Brown,

2010a; Diener and Fagereng, 2014). Melt loss generally occurs during prograde heating, but

it may also occur during cooling and melt crystallization, in particular where there is

synchronous deformation (Koblinger and Pattison, 2017). Evidence of melt loss includes: (1)

the preservation of peak metamorphic assemblages (Brown, 2002; White and Powell, 2002b);

(2) the residual (melt-deficient) composition of many migmatites and granulites compared to
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their inferred protoliths (Johnson et al., 2013; Korhonen et al., 2010a); and, (3) the presence

of structures consistent with a decrease in volume (Bons et al., 2008; Diener and Fagereng,

2014). Melt may migrate from centimetres to metres, to accumulate in local melt-induced

deformation-band networks, or from metres to kilometres, to accumulate in crustal-scale

plutons, as discussed in Section 2.4.

Melt loss changes the composition of an anatectic system, which leads to a number of

effects, including: (1) an increase in the temperature of the solidus due to a decrease in bulk

H2O contents and aH2O (Korhonen et al., 2010a; Schwindinger et al., 2019; Stuck and Diener,

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2018); (2) shifts in the topology of a phase diagram due to preferential loss of those elements

concentrated in the extracted melt (notably H2O, K, Na, and Si; (Mayne et al., 2020a); (3) an
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increase in the stability of anhydrous minerals due to the extraction of relatively H2O-rich
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melt (Johnson et al., 2011; Yakymchuk and Brown, 2014a), and the preservation of high-
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temperature mineral assemblages (Hernández-Montenegro et al., 2019; White and Powell,

2002a; White and Powell, 2010); (4) reduced fertility of the residue with increasing melt
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extraction (Yakymchuk and Brown, 2014b); (5) depletion of the source in the relatively
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incompatible elements that preferentially enter the melt (Mayne et al., 2020b); (6) an increase
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or decrease in the stability of accessory minerals depending on the concentration of essential

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structural elements in the extracted melt (Rapp et al., 1987; Yakymchuk and Brown, 2014b);

and, (7) modified trace element compositions of the source (Kendrick and Yakymchuk, 2020)

and of accessory minerals (Holder et al., 2020). Of these effects, the preservation of high-

temperature mineral assemblages and an increase in the solidus temperature are the most

relevant to studies of natural migmatites and granulites. In particular, the solidus temperature

is important for interpreting geochronological data, as it strongly influences when accessory

minerals crystallize from melt during cooling (Korhonen et al., 2013b). In this section, we
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consider strategies to address the effects of melt loss on both source and melt compositions

using phase equilibrium modelling.

The effect of melt drainage on the composition, fertility and mineral assemblage of

residual rocks can be investigated by forward modelling of phase equilibria. First, forward

modelling may be used to predict how the mineral assemblages and fertility of a source rock

change with increasing temperature through loss of melt (White and Powell, 2010;

Yakymchuk and Brown, 2014b). Second, forward modelling may be used to solve the inverse

problem where melt is added back into a residual composition to create a fictive but plausible

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subsolidus protolith, an approach generally called melt reintegration (Bartoli, 2017;

Korhonen et al., 2013a; White et al., 2004).

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Forward modelling of melt drainage has been used to consider: (1) a single melt loss
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event close to peak T (Indares et al., 2008); (2) multiple melt loss events to reflect a system
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that episodically reaches a specified MCT during heating (Diener and Fagereng, 2014;

Johnson et al., 2011; Schwindinger et al., 2019; Stuck and Diener, 2018; Yakymchuk and
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Brown, 2014b); and, (3) quasi-continuous melt extraction along a prograde path (Mayne et
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al., 2016; Yakymchuk and Brown, 2019). The composition of the extracted melt is usually
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dictated by the source composition and the P–T conditions of melt drainage, as determined
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using phase equilibrium modelling. However, the amount of melt to remove at this P–T

condition will vary depending on whether the modelled system is expected to be static

(Handy et al., 2001a) or dynamic (Marchildon and Brown, 2001; Stuart et al., 2018). For a

static system in which drainage is episodic, we may assume that melt loss will occur when

the melt fraction reaches the MCT (Rosenberg and Handy, 2005). In this case, it may be

appropriate to retain a portion of melt to account for that trapped along grain boundaries, as

inferred from microstructural studies of anatectic rocks (Holness and Sawyer, 2008;

Marchildon and Brown, 2002; Sawyer, 2001). For example, Yakymchuk and Brown (2014b)
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modelled melt drainage from migmatites by removing 6 mol.% melt from the system when a

7 mol.% extraction threshold was reached along a P–T path, leaving 1 mol.% melt in the

system to represent that expected to have been trapped along grain boundaries. Whether melt

extraction was episodic or continuous does not appear to significantly impact the predicted

mineral assemblages and modes in the residue or the composition of the melt (Mayne et al.,

2020b).

To illustrate the effects of melt drainage in migmatites, Yakymchuk and Brown

(2014b) compared the fertility of metapelites and greywackes. They showed that an average

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amphibolite-facies metapelite generates ~36 vol.% melt along an isobaric heating path to 890

ºC at 1.2 GPa in a closed system, but in a conditionally open system undergoing four melt
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drainage events generates only ~30 vol.% along the equivalent path due to the loss of H2O
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and other incompatible components in melt that drained from the system (Fig. 10a). In this
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case the residue does not generate additional melt during high-T decompression due to its

H2O-depleted composition, and in some cases the trapped melt may begin to crystallize and
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may cross the solidus. Thus, an important consequence of episodic melt extraction is that the
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efficacy of decompression melting is significantly decreased (Yakymchuk and Brown,

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2014b), calling into question tectonic models that rely on decompression melting in the
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genesis of gneiss domes (Teyssier and Whitney, 2002). By contrast, the fertility of

greywackes is less sensitive to melt loss (Fig. 10b). For a metagreywacke composition

following the same P–T path as the metapelite, an undrained system yields 21 vol.% melt,

whereas a drained system produces ~16 vol.% melt (Yakymchuk and Brown (2014b).

Similar to other rock types, metabasites will generate less melt in a drained system

when compared with an undrained system (Stuck and Diener, 2018). However, like

metapelites and metagreywackes (Johnson et al., 2011; Yakymchuk and Brown, 2014b)),

although the modelled residual mineral assemblage does not change significantly with
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episodic melt drainage, both reactants and products may be stabilised to higher temperatures

when compared with an undrained system (Palin et al., 2016c). Major and trace element

compositions of melt are also expected to be slightly different between drained and undrained

systems (Huang et al., 2020; Kendrick and Yakymchuk, 2020).

Reintegration of melt into a residual composition requires assumptions about the

number of steps to use and the total amount of melt to reintroduce into the system, the P–T

conditions at which each step should occur, and the composition of the melt at each step. One

approach is to use the amount of melt required to shift an elevated solidus down temperature

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to a predetermined P–T condition using the composition of melt predicted by phase

equilibrium modelling (Diener et al., 2008; White et al., 2004). Alternative approaches use
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either the composition of a melt produced in an experiment at a known P–T condition or the
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composition of nanogranite/melt inclusions (Bartoli, 2017, 2019). Melt may be reintegrated
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in a single step (Guilmette et al., 2011; Indares et al., 2008), in multiple steps (Alessio et al.,

2017; Korhonen et al., 2013a; Yakymchuk et al., 2015), or using T–Mmelt diagrams (Anderson
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et al., 2013). These different approaches generally produce diagrams with similar topologies,
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although the fertility of the reintegrated composition may vary (Bartoli, 2017).
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The largest uncertainty in modelling melt reintegration is the assumed prograde P–T
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path, which affects the minerals present at the P–T condition of melt loss and the composition

of the melt. Although reintegration of melt into a residual migmatite or granulite offers

insight into the original composition of the protoliths in circumstances where subsolidus

equivalents are not exposed, considering the uncertainties involved, the results of this

procedure should be treated with caution.

6. Melting of metaigneous rocks

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Igneous rocks and their deformed and metamorphosed equivalents (orthogneisses)

comprise by far the largest proportion of the crust, which is bimodal in terms of its chemical

composition (Bonnefoi et al., 1995; Collins et al., 2020b; Daly, 1925; Keller et al., 2015) and,

at least since the end of the Archean, its hypsometry (elevation) (Flament et al., 2008;

Schubert and Reymer, 1985; Wise, 1974). On the modern Earth, this bimodality is clearly

manifest as oceanic crust that is dominantly basaltic in composition and subaqueous, and

continental crust that is on average andesitic in composition and mostly subaerial. However,

continental crust also shows pronounced compositional bimodality, with peaks at ~50 wt%

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SiO2 and ~70–75 wt% SiO2, in particular for the intrusive rock record (Keller et al., 2015).

The most abundant magmatic rock type within the middle to upper continental crust is
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granite, with mafic rocks and/or residual granulites dominating the lower crust (Hans
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Wedepohl, 1995; Rudnick and Gao, 2003; Rudnick and Fountain, 1995).
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Although a detailed treatment of crustal magmatism per se is beyond the scope of this

contribution, in this section, we discuss the most important (by volume) crustal magmatic
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protoliths, placing a particular emphasis on the basic (basaltic/gabbroic) and felsic

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(rhyolitic/granitic sensu lato) end members. In terms of phase equilibria, we focus on the
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anatexis of metabasic rocks, for which there are far more experimental constraints (see
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section 4.1.2).

6.1. Magmatic protoliths

Mafic crust is formed through melting of the mantle driven by decompression (for

example at mid-ocean ridges and in plumes), advection of heat (e.g. in plumes) or the

introduction of H2O (for example, slab-derived fluids beneath island arcs). Regardless of the

mechanism, these primitive (juvenile) magmatic rocks represent the source from which
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almost all continental crust was ultimately derived (Albarède, 1998; Hawkesworth and

Kemp, 2006; Taylor and McLennan, 1985). However, the processes by which continental

crust forms from mafic crust, whether through partial melting or fractional crystallisation,

and how these processes may have changed through time are topics of longstanding and

ongoing debate (Annen et al., 2006; Arndt, 2013; Collins et al., 2020b; Davidson et al., 2007;

Jacob et al., 2021; Jagoutz and Klein, 2018; Johnson et al., 2017; Moyen et al., 2021).

However, there is agreement that to partially melt mafic crust at temperatures that may

plausibly be attained during orogenesis (up to ~1000 °C), mafic rocks must be hydrated,

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requiring a source of H2O in the generation of continental crust (Campbell and Taylor, 1983).

Of particular importance to understanding the formation of the Archean continental

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crust is partial melting of hydrated mafic rocks to generate the tonalite–trondhjemite–
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granodiorite (TTG) suite, and on modern Earth compositionally-similar high-silica adakites
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(Barker and Arth, 1976; Castillo, 2006; Condie, 2014; Martin et al., 2005; Moyen, 2011;

Moyen and Martin, 2012; Rollinson and Martin, 2005; Smithies, 2000). TTGs are sodic
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granites with high Sr/Y and La/Yb ratios, and they are the volumetrically-dominant rock-type
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within the deeper levels of exposed Archean continental crust (Condie, 1981; Martin, 1994;
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Windley, 1996). These TTGs represent the most primitive (least evolved, with K2O/Na2O
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ratios < or << 0.6) continental crust (Smithies et al., 2021). Although some TTG suites may

be the result of fractional crystallisation of basaltic magmas (Kramers, 1988; Liou and Guo,

2019), there is general agreement that most were derived by partial melting of amphibolite

within the stability field of garnet, corresponding to source depths of 25–50 km (Johnson et

al., 2017; Smithies et al., 2019). Whereas some propose TTGs represent supra-subduction-

zone magmas (Foley, 2008; Foley et al., 2003; Kusky and Polat, 1999; Polat et al., 2014;

Windley et al., 2020) others argue for their formation near the base of thick mafic plateau-

like mafic crust in a stagnant-lid setting that may have characterised the early Earth (Bédard,
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2006a; Bédard, 2018; Johnson et al., 2017; Smithies et al., 2009, 2019). In contrast to TTGs,

and although rare, high-silica adakites occur in the modern rock record. Most form at plate

margins and are interpreted to indicate high-pressure melting of down-going oceanic

lithosphere associated with ‘hot’ (young) subduction zones, in which the ascending slab-

melts variably interact with the mantle wedge (Martin et al., 2005; Smithies, 2000).

The most evolved volumetrically-abundant igneous rocks within the continental crust

are granites sensu stricto. These are high silica, high-K rocks that dominate active and

ancient continental arcs, and which span the entire geological rock record, first becoming

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abundant towards the end of the Archean (Chowdhury et al., 2020; Johnson et al., 2019;

Moyen, 2020a; Moyen et al., 2003; Nebel et al., 2018; Zhao et al., 2017). High-K granites
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can form by a range of processes, including partial melting of common metasedimentary
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rocks (see section 7), low-degree melting of a wide range of igneous protoliths and fractional
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crystallisation of mafic and other magmas. Fractionation clearly has a role to play in the

petrogenesis of high-K granites, which ultimately drives the formation of pegmatites and
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hydrothermal fluids that are the source of numerous rare and more common metals and other
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ore deposits on which humankind depends.

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In terms of partial melting of different source lithologies, and based originally on data
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from granites in the Lachlan Fold Belt, southeastern Australia (Chappell, 1974), a key

compositional subdivision of granite is into I-, S- and A-types (Chappell, 1999; Chappell and

White, 1992; Clemens et al., 1986; Clemens, 2003; Collins, 1996; Collins et al., 2020a; Eby,

1992; Foden et al., 2015; Frost et al., 2001). I-type granites, which form during collision and

in the lower crust of some arcs, are mostly calcic and sodic metaluminous (ASI < 1) to

weakly-peraluminous (ASI > 1) rocks derived from predominantly mafic igneous (hence the

‘I’) precursors, although elevated zircon δO18 suggests that many incorporate a supracrustal

component (Kemp et al., 2007). In addition, the relative role of partial melting versus
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fractionation is debated (Collins et al., 2020b; Jagoutz and Schmidt, 2012; Keller et al.,

2015). By contrast, syn- to post-collisional S-type granites are high-K peraluminous rocks

mostly derived by anatexis of sedimentary (‘S’) protoliths (Collins and Richards, 2008;

White and Chappell, 1988), although Sr and Nd isotope data indicate a mantle-derived

component is also commonly involved (Healy et al., 2004). Post-collisional or anorogenic A-

type granites, which are commonly located in extension (rift) settings, are hot, dry magmas

that mostly reflect relatively low-P partial melting of residual (melt-depleted) source rocks of

varying composition that underwent an earlier metamorphic cycle (Clemens et al., 1986;

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Collins et al., 1982; Eby, 1992; Patiño Douce, 1997; Turner and Rushmer, 2009; Whalen et

al., 1987).
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6.2. Field and petrographic characteristics of migmatised metaigneous rocks
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6.2.1. Metabasic rocks

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Relative to more fertile protoliths, such as pelites and greywackes (section 7), there
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have been relatively few detailed field-based studies on partially-melted basic rocks (i.e.,
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metabasic migmatites). On a regional scale, areas where such metamorphic studies have been
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undertaken include the Grenville front in Quebec (Sawyer, 1991) and the Kapuskasing Zone

in Ontario (Hartel and Pattison, 1996), Canada, the Lewisian Complex of NW Scotland

(Johnson et al., 2012), the Ivrea Zone in northern Italy (Kunz et al., 2014), and the

Sveconorwegian orogen of SW Sweden (Hansen et al., 2015). Many of the features described

below are nicely illustrated in these (and other) publications, in particular in the Atlas of

Migmatites (Sawyer (2008).

Hydrated metabasic rocks generally comprise assemblages dominated by hornblende

and plagioclase, commonly with quartz, as they begin to partially melt. Depending on bulk
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composition and the metamorphic pressure, they may also contain variable quantities of

garnet, clinopyroxene, biotite, epidote, titanite, magnetite, ilmenite and rutile, and less

commonly gedrite, muscovite and/or K-feldspar. Although much less abundant than in

migmatites with pelitic or greywacke protoliths, metabasic migmatites may contain zircon or,

if silica-undersaturated, baddeleyite, allowing them to be dated (Fischer et al., 2021).

When the inferred degree of partial melting is small, leucosomes may form irregular

isolated pockets or discontinuous stromatic veins, the latter of which may mimic original

magmatic and/or deformation-induced layering (Fig. 11a, b). As temperature (and the

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inferred degree of melting) increases, leucosomes are seen to coalesce into larger-scale

structures, commonly sheets or more irregular accumulations facilitating drainage of melt

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from the system (Fig. 11c, d). The leucosome in metabasic migmatites consists mostly of
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plagioclase and quartz with minor K-feldspar and may contain variable quantities of
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entrained material. Leucosome may also contain peritectic minerals, including garnet,

clinopyroxene and/or orthopyroxene, although these are commonly altered to some degree,
al

and in some cases hydrous peritectic minerals, including hornblende, biotite and epidote
n

(Yakymchuk et al., 2019b), consistent with melting via incongruent reactions. However,
ur

peritectic minerals are commonly absent, suggesting H2O-fluxed congruent melting may play
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an important role in the anatexis of many metabasic rocks (Collins et al., 2020b; Nehring,

2012; Pourteau et al., 2020; Yakymchuk et al., 2019b). As peak temperature increases

further, the rocks generally become coarser-grained and the proportions of hornblende,

plagioclase and quartz decrease, whereas those of garnet, clinopyroxene and/or

orthopyroxene increase.

Collectively, the field, petrographic and experimental data (section 4.1) indicate that

the following two generalised reactions are of fundamental importance to the partial melting

of hydrous mafic rocks at crustal depths:

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Hbl + Qtz ± Bt ± Pl → Cpx ± Grt ± Opx + L, and (18)

Pl + Qtz + H2O ± Kfs → L. (19)

(Hartel and Pattison, 1996; Sen and Dunn, 1994). In the case of fluid-absent melting, a first

order control on the amount of melt that can be generated by reaction 18 is the abundance of

hornblende in the protolith. In terms of fluid-present melting, given a supply of H2O, the

quantity of melt that can be produced is limited by the abundance of quartz and feldspar in

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the protolith, which in primitive mafic compositions may be low.

6.2.2. Metamorphosed felsic igneous rocks

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Similar to metabasic rocks, there are comparatively few studies documenting the
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features of partially-melted felsic igneous rocks. Exceptions include the Central Gneiss

Complex in Alaska, USA (Kenah and Hollister, 1983; Lappin and Hollister, 1980; McLellan,
al

1988), the Opatica Subprovince in the Canadian Shield (Sawyer, 2010), the Grenville
n

Province in Ontario, Canada (Slagstad et al., 2005), the Gallatin Range of Montana, USA
ur

(Mogk, 1992), the Central Alps (Berger et al., 2008), the Bohemian Massif in the Czech
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Republic (Hasalová et al., 2008a, b; Schulmann et al., 2008; Štípská et al., 2019), the

Lewisian Gneiss Complex of NW Scotland (Johnson et al., 2013), the Campo Belo

metamorphic complex in the São Francisco Craton, Brazil (Carvalho et al., 2016) and the

Taishan region of the Western Shandong Province, China (Yakymchuk et al., 2019b).

Notably, unlike other common crustal rock types that have undergone anatexis, the colour

contrast between leucosome and residuum in felsic igneous rocks, which are both

quartzofeldspathic, may be subtle, and clear migmatitic features indicative of partial melting

become much harder to recognize (Johnson et al., 2013; Sawyer, 2010).

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Partially-melted felsic orthogneisses exhibit a full range of migmatitic structures,

from stromatic, patch and net-structured metatexites to nebulites and schollen diatexites

(Sawyer, 2008, 2010; Slagstad et al., 2005) (Fig. 11e, f). However, a key observation is that

the volumes of melt produced by fluid-absent melting, as inferred from the presence of

anhydrous peritectic minerals within leucosome, are small, even where peak metamorphic

temperatures were extreme (950–1000 °C) (Johnson et al., 2013); Fig. 11e,f). For example,

reaction 18 also describes fluid-absent melting in calcic intermediate and felsic ‘I-type’

igneous rocks, such as tonalites and trondhjemites (Johnson et al., 2017), but is limited by the

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abundance of hornblende (with or without biotite), which is much lower than in metabasic

rocks. Fluid-absent melting of peraluminous ‘S-type’ granites proceeds mostly by reactions

pr
consuming biotite and/or muscovite, and mimics reactions that govern suprasolidus phase
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equilibria in metapelites and aluminous metagreywackes, as described in section 7. In
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partially-melted felsic orthogneisses, larger melt volumes, including diatexites, only occur

where melting (for example, by reaction 19) was fluxed by ingress of an H2O-rich fluid
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(Carvalho et al., 2016; Clos et al., 2019; Sawyer, 2010) due to the high modal abundance of
n

quartz and feldspars.

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6.3. Calculated phase equilibria

Fully-quantitative calculations investigating partial melting of hydrated mafic rocks

(amphibolites) and other Ca-rich, K-deficient intermediate to felsic protoliths (diorites,

tonalites, etc.) have only been possible since publication of the a–X models of Green et al.

(2016). Importantly, in addition to a new solution model for (trondhjemitic–tonalitic) melt,

this work included models for high-T clinopyroxene and hornblende. Of particular

importance, the hornblende model includes K, such that both biotite-present and biotite-
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absent equilibria may be considered. Some key papers utilising these models include those by

Palin et al. (2016c), Palin et al. (2016b), Johnson et al. (2017), White et al. (2017), Feisel et

al. (2018), Kunz and White (2019), Hernández-Uribe and Palin (2019), Huang et al. (2020)

and Kendrick and Yakymchuk (2020). We illustrate the calculated phase equilibria with

reference to metabasic protoliths. Intermediate to felsic ‘I-type’ compositions show similar

topologies, although hornblende is consumed at lower T and quartz and feldspars at higher T

in these lithologies. The phase equilibria for K-rich peraluminous protoliths (granites) are

similar to those described in the following section.

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6.3.1. Fluid-absent melting
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Given the importance of the role of partial melting of metabasic rocks to the
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production of primitive continental crust in the early Earth, we first illustrate phase relations
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with reference to a bulk composition that has been shown to be appropriate to the production

of common TTGs with respect to both major and trace element compositions (Johnson et al.,
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2017; Smithies et al., 2009). The modelled composition, an average (n = 10) of the c. 3.5 Ga
n

Coucal basalts (hereafter CF2) from the East Pilbara Terrane in Western Australia, is
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compositionally evolved, exhibiting a low XMg (0.38) and enrichment in K, LILE, Th and
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LREE relative to primary basalts such as MORB. A P–T pseudosection calculated between

0.35 and 1.35 GPa and from 630 to 1000 ºC for CF2, and containing sufficient H2O to

minimally saturate the solidus at 1.2 GPa, is shown in Fig. 12a, with a simplified version

highlighting the key petrological features shown in Fig. 12b. We describe phase relations

with reference to melting along three paths with thermobaric (T/P) ratios of 700, 900 and

1100 °C/GPa (Fig. 12), which correspond to relatively low, intermediate and high crustal

geotherms. The changing abundance of phases along these three prograde melting paths are

shown in Fig. 13.

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Within the modelled P–T window, at high-T subsolidus conditions the phase

assemblage corresponds to a quartz-amphibolite containing >50 mol.% hornblende. Minor

biotite is present at all pressures, and coexists with minor titanite at higher P and ilmenite at

lower P. At P > 1.2 GPa small quantities of muscovite are predicted to be present and epidote

is predicted at similar pressures in other bulk compositions––these minerals may play a minor

role in fluid-absent melting of metaigneous rocks in the deep crust. The wet solidus occurs at

temperatures between ~650 °C at high P and ~700 °C at low P. Significant melting begins

through fluid-absent reactions that consume biotite, hornblende and quartz, producing ~15%

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melt as biotite is exhausted, and a total of 25–30% melt as hornblende (± quartz) is exhausted

at 800–870 °C (Figs 12 and 13). Above these temperatures, melting continues by

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consumption of anhydrous minerals, decreasing the H2O content of the melt.
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At relatively low P (yellow fields in Fig. 12b), neither garnet nor rutile is predicted to
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be stable; at intermediate P (green fields) garnet is stable without rutile; at high P (blue

fields) garnet and rutile coexist. These fields correspond to the low-pressure, medium-
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pressure and high-pressure TTG subdivisions of (Moyen, 2011). Plagioclase is predicted to

n

be stable throughout the P–T window of interest, consistent with experiments on quartz-rich
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amphibolite starting compositions. Importantly, garnet, which defines the lower pressure
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limit for MP-TTGs, is predicted to be stable in CF2 at pressures significantly lower (by up to

0.8 GPa) than suggested by melting experiments using other amphibolite starting materials

(Moyen and Stevens, 2006).

The main mineralogical effects of the paths with different thermobaric ratios are

shown in Fig. 13a. With increasing T/P or along lower pressure isobaric heating paths, the

proportion of garnet decreases significantly and of quartz a little. Rutile is predicted at high-T

along the 700 °C/GPa path, but ilmenite is stable at higher thermobaric ratios. For the

composition of CF2, orthopyroxene is only predicted along the 1100 °C/GPa path. In all
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cases melt fractions show a broadly linear increase with T, although fertility increases

slightly with increasing thermobaric ratio (Fig. 13).

To illustrate the compositional evolution of the melt, we use as an example partial

melting along the 900 °C/GPa path at melt fractions between 5 and 40 mol.% (Fig. 13d). At

low melt fractions (5–10 mol.%), the calculated melts are H2O-rich and granitic with

K2O/Na2O > 0.8. At 20% melting, the calculated K2O/Na2O ratio (0.54) of the melt is similar

to the upper range observed in TTGs, and at 30% melting this ratio (0.38) is very close to the

average measured value in TTGs. In addition, using published partition coefficients and the

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predicted melt residua (Fig. 13), and the methodology detailed in section 9, trace element

modelling of the calculated melt compositions along the 900 °C/GPa at melt fractions of
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around 25 vol.% show good correspondence with the composition of the average composition
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of the TTGs from the East Pilbara Terrane (Johnson et al., 2017).
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To illustrate the effects of changing major oxide bulk composition on suprasolidus

phase equilibria in metabasites, in Fig. 14 we show for comparison P–T pseudosections for
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an average N-MORB composition (Sun and McDonough, 1989) with plagioclase in excess,
n

and an average Eoarchean basalt from Isua, SW Greenland (Hoffmann et al., 2011) with
ur

hornblende in excess, both of which contain sufficient H2O to minimally hydrate the solidus
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at 1.2 GPa. Relative to CF2, the average N-MORB contains less silica, much more CaO, has

a lower K/Na ratio and a significantly higher XMg of 0.64 (Table 1). Although these

compositional differences cannot be treated in isolation, the most notable cumulative effects

on the average N-MORB during heating are that quartz is consumed at lower T, hornblende is

stable to much higher T (>1000 °C) and there is only a very narrow field in which

suprasolidus biotite is stable (compare Fig. 14a with Fig. 12a). In terms of pressure, the

maximum stability of rutile and ilmenite occurs at much lower P and, of particular

significance, the lowest P stability of garnet is at ~0.95 GPa compared to ~0.75 GPa in CF2,
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due mainly to the much higher XMg of N-MORB (Johnson et al., 2017). In addition,

plagioclase is not predicted to be stable in the high P, low T part of the modelled P–T

window.

Relative to CF2, the average Isua basalt is much more primitive and contains less

SiO2, lower TiO2 and Al2O3, less Na2O and K2O (although the K/Na ratio is similar) and

almost three times the MgO, with a much higher XMg (0.67) that is similar to the average N-

MORB (Table 1). Compared to CF2, the principal effects on the average Isua basalt are that

the maximum thermal stability of quartz is reduced even more than for the average N-

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MORB, hornblende is stable to T > 1000 °C and the lower stabilities of rutile and garnet and

the upper stability of ilmenite occur at higher pressures than for the average N-MORB
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(compare Fig. 14b with Figs 12a and 14a). The other notable difference is that the stability of
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plagioclase is greatly reduced, and plagioclase occurs only in the low P–T part of the
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diagram, at P < 0.85 GPa and T < 830 °C, such that the H2O-saturated solidus at P > 0.85

GPa occurs at temperatures up to 50 °C higher than in the other two compositions. In terms
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of fertility, at a given suprasolidus T, CF2 produces more melt than the average N-MORB,
n

whereas the average Isua basalt is even less fertile (Figs 12a, 14a, b). However, at least in
ur

terms of major oxides, the compositions of melts produced from these different protoliths
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varies little, evolving from granite at low melt fractions to trondhjemite–tonalite at higher

melt fractions.

As stated previously, intermediate to felsic metaluminous (‘I-type) granites will also

melt mostly by reactions consuming hornblende (reaction 18). The main difference in the

phase equilibria for these more evolved (silicic) rocks will be a reduction in the stability of

hornblende, an increase in the stability of quartz, plagioclase and biotite, and, in the most

evolved compositions, muscovite and/or K-feldspar. For a more comprehensive treatment of

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the effects of varying major oxide compositions, the reader is referred to the articles by Palin

et al. (2016c) and White et al. (2017).

6.3.2. Fluid-present (H2O-fluxed) melting

Partial melting driven by an influx of H2O-rich fluid is argued to be important in the

generation of some magmatic rocks, as discussed in section 5. In particular, H2O-fluxed

melting of mafic underplate in arcs has recently been argued to be a primary driver in the

production of silicic arc magmas (Collins et al., 2016, 2020b), although the relative

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importance of fluid-present versus fluid-absent melting and the role of fractional

crystallisation is debated (Clemens et al., 2021; Jagoutz et al., 2011; Jagoutz and Schmidt,

2012; Sisson et al., 2005).

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To illustrate the process of modelling H2O-fluxed melting of metabasites, we take as
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an example the composition of a ‘fine-grained, quench-textured hornblende gabbro’ (sample

87S35A) used in the experiments of Sisson et al. (2005) to investigate the potential origin of
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high-K granites in continental arcs. We model the effects of introducing a pure H2O fluid
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phase at 0.8 GPa, chosen to approximate the base of thickened continental arc crust (see
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(Collins et al., 2020b) for more details). For reference, a P–T pseudosection for the
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composition of sample 87S35A containing sufficient H2O to minimally saturate the solidus at

0.8 GPa is shown in Fig. 15, in which plagioclase and hornblende are in excess. Compared to

the samples modelled so far in this section, this composition is depleted in SiO2, moderately

enriched in K2O, such that suprasolidus K-feldspar is stable at P > 0.7 GPa, and has an

intermediate XMg of 0.56. Garnet is only stable in the high P–T corner of Fig. 15a.

An isobaric (P = 0.8 GPa) T–X pseudosection is shown in Fig. 15b, for which T varies

from 650 to 800 °C (thick dashed white line in Fig. 15a) and X (= H2O content in wt%) varies

from the value used in Fig. 15a (~1 wt.%) to 6 wt%, corresponding to the addition of an extra
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5 wt% H2O. Melt fractions (F) varying from 5 to 50 mol.% are shown as the red dashed lines.

Two arrowed paths are shown on Fig. 15b, the yellow arrow representing introduction of

H2O at 700 °C, ~50 °C above the solidus, and the pink arrow representing influx at 750 °C.

In both cases, for minimally-saturated conditions (yellow and pink stars on Fig. 15a, left hand

edge of the yellow and pink arrows on Fig. 15b) in which all the H2O is locked within

amphibole and biotite, or just amphibole, respectively, trivial amounts of melt (<5 mol.%) are

produced, quantities that may be insufficient for segregation and migration to occur

(Rosenberg and Handy, 2005). However, with the addition of just 1 wt.% H2O (bringing the

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total to ~2 wt%; yellow and pink diamonds), melt fractions increase to ~12 mol.% and ~15

mol.%, respectively. With the addition of 4 wt% H2O (bringing the total to ~5 wt%; yellow
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and pink discs) melt fractions are predicted to be >35 mol.% and >40 mol.%, respectively,
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volumes that may be sufficient for bulk flow to occur (Arzi, 1978; Renner et al., 2000;
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Rosenberg and Handy, 2005; Vigneresse et al., 1996). Increasing H2O content still further at

750 °C (pink arrow) produces more melt. However, with 4 wt% added H2O (i.e. 5 wt% H2O
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in total), at 700 °C the melt is saturated (i.e. the path has crossed the H2O-out curve), such
n

that the excess H2O forms a separate fluid phase that coexists with melt. Whether melt drains
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from the system likely depends on whether the local structural setting allows melt
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accumulation or not (see section 5).

In Fig. 15b, following either path towards higher H2O contents (i.e. to the right in the

figure) leads to the exhaustion of first K-feldspar then, following the consumption of

clinopyroxene and growth of titanite at 750 °C, quartz and eventually ilmenite. Plagioclase is

also consumed, although it is not exhausted at the maximum H2O contents shown, consistent

with fluid-fluxed melting by reaction 19. While generally underappreciated, the importance

of H2O-fluxed melting to the generation of both modern and ancient continental crust is

gaining increasing traction (Collins et al., 2020b; Nehring, 2012; Pourteau et al., 2020;
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Weinberg and Hasalová, 2015; Yakymchuk et al., 2019b) and is an exciting avenue of future

research.

7. Melting of clastic metasedimentary rocks

Clastic sedimentary rocks accumulate in many different tectonic settings, leading to

wide variation in their bulk compositions depending on provenance and maturity. Within

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sequences of deformed and metamorphosed sedimentary rocks (paragneisses), metapelites

and metagreywackes are particularly important as they represent the primary source rocks of
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peraluminous (‘S-type’) granites (Chappell, 1974; Chappell and White, 2001), although other
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source rocks may also produce minor quantities of peraluminous granite (Clarke, 2019;
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Clemens, 2006; Gao et al., 2016a). This section focusses on these two key protoliths.

Metapelites have clay-rich protoliths (pelites) that accumulate in many subaqueous

al

environments, from abyssal plains to lakes. Metapelites are widely studied, in part because
n

during prograde metamorphism they develop a distinctive suite of index minerals (Barrow,
ur

1893; Barrow, 1912) that can be readily used to qualitatively constrain P–T conditions in
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both subsolidus and suprasolidus rocks (Chinner, 1966; Johnson et al., 2001c). However, the

pelite component of most paragneiss sequences is subordinate to coarser-grained clastic

sedimentary rocks such as greywacke. Greywacke, a type of sandstone (or psammite), is a

term that covers a compositionally diverse suite of sediments with varying proportions of

different clastic components. As a consequence, the mineral assemblages and fertility of

metagreywackes are also widely variable, since both are sensitive to bulk composition

(Johnson et al., 2008).

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If temperatures are sufficiently high, metapelites and metagreywackes are fertile

sources, although metapelites will produce a larger volume of melt at any given P–T

condition than metagreywackes (Johnson et al., 2008). Importantly, anatectic (and

subsolidus) metapelites and metagreywackes commonly contain a wide variety of mineral

chronometers, including garnet, zircon, monazite, titanite and apatite. Strategies linking the

ages derived from these minerals to stages of the evolution of melt-bearing rocks (i.e.

petrochronology) are explored in sections 9 and 10.

The presence of a large volume of peraluminous granite in orogenic systems—such as

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in the Himalaya (Harris et al., 1995)––requires the accumulation then burial of sediment to

pressures and temperatures sufficient for partial melting, although the timescale may still be
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rather short (Harris et al., 2000). Their presence commonly reflects late orogenic melting
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during continent–continent collision (Barbarin, 1996; Sylvester, 1998), although
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peraluminous granites may also form during back-arc extension in accretionary orogens

(Collins and Richards, 2008). Peraluminous granite is scarce in the early to middle Archean
al

compared with TTGs (section 6), which may provide support for an origin unrelated to plate
n

tectonic processes. These Archean granites may represent low-volume partial melting of
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metabasic rocks, partial melting of sodic granites themselves or anatexis of metasedimentary

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rocks (Johnson et al., 2017; Li et al., 2020; Watkins et al., 2007).

7.1. Field and petrographic observations

Metapelite and metagreywacke are commonly interlayered in metasedimentary

successions (Fig. 2e), which can lead to a complex distribution of leucosome (Brown and

Solar, 1998; Marchildon and Brown, 2003; Weinberg et al., 2013; Yakymchuk et al., 2013).

A common observation is that metapelite layers contain more leucosome than

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metagreywacke layers, but this need not relate to the amount of melt generated in situ (Diener

and Fagereng, 2014). In the field, fluid-absent melting of metapelite and metagreywacke may

be identified based on the spatial association of leucosome and anhydrous peritectic minerals,

whereas a large proportion of leucosome retained in an outcrop may provide support for

fluid-present melting, which generally does not produce peritectic minerals. The

concentration and alignment of phyllosilicate minerals (biotite, muscovite) into layers

between leucosomes in some metasedimentary migmatites may create a potential barrier to

cross-layer melt migration (Laporte and Watson, 1995). However, some structures that

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develop in different orientations to the dominant fabric (e.g. axial planar foliation and shear

bands) can allow melt to locally cross these barriers (e.g. (Weinberg et al., 2013).
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In metasedimentary migmatites, the leucosome and melanosome generally record
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different information about the metamorphic history. Since the melanosome is dominated by
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residual minerals, it is more likely to record important petrographic information about the

prograde to peak metamorphic P–T evolution. Furthermore, except at its margins, the
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melanosome is less susceptible to the retrogression that accompanies local melt

n

crystallization (White and Powell, 2010). Notably, inclusions shielded in peritectic minerals
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(e.g. garnet) provide important information about the prograde history and also may host
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accessory mineral chronometers that were not influenced by retrograde processes.

By contrast, the petrography of the leucosome usually provides information about the

cooling and melt crystallization history, providing insight into the processes that influenced

the evolution of the melt during fractional crystallization and deformation (Brown et al.,

2016; Koblinger and Pattison, 2017). Biotite-rich selvages adjacent to leucosomes in

metasedimentary migmatites are common features (Fig. 2e). Although they may have

multiple origins (Brown, 2002), in many cases these selvages are related to recrystallization

driven by diffusion of H2O from the leucosome into the melanosome as melt crystallizes
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(White et al., 2008). However, the common preservation of close-to-peak mineral

assemblages in many migmatites and granulites demonstrates that extensive reaction with

melt is uncommon, consistent with melt drainage (Brown, 2002).

7.2. Compositions and typical minerals

The bulk composition of pelites varies depending on the relative proportions of clay

minerals, quartz, feldspar and other minerals. Clay minerals, such as kaolinite, illite and

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montmorillonite, are aluminous and hydrous, features that allow metapelites to develop

distinctive aluminosilicate mineral assemblages during metamorphism across a range of T/P

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conditions and to be fertile protoliths with respect to melt production. Oxidation state also
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plays a role in controlling the suprasolidus metamorphic mineral assemblage of metapelites
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(Boger et al., 2012).

Metapelites can be divided into aluminous and subaluminous varieties based on their
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position in the A(K)FM ternary diagram relative to a garnet–cordierite tie line (Fig. 16). The
n

average compositions of many shales (Condie, 1993) and their amphibolite-facies equivalents
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(Ague, 1991; Shaw, 1956) are aluminous, and most contain a higher molar proportion of Fe2+
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than Mg (Fig. 16). Prograde subsolidus metamorphism is not an isochemical process, and the

bulk composition of metapelites immediately prior to partial melting has been modified from

that of the original pelite by the progressive loss of H2O and water-soluble components (e.g.

SiO2) to become more Al-rich (Ague, 1991). Aluminous metapelites contain peraluminous

minerals such as garnet and kyanite at high pressure, sillimanite at intermediate pressure, and

cordierite and orthopyroxene at low pressure. Suprasolidus andalusite is not expected to be

stable except at very low pressures and temperatures just above the solidus (Cesare et al.,

2003; Greenfield et al., 1996).

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Although rare, magnesium-rich metapelites are important in studies of ultrahigh-

temperature (UHT) metamorphism because their compositions allow the development of

sapphirine-quartz and osumilite-bearing assemblages at UHT conditions (Harley, 2008;

Kelsey and Hand, 2015). The assemblage sapphirine + quartz is restricted to rare aluminous

bulk rock compositions with XMg > 0.5–0.6 (Kelsey and Hand, 2015). The Mg- and Al-rich

compositions are most likely inherited from a sedimentary protolith, but some may have been

produced from syn-metamorphic metasomatism (Kelsey and Hand, 2015). Overall, these

rocks represent a small proportion of common (meta)sedimentary sequences, but since they

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generally generate less melt than common metapelites, they play only a limited role in crustal

differentiation.
pr
Greywackes have highly variable compositions according to their tectonic setting,
e-
reflecting a combination of source characteristics (mafic island arcs versus more felsic
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continental arcs) and sediment maturity. For example, more mature greywackes from passive

margin turbidite sequences may have >75 wt.% SiO2, indicating of a high proportion of
al

quartz fraction, whereas less mature greywackes from arc settings may contain much less
n

SiO2. Notwithstanding, greywackes generally contain more SiO2 than pelites, and average
ur

compositions are aluminous on an A(K)FM diagram (Fig. 16) and commonly develop similar
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aluminous mineral assemblages to aluminous metapelites (Johnson et al., 2008; Yakymchuk

and Brown, 2014b). However, sub-aluminous compositions may lack sillimanite and contain

more biotite. Metaluminous variant develop hornblende- and clinopyroxene-bearing

assemblages above the solidus (Patiño Douce and Beard, 1996; Vielzeuf and Montel, 1994;

Vielzeuf and Schmidt, 2001), and relatively Na-rich compositions may stabilize

orthoamphibole (e.g. gedrite) at suprasolidus conditions (Johnson et al., 2008).

7.3. Reactions
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We first consider the reactions crossed during suprasolidus heating in the simplified

KFMASH system. Note that the absence of Na and Ca from this modelled system precludes

consideration of plagioclase, which is a key reactant and product mineral in anatectic

reactions (Spear et al., 1999). Nevertheless, the KFMASH provides a useful system to

investigate the behaviour of the key ferro-magnesian minerals that participate in suprasolidus

reactions. A petrogenetic grid from White et al. (2014a) along with simplified A(K)FM

diagrams from (Spear et al., 1999) is shown in Fig. 17 (see also (Grant, 1985; Thompson,

f
oo
1982). Although this simplified system shows the key reaction relationships for metapelites

and metagreywackes, in natural systems these are multivariant (continuous) rather than

univariant equilibria.
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e-
Consider an isobaric heating path at 0.6 GPa in the KFMASH system (Fig. 17)––
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quartz is considered to be in excess, so is not included in the reactions, although it is almost

always a reactant. The first melting reaction encountered with heating equates to crossing of
al

the wet solidus by the reaction:

n
ur

Bt + Ms + Kfs + H2O + Grt → Liq. (20)

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In the absence of any external supply of fluid, the limiting reactant is usually H2O as the

amount of H2O present within pore spaces will be very small (< or <<1 vol.%; (Yardley and

Valley, 1997). As a result, the quantity of H2O-saturated melt produced is also small. Further

heating under fluid-absent conditions (aH2O < 1) results in the terminal breakdown of

muscovite via the incongruent melting reaction:

Ms + Grt → Sil + Kfs + Bt + Crd + Liq, (21)

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which is the equivalent of reaction 12 in the simpler KASH system. The distinctive products

of this reaction are K-feldspar and, depending on pressure, sillimanite or kyanite. At higher

temperatures, biotite and sillimanite breakdown occurs via the incongruent melting reaction:

Bt + Sil → Grt + Crd + Kfs + Liq. (22)

which marks the transition to granulite facies conditions (Waters, 1988). In quartz-bearing

f
oo
aluminous pelites in KFMASH, biotite will be completely consumed by reaction 22, resulting

in the formation of a nominally-anhydrous mineral assemblage (garnet–sillimanite–-

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cordierite) coexisting with melt. However, in subaluminous pelites in KFMASH, sillimanite
e-
will be completely consumed before biotite by reaction 22, so that further heating leads to the
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reaction:
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Bt + Grt → Opx + Crd + Kfs + Liq. (23)

n
ur

Reaction 23 produces orthopyroxene–cordierite granulites, with or without biotite or garnet

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(Johnson et al., 2001c). In aluminous pelites, at temperatures above those of reaction 22, the

reaction:

Grt + Sil → Spl + Crd + Kfs + Liq. (24)

leads to the formation of aluminous (hercynitic) spinel.

To summarize, melting initiates at the wet solidus, which consumes any free H2O.

Further heating causes muscovite-breakdown melting to produce K-feldspar and

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aluminosilicate over a very narrow T interval such that it is effectively univariant, even in

natural rocks. At higher temperatures, melt is generated by the incongruent breakdown of

biotite and/or sillimanite via reactions that generate anhydrous (or low aH2O cordierite)

peritectic minerals. At temperatures above biotite and sillimanite exhaustion, melting

continues through the consumption of nominally anhydrous minerals. Although a

simplification, the KFMASH phase equilibria provide an extremely useful qualitative

framework in which to understand partial melting equilibria in natural pelites and greywackes

(Droop et al., 2003; Harley and Thompson, 2004; Johnson et al., 2001a; Kelsey et al., 2005;

f
oo
Pattison and Harte, 1984; Spear et al., 1999; Thompson Jr, 1957; White et al., 2001, 2007,

2014a).
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e-
7.4. Average metapelite
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Now consider a P–T pseudosection calculated based on the composition of an average

al

amphibolite-facies metapelite (Ague, 1991) in the enlarged and more robust

n

MnNCKFMASHTO chemical system (Fig. 18a). The terminal muscovite-out reaction occurs
ur

at relatively low temperatures above the H2O-saturated solidus (at ~680 °C at P > 0.5 GPa
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and ~780 °C at 1.2 GPa). Notably, orthopyroxene is not stable in the pseudosection for the

average metapelite due to its aluminous bulk composition (Figs 16, 18a). Garnet is stable

across most of the pseudosection; at mid-crustal pressures, biotite is absent above ~850 °C,

whereas at lower pressures and temperatures above ~730 °C, cordierite-bearing assemblages

are stable (Fig. 18b). In contrast to the univariant (discontinuous) reactions in the KFMASH

petrogenetic grid (Fig. 17), reactions in the MnNCKFMASHTO chemical system are almost

always continuous (F > or >> 1) and a closer approximation to how natural rocks behave.

The continuous nature of suprasolidus reactions can be visualized through mol.% isopleths
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for a particular phase, such as mol.% melt, as shown in Fig. 18c, or using an isobaric T–molar

proportion diagram (Fig. 19a).

Consider isobaric heating at 0.6 GPa for a minimally-hydrated average amphibolite-

facies metapelite (arrow in Fig. 19a). The wet solidus is crossed at ~675 ºC consuming any

free H2O present, which is generally assumed to be minimal, by a reaction similar to reaction

20 (White et al., 2007). With further heating, the proportion of muscovite decreases slightly

from the wet solidus to ~700 ºC, where it is completely consumed within ~2 ºC by an

expanded version of reaction 21 in the simplified KFMASH system. During further heating,

f
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biotite, quartz, sillimanite and plagioclase are consumed to produce garnet, K-feldspar and

melt. At ~810 ºC cordierite is predicted to become stable and further heating consumes
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biotite, quartz and plagioclase to produce cordierite, K-feldspar, garnet and melt by an
e-
expanded version of reaction 22 in the simplified KFMASH system (Fig. 19a), which
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consumes all biotite over a small temperature interval of ~3 ºC. Considering the strongly

endothermic nature of biotite-breakdown melting, a limiting factor may be the rate of heat
al

flow (Schorn et al., 2018). Notwithstanding, if heating continues after exhaustion of biotite,
n

consumption of quartz and feldspar continues to generate melt until quartz is exhausted at
ur

~910 ºC; spinel first forms at ~920 ºC (Fig. 19a).

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Melt is generated continuously, albeit at an uneven rate, during suprasolidus heating

in metapelites (Fig. 18c). In addition, for a closed system, melt is also generated during

decompression due to the positive slopes of melt isopleths in P–T space (Fig. 18c; see section

5.5 for open system scenarios). For the average metapelite, ~67 mol.% melt is generated

during isobaric heating between the wet solidus at ~675 ºC and ~950 ºC, an average of ~0.2

mol.% melt/ºC along the modelled path. However, there are two abrupt increases in the

proportion of melt at ~700 ºC and ~810 ºC. The first is related to the muscovite-out reaction,

which occurs over a narrow temperature range (similar to reaction 21), generating ~3 mol.%
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melt between ~700 and ~702 ºC. The second is during the growth of cordierite at the expense

of biotite (via a reaction similar to 22), which generates ~5 mol.% melt over ~3ºC (Fig. 19a).

Heating at higher pressures will generate less melt at a given temperature than at lower

pressure (Fig. 18c). However, the amount of melt and the reaction sequence experienced by

natural metapelites will vary depending on the particular bulk rock composition.

7.5. Greywacke

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Greywackes can be more compositionally diverse than pelites and experience different

reaction sequences, have different mineral assemblages, and be variably fertile (Johnson et
pr
al., 2008). Consider an average passive margin greywacke that is representative of turbidite
e-
sequences commonly involved in orogenesis at plate margins. An MnNCKFMASHTO P–T
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pseudosection for this composition is shown in Figure 20a. Muscovite is present at low

temperatures and P > 0.75 GPa, biotite is absent at high temperatures, cordierite is stable at
al

low pressures, and garnet is stable over the entire P–T range shown (Fig. 20b). Notable
n

differences include the absence of a field representing muscovite breakdown to K-feldspar

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and melt (reaction 21) and the presence of orthopyroxene at low pressure due to the less
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aluminous nature of this composition (Figs 16, 20b).

Along an isobaric heating path at 0.6 GPa for the greywacke (Fig. 19b), muscovite is

not stable having been consumed under subsolidus conditions. Melting begins at the wet

solidus at ~680 ºC by a reaction similar to reaction 20, consuming the small amount of free

H2O and producing ~2 mol.% melt. With increasing temperature, biotite is partially

consumed to produce garnet and melt. Cordierite first appears at ~790 ºC by the reaction of

biotite and sillimanite to cordierite, K-feldspar, minor garnet and melt (via a reaction similar

to 22) over a narrow temperature range (~5 ºC). Further heating results in the complete
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consumption of biotite at ~840 ºC and K-feldspar at ~905 ºC (Fig. 19b). At higher

temperatures melting continues through the breakdown of quartz, plagioclase and cordierite.

Orthopyroxene is not stable along this heating path but it is predicted to be stable at lower

pressures, where crossing of the narrow field containing coexisting orthopyroxene and biotite

is similar to the KFMASH reaction 23 (Fig. 20b).

The proportion of melt in the greywacke increases continuously along the modelled

isobaric heating path, although slightly lower melt productivity is predicted with increasing

pressure (Fig. 20c). From the wet solidus at ~680 to ~950 ºC, ~33 mol.% melt is predicted, an

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average rate of ~0.1 mol.%/ºC, roughly half that in the metapelite. One abrupt increase in

melt proportion occurs at ~795 ºC by a reaction similar to 22 that produces ~2 mol.% melt

over ~5 ºC (Fig. 20c).

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e-
Pr

7.6. Melt compositions

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Melt compositions predicted from the phase equilibrium modelling of metapelite and
n

greywacke vary with pressure and temperature, reflecting differences in the starting
ur

compositions and the evolving residual mineral assemblages. We emphasize that the wide
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array of possible metapelite and greywacke starting compositions means that the range of

melt compositions is wider than those discussed here.

For the modelled metapelite and metagreywacke, the concentration of SiO2 in the

melt increases with heating (Fig. 21a, d). This partly reflects the dilution of H2O at higher

melt fractions with increasing temperature. At temperatures above quartz exhaustion (Fig.

21a), the concentration of SiO2 is expected to decrease with further heating because quartz is

no longer present to buffer the composition of the melt, which has implications for the use of

trace element equilibria that rely on the activity of silica, such as the Ti-in-zircon (Ferry and
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Watson, 2007; Kirkland et al., 2021) and Zr-in-titanite thermometers (Hayden et al., 2008;

Kirkland et al., 2020).

Over the modelled P–T range, all melt compositions derived from the metapelite and

greywacke are peraluminous (Figs 21b, e; Fig. 22a), i.e. molar Al2O3/[CaO + Na2O + K2O] >

1 (Clarke, 1992; Shand, 1927). However, this is unlikely to be the general case, especially for

sub-aluminous greywacke compositions. For the modelled aluminous compositions, the

A/CNK values increase with temperature resulting in progressively more peraluminous melt

compositions (Fig. 21b, e), which eventually reach the ‘strongly’ peraluminous field at >800

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ºC (c.f. (Clarke, 2019). The presence or absence of sillimanite plays a role in controlling the

A/CNK value of the melt, as indicated by the inflection in A/CNK contours in Fig. 21b, e.
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The molar proportion of Fe, or Fe# (molar Fe2+/(Fe2+ + Mg)), is used to differentiate
e-
ferroan from magnesian granites (Frost et al., 2001). All of the modelled melt compositions
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are magnesian, which includes granites with Fe# < 0.75 at the modelled concentrations of

SiO2 (Frost et al., 2001). The Fe# of melt is expected to decrease up temperature due to the
al

preferential partitioning of Fe into garnet for the modelled metapelite and greywacke. After
n

exhaustion of biotite, the Fe# initially decreases then increases with continued heating (Fig.
ur

21c, f).
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The variable proportions of plagioclase to clay minerals in pelite versus psammite

source rocks has been used to develop a geochemical proxy for granites generated from these

two rock types (Chappell and White, 1992; Sylvester, 1998). Sylvester (1998) proposed that

strongly-peraluminous pelite-derived melts generally have low CaO/Na2O ratios (<0.3),

whereas psammite-sourced melt has higher ratios (>0.3). These different ratios are a

consequence of the behaviour of plagioclase and the Ca-rich ferromagnesian minerals during

partial melting. However, the compositional diversity of both pelites and psammites is greater
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than the compositions considered by Sylvester (1998), such that the CaO/Na2O ratio may be

less useful than envisaged.

For the two compositions modelled, the metapelite is predicted to generate melt

compositions with CaO/Na2O ratios from <0.1 to >0.3 (Fig. 22b), whereas the greywacke is

predicted to yield melt compositions with ratios <0.3 (Fig. 22b), inconsistent with the 0.3

threshold of Sylvester (1998). The reason for this difference is that the modelled

compositions have similar and sufficient quantities of both plagioclase and garnet (Fig. 19),

whereas the pelites considered by Sylvester (1998) had substantially less plagioclase, leading

f
oo
to exhaustion of plagioclase at lower temperatures. Loss of plagioclase means Na2O

partitions into the melt whereas CaO entered peritectic garnet, resulting in lower CaO/Na2O
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ratios in the melt. In the average metapelite modelled here, plagioclase is stable to ~950 ºC
e-
(Fig. 18a), such that the CaO/Na2O ratio in melt does not decrease. Thus, although the
Pr

amount of plagioclase in the source may be an important control on melt composition and in

distinguishing pelitic from psammitic sources, the situation is more complex, and other trace
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element proxies (e.g. Rb/Ba and Rb/Sr; Sylvester, 1998) may be required to distinguish the
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putative source.
ur

Lastly, as a check on how close to natural melt compositions those derived using
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phase equilibrium modelling are, we may compare the compositions obtained from

experiments on crustal rocks or synthetic compositions with those derived by modelling of

the same starting materials (Johnson et al., 2008; White et al., 2011; Bartoli and Carvalho,

2021; Bartoli, 2021). Furthermore, the degree of sophistication now achieved in phase

equilibrium modelling means that this approach also has the potential to highlight not only

differences, but also problems with the experiments (Johnson et al., 2008; White et al., 2011;

Bartoli, 2021; Bartoli and Carvalho, 2021). Indeed, the recent study by Bartoli (2021) has

confirmed that muscovite was a metastable phase in the experiments of Patiño Douce and
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Harris (1998) and that, contrary to the original authors’ assertions, that metastability seriously

affected melt compositions.

8. Melting during exhumation from ultrahigh-pressure metamorphic conditions

In orogenic belts, crustal rocks that have been returned to shallow depths following

deep subduction to ultrahigh-pressure (UHP) conditions—defined by the stability of coesite

f
oo
rather than quartz—commonly show features interpreted to record partial melting. These

features include multiphase solid inclusions (including nanogranites) and/or glassy inclusions
pr
in rock-forming and accessory minerals, microstructures in which quartz or feldspar infills
e-
grain boundaries, commonly with low dihedral angles at triple grain-boundary junctions, and
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macroscopic leucosomes (Feng et al., 2021; Ferrero et al., 2019; Gao et al., 2017b; Wang et

al., 2016, 2017, 2020). However, where and when during the P–T evolution these features
al

formed, and whether they are related to the generation and evolution of supercritical fluid, or
n

fluid-present or fluid-absent melting remain open questions.

ur

With changing P–T conditions, silicate-buffered fluids at high-pressure (HP) and

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UHP metamorphic conditions vary dramatically in composition and properties, including

solute content, density, polymerization and viscosity (Hack and Thompson, 2011; Mysen,

2014). As pressure increases, at temperatures below the wet solidus minerals become more

soluble in aqueous fluid, whereas at temperatures above the wet solidus silicate melts can

accommodate more H2O in their structure (Fig. 23). Enhanced mutual solubility implies that

aqueous fluids and silicate melts become increasingly similar until pressure exceeds the

second critical endpoint for the particular silicate–H2O system (Fig. 23, SCE 1, 2 or 3,

according to composition), where the solvus between fluid and melt closes, and a discrete
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solidus can no longer be distinguished (Hack et al., 2007; Hermann et al., 2006). Along the

critical line, which extends from each critical endpoint to higher temperatures, the solute

content increases (Fig. 23). At pressures above the second critical endpoints and critical lines,

miscibility yields a supercritical fluid that varies continuously from aqueous fluid at lower

temperatures and solute content <30% to supercritical fluid with increasing solute content

and properties similar to hydrous melt at higher temperatures (Fig. 23).

Informally, we distinguish sub-critical from supercritical P–T conditions. At sub-

critical P–T conditions (i.e. at pressures below the second critical endpoints or critical lines,

f
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but at temperatures above the fluid-saturated solidus for common crustal source rock

compositions), a saturated hydrous melt coexists with an aqueous fluid (Fig. 23), whereas at
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supercritical P–T conditions (i.e. at P–T conditions above the second critical endpoints or
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critical lines), hydrous melt and aqueous fluid are completely miscible and are replaced by a
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single supercritical fluid (Fig. 23). In particular, even at sub-critical pressures above ~1 GPa,

silicate-rich fluids/H2O-rich melts become largely depolymerized, decreasing viscosity and

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increasing mobility (Audétat and Keppler, 2004).

n

Partial melting at HP or UHP metamorphic conditions is sometimes argued to have

ur

been fluid-present, but more commonly is inferred to have been related to fluid-absent
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hydrate breakdown reactions, such as Ph + Cpx + Qz → Bt + Pl + Grt + L (Auzanneau et al.,

2006), even where microstructural evidence of hydrate breakdown is lacking. However, in

some of these cases the P–T conditions were higher than those of the second critical endpoint

for the protolith composition (Fig. 23), suggesting that leucosomes may have crystallized

from supercritical fluids or from hydrous melts that evolved from supercritical fluids. Better

characterisation of where these leucosomes form along the P–T path and by what mechanism

is of great interest, because: (1) ascending fluid/melt transports mass and heat, which

facilitates hydration and retrogression of UHP metamorphic rocks at shallower HP eclogite

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and amphibolite facies conditions (Chen et al., 2007; Wang et al., 2017; Zheng et al., 2009);

and, (2) the presence of melt lowers the viscosity of the crust and promotes exhumation

(Brown and Rushmer, 2006b; Ferrero et al., 2015; Gerya and Meilick, 2011; Labrousse et al.,

2011, 2015; Sizova et al., 2012). Thus, the evolution of supercritical fluid to hydrous melt

during decompression from UHP to HP conditions (i.e. crossing from the coesite to the

quartz stability field; Fig. 23) may be an underappreciated mechanism assisting the

exhumation of deeply-subducted crust (Wang et al., 2020). In addition, drainage of fluid

and/or melt from deeply-subducted lithosphere may lead to substantial metasomatic

f
oo
modification of the overlying crust and/or mantle (Borghini et al., 2020; Hermann and

Rubatto, 2014; Hermann et al., 2006, 2013; Keppler, 2017; Malaspina et al., 2006, 2009,
pr
2010; Scambelluri et al., 2008; Scambelluri and Philippot, 2001; Zheng, 2012).
e-
During subduction and prograde metamorphism of the lithosphere, any fluid and most
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melt generated via hydrate-breakdown reactions is generally lost, which may lead to fluid-

deficient or fluid-absent conditions approaching peak pressures (Yardley and Valley, 1997).
al

Notwithstanding, some hydrous minerals are stable at HP and UHP conditions, including
n

phengitic mica, sodic amphibole, epidote–zoisite and lawsonite, which collectively may
ur

retain significant amounts of H2O at upper mantle depths. Furthermore, at peak UHP
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conditions eclogites may store up to several hundred ppm primary 'water' (as OH;

colloquially water) structurally bound within nominally anhydrous minerals (NAMs),

including pyroxene, garnet and rutile in eclogites and, possibly, metastable feldspar in

gneisses (Wang et al., 2018). In addition, molecular H2O may be preserved as fluid

inclusions. In these circumstances, since the solubility of water in NAMs generally decreases

with decreasing pressure, during exhumation from pressures above the second critical end

point exsolution of water from NAMs (strictly dehydroxylation) will generate a supercritical

pore fluid (Hermann and Rubatto, 2014; Hermann et al., 2013; Wang et al., 2017, 2020;
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Zheng et al., 2011; Zheng and Hermann, 2014). With ongoing exhumation, this fluid

dissolves more solute, becoming denser, more viscous and more polymerized until it stalls

and partially or completely crystallizes. Exactly how the fluid evolves during exhumation

depends not only on the P–T path but also on: (1) the variance of the phase assemblage—the

host silicate mineral assemblage in equilibrium with the supercritical fluid—because in high

variance assemblages (components >> phases) in which minerals exhibit extensive solid

solution, the fluid composition is not buffered by the mineral assemblage alone but also

depends on the rock/fluid ratio; and, (2) whether the fluid has sufficient volume to migrate

f
oo
from one host rock into another, which may lead to solute loss or gain by precipitation or

dissolution in the new chemical environment (Hack et al., 2007).

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In contrast to Hermann et al. (2006), we do not arbitrarily separate supercritical fluid
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from hydrous melt at 65 wt% solute (Frezzotti and Ferrando, 2015). With decreasing pressure
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and increasing temperature along the critical line (Fig. 23) solute content increases from ~65

wt% at the second critical endpoint to ~95 wt% at 900 °C, and the supercritical fluid
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increasingly has properties closer to those of hydrous melt with, for example, a fivefold
n

increase in viscosity (Audétat and Keppler, 2004; Hack and Thompson, 2011). Although we
ur

acknowledge that at high temperatures the difference between a high-solute supercritical fluid
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and a hydrous melt could be considered semantic, the advantage of thinking in terms of a

supercritical fluid that evolves with decreasing P or increasing T to hydrous melt is that the

process involved is solute dissolution, and distinguishing between fluid-present and fluid-

absent (hydrate breakdown) melting becomes moot.

The distinction between supercritical fluid and hydrous melt has implications for the

generation of leucosomes during decompression from UHP to HP metamorphic conditions,

which may represent crystallized supercritical fluid or cumulate material precipitated from

supercritical fluid rather than melt or cumulate material precipitated from melt. Such an
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origin has been proposed for leucosome sheets and composite granite–quartz veins that occur

in UHP eclogite in the central Sulu belt of eastern China (Wang et al., 2017, 2020). In this

case, the leucosomes crystallized at pressures from 3.5 to 2.2 GPa, well above the pressure of

the second critical endpoint for felsic compositions, supporting their origin from supercritical

fluid.

More than three dozen UHP terrains have been identified during the last four decades,

many of which contain leucosome interpreted to have formed by either fluid-present or fluid-

absent partial melting during exhumation. We anticipate that leucosomes in many of these

f
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UHP metamorphic belts will be found to have formed by crystallization from a solute-rich

supercritical fluid or hydrous melt itself derived from an evolving solute-rich supercritical
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fluid during exhumation. For example, leucosomes in migmatitic paragneisses on an island in
e-
Jøkelbugt at the eastern margin of the North-East Greenland eclogite province (Gilotti, 1993)
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were generated during decompression from P–T conditions of 3.6 GPa and 970 °C (Lang and

Gilotti, 2007; Lang and Gilotti, 2015). Melting was inferred to have occurred by fluid-absent
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phengite-breakdown at P between 2.7 and 2.2 GPa, but it may be more likely that leucosomes
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crystallised from a supercritical fluid formed by dehydroxylation of nominally anhydrous

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minerals in the inferred peak metamorphic mineral assemblage. Other examples of

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metasedimentary rocks decompressing from extreme P–T conditions include diamondiferous

quartzo-feldspathic rocks from the Saxonian Erzgebirge, Germany (~7 GPa, >1200 °C;

Massonne, 2003; Massonne and Fockenberg, 2012) and paragneisses from the Kokchetav

Massif, Kazakhstan (>4.5 GPa, 1000 °C; Stepanov et al., 2014, 2016). Under these extreme

conditions, whether the processes involved are magmatic or metamorphic, and whether the

liquid is a solute-rich supercritical fluid or a hydrous melt are difficult to distinguish and

largely semantic.
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Migmatitic continental crust, including eclogite, in the Western Gneiss region of

Norway has been interpreted to record fluid-present melting coeval with peak P–T conditions

(>2.5 GPa, ~800 °C; Ganzhorn et al., 2014; Labrousse et al., 2011, 2015). Although

continuous release and loss of fluid during progressive metamorphism likely led to fluid

absent conditions at high pressures (Yardley and Valley, 1997), infiltration of fluid associated

with deformation during subduction and/or exhumation could have occurred. Additional

sources of fluid during exhumation include dehydroxylation of nominally anhydrous minerals

and breakdown of hydrous minerals. Thus, any fluid attending peak metamorphism and

f
oo
exhumation was likely to have been solute-rich supercritical fluid that could have increased

in volume during exhumation and evolved to a hydrous melt at P < 1.5 GPa. This expectation
pr
is consistent with zircon U–Pb geochronology and trace element concentrations that show
e-
earlier leucosomes crystallized in equilibrium with garnet in the absence of plagioclase,
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whereas younger leucosomes crystallized in the absence of garnet but in the presence of

plagioclase, suggesting an evolution during crystallization from higher to lower pressure

al

(Gordon et al., 2013). Similarly, a recent study of scapolite pegmatites from the northern
n

segment of the Western Gneiss region (Bryden and Jamieson, 2020) considers a possible
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supercritical fluid source in the petrogenesis of the precursor melts, even though
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crystallization occurred at much shallow crustal depths under amphibolite facies conditions.

In summary, leucosomes and pegmatites in UHP eclogites provide insight into the

generation and evolution of supercritical fluid and/or hydrous melt during exhumation of

deeply subducted continental crust. In many cases, leucosomes and pegmatites may have

crystallised from hydrous melt that evolved from a supercritical fluid. As supercritical fluid

generated by exsolution of water from nominally anhydrous minerals during decompression

increases in volume, it may become interconnected along grain boundaries and drain through

the exhuming crust. As it migrates, the fluid will evolve to a denser, more viscous and more
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polymerized hydrous melt by dissolution of the silicate matrix. During progressive

entrapment of the resulting hydrous melt across a crystallization interval beginning at the

critical line for the appropriate chemical system (Fig. 23), the chemical potential of H2O will

be higher in the hydrous melt than in the host rocks, promoting diffusion of H2O from the

melt into the host rocks driving crystallization of the melt and retrogression of the hosts

(White and Powell, 2010). After solidification, some leucosomes may record evidence of

limited partial melting due to phengite breakdown (e.g. Fig. 3b) during ongoing exhumation

to amphibolite facies conditions. However, at these P–T conditions, this reaction only

f
oo
produces a small volume of melt (<< the MCT) that likely will remain trapped in the host

(Wang et al., 2017, 2020).

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e-
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9. Behaviour of trace elements in anatectic systems

al

9.1. Importance of trace elements as petrogenetic indicators

n
ur

Characterizing the behaviour of trace elements during crustal melting provides a tool
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to understand the petrogenesis of the continental crust and secular change in its composition.

Empirical, experimental and modelling approaches are used to determine which elements

partition into anatectic melt and which remain in the residue. Here, we describe modelling

trace element behaviour during anatexis, explore the assumptions and limitations of this

approach and discuss some trace element modelling applications to migmatites. The

behaviour of some trace elements is also controlled by the dissolution and growth of

accessory minerals, which is discussed in more detail in section 10.

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9.2. Modelling methodology

Trace element concentrations in melt and its complementary residue are modelled

following the methodology established for aqueous and igneous processes using a mass

balance approach coupled with Nernst partition coefficients (Kd):

Kd =Cmineral
i /Cmelt
i . (25)

f
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where Cmineral
i is the concentration of trace element i in a mineral and Cmelt
i is the

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concentration of this element in the melt. Concentrations are in weight fractions (e.g. mg/kg)

but the formula weights cancel each other such that Kd is dimensionless.
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We can model a variety of modal and non-modal melting scenarios, such as batch
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melting, fractional melting, and continuous melting (Hanson, 1978; Shaw, 1970). Mass

balance between solid (residue) and liquid in a system dictates that:

n al

C0 = F CL + (1 – F) Cs. (26)
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Jo

where C0 is the concentration of element C in the system, CL is the concentration in the liquid

and Cs is the concentration in the solid, and F is the weight fraction of melt in the system.

This equation may be combined with partition coefficients (Kd) as follows, to determine the

distribution of the trace element between the solid assemblage and the equilibrated residue:

D = X.Kd = CS/CL. (27)

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where D is the bulk solid (residue)–melt partition coefficient and X is the weight fraction of

each mineral in the solid residue. The equation for batch melting may be derived by

combining equations 26 and 27 into:

CL/C0 = 1 / (D (1 – F) + F). (28)

The concentration of a trace element in melt is a function of the concentration of the trace

element in the system, the bulk solid–melt partition coefficient, and the melt fraction. The

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concentration of the trace element in the solid residue may be calculated from the mass

balance equation above. Because the proportion of minerals in the residue changes with
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progressive melting (see sections 6 and 7), this requires changes to X and F (and Kd; see
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section 9.3) in the equations above at each modelled P–T condition.
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Modelling trace element behaviour during melting requires: data for mineral/melt

partition coefficients (Bédard, 2006b; Hanson, 1978) or expressions that account for changes
al

in partition coefficients with P, T and composition (Bédard, 2007); the trace element
n

composition of the system (e.g. a measured whole-rock composition); and, the weight
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fractions and composition of minerals and melt (and possibly fluid) at specified P–T
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conditions. With the exception of the partition coefficients, these variables can be retrieved

from phase equilibrium modelling or estimated based on petrographic observations (Sawyer,

1987). The calculations can be done manually, but automated software packages are being

developed that integrate phase equilibrium modelling with trace element partitioning (Mayne

et al., 2020b). Most, although not all, partition coefficients are determined through

experiments.
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Open system behaviour can be modelled to account for the extraction of a single

batch or multiple batches of melt through mass balance. For example, the extraction of 6 wt%

melt from a rock with 7 wt% melt will result in a new system concentration as follows:

C0 = (93/94) CS + (1/94) CL. (29)

The new calculated concentrations can then be applied to the next step in the melting process

and used to evaluate the changing composition of the residue and different batches of melt

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generated through open system melting.

9.3. Assumptions and limitations

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e-
Trace elements that are concentrated in rock-forming minerals (e.g. the large-ion
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lithophile elements: K, Rb, Sr, Cs, Ba) can be modelled based on mass balance and partition

coefficients. However, the behaviour of trace elements concentrated primarily in accessory

al

minerals—such as most high-field-strength elements (e.g. Zr, Hf, Th)—is more difficult to
n

model given uncertainties in their behaviour during melting (Yakymchuk et al., 2017). In
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addition, there are several key assumptions that go into trace element modelling in anatectic
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systems, including: (1) that trace elements behave according to Henry’s law; (2) that the

partition coefficient (or expression for how it changes) is applicable to the P–T–X conditions

of the modelled system; and, (3) that all minerals are in equilibrium with melt and each other.

An underlying assumption in using partition coefficients is that concentrations of the

trace element of interest are low enough that they follow Henry’s law (Mysen, 1978; Wood

and Fraser, 1976), whereby the concentration in the mineral is proportional to its

concentration in the melt. The threshold for Henry’s law behaviour varies for different

elements and minerals, but it is generally <<1 wt% of the element concerned. Therefore,
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modelling the behaviour of trace elements in rock-forming minerals, for example Yb in

garnet (Johnson et al., 2017; Semprich et al., 2015; Yakymchuk et al., 2020), is more robust

using this approach than modelling trace elements that can reach wt% levels in minerals

where they are essential structural constituents, such as Th in monazite (Skora and Blundy,

2010; Yakymchuk et al., 2018).

Partition coefficients will vary as a function of temperature and pressure, and the

compositions of melt and minerals. For some elements, such as Y in garnet, these variations

are small or negligible (Pyle et al., 2001). For others, a careful parameterization of partition

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coefficients is needed. Consider trace element partitioning between plagioclase and melt.

Partitioning of Sr between plagioclase and melt is influenced by the anorthite content of

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plagioclase and pressure, whereas partitioning of REE between plagioclase and melt is
e-
sensitive to the H2O content of the melt (Bédard, 2006b). There is still a paucity of partition
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coefficients for key high-temperature metamorphic minerals. For example, the available

partition coefficients for trace elements in cordierite are based on an empirical approach
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comparing the concentrations of trace elements in minerals and those in leucosome (Bea et
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al., 1994), but for a variety of reasons the leucosome may not have represented the
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composition of equilibrated melt (Sawyer, 1987; Yakymchuk, 2019). In addition, variable

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speciation of trace elements sensitive to oxidation state (e.g. Eu3+ and Eu2+) requires multiple

partition coefficients (Holder et al., 2020).

A crucial assumption in the modelling of trace elements in anatectic systems (e.g.

migmatites and most granulites) is that minerals and melt achieved perfect equilibrium. In

such circumstances, phases are compositionally homogenous, can adjust their compositions

and modes instantly to changes in P–T–X conditions with no kinetic hindrances, and are

available to the reacting volume (i.e. there is no shielding of some minerals as inclusions in

others). In natural migmatites, minerals may record zoning in trace element concentrations
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(Jung and Hellebrand, 2006; Pyle and Spear, 1999, 2003; Spear and Kohn, 1996) and

accessory minerals commonly occur as inclusions in rock-forming minerals (Watson, 1996).

Some of these features can be accounted for, such as REE zoning in garnet (Kendrick and

Yakymchuk, 2020) and inclusion of accessory minerals in rock-forming minerals

(Yakymchuk and Brown, 2014a), but others are more difficult to model, such as the kinetic

hindrance to the dissolution of accessory minerals in melt (Harrison and Watson, 1983, 1984;

Rapp and Watson, 1986). In general, high-temperature metamorphic rocks, such as

migmatites and granulites, are less susceptible to kinetic barriers (Carlson et al., 2015).

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However, careful consideration of trace element diffusivities in the modelled minerals at the

temperatures and timescales of interest is required. Finally, the different diffusivities of major
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and trace elements in minerals and melt makes the approach of using a single ‘effective bulk
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composition’ (Lanari and Engi, 2017) problematic, especially when rocks preserve
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microstructural evidence of chemical potential gradients, such as symplectites and coronae.

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9.4. Applications
n
ur

Studies of the concentrations and distributions of trace elements in migmatites and

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granulites provide key insights into: (1) establishing the protoliths of these rocks; (2)

elucidating open- and closed-system processes that may have occurred during anatexis

(Sawyer, 1987; Slagstad et al., 2005); (3) linking the growth of mineral chronometers to P–T

paths (i.e. petrochronology; (Kylander-Clark et al., 2013); (4) establishing the degree of

melting and melt loss (Guernina and Sawyer, 2003); (5) understanding how melt exfiltration

leads to compositional stratification of the continental crust (Morfin et al., 2013; Sawyer,

2020; Yakymchuk and Brown, 2019); (6) assessing chemical equilibrium during melt–

residue separation (Nabelek, 1999; Sawyer, 1991); and, (7) linking granites to their source
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rocks (Iles et al., 2018; Johnson et al., 2018). Many of these applications require an

assessment of melt compositions, particularly during the early stage of anatexis, and of melt

that subsequently drained from the system.

The first step in any study of an anatectic system is to develop a sampling strategy, as

discussed by Sawyer (2008). It is also important to estimate an initial composition for the

melt prior to melt extraction, which can be accomplished using trace element concentrations

(e.g. REE, LILE) of whole rocks, minerals and nanogranites (Bartoli et al., 2016) or glass

compositions from experimental studies on similar rocks (Beard and Lofgren, 1991; Gardien

f
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et al., 1995). Most leucosome compositions do not represent unmodified melt; more

commonly they represent a product of fractional crystallization, and/or melt–residue

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interaction and/or open-system infiltration of melt (Brown et al., 2016; Morfin et al., 2014;
e-
Sawyer, 1987, 2020). Trace element concentrations are generally complementary to the
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major oxides in deciding whether leucosome compositions represent unfractionated anatectic

melt, cumulate-rich magma or complementary fractionated and evolved compositions

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(Brown et al., 2016; Morfin et al., 2014; Solar and Brown, 2001b). These processes are
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particularly well expressed in some diatexite terrains, where compositions vary from residue-
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rich diatexites that have lost melt to strongly-fractionated leucogranites (Milord et al., 2001;
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Sawyer, 1998, 2020).

A powerful application of trace element modelling is inferring the P–T conditions of

partial melting of source rocks that produced granite, particularly whether garnet was present

or not in the source during melting. This approach has proven particularly useful in

estimating pressures related to the generation of tonalite–trondhjemite–granodiorite (TTG)

melts from hydrated metabasites in Archean cratons (Johnson et al., 2017, 2019; Moyen and

Stevens, 2006, 2013; Yakymchuk et al., 2020). Furthermore, some of the complexities in
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trace element behaviour related to garnet fractionation and drainage of melt in the source can

be integrated into the modelling (Kendrick and Yakymchuk, 2020).

Petrochronology involves integration of the trace element compositions of dated

accessory minerals and particular rock-forming minerals that sequester (during growth) or

release (during breakdown) these elements during metamorphism (Taylor et al., 2016). For

example, heavy rare earth element (HREE) concentrations in zircon can be linked to the

growth and breakdown of garnet (Rubatto, 2002; Rubatto et al., 2013; Rubatto and Hermann,

2007; Taylor et al., 2015a) and equilibrium between these minerals may be assessed using

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REE partitioning arrays (Taylor et al., 2017). Other examples include Eu anomalies in

monazite as a monitor for the behaviour of feldspar during melting and melt crystallization
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(Dumond et al., 2015; Rubatto, 2002), linking Y concentrations in monazite to garnet growth
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and breakdown (e.g. Hacker et al., 2019), linking Th/U ratios in zircon to the behaviour of
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monazite (Harley and Kelly, 2007; Harley et al., 2007; Rubatto, 2017; Yakymchuk et al.,

2018), and tracking oxidation state using Eu anomalies in major and accessory minerals
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during partial melting (Holder et al., 2020; Yakymchuk et al., 2019a).

n

Three important considerations in applying petrochronology to anatectic systems are:

ur

(1) that whole-rock compositions will influence the trace element concentrations in accessory
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minerals (Kaczmarek et al., 2008; Schaltegger et al., 1999; Yakymchuk et al., 2019a), which

is why absolute values for concentrations are less reliable than the ratios between the

accessory and rock-forming minerals of interest (Taylor et al., 2017); (2) that enhanced

mobility of Pb in zircon at high temperature (>900ºC) combined with the limited diffusivity

of many trace elements in accessory minerals may result in ages that are decoupled from

trace element compositions (Flowers et al., 2010; Kunz et al., 2018); and, (3) that equilibrium

between accessory and rock-forming minerals may have been hindered by kinetic issues

associated with mineral dissolution in melt (Watt et al., 1996), as well as sluggish
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intracrystalline diffusion of trace elements in accessory minerals (Bea, 1991) and possibly

melt (Acosta-Vigil et al., 2017), and armouring of accessory minerals in residual or growing

minerals (Watson, 1996). Notwithstanding these limitations, petrochronology applied to

anatectic systems provides key constraints on the absolute timing of rock-forming mineral

growth that is difficult to achieve with other methods. An example of forward modelling

accessory mineral compositions is presented in section 10.

Trace element geochronology of rock-forming minerals (e.g. garnet) is now routine,

avoiding the assumptions and limitations of linking accessory mineral ages and

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concentrations of trace elements with the growth and breakdown of the P–T sensitive rock-

forming minerals. Garnet geochronology can be measured with two radioactive isotope
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systems: 147Sm–143Nd and 176Lu–176Hf (Baxter et al., 2017; Cheng et al., 2018). In general,
e-
the Lu–Hf system has a higher closure temperature (Bloch et al., 2015; Scherer et al., 2000;
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Smit et al., 2013) and it may be more robust for estimating high-temperature metamorphic

processes, such as the timing of garnet growth and partial melting. Although the ages
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retrieved from these techniques may be quite precise, how they relate to the P–T path is not
n

always straightforward, especially if whole garnet aliquots were analysed. In these

ur

situations, the spatial zoning of the parent isotope in garnet provides additional context––if
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the parent isotope (Lu or Sm) is concentrated in the garnet cores, then the age will be biased

towards the early stage of garnet growth, whereas high concentrations in garnet rims may

bias ages towards the later stages of garnet growth (commonly the metamorphic peak).

Alternatively, rims may be enriched due to garnet resorption and preferential retention of the

parent isotope, which complicates a simple age interpretation. Avoiding these complexities

may require micro-sampling of garnet core and rim domains (Dragovic et al., 2015; Ducea et

al., 2003), but this approach may be limited by the size of the garnets and the concentration

of parent and daughter isotopes in the micro-sampled aliquots. Nonetheless, garnet

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geochronology is a powerful tool especially when linked with the results of accessory

mineral geochronology.

10. Accessory Minerals

10.1 Importance of accessory minerals to studies of anatectic systems

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The importance of accessory minerals far outweighs their abundance in common rock

types. They are the main hosts for multiple trace elements (Ayres and Harris, 1997; Bea et
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al., 1994; Spear and Pyle, 2002; Ward and Werner, 1964; Zeng et al., 2005) and volatile
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elements such as S (Evans et al., 2010). Accessory minerals are used routinely as
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chronometers (Harley and Nandakumar, 2014; Harris et al., 2000; Rubatto et al., 2009, 2013;

Sawyer, 1991; Taylor et al., 2016), particularly in migmatites and granulites, and they may
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control the isotope composition of the melt that drains to shallower crust to form granites
n

(Ayres and Harris, 1997; Zeng et al., 2005). We divide this section into those accessory
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minerals we can model well, those we would like to model better, and those we cannot
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(currently) consider. We also include some applications and insights regarding the behaviour

of accessory minerals in migmatites and granulites.

10.2. Minerals we can model reasonably well

Many of the accessory minerals that contain Fe and Ti as essential structural

constituents can be modelled reasonably well in anatectic systems (Diener and Powell, 2010;

White et al., 2000, 2007). In general, this includes the common oxide accessory minerals
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(rutile, ilmenite, magnetite, spinel, hematite) and some silicates (titanite). Some accessory

minerals may be treated as pure phases lacking solid solution, such as rutile and titanite. In

these cases, our confidence in modelling their behaviour is related to our understanding of the

underlying thermodynamic properties of these minerals (Holland and Powell, 1998b, 2011;

Powell et al., 2014) and our ability to model other phases that incorporate significant amounts

of the essential structural constituents they contain, such as Ti and Fe3+ (Boger et al., 2012;

Diener and Powell, 2012; Wheller and Powell, 2014) For accessory minerals that exhibit

solid solution (e.g. spinel group and ilmenite), our confidence in terms of modelling is based

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on the underlying activity–composition models (Diener and Powell, 2010; Powell et al.,

2014), which are limited by the restricted number of experiments examining the distribution
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of ferric and ferrous iron between coexisting rock-forming and accessory minerals.
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10.3. Minerals we can model, but would like to do better

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The accessory minerals zircon, monazite and apatite have been the focus of both
n

experimental melting studies (Boehnke et al., 2013; Harrison and Watson, 1983; Klimm et
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al., 2008; Stepanov et al., 2012; Watson and Harrison, 1983, 1984) and empirical studies
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(Bingen et al., 1996; Cottle et al., 2018; Glasson et al., 2019; Kunz et al., 2018; Rubatto et al.,

2006; Williams, 2001), as they are important for both geochronology (Prent et al., 2020;

Rubatto, 2017; Taylor et al., 2016; Weinberg et al., 2020) and thermometry (Ferry and

Watson, 2007). Consequently, we have a reasonable understanding of the behaviour of these

minerals in simple experimental systems, although various complications arise in natural

anatectic systems that limit our ability to model quantitatively their growth and breakdown.

Assuming equilibrium among melt and minerals, the behaviour of zircon, monazite

and apatite is mostly controlled by the solubility limits of their essential structural
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constituents in melt. Phase equilibrium modelling coupled with experimentally-derived

solubility models predicts that zircon, monazite and apatite should dissolve during heating

and melting to saturate the increasing fraction of melt in their essential structural constituents.

An example of a solubility equation for zircon (Gervasoni et al., 2016) is:

lnZrsat = (4.29 ± 0.34) – (1.35 ± 0.10) x lnG + (0.0056 ± 0.0002) x T(°C), (30)

where G is a compositional parameter for the melt (= 3 x (Al2O3 + SiO2)/(Na2O + K2O + CaO

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+ MgO + FeO)) in molar proportions and with 1σ uncertainties, and Zrsat is the concentration

of Zr in zircon-saturated melt in µg/g. Although the formulations of solubility expressions

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vary, most have temperature and melt composition as variables. The amount of zircon
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dissolution (Zrdis%) in a rock required to saturate the melt can be modelled through mass
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balance considering the weight fraction of melt (F) and the total concentration of Zr (Zrsystem)

within the system. In a simple model, Zr is assumed to reside only in zircon and melt (Kelsey
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et al., 2008), for which Zrdis% = F(Zrsat/ Zrsystem). A similar approach can be applied to
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monazite for the LREE, which are essential structural constituents in that mineral, assuming
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that phosphorous is also available.

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Examples of the modelled behaviour of zircon and monazite during melting of an

average amphibolite-facies metapelite (Ague, 1991) and an average passive margin

greywacke (Yakymchuk and Brown, 2014a) are shown in Fig. 24 for a closed system

scenario, considering bulk rock compositions with 150 ppm Zr and 150 ppm LREE, and that

the only repository for these elements are zircon (Zr) and monazite (LREE). For both rock

types, the amount of zircon (Fig. 24a, c) and monazite (Fig. 24b, d) decreases with increasing

temperature in a non-linear manner until each is completely dissolved between 800 and

900ºC. At no point does the proportion of either mineral in the system increase with heating
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(Fig. 24), such that prograde zircon and monazite growth at suprasolidus conditions is not

expected in a closed system. However, the corollary is that the predicted proportion of both

minerals increases as T decreases, such that growth is expected to occur during cooling and

melt crystallization. Zircon and monazite are modelled to be stable to higher temperatures for

the greywacke than the metapelite for the same bulk rock concentrations of Zr and LREE.

This difference reflects the lower fertility of the greywacke compared with the metapelite.

For higher concentrations of Zr and LREE in the modelled system, exhaustion of zircon and

monazite is expected to occur at even higher temperatures. For example, zircon is expected to

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persist to >940 ºC for bulk rock Zr concentrations of 500 ppm in the metapelite compared

with 840–880 ºC with 300 ppm Zr (Fig. 24a).

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The examples above demonstrate that new growth of accessory minerals in anatectic
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systems is only expected during cooling and melt crystallization when the melt becomes
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supersaturated with respect to those elements that are essential structural constituents of the

accessory minerals considered (Kelsey et al., 2008; Kelsey and Powell, 2011; Wang et al.,
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2014; Yakymchuk, 2017b; Yakymchuk and Brown, 2014a; Yakymchuk et al., 2017).
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However, this sequence of dissolution and growth contrasts with some interpretations that
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suggest prograde suprasolidus growth of accessory minerals can occur by Ostwald ripening
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(Kawakami et al., 2013; Nemchin et al., 2001; Vavra et al., 1999). Another mechanism to

recrystallize zircon without necessarily increasing its mode is melt-induced dissolution–

reprecipitation (Hay et al., 2010; Rubatto and Hermann, 2003). Notwithstanding, mass

balance calculations support the inference that most suprasolidus zircon, monazite and apatite

growth should occur during cooling and melt crystallization (Kohn et al., 2015).

Consider a mass balance approach for zircon and its essential structural constituent,

Zr, in an anatectic system that maintains equilibrium. Zircon solubility in melt is related to

the amount of Zr that can be accommodated by the melt, which is a function of T, P and melt
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composition (Boehnke et al., 2013; Watson and Harrison, 1983). However, other factors will

influence the behaviour of zircon, such the amount of Zr in the system (Kelsey et al., 2008;

Yakymchuk and Brown, 2014a). Another factor that can affect zircon solubility is the

presence and behaviour of other rock-forming or accessory minerals that can accommodate

Zr. For example, garnet and hornblende are both relatively Zr-rich rock-forming minerals

(Fraser et al., 1997; Kohn et al., 2015) so that the growth of peritectic garnet or hornblende

during heating and partial melting will accommodate some Zr, limiting the amount of Zr

available to the melt and enhancing dissolution of zircon. For suprasolidus prograde growth,

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breakdown of a Zr-rich mineral such as ilmenite could liberate enough Zr to create a local

volume of melt that is saturated with respect to zircon (Bingen et al., 2001; Glasson et al.,
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2019). However, with further heating and an increase in melt volume this zircon may be
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consumed. New studies directed at identifying potential sources of Zr that may be responsible
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for prograde suprasolidus zircon growth would be useful in this context. A final consideration

is that zircon (and other accessory minerals) may be shielded from dissolution in stable or
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growing peritectic minerals (e.g. garnet) during melting. These grains are not expected to
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participate in equilibration with melt and other minerals, and are more likely to record
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evidence of the prograde subsolidus history.

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Monazite solubility in melt is also a function of T, P and melt composition (Stepanov

et al., 2012), but its behaviour is complicated by competition with apatite for phosphorous in

anatectic systems (Duc-Tin and Keppler, 2015; Johnson et al., 2015; Schwindinger et al.,

2020; Yakymchuk, 2017b). Similar to zircon, the mode of monazite in an anatectic system is

expected to decrease during melting as the melt saturates in the LREE (Kelsey et al., 2008).

One exception may be dissolution of LREE-rich apatite during heating, in which diffusivity

of LREE away from the apatite–melt interface may be much slower than for P, resulting in a

local monazite growth (García-Arias et al., 2012; Wolf and London, 1995). However, as with
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zircon, further heating may lead to dissolution of this monazite as diffusion rates and melt

volumes increase. The main limiting factor in our ability to model monazite is the behaviour

of Th in anatectic systems. Thorium substitution into monazite (as the huttonite or cheralite

end member) is expected to increase the stability of monazite allowing it to persist to UHT

conditions (Weller et al., 2020; Williams et al., 2018). With respect to calculated phase

equilibria, we cannot currently integrate Th in monazite or melt, which is a crucial next step

in modelling the behaviour of this important accessory mineral chronometer in formerly

suprasolidus rocks.

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Trace element concentrations in zircon and monazite are linked to the behaviour of

rock-forming minerals (petrochronology; section 9.4). An example of forward modelling

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applied to petrochronology for an average amphibolite-facies metapelite (Ague, 1991) is
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shown in Fig. 25. Accessory mineral compositional proxies for garnet behaviour are the
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concentration of HREE in zircon and monazite, and of Y in monazite (Taylor et al., 2016).

The chondrite-normalized Gd/Yb (GdN/YbN) ratio of zircon is commonly used to infer

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whether zircon grew or equilibrated in the presence of garnet, because Yb is preferentially

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incorporated into garnet (Rubatto, 2002). In general, low GdN/YbN ratios characterise zircon
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in equilibrium with relatively low P and low T mineral assemblages, where garnet
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proportions are low or where garnet is absent (Fig. 25a). The amount of garnet in the residue

has a strong influence on the slope of chondrite-normalized HREE concentrations in zircon.

A high proportion of garnet is consistent with relatively flat HREE patterns whereas low

proportions are indicated by positive slopes (Fig. 25d). Concentrations of Y in monazite are

also commonly linked to growth in the presence or absence of garnet, because garnet is a key

repository of Y in metamorphic rocks (Williams et al., 2007) and concentrations of Y in

monazite (calculated as wt% Y2O3 in Fig. 25b) are inversely proportional to the mode of

garnet (Fig. 25b, c). Similar to zircon, monazite in equilibrium with a garnet-rich residue has
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low concentrations of HREE, resulting in chondrite-normalized REE patterns with steep

negative slopes (Fig. 25e).

Relating the concentrations of trace elements in accessory minerals to a metamorphic

P–T path requires knowledge of when that accessory mineral grew. Although the behaviour

of accessory minerals during anatexis is complex, during heating along an isobaric

suprasolidus path at 0.6 GPa for an average amphibolite-facies metapelite and an undrained

system, as shown in Fig. 25, the proportion of monazite and zircon are expected to decrease

(Fig. 25c). Along this path, the proportion of garnet in the system is low at the solidus, but

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increases with heating to ~900ºC when its abundance remains constant (Fig. 25c). Most

zircon and monazite growth is expected to occur during cooling and melt crystallization from
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around 880–850 ºC until the solidus is crossed, during which the amount of garnet in the
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system decreases to ~1 wt% (Fig. 25c). In Fig. 25, the first zircon and monazite to crystallize
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from melt at ~880–850 ºC are expected to have the lowest concentrations of the HREE (Fig.

25d, e). Monazite is also expected to have the lowest concentration of Y at ~850 ºC, which
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reflects the high modal abundance of garnet in the system. Monazite with high concentrations
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of Y, and zircon and monazite with relatively high concentrations of the HREE (and low
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GdN/YbN ratios), record crystallization near the solidus. Alternatively, high-Y monazite and
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low-HREE monazite and zircon could record prograde or retrograde subsolidus monazite or

zircon growth.

There are three key assumptions in phase equilibrium modelling when applied to

accessory minerals and petrochronology. First, we assume that the trace elements have

equilibrated between the rock-forming and accessory minerals, which is difficult to reconcile

with the limited diffusivity of the HREE in zircon, monazite (Cherniak, 2010; Cherniak et al.,

1997) and silicate liquid (Holycross et al., 2018; Mungall et al., 1999). Second, we assume

there is no temperature dependence of partitioning of REE (and Y) in garnet, zircon,

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monazite and melt, which is a simplification (Hacker et al., 2019; Taylor et al., 2017).

Finally, we assume that zircon and monazite grow and dissolve instantaneous in melt based

on mass balance consideration, which is unlikely to be true in nature. Notwithstanding,

linking the results of phase equilibrium modelling with partitioning expressions between

rock-forming and accessory minerals provides a framework in which to interpret the

geological significance of petrochronological data from zircon and monazite.

The behaviour of apatite is anatectic systems is expected to be similar to zircon and

monazite whereby, on heating, the fraction of melt increases and the amount of apatite

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decreases until the melt becomes saturated in phosphorous (Watson and Harrison, 1984).

There are several experimentally-determined solubility expressions for apatite (Bea et al.,
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1992; Harrison and Watson, 1984; Pichavant et al., 1992; Tollari et al., 2006; Wolf and
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London, 1994), but these do not reproduce well the measured concentrations of P in natural
Pr

glasses and nanogranites (Yakymchuk and Acosta-Vigil, 2019). Nonetheless, apatite

solubility in melt increases with aluminium saturation index and temperature. A complication
al

in modelling apatite behaviour is that calcium is an essential structural constituent of many

n

rock-forming minerals, limiting the availability of Ca. New insights into apatite behaviour
ur

awaits advances in the in situ analysis of Nd isotope ratios (Fisher et al., 2020; Hammerli et
Jo

al., 2019).

Xenotime is a Y-bearing phosphate mineral that is normally restricted to subsolidus

metamorphic conditions, although it does occur in some migmatites (Engi, 2017; Pyle et al.,

2001; Spear and Pyle, 2002). It has been used as a thermometer when combined with the

compositions of monazite and garnet (Pyle et al., 2001) and can be used as a U–Pb

chronometer (Cottle et al., 2018; Parrish, 1990; Shrestha et al., 2019). Xenotime is expected

to be consumed during heating and, above the solidus, should saturate the melt in in P (Wolf

and London, 1995), although the solubility of P in xenotime-saturated melt is expected to be

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quite low. In addition, peritectic garnet grown during incongruent melting will incorporate Y

and HREE possibly at the expense of xenotime. This is supported by the presence of

xenotime as inclusions in garnet but its absence from the matrix of high-grade rocks (Pyle

and Spear, 1999). Spear and Pyle (2010) used phase equilibrium modelling to show that

xenotime is expected to be completely consumed just above the solidus, although the specific

P–T conditions of xenotime exhaustion are sensitive to the bulk rock concentration of Y.

Xenotime should grow during melt crystallization (Crowley et al., 2009; Pyle and Spear,

1999). In general, we have a reasonable understanding of xenotime behaviour in migmatites

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and a rudimentary ability to model its behaviour. Further studies should consider the role of

xenotime in partitioning HREE during relatively low-temperature anatexis.

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10.4. Minerals we cannot (yet) model
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Allanite is a LREE-rich epidote-group mineral and a key repository for the LREE and

Th in high-pressure intermediate to basic metamorphic rocks (Engi, 2017; Hermann, 2002).

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Although it is more common in low- to medium-temperature metamorphic rocks, allanite has

n

been documented in upper-amphibolite facies Ca-rich rocks (Bingen et al., 1996; Pan and
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Fleet, 1996) including migmatites (Gregory et al., 2012). Experimental studies have
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demonstrated that allanite solubility in melt is a function of temperature, melt composition,

pressure and LREE concentrations (Klimm et al., 2008). Similar to other accessory minerals,

allanite is expected to break down during partial melting. Berger et al. (2008) suggested that

epidote in leucosomes formed by partial resorption of earlier-formed epidote then growth

during subsequent melt crystallization, consistent with the inference that allanite should break

down during melting and grow during melt crystallization. One complication in

understanding the behaviour of allanite is the role of fluorine and complex solid solution

between trace elements and major elements in epidote-group minerals (Gieré and Sorensen,
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2004). Nonetheless, furthering our understanding of allanite in high-pressure rocks is crucial

for studies into the role of melt and mobilization of Th and LREE in subduction systems

(Hermann et al., 2006). Finally, allanite has potential as a U–Pb chronometer (Gregory et al.,

2012; Smye et al., 2014), although we need a better understanding of its stability and

behaviour in migmatites to be able to interpret these data.

10.5 Implications for isotope geochemistry

Isotope ratios of trace elements are commonly used to link granites to their sources at

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deeper crustal levels. In particular, neodymium and hafnium isotope ratios are used to infer if

the source rocks of granites were radiogenic (i.e. juvenile) or non-radiogenic (i.e. evolved),
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and to model the duration of crustal residence (Gardiner et al., 2019a, b, 2020; Vervoort and
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Kemp, 2016). Accessory minerals are the dominant hosts of REE and Hf in high-grade
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metamorphic rocks (Bea and Montero, 1999; Hermann, 2002) and can exert a first order

influence on the isotopic composition of drained melt (Ayres and Harris, 1997; Zeng et al.,
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2005).
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Zircon is the dominant host of Hf in many anatectic systems and Lu is concentrated in

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phosphate minerals (e.g. apatite and monazite) as well as garnet. Therefore, the behaviour of
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these minerals during partial melting will affect the Lu/Hf ratio of the melt and the Hf isotope

ratio of zircon that crystallizes from it. In a closed system undergoing melting, Hf liberated

from dissolved zircon may be incorporated into newly grown zircon during crystallization,

and this neoblastic zircon will have an Hf isotope composition similar to that of the older

zircon (Flowerdew et al., 2006; Li et al., 2018; Wu et al., 2007). In metasedimentary

migmatites, this implies that the Hf isotope composition of the melt (and zircon that

crystallizes from it) may reflect an isotopically-diverse population of detrital zircon. The

breakdown of Lu-rich minerals (e.g. garnet and apatite) may also release relatively radiogenic
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Hf into the melt that could be incorporated into new zircon that will have a more radiogenic

(more juvenile) isotope ratio (Chen et al., 2015). Similar to Hafnium, Nd isotope ratios in the

melt are controlled by the behaviour of monazite and apatite (Ayres and Harris, 1997;

Hammerli et al., 2018; Hammerli et al., 2014; Korhonen et al., 2010b; Macera et al., 2011;

Villaros et al., 2009; Watt and Harley, 1993; Zeng et al., 2005). Equilibration between these

minerals and melt is an important consideration in linking the Nd isotope ratio of granites to

their sources due to slow dissolution of these two minerals in melt (Rapp and Watson, 1986).

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11. Summary and future research
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In this review, we hope to have provided information to help both novices and
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professionals in their studies of the fundamental process of irreversible differentiation of the

continental crust by partial melting. This process requires the production, segregation and
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migration of silica-rich (felsic) melts from deeper source rocks to shallower sinks where they
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erupt or, more commonly, crystallise as granite sensu lato. Evidence of partial melting and
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drainage of melt from crustal rocks is preserved in outcrops and thin sections of migmatite
Jo

and residual granulite. At the crustal scale, these processes are implicit in the complementary

compositions of residual lower crust and enriched upper crust.

Investigation of partial melting and open versus closed system processes utilises

calculated phase equilibria, which may now be applied to a wide variety of crustal source

rocks, including basalts and gabbros, clastic sedimentary rocks such as greywackes, siltstones

and mudstones (pelites), and granites themselves. Leucosomes and pegmatites in ultrahigh-

pressure metamorphic rocks have become a focus of recent studies, but rather than being

formed by aqueous fluid-present or fluid-absent hydrate-breakdown melting, they may have

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crystallised from hydrous melt that evolved from a supercritical fluid. We also introduced the

reader to recent studies that have advanced our understanding of the behaviour of trace

elements and the role of accessory minerals during partial melting, including the implications

for isotope geochemistry.

To conclude, we offer some directions in which future studies might be focussed.

 In relation to natural examples, it would be helpful to have a better understanding of the

mechanisms by which melt moves from source to sink in various tectonic settings. As a first

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step, more quantitative studies at thin section, outcrop and crustal scale are required. In

pr
particular, we need quantitative assessments of the proportion of melt that reaches the surface

versus the proportion that crystallises at depth. This information will permit a more complete
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understanding of crustal behaviour through 2D and 3D numerical modelling of geodynamics
Pr

through Earth history.

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 Along with the mechanisms, future studies should focus on the timescales of melt
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generation, segregation, migration, emplacement and crystallization. We should combine

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high-precision geochronology (e.g. CA–ID–TIMS) with field observations and samples from
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various crustal depths. This approach will yield a better understanding of the geological

significance of ages determined using less precise geochronometers from both source rocks

(migmatites and residual granulites) and granites. In addition, recent developments in

reaction cell technology mean that we will soon be able to undertake in situ Lu–Hf dating of

garnet (and other minerals) by LA–ICP–MS spot analysis. The method will provide a means

to constrain the metamorphic (and anatectic) history of rocks that may lack traditional

chronometers, including garnet-bearing mafic and ultramafic rocks, in a manner that is far
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more time and cost efficient than is currently available. A better determination of timescales

will improve our understanding of anatectic systems as a whole.

 With respect to calculated phase equilibria, there is a need for more targeted experiments

in simple (synthetic) compositional systems to enable the energetic contributions of

individual components in solid solutions to be better understood, which will allow a–X

(solution) models to be refined. This is particularly important for the ferric iron component in

ferromagnesian minerals, where our understanding of a–X relationships is hindered by the

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paucity of experimental data. In addition, we need continued improvements to the a–X

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thermodynamic models used in phase equilibrium calculations, including extending the range

of compositions to which they may be applied and the P–T conditions for which they may be
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used. To supplement new data from targeted experimental studies, we should increase the use
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of comprehensive compositional data (i.e. major and trace elements) for coexisting minerals

in equilibrated natural samples.

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 To improve our understanding of open versus closed system melting, we should critically
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assess the role of H2O-fluxed melting in producing and reworking continental crust. In
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particular, we should better characterise the sources of H2O, the solute content of the

attending fluid, and the thermochemical consequences of pervasive fluid infiltration during

high-grade metamorphism, as well as developing a better understanding of the mechanics of

fluid infiltration. This is of particular importance for arc magmatism on the modern Earth and

potentially for TTG production in the early Earth.

 The role of supercritical fluid during exhumation of deeply-subducted continental crust is

underappreciated in the UHP metamorphic community. As a first step, an assessment of the

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potential role of dehydroxylation and the formation of a supercritical fluid in the generation

of hydrous melt during exhumation of all major UHP terranes would be useful.

 The importance of trace element partitioning and the role of accessory minerals in the

petrogenesis of granites have been appreciated for several decades. However, it would be

useful to have a better understanding of the behaviour of accessory minerals in anatectic

systems. This requires additional empirical and experimental studies on the partitioning of

elements between the accessory minerals, rock-forming minerals and melt, in particular for

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those elements that form essential structural constituents of the accessory minerals. This is

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crucial if we are to better assess the geological significance of the precise ages now being

retrieved from accessory minerals. A wider range of partitioning data will allow better links
e-
to be made between the growth or recrystallisation of accessory minerals and estimated P–T
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conditions along a metamorphic P–T path. Furthermore, we recommend increasing the use of

rapid mapping of trace elements by LA–ICP–MS as a complement to major element mapping

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by EPMA to better link accessory mineral behaviour with that of the rock-forming minerals.
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This would also enable a better understanding of trace element partitioning between the rock-
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forming and accessory minerals with melt in anatectic systems, which is important for
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furthering our understanding of long-term crustal differentiation using elemental and isotopic

data compiled in large datasets. Two additional goals are the identification of potential

sources of Zr that may support prograde suprasolidus growth of zircon, and the integration of

Th into monazite solubility models to refine our understanding of monazite ages retrieved

from formerly suprasolidus crustal rocks. Lastly, for both rocks and accessory minerals, we

should determine the relationship between changes in elemental or isotopic composition and

tectonic setting in both modern and ancient environments.

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To close, we identify two topics that should be addressed in future studies. First, we

should develop a better understanding of the role of bolide impacts on large-scale crustal

melting and differentiation, particularly to assess the contribution of these processes to the

evolution of the mantle, crust, hydrosphere, atmosphere and biosphere on Earth and other

terrestrial bodies. Second, we should assess the physicochemical drivers behind the formation

of rare metal deposits from granite magmas and pegmatites. Our enhanced understanding of

the processes involved in the concentration of these elements in evolved melts is crucial for

identifying new deposits of these raw materials, since they are becoming increasingly

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important to current and future technological advances, particularly in green-energy

technologies.
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Author contributions
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Tim Johnson: Conceptualization; Visualization; Writing – sections of original draft; Writing

– review & editing. Chris Yakymchuk: Visualization; Writing – sections of original draft;
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Writing – review & editing. Michael Brown: Conceptualization; Writing – sections of

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original draft; Writing – review & editing.

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Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal

relationships that could have appeared to influence the work reported in this paper.

Acknowledgements

Over several decades we have collectively benefited from countless discussions with

colleagues too numerous to mention individually—we are grateful to you all. Tim Horscroft

is thanked for the invitation to write this review. We are particularly indebted to Antoine
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Godet and Roberto Weinberg for their perceptive, detailed and helpful reviews, and for their

resilience in getting through the entire manuscript. Douwe van Hinsbergen is acknowledged

for his editorial handling and generosity in extending deadlines. Any remaining errors or

misconceptions are entirely ours.

Appendix

Glossary of terms relating to partial melting of crustal rocks

Many of these terms (and others) are also explained in the Atlas of Migmatites (Sawyer,

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2008).

 Anatexis—see partial melting,

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 Congruent melting: partial melting in which one or more reactants (minerals with or
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without volatile species) break down to form a melt of the same composition as the only
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product.

 Diatexite—see migmatite.
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 Dihedral angle: the angle subtended at the junctions of two solid grains in textural
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equilibrium with a fluid or melt phase is the fluid–solid–solid dihedral angle.

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 Exhumation: the exposure of a rock unit on the land surface by removal of the
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overburden at the metamorphic peak (not to be confused with uplift, which is the upward

movement of a rock unit relative to adjacent units).

 Fertility: the property of some protolith compositions to produce more melt than others at

the same P–T conditions.

 Fluid (also Volatile): a low-viscosity liquid or gas phase (commonly H2O) that may form

or be present in both subsolidus and suprasolidus rocks.

 Fusion: see partial melting.

 H2O-saturated solidus: see solidus.

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 H2O-undersaturated solidus: see solidus.

 Heat: thermal energy within, or transferred to or from, a thermodynamic system.

 Heat producing element: an unstable atom that produces heat by radioactive decay, most

importantly isotopes of K, Th and U.

 Hydrous mineral (also Hydrate): a mineral containing OH– or H2O in its crystal

structure (e.g. mica, amphibole, epidote, cordierite, etc.); hence hydrate-breakdown

melting is incongruent melting involving the breakdown of one (or more) hydrous

f
minerals.

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 Incongruent melting: partial melting in which both liquid and one or more peritectic

pr
minerals are the products of the melting reaction.

 In-situ leucosome—see Leucosome

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 In-source leucosome—see Leucosome
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 Internal energy: the total energy a substance possesses.

 Latent heat of fusion: at fixed pressure, the amount of heat required to convert one unit
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of a substance from the solid to the liquid phase without changing the temperature of the
n
ur

system.

 Leucosome: the lighter-coloured part of the neosome that represents material crystallized
Jo

mostly from the segregated melt; it is commonly dominated by quartz and feldspar, and it

may or may not correspond to a melt composition. In-situ leucosome is the product of

crystallization of anatectic melt, or part of the anatectic melt, that has segregated from its

residuum, but has remained where it formed, whereas in-source leucosome is the product

of crystallisation of an anatectic melt, or part of an anatectic melt, that has migrated away

from the place where it formed, but is still located within its source layers.

 Liquidus: a line in P–T space above which a substance is completely liquid.

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 Melanosome: the darker coloured part of the neosome that represents residual material

that did not melt and from which melt has drained.

 Melt: A viscous polymerised hydrous silicate liquid that begins to form when a rock

exceeds the temperatures of its solidus.

 Melt connectivity transition (MCT): the melt fraction (around 7 vol.% melt) above

which the melt forms an interconnected network and the strength of a partially-molten

rock drops by an order of magnitude or more.

 Metamorphic peak: the maximum temperature (or less commonly pressure) recorded by

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a metamorphic rock.

 Metamorphic facies: commonly-occurring sets of mineral assemblages developed in

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rocks of different compositions that recur in space and time.
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 Metatexite—see Migmatite
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 Microstructure: the relative size, shape and spatial arrangement of grains that comprise a

rock (NB. texture is reserved for the internal features of the individual grains).
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 Migmatite: a metamorphic rock formed by anatexis that is generally heterogeneous and

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preserves evidence of partial melting at the microscopic to macroscopic scale

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(Yakymchuk, 2020). The first-order classification of migmatites is based on the inferred

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melt fraction in the rock (Sawyer, 2008). Metatexite migmatites are characterized by a

low melt fraction, which allows pre-anatectic structures generally to be preserved, whereas

diatexite migmatites are characterized by high melt fraction, which generally means that

pre-anatectic structures have been disrupted by flow. The second-order classification of

migmatites relates to the amount of syn-anatectic strain. Patch, net-structured and

stromatic metatexite migmatites represent increasing syn-anatectic strain at low melt

fraction, whereas raft or schollen and schlieren diatexite migmatites represent

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increasing syn-anatectic strain at high melt fraction. The interested reader is referred to

Sawyer (2008) for further details.

 Mineral assemblage: a collection of locally coexisting minerals interpreted to have

chemically interacted; the term equilibrium mineral assemblage may be used when a

state of chemical equilibrium is implied.

 Neosome: the part of a migmatite that was newly formed or reconstituted by partial

melting.

 Paleosome: the part of a migmatite that was unaffected by partial melting due to protolith

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composition or isolation from a hydrous fluid that fluxed melting.

 Partial melting (also Anatexis and Fusion): Partial melting is the process or action of
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transforming a substance into a liquid plus residual solids usually, but not exclusively, by
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the addition of heat.
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 Peritectic mineral(s): the solid product(s) of an incongruent melting reaction.

 Prograde metamorphism: the changes in mineral assemblage and microstructure that

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occur during heating.

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 Protolith: the original crustal rock before modification by partial melting and loss of melt.
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 Reaction: the process by which one or more phases, the reactants, are converted to one or
Jo

more different phases, the products.

 Reaction rate: the rate of change of the abundance (mode) of reactants or products as a

function of changing T and/or P.

 Residue or Residuum (adj. residual): material from which partial melt has drained

leaving behind melt-depleted solids.

 Retrograde metamorphism: the changes in mineral assemblage and microstructure that

occur during cooling.

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 Solidus: a line in P–T space at temperatures below which melt is not stable; this line

separates subsolidus from suprasolidus P–T conditions. The H2O-saturated (wet)

solidus is the locus of P–T conditions at which, with increasing T, H2O-saturated melt first

forms in equilibrium with a discrete H2O fluid phase. The H2O-undersaturated solidus is

the locus of P–T conditions at which, with increasing T, an H2O-undersaturated

composition will begin to melt.

 Ultrahigh pressure metamorphism: metamorphism that results in the presence of a high-

f
pressure polymorph of silica (coesite) or carbon (diamond) in a rock; the presence of

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either mineral, whatever its grain size or abundance, indicates a minimum pressure on the

order of 3 or 4 GPa, respectively.

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 Ultrahigh temperature metamorphism: metamorphism in which peak temperature
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exceeded 900°C at a pressure below the sillimanite–kyanite transition.
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Declaration of interests
The authors declare that they have no known competing financial interests or personal
relationships that could have appeared to influence the work reported in this paper.
n al

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Figure captions
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Fig. 1. In (a), the coloured data points show P–T conditions for 564 localities from the global
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age, temperature and pressure dataset for secular change in metamorphism (Brown and
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Johnson, 2019a). The data are grouped into three types of metamorphism: low T/P (blue),

intermediate T/P (orange) and high T/P (red). Superimposed on the data in (a) are the

metamorphic facies. At pressures below coesite stability the facies boundaries are transitional

to indicate the control of bulk composition on the change in mineral assemblages from one

facies to another. Low-to-moderate pressure facies are: L = low-grade metamorphism,

including the zeolite facies; Gs = greenschist facies; A = amphibolite facies; and, G =

granulite facies (including ultrahigh temperature metamorphism at T > 900 °C). High-to-

ultrahigh pressure facies are: Bs = blueschist facies; Ec = eclogite facies; and, UHP =
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ultrahigh pressure metamorphism, which is the part of the eclogite facies at pressures where

coesite rather than quartz is stable. Progressive metamorphism across a sequence of facies is

a metamorphic facies series. In (b), we show the range of thermobaric ratios (T/P) defined by

each type of metamorphism: low T/P, < 375 °C/GPa; intermediate T/P, 375 to 775 °C/GPa;

and, high T/P, > 775 °C/GPa. In (c), we plot T/P vs age to show the evolution of bimodality

in the Paleoproterozoic and the dominance of lower thermobaric ratios since the

Neoproterozoic. Contours, which are for the dataset as a whole, represent the proportion of

the data inside 1 sd, 2 sd and 3 sd, respectively.

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Fig. 2. Evidence of partial melting at outcrop and nomenclature of migmatites. (a). Fluid-
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present partial melting of amphibolite where the melt has migrated to form leucosome-
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dominated patches leaving behind coarse-grained amphibole-dominated areas of residue
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within a medium-grained amphibolite protolith. (b). Incongruent partial melting in which

peritectic garnet, a solid product of the melting reaction, is located within the leucosome
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veins, suggesting that the locations of garnet nucleation control the concentration of melt at
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these sites. (c). Stromatic metatexite migmatite at the top becomes disrupted across a one-
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meter transition to schlieric diatexite migmatite. Note the paleosome within the transition
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zone and the scholle of paleosome at the bottom-right within the diatexite. (d). Outcrop

comprising areas of patch metatexite migmatite and areas where the patches have merged to

form a dilatant metatexite migmatite. (e). Stromatic metatexite migmatite; the thin dark-

coloured mica-rich layers at the edges of the leucosomes are sometimes called mafic

selvedges. (f). Net-structured metatexite migmatite; this structure is common in

homogeneous protoliths. Migmatite nomenclature follows Sawyer (2008).

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Fig. 3. Microstructural evidence of partial melting and melt crystallisation in thin section. (a).

Backscattered electron image to show H2O-saturated partial melting of muscovite (Ms) +

quartz. An early stage of melting is shown in which a layer of former melt (L) developed

along the muscovite–quartz grain boundary with the localised nucleation of mullite (M).

Small grains of biotite (high contrast) are also present. Reproduced from D.C. Rubie and A.J.

Brearley (1990, A Model for rates of disequilibrium melting during metamorphism. In:

Ashworth, J.R. and Brown, M., 1990, High‐temperature Metamorphism and Crustal

Anatexis. Unwin Hyman, pp. 57–86) with permission. (b). Optical image to show the

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occurrence of K-feldspar as thin interstitial cuspate films with low dihedral angles along

grain boundaries of phengite and quartz (cross-polarized light). (c). Cordierite-rich mantle
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around large garnet (at bottom). The compacted microstructure of the cordierite suggests melt
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drainage, but the cuspate interstitial quartz around the small garnet represents a pseudomorph
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of a trapped pocket of melt. Note the low dihedral angles of the quartz against the

surrounding cordierite.
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Fig. 4. Microstructural evidence of incongruent partial melting in thin section of eclogite. (a)
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and (c). Plane polarized light; (b) and (d). Crossed polarized light with 1 λ plate. Networks of
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optically-continuous plagioclase pseudomorph former grain boundary films of melt (pale

orange in (b) and (d)). Although the eclogite contains both phengite and zoisite, melting was

predominantly by omphacite breakdown with only a minor contribution from these two

minerals plus quartz, yielding omphacite with a lower concentration of the Na–Al pyroxene

(jadeite) component than the large grains of Na–Al-rich pyroxene (omphacite) and melt

(Feng et al., 2021). Microstructural evidence of this reaction is seen on the left and at the

bottom right in (a) and (b), and in the centre of (c) and (d), where large omphacite grains

(lavender or blue in (b) and blue in (d)) are partially replaced by finer-grained omphacite and
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optically-continuous plagioclase. Subhedral hornblende has crystallized from the melt (e.g.

lower left in (d)). A thin layer of plagioclase (blue) pseudomorphs melt along an omphacite–

garnet grain boundary in the upper left in (c) and (d), where the omphacite is seen to have a

ragged grain boundary against plagioclase but the garnet (purple in (d)) retains a straight

grain boundary (white oval in (c)), consistent with no contribution from garnet to the melting

reaction. The scale bar is 500 m wide.

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Fig. 5. Leucogranite forming a sill and dike network in stromatic metatexite migmatite at

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Maigetter Peak (height 480m) in the Fosdick Mountains of West Antarctica (76°26’38”S,

146°30’00”W). The view is to the southeast and was taken from the air (Twin Otter wing tip
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in upper right). From the aerial perspective and also on close examination in outcrops,
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intersecting sills and dikes do not appear to truncate or displace each other. Furthermore, the
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sills and dikes of leucogranite crosscut foliation but may be either continuous with or

discordant to garnet and cordierite-bearing leucosomes in the migmatites. Thus, during

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anatexis this level in the crust was both a source of melt and a melt transfer zone.
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Fig. 6. P–T diagram showing the stability of the aluminosilicate minerals andalusite, kyanite
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and sillimanite in the one-component Al2SiO5 system. The various points and paths are

discussed in the text.

Fig. 7. Hypothetical isobaric diagrams illustrating phase equilibria in the binary system A–B

in which no phase shows solid solution. (a) simple system with no intermediate phases; (b)

system with an intermediate phase AB that melts congruently; (c) system with an

intermediate phase AB that melts incongruently. See text for discussion. A more detailed
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treatment of these diagrams and of phase equilibria in more complex ternary and quaternary

systems is provided by (Cox et al., 1979).

Fig. 8. Qualitative phase relations in the KASH system. (a) Compatibility triangle in the K–

A–H system projected from quartz (S) showing the compositions of the phases considered.

The only phase showing solid solution is melt that contains variable H2O contents. (b–f)

Sequential development of a Schreinemakers’ bundle showing the stable (solid red) and

metastable (dotted red) segments of univariant equilibria around the invariant point (IP) at

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which all six phases coexist. Also shown each panel is the compatibility diagram appropriate

for that univariant equilibria, from which the reaction can be deduced. See text for more

details.
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Fig. 9. Calculated phase diagrams based on the experimental starting composition of Taylor

et al. (2015b) in the NKFMASH system to illustrate the features of, and logic behind,
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pseudosections. (a) P–T pseudosection. The red dotted lines are for a constant abundance
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(mode isopleths in mol.% ~vol.%) of biotite. The inset shows the changing variance (F) of
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the four fields within the black dashed box; (b) isobaric (P = 0.9 GPa) T–X pseudosection, in
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which X shows XMg varying from 0.1 to 0.9. See text for more details. The white dashed lines

in (a) and (b) are equivalent. (c) Modebox diagram showing the changing abundance (as

mol.% ~vol.%) along the isobaric heating path between A and B shown in (a). See the main

text or more details.

Fig. 10. Modebox diagrams illustrating the contrasting behaviour during open vs

conditionally closed system melting of a model metapelite (a) and metagreywacke (b)

(Yakymchuk and Brown, 2014b). See the text for more details.
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Fig. 11. Field relations of migmatised metabasic (a–d) and metatonalitic (e and f) rocks from

the Lewisian Gneiss Complex, NW Scotland, illustrating the generation, segregation and

migration of TTG-like melts/magmas. (a) Metatexite containing irregular patch of peritectic

Cpx-bearing leucosome; (b) Stromatic metatexite comprising discontinuous stroma of

leucosome that interconnect with coarser-grained patches, some containing retrogressed

peritectic Cpx grains; (c) A peritectic Cpx-bearing sheet (bottom) feeds into a trondhjemite

sheet (top). The Cpx-bearing sheet is associated with a diffuse mafic selvedge and

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interconnects with thin veins of leucosome within the melanosome. (d) Large peritectic Cpx

grains within a leucosome channel are surrounded by a thin rind of hornblende, suggesting
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limited retrograde reaction with melt. For more information see Johnson et al. (2012) and
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Feisel et al. (2018). (e) and (f) Stromatic leucosomes in petrographic continuity with a
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coarse-grained cross-cutting leucosome within a shear band. The cross-cutting leucosome

contains abundant peritectic pyroxene consistent with fluid-absent incongruent melting

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reactions consuming hornblende.

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Fig. 12. Calculated phase relations for the average Coucal basalt in the 10-component Na2O–
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CaO–K2O–FeO–MgO–Al2O3–SiO2–H2O–TiO2–O (NCKFMASHTO) chemical system. (a)

P–T pseudosection using an Fe3+/Fe of 0.1 and an H2O content just sufficient to saturate the

solidus at 1.0 GPa. The red dotted lines show melt proportions (F) as mol.% (~vol.%). The

thick white dashed line shows the a 900 °C/GPa thermobaric gradient and the thinner dashed

lines the 700 and 1100 °C/GPa thermobaric gradients discussed in detail in the main text (see

also Fig. 14). (b) Simplified version of (a) emphasising some key features. At low melt

fractions (<10%) the melts are granitic (high K) in composition. At higher melt fractions, the

yellow, green and blue fields show the stability of low-, medium- and high-P TTGs
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according to (Moyen, 2011), which are inferred to record the presence or absence of garnet

and rutile. The white dashed lines are linear geotherms (°C/GPa), with the 900 °C/GPa

thermobaric ratio emboldened. Modified after Johnson et al. (2017).

Fig. 13. Calculated modebox diagrams showing the changing abundance of phases with

heating along the 700 °C/GPa (a), 900 °C/GPa (b) and 1100 °C/GPa (c) thermobaric ratios,

which correspond to relatively low, moderate and high geotherms, respectively. (d)

Calculated major oxide composition of melt produced from the average Coucal basalt along

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the 900 °C/GPa thermobaric gradient at various melt fractions (5–40%) normalised to the

average Paleoarchaean East Pilbara TTG. The modelled melt compositions at a melt fraction
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of 25% fit within the 2 envelope on the average Paleoarchaean East Pilbara TTG data,
e-
which is indicated by the grey shaded region. Also shown are the global average
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compositions of TTGs and potassic granites (Moyen, 2011). Modified from Johnson et al.

(2017).
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Fig. 14. P–T pseudosection from 0.35 to 1.35 GPa and 640–1000 °C based on the hydrated
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compositions of an average: (a) MORB (with plagioclase in excess; (Sun and McDonough,
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1989)) and; (b) Eoarchean basalt from Isua, Greenland (with hornblende in excess;

(Hoffmann et al., 2011)). Both modelled compositions contain sufficient H2O to minimally

saturate the wet solidus at 1.3 GPa. The thin red dashed lines in (b) show melt proportions (as

mol.% ~vol.%). Calculations use the end-member thermodynamic data of (Holland and

Powell, 2011) and activity–composition models of Green et al. (2016) and White et al.

(2014a). For more details see Gardiner et al. (2018), Gardiner et al. (2019a) and the main

text.
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Fig. 15. (a) P–T pseudosection from 0.15 to 1.0 GPa and 640–900 °C and (b) isobaric (P =

0.8 GPa) T–X pseudosection for a hornblende-gabbro sample 87S35a used in the experiments

of Sisson et al. (2005), with hornblende and plagioclase in excess. In (a), the bulk

composition contains sufficient H2O to minimally saturate the wet solidus at 0.9 GPa. In (b),

the x-axis illustrates the influence of adding H2O (up to a total of 6 wt%) at temperatures of

650–800°C at a pressure equivalent to the base of thickened arc crust. The thin red dashed

lines in (b) show melt proportions (as mol.% ~vol.%). Calculations use the end-member

thermodynamic data of (Holland and Powell, 2011) and activity–composition models of

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Green et al. (2016) and White et al. (2014a). For more details see Collins et al. (2020b) and

the main text.

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Fig. 16. Simplified A(K)FM diagram projected from K-feldspar showing the garnet–
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cordierite tie line that is generally considered to separate aluminous from subaluminous

metapelites. Various average compositions of shales, metapelites and greywackes are also
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shown. S56, Shaw (1956); A91, Ague (1991); C93, Condie (1993); YB14, Yakymchuk and
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Brown (2014b); NASC, North Atlantic Shale Composite; PAAS, average post-Archean
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Australian shale.
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Fig. 17. Petrogenetic grid in the K2O–FeO–MgO–Al2O3–SiO2–H2O (KFMASH) system

showing suprasolidus univariant reactions. Modified from White et al. (2014a). Simplified

A(K)FM diagrams showing co-existing mineral assemblages are modified from Spear et al.

(1999). The numbered reactions are discussed in the text.

Fig. 18. Suprasolidus phase relationships for an average amphibolite-facies metapelite

composition (Ague, 1991). (a) P–T pseudosection (isochemical phase diagram) in the MnO–
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Na2O–CaO–K2O–FeO–MgO–Al2O3–SiO2–H2O–TiO2–O (MnNCKFMASHTO) system

(modified from Yakymchuk (2017a)). All fields include liquid and ilmenite. For clarity, not

all of the small multivariant fields are labelled, but are provided in Yakymchuk (2017a). The

H2O content was chosen so that the bulk composition does not contain any free H2O at the

solidus at 0.7 GPa. The numbers in circles indicate reactions equivalent to the numbered

KFMASH equilibria given in the text. (b) Simplified P–T diagram showing the stability

fields of key minerals. (c) Simplified P–T diagram showing isopleths for the proportion of

melt in the system. Note that the H2O content was adjusted for calculations relevant to this

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diagram so that there is no free H2O at 0.6 GPa. Consequently, quartz is stabilized to slightly

higher temperatures than in (a) and spinel stability is slightly decreased.

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Fig. 19. Modebox diagrams showing the changing abundance (as mol.% ~vol.%) of phases
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along an isobaric (P = 0.6 GPa) heating path for an average metapelite (a) and

metagreywacke (b). See text for more details. Note that the H2O content was adjusted such
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that there is no free H2O at 0.6 GPa, which is different than the scenario of no free H2O at 0.7
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GPa for the P–T diagrams in Fig. 19a (metapelite) and Fig. 21a (greywacke). Consequently,
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the stability fields are slightly different between diagrams for the same rock type. For the
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metapelite, quartz is stabilized to slightly higher temperatures than in Fig. 19a and spinel

stability is slightly decreased. For the greywacke, the differences are negligible.

Fig. 20. Suprasolidus phase relationships for an average passive margin greywacke

(Yakymchuk and Brown, 2014b). (a) P–T pseudosection (isochemical phase diagram) in the

MnO-Na2O-CaO-K2O-FeO-MgO-Al2O3-SiO2-H2O-TiO2-O (MnNCKFMASHTO) system

(modified from (Yakymchuk, 2017a). All fields include quartz, liquid and ilmenite. The H2O

content of the bulk composition was chosen such that there is no free H2O at the solidus at
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0.7 GPa. The numbers in circles indicate reactions equivalent to the numbered KFMASH

equilibria given in the text. (b) Simplified P–T diagram showing the stability fields of key

minerals. (c) Temperature–proportion (modebox) diagram showing the changes in predicted

mineral proportions during isobaric heating at 0.6 GPa. Note that the H2O content was

adjusted in this diagram so that there is no free H2O at 0.6 GPa. (d) One-oxide normalized

molar percentage (approximately equivalent to vol.%) of melt.

Fig. 21. Modelled melt compositions from a metapelite (a–c) and greywacke (d–f).

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Concentrations of SiO2 in melt are generally predicted to increase with heating (a, d) except

after quartz exhaustion in the metapelite (a). A/CNK (molar Al2O3 / [Na2O + K2O + CaO])
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increases with heating. The inflection in the predicted A/CNK values coincides with the
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exhaustion of sillimanite. The Fe# (molar Fe / [Fe + Mg]) of the melt decreases with
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temperature until biotite exhaustion in both rock types (c, f) and then increases.
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Fig. 22. Range of melt compositions from 0.4–1.2 GPa and the solidus to 950C for an
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average amphibolite-facies metapelite and an average passive margin greywacke. The fields
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enclose all of the melt compositions for each rock type over these P–T conditions. (a) A/NK
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versus A/CNK diagram to differentiate peralkaline, metaluminous and peraluminous melt

compositions (Shand, 1927). Both modelled compositions are predicted to generate

peraluminous melt and strongly peraluminous (Clarke, 2019) melt compositions. (b)

CaO/Na2O versus A/CNK diagram showing the predicted melt compositions (fields). The

horizontal dashed line at CaO/Na2O = 0.3 is commonly used to differentiate melt generated

from metapelitic (<0.3) and metapsammitic (>0.3) sources (Sylvester, 1998). Note the

overlap between the two sources and the inconsistency with the commonly used boundary for

separating metapelite- and metapsammite-derived melt compositions.

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Fig. 23. Simplified P–T phase diagram for rock-buffered silicate mineral–H2O systems. The

thick red curve between the two black lines is the low P wet solidus for compositions

between haplogranite (no CaO; lower-T line, S1) and Ca-bearing granite (CaO of 1.93 wt%,

plagioclase An20; higher-T line, S2), respectively, which terminates at the second critical

endpoints SCE 1 (haplogranite) and SCE 2 (Ca-bearing granite) with the critical lines (CL 1

and CL 2) extending to lower P and higher T (Hack et al., 2007). The critical lines separate

the phase assemblage field of silicate minerals plus supercritical fluid (SCF) at high P from

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that of silicate minerals plus hydrous melt and aqueous fluid (M + F) at low P. The solid

curve extending to high P from SCE 2 is the isopleth of 30 wt% solute in the fluid phase,
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which separates the P–T field of aqueous fluid (at low T) from that of supercritical fluid (at
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high T) in equilibrium with silicate minerals (purple dashed lines on either side of 30 are
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isopleths of solute content in fluid (at lower T) and supercritical fluid (at higher T),

respectively). Also shown is the wet solidus for basalt (S 3), which terminates at the second
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critical endpoint SCE 3 with the critical line CL 3 separating the phase assemblage field of
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silicate minerals plus supercritical fluid (SCF) at high P from that of silicate minerals plus
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hydrous melt and aqueous fluid (M + F) at low P. Solid green lines show the high-P stability
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limit of albite, and the transformation of quartz to coesite and graphite to diamond.

Fig. 24. Modelled stability of zircon and monazite in an average metapelite (a, b) and an

average passive margin greywacke (c, d) during closed-system melting. The diagram was

constructed by extracting mineral/melt modes and compositions over a grid every 25 °C and

0.05 GPa and contouring the diagram at this resolution based on the solubility of zircon and

monazite, using the solubility models of Boehnke et al. (2013) and Stepanov et al. (2012).

Solid black lines show the amount of zircon and monazite remaining in the residue relative to
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the amount at the solidus (dashed black line) for a scenario with whole-rock concentrations of

150 ppm Zr and 150 ppm LREE. The solid blue lines show the limit of monazite and zircon

stability for the specified concentrations of Zr and the LREE. The background colours show

the stability of the major minerals for the metapelite (see Fig. 19) and the greywacke (see Fig.

21). For all scenarios, the amounts of zircon and monazite are expected to decrease with

increasing temperature. For more details see Yakymchuk and Brown (2014a) and

Yakymchuk et al. (2017).

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Fig. 25. Concentrations of trace elements in accessory minerals as a function of pressure and

temperature in an average amphibolite-facies metapelite (Ague, 1991). (a) Chondrite-

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normalized Gd/Yb ratio of zircon in equilibrium with the major phase assemblage using the
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partition coefficients of the REE in zircon from the Taylor et al. (2015b) lattice-strain model
Pr

and the zircon solubility expression of Boehnke et al. (2013). The coloured fields are the

same as in Fig. 19b. (b) Modelled concentration of Y2O3 in monazite as a function of

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pressure and temperature using the partition coefficients determined from the C3308
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experimental run of Stepanov et al. (2012) combined with their monazite solubility
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expression. (c) Modelled proportions of zircon and monazite (relative to the amount at the
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solidus) and of garnet for an isobaric heating path at 0.6 GPa. The proportions of zircon and

monazite decrease non-linearly with temperature whereas the quantity of garnet increases. (d)

Modelled concentrations of REE in zircon along a 0.6 GPa isobaric heating path at 25 °C

intervals. (e) Modelled concentrations of REE in monazite along a 0.6 GPa isobaric heating

path at 25 °C intervals. Line colours in (d) and (e) represent the amount of garnet in the

system at the modelled P–T condition. For all models, partition coefficients of ilmenite,

rutile, apatite, plagioclase and biotite were taken from Bédard (2006b); cordierite, K-feldspar,

quartz, sillimanite and kyanite were assumed to host negligible REE and Y. The bulk
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composition of the metapelite was assumed to be that of the average Proterozoic shale of

Condie (1993) except for Zr, which was assumed to be 150 ppm. All chondrite values are

from McDonough and Sun (1995). Apatite solubility was modelled with the expression of

Pichavant et al. (1992).

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