Physics of the Earth and Planetary Interiors 300 (2020) 106430

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Physics of the Earth and Planetary Interiors

journal homepage: www.elsevier.com/locate/pepi

Thermodynamic modeling of hydrous-melt–olivine equilibrium using T

exhaustive variable selection
Kenta Uekia,⁎, Tatsu Kuwatania,b, Atsushi Okamotoc, Shotaro Akahod, Hikaru Iwamoria,e,f
a
Research Institute for Marine Geodynamics, Japan Agency for Marine-Earth Science and Technology, 2-15 Natsushima-cho, Yokosuka 237-0061, Japan
b
PRESTO, Japan Science and Technology Agency (JST), 4-1-8 Honcho, Kawaguchi, Saitama 332-0012, Japan
c
Graduate School of Environmental Studies, Tohoku University, Sendai 980-8579, Japan
d
Human Informatics Research Institute, National Institute of Advanced Industrial Science and Technology, 1-1-1 Umezono, Tsukuba, Ibaraki 305-8568, Japan
e
Earthquake Research Institute, The University of Tokyo, 1-1-1 Yayoi, Bunkyo-ku, Tokyo 113-0032, Japan
f
Department of Earth and Planetary Sciences, Tokyo Institute of Technology, 2-12-1 Ookayama, Meguro-ku, Tokyo 152-8550, Japan

ARTICLE INFO ABSTRACT

Keywords: Water in silicate melt influences the phase relations of a hydrous-melt system. Given the importance of water in
Thermodynamics silicate melts, a quantitative thermodynamic understanding of the non-ideality of hydrous melt is necessary to
Machine learning properly model natural magmatic processes. This paper presents a novel method for quantitative thermodynamic
Hydrous melt modeling of hydrous-melt–olivine equilibrium. Specifically, a machine learning method, exhaustive variable
Mantle melting
selection (ES), is used to model the non-ideality of hydrous melts. Using the ES method, we quantitatively
Thermodynamic equilibrium model
validate the predictive capacities of all possible combinations of variables and then adopt the combination with
Basalt
the highest predictive capacity as the optimal model equation. The ES method allows us to obtain the underlying
thermodynamic relationship of the hydrous-melt–olivine system, such as the relative importance of different
variables to the thermodynamic equilibrium, as well as to construct a robust and generalized model. We show
that the combination of a linear term and a squared term of the total water concentration of melt is significant for
describing the hydrous-melt–olivine equilibrium. This result is interpreted in terms of the microstructural
changes related to the dissociation of water in silicate melt. Calculations using the optimal model reproduce the
experimentally determined effects of water on the olivine liquidus and the distribution coefficient for Mg be-
tween olivine and hydrous melt. Our study demonstrates that the ES method yields a thermodynamic equili-
brium model that captures the essential thermodynamic relationship explaining the high-dimensional and
complex experimental data.

1. Introduction
Understanding the phase relations of hydrous melt is fundamental
to ascertaining the processes of mantle melting under hydrous condi-
tions and the differentiation of hydrous magmas in arc settings (e.g.,
Tatsumi, 1989; Sisson and Grove, 1993; Kawamoto, 1996; Grove et al.,
2003). Melting experiments have revealed that water drastically
changes the phase relations of hydrous-melt systems (e.g., Kushiro
et al., 1968; Kushiro, 1969; Green, 1973; Mysen and Boettcher, 1975a,
1975b; Médard and Grove, 2008; Green et al., 2010, 2014). Such ex-
periments are performed by varying the pressure, temperature, melt
water concentration, and bulk composition of the system (Fig. 1).
Thermodynamic modeling allows such discrete experimental data to be
integrated and a model calculation to be conducted under various
conditions (e.g., Ghiorso and Sack, 1995; Ghiorso et al., 2002; Gualda
et al., 2012; Ueki and Iwamori, 2013, 2014; Jennings and Holland,
2015).
Natural magmatic systems are open systems in which the bulk
chemical composition and total energy of the system evolve with
melting, solidification, and melt migration (e.g., Langmuir et al., 1977).
The relationships between pressure (P), temperature (T), bulk compo-
sition, phase stability, and phase properties (composition, fraction, and
volume), and the mass and energy balances between phases need to be
considered to properly investigate a dynamic and open-system magma
environment. Thermodynamic calculations can yield consistent re-
lationships between mass and energy balances. Various equations from
an ideal mixing model (e.g., Ueki and Iwamori, 2013) and from more
complex models that consider the interactions between various end-
member components (e.g., Ghiorso and Sack, 1995) have been pro-
posed to model the thermodynamic relationship between the

⁎
Corresponding author.
E-mail address: kenta_ueki@jamstec.go.jp (K. Ueki).

https://doi.org/10.1016/j.pepi.2020.106430
Received 19 June 2019; Received in revised form 29 November 2019; Accepted 17 January 2020
Available online 20 January 2020
0031-9201/ © 2020 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY license
(http://creativecommons.org/licenses/BY/4.0/).
K. Ueki, et al.
composition of silicate melt and its Gibbs free energy. Ueki and Iwamori
(2013, 2014) demonstrated that a relatively simple thermodynamic
equation for silicate melt could reproduce the melting phase relation of
anhydrous alkaline-absent spinel lherzolite. However, hydrous melts
have not been considered in some recent thermodynamic models of
mantle melting (e.g., Ueki and Iwamori, 2013, 2014; Jennings and
Holland, 2015) because of the difficulty of performing such modeling.
As the detailed microstructural and chemical properties of hydrous
melt under high pressure and temperature are complicated, the ex-
perimental and theoretical understandings of the structure-free energy
relation (i.e., the thermodynamic configurations and equations for
modeling) are correspondingly poorly constrained. Consequently, de-
spite its importance, the phase relation of multi-component hydrous
melt has not yet been adequately thermodynamically modeled.
Experimental studies on the microstructure (e.g., Mysen, 2007, 2014;
Yamada et al., 2011) and first-principles molecular dynamics simula-
tions (Mookherjee et al., 2008; Karki and Stixrude, 2010; Karki et al.,
2010) have shown that water in silicate melt acts to depolymerize the
melt via the reaction Si − O − Si + H2O → 2Si − OH (e.g.,
Wasserburg, 1957; Stolper, 1982). Ueki and Iwamori (2016) argued
that a non-ideal interaction that considered the dissociation of water in
silicate melt would be required to model the phase relation of a hy-
drous-melt system on the basis that such a system shows strongly non-
linear relationships between melt compositions and phase relations
(e.g., Hirschmann et al., 1998; Médard and Grove, 2008). To model the
thermodynamic behavior of hydrous melt in continuous pressur-
e–temperature–composition space, the appropriate model equation and
parameters for composition-related non-ideality must be developed.
Machine learning (ML) techniques (i.e., the science of using com-
puters for the automatic detection of patterns in data; e.g., Bishop,
2006) can be used to understand the relationships between variables
and construct predictive models. ML techniques are being rapidly in-
troduced to petrological and geochemical studies. For example, ML has
been used for discrimination and feature extraction using labeled geo-
chemical data (e.g., Kuwatani et al., 2014; Petrelli and Perugini, 2016;
Ueki et al., 2018) and for pattern recognition in high-dimensional
geochemical data (e.g., Iwamori and Albaréde, 2008; Ueki and
Iwamori, 2017; Yoshida et al., 2018).
The present paper reports the novel results of an ML-based model-
selection approach to the thermodynamic modeling of hydrous melt.
“Model selection” refers to the ML task of selecting a statistical model
that best reflects the various possible underlying mechanisms that
might have produced the patterns in the data. Using the ML method of
2
Physics of the Earth and Planetary Interiors 300 (2020) 106430
Fig. 1. Variations in temperature and pressure (a) and
in temperature and the total water concentration of
melt (b) for the dataset of experimental results used in
this study. The anhydrous-melting experimental re-
sults are those reported by Ueki and Iwamori (2014)
(i.e., Takahashi, 1980; Kinzler and Grove, 1992;
Falloon et al., 1997, 1999, 2001; Kinzler, 1997;
Kogiso et al., 1998; Robinson et al., 1998; Wagner and
Grove, 1998; Falloon and Danyushevsky, 2000;
Pickering-Witter and Johnston, 2000; Schwab and
Johnston, 2001; Longhi, 2002; McDade et al., 2003;
Wasylenki et al., 2003; Laporte et al., 2004; Parman
and Grove, 2004), and the hydrous-melting experi-
mental results are those reported by Hirose and
Kawamoto (1995), Hirose (1997), Gaetani and Grove
(1998), Falloon and Danyushevsky (2000), Laporte
et al. (2004), Parman and Grove (2004), and Mitchell
and Grove (2015).
exhaustive variable selection (ES), we are able to construct a predictive
model from high-dimensional and complex data, and understand the
physical mechanisms and processes underlying the data (e.g.,
Nakamura et al., 2017).
The objective of the present study is to model the thermodynamic
equilibrium of hydrous basaltic melt and olivine under conditions of the
uppermost upper mantle. A large number of possible equations are
expected for modeling multicomponent silicate melts. For example, to
select an equation that properly models the thermodynamic relation-
ships among the multiple components in silicate melt, we need to
evaluate which components, including their interactions, are thermo-
dynamically more important. In this study, we use an ML-based model-
selection approach, in which we evaluate a set of candidate model
equations for the equilibrium of hydrous basaltic melt and olivine and
select the optimal model equation. The compiled experimental data set
(experimental temperature, pressure, and melt and olivine composi-
tions) is used as input data to determine the optimal equations for the
thermodynamic model and its parameters. We use the leave-one-out
cross-validation technique to select the optimal equation from the
various possible equations. The leave-one-out cross-validation method
leaves out one data case from the data set (i.e., validation data) and
performs multiple linear regression on the remaining data to construct
the model. Using the validation data, we evaluate how well the model
can predict unknown data; i.e., how well the model predicts the equi-
librium between olivine and melt for the temperature, pressure, and
melt and olivine compositions of the validation data. This procedure is
repeated for all data points in the data set, and the mean of the squared
residuals between the model prediction (difference in molar Gibbs free
energy between melt and olivine) and the validation data (=equili-
brium state) is considered as the predictive capacity of the model
equation for the unknown data (e.g., Bishop, 2006). The total number
of candidate model equations is 1024 in the present study. We evaluate
all possible model equations on the basis of the predictive capacities of
the equations and select the optimal model equation.
Through the modeling of this fundamental system for magma gen-
eration, we demonstrate that the ML approach used in this study is a
robust method that allows a generalized model of complex magma
system to be constructed. The ML method also allows an understanding
of the underlying thermodynamic relationship through, for example,
quantifying the relative importance of different explanatory variables.
The ML method and the constructed model should act as reference
points for the future development of multi-component and multi-phase
melting thermodynamic models (Ueki and Iwamori, 2013, 2014) as
K. Ueki, et al.
well as for the modeling of various geological and geochemical pro-
cesses, mechanisms, and conditions, including metamorphic reactions
(e.g., Okamoto and Toriumi, 2004) and ultrahigh-pressure phase rela-
tions such as metal–melt equilibria (e.g., Walter and Cottrell, 2013).
2. Basic thermodynamics
We model the thermodynamic equilibrium between hydrous ba-
saltic melt and olivine at a pressure range corresponding to spinel
lherzolite stability (~1.0–2.5 GPa). Specifically, we model the ther-
modynamic relationship between the silicate components, water con-
centration, pressure, and temperature of melt and the composition of
olivine (Mg/(Mg + Fe)). Olivine is the primary constituent mineral of
the upper mantle and is also the primary crystalline phase derived from
basaltic melt. Therefore, the thermodynamic modeling of this system
yields essential constraints on hydrous-mantle melting (e.g.,
Hirschmann et al., 2009) and on the differentiation of hydrous basaltic
magma (e.g., Sisson and Grove, 1993). To model the hydrous basaltic
melt–olivine equilibrium, we consider the following reaction:
Mg 2SiOmelt = Mg2SiOol
4 4 (1)
melt
where superscript denotes the silicate melt phase, and superscript ol
denotes the olivine phase.
The molar Gibbs free energy of the melt phase is modeled on the
basis of the thermodynamic equation formulated by Ueki and Iwamori
(2013, 2014), in which the difference in molar Gibbs free energy (μ)
between the melt (μmelt) and the corresponding solid end-member
component (μsolid) is expressed as Δμ (=μmelt − μsolid).
The Δμ of the reaction in Eq. (1) is written as
µ = G 0 (P , T ) + RT ln Q (2)
0
where ΔG (P, T) is the difference in molar Gibbs free energy between
pure melt and the corresponding pure solid end-member component
(see Appendix A for details). Consequently, ΔG0(P, T) is dependent on
temperature and pressure, and is independent of melt and olivine
compositions. Q denotes the reaction quotient (e.g., Putirka, 2017). As a
reaction proceeds, the reaction quotient changes to reduce the total
Gibbs free energy of the system. When an equilibrium state is achieved
(Δμ = 0), Q is equal to the equilibrium constant, and Eq. (2) can be
written as
0 = G 0 (P , T ) + RT ln
amelt
aol (3)
where a is the activity.
By assuming the dissociation of the forsterite end-member in melt as
Mg2SiO4melt = 2MgOmelt + SiO2melt, amelt in Eq. (3) can be rewritten as
melt melt melt melt 2
amelt = XSiO 2 SiO2 (XMgO MgO ) (4)
where Xi is the molar fraction of end-member component i in a phase,
and γ is a composition-related non-ideality. γ = 1 corresponds to an
ideal solution.
In the present study, we focus on γ. Selection of a non-ideality
model of silicate melt is critical to constructing a model that adequately
reproduces the experimentally determined melting phase equilibria
(e.g., Beattie, 1993; Putirka, 2017). It has been suggested that non-ideal
interactions between H2O and other melt end-member components are
required to reproduce the non-linear relationship between the total
water concentration of a melt (i.e., the total amount of dissolved water
in the melt) and the phase equilibria (e.g., Médard and Grove, 2008;
Ueki and Iwamori, 2016). The immiscibility between silicate melt and
aqueous fluid (e.g., Hunt and Manning, 2012) also indicates the non-
ideal mixing behavior of water in silicate melt. The γ term (Eq. (4)),
which describes the relationship between the total water concentration
of melt and the Gibbs free energy, needs to be considered in hydrous-
melt thermodynamics. To develop such a numerical model for
3
Physics of the Earth and Planetary Interiors 300 (2020) 106430
melt–olivine equilibrium, we use an ML approach to formulate a robust
equation that describes the relationship between melt composition and
Gibbs free energy.
3. Variable selection and model optimization using an ML
approach
3.1. Basic configuration of the thermodynamic model
We select and optimize the variables in γ, the composition-related
non-ideality (Eq. (4)), that adequately capture the underlying thermo-
dynamic relationship of the hydrous-melt–olivine thermodynamic
system. For this purpose, we first present a basic equation for variable
selection. We enumerate all possible terms in the basic equation and
then select the essential terms using an ML approach.
We consider an equation based on a symmetric regular solution as
the basic equation. The composition-related non-ideality of multi-
component silicate melt can be thermodynamically modeled using a
symmetric regular solution type equation (e.g., Ghiorso et al., 1983).
The composition-related non-ideality of an n end-member component
symmetric regular solution is written as follows (e.g., Ghiorso et al.,
1983):
n n k 1
RT ln melt
= Wij Xj Wjk Xj Xk
i
j i k=2 j =1 (5)
where Wi (J/mol) represents the interaction parameters of end-member
component i.
The maximum number of unknown thermodynamic parameters (W)
in Eq. (5) is nC2 = n!/[(n − 2)!2!] because symmetric interactions
between two different end-member components are considered in this
equation. The model-selection approach determines the optimal com-
bination of variables from the nC2 variables. Consequently, the total
number of possible equations in this case is 2nC2. Such a large number of
unknown parameters would make the computational cost too high to
adopt the ML method employed in this study (i.e., the problem of
combinatorial explosion). In addition, a large dataset would be required
to obtain generalized and robust results when optimizing a large
number of parameters (e.g., Bishop, 2006). Therefore, we employ a
simplified equation based on Eq. (5) as the basic equation for the non-
ideality model of this study.
Carmichael (2002) analyzed RT ln SiO melt
2
of experimental hydrous
melts, and found the linear relationship between the molar fractions of
major-element oxide end-member components ( XMgO melt
and XNa
melt
2 O + K2 O
)
and RT ln SiO2 of hydrous melts in the compositional range of basalt to
melt
andesite. In particular, XMgO
melt
was found to strongly affect RT ln SiO
melt
2
.
Their results suggest that the linear term (first term of the right-hand
side of Eq. (5)) could satisfactorily model the effects of major-element
oxide end-member components on the non-ideality of mafic silicate
melts. Following Carmichael (2002), we consider the following equa-
tion as the basic equation of the non-ideality model developed in the
present study:
RT ln melt melt 2
= Wi Ximelt
SiO2 MgO (6)
Eq. (6) is a simplified equation obtained by omitting the second
term of the right-hand side of Eq. (5). As a result, the maximum number
of unknown thermodynamic parameters (W) is 10 in this study. The
total number of possible model equations is reduced to 210 with the
simplified equation. As shown in Section 4, this simplified equation
properly models the thermodynamic relationship between hydrous melt
and olivine.
Although only SiO2 and MgO are involved in the chemical reaction
considered here (Eq. (1)), alkalis (Na2O and K2O) also have substantial
effects on the thermodynamic properties of mafic silicate melts (e.g.,
Kushiro, 1975; Carmichael, 2002; Hirschmann et al., 1998; Putirka et al.,
K. Ueki, et al. Physics of the Earth and Planetary Interiors 300 (2020) 106430

2007), meaning that other end-member components (in addition to SiO2 total number of such candidate model equations is 1024 (=210).
and MgO) may also need to be considered in modeling the hydrous- We evaluate the various combinations of variables to model the
melt–olivine equilibrium. Therefore, the importance of the various oxide equilibrium of hydrous basaltic melt and olivine using an ML-based
end-member components in the thermodynamic equation should be model-selection approach. All possible combinations of variables are
quantified when modeling the thermodynamic behavior of silicate melt. evaluated, and the optimal combination of end-member components for
Consequently, we consider SiO2–Al2O3–FeO–MgO–CaO–Na2O–K2O as representing the hydrous-melt–olivine equilibrium is selected.
the major-element oxide end-member components of melt.
To describe dissociated water in silicate melt, we consider two terms 3.2. Exhaustive variable selection
in addition to total water concentration in the melt (e.g., Stolper, 1982;
Nowak and Behrens, 1995). Hunt and Manning (2012) performed On the basis of the basic configuration (Eq. (9)), we implement an
thermodynamic modeling of the SiO2–H2O system by considering the ML-based model-selection approach to understand the underlying
molecular H2O, bridging oxygens, and OH group attached to a silicate thermodynamic relationship that explains the data and construct a ro-
polymer in silicate melt and reproduced experimentally derived SiO2 bust and generalized model of the thermodynamic equilibrium state
solubility in the aqueous fluid, hydrous melting of quartz, and the cri- between hydrous melt and olivine, in which the most informative set of
tical endpoint between silicate melt and aqueous fluid. Their results variables to describe the relationship between melt composition and the
based on the SiO2–H2O system suggest that thermodynamic modeling molar Gibbs free energy is incorporated. The problem is to find the
considering the speciation of water may improve the model's ability to appropriate combination of variables from the major-element oxide
reproduce the thermodynamic behavior of hydrous silicate melt. end-member components WSiO2 XSiO melt
2
, WA12 O3 X Amelt
12 O3 ,
melt
WFeO XFeO ,
The dissociation reaction of water in silicate melt is written as fol- melt
WMgO XMgO , WCaO XCaO
melt
, WNa2O XNa
melt
, and W X melt
K2O K2O , and the water-related
2O
lows (Stolper, 1982): 2 0.5
terms WH2 O XHmelt
2O
,WH2 O2 X Hmelt
2O
, and WH2 O0.5 X Hmelt
2O
in Eq. (9).
H2 Omolecular (melt) + O0 (melt) 2OH(melt) (7) This type of problem can generally be formulated within multiple
0
linear regression, a type of multivariate analysis that is used to con-
where H2Omolecular, O , and OH denote the molecular H2O, bridging
struct a multinomial model that relates many explanatory variables to
oxygens, and OH group attached to a silicate polymer in silicate melt,
the objective variable (e.g., Chatfield and Collins, 1980; Le Maitre,
respectively.
1982). In the optimization of thermodynamic equilibrium experiments,
The mass balance of the reaction in Eq. (7) is written as
the multinomial equation can be written as follows:
CH2 Ototal (melt) = CH2Omolecular (melt) + 1/2COH(melt) (8) n
y = f (W ) = ci Wi
where C denotes the concentrations of the species in a silicate melt, and i=1 (11)
H2Ototal denotes the total water concentration of a silicate melt. With a
fixed equilibrium constant of the reaction in Eq. (7), COH(melt) is pro- where y indicates the objective variable calculated using the experi-
0.5 2 mental results as y = − ΔG + RTlnaol − RTln XSiO melt melt2
X ; n indicates
portional to X Hmelt is proportional to X Hmelt (Stolper, 1982). Bridging 2 MgO
2O 2O
the number of explanatory terms; ci indicates the explanatory variables,
oxygens are consumed in the reaction of Eq. (7), meaning that the
2 which are the observed composition of melt ( XSiO
melt
, X Al
melt
2 O3
, … XHmelt
2O
) and
amount of bridging oxygen decreases in proportion to X Hmelt (Stolper,
2
2O 2
the squared and square-root terms of water composition, X Hmelt and
1982). Consequently, in addition to the linear term ( XHmelt 2O
), we consider 0.5
2O
2 0.5 X Hmelt , respectively; and Wi indicates each unknown thermodynamic
two terms for H2O concentration (WH2 O2 X Hmelt , WH2 O0.5 X Hmelt ) to model 2O
2O 2O
parameter to be estimated (i.e., WSiO2 , WA12 O3 , WFeO , …, WH2 O , WH2 O 2 , and
the dissociation of water. Consequently, we have
WH2 O0.5 ).
Wi Ximelt In cases where the required explanatory variables have already been
melt specified and where the amount and quality of the observed data are sui-
= WSiO2 XSiO + WA12 O3 X Amelt melt melt
12 O3 + WFeO XFeO + WMgO XMgO
2 table, the unknown parameters can be appropriately estimated, meaning
that multiple linear regression can be used to construct a statistical model
melt melt
+ WCaO XCaO + WNa2 O XNa2O
+ WK2 O X Kmelt
2O
2 0.5 that has a high predictive capacity (e.g., Chatfield and Collins, 1980).
WH2 O X Hmelt
2O
+ WH2 O2 X Hmelt
2O
+ WH2 O0.5 X Hmelt
2O (9) However, in most problems of thermodynamic parameter optimization the
where the linear term (WH2 O XHmelt
2O
) represents the total amount of dis- parameters are presumably unknown and the variation in the experimental
solved water in the melt, the squared term (WH2 O2 X Hmelt
2
) is a proxy conditions of the observed data (pressure, temperature, and composition)
2O
thermodynamic term for H2Omolecular(melt) with the consumed bridging are generally insufficient for properly determining all the thermodynamic
0.5 parameters that exhibit high predictive capacity in the entire pressure,
oxygen, and the square-root term (WH2 O0.5 X Hmelt
2O
) is a proxy thermo-
dynamic term for OH (melt). Finally, substituting Eq. (9) into Eqs. (3), temperature, and composition range of interest. In the present study, the
(4), and (6), we have model equation is unknown, and the P, T, and melt composition of the input
experimental data are discrete and heterogeneous. Applying a simple
2
G 0 (P , T ) + RT ln aol melt melt
RT ln XSiO X
2 MgO
= Wi Ximelt (10) multiple linear regression analysis to such a problem could cause overfitting
(e.g., Bishop, 2006); i.e., the model is incorrectly fitted to (noisy) observed
The left-hand side of Eq. (10) can be calculated using experimental data using too many irrelevant and unnecessary variables, which results in
results (pressure, temperature, and melt and olivine compositions) and an extremely low predictive capacity of the obtained model when applied to
the non-ideality model of olivine (Sack and Ghiorso, 1989). Therefore, a new dataset. In multiple linear regression analysis, a model that uses ir-
we can use linear regression to determine W from experimental results relevant (redundant) variables can reproduce the input data set used for
(Fig. 1). The maximum number of explanatory variables in the regression but may not predict unknown data. To construct a model that has
present case is 10. On the basis of Eq. (10), various combinations of high predictive capacity, appropriate combinations of explanatory variables
variables are possible, such as Wi Ximelt = WSiO2 XSiO melt
2
+ WA12 O3 X Amelt
12 O3 should be determined by removing unnecessary variables. In doing so, an
+ WFeO XFeO + WMgO XMgO + WCaO XCaO + WNa2O XNa2O + WK2O XKmelt
melt melt melt melt
2O alternative evaluation criterion is required based not only on the reprodu-
+ WH2 O XHmelt
2O
where only the linear term is considered for the effect of cibility of observed data (e.g., sum of squared residuals) but also on pre-
water, Wi Ximelt = WSiO2 XSiO melt
2
+ WA12 O3 X Al
melt
2 O3
+ WFeO XFeO
melt
+ dictive capacity when applied to new datasets (e.g., Bishop, 2006; Kuwatani
WMgO XMgO + WCaO XCaO + WNa2O XNa2O + WK2O XK2O where the water-
melt melt melt melt et al., 2014).
related terms are not considered, and more sparse equations such as The ES method is the most robust approach for variable selection
Wi Ximelt = WSiO2 XSiO
melt
2
, Wi Ximelt = WH2 O XHmelt
2O
and Wi Ximelt = 0. The (Nagata et al., 2015; Igarashi et al., 2016). This method automatically

4
K. Ueki, et al.
extracts the essential variables for describing high-dimensional data
and constructs the model with the highest predictive capacity. The ES
method has been used in many previous studies in a range of scientific
fields, including psychology (Ichikawa et al., 2014; Nagata et al., 2015),
astronomy (Igarashi et al., 2018), and Earth sciences (Kuwatani et al.,
2014; Nakamura et al., 2017). The ES method evaluates the predictive
capacity of the constructed model for all combinations of explanatory
variables. In testing all possible combinations of variables, there are
two possible states for each variable: a used state and a discarded state.
If this is expanded to all variables, the total number of possible states is
2n, where n is the number of explanatory variables. In this study, we
adopted a cross-validation (CV) technique to evaluate the predictive
capacity of the model for unknown data (i.e., the generalization cap-
ability of the model). The CV technique can estimate the generalization
capability for new datasets using only the available observed dataset.
The technique divides the available dataset into two parts: the regres-
sion data, which are used to construct the model, and the validation
data, which are used to evaluate the generalization capability of the
model. By using the ES method with the CV technique, the general-
ization capability of thermodynamic equations for magmatic equilibria
can be objectively evaluated, and the model with the best general-
ization capability can be identified.
We used the ES method for variable selection based on Eq. (10). The
maximum number of unknown thermodynamic parameters (W) is 10,
meaning that the predictive capacity of the model for 1024 (=210)
combinations of variables was evaluated using the CV technique. In this
study, we used the leave-one-out CV technique, whereby M − 1 data
(where M = the total number of data in the dataset = 296 in the
present study) of the melting experiments were considered as the re-
gression data {(ym, Xm), (ym−1, Xm−1), (ym+1, Xm+1), …(yM, XM)} and the
remaining one case was taken as the validation data (ym, Xm). Multi-
variate linear regression was applied to the regression data to construct
the training models f−m(W). Generalization capability (predictive ca-
pacity) was evaluated using the constructed model and the validation
data. To obtain the generalization capability, we used the cross-vali-
dation error (CVE), defined by the root mean square error which is
obtained by repeating the above calculation for all M samples:
( ) /M .
M 2
ym
CVE = f m (W )
m=1 (12)
Using this calculation, all possible ways (=M ways) of dividing the
original data into the regression data and the validation data were able
to be tested, and the root mean squared residual between model pre-
diction and the validation data (i.e., CVE) was regarded as the measure
of the validity of the model equation (i.e., its generalization capability).
Using the leave-one-out CV technique, we uniquely determined the CVE
of each equation. To implement the calculations, we used the R lan-
guage (R Core Team, 2019), an open-source programming language for
statistical computing. The R source code and the input data are pro-
vided in Supplementary materials 1 and 2, respectively.
3.3. Dataset for optimization
The dataset for model-selection and parameter optimization com-
prised previously reported experimental results that were obtained
according to the following three criteria:
1. The data describe ultramafic and mafic bulk compositions.
2. The system consists of at least the following six major-element oxide
components: SiO2, Al2O3, Fe2O3 or FeO, MgO, CaO, and Na2O,
without CO2.
3. The system includes olivine and melt ± orthopyroxene ± clinopyr-
oxene ± spinel, without garnet or plagioclase.
Accordingly, 296 individual experimental runs, 72 of which are
5
Physics of the Earth and Planetary Interiors 300 (2020) 106430
hydrous experiments, were used for model-selection and optimization
during this study. Some of the experimental results were obtained from
the Library of Experimental Phase Relations open database of melting
experiments (Hirschmann et al., 2008). Anhydrous experiments were
obtained from experimental datasets compiled by Ueki and Iwamori
(2014). P–T ranges and the total water concentrations of melt are dis-
played in Fig. 1, and data sources are given in the caption to that figure.
The dataset used for the present study is given in Supplementary ma-
terial 2. The P–T range of the dataset is 0.8–2.5 GPa and 1050–1600 °C,
and the total water concentration of melt ranges from 0 (anhydrous) to
8.96 wt% (Fig. 1). As we focused on those experiments that were based
on mantle systems, almost all experimental melts (294 experimental
results) exhibit basaltic to basaltic-andesite compositions. Two experi-
mental melts exhibit andesitic and dacitic compositions. For the water
concentration of melt, we used the values reported in each paper; i.e.,
we did not perform an independent estimation, such as a calculation
based on a solubility model (e.g., Newman and Lowenstern, 2002).
Fig. 1 shows that the experimental conditions are discrete and hetero-
geneous. For example, the number of experimental runs decreases with
increasing pressure. Both partial-melting and crystallization experi-
ments are included, as are K2O-present and K2O-absent experiments.
4. Results and discussion
4.1. Model assessment and the relative importance of explanatory variables
By investigating the CVE-based ranking of models and comparing
the top models, we can identify informative variables in describing the
data, and relationships between variables. Fig. 2 presents the re-
lationship between the CVE (the measure of model generalization
capability) and the number of variables used in the equations. The
variables used, parameters, and CVEs of the best 100 models are shown
in Fig. 3 (Supplementary material 3, for the full list of models). The
variables used, optimized parameters, and CVEs of the top 10 model
equations are given in Table 1. Residuals obtained by CV analysis
(determined as the differences between the values predicted using the
constructed model and each validation data; i.e., ym − f−m(W) in Eq.
(12)) are plotted against total water concentration in the melt ( XHmelt ) in
2O
Fig. B1 of Appendix B. The root mean squared residual of Fig. B1 was
regarded as the measure of the validity of the model equation.
The non-ideality model with the lowest CVE (i.e., the model with
the best generalization capability or optimal model) was obtained using
nine variables (SiO2, Al2O3, FeO, MgO, CaO, Na2O, K2O, H2O, and
H2O2) and is written as
melt
RT 1n
melt
= 165702 XSiO 2
+ 115981 X Amelt melt melt
12 O3 + 198584 XFeO + 142204 XMgO
melt
+ 164325 XCaO melt
+ 318651 XNa + 240832 X Kmelt
2O 2O
2
+ 123461 X Hmelt
2O
+ 189732 X Hmelt
2O (13)
We note that using all 10 variables yields a model with the second-
lowest CVE, indicating that using all 10 variables results in overfitting
(Fig. 3). Although intuitively it might seem that the most complex
model (i.e., the 10-variable model) should yield the highest general-
ization capability, the use of redundant explanatory variables that ex-
plain negligible variation in the objective variable acts to reduce the
generalization capability of models of the hydrous-melt–olivine equi-
librium.
The ideal-solution model (Eq. (6) = 0) yields the highest CVE; i.e.,
the worst generalization capability (Fig. 2). SiO2, Al2O3, FeO, MgO,
CaO, and Na2O are present in all of the top 10 models, and K2O, in
addition to the six major elements, is present in all of the top 5 models
(Fig. 3), implying that these seven major elements are particularly in-
formative in describing the phase equilibrium between hydrous basaltic
melt and olivine. Also of note, all of the top 100 models used the SiO2
K. Ueki, et al. Physics of the Earth and Planetary Interiors 300 (2020) 106430

CVE (J)
ideal +SiO2
water no SiO2
100000 water+K2O no water
water+alkalines
SiO2+FeO+MgO
10000
1000
0 2 4 6 8 10
Number of variables
Fig. 2. Bivariate plot of cross-validation error (CVE) values versus the number
of variables used in the model equations. Equation types are indicated by circles
and colors: the filled red circle represents the ideal model; filled light-gray
circles represent models using water-related terms exclusively; filled dark-gray
circles represent models using water-related terms and K2O exclusively; filled
dark-blue circles represent models using water- and alkaline (Na2O and K2O)-
related terms exclusively; filled yellow circles represent models using the SiO2,
FeO, and MgO terms; open black and open blue circles represent models using
and not using the SiO2 term, respectively; and open green circles represent
models not using water-related terms. (For interpretation of the references to
color in this figure legend, the reader is referred to the web version of this
article.)
and MgO terms. FeO, CaO, H2O, H2O2, Al2O3, Na2O, H2O0.5, and K2O
were selected in 79, 74, 65, 64, 63, 63, 53, and 50 of the top 100
models, respectively. These results mean that of the major-element end-
member components, the SiO2, MgO, and FeO concentrations of melt
are particularly informative in modeling of the silicate-melt–olivine
equilibrium. Although this result might appear to be self-evident, given
that we consider Mg–Fe olivine here, the result should be emphasized
because this information was objectively and automatically defined
using the ES method. The CVE values of the top 10 models range from
2.32 to 2.47 kJ, comparable with the experimental uncertainty on the
enthalpy of fusion for forsterite of ±2.6 kJ (Sugawara, 2005).
WH2 O XHmelt
2O
is the most commonly used water-related term (among
2 0.5
WH2 O XHmelt
2O
, WH2 O2 X Hmelt
2O
, and WH2 O0.5 X Hmelt
2O
) in the top 100 models.
0.5
Conversely, WH2 O0.5 X Hmelt
2O
is the least commonly adopted of these terms
in the top 100 models and is not adopted in the best model. All of the
top five models include all seven major elements, and different com-
binations of water-related terms are present in the top five models.
Regarding the parameters of the water-related terms, WH2 O 2 tends to
exhibit the highest absolute values among the W of the three water-
related terms. In contrast, WH2 O0.5 exhibits the lowest absolute values of
all W (Table 1), which means that of the water-related terms, the
square-root term is the least informative regarding phase equilibrium.
Fig. 2 indicates that models using SiO2, MgO, FeO, and the water-
related terms tend to exhibit better generalization capabilities (i.e.,
lower CVEs) than those of models not using these terms. Models con-
sidering only water-related terms and/or alkaline (Na2O and K2O)
terms tend to exhibit high CVEs. In addition, SiO2-absent models exhibit
high CVEs and have poor predictability.
The high CVE values of the models using water-related terms ex-
clusively (i.e., models in which WH2 O XHmelt , WH2 O2 X Hmelt
2
, and/or
2O 2O
0.5
WH2 O0.5 XHmelt
2O
were used but major oxide end-components were not) can
be interpreted in terms of the input experimental data. Models con-
sidering only the water-related terms would be expected to perform
poorly in predicting the results of anhydrous experiments, and the
model calculation for the anhydrous condition is the same as the ideal
model in this case. In addition, the analytical error on the water con-
centration might be large compared with those on the major oxide
components. Therefore, models using water-related terms exclusively
have the lowest predictive capacities of all variable combinations tested
here.
Generally, concentrations of alkalis (Na2O and K2O) in silicate melt
have a strong correlation. As the model-selection approach involves
highly correlated values, only one variable with less noise tends to be
selected from a highly correlated group of variables as a significant
variable. However, Na2O and K2O are present in all of the top five
models, meaning that both of these elements have a considerable in-
fluence on the thermodynamic equilibrium between silicate melt and

CVE (J) Fig. 3. CVE values, variables, and parameters of the

SiO2 Al2O3 FeO MgO CaO Na2O K2O H2O H2O H2O
0 1000 2000 3000 4000 top 100 (lowest CVE) equations. Each row represents
2 0.5
a single equation. The CVE of each equation is
shown at the far right. Parameter values in each
equation are represented by color according to the
scale shown. A blank (white space) in the matrix
indicates that a particular variable was not used in
that equation. (For interpretation of the references
to color in this figure legend, the reader is referred to
the web version of this article.)

W (J/mol)
0 200000 400000 600000 800000

6
K. Ueki, et al. Physics of the Earth and Planetary Interiors 300 (2020) 106430

Table 1
Parameters (J/mol) and cross-validation error (CVE) values of the top 10 (lowest CVE) model equations.
CVE (J) Rank WSiO2 WAl2O3 WFeO WMgO WCaO WNa2O WK2O WH2O WH2O2 WH2O0.5

2319 1 165,702 115,981 198,584 142,204 164,325 318,651 240,832 123,461 189,732
2326 2 165,676 116,006 198,491 142,368 164,235 318,708 241,339 132,531 168,468 −2158
2330 3 164,845 118,056 198,309 143,594 164,276 319,304 243,483 195,683 −15,638
2357 4 166,833 113,856 199,559 139,773 164,586 317,045 234,356 497,525 27,805
2376 5 162,164 126,073 200,690 143,310 167,548 319,937 235,383 157,992
2422 6 172,617 117,492 199,796 134,838 152,627 299,425 123,550 181,418
2432 7 172,620 117,486 199,815 134,807 152,651 299,422 121,646 185,885 453
2436 8 171,770 119,765 199,627 136,087 152,583 299,892 191,284 −14,409
2454 9 173,500 115,469 200,762 132,621 153,283 298,405 488,172 27,951
2470 10 169,080 127,119 201,786 136,056 155,965 301,073 156,599

olivine (e.g., Kushiro, 1975; Hirschmann et al., 1998). In contrast, 50

models using exclusively alkaline (Na2O and K2O) terms tend to exhibit
This study (optimal model)
This study (linear model)
high CVEs, and K2O is the least commonly adopted variable in the top Experiments (just above liquidus)
100 models. Similar to the case of water, both K2O-present and K2O- 0 Experiments (just below liquidus)
absent experiments were included in the experimental dataset. In terms

Liquidus depression (°C)

of the thermodynamic equation (Eq. (4)), XSiO melt
2
and XMgO
melt
directly
contribute to the molar Gibbs free energy of melt through the RT ln X
term, whereas the concentrations of other oxide end-member compo-
nents, as well as XHmelt
2O
, indirectly contribute to the molar Gibbs free
energy of melt by the dilution of XSiO
melt
2
and XMgO
melt
. As such, the WX terms
represent the excess contribution of elements to free energy above that
contributed by the RT ln X term. As we are concerned with ultramafic
and mafic systems in this study, only trace amounts of alkaline elements
were involved in the experiments, meaning that contributions of their
non-ideal excess energy (the WX terms) to the total Gibbs free energy of
the system are small in comparison with the contributions made
through dilution. In addition, experimental and analytical errors on the
trace amounts of concentrations of alkalis might be large compared
with those of other major-element concentrations. Consequently, the
experimental data on alkalis are relatively noisy, and K2O and Na2O are
the least and second-least commonly selected major elements in the top
100 models, respectively, and models using exclusively alkaline (Na2O
and K2O) terms tend to exhibit high CVEs. Our results obtained using
the ES method suggest that experimental settings and related errors
should be considered when constructing a robust thermodynamic
equilibrium model based on the experimental results.
To test reproducibility, anhydrous melt–olivine equilibrium tem-
peratures calculated for a given pressure and melt and olivine compo-
sitions using the optimal model are compared with the results of the
melting experiments of peridotite at 1–3 GPa of Hirose and Kushiro
(1993) in Supplementary material 4. The results calculated using the
optimal model are also compared with those calculated using the oli-
vine–anhydrous melt thermometry of Beattie, (1993) in Supplementary
material 4. The experimental results of Hirose and Kushiro (1993) have
not been used for parameter calibration and are suitable to test the
reproducibility of our optimal model under the anhydrous condition.
The olivine–melt thermometry of Beattie, (1993) accurately reproduces
olivine– anhydrous melt equilibrium temperatures in the pressure range
of 0.0001 to 15.5 GPa Putirka, (2017) and is suitable for testing con-
sistency between models for the anhydrous condition. Overall, the
equilibrium temperatures derived using the optimal model are con-
sistent with the experimental temperatures and with those calculated
using the thermometry of Beattie, (1993). However, the calculation
results for 3 GPa exhibit systematically lower temperatures than those
of the experimental results and those derived using the approach of
Beattie, (1993), indicating that the model cannot be extrapolated with
respect to pressure; the pressure range of our dataset is 0.8–2.5 GPa.
To demonstrate the effects of water on liquidus depression, the
olivine liquidus depression calculated using the lowest-CVE model (Eq.
(13)) as a function of the total water concentration of a melt is pre-
sented in Fig. 4. The experimental results plotted in this figure
(Tatsumi, 1982; Pichavant et al., 2002; Almeev et al., 2007; Médard
-50 Liquid
Sg
-100 FD Ct
pM
Av
-150 MG
Liquid+ol
-200
0 1 2 3 4 5 6
Water in melt (wt%)
Fig. 4. Calculated and experimentally determined olivine liquidus depression
as a function of the total water concentration of melt. Liquidus depression was
calculated as the difference between the experimental wet liquidus temperature
and the dry liquidus temperature. The black region in the diagram represents
the result derived using the optimal model (Eq. (13)). Open and closed symbols
represent data for just above and just below olivine liquidus conditions, re-
spectively, obtained from the experiments of Tatsumi (1982), Pichavant et al.
(2002), Almeev et al. (2007), and Médard and Grove (2008). The experimental
results plotted in this figure were obtained from experiments that did not satisfy
our data compilation criteria or from studies that lacked the analytical data
required for model-selection and parameter optimization; consequently, these
data were not used for these tasks in the present study. Calculations were
performed using the same melt compositions as those of the plotted experi-
mental results. Representative values of each experiment were used for pressure
and olivine composition in the calculations. Therefore, the temperature range of
the calculated liquidus depression in this figure represents the variations in the
melt and olivine compositions and pressure conditions of the experiments. Li-
quidus depression lines were calculated using the empirical models of Falloon
and Danyushevsky (2000), Sugawara (2000), Ariskin and Barmina (2004;
“COMAGMAT”), Almeev et al. (2007), Médard and Grove (2008), and the
thermodynamic model pMELTS (Ghiorso et al., 2002). The result obtained
using the linear model [a model containing only the linear term of the water-
related terms (in addition to the element-oxide terms); see text for details] is
also shown. For pMELTS and linear-model calculations, the melt composition
reported by Pichavant et al. (2002) was used. The results obtained using pre-
vious models are indicated by the following abbreviations: Av, Almeev et al.
(2007); Ct, COMAGMAT; FD, Falloon and Danyushevsky (2000); MG, Médard
and Grove (2008); pM, pMELTS; Sg, Sugawara (2000).
and Grove, 2008) are from experiments that were not used for regres-
sion and model selection in the present study. As pressure has little
influence on the effect of water on liquidus depression (Médard and
Grove, 2008), experiments conducted at the pressure range corre-
sponding to the extrapolation of our data set (<0.8 GPa) are also
plotted in Fig. 4 for comparison. Liquidus depression lines calculated

7
K. Ueki, et al. Physics of the Earth and Planetary Interiors 300 (2020) 106430

using the empirical models of Falloon and Danyushevsky (2000), Model 1100°C 1200°C 1300°C 1400°C 1500°C

Sugawara (2000), Ariskin and Barmina (2004; “COMAGMAT”), Almeev Experiments <1200°C <1250°C <1350°C <1450°C 1450°C

et al. (2007), and Médard and Grove (2008), and the thermodynamic 18
model pMELTS (Ghiorso et al., 2002), are also plotted for comparison.
The liquidus depression was calculated as the difference between ex- 16
perimental wet liquidus and dry liquidus temperatures. The result ob-
14
tained using a linear model (i.e., calculated using WSiO2 XSiO melt
2
,
melt
WA12 O3 X Al2 O3
, W X melt
FeO FeO , W X melt
MgO MgO , W X melt
CaO CaO , W X melt
Na2 O Na2 O , WNa2O K2O ,
X melt
12
and the linear term (WH2 O XHmelt 2O
) of the water-related terms) is also
shown in Fig. 4. Calculations were performed using the same melt 10

DMg
compositions as those of the plotted experimental results. Re-
presentative values of each experiment were used for pressure and 8
olivine composition in the calculations. For pMELTS and linear-model
6
calculations, the melt composition reported by Pichavant et al. (2002)
was used. Although our thermodynamic formulation was a function of 4
melt composition, olivine composition, pressure, and temperature, the
liquidus calculations were simplified using fixed olivine composition 2
and pressure to demonstrate the effects of water in our models and to
provide a comparison with independent results from previously re- 0
ported experimental results and models for liquidus depression. Fig. 4 0 1 2 3 4 5 6 7 8 9
shows that our thermodynamic calculations for the hydrous-melt–oli- Water in melt (wt%)
vine equilibrium using the optimal model reproduce the independent
Fig. 5. Calculated and experimentally determined values of the distribution
experimental results well at all water concentrations; the slope of the
coefficient D Mg = X Mg
ol melt
/ XMgO for melt–olivine plotted against the total water
liquidus depression curve decreases with increasing H2O content. In 2 SiO4
concentration of melt. The solid lines show the results obtained using the op-
contrast, the calculation using only the linear term to represent the
timal model, and the dashed lines show the results obtained using the linear
effect of water failed to reproduce the non-linear relationship between model (i.e., the model using only the linear term of the water-related terms in
the total water concentration and olivine liquidus temperature, al- addition to the element-oxide terms; see text for details). For melt and olivine
though it is the fifth-best model overall (Table 1; Fig. 3). Liquidus compositions, the averaged values of the experimental dataset were used. The
temperature decreases monotonically in the result obtained by the pressure was fixed at 1 GPa. Also shown are DMg values calculated from the
linear model. experimental results that were used for model-selection and parameter opti-
mization.

4.2. Thermodynamic implications

melt, in addition to the RT ln X term and seven major elements in-
cluding alkalis (SiO2, Al2O3, FeO, MgO, CaO, Na2O, and K2O).
Ghiorso et al. (1983) argued that H2O does not behave like a regular
The optimal model equation selected using the ES approach (Eq.
solution component and proposed an additional term to describe the
(13)) is considered to describe the underlying melt structure that ex-
relationship between the total water concentration and the Gibbs free
plains the data; i.e., the relationship between free energy and the mi-
energy of silicate melt. The equation proposed by Ghiorso et al. (1983)
croscopic chemical features of hydrous melt. As shown above,
was used for the MELTS (Ghiorso and Sack, 1995; Gualda et al., 2012)
WH2 O XHmelt
2O
(linear term) represents the effect of the total water con-
and pMELTS (Ghiorso et al., 2002) software programs for the thermo- 2
dynamic modeling of phase equilibria in magmatic systems. However, centration, and WH2 O2 X Hmelt
2O
(squared term) represents H2Omolecular
(melt) and the amount of bridging oxygen consumed by the dissolution
MELTS and pMELTS failed to reproduce the relationship between the
of water. To demonstrate the contribution of the polynomial function to
total water concentration of melt and the liquidus temperature of oli-
hydrous-melt–olivine equilibrium and to examine the relationship be-
vine (Almeev et al., 2007; Médard and Grove, 2008). In addition, some
tween thermodynamic equilibrium and the microscopic chemical fea-
critical factors, such as the dissociation of water in silicate melt
tures of hydrous melt, calculated DMg values are presented as a function
(Stolper, 1982) and its interaction with other oxide end-member com-
of the total water concentration of melt in Fig. 5. DMg for olivine–melt
ponents in the melt (e.g., Hunt and Manning, 2012), were not con-
was calculated using Eq. (13) as DMg = XMg ol melt
/XMgO . The temperature
sidered in the MELTS and pMELTS models. Putirka et al. (2007) argued 2 SiO4
was varied from 1100 to 1500 °C, the pressure was fixed at 1 GPa, and
that the total water concentration of melt affects the lnDMg (logarithm
melt and olivine compositions were fixed as the mean values of the
of distribution coefficient for Mg between olivine and melt) for olivi-
entire experimental dataset. DMg values of the experimental dataset are
ne–melt, and therefore those authors parameterized ln DMg for olivi-
also plotted in Fig. 5. The experimental DMg values exhibit wide var-
ne–melt as a function of temperature, pressure, water, and the Na2O
iations at lower temperatures (<1200 °C), possibly related to the dif-
and K2O concentrations of melt. Putirka et al. (2007) parameterized the
ficulties in performing low-temperature near-solidus hydrous experi-
effect of water on lnDMg as a function of the total water concentration of
ments (e.g., Green et al., 2012). Although some of the experimental DMg
melt. Carmichael (2002, 2004) parameterized the composition-related
values exhibit scatter, a parabolic relationship between experimental
non-ideal excess energy of hydrous melt as a linear function of XHmelt ,
2O
DMg and the total water concentration of melt is observed in Fig. 5 and
melt
XMgO , and total alkalines ( XNamelt
+ X melt
). Hirschmann et al. (1999,
2O K2O
is particularly recognizable at temperatures of 1200–1300 °C. Fig. 5
2009) and Aubaud et al. (2004) modeled the effect of dissolved water in
indicates that our optimal model, which uses both the WH2 O XHmelt and
melt on the peridotite solidus by considering dilution by dissolved 2
2O

water through the RT ln X term. In the present study, we adopted a
model-selection method to formulate a model of the non-ideality of
hydrous melt. The result produced by the model-selection approach
2 creasing total water concentration of melt from 0 to 5 wt%, and then
shows that WH2 O XHmelt
2O
(linear term) and WH2 O2 X Hmelt (squared term) were
2O
retained in the selection process; consequently, we infer that those two
terms are important for describing the relationship between the total
water concentration and the molar Gibbs free energy of the silicate
WH2 O2 X Hmelt
2O
terms for the effect of water, captures the parabolic struc-
ture of the variation in DMg with changing total water concentration.
Both the experimental and calculated DMg values decrease with an in-
increase with a further increase in the total water concentration to 9 wt
%. In contrast, the linear model, in which only WH2 O XHmelt of the water-
2O
related terms was used, does not reproduce the relationship between

8
K. Ueki, et al.
DMg and the total water concentration of melt; DMg decreases mono-
tonically with increasing total water concentration for the result ob-
tained by the linear model.
DMg for anhydrous-melt–olivine depends on the melt composition and,
consequently, on the microstructure of melt, and it exhibits a parabolic
relationship as a function of NBO/T (nonbridging oxygen per tetrahedrally
coordinated cations) (Kushiro and Mysen, 2002; Mibe et al., 2006; Filiberto
and Dasgupta, 2011). Kushiro and Mysen (2002) attributed the parabolic
relationship to the change in the coordination states of Mg in melt asso-
ciated with depolymerization (Fiske and Stebbins, 1994). Mg2+ in poly-
merized melts (low NBO/T) is predominantly four coordinated, and it
changes to six coordination with an increase in NBO/T. As a result, Mg in
polymerized melts tends to enter olivine in which Mg is six coordinated, and
with an increase in six-coordinated Mg in the melt, more Mg enters the melt
(Kushiro and Mysen, 2002; Mysen and Dubinsky, 2004; Mysen and Shang,
2005). With respect to hydrous melt, Putirka et al. (2007) showed that
lnDMg is sensitive to the water concentration of melt. Pu et al. (2017) at-
tributed this dependence of DMg to the coordination environments of Mg.
Other studies have suggested that the reaction between Mg and OH in melt
could affect the partitioning behavior of Mg and mafic minerals (Crabtree
and Lange, 2011; Frey and Lange, 2011; Waters and Lange, 2013). NBO/T
changes systematically with the total water concentration of melt (e.g.,
Mysen, 2014). Therefore, the proportions of the different coordination
states of Mg could be a function of the total water concentration of melt,
and, consequently, DMg could also be a function of the total water con-
centration of melt. The minimum DMg value of mantle peridotite partial
melt is located at NBO/T > 2.5 (Kushiro and Mysen, 2002; Mibe et al.,
2006), which is more depolymerized than NBO/T values for anhydrous-
based compositions of the input data of this study (0.15 to 1.88, calculated
according to Jaeger and Drake, 2000). As dissolved water increases NBO/T,
the actual NBO/T values of hydrous melts in the input data could be higher
than the anhydrous-based calculated values. The minimum DMg value at
~5 wt% H2O (Fig. 5) might represent the NBO/T value corresponding to
the maximum proportion of six-coordinated Mg in hydrous melt. As ex-
plained in Section 3.1, the amount of consumed oxygen associated with
2
dissociation of water in melt is proportional to WH2 O2 X Hmelt
2O
(Stolper, 1982).
2 include multiple phases, and could be incorporated into a total energy
Accordingly, we infer that WH2 O2 X Hmelt
2O
represents the structural change of
the silicate melt associated with the dissociation of water.
The relationship between DMg, the total water concentration, and
the microscopic structure of melt could be further investigated with a
detailed experimental analysis of the microscopic structures of Mg-
bearing hydrous melts. Furthermore, first-principles calculations (e.g.,
De Koker and Stixrude, 2009; Taniuchi and Tsuchiya, 2018) may pro-
vide quantitative understandings of the detailed relationship between,
and the mechanism connecting, thermodynamic properties and micro-
scopic structures, potentially including the water speciation, co-
ordination environment, and NBO/T of hydrous silicate melt.
4.3. Machine learning for petrological thermodynamic modeling
We constructed a thermodynamic model based on the selection of
important variables by using data for melting experiments. This type of
data-driven approach is becoming increasingly popular in various fields
of natural science (Hey et al., 2009; Igarashi et al., 2016; Ueki et al.,
2018). Specifically, we used the ES method to select the important
variables and the CV technique to quantitatively validate the predictive
capacity of various equations. On the basis of the predictive capacities
of the model equations, we were able to obtain a generalized and robust
equation for the hydrous-melt–olivine equilibrium, as well as to capture
the underlying thermodynamic relationship, such as the importance of
variables, the most informative combination of variables (Figs. 2 and
3), and the reproducibility of observed data (Appendix B). The pro-
posed method for model-selection using heterogeneous input data could
be applied to other petrological and geochemical problems, such as the
modeling of metamorphic reactions and of high-pressure experimental
9
Physics of the Earth and Planetary Interiors 300 (2020) 106430
data corresponding to lower-mantle conditions.
We simplified the thermodynamic equation and the model settings, and
we will expand our modeling approach in the future for application to
multi-component and more complex natural magmatic systems. Although
we considered a maximum of 10 possible terms, the number could be in-
creased, and the use of non-linear terms could also be further explored. For
example, if we consider the full equation of the symmetric regular solution
(Eq. (5)), 245 combinations of variables must be evaluated because the
maximum number of unknown thermodynamic parameters (W) is 45. The
maximum number of unknown thermodynamic parameters increases as
more complex equations (e.g., asymmetric regular solutions, or tempera-
ture- or pressure-dependent non-ideality) are introduced. Furthermore,
other aspects, such as the influence of magma oxygen fugacity (e.g., Moore
et al., 1995; Toplis and Carroll, 1995), and of trace components in olivine
(e.g., Ca; Libourel, 1999; Aubaud et al., 2004; Gavrilenko et al., 2016),
could be important for application to natural magmatic systems. In such
cases, the potentially large number of combinations of variables and the size
of the input dataset will need to be considered when employing the ES
method (i.e., the problem of combinatorial explosion). For such a case, an
alternative would be to use a different statistical treatment, such as ℓ1-norm
constraints (e.g., Tibshirani, 1996) or Akaike's Information Criterion (e.g.,
Akaike, 1974), to obtain optimal model equations.
As we used experiments based exclusively on mantle conditions, the
investigated compositional range was limited to mafic primary magma
compositions. Evolved melt compositions corresponding to natural arc
magmas should be incorporated in future modeling by expanding the
compositional range of the input dataset. Also, our present model considers
only the forsterite (Mg2SiO4) component in olivine, meaning that we have
fewer equations to constrain genetic or equilibrium conditions based on the
composition of natural basaltic samples using Eq. (13). By expanding our
present model to include the fayalite (Fe2SiO4) end-member component in
olivine, we could use the Fe/Mg exchange reaction to constrain the tem-
perature and melt water concentration simultaneously from the magma and
olivine compositions. Our results indicate that the ML-based model-selec-
tion approach is a robust and useful approach for constructing a thermo-
dynamic petrological model. The model construction can be expanded to
minimization and bulk conservation algorithm for thermodynamic calcu-
lation of multi-component systems (Ueki and Iwamori, 2013, 2014) to
model multi-component and multi-phase natural magmatic systems.
5. Summary
We presented a novel method and outcome for thermodynamic
modeling of the hydrous basaltic melt–olivine equilibrium. Specifically,
we applied a machine-learning-based model-selection approach, the
exhaustive variable selection method, to formulate a robust and gen-
eralized thermodynamic model that describes the underlying thermo-
dynamic relationship of the hydrous basaltic melt–olivine equilibrium.
A linear term and a squared term of the total water concentration of
2
melt (WH2 O XHmelt
2O
and WH2 O2 X Hmelt
2O
) were found to be significant ex-
planatory variables in the optimal model of the hydrous-melt–olivine
equilibrium. This relationship may be attributed in physical terms to
the microstructural changes that occur as a result of the dissociation of
water in silicate melt. Calculations using the constructed optimal model
reproduced the experimentally determined effects of water on the li-
quidus temperature of olivine and the distribution coefficient for Mg
between olivine and melt. Our results indicate that ML is a useful ap-
proach for constructing a petrological numerical model and for ana-
lyzing experimental results characterized by high-dimensional and
complex data, from which we are able to extract fundamental in-
formation, in the present case regarding hydrous-melt–olivine ther-
modynamics.
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.pepi.2020.106430.
K. Ueki, et al. Physics of the Earth and Planetary Interiors 300 (2020) 106430

CRediT authorship contribution statement Petrelli and an anonymous reviewer are thanked for useful and detailed
comments on an earlier version of the manuscript. We thank Taku
Kenta Ueki:Conceptualization, Methodology, Software, Formal Tsuchiya, Ryuichi Nomura, and Atsushi Yasumoto for insightful dis-
analysis, Investigation, Data curation, Writing - original draft.Tatsu cussions. We gratefully acknowledge grants from The Joint Usage/
Kuwatani:Conceptualization, Methodology, Writing - original Research Center programs of the Earthquake Research Institute,
draft.Atsushi Okamoto:Supervision.Shotaro Akaho:Software, University of Tokyo, Japan, 2015-B-04 (Geochemical Data Analysis
Supervision.Hikaru Iwamori:Writing - review & editing, Using Machine Learning) and 2018-B-01 (Data-driven Geoscience:
Supervision. Application to Dynamics in Mobile Belts). K.U. was supported by Japan
Society for the Promotion of Science KAKENHI Grant Numbers
Declaration of competing interest JP15H05833, JP17H02063, and JP19K04026, and T.K. was supported
by Japan Society for the Promotion of Science KAKENHI Grant numbers
The authors declare that they have no known competing financial JP15K20864 and JP25120005 and by Japan Science and Technology
interests or personal relationships that could have appeared to influ- Agency PRESTO Grant Number JPMJPR1676. S.A. and T.K. were sup-
ence the work reported in this paper. ported by Japan Science and Technology Agency CREST Grant No.
JPMJCR1761. Some of the experimental data used for the model-se-
Acknowledgments lection and parameter optimization were obtained from the Library of
Experimental Phase Relations open database of melting experiments
We thank Keith Putirka for a constructive and detailed review, and (Hirschmann et al., 2008). The R source code and dataset used in this
Kei Hirose for careful editorial handling of the manuscript. Maurizio study are provided in Supplementary materials 1 and 2 respectively.

Appendix A. Molar Gibbs free energy of pure solid and melt end-member components

Following the formulation by Ueki and Iwamori (2013) and Putirka (2017), the Gibbs free energy of the melt–olivine (ol) reaction is written as
T T Cpi P
µi = H jfus + Cpi dT T S jfus + dT + Vi dP + RT ln Q
T jfus T jfus T 1bar (A1)
where T jfus , Hjfus ,
and Sjfus are
the temperature, enthalpy, and entropy of the fusion of solid end-member component j at 1 bar, respectively. Q
denotes the reaction quotient (e.g., Putirka, 2017). When an equilibrium state is achieved (Δμ = 0), Q is equal to aimelt / ajol , where ai is the activity
coefficient of end-member component i. Δμi denotes the difference in molar Gibbs free energy between the melt and the corresponding solid end-
member components. ΔCpi is the difference in molar specific heat between the solid end-member component j and the melt end-member component
i, and is written as Cpi = Cpimelt Cpjsolid . ΔVi is the difference in molar volume between solid end-member component j and melt end-member
component i, written as Vi = Vimelt V jsolid .
Although the P–V relation of silicate melt exhibits a non-linear relationship (e.g., Ueki and Iwamori, 2016), ΔVi values during melting within the
mantle can be assumed to be constant at the pressures of interest in this study, regardless of temperature (Ueki and Iwamori, 2014). In addition, the
total volume and compressibility of silicate melt can be treated as linear combinations of these parameters of oxide end-member components (Lange
and Carmichael, 1987, 1990) and the H2O end-member component of the melt. Therefore, ΔVi was simply derived by a linear regression between the
partial molar volumes of silicate melt and olivine using the equation of state for hydrous melt (Ueki and Iwamori, 2016) and that for olivine (Berman,
1988). ΔVi used in this study is a function of pressure [P (bar)], as follows: V = 2 × 10 6P + 0.0713
As noted in our previous study (Ueki and Iwamori, 2014), only a weak pressure dependence (10−6) is obtained.
Previous experimental studies have shown that excess specific heat related to the mixing of end-member components, including water, in silicate
melt is negligible (e.g., Bouhifd et al., 2006; Di Genova et al., 2014). Ueki and Iwamori (2013, 2014) reported that the value of ΔCp during melting
can be assumed to be constant at the temperatures and pressures of interest in the present study. Values of T jfus , ΔCp, H jfus , and S jfus were taken
from previous experimental results, with T jfus = 2174 K (Sugawara, 2005), ΔCp = 100 (J/mol-K) (Richet and Bottinga, 1985; Gillet et al., 1991;
Médard and Grove, 2008), H jfus = 138.90 (kJ/mol) (Sugawara, 2005), and S jfus = 63.89 (J/K-mol) (Sugawara, 2005). The model of Sack and
Ghiorso (1989) was used for aol.
To summarize the temperature- and pressure-dependent and melt-composition- and olivine-composition-independent terms, we introduced a
term ΔG0(P, T) as
T T Cpi P
G 0 (P , T ) = H jfus + Cpi dT T S jfus + dT + Vi dP .
T jfus T jfus T 1bar (A2)
0
By introducing the term ΔG (P, T), Eq. (A1) can be rearranged into Eq. (2) of the main text.

10
K. Ueki, et al. Physics of the Earth and Planetary Interiors 300 (2020) 106430

Appendix B. Residuals vs total water concentration (mole fraction) of the top 10 models

The best model Other models

15000

15000

15000

15000

15000
1st 2nd 3rd 4th 5th

10000

10000

10000

10000

10000
Predicted minus validation data (J)
5000

5000

5000

5000

5000
0

0
5000

5000

5000

5000

5000
10000

10000

10000

10000

10000
15000

15000

15000

15000

15000
0.00 0.05 0.10 0.15 0.20 0.00 0.05 0.10 0.15 0.20 0.00 0.05 0.10 0.15 0.20 0.00 0.05 0.10 0.15 0.20 0.00 0.05 0.10 0.15 0.20
H2O (mole fraction) H2O (mole fraction) H2O (mole fraction) H2O (mole fraction) H2O (mole fraction)

15000

15000

15000

15000

15000
6th 7th 8th 9th 10th

10000

10000

10000

10000

10000
Predicted minus validation data (J)
5000

5000

5000

5000

5000
0

0
5000

5000

5000

5000

5000
10000

10000

10000

10000

10000
15000

15000

15000

15000

15000
0.00 0.05 0.10 0.15 0.20 0.00 0.05 0.10 0.15 0.20 0.00 0.05 0.10 0.15 0.20 0.00 0.05 0.10 0.15 0.20 0.00 0.05 0.10 0.15 0.20
H2O (mole fraction) H2O (mole fraction) H2O (mole fraction) H2O (mole fraction) H2O (mole fraction)

Fig. B1. Residuals (difference between values predicted using the constructed model and the validation data; i.e., ym − f−m(W) in Eq. (12)) obtained during CV
analysis plotted against the total water concentration in melt ( XHmelt
2 O ). Residuals were calculated using Eq. (10) (difference between the right- and left-hand sides of Eq.
(10)). Each circle represents an independent experimental result.

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